KR100305160B1 - Metal foil with improved bonding to substrates and metnod for making said foil - Google Patents

Abstract

The present invention relates to a method of treating a metal foil,

Contacting the metal foil with an acidic solution;

The metal foil is placed in a nickel treatment bath comprising at least two plating zones, about 1 - 50 g / l of ammonium salt, and about 10 - 100 g / l of nickel compound, Applying; And

Applying a nickel flash layer to the metal foil, and a metal foil manufactured by the method.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a metal foil having improved bonding to a gas,

The present invention relates to a method of treating a metal foil and a metal foil treated by the method.

In particular, the present invention includes a method of treating metal foils wherein the treated wastes can be easily pulverized while the treated metal foils maintain or retain improved binding properties.

Metal foils, such as copper foils, are often laminated to a substrate.

The laminate undergoes many processes as well as inevitable wear and tear.

In this connection, it is desirable to provide a laminate having a high peel strength.

The high peel strength allows for structural integrity during processing (exposure to chemicals and various corrosives (etchants)) and during normal wear and tear (tear strength, physical agitation, etc.).

The metal foil is typically treated to improve surface roughness, thereby increasing the peel strength of the laminate.

However, a metal foil with a very high level of roughness experiences a " treatment transfer, " which is the transfer of undesirable metal material from the metal foil to the dielectric substrate.

The treatment transfer not only lowers the peel strength but also deteriorates the insulating property of the dielectric material.

The treatment transfer also contributes to the formation of unsightly yellow stains after the metal foil is etched.

Therefore, it is desirable to provide a metal foil that exhibits high peel strength when bonded with a laminate, and that does not affect the dielectric properties of the dielectric gas.

Since ammonium ions form complexes with metal ions when ammonium and metal ions are present in solution, an increase in the concentration of ammonium ions in a given solution increases the solubility of the metal ions.

Solutions containing metal ions constitute the waste to be treated before being discarded.

Generally, the higher the concentration of complex metal ions in the waste solution, the more difficult it becomes to treat the waste solution.

Accordingly, it is desirable to provide a process for producing a waste stream that is easily processed.

It is an object of the present invention to provide a metal foil treatment method and a metal foil treated as described above, which not only improves the bond strength or peel strength between a metal foil and a gas, but also has a good metal ion waste treatment ability.

In one example, the present invention provides a method comprising: contacting a metal foil with an acidic solution; Placing the metal foil in a nickel treatment bath comprising at least about two plating zones, about 1 to about 50 g / l of an ammonium salt and about 10 to about 100 g / l of a nickel compound, Applying the first layer to the second layer; And applying a nickel flash layer to the metal foil. ≪ RTI ID = 0.0 > [0002] < / RTI >

In another example, the present invention provides a method of manufacturing a metal foil, comprising: contacting a metal foil with an acidic solution; Placing the metal foil in a nickel treatment bath comprising at least about two plating zones, about 1-50 g / l of ammonium chloride and about 10-100 g / l of nickel chloride and applying an electrical current through the nickel treatment bath ; And applying a nickel flash layer to the metal foil in an electrodepostion bath. ≪ RTI ID = 0.0 > [0002] < / RTI >

In another example, the present invention provides a method comprising: contacting a metal foil that does not comprise a copper treatment layer with an acidic solution; Placing the metal foil in a nickel treatment bath comprising at least about two plating zones, about 25-45 g / l of ammonium salt and about 10-100 g / l of nickel compound, and applying current through the nickel treatment bath ; And applying a nickel flash layer to the metal foil in an electrodeposition bath.

In yet another example, the present invention relates to a metal foil that has been treated according to any one of the above methods.

It is possible with the present invention to provide a metal foil that exhibits high peel strength and exhibits little or no treatment transfer when bonded with a laminate.

The present invention provides a method and metal foil for producing waste that is easier to treat because the waste solution contains relatively low concentrations of complexed metal ions.

The metal foil used in the present invention is preferably an electrically conductive foil containing copper, particularly preferably a copper-based alloy foil.

Other examples include aluminum, nickel, tin, silver, gold and alloys thereof.

Metal foils are manufactured using one of two technologies.

A machined or rolled metal foil is produced by mechanically reducing the thickness of a copper or copper alloy strip or ingot by a process such as rolling.

Electrodeposited foils are prepared by electrodepositing metal ions such as copper ions on a rotating negative electrode drum, and then stripping the electrodeposited strip of the negative electrode.

Electrodeposited copper foils are particularly preferred.

Metal foils typically have a nominal thickness range of about 0.0002-0.02 inches.

The metal foil thickness is sometimes expressed in terms of weight, the foils of the present invention having a weight or thickness in the range of about 1/8 to 14 oz / ft ² .

Particularly useful metal foils are those having a weight of 1/2, 1 or 2 oz / ft ² , and more preferred are copper foils having a weight of 1/2, 1 or 2 oz / ft ² .

The electrodeposited metal foil has a soft or shiny (drum) side and a rough or uneven matte (metal deposit growth front) surface.

The faces or faces of the metal foil (electrodeposited or worked) that can be treated in accordance with the present invention can be rough or non-glossy, polished or two-sided.

The surfaces can be a "standard-profile surface", a "low-profile surface", or a "very-low-profile surface".

Particularly preferred examples include the use of a foil having a non-shiny surface and a standard-profile surface.

The term " standard-profile surface " herein refers to a foil surface having an R _tm of about 7-12 microns.

The term "low-profile surface" refers to a foil surface having an R _tm of about 7 microns or less.

The term " extremely low-profile surface " refers to a foil surface having an R _tm of about 4 microns or less.

The R _tm is an average value of the maximum peak-to-valley vertical measurement in each of the five consecutive sampling measurements and is reported by Rank Taylor Hobson, Ltd., (Leicester, England) It can be measured using a Surtronic 3 profilometer.

In one example, it may be a feature of the metal foil of the present invention that no additional surface roughening treatment is performed on the base surface of the surface or surfaces on which the present invention is carried out.

The term " base surface " of the foil surface refers to a surface of a non-treated (untreated) foil surface that has not been subjected to any subsequent treatment of the type described below to refine or enhance the foil characteristics and / (raw foil surface).

The term " additional surface roughness treatment " means any treatment carried out on the base surface of the foil for the purpose of improving the surface roughness of the foil, not according to the invention.

In one example, the additional surface roughness treatment increases the R _tm by 3 microns or more; And in another example, the additional surface roughness treatment increases the R _tm by 10 microns or more.

In one example, a metal treatment such as a copper treatment adding surface roughness is excluded from the method of the present invention.

The metal treatment includes copper or zinc electrodeposited in nodular or dendritic form and copper oxide grown in nodular or dendritic form on the base surface of the foil.

Metal foils having relatively coarse layers (serrations) that occur naturally on the uneven surface of the base surface are not excluded within the scope of the present invention.

In one example, the mechanical roughness imposed on the metal foil during rolling or subsequent machining by increasing the roughness beyond the roughness range of the standard profile surface is excluded from the present invention, since it is considered to be additional surface roughness treatment.

In one example, the illuminance imparted to the electrodeposited metal foil during electrodeposition, which increases the illuminance beyond the illuminance range of the standard profile surface, is considered to have been subjected to additional surface roughness.

In one example, any roughness imparted to the base surface of the metal foil that increases the roughness of the foil beyond the roughness range of the standard profile surface is considered to be additional surface roughness.

In one example, any roughness imparted to the base surface of the metal foil that increases the roughness of the foil beyond the low-profile surface illumination range is considered to be additional surface roughness treatment.

In one example, any roughness imparted to the base surface of the metal foil that increases the roughness of the foil beyond the roughness profile of the extra-low profile surface is considered to be additional surface roughness.

In one example, the surface of the metal foil or the base surface of the surfaces is untreated before being treated according to the present invention.

Quot; untreated " is used herein to refer to the base surface of a metal foil that has not been subjected to subsequent processing for the purpose of improving or improving foil characteristics and / or for improving surface roughness.

In one example, the untreated foil has a naturally occurring non-dendritic or non-cannular layer of copper oxide or other metal or metal alloy attached to its base surface.

The naturally occurring non-dendritic layer is not addition metal-treated.

In one example, the surface of the foil or the base surface of the surfaces is treated with one or more surface treatment layers for the purpose of improving or improving the foil characteristics before the invention is applied, but no surface roughness is added.

In addition, any side of the metal foil to which the method of the present invention is not applied may optionally have one or more of the above-mentioned treatment layers applied thereto.

Such surface treatment is well known in the art.

For example, the surface treatment includes application of a metal layer that does not improve surface roughness prior to carrying out the invention, wherein the metal is selected from the group consisting of indium, zinc, tin, nickel, cobalt, copper- , And mixtures of two or more thereof.

These types of metal layers are sometimes referred to as barrier layers.

These metal layers preferably have a thickness in the range of about 0.01-1 microns, more preferably in the range of about 0.05-0.1 microns.

In addition, the surface treatment includes the application of a metal layer which does not increase the surface roughness before carrying out the present invention, wherein the metal is a tin, chromium-zinc mixture, nickel, molybdenum, aluminum, or a mixture of two or more thereof .

These types of metal layers can be applied to the base surface of the foil or they can be applied to the previously applied barrier layer.

This type of metal layer is sometimes referred to as a stabilization layer.

These stabilizing layers preferably have a thickness in the range of from about 0.005 to 0.05 microns, more preferably from about 0.01 to 0.02 microns.

In one example, one or both sides of the foil is first treated with at least one barrier layer.

In another example, one or both sides of the foil is first treated with at least one stabilizing layer.

In another example, one or both sides of the foil is first treated with at least one barrier layer, and then at least one side of the treated side is treated with at least one stabilizing layer prior to performing the method of the present invention.

The metal foil in accordance with the present invention may be a single layer metal foil such as a copper foil, an aluminum foil or a nickel foil, or a foil of a metal alloy.

The metal foil in accordance with the present invention may be a foil comprising foil made of layers of copper and brass or a foil comprising multiple layers of metal alloys.

The number of metal layers in any given metal foil is not particularly limited.

The inventive method comprises sequentially performing at least the following three steps.

First, the metal foil contacts the acid solution.

Next, the metal foil is subjected to a nickel treatment step.

Next, a nickel flash layer is applied to the metal foil.

The term " sequentially " means that the three steps are performed in the order presented.

That is, the nickel treatment step should be performed after contacting the metal foil with the acidic solution and before applying the nickel flush layer.

However, the three steps need not be performed immediately after the preceding step when the additional steps are executed.

For example, a rinsing step may be performed after the metal foil is contacted with the acid solution, but before the metal foil undergoes the nickel treatment step.

Thus, the term " sequentially " refers to three essential steps of the method of the invention, rather than any additional steps in various examples of the method of the present invention.

The first step of the process of the present invention involves contacting the metal foil with an acidic solution.

The acidic solution has a pH of about 5 or less, preferably a pH of about 3 or less, and more preferably a pH of about 2 or less.

Such acidic solutions include acids and water, polar organic liquids such as alcohols and glycols, and solvents such as mixtures thereof.

The contact between the metal foil and the acidic solution serves to remove the surface oxide from the metal foil and to clean the surface of the metal foil.

The debris, which can detrimentally interfere with the subsequent nickel treatment step, is removed by the acidic solution.

The acidic solution also serves to facilitate the subsequent processing steps by activating the surface of the metal foil.

In particular, the effectiveness of the subsequent nickel treatment step is increased by contacting the metal foil with an acidic solution.

The metal foil is placed in contact with the acid solution for a time sufficient to clean the foil, generally about 1 second to 2 minutes, preferably about 10 seconds to 40 seconds.

The metal foil is contacted with the acidic solution through conventional means including immersion, spraying, wiping, immersing, etc., but is not limited to the above means.

In a preferred example, the metal foil is contained in an acidic solution.

In another preferred embodiment, the temperature of the acidic solution is from about 20 캜 to 60 캜, more preferably from about 30 캜 to 40 캜.

The acidic solution contains at least one acid and a suitable solvent, which is typically water or a combination of water and polar organic, although polar organic liquids can be used.

Any of inorganic or organic acids may be used, but inorganic acids are preferred.

Examples of inorganic acids that can be used in the acid solution include halogen acids such as hydrofluoric acid, hydrochloric acid, bromic acid and iodic acid, sulfuric acid, sulfuric acid, nitric acid, perchloric acid, boric acid and phosphorous acid such as phosphorous acid and phosphoric acid and mixtures thereof. Nitric acid and sulfuric acid are preferred inorganic acids. Examples of the organic acid include carboxylic acid and polycarboxylic acid such as formic acid, acetic acid, propionic acid, citric acid, oxalic acid and the like; Organic phosphoric acids such as dimethylphosphoric acid and dimethylphosphinic acid; Or sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, 1-pentanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, benzenesulfonic acid and toluenesulfonic acid and mixtures thereof.

In a preferred example, after the metal foil is contacted with the acidic solution, the metal foil is optionally rinsed with a neutral or weakly alkaline solution and, in most cases, optionally rinsed with an aqueous system solution, such as water containing buffer. A neutralizing liquid or a rinsing liquid is used to remove excess acid and / or debris from the surface of the metal foil.

After the metal foil is contacted with the acidic solution, the metal foil is subjected to a nickel treatment step. This step is performed by placing a metal foil in a nickel treatment bath and applying an electric current through a nickel treatment bath. The nickel treatment step changes the structure of the metal foil surface. More specifically, the nickel treatment step increases the surface area by forming a nodule or a dendrite on the surface of the metal foil.

The nickel treatment bath contains an ammonium salt, a nickel compound and a suitable solvent. Although polar organic solvents are used, the solvent is typically an aqueous system. Examples of the ammonium salt include quaternary organic ammonium salts such as tetramethylammonium chloride and tetraethylammonium chloride, as well as ammonium chloride, ammonium bromide, ammonium benzoate, ammonium carbonate, ammonium dihydrogenphosphate, ammonium fluoride, ammonium hydrogen carbonate, Ammonium nitrate, ammonium phosphate, ammonium sulfate, and ammonium bisulfate. The ammonium salt is present in an amount of about 1-50 g / l, preferably about 25-45 g / l and most preferably about 30-40 g / l. An important characteristic of the present invention is that the amount of the ammonium salt in the nickel treatment bath does not exceed 50 g / l and preferably does not exceed 45 g / l.

Ammonium ions may be difficult to remove as waste. In addition, the larger the ammonium ion concentration, the greater the solubility of metal ions through complexation, making the ammonium waste more dangerous and / or difficult to treat.

The nickel compound refers to any nickel-containing compound capable of decomposing in solution such as a nickel salt. The nickel compounds include nickel chloride, nickel bromide, nickel acetate, nickel carbonate, nickel fluoride, nickel iodide, nickel nitrate, nickel oxide, and nickel sulfate. Nickel chloride is preferred for use.

The nickel compound is contained in the nickel treatment bath in an amount ranging from about 10 to 100 g / l, preferably from about 20 to 60 g / l, and most preferably from about 30 to 50 g / l.

In one example, the current density applied to the nickel treatment bath is about 150-500 ASF.

In another example, the current density is about 200-400 ASF, preferably about 250-300 ASF.

In one example, the temperature of the nickel treatment bath is about 20-50 ° C.

In another example, the temperature is about 25 - 45 캜, preferably about 30 - 40 캜.

In one example, the pH of the nickel treatment solution is about 4-7.

In another example, the pH is from about 5 to about 6.5, preferably from about 5.5 to about 6.

The metal foil is placed in the nickel treatment bath for a time sufficient to allow the formation of a nodule on its surface.

In one example, the metal foil is placed in the nickel treatment bath for about 10-60 seconds.

In a preferred example, the metal foil is placed in the nickel treatment bath for about 20-40 seconds.

Another important feature of the present invention is that the nickel treatment bath comprises at least two plating zones.

In a preferred example, the nickel treatment bath comprises at least about three plating zones, more preferably the nickel treatment bath comprises at least about four plating zones.

The use of at least about two zones results in improved peel strength for laminates using treated metal foils.

A plurality of plating zones contribute to a uniform application of the nickel treatment step.

In a preferred example, the current density is varied when the nickel treatment step is performed.

That is, in one example, the current density is maintained at a relatively high level within a temporarily acceptable range and then adjusted to a relatively low level within an acceptable range.

The application of current densities of high-low-high-low, etc. provides a more desirable nickel treatment, resulting in a higher peel strength after the treated metal foil is laminated to the gas It comes.

In one example, the average thickness of the nickel treated layer is about 0.5-4 microns.

In a preferred embodiment, the average thickness of the nickel treated layer is from about 1.5 to about 2.5 microns.

The thickness of the nickel treated layer can be measured by a conventional automatic apparatus.

Depending on the condition that the nickel treatment layer is applied to the metal foil, the nickel treatment layer has an acicular structure, especially when compared with the crystal structure of the metal foil or the nickel flash layer.

The needle-like structure provides a non-homogeneous surface to the treated metal foil, resulting in improved peel strength when the treated metal foil is laminated to the gas.

In a preferred example, after the nickel treatment step is performed, the metal foil is optionally rinsed with a neutral or slightly acidic solution, and in most cases optionally rinsed with an aqueous based solution such as water containing buffer Loses.

The neutral or rinsing liquid serves to remove excess ammonium ions and / or loose debris from the surface of the metal foil.

The step involving applying a nickel flash layer to the metal foil is preferably carried out in an electrodeposition bath through electrodeposition of nickel or a nickel alloy.

This step is performed after the nickel treatment step.

The term " nickel flash layer " refers to a thin nickel coating layer having a low profile compared to the surface to which it is coated.

That is, the nickel flash layer is flat or substantially non-dendritic.

When applied to a dendritic surface, the nickel flash layer is fairly uniform in that it follows a nodule or dendritic profile whose thickness is essentially constant over the entire area of the metal foil applied.

In one example, the nickel flash layer is applied at a thickness less than the profile of the nodule or dendritic layer to be deposited.

In a more preferred embodiment, the nickel flash layer has an average thickness not greater than about 20% of the average height of the nodule or resin on the metal foil.

The average height of the nodule or resin phase on the metal foil is the average depth of the valley between the nodules or dendrites in terms of the average height of the nodule or dendritic peaks in the metal foil.

In this regard, the average profile height is similar to R _tm .

The average profile height can be determined in the same manner as R _tm .

In a preferred example, the average thickness of the nickel flash layer is not greater than about 10% of the average profile.

In a more preferred example, the average thickness of the nickel flash layer is not greater than about 5% of the average profile height.

In one example, the average thickness of the nickel flash layer is about 0.2-3 microns.

In a preferred example, the average thickness of the nickel flash layer is from about 0.7 to 1.5 microns.

In another example, the average thickness of the nickel flash layer is less than the average thickness of the nickel treated layer.

The thickness of the nickel flash layer can be measured by a conventional automatic apparatus.

The electrodeposition bath for applying a nickel flash layer to a metal foil contains at least one nickel compound in a suitable solvent.

In addition, the electrodeposition bath may be uniform, relatively flat, and contain various additives to promote deposition of the non-dendritic nickel flash layer.

The nickel compound is as described in connection with the nickel treatment solution.

Nickel sulphate is the preferred nickel compound for nickel flash electrodeposition baths.

Various additives include buffering agents such as boric acid, anti-pitting compounds such as a flatening agent, surface active agent such as saccharin.

When boric acid is contained in the bath as a buffer, it contains in the range of about 10 to 100 g / l, preferably about 20 to 60 g / l, and most preferably about 30 to 50 g / l.

In a preferred example, at least two nickel compounds are contained in the nickel flash electrodeposition bath.

In the above examples, nickel compounds such as nickel sulphate and nickel chloride are preferable.

In one example, the amount of nickel compound contained in the nickel flash electrodeposition bath is about 200-500 g / l.

In a preferred example, the total amount is about 250-450 g / l, preferably about 300-400 g / l.

When two or more nickel compounds are contained in the nickel flash electrodeposition bath, the ratio of the first nickel compound to the second nickel compound is from about 3: 1 to 10: 1, preferably from 4: 1 to 8: 1.

In one example, the current density applied to the nickel flash electrodeposition solution is about 10-100 ASF.

In another example, the current density is about 20-90 ASF, preferably about 40-80 ASF.

In one example, the current density applied to the nickel flash electrodeposition solution is less than about a half of the current density applied to the nickel treatment bath.

In a preferred example, the current density is varied when a nickel flash layer is applied.

That is, in one example, the current density is temporarily maintained at a relatively high level within the acceptable range, and then adjusted to a relatively low level within the acceptable range.

Applications such as high-low-high-low-current densities provide a more preferred nickel flash layer, resulting in a treated metal foil with higher quality.

In one example, the temperature of the nickel flash electrodeposition bath is about 30-80 占 폚.

In another example, the temperature of the nickel flash electrodeposition bath is about 40-70 占 폚, preferably about 50-60 占 폚.

In one example, the temperature of the nickel flash electrodeposition bath is higher than the temperature of the nickel bath.

In one example, the pH of the nickel flash electrodeposition bath is about 2.5 to 5.5 or less.

In another example, the pH is about 3-5, preferably about 3.5-4.5.

In one example, the pH of the nickel flash electrodeposition bath is lower than the pH of the nickel bath.

The metal foil is homogeneous and is placed in the nickel flash electrodeposition bath for a time sufficient to form a relatively flat deposit on its surface.

In one example, the metal foil is positioned in the nickel flash electrodeposition bath for about 10-60 seconds.

In a preferred example, the metal foil is placed in the nickel flash electrodeposition bath for about 20-40 seconds.

In one example, the metal foil is located in the nickel flash electrodeposition bath for a time longer than the time it is located in the nickel treatment bath.

In one example, while applying a nickel flash layer to the metal foil, the electrodeposition bath comprises at least one plating zone.

In a preferred example, the electrodeposition bath for plating the nickel flash layer comprises at least two plating zones.

In another preferred embodiment, the electrodeposition bath for plating the nickel flash layer comprises at least three plating zones, and more preferably comprises four plating zones.

Depending on the conditions in which the nickel flash layer is applied to the metal foil, the nickel flash layer has a finer crystal structure than the crystal structure of the metal foil or the nickel-treated layer in particular.

The fine crystalline structure provides enhanced strength to the treated metal foil and results in improved peel strength when the treated metal foil is laminated to the gas.

The treated foil may include one or more suitable adhesion promoting layers to further enhance the adhesion between the foil and the gas.

The adhesion promoting layer may comprise at least one silane compound and / or at least one thermosetting and thermoplastic polymer and copolymer.

Thermosetting and thermoplastic polymers and copolymers include epoxy resins (including monofunctional and polyfunctional epoxy resins), formaldehyde resins, phenol formaldehyde resins, polyester resins, butadiene and acrylonitrile rubbers, polyvinyl butyral resins and / or Phenol resin. In one example, the feature of the adhesion promoting layer is that there is no chromium mixed in between.

According to one example, the adhesion promoting layer may be prepared by applying one or more silane compounds to at least one side or surface of the treated metal foil. The silane compound is present in the solution in an amount of about 0.1-10% v / v, and preferably about 0.2-5% v / v, and more preferably about 0.3-3% v / v.

A preferred silane compound is a silane coupling agent. Preferred silane coupling agents are amino-silane compounds, epoxy-silane compounds and alkoxy-silane compounds.

According to one embodiment, the silane compound can be represented by the following formula.

Provided that G ¹ , G ² , G ³ , G ⁴ , G ⁵ and G ⁶ are independently halogen, hydrocarbyloxy or a hydroxy group;

R ¹ is a hydrocarbon group or a nitrogen-containing hydrocarbon group;

n is 0 or 1;

According to one aspect, each of G ¹ , G ² , G ³ , G ⁴ , G ⁵ and G ⁶ is independently chloro, alkoxy, alkoxyalkoxy or alkoxyalkoxyalkoxy and R ¹ is up to about 10 carbon atoms Alkylene or arene group or a single amino- or polyamino-substituted alkylene or arylene group of up to 10 carbon atoms. According to one example, each of G ¹ , G ² , G ³ and G ⁶ is an alkoxy, alkylalkoxy, alkoxyalkoxy or alkoxyalkoxyalkoxy group having up to 10 carbon atoms, and n is 0.

Examples of these silane compounds include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra-n-butoxysilane, tetrakis (2-ethoxyethoxy) silane, tetrakis (2-ethylbutoxy) Silane, tetrakis (2-ethylhexoxy) silane, tetrakis (methoxyethoxyethoxy) silane, tetrakis (2-methoxyethoxy) silane, tetrakis (1-methoxy- Bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) propylamine, bis [3- (trimethoxysilyl) propyl] ethylenediamine, Bis (trichlorosilyl) ethane, 1,6-bis (trichlorosilyl) hexane and 1,8-bis (trichlorosilyl) ) ≪ / RTI > octane.

According to another example, the silane compound may be a compound represented by the following formula.

R ² , R ³ , R ⁴ and R ⁵ are independently selected from the group consisting of hydrogen, a halogen group, a hydrocarbyloxy group, a hydroxyl group, an organofunctional group, an organic functional group that is reactive or affinity for other gases (such as prepreg) to be. Examples of organic functional groups include amino-containing, amido-containing, hydroxy-containing, alkoxy-containing hydrocarbons, vinyl-containing hydrocarbons, aromatic, heterocyclic groups, allyl-containing groups, Group, a carboxy-containing group, an isocyanato-containing group, a glycidoxy-containing group and an acryloxy-containing group. According to one embodiment, each of R ³ , R ⁴ and R ⁵ is chloro, methoxy or ethoxy, and R ² is an organic functional group. According to one embodiment, each R ⁴ and R ⁵ is chloro, methoxy or ethoxy, and R ² and R ³ are organic functional groups.

Examples of these silane compounds include tetramethoxysilane; Tetraethoxysilane; Diaminosilane; N- (2-aminoethyl) -3-aminopropyltrimethoxysilane; 3- (N-stilylmethyl-2-aminoethylamino) propyltrimethoxysilane; 3-aminopropyltriethoxysilane; Bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane; ? - (3,4-epoxycyclohexyl) -ethyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane; 3-methacryloxypropyltrimethoxysilane; 3-chloropropyltrimethoxysilane; Vinyl trichlorosilane; Vinyltriethoxysilane; Vinyl-tris (2-methoxyethoxy) silane; Aminopropyltrimethoxysilane; N-methylaminopropyltrimethoxysilane; N-phenylaminopropyltrimethoxysilane; 3-acetoxypropyltrimethoxysilane; N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane; 3-acryloxy-propyltrimethoxysilane; Allyltriethoxysilane; Allyltrimethoxysilane; 4-aminobutyltriethoxysilane; (Aminoethylaminomethyl) phenethyltrimethoxysilane; N- (2-aminoethyl-3-aminopropyl) trimethoxysilane; N- (2-aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane; 6- (aminohexylaminopropyl) trimethoxysilane; Aminophenyl trimethoxysilane; 3- (1-aminopropoxy) -3,3, -dimethyl-1-propenyltrimethoxysilane; 3-aminopropyltris (methoxyethoxyethoxy) silane; 3-aminopropyltriethoxysilane; 3-aminopropyltrimethoxysilane; ω-aminoundecyltrimethoxysilane; 3- [2-N-benzyl-aminoethylaminopropyl] trimethoxysilane; Bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane; 8-bromooctyltrimethoxysilane; Bromophenyltrimethoxysilane; 3-bromopropyltrimethoxysilane; 2-chloroethyltriethoxysilane; p- (chloromethyl) phenyltrimethoxysilane; Chloromethyltriethoxysilane; Chlorophenyltriethoxysilane; 3-chloropropyltriethoxysilane; 3-chloropropyltrimethoxysilane; 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane; 3- (cyanoethoxy) -3,3-dimethyl-1-propenyltrimethoxysilane; 2-cyanoethyltriethoxysilane; 2-cyanoethyltrimethoxysilane; (Cyanomethylphenethyl) trimethoxysilane; 3-cyanopropyltriethoxysilane; 3-cyclopentadienylpropyltriethoxysilane; (N, N-diethyl-3-aminopropyl) trimethoxysilane; Diethylphosphatoethyltriethoxysilane; (N, N-dimethyl-3-aminopropyl) trimethoxysilane; 2- (diphenylphosphino) ethyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-iodopropyltrimethoxysilane; 3-isocyanatopropyltriethoxysilane; 3-mercaptopropyltriethoxysilane; 3-mercaptopropyltrimethoxysilane; Methacryloxypropenyltrimethoxysilane; 3-methacryloxypropyltrimethoxysilane; 3-methacryloxypropyl tris (methoxyethoxy) silane; 3-methoxypropyltrimethoxysilane; N-methylaminopropyltrimethoxysilane; O-4-methylquomarinyl-N- [3- (triethoxysilyl) propyl] carbamate; Oct-1-enyltrimethoxysilane; N-phenethyl-N'-triethoxysilylpropylurea; N-phenylaminopropyltrimethoxysilane; 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane; 3-thiocyanatopropyltriethoxysilane; N- (3-triethoxysilylpropyl) acetylglycinamide; N- (triethoxysilylpropyl) dodecylamide; N- [3- (triethoxysilyl) propyl] -2,4-dinitrophenylamine; Triethoxysilylpropylethylcarbamate; N- [3- (triethoxysilyl) -propyl] -4,5-dihydroimidazole; N-triethoxysilylpropyl-o-mentocarbamate; 3- (triethoxysilylpropyl) - p-nitrobenzamide; N- [3- (triethoxysilyl) propyl] phthalamic acid; N- (triethoxysilylpropyl) urea; 1-trimethoxy silyl-2- (p, m-chloromethyl) -phenyl ethane; 2- (trimethoxysilyl) ethylphenylsulfonyl azide; beta -trimethoxysilylethyl-2-pyridine; Trimethoxysilyloctyltrimethylammonium bromide; Trimethoxysilylpropyl cinnamate; N- (3-trimethoxysilylpropyl) -N-methyl-N, N-diallylammonium chloride; Trimethoxysilylpropyldiethylenetriamine; N - [(3-trimethoxysilyl) propyl] ethylenediaminetriacetic acid trisodium salt; Trimethoxysilylpropylisothiouronium chloride; N- (3-trimethoxysilylpropyl) pyrrole; N-trimethoxysilylpropyltri-N-butylammonium bromide; N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride; Vinyltriethoxysilane; Vinyl triisopropoxysilane; Vinyltrimethoxysilane; Vinyltris-t-butoxysilane; Vinyltris (2-methoxyethoxy) silane; Vinyltriisopropenoxysilane; Vinyltris (t-butylperoxy) silane; 2-acetoxyethyltrichlorosilane; 3-acryloxypropyl trichlorosilane; Allyltrichlorosilane; 8-bromooctyltrichlorosilane; Bromophenyl trichlorosilane; 3-bromopropyltrichlorosilane; 2- (carbomethoxy) ethyl trichlorosilane; 1-chloroethyltrichlorosilane; 2-chloroethyltrichlorosilane; p- (chloromethyl) phenyl trichlorosilane; Chloromethyl trichlorosilane; Chlorophenyl trichlorosilane; 3-chloropropyltrichlorosilane; 2- (4-chlorosulfonylphenyl) ethyltrichlorosilane; (3-cyanobutyl) -trichlorosilane; 2-cyanoethyltrichlorosilane; 3-cyanopropyl trichlorosilane; (3-chloromethyl) trichlorosilane; (Dichlorophenyl) trichlorosilane; 6-hex-1-enyl trichlorosilane; 3-methacryloxypropyl trichlorosilane; 3- (4-methoxyphenyl) propyltrichlorosilane; Oct-1-enyl trichlorosilane; 3- (N-phthalimido) propyltrichlorosilane; 1-trichlorosilyl-2- (p, m-chloromethylphenyl) ethane; 4- [2- (trichlorosilyl) ethyl] cyclohexene; 2- [2- (trichlorosilyl) ethyl] pyridine; 4- [2- (trichlorosilyl) ethyl] pyridine; 3- (trichlorosilyl) propyl chloroformate, and vinyl trichlorosilane.

According to one example, preferred silanes are 3-aminopropyltriethoxysilane; 3-glycidoxypropyltrimethoxysilane; And N- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole. Mixtures of two or more of the above listed compounds may be used. For example, in one example, the silane compound may be combined with tetraethoxysilane or tetramethoxysilane to form N- (2-aminoethyl-3-aminopropyl) trimethoxysilane, 3-aminopropyltrimethoxysilane, 3- Glycidoxypropyltrimethoxysilane. ≪ / RTI >

The silane solution may be used in the form of a dispersion or solution in water, a mixture of water and an alcohol, or in an appropriate organic solvent, or as an aqueous emulsion of a silane mixture, or as an aqueous emulsion of a solution of a silane compound in a suitable organic solvent. Conventional organic solvents may be used and include alcohols, ethers, ketones, and mixtures thereof with aliphatic or aromatic hydrocarbons, or amides such as N, N-dimethylformamide. Useful solvents have good wetting and drying properties, including, for example, water, ethanol, isopropanol, and methyl ethyl ketone. Aqueous emulsions of silane compounds can be produced in a conventional manner using conventional dispersants and surface active agents, including nonionic dispersants. The step of contacting the metal foil with the silane solution may be repeated several times if desired. However, since a single step generally produces useful results, it is desirable to use it as a single step. The contact may be made through known application methods including reverse roller coating, doctor blade coating, dipping, immersion, application and spraying.

The silane solution is typically used at a temperature of preferably about 15-45 [deg.] C, more preferably about 20-30 [deg.] C. After the treated metal foil is contacted with the silane solution, the metal foil is preferably heated at a temperature of about 60-170 DEG C, more preferably about 90-150 DEG C, preferably about 0.03-5 minutes, And may be heated over about 0.2-2 minutes to promote drying of the surface. The dry film thickness of the silane compound on the metal foil is preferably from about 0.002 to 0.1 microns, more preferably from about 0.005 to 0.02 microns.

The metal foil treated according to the present method can be bonded to the gas to provide dimensional stability and structural stability. The treated metal foil of the present invention improves bond or peel strength between the treated metal foil and the substrate. The advantage of the treated metal foil is that the added copper can be avoided from roughening the surface while exhibiting effective bond or peel strength to the gas. Another advantage is that the metal particles for the treated metal foil do not migrate or diffuse into the later-laminated gas. These foils may have standard profile surfaces, low-profile surfaces, and even very low-profile surfaces, while providing the desired peel strength. Another advantage of the treated metal foil is that either matte or shiny surfaces can be effectively bonded to the gas after processing.

Useful gases may be prepared by impregnating a partially cured resin, typically an epoxy resin (e.g., bifunctional, tetrafunctional and multifunctional epoxies) with a woven glass reinforcement. Other useful resins include resins such as formaldehyde and urea or formaldehyde and melamine, polyester, phenol, silicone, polyamide, polyimide, diallyl phthalate, phenylsilane, polybenzimidazole, diphenyl oxide, polytetrafluoroethylene, Cyanate esters, and the like. These gases are sometimes referred to as dielectric gases or prepregs.

Generally, methods of making laminates are known in the art.

In producing the laminate, the treated metal foil and prepreg material may first be cut into sheets and then laminate treated.

The prepreg may comprise a woven glass reinforcement fabric impregnated with a partially cured two-stage resin.

By applying heat and pressure, the treated metal foil is pressed firmly against the prepreg, and the temperature at which the assembly is processed is controlled by curing, i. E., Cross-linking of the resin, resulting in a firm bond of the foil to the prepreg Activate.

The treated metal foil can be used in many possible possible end use applications, but can generally be used in electronic devices or electronics related fields.

The following examples illustrate various and novel features of the invention, although not limited thereto.

Unless otherwise indicated, in the following examples and detailed description and in the claims, all parts and percentages are by weight, all temperatures are in degrees Celsius, and the pressures represent atmospheric pressures.

Hereinafter, the present invention will be described more specifically by way of examples.

Example 1

The copper foil was contacted with a dilute sulfuric acid solution.

The copper foil was rinsed with water and then advanced through a water bath containing 40 g / l of ammonium chloride and 40 g / l of nickel chloride at 25 DEG C for about 25 seconds under a current density of 202 ASF.

The bath comprises two plating zones.

Next, the metal foil was placed in a nickel flash electrodeposition bath containing 320 g / l of nickel sulphate, 40 g / l of nickel chloride, and 30 g / l of boric acid in water.

The metal foil was placed in the nickel flash electrodeposition bath at a temperature of 50 DEG C for about 30 seconds under a current density of about 40 ASF.

The nickel flash electrodeposition bath comprises two plating zones.

Example 2

The copper foil was contacted with a dilute sulfuric acid solution.

The copper foil was rinsed with water and then advanced through a water bath containing 40 g / l of ammonium sulphate and 40 g / l of nickel chloride at 25 DEG C for about 25 seconds under a current density of 278 ASF.

The bath comprises four plating zones.

Next, the metal foil was placed in a nickel flash electrodeposition bath containing 320 g / l of nickel sulphate, 40 g / l of nickel chloride and 30 g / l of boric acid in water.

The metal foil was placed in the nickel flash electrodeposition bath at a temperature of 50 DEG C for about 30 seconds under a current density of about 40 ASF.

The nickel flash electrodeposition bath comprises two plating zones.

Comparative Example 1

The copper foil was contacted with a dilute sulfuric acid solution.

The copper foil was rinsed with water and then advanced through a water bath containing 40 g / l of ammonium chloride and 40 g / l of nickel chloride at 25 DEG C for about 25 seconds under a current density of 202 ASF.

The bath comprises one plating zone.

Next, the metal foil was placed in a nickel flash electrodeposition bath containing 320 g / l of nickel sulphate, 40 g / l of nickel chloride and 30 g / l of boric acid in water.

The metal foil was placed in the nickel flash electrodeposition bath at a temperature of 50 DEG C for about 30 seconds under a current density of about 40 ASF.

The nickel flash electrodeposition bath comprises two plating zones.

Comparative Example 2

The copper foil was contacted with a dilute sulfuric acid solution.

The copper foil was rinsed with water and then advanced through a water bath containing 70 g / l of ammonium chloride and 28 g / l of nickel chloride at 25 DEG C for about 35 seconds under a current density of 202 ASF.

The bath comprises one plating zone.

Next, the metal foil was placed in a nickel flash electrodeposition bath containing 320 g / l of nickel sulphate, 40 g / l of nickel chloride, and 30 g / l of boric acid in water.

The metal foil was placed in the nickel flash electrodeposition bath at a temperature of 50 DEG C for about 35 seconds under a current density of about 40 ASF.

The nickel flash electrodeposition bath comprises two plating zones.

Four treated copper foils were laminated to a General Electic FR-4 epoxy prepreg and the peel strength was measured and the results are shown in Table 1 below.

In addition, Table 1 below shows the metal ion pulp-disposing capacity associated with the production of four copper foil laminates.

Example No. 2. Peel strength (lb / sq in) Metal ion waste treatment capacity Example 1 15.6 Good Example 2 16.2 - 17 Good Comparative Example 1 11.8 Good Comparative Example 2 11 Poor

While the present invention has been described in connection with the preferred embodiments, various ways may be apparent to those skilled in the art from the detailed description of the invention.

Accordingly, the invention includes such modifications as fall within the scope of the claims.

INDUSTRIAL APPLICABILITY As described above, the present invention has the effect of providing a metal foil processing method that not only improves the peel strength of the laminate but also has a good ability to treat metal ions, and the metal foil thus treated.

Claims (28)

A method of treating a metal foil, Contacting the metal foil with an acidic solution; Placing the metal foil in a nickel treatment bath comprising at least two plating zones, 1 to 50 g / l of ammonium salt and 10 to 100 g / l of nickel compound, and applying current through the nickel treatment bath ; And And applying a nickel flash layer to said metal foil. ≪ RTI ID = 0.0 > 8. < / RTI & A metal foil processing method according to claim 1, characterized in that the metal foil does not comprise a copper treatment layer The metal foil processing method according to claim 1, wherein the acidic solution comprises sulfuric acid A metal foil processing method according to claim 1, characterized in that the nickel treatment bath comprises at least three plating zones The metal foil processing method according to claim 1, characterized in that the nickel treatment bath comprises at least four plating zones The metal foil processing method according to claim 1, wherein the nickel treatment bath comprises 25 to 45 g / l of ammonium salt The metal foil processing method according to claim 1, wherein the nickel compound of the nickel treatment bath comprises nickel chloride The metal foil processing method according to claim 1, wherein the nickel flash layer is applied by electrodeposition in an electrodeposition bath The method of claim 8, wherein the electrodeposition bath comprises nickel sulphate and nickel chloride. 9. A method according to claim 8, characterized in that a current of 20 to 100 ASF is applied to the electrodeposition bath The method of claim 8, wherein the nickel flash layer is electrodeposited in alternating current densities The method of claim 1, wherein the ammonium salt comprises at least one ammonium chloride and ammonium sulphate. The method of claim 1, further comprising applying a silane coupling agent to the metal foil after applying the nickel flash layer A method of treating a metal foil, Contacting the metal foil with an acidic solution; Placing the metal foil in a nickel treatment bath comprising at least two plating zones, 1 - 50 g / l ammonium chloride, and 10 - 100 g / l nickel chloride, and applying current through the nickel treatment bath ; And And applying a nickel flash layer to the metal foil in an electrodeposition bath. ≪ RTI ID = 0.0 > 8. < / RTI & 15. A metal foil processing method according to claim 14, characterized in that the metal foil does not comprise a copper treatment layer 15. A metal foil processing method according to claim 14, characterized in that the nickel treatment bath comprises at least three plating zones 15. A metal foil processing method according to claim 14, characterized in that the nickel treatment bath comprises at least four plating zones 15. A metal foil processing method according to claim 14, characterized in that the nickel treatment bath comprises 25 - 45 g / l of ammonium chloride 15. A method according to claim 14, wherein the nickel flash layer is electrodeposited at an alternating current density 15. The method of claim 14, further comprising applying a silane coupling agent to the metal foil after applying the nickel flash layer A method of treating a metal foil, Contacting a metal foil not comprising a copper treatment layer with an acidic solution; Placing the metal foil in a nickel treatment bath comprising at least two plating zones, 25 to 45 g / l of ammonium salt, and 10 to 100 g / l of nickel compound, and applying current through the nickel treatment bath ; And And applying a nickel flash layer to the metal foil in an electrodeposition bath. ≪ RTI ID = 0.0 > 8. < / RTI & 22. A method according to claim 21, wherein the nickel treatment bath comprises at least three plating zones 22. A method according to claim 21, wherein the nickel treatment bath comprises at least four plating zones The method of claim 21, wherein the nickel flash layer is electrodeposited at an alternating current density The method of claim 21, further comprising applying a silane coupling agent to the metal foil after applying the nickel flash layer A metal foil treated by the method of claim 1 A metal foil treated by the method of claim 14 A metal foil treated by the method of claim 21