KR20160099439A - Treated copper foil, and copper-clad laminate and printed wiring board using the treated copper foil - Google Patents

Abstract

The present invention provides a treated copper foil which has excellent transfer characteristics and high peel strength with a resin base material, and also has a low haze value after etching, and is desirable to a printed wiring board having high transmittance. The treated copper foil for a copper-clad laminate comprises a coarse treatment layer on one surface of an un-treated copper foil and an anti-oxidation treatment layer on the coarse treatment layer. The coarse treatment layer is formed with fine copper particles whose first particle diameter is 40 nm - 200 nm. The anti-oxidation treatment layer contains molybdenum and cobalt. Average roughness Rz of ten points of a treated surface bonded with an insulating resin base material is 0.5 m - 1.6 m. Color difference E*ab between the untreated copper foil and the treated surface is 45-60.

Description

TECHNICAL FIELD [0001] The present invention relates to a copper clad laminate and a printed circuit board using the copper clad laminate and a copper clad laminate having the copper clad laminate,

The present invention has excellent transmission characteristics, has a high peeling strength with an insulating resin substrate (hereinafter referred to as " resin substrate "), has a low haze value (HAZE value) of a resin substrate after etching, To a treated copper foil.

BACKGROUND ART A printed wiring board used for information communication equipment or the like is formed with a conductive wiring pattern on a resin substrate. Examples of the resin base material include a rigid printed wiring board in which a reinforcing material such as glass cloth or paper is impregnated with an insulating phenol resin, an epoxy resin, a polyphenylene ether resin, a bismaleimide triazine resin, etc., a polyimide resin or a cycloolefin A polymer resin, and the like. On the other hand, a copper foil is generally used as a material for a conductive wiring pattern.

The printed wiring board can be produced by producing a copper clad laminate by heating and pressing the resin base and the copper foil and then removing unnecessary portions of the copper foil by etching to form a wiring pattern.

The copper foil is roughly classified into two types, electrolytic copper foil and rolled copper foil, according to the manufacturing method, and the copper foil is used separately from each of the features in accordance with the use. In addition, any copper foil is rarely used as it is, and a copper foil having various treatment layers such as a roughened layer, a heat-resistant layer, and a rust-preventive layer is used (hereinafter referred to as & Copper foil ").

In the practical use of the printed wiring board without problems, the peel strength or adhesion between the resin substrate and the treated copper foil is one of the important characteristics.

The peel strength is required not only in the steady state but also in the heat resistance, chemical resistance and moisture absorption resistance, and the peel strength must be maintained.

As one effective means for achieving this, it has been practiced to form a roughened layer on the copper foil.

In recent years, there is a growing demand for high-speed and high-frequency transmission compatible printed wiring boards. In addition to the above characteristics, "transmission characteristics" represented by transmission losses are also important for such printed wiring boards.

The transmission loss means the degree to which a current flowing in the printed wiring board is attenuated according to a distance or the like. In general, the transmission loss tends to increase as the frequency increases. The fact that the transmission loss is large means that only a part of the predetermined current is not transmitted to the load side, so that the transmission loss must be suppressed to a lower level for practical use without any problem.

The transmission loss of the printed wiring board is the sum of both the dielectric loss and the conductor loss. The dielectric loss is derived from a resin substrate and is caused by dielectric constant and dielectric loss tangent. On the other hand, the conductor loss is derived from a conductor, that is, a copper foil, which is caused by a conductor resistance. Therefore, in order to lower the transmission loss, it is necessary to reduce the dielectric constant and dielectric tangent of the resin substrate, and to reduce the conductor resistance of the copper foil.

As described above, the transmission loss tends to increase as the frequency of the current increases. However, since the conductor loss, that is, the conductor resistance increases, the "skin effect" and the "surface shape of the treated copper foil" are related to each other.

The skin effect refers to the effect that the electric current flowing through the conductor flows near the surface of the conductor as the frequency becomes higher. The skin depth (delta) defined by the distance to the point where the electric current is 1 / e times the electric current on the surface of the conductor is expressed by Equation (1).

(식 1)

(Equation 1)

ω is the angular frequency, σ is the conductivity, and μ is the permeability.

In the case of copper, equation (1) is as follows from the conductivity and the specific permeability.

(식 2)

(Equation 2)

f is the frequency.

From equation (2), it can be seen that the current flows closer to the surface of the conductor as the frequency rises. For example, at a frequency of 10 MHz, the skin depth is about 20 μm, Lt; / RTI > is about 0.3 mu m and flows only on the surface.

Therefore, when a high-frequency current is flowed through the treated copper foil on which the roughened treatment layer is formed in order to enhance the adhesion with the resin base as in the conventional case, the current flows along the surface shape of the roughened treatment layer, , The propagation distance is increased, so that the conductor resistance is increased, leading to an increase in transmission loss.

Therefore, it is necessary to suppress the conductor resistance to a low level for the treated copper foil for the high-speed and high-frequency transmission-compatible printed wiring board. For this purpose, it is preferable to reduce the particle diameter of the coarse particles constituting the coarsened layer and reduce the surface roughness do.

On the other hand, although not limited to high-speed and high-frequency transmission applications, the visibility of printed wiring boards is also an important characteristic. Specifically, it refers to the visibility of the resin base material portion after forming the wiring pattern, that is, the portion where the copper foil is etched and exposed in the polyimide resin-based flexible printed wiring board.

This is a characteristic that is required as an anisotropic conductive film (ACF) is used as a soldering-free mounting technique. For example, when a printed circuit board (PCB) and a flexible printed wiring board (FPC) are vertically connected, an ACF is sandwiched therebetween and heated and pressed to obtain electrical continuity in the vertical direction. If the position at which the FPC and the PCB are electrically connected is not properly aligned, the upper and lower interconnections are not necessarily taken. Therefore, the positioning mark is marked on each of them, and these are aligned while being recognized by the CCD camera.

At this time, since the CCD camera photographs the copper foil of the FPC from directly above from the exposed resin substrate, if the resin substrate is blurred, the transmittance is lowered, and the cover can not be recognized, I will not. Therefore, it is preferable that it does not become as cloudy as possible.

In addition, the completion inspection of the printed wiring board by the automatic optical inspection apparatus (AOI) is also one of the reasons that visibility is required. AOI is an apparatus for optically grasping a wiring pattern of a printed wiring board and judging whether it is good or bad by image processing, and can detect defects such as defects, tapering, thickening, pinholes, and scratches.

At this time, if the copper foil of the printed wiring board is etched and the exposed resin substrate is blurred, the degree of permeability is lowered, so that the wiring pattern can not be grasped and accurate inspection becomes impossible. Therefore, it is preferable that it does not become as cloudy as possible.

Assuming that the property of visually grasping the wiring pattern of the printed wiring board is visibility, if the blurring of the resin substrate is small, the degree of transparency is high and the wiring pattern is easy to visually recognize visually.

The visibility can be quantified by measuring the haze, that is, the haze value. Generally, when the HAZE value is 80% or less, the visibility is good.

This HAZE value is strongly influenced by the surface shape of the treated copper foil, and the smaller the particle diameter of the roughening particles constituting the roughening treatment layer and the surface roughness of the treated copper foil, the smaller the haze value and the higher the transmittance. That is, the visibility tends to be good.

As described above, it is important that the adhesion between the resin substrate and the treated copper foil is sufficiently ensured in order to use the printed wiring board without problems in practical use. However, in order to cope with high speed and high frequency transmission, ACF mounting and AOI inspection, It is necessary to simultaneously provide transmission characteristics and visibility.

Considering the transfer characteristics among the characteristics required for these printed wiring boards, the untreated copper foil not provided with the roughening treatment layer can reduce the propagation distance of the electric current because the surface roughness is small. As a result, It is considered to be the best conductor.

However, when attention is paid to the adhesion, since the anchoring effect is small and the adhesion with the resin base material is weak, the peeling strength can not be ensured, and thus it is difficult to use it in a printed wiring board.

If the roughening treatment layer is formed on the untreated copper foil and the amount of the roughening particles forming the roughening treatment layer is increased or the diameter of the roughening treatment layer is increased or the diameter of the roughening layer is increased, the peeling strength can be increased because the anchor effect is increased. When the processing layer is formed, the propagation distance of the current becomes longer, the conductor resistance increases, and the transmission loss increases.

Also, in this case, visibility is deteriorated because the HAZE value of the exposed resin substrate is increased by etching the copper foil of the printed wiring board.

As described above, the adhesion between the resin substrate and the copper foil is basically the opposite of the transmission characteristic and the visibility, but the printed wiring board corresponding to high-speed and high-frequency transmission must satisfy all of them practically.

Therefore, development of a treated copper foil which has a sufficient peel strength to a resin substrate, has a transmission loss as good as that of the untreated copper foil, can produce a printed wiring board having a small haze value of the exposed resin substrate by etching the copper foil, .

Japanese Laid-Open Patent Publication No. 2013-155415 International Publication No. WO2003 / 102277 International Publication No. WO2014 / 133164

Patent Document 1 discloses a treated copper foil in which a roughening treatment layer and a heat-resistant treatment layer are formed in order to improve adhesion to an insulating resin for high frequency transmission.

The insulating resin corresponding to the high frequency transmission tends to secure the peeling strength by increasing the particles constituting the roughened layer because the insulating resin corresponding to the high frequency transmission has a small number of functional groups with high polarity and low bonding property which contributes to adhesion .

However, if the coarsened particles are large, there is a problem that the current propagation distance becomes long and the transmission loss increases.

Further, the transmission loss is further increased by the heat-resistant treatment layer, the rust prevention treatment layer and the silane coupling agent layer, and particularly when the heat-resistant treatment layer contains Ni, the skin depth becomes shallow, There is a problem that the transmission loss further increases due to the influence of the irregularities on the surface of the treatment layer.

Patent Document 2 discloses a method in which a rust-preventive treatment layer containing a roughened treatment layer and zinc and nickel, a chromate layer on a rust-preventive treatment layer, a silane coupling agent adsorbed on a chromate layer There is disclosed a treated copper foil for suppressing transmission loss by preparing surface roughness of a treated surface within a predetermined range.

However, since the roughened particles of the roughened layer are large, the current propagation distance becomes long and the transmission loss increases.

In addition, since the rust preventive treatment layer contains Ni, the depth of the skin becomes shallow, and current flows intensively to the surface portion of the copper foil, thereby causing a problem of further increasing transmission loss.

Patent Document 3 discloses a treated copper foil having 400 to 2500 copper particles with a particle diameter of 10 nm to 250 nm adhered in a region of 3 占 퐉 占 3 占 퐉, wherein the maximum height difference Wmax of undulations of the treated surface is 1.2 占 퐉 or less, A treated copper foil having a hue of L * a * b * colorimetric system L * of 30 or less and having a low haze value was disclosed. In this example, a copper foil having a rust preventive treatment layer containing Ni and a silane coupling agent layer A treated copper foil is disclosed.

However, the treated copper foil disclosed in Patent Document 3 has a problem that the peeling strength of the copper-clad laminate using the treated copper foil is weak because the amount of coarsened particles adhered is small.

In addition, when Ni is contained in the rust-preventive treatment layer, the depth of the skin becomes shallow, and current flows intensively to the surface portion of the copper foil, thereby increasing the transmission loss as compared with the untreated copper foil.

DISCLOSURE OF THE INVENTION The present inventors have conducted a series of trial and error experiments and experiments to solve the above-mentioned problems. As a result, the present inventors have found that the coarsened layer is formed of fine copper particles having a primary particle size of 40 nm to 200 nm, Wherein the anti-corrosion layer contains molybdenum and cobalt, the ten-point average roughness Rz of the treated surface adhered to the insulating resin base is 0.5 mu m to 1.6 mu m, the color difference DELTA E * ab between the untreated copper foil and the treated surface is 45 mu m, 60, it is possible to realize a high peel strength even when the roughened layer is formed, even when the roughened layer is an excellent conductor having a transmission loss similar to that of the untreated copper foil and adhered to the resin base material. Further, The coated laminated plate has a remarkable knowledge that the HAZE value of the exposed resin substrate after etching removal is low and the transparency is high, Soundness will.

The technical problem described above can be solved by the present invention as follows.

The present invention provides a treated copper foil for a copper clad laminate comprising an unhardened treatment layer on at least one surface of an untreated copper foil and an oxidation preventive treatment layer on the harmonized treatment layer, wherein the harmonized treatment layer has a primary particle diameter of 40 nm to 200 Wherein the antioxidation treatment layer contains molybdenum and cobalt, and the 10-point average roughness Rz of the treated surface to be adhered to the insulating resin base is 0.5 탆 to 1.6 탆, and the untreated copper foil and the treated surface Is 45 to 60 (claim 1). The copper-clad laminate according to claim 1, wherein the color difference DELTA E * ab is 45 to 60.

Further, the present invention is the treated copper foil for a copper clad laminate according to claim 1, comprising a chromate layer and / or a silane coupling agent layer on the antioxidant layer (claim 2).

Further, the present invention is a copper clad laminate wherein the treated copper foil for a copper clad laminate according to claim 1 or 2 is applied to an insulating resin base material (claim 3).

Further, the present invention is the copper clad laminate according to claim 3, wherein the peel strength of the resin base material containing the polyimide compound is 1.0 kN / m or more (claim 4).

In another aspect, the present invention, copper sulfate pentahydrate 10 ~ 70 g / ℓ on the diethylenetriamine salt 50 ~ 150 g / ℓ aqueous solution with 0.5 ~ 5 A / dm ^2, the current density was added to the stored electricity quantity 40 ~ 140 C / dm ^2, The copper foil for copper clad laminate according to claim 1 or 2, wherein the roughening treatment layer is formed on the untreated copper foil by electrolysis at a liquid temperature of 25 to 50 ° C.

Further, the present invention is the method for producing a copper clad laminate according to claim 3 or 4, wherein the copper foil for processing a copper clad laminate and the insulating resin base are pressed while being heated.

Further, the present invention is a printed wiring board formed using the copper clad laminate according to claim 3 or claim 4 (claim 7).

Further, the present invention is a method for manufacturing a printed wiring board according to claim 7 (claim 8).

In the present specification, the roughened layer in the present invention is sometimes referred to as a resin-induced penetration layer in particular.

The treated copper foil of the present invention is fine copper particles having a primary particle diameter of 40 to 200 nm of the coarse particles constituting the roughened treatment layer (resin induced infiltration layer), and also the untreated copper foil, Is in the range of 45 to 60 and the antioxidation treatment layer contains molybdenum and cobalt and does not contain a metal that increases the transmission loss of nickel or the like. Therefore, even if each treatment layer is formed, The transmission loss in the resin-induced permeation layer is -5.5 dB / 100 mm or more, and the transmission loss due to the resin-induced permeation layer can be suppressed to less than 5%.

Further, when the resin substrate is heated and pressure-formed, the resin uniformly penetrates between the coarsened grains, and the surface of the treated copper foil and the resin adhere in a large area in three dimensions. And a high peel strength of 1.0 kN / m or more can be realized even for a resin substrate containing a polyimide compound.

In addition, since the exposed resin substrate after etching removal has a HAZE value as low as 30 to 80% and becomes a printed wiring board with high transmittance, inspection using AOI or positioning using a CCD camera can be accurately performed.

In addition, since the 10-point average roughness Rz of the treated surface is 0.5 탆 to 1.6 탆, it can be strongly adhered to the resin base material.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of a treated copper foil section in the present invention. Fig.
2 is a scanning electron micrograph of a treated copper foil section in the present invention.

<Untreated copper>

The copper foil (hereinafter referred to as &quot; untreated copper foil &quot;) to be used in the present invention is not particularly limited, and a copper foil having no distinction between front and rear faces and a copper foil having both front and back faces can be used.

(Hereinafter referred to as &quot; treated surface &quot;) to be subjected to the surface treatment is not particularly limited, and the rolled copper foil may be of any surface, of course, and of course, in electrolytic copper foil, .

When the rolled copper foil is used, it is preferable that the copper foil is immersed in a hydrocarbon-based organic solvent to remove the rolling oil, and then subjected to a roughening treatment.

The thickness of the untreated copper foil is not particularly limited as long as it can be used for the printed wiring board after the surface treatment, but is preferably 6 to 300 占 퐉, and more preferably 9 to 70 占 퐉.

The surface to be subjected to the surface treatment of the untreated copper foil has a surface area of L * 83 to 88, a * 14 to 17, b * 15 to 19 .

&Lt; Resin-induced penetration layer (Harmonized layer) >

The primary particle size of the fine copper particles constituting the resin-induced permeation layer is preferably from 40 to 200 nm, more preferably from 50 to 190 nm.

In the present invention, the lower limit is set to 40 nm, but it is not excluded that particles containing less than 40 nm are included. However, if the number of particles smaller than 40 nm is large, there is a possibility that a sufficient peel strength can not be obtained for use in a flexible printed wiring board, and if it exceeds 200 nm, the HAZE value becomes high.

It is also preferable that the distance between the convex portions of the fine copper particles is in the range of 40 to 200 nm.

The thickness of the resin-induced permeation layer is preferably from 75 to 380 nm, more preferably from 120 to 200 nm.

If the thickness is less than 75 nm, a sufficient peel strength may not be obtained, and if it exceeds 380 nm, the HAZE value becomes high, which is not preferable in any case.

The primary particle size of the resin-induced infiltration layer and the interval and thickness of the convex portions of the fine copper particles can be measured by, for example, magnification observation at 30,000 to 80,000 times using a field emission scanning electron microscope or the like, and measurement.

The electrolyte used for forming the resin-induced permeation layer is preferably an aqueous solution prepared by adding 10 to 70 g / l of copper sulfate pentahydrate and 50 to 150 g / l of diethylenetriamine salt to the pH of 3 to 6 with sulfuric acid .

When the concentration of copper sulfate pentahydrate is less than 10 g / l, particles having a primary particle diameter of less than 40 nm are elongated, and when the concentration is more than 70 g / l, particles having a primary particle diameter exceeding 200 nm are elongated Which is not preferable.

The diethylenetriamine salt to be added to the electrolytic solution is not particularly limited, but diethylenetriamine acetoacetate is preferably used.

A cobalt-containing compound may be added to the electrolytic solution in such a range that the transmission loss is not increased.

The electrolytic solution was immersed in an electrolytic solution containing an insoluble electrode such as titanium oxide coated with a metal oxide as a positive electrode and an untreated copper foil as a negative electrode to obtain a battery having a current density of 0.5 to 5 A / dm ² , an electricity quantity of 40 to 140 C / dm ² , It is preferable that the resin-induced permeation layer is formed by electrolysis under electrolysis conditions.

If the current density is less than 0.5 A / dm ² and the electricity quantity is less than 40 C / dm ² , if the fine copper particles are not sufficiently adhered and the current density is 5 A / dm ² and the electricity quantity is higher than 140 C / dm ² , Is not more than 200 nm.

<Antioxidation Treatment Layer>

The treated copper foil of the present invention has an antioxidation treatment layer on the resin-induced penetration layer.

The deposition amount of the antioxidation treatment layer is preferably 30 to 300 mg / m 2, more preferably 50 to 120 mg / m 2.

If the adhesion amount of the antioxidation treatment layer is less than 30 mg / m 2, the resin induced permeation layer can not be completely covered. If the adhesion amount exceeds 300 mg / m 2, the transmission loss may increase, and if more than 300 mg / The improvement of the prevention performance can not be expected.

The cobalt contained in the antioxidation treatment layer is preferably 20 to 155 mg / m 2, and the molybdenum is preferably 10 to 145 mg / m 2.

If the concentration is lower than the lower limit value, the antioxidation performance is not sufficient. If the concentration exceeds the upper limit value, the transmission loss may increase.

The electrolytic solution forming the antioxidation treatment layer preferably contains an aqueous solution containing 1 to 80 g / l of a molybdenum-containing compound in an aqueous solution of 10 to 100 g / l of a cobalt-containing compound at a pH of 4 to 10.

The cobalt-containing compound includes, for example, cobalt sulfate heptahydrate.

The molybdenum-containing compound includes, for example, disodium molybdate dihydrate.

An electrolytic solution was prepared by dissolving an insoluble electrode such as titanium oxide coated with a metal oxide as an anode and an untreated copper foil as a negative electrode to obtain a battery having a current density of 0.1 to 10 A / dm ² , an electricity quantity of 5 to 20 C / dm ² , To form an antioxidant treatment layer.

&Lt; Chromate layer and silane coupling agent layer >

The treated copper foil of the present invention can form a chromate layer and / or a silane coupling agent layer on the antioxidation treatment layer, if necessary.

The electrolytic solution forming the chromate layer preferably contains 10 to 100 g / l aqueous solution of the chromic acid-containing compound at a pH of 2 to 12.

As the chromic acid-containing compound, for example, sodium dichromate dihydrate can be mentioned.

A chromate layer is immersed in an insoluble electrode such as a back metal oxide coated titanium in the electrolytic solution in an anode, forming an anti-oxidation layer copper foil as a negative electrode, and a liquid temperature of 20 ~ 50 ℃, 0.1 ~ 10 Current Density A / dm ² , And an electricity quantity of 0.5 to 20 C / dm ² .

The chromate layer may contain zinc.

The silane coupling agent layer can be formed on the chromate layer or on the antioxidation treatment layer.

The silane coupling agent used for the silane coupling agent layer is not particularly limited, and a silane coupling agent containing a vinyl group, an epoxy group, a styryl group, a methacrylic group, an acrylic group, an amino group, a ureide group and a mercapto group can be used However, a silane coupling agent containing an amino group, an epoxy group or a vinyl group is more preferable because it has a very high hygroscopicity and rust prevention effect.

One kind of silane coupling agent may be used, or two or more kinds of silane coupling agents may be used in combination.

It may be formed by immersing it in an aqueous solution of a silane coupling agent prepared at a liquid temperature of 20 to 50 ° C, spraying it by spraying or the like, and then rinsing with water.

&Lt; Resin substrate &

Examples of the resin substrate used in the copper clad laminate of the present invention include those containing an epoxy resin, a polyphenylene ether resin, a bismaleimide triazine resin, and a cycloolefin polymer resin.

Further, even in a resin base material containing a polyimide compound, a high peel strength can be obtained.

<Measurement of color difference ΔE * ab>

([? L *] ² + [? A *] ² + [? B *] ² ) ¹ after the measurement of the color coordinate system L * a * b * defined in JIS Z 8781 of the untreated copper foil- ^{/ 2. &Lt}; ^/ RTI &gt;

Example

Examples of the present invention are shown below, but the present invention is not limited thereto.

<Untreated copper>

As the untreated copper foils of Examples and Comparative Examples, a rolled copper foil or electrolytic copper foil having a thickness of 12 占 퐉 was used.

The rolled copper foil was immersed in a hydrocarbon-based organic solvent for 60 seconds to remove the rolling oil, and then each treatment was carried out.

(Examples 1 to 6)

&Lt; Formation of Resin Induced Penetration Layer &

As the electrolytic solution, the aqueous solution prepared by using the copper sulfate pentahydrate and the sodium diethylenetriamine acetic acid concentration, pH and liquid temperature as shown in Table 1 was used. The pH was adjusted by sulfuric acid.

An untreated copper foil was immersed in the electrolytic solution as the anode and the untreated copper foil was coated as the anode and the anode was electrolyzed under the respective electrolytic conditions shown in Table 1 to prepare a resin- .

&Lt; Cobalt-Molybdenum-Containing Antioxidant Treatment Layer >

A pH of 5.6 and a liquid temperature of 30 占 폚 containing 38 g / l of cobalt sulfate heptahydrate, 23 g / l of disodium molybdate dihydrate, 45 g / l of trisodium citrate dihydrate and 80 g / l of sodium sulfate, by coating the surface of a metal oxide of titanium, the use of a treated copper foil provided with a resin derived permeation layer as a cathode, and resins derived by the current density 7.0 a / dm ^2, the electrolytic conditions of the quantity of electricity 14 C / dm ² with respect to both polar penetration layer To thereby form a cobalt-molybdenum-containing antioxidant treatment layer.

&Lt; Chromate layer >

Treated copper foil having an antioxidant treatment layer containing platinum as a positive electrode and a resin induction layer containing cobalt-molybdenum as an anode was added to a chromate aqueous solution prepared by dissolving a 40 g / l aqueous solution of sodium chromate dihydrate at a liquid temperature of 35 캜 at a pH of 12.0 with sodium hydroxide , And a chromate layer was formed on the cobalt-molybdenum-containing antioxidation treatment layer under electrolysis conditions of a current density of 2.0 A / dm ² and an electricity quantity of 10 C / dm ² for both poles.

&Lt; Silane coupling agent layer &

A treated copper foil having each treatment layer was immersed for 10 seconds in an aqueous solution containing 5 ml / liter of? -Aminopropyltriethoxysilane at a solution temperature of 30 占 폚 to form a silane coupling agent layer on the chromate layer.

A silane coupling agent layer was formed thereon, followed by natural drying at a temperature of about 25 캜 to obtain a treated copper foil of each example.

(Comparative Example 1)

The resin-induced penetration layer was not formed, and the same conditions as in Example 1 were used.

(Comparative Example 2)

An untreated copper foil was immersed in an electrolytic solution consisting of 47 g / l copper sulfate pentahydrate and 100 g / l sulfuric acid and electrolyzed under an electrolytic condition of a current density of 50 A / dm ² , an electricity quantity of 130 C / dm ² and a solution temperature of 30 ° C, And then electrolyzed under an electrolytic condition of a current density of 5 A / dm ² , an electricity quantity of 400 C / dm ² , and a liquid temperature of 40 ° C, Layer was formed in the same manner as in Example 1. The results are shown in Table 1. &lt; tb &gt;&lt; TABLE &gt;

(Comparative Example 3)

An untreated copper foil was immersed in an electrolytic solution consisting of 40 g / l of copper sulfate pentahydrate, 120 g / l of sodium citrate dihydrate and 10 g / l of triethanolamine, and a current density of 1.25 A / dm ² , an electricity quantity of 100 C / dm ² , Lt; 0 &gt; C under electrolytic conditions to form a resin-induced permeation layer.

(Comparative Example 4)

An untreated copper foil was immersed in an electrolytic solution composed of 60.9 g / l of copper sulfate pentahydrate, 28.6 g / l of cobalt sulfate heptahydrate and 49.2 g / l of nickel sulfate hexahydrate and adjusted to pH 2.5 by sulfuric acid, and a current density of 20 A / dm ² , an electric quantity of 40 C / dm ² , and a liquid temperature of 30 ° C to form a resin-induced permeation layer.

(Comparative Example 5)

The same procedure as in Example 1 was carried out except that an untreated copper foil was immersed in the electrolytic solution of Comparative Example 3 and electrolytic conditions were carried out at a current density of 0.5 A / dm ² , an electricity quantity of 100 C / dm ² and a liquid temperature of 45 캜 to form a resin- Lt; / RTI &gt;

(Comparative Example 6)

The same procedure as in Example 1 was carried out except that an untreated copper foil was immersed in the electrolytic solution of Comparative Example 4 and electrolytic conditions were carried out at a current density of 30 A / dm ² , an electric quantity of 40 C / dm ² and a solution temperature of 30 캜 to form a resin- Lt; / RTI &gt;

(Comparative Example 7)

A current density of 5.0 A / dm ² , an electricity quantity of 10 C / dm ² , and a volume of 10 C / dm ² as an electrolyte solution containing 30 g / L of nickel sulfate hexahydrate, 2.0 g / L of sodium hypophosphite monohydrate, 10 g / L of sodium acetate trihydrate, The electrolytic solution was electrolyzed at a liquid temperature of 30 占 폚 to form an antioxidant treatment layer.

(Comparative Example 8)

Electrolytic solution containing 55 g / l of nickel sulfate hexahydrate, 22 g / l of cobalt sulfate heptahydrate and pH 3.0 and electrolysis conditions at a current density of 5 A / dm ² , an electricity quantity of 10 C / dm ² , Was prepared under the same conditions as in Example 3, except that the antistatic layer was formed.

&Lt; Copper clad laminate &

(Manufactured by Saneoka, product name: FRS-142, manufactured by Sekisui Chemical Co., Ltd.) using a vacuum thermal press machine (KVHC-II manufactured by Kitagawa Co., Ltd.) 25 탆) was preheated under a vacuum (7 torr) at a temperature of 260 캜 for 15 minutes and then heated under vacuum (7 torr) at a temperature of 300 캜 under a pressure of 4 MPa for 10 minutes to obtain a copper clad laminate .

Evaluation of untreated copper foil or treated copper foil was carried out by the following method.

&Lt; Measurement of surface roughness &

The surface of the untreated copper foil or the treated copper foil on which each treatment layer was formed was subjected to surface treatment using Surfcoder SE1700 alpha (manufactured by Kosaka Laboratory Co., Ltd.) suitable as a contact type surface roughness meter specified in JIS B 0651-2001 , The cutoff value for the roughness curve was 0.8 mm, and the measurement distance was 4.0 mm, and the 10-point average roughness Rz as defined in JIS B 0601-1994 was measured.

&Lt; Measurement of primary particle size &

Using a field emission scanning electron microscope FE-SEM (JSM-7800F manufactured by Nippon Electric Company), the sample was observed at a magnification of 80,000 times while being inclined by 40 DEG, and the primary particles of copper microparticles constituting the observed resin- The average value obtained by measuring the length at 10 points was taken as the value of the primary particle diameter.

<Color difference ΔE * ab>

The colorimetric system L * a * b * defined in JIS Z 8781 of each treated copper foil was measured using a spectroscopic colorimeter (CM-600d manufactured by Konica Minolta), and the color difference ΔE * ab * of L * a * b * ^{(= ([ΔL *] 2} + [Δa *] 2 + [Δb *] 2) 1/2) was determined for.

The evaluation of the copper clad laminate was carried out by the following method.

<Peel strength>

A copper circuit sample having a width of 1 mm was produced by etching using an etching machine (SPE-40, manufactured by Ninomiya System). In accordance with JIS C 6481, the peel strength was measured using a universal testing machine.

<HAZE value (degree of blur)>

Copper of the copper clad laminate was entirely etched by using an etching machine. The HAZE value of the polyimide resin after etching was measured using a haze meter (NDH7000 manufactured by Nippon Unicar Co., Ltd.) in accordance with JIS K7136.

<Transmission Loss>

A single-ended microstrip line was formed by etching using an etching machine. In addition, the circuit width of this substrate was set to 110 mu m in width so that the characteristic impedance was 50 OMEGA. The manufactured circuit board was measured for an S parameter (S21) at a frequency of 40 GHz using a network analyzer (Agilent N5247A).

 The evaluation results are shown in Table 2.

It can be seen from Examples 1 to 6 that the treated copper foil of the present invention exhibits a high transmission characteristic without increasing the transmission loss by forming the resin induced permeation layer and the peeling strength with the polyimide resin base material is increased by three times or more .

The treated copper foil of the present invention can provide a conductor having the same transmission loss as the untreated copper foil and can increase the peel strength with the resin base material and the copper clad laminate using the treated copper foil of the present invention can be used for the resin substrate The HAZE value is low and the transmittance is high. Therefore, it is possible to accurately perform the inspection using the AOI or the positioning using the CCD camera.

Therefore, the treated copper foil of the present invention is highly industrially applicable invention.

1: Copper
2: Resin-induced penetration layer
3: Antioxidation treatment layer

Claims (8)

A treated copper foil for a copper clad laminate, comprising: a roughening treatment layer on at least one surface of an untreated copper foil; and an antioxidant treatment layer on the roughening treatment layer, wherein the roughening treatment layer is a copper foil having a primary particle diameter of 40 nm to 200 nm Wherein the antioxidation treatment layer contains molybdenum and cobalt, and the 10-point average roughness Rz of the treated surface to be adhered to the insulating resin base is 0.5 탆 to 1.6 탆, and the color difference ΔE between the untreated copper foil and the treated surface * treated copper for copper clad laminate with ab of 45 to 60. The method according to claim 1,
And a chromate layer and / or a silane coupling agent layer on the antioxidant layer. A copper clad laminate, wherein the treated copper foil for copper clad laminate according to claim 1 or 2 is applied to an insulating resin base material. The method of claim 3,
And a peel strength with a resin base material containing a polyimide compound of 1.0 kN / m or more. A current density of 0.5 to 5 A / dm ² , an electricity quantity of 40 to 140 C / dm ² , a solution temperature of 25 to 50 ° C, and an aqueous solution containing 50 to 150 g / l of diethylenetriamine salt to 10 to 70 g / Wherein the roughening treatment layer is formed on the untreated copper foil. 2. The process for producing a copper foil for copper clad laminate according to claim 1 or 2, wherein the roughening treatment layer is formed on the untreated copper foil. The process for producing a copper clad laminate according to Claim 3 or 4, wherein the treated copper foil for a copper clad laminate and the insulating resin base are pressed while being heated. A printed wiring board formed using the copper clad laminate according to claim 3 or 4. A method for manufacturing a printed wiring board according to claim 7.

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