KR102347860B1 - Treated copper foil having high chroma, copper-clad laminate using the treated copper foil and manufacturing method of the treated copper foil - Google Patents

Abstract

(Problem) Low transmission loss, high peel strength can be maintained in steady state and after heating or chemical immersion, and the HAZE value of the etched part is low, and the boundary between the etched part and the wiring pattern part is clear. The processed copper foil which can be used suitably for a printed wiring board is provided.
(Solution) A treated copper foil comprising an anti-oxidation treatment layer on at least one surface of an untreated copper foil surface, and a 10-point average roughness RzJIS94 of the treated surface of 1.2 µm or less (however, 0 µm is not included), wherein the oxidation The prevention-treated layer contains cobalt and molybdenum, and the colorimetric system XYZ(Yxy) defined in JIS Z 8701 of the treated surface to which the oxidation-preventing treatment is given is 10 to 30 in Y, 0.24 to 0.31 in x, 0.29 to 0.33 in y. Treated copper foil for copper clad laminates.

Description

A highly saturated copper foil, a copper-clad laminate using the treated copper foil, and a manufacturing method of the treated copper foil TECHNICAL FIELD

The present invention is a processed copper foil that can be preferably used for a printed wiring board compatible with high-speed and high-frequency transmission, the color of the treated copper foil-treated surface is highly saturated, and a printed wiring board manufactured by etching a copper-clad laminate with the treated copper foil, The adhesion between the treated copper foil and the resin substrate and high-frequency transmission characteristics are excellent, and the HAZE value of the resin substrate exposed by etching is low, and the boundary between the etching part and the wiring pattern part can be accurately recognized through the CCD camera. It is related with the processed copper foil which can manufacture the copper clad laminated board which can perform accurately the alignment of the positioning and the inspection by an optical appearance automatic inspection apparatus.

Printed wiring boards used in information and communication equipment are those in which conductive wiring patterns are formed on a resin substrate, and after a copper clad laminate is manufactured by heating and pressurizing a resin substrate and copper foil, unnecessary copper foil is removed to form a wiring pattern. It can be manufactured by removing the part by etching.

As a resin substrate used for a printed wiring board, a rigid printed wiring board in which a reinforcing material such as glass cloth or paper is impregnated with insulating phenol resin, epoxy resin, polyphenylene ether resin, bismaleimide triazine resin, etc., polyimide The objects for flexible printed wiring boards comprised from resin, cycloolefin polymer resin, etc. are mentioned.

Copper foil is generally used as a material for a conductive wiring pattern.

Copper foil is roughly divided into two types of electrolytic copper foil and rolled copper foil by the manufacturing method, and is used according to a use by distinguishing it from each characteristic.

There is hardly any case where any copper foil is used as it is, and what formed various processing layers, such as a roughening process layer, a heat-resistant process layer, and a rust prevention process layer, is used (Hereinafter, copper foil provided with various process layers is called "processed copper foil". do).

As one of the important characteristics for using a printed wiring board without a problem practically, the adhesiveness of a resin base material and copper foil, ie, peeling strength, is mentioned.

The peel strength needs to maintain high peel strength without being deteriorated not only in a normal state, but also after heating or chemical|medical agent immersion.

As one of the effective means for improving the peeling strength after a steady state, heating, and chemical|medical agent immersion, it is often performed to form a roughening process layer on copper foil.

In recent years, the demand for printed wiring boards compatible with high-speed and high-frequency transmission is increasing, and in a printed wiring board supporting high-speed and high-frequency transmission, in addition to adhesion, transmission characteristics represented by transmission loss are one of the important characteristics.

The transmission loss indicates the degree to which the current flowing through the printed wiring board is attenuated according to the distance or the like, and in general, the transmission loss tends to increase as the frequency increases. If the transmission loss is large, since only a part of the predetermined current is transmitted to the load side, in order to use it practically without problems, it is necessary to suppress the transmission loss to a lower level.

The transmission loss of a printed wiring board is the sum of both a dielectric loss and a conductor loss. Dielectric loss is derived from the resin substrate, and is caused by dielectric constant and dielectric loss tangent.

On the other hand, the conductor loss is derived from the conductor, that is, the copper foil, and is caused by the conductor resistance.

Therefore, in order to lower a transmission loss, it is necessary to make small the dielectric constant and dielectric loss tangent of a resin base material, and also to make small the conductor resistance of copper foil.

The tendency that the transmission loss increases as the frequency of the current increases is because the conductor loss, ie, the conductor resistance, increases, and the “skin effect” and “the surface shape of the treated copper foil” are related.

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

δ = (2/(ωσμ)) ^1/2 (1)

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

In the case of copper, from the electrical conductivity and relative magnetic permeability, Formula (1) becomes as follows.

δ = 0.066/f ^1/2 (2)

However, 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 increases. When , it is about 1 µm, and almost only the surface flows.

When a high-frequency current flows through the treated copper foil on which the roughening treatment layer is formed in order to increase the peeling strength from the resin substrate as in the prior art, the current flows along the surface shape of the roughening treatment layer, compared to the case where it mainly flows straight through the center As the propagation distance increases, conductor resistance increases, leading to an increase in transmission loss.

Paying attention to the transmission loss, the smaller the particle diameter of the roughened particles constituting the roughening treatment layer, the shorter the propagation distance and it is thought that transmission loss can be suppressed. Ideally, copper foil should not be subjected to a roughening treatment.

However, when attention is paid to adhesiveness, since an anchor effect is small and adhesiveness with a resin base material is weak what is not equipped with a roughening process layer, it is difficult to ensure peeling strength.

Thus, it can be said that the improvement of adhesiveness and suppression of a transmission loss are opposite characteristics.

In addition, although it is not limited to a printed wiring board compatible with high-speed and high-frequency transmission, the transparency of the resin base part after forming the wiring pattern of the printed wiring board is high, and the boundary between the etching part and the wiring pattern part (copper foil remaining part) Visibility that can be recognized clearly is also mentioned as one of the important characteristics.

This is a characteristic which came to be calculated|required as an anisotropic conductive film (it may be referred to as "ACF" hereafter) used as a mounting technique which does not use a solder.

When connecting a printed wiring board (hereinafter sometimes referred to as “PCB”) and a flexible printed wiring board (hereinafter sometimes referred to as “FPC”) up and down, the ACF is sandwiched between them and heated and pressurized in the vertical direction. is gaining momentum.

If the positions of the FPC and the PCB are not accurately aligned, the upper and lower conduction will not be achieved. Positioning marks are marked on each, and they are aligned with the CCD camera.

Positioning is carried out by photographing with a CCD camera from directly above the resin substrate exposed by etching the copper foil of the FPC, so if the resin substrate is opaque, the transparency is low, and the display becomes difficult to recognize, so accurate positioning is possible. can't

Therefore, for accurate positioning, it is preferable that the exposed resin substrate has as low opacity as possible and high transparency.

Moreover, it is also one factor by which visibility is calculated|required that the completion|finish inspection of the printed wiring board by the optical appearance automatic inspection apparatus (it may be hereafter referred to as "AOI") came to be implemented in recent years. AOI is a device that optically grasps a wiring pattern of a printed wiring board and judges good or bad by image processing, and can detect defects such as pattern defects, thinning, thickening, pinholes, and scratches.

When the copper foil of the printed wiring board is etched and the exposed resin base material is opaque, the transparency is low, so that the wiring pattern cannot be grasped and an accurate inspection cannot be performed.

Therefore, even for accurate inspection, it is preferable that the opacity of the exposed resin substrate is as low as possible and the transparency is high.

The opacity of the resin substrate can be quantified by measuring the HAZE value. Generally, transparency is high that HAZE value is 80 % or less, and it is considered that it is easy to visually recognize.

The HAZE value is strongly influenced by the surface shape of the treated copper foil, and the particle diameter of the roughened particles constituting the roughening treatment layer and the surface roughness of the treated copper foil are small, or if the roughening treatment is not performed, the HAZE value is low and the transparency is increased .

However, since the anchor effect is small and adhesiveness with a resin base material is weak when the particle diameter of a roughening particle is small or a roughening process is not performed, it is difficult to ensure peeling strength.

In this way, it can be said that adhesiveness and transparency are opposite characteristics.

As mentioned above, with respect to the adhesiveness of a resin base material and copper foil, although a transmission characteristic and transparency are characteristics that are opposite, a printed wiring board corresponding to high-speed and high-frequency transmission must satisfy all of them practically.

In addition, for accurate positioning and inspection, it is preferable that the boundary between the resin substrate exposed by etching and the wiring pattern (remaining copper foil) is clear.

Therefore, the peeling strength from the resin substrate is sufficient, and the transmission loss is excellent to the same degree as that of the untreated copper foil, the HAZE value of the resin substrate exposed by etching the copper foil is low, the transparency is high, and the exposed resin substrate portion Development of the processed copper foil used as the printed wiring board which the boundary of a wiring pattern is clear and is excellent in visibility is desired.

Japanese Laid-Open Patent Publication No. 2013-155415 Japanese Patent Laid-Open No. 2014-111814

In patent document 1, in order to improve adhesiveness with the insulating resin corresponding to high frequency transmission, the processed copper foil which provided the roughening process layer and the heat-resistant process layer is disclosed.

Since the insulating resin for high-frequency transmission has few highly polar functional groups contributing to adhesion and has low adhesion properties, the treated copper foil disclosed in Patent Document 1 is intended to secure peel strength by enlarging the particles constituting the roughening treatment layer. .

However, there is a problem in that, when the harmonic particles are large, the transmission loss increases because the electric current propagation distance becomes long.

In addition, the transmission loss is further increased by the heat-resistant treatment layer, the anti-rust treatment layer, and the silane coupling agent layer. In particular, when the heat-resistant treatment layer contains nickel, the skin depth becomes shallow, so that the current is concentrated on the surface portion of the copper foil. flow, and there is a problem that transmission loss is further increased under the influence of the unevenness of the processing layer.

In patent document 2, it adheres favorably to resin, and when it observes through resin, it is a surface-treated copper foil which implement|achieves the outstanding visibility, After giving the roughening process which consists of copper- cobalt- nickel on the copper foil of low illumination intensity, a rust prevention process A method of coating a cobalt-nickel layer and additionally coating a zinc or zinc-nickel layer has been proposed.

However, it has been found that in this method, the transparency after etching is low, and since nickel is used for the rust preventive layer, there is a large transmission loss, and also there is a problem that the chemical resistance is low, and there is a problem that permeation occurs in the immersion of the active treatment liquid.

The present inventors made it a technical problem to solve the above-mentioned various problems, and as a result of repeating trial and error numerous trial productions and experiments, an antioxidant treatment layer is provided on at least one surface of the untreated copper foil surface, A treated copper foil having a 10-point average roughness RzJIS94 of 1.2 µm or less, wherein the antioxidant-treated layer contains cobalt and molybdenum, and the colorimetric system XYZ(Yxy) defined in JIS Z8701 of the treated surface subjected to the antioxidant treatment has Y of 10 If to 30, x is 0.24 to 0.31, and y is 0.29 to 0.33 treated copper foil, even if it does not form a roughening process layer, while being able to ensure peeling strength with a resin base material, since a roughening process layer is not formed, transmission characteristic This is excellent, and the copper-clad laminate in which the treated copper foil is adhered to the resin substrate has a low HAZE value of the resin substrate exposed by etching, and the boundary between the etched portion and the treated copper foil remaining portion (wiring pattern portion) is remarkable Therefore, the above-mentioned technical problem was achieved by obtaining the remarkable knowledge that optical positioning at the time of AOI inspection performed using a CCD camera or connection performed using an ACF can be accurately performed because of the excellent visibility.

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

The present invention is a treated copper foil comprising an anti-oxidation treatment layer on at least one surface of the untreated copper foil surface, and a 10-point average roughness RzJIS94 of the treated surface of 1.2 µm or less (however, 0 µm is not included), The preventive treatment layer contains cobalt and molybdenum, and the colorimetric system XYZ(Yxy) defined in JIS Z 8701 of the treated surface to which the oxidation prevention treatment is given is 10 to 30 Y, 0.24 to 0.31 for x, 0.29 to 0.33 for y It is the processed copper foil for copper clad laminated boards (claim 1).

Moreover, this invention is the processed copper foil for copper clad laminated boards of Claim 1 whose content rate of the molybdenum contained in the said antioxidant process layer is 25 to 50 weight% (claim 2).

Moreover, this invention is the processed copper foil for copper clad laminated boards of Claim 1 or 2 provided with a chromate layer and/or a silane coupling agent layer on the said antioxidant process layer (claim 3).

Moreover, in this invention, etching is given to the whole surface of any one surface of the copper clad laminated board to which the said process copper foil is affixed on both surfaces of the insulating resin base material, and the other surface is partially etched copper. A clad laminate or a copper clad laminate in which the treated copper foil is adhered only to one side of an insulating resin substrate and a part of the treated copper foil is etched has a HAZE value of 60% or less in the T section below, and JIS Z from the following D direction In the color space L*·a*·b* defined in 8781, the color space L*·a* measured on a single color in which L* is in the range of 88 to 100, a* is -0.14 to 1.10, and b* is -0.13 to 15 It is the treated copper foil for copper clad laminates in any one of Claims 1-3 which is a copper clad laminated board whose color difference E*ab of the T part of b* and the treated copper foil residual part is 60 or more (claim 4).

Part T: a portion etched on both sides of a copper clad laminate having the treated copper foil on both sides, and a portion etched in a copper clad laminate having the treated copper foil on only one side

D direction: the direction of the surface on which the entire surface is etched for a copper-clad laminate having the treated copper foil on both sides;

Moreover, this invention is a copper clad laminated board which made the processed copper foil for copper clad laminated boards in any one of Claims 1-4 adhere to at least one surface of an insulating resin base material (claim 5).

Moreover, in this invention, etching is given to the whole surface of any one surface of the copper clad laminated board to which the said process copper foil is affixed on both surfaces of the insulating resin base material, and the other surface is partially etched copper. A clad laminate or a copper clad laminate in which the treated copper foil is adhered to only one side of an insulating resin substrate and a part of the treated copper foil is etched, wherein the HAZE value of the T part below is 60% or less, and JIS Z from the following D direction In the color space L*·a*·b* defined in 8781, the color space L*·a* measured on a single color in which L* is in the range of 88 to 100, a* is -0.14 to 1.10, and b* is -0.13 to 15 It is the copper clad laminated board of Claim 5 whose color difference E*ab of the T part of b* and the processing copper foil residual part is 60 or more (Claim 6).

Part T: a portion etched on both sides of a copper clad laminate having the treated copper foil on both sides, and a portion etched in a copper clad laminate having the treated copper foil on only one side

D direction: the direction of the surface on which the entire surface of a copper-clad laminate having the treated copper foil on both sides is etched, and the direction opposite to the surface of a copper-clad laminate having the treated copper foil on only one side of the copper-clad laminate

Moreover, this invention is the copper clad laminated board of Claim 5 or 6 whose said insulating resin base material is a resin base material containing a polyimide compound (Claim 7).

Moreover, this invention is a manufacturing method of the processed copper foil for copper clad laminates in any one of Claims 1-4 in which the said antioxidant process layer is formed in the alkaline electrolytic bath containing cobalt and molybdenum (claim 8).

Moreover, this invention is a manufacturing method of the treated copper foil for copper clad laminated boards of Claim 8 whose said alkaline electrolytic bath is an electrolytic bath containing pyrophosphoric acid (Claim 9).

Moreover, this invention is the manufacturing method of the copper clad laminated board in any one of Claims 5-7 characterized by the pressurization of the processed copper foil for copper clad laminated boards and an insulating resin base material, and heating it (claim 10).

Moreover, this invention is a printed wiring board formed using the copper clad laminated board in any one of Claims 5-7 (claim 11).

T in the present invention is a copper-clad laminate having a treated copper foil on both sides (hereinafter, sometimes referred to as a “double-sided copper-clad laminate”), a copper-clad laminate having a treated copper foil only on one side (hereinafter “single-sided copper-clad laminate”) ') all refer to parts other than the treated copper foil remaining part (1).

Since the processed copper foil in this invention is not provided with a roughening process layer and the propagation distance of an electric current is short, there is little transmission loss by the skin effect, and it can use suitably also for the printed wiring board corresponding to high-speed, high-frequency transmission.

In addition, since the anti-oxidation treatment layer exhibiting a color of high chroma is provided on the untreated copper foil of low illuminance, the copper clad laminate with the treated copper foil in the present invention has a low HAZE value in the etched portion, and the remaining portion of the treated copper foil ( Since the wiring pattern part) shows a highly saturated color, even through a CCD camera, the boundary of an etching part and a wiring pattern part is remarkable, and it is excellent in visibility.

Therefore, positioning and AOI inspection at the time of mounting the ACF can be performed with high accuracy.

In addition, in the present invention, the color of the treated surface of "high saturation" means a color in the color space XYZ (Yxy) defined in JIS Z 8701, Y is 10 to 30, x is 0.24 to 0.31, and y is 0.29 to 0.33. , which is seen as a blue color with the naked eye.

Since the treated copper foil in the present invention includes an antioxidant treatment layer containing cobalt and molybdenum, peel strength can be maintained even after heating or chemical immersion, and permeation at the time of chemical immersion can also be suppressed. .

If a chromate layer and/or a silane coupling layer are formed on the oxidation-treated layer, peel strength can be further maintained even after heating or after chemical immersion, and permeation at the time of chemical immersion can be further suppressed.

Moreover, when the processed copper foil in this invention is made to adhere to the insulating resin base material containing a polyimide, especially strong peeling strength can be implement|achieved.

Moreover, if it is the processed copper foil in this invention, etching process is carried out on the whole surface of one side of the copper clad laminated board provided with the processed copper foil on both surfaces of an insulating resin base material, On the other side, a wiring pattern part is etched. Even when formed, the HAZE value of the T part can be made 60% or less, and L* of the color space L*·a*·b* defined in JIS Z 8781 is 88 to 100, and a* is -0.14 to 1.10 , b* in the range of -0.13 to 15, the color difference E*ab between the T portion measured from the direction of the entire surface etched and the remaining portion of the treated copper foil can be 60 or more, so that the etched portion and the wiring pattern The negative boundary is clear, and positioning and AOI inspection using a CCD camera at the time of mounting the ACF can be performed with high accuracy.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the copper clad laminated board after an etching process.
It is a schematic diagram in the case of using a CCD camera.

<Untreated copper foil>

The copper foil before each process used for this invention (henceforth "untreated copper foil") is not specifically limited, Both the rolled copper foil which does not distinguish front and back, and the electrolytic copper foil with distinction of front and back can be used.

It goes without saying that the rolled copper foil may have any surface, and either the precipitation surface or the glossy surface may be used in the electrodeposited copper foil.

Moreover, when using rolled copper foil, it is preferable to perform various processes, after immersing in a hydrocarbon type organic solvent and removing rolling oil.

Since 10-point average roughness RzJIS94 of the processed copper foil process surface in this invention is 1.2 micrometers or less, 10-point average roughness RzJIS94 of the unprocessed copper foil surface is 1.2 micrometers or less.

Although it will not specifically limit if the thickness of untreated copper foil is thickness which can be used for a printed wiring board after surface treatment, 6-300 micrometers is preferable, More preferably, it is 9-300 micrometers.

<Antioxidant treatment layer>

The process copper foil in this invention is equipped with the antioxidant process layer containing cobalt and molybdenum on the unprocessed copper foil.

The anti-oxidation treatment layer is an electrolytic bath containing a cobalt-containing compound and a molybdenum-containing compound, and each concentration is 100 g/L or less, adjusted to alkali, an insoluble electrode such as platinum oxide-coated titanium is used as an anode, , can be formed by immersing an untreated copper foil as a cathode and electrolyzing under the conditions of a current density of 0.1 to 20 A/dm 2 , an electric quantity of 5 to 50 C/dm 2 , and a liquid temperature of 20 to 50°C.

Although the cobalt-containing compound to be dissolved in the electrolytic bath is not particularly limited, for example, cobalt sulfate heptahydrate, cobalt ammonium sulfate, cobalt citrate, cobalt acetate and the like can be used.

The molybdenum-containing compound dissolved in the electrolytic bath is not limited, and examples thereof include disodium molybdate dihydrate, sodium molybdate, potassium molybdate, and ammonium molybdate.

The electrolytic bath is adjusted to alkaline. In the case of an acidic electrolytic bath, the color system XYZ (Yxy) defined in JIS Z 8701 for the color of the treated surface does not belong to the range of Y is 10 to 30, x is 0.24 to 0.31, and y is 0.29 to 0.33. This is because it is difficult to distinguish the boundary between the etched portion and the treated copper foil remaining portion (wiring pattern portion) when viewed through a CCD camera, since it appears as a light brown color that is difficult to contrast with the polyimide resin substrate.

Although the substance added in order to adjust to alkalinity is not specifically limited, A pyrophosphate is preferable.

As pyrophosphate, potassium pyrophosphate, sodium pyrophosphate, and calcium pyrophosphate can be illustrated.

As for the adhesion amount of an antioxidant treatment layer, 150-300 mg/m<2> is preferable, More preferably, it is 170-270 mg/m<2>.

When the adhesion amount is less than 150 mg/m2, the highly saturated color in the present invention is not exhibited. On the other hand, when it exceeds 300 mg/m2, it is not economical because the saturation does not change even if it is further attached, and This is not preferable because the transmission characteristics tend to deteriorate.

As for content of the molybdenum contained in an antioxidant process layer, 25 to 50 weight% is preferable, More preferably, it is 30 to 48 weight%.

When content of molybdenum is less than 25 weight%, since the deterioration rate of peeling strength after heat processing or chemical|medical agent immersion treatment becomes large, and the amount of permeation at the time of chemical|medical agent immersion also increases, it is unpreferable.

Moreover, even if it contains exceeding 50 weight%, it is because the further improvement of the deterioration rate of peeling strength and the inhibitory effect of the permeation amount is undesirable.

<Chromate layer/silane coupling agent layer>

The processed copper foil in this invention can form a chromate layer and/or a silane coupling agent layer on an antioxidant process layer as needed.

The chromate layer is immersed in an electrolytic bath using an insoluble electrode such as platinum oxide-coated titanium as an anode, and copper foil provided with an antioxidant layer as a cathode, a liquid temperature of 20 to 50°C, and a current density of 10 A/dm 2 or less , it can also be formed by electrolysis under the condition of an electric quantity of 20 C/dm 2 or less, or by simply immersing in the solution.

It is preferable that the electrolytic bath or immersion liquid prepare 3-50 g/L aqueous solution of a chromic acid containing compound to pH 2-12.

As a chromic acid containing compound, sodium dichromate dihydrate, chromic anhydride, etc. are mentioned, for example.

Further, zinc may be contained in the chromate electrolytic bath.

A silane coupling agent layer can be formed on the chromate layer or on the antioxidant treatment layer.

The silane coupling agent used in 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 methacryl group, an acryl group, an amino group, a urea group and a mercapto group can be used. However, the silane coupling agent containing an amino group, an epoxy group or a vinyl group has very high hygroscopic resistance and anti-rust effect, and can be used more preferably.

One type may be sufficient as a silane coupling agent, and it may use it in combination of 2 or more type.

It can form by immersion in the silane coupling agent aqueous solution prepared at the liquid temperature of 20-50 degreeC, or by spreading|spreading by methods, such as spraying.

As for 10-point average roughness RzJIS94 of the processed copper foil process surface in this invention, 1.2 micrometers or less are preferable, More preferably, it is 1.1 micrometers or less.

It is because the HAZE value of the etching part at the time of setting it as a copper clad laminated board increases when larger than 1.2 micrometers.

The colorimetric system XYZ(Yxy) of the treated surface can be measured using a spectrophotometer.

<resin material>

Examples of the insulating resin substrate to which the treated copper foil of the present invention is adhered include those containing polyimide resin, epoxy resin, polyphenylene ether resin, bismaleimide triazine resin, and cycloolefin polymer resin.

Since polyimide resin is excellent in heat resistance, chemical resistance, and flexibility, it is used for a flexible substrate in many cases.

In order to further suppress the transmission loss of a printed wiring board, a low dielectric resin base material can also be used.

Examples of the low dielectric resin substrate include a liquid crystal polymer, polyethylene fluoride, an isocyanate compound, and a resin containing modified polyphenylene ether.

<HAZE value>

The HAZE value of the T part of the double-sided copper-clad laminate and the single-sided copper-clad laminate can be measured with a haze meter in accordance with JIS K 7136.

<Color difference ΔE*ab>

The value measured by the colorimeter from the D direction for the colorimetric system L*a*b* (hereinafter referred to as "colorimetric system L*a*b*") defined in JIS Z 8781 of the double-sided copper-clad laminate and the single-sided copper-clad laminate T part And, it computes by substituting the value measured by the colorimeter from the D direction to a process copper foil residual part to a following formula.

ΔE*ab = ([ΔL*] ² + [Δa*] ² + [Δb*] ² ) ^1/2

Since the etched part shows the color of the measuring band through and affects the value of the color difference ΔE*ab, in the present invention, the color of the measuring band is L* of the color space system L*a*b* of 88 to 100, and a* of -0.14 1.10, b* was defined as a single color in the range of -0.13 to 15.

In addition, the color of the measuring band in the above range is a single color belonging to the range of colors that are visually visible from white to cream.

As an example, Table 1 shows the measured values of the color space L*a*b* on a white copy paper, a cream-colored test bench, and a colorimeter standard plate.

Example

Although the Example of this invention is shown below, this invention is not limited to this.

(Untreated copper foil)

As the unprocessed copper foil of the Example and the comparative example, the 12-micrometer-thick electrolytic copper foil was used.

The 10-point average roughness of the treated copper foil treated surface was measured by using a surfcoder SE1700α (manufactured by Kosaka Laboratories, Ltd.) suitable for a stylus type surface roughness meter stipulated in JIS B0651-2001, using a stylus having a tip radius of 2 µm, and a roughness curve 10-point average roughness RzJIS94 defined in JIS B0601-1994 was measured as a cut-off value of 0.8 mm and a measurement distance of 4.0 mm.

(Examples 1 to 10)

In Examples 1 to 10, an antioxidant treatment layer, a chromate layer, and a silane coupling agent layer were formed as follows.

<Antioxidant treatment layer>

As shown in Table 2, titanium coated with a platinum oxide as an anode in an electrolytic bath containing cobalt(II) sulfate heptahydrate, sodium molybdenum(VI) dihydrate, and potassium pyrophosphate, pH and liquid temperature adjusted; Using an untreated copper foil for the negative electrode, an antioxidant treatment layer containing cobalt and molybdenum was formed on the untreated copper foil under the electrolytic conditions shown in Table 2 in the same manner.

<chromate layer>

In an aqueous chromate solution prepared by preparing an aqueous solution of 40 g/L sodium dichromate dihydrate at a liquid temperature of 35° C. and pH 4.0, platinum was used for the anode and each treated copper foil provided with an antioxidant treatment layer for the cathode was used, and a current density of 0.5 A was used. A chromate layer was formed on the anti-oxidation treatment layer under electrolysis conditions of /dm 2 and an electric quantity of 1 C/dm 2 .

<Silane coupling agent layer>

Each treated copper foil provided with a chromate layer was immersed for 10 second in the aqueous solution containing 5 ml/L of (gamma)-aminopropyltriethoxysilane with a liquid temperature of 30 degreeC, and the silane coupling agent layer was formed.

After forming the silane coupling agent layer, it was air-dried at normal temperature (about 25 degreeC), and various measurements were performed as the processed copper foil of Examples 1-10.

(Comparative Example 1)

Comparative Example 1 did not form an anti-oxidation treatment layer. The chromate layer and the silane coupling agent layer were formed in the same manner as in Examples.

(Comparative Examples 2 to 4)

In the electrolytic bath adjusted as shown in Table 2, a treatment layer was formed on the untreated copper foil under the conditions shown in Table 2 similarly.

In Comparative Example 2, sodium citrate was used instead of potassium pyrophosphate.

The chromate layer and the silane coupling agent layer were formed in the same manner as in Examples.

(Comparative Example 5)

Copper sulfate pentahydrate 15 g/L, cobalt sulfate heptahydrate 8.5 g/L, nickel sulfate hexahydrate 8.6, pH 2.5, and a solution adjusted to a liquid temperature of 38 ° C., using titanium coated on the surface with a platinum oxide as an anode, Cathodic electrolysis was performed for 1 second at 45 A/dm<2> using the 12 micrometers untreated electrolytic copper foil whose RzJIS94 is 0.75 micrometers as a cathode, and the roughening process layer which consists of copper- cobalt- nickel was formed.

Next, using a solution adjusted to 10 g/L of cobalt sulfate heptahydrate, 10 g/L of nickel sulfate hexahydrate, pH 3.0, and a solution temperature of 30° C., titanium coated on the surface with a platinum oxide as an anode is used; Cathodic electrolysis was performed for 5 seconds at 2 A/dm<2> using the electrolytic copper foil in which the roughening process layer which consists of copper- cobalt- nickel was formed as a cathode, and the cobalt- nickel alloy layer was formed on the roughening process layer.

After that, in a solution adjusted to 150 g/L of zinc sulfate heptahydrate, pH 3.0, and a liquid temperature of 50 degrees, a cobalt-nickel alloy layer was formed on titanium coated with a platinum oxide as an anode and a roughened layer as a cathode. Using the copper foil, cathode electrolysis was performed at 0.5 A/dm 2 for 5 seconds to form a zinc layer.

The chromate layer and the silane coupling agent layer were formed in the same manner as in Examples. When roughness RzJIS94 was measured after performing all surface treatment, it was 1.32 micrometers.

About each processed copper foil, the following measurements were performed.

<Color system XYZ (Yxy)>

With respect to the surface on which each treatment layer was formed, the colorimetric system XYZ(Yxy) defined in JIS Z8701 was measured using a spectrophotometer CM-600d (manufactured by Konica Minolta Co., Ltd.).

<Amount of adhesion of antioxidant treatment layer>

Using RIX2000 manufactured by Rigaku Electric Co., Ltd., the amount of deposition and deposition of each element of cobalt and molybdenum in the antioxidant treatment layer was measured, and the sum of both elements was defined as the deposition amount.

<The content of molybdenum>

Using the precipitation and adhesion amounts of each element of cobalt and molybdenum obtained from the precipitation adhesion amount of the antioxidant treatment layer, the content rate (wt%) of each element was substituted into the following formula, and it computed.

Mo content (wt%) =

{(Mo precipitation adhesion amount)/(Co precipitation adhesion amount + Mo precipitation adhesion amount) x 100

Each treated copper foil was affixed to an insulating resin base material, a copper-clad laminate was manufactured, and each measurement was performed.

<Copper clad laminate A>

A polyimide resin substrate (product name: FRS-142, thickness 25 µm, manufactured by Kaneka Corporation) using a vacuum hot press machine KVHC-II (manufactured by Kitagawa Seiki Co., Ltd.) with the side on which the treated layer of each treated copper foil was formed as the side to be adhered. ) under vacuum (7 torr) and at a temperature of 260°C for 15 minutes, then under vacuum (7 torr), at a temperature of 300°C, and at a pressure of 4 MPa for 10 minutes, followed by hot-press molding.

Then, in the same manner on the other surface of the polyimide resin substrate, each treated copper foil of Examples and Comparative Examples was pasted, and copper-clad laminates of Examples and Comparative Examples in which each treated copper foil was adhered to both surfaces were produced.

The copper-clad laminate in which the resin substrate is a polyimide resin substrate is referred to as a copper-clad laminate A.

As for the copper clad laminated board A, the whole surface etched one surface, the other surface etched only a part, and each measurement was performed in the state in which various processed copper foils remain|survived for remainder.

<HAZE value>

Based on JISK7136, the HAZE value of the T part of the copper clad laminated board A was measured using hazemeter NDH7000 (made by Nippon Denshoku Industries Co., Ltd.).

<Color difference ΔE*ab>

It implemented according to JIS Z 8730. Using a spectrophotometer CM-600d for each color system of the T portion of the copper clad laminate A and the treated copper foil remaining portion 1, the color system L*a*b* was measured from the D direction, and then incorporated into the following formula to calculate ΔE It was set as the value of *ab.

ΔE*ab = ([ΔL*] ² + [Δa*] ² + [Δb*] ² ) ^1/2

The color difference was measured on a white copy paper (L* = 92.25, a* = 0.38, b* = 2.31), as shown in the "Measurement table" column of Table 4, on a cream-colored test bench (L* = 88.64, a* = 1.06, b*=13.49) and color difference standard plate (L*=99.47, a*=-0.14, b*=-0.13).

Moreover, each copper clad laminated board A manufactured using each treated copper foil of Examples 3, 7, and 10 was measured on copy paper, a cream-colored test bench, and a color difference meter standard plate, respectively, and color difference ΔE*ab was compared.

<Normal state peel strength>

A copper circuit sample having a width of 1 mm was prepared by etching using an etching machine SPE-40 (manufactured by Ninomiya Systems Co., Ltd.). In accordance with JIS C6481, the peel strength was measured using a universal tester.

The steady-state peel strength is shown in the "Peel" column of Table 4.

<Deterioration rate of peel strength after heat treatment>

The peel strength was measured after returning to normal temperature after heat-processing the sample which measured the peeling strength of the steady state on the conditions of the temperature of 150 degreeC and 240 hours using atmospheric oven. The deterioration rate was computed by the following formula.

In the formula, α represents the value of the peel strength before the heat treatment (steady state), and β represents the value of the peel strength after the heat treatment.

Degradation rate (%) = (α - β)/α × 100

The deterioration rate of peeling strength after heat processing is shown in Table 4 "degradation rate" column.

＜Permeation amount＞

The copper circuit sample of the said 1 mm width was immersed in 5 wt% sulfuric acid aqueous solution on the conditions of 65±3 degreeC of liquid temperatures for 30 minutes. Then, after washing with water and drying, the circuit of copper was peeled from the copper clad laminated board.

Since a color difference occurred in the portion where the aqueous sulfuric acid solution permeated, the peeling-treated copper foil surface was observed with an optical microscope, and the amount of permeation (µm) of the aqueous sulfuric acid solution was read from the color difference.

<Visibility>

The processed copper foil of either surface of the copper clad laminated board A was completely etched, and the 50 micrometers x 50 micrometers rectangle 1 which consists of each processed copper foil by etching was formed in the other surface.

Each copper-clad laminate A was placed with a square (1) face down on either white copy paper, a cream-colored test bench, or a colorimeter standard plate, and a CCD line sensor camera PIE-550 (monochrome line sensor, 5150 pixels (40 MHz) )/Ikegami Communications Co., Ltd.) was placed on the entire surface of the copper clad laminate A at a distance of 70 mm from the etching treatment side, and passed 10 times under the CCD line sensor camera 6 at 5 m/min, and 50 µm In a square (1) of x 50 µm, the CCD line sensor camera can detect 9 or more times, ◎, 7 to 8 times, ○, 6 times, △, and 5 or less. The thing which could not be evaluated was made into x. In addition, metal halide lighting was used for lighting.

<Transmission loss: copper clad laminate A>

Using an etching machine, single-ended micro strip lines were formed by etching. In addition, the circuit width of this board|substrate was made into 50 micrometers in width so that the characteristic impedance might be set to 50 ohms. The S-parameter (S21) of the frequency of 160 MHz - 20 GHz was measured for the manufactured circuit board using the network analyzer (N5247A by Azirent Technology Co., Ltd.).

<Copper-clad laminate B>

On one side of a liquid crystal polymer resin base material (product name: CT-Z, thickness 50 μm, manufactured by Kuraray Co., Ltd.), the side on which each treatment layer of the treated copper foils of Examples and Comparative Examples is formed is aligned as a to-be-adhesive surface, and the other side A copper foil for ground (70 μm) was applied to the surface, and preheated for 15 minutes at a temperature of 260° C. under vacuum (7 torr) using a vacuum hot press machine KVHC-II, and then under vacuum (7 torr), a temperature of 300° C., At a pressure of 4 MPa, heat press molding was performed for 10 minutes to obtain a copper-clad laminate.

A copper-clad laminate in which the resin substrate is a liquid crystal polymer resin substrate is referred to as a copper-clad laminate B.

<Transmission loss: copper clad laminate B>

Using an etching machine, single-ended micro strip lines were formed by etching. In addition, the circuit width of this board is 110 µm in width and a polyimide resin substrate (Kane Corporation, Inc. Car made, product name: FRS-142, thickness 25 µm), the width was set to 50 µm. The S-parameter (S21) of the frequency of 160 MHz - 40 GHz was measured for the manufactured circuit board using a network analyzer.

The type of the copper-clad laminate on which each measurement was performed is shown in the "Measured laminated plate" column of Table 4.

As shown in Table 4, the copper clad laminated board provided with the treated copper foil in the present invention maintains high peel strength even in a steady state and after heating, there is no permeation of chemicals, and the HAZE value of the etched part is low, and as shown in Table 3, since the treated surface of the treated copper foil in the present invention exhibits a color of high chroma, the color difference ΔE*ab between the etched portion and the treated copper foil remaining portion is 60 or more, and very excellent visibility Therefore, it was shown that the detection by a CCD line sensor camera is easy to make, and there is little transmission loss and it becomes a copper clad laminated board.

Moreover, as shown in Table 5, it was confirmed that all ΔE*ab calculated by measuring the same sample on copy paper, a cream-colored test bench, or a color-difference meter standard plate showed 60 or more.

The copper clad laminated board provided with the processed copper foil in this invention secures high peeling strength after heating and chemical|medical immersion not only in a steady state, but also has little transmission loss. In addition, since the HAZE value of the etched part is low and the boundary between the etched part and the wiring pattern part is clear and the visibility is excellent, the copper coating that can accurately perform positioning and AOI inspection using a CCD camera becomes a laminate.

Accordingly, the present invention is an invention with high industrial applicability.

1: Processed copper foil remaining part (wiring pattern part)
2: Insulative resin base material
3a: whole surface etched part
3b: etching part
4: Copper clad laminate
5: large
6: CCD camera

Claims (11)

An antioxidant-treated layer is provided on at least one surface of the untreated copper foil surface, the antioxidant-treated layer contains cobalt and molybdenum, and the 10-point average roughness RzJIS94 of the treated surface subjected to the antioxidant treatment is 1.2 µm or less ( However, 0 µm is not included), and the color system XYZ (Yxy) defined in JIS Z 8701 on the treated surface is 10 to 30 Y, 0.24 to 0.31, 0.29 to 0.33 for x, and 0.29 to 0.33 for the antioxidant treatment layer A treated copper foil for a copper-clad laminate, wherein the electrolytic bath for forming the electrolytic bath is an alkaline electrolytic bath containing cobalt and molybdenum. The method of claim 1,
The processed copper foil for copper clad laminates whose content rate of the molybdenum contained in the said antioxidant process layer is 25 to 50 weight%. The method of claim 1,
The processed copper foil for copper clad laminates provided with a chromate layer, a silane coupling agent layer, or a chromate layer and a silane coupling agent layer on the said antioxidant process layer. The method of claim 1,
The copper-clad laminate or the treated copper foil in which the entire surface of one of the copper-clad laminates to which the treated copper foil is adhered to both surfaces of the insulating resin substrate is etched, and the other surface is partially etched. The copper clad laminated board adhered to only one side of the insulating resin substrate and etched on a part of the treated copper foil has a HAZE value of 60% or less in the T section below, and a color system L defined in JIS Z 8781 from the D direction below. The T portion of the colorimetric system L*·a*·b* measured on a single color in which L* of *·a*·b* is in the range of 88 to 100, a* is in the range of -0.14 to 1.10, and b* is in the range of -0.13 to 15. And the treated copper foil for copper clad laminates which is a copper clad laminated board whose color difference E*ab of the processing copper foil residual part is 60 or more.
Part T: a portion etched on both sides of a copper-clad laminate having the treated copper foil on both sides, and a portion etched in a copper-clad laminate having the treated copper foil on only one side
D-direction: the direction of the side etched on the entire surface of a copper-clad laminate having the treated copper foil on both sides, and the opposite direction of the copper-clad laminate having the treated copper foil on only one side of the surface with the treated copper foil A copper-clad laminate in which the treated copper foil for a copper-clad laminate according to any one of claims 1 to 4 is adhered to at least one surface of an insulating resin substrate. 6. The method of claim 5,
The copper-clad laminate or the treated copper foil in which the entire surface of one of the copper-clad laminates to which the treated copper foil is adhered to both surfaces of the insulating resin substrate is etched, and the other surface is partially etched. It is a copper clad laminated board adhered to only one side of this insulating resin base material and etched on a part of the treated copper foil, wherein the HAZE value of the T part below is 60% or less, and the colorimetric system defined in JIS Z 8781 from the following D direction T of the colorimetric system L*·a*·b* measured on a single color in which L* of L*·a*·b* is in the range of 88 to 100, a* is -0.14 to 1.10, and b* is -0.13 to 15. A copper clad laminate having a color difference E*ab of 60 or more of the portion and the remaining portion of the treated copper foil.
Part T: a portion etched on both sides of a copper-clad laminate having the treated copper foil on both sides, and a portion etched in a copper-clad laminate having the treated copper foil on only one side
D direction: the direction of the surface on which the entire surface of a copper-clad laminate having the treated copper foil is provided on both sides, and the direction opposite to the surface of the copper-clad laminate having the treated copper foil on only one side of the copper-clad laminate 6. The method of claim 5,
The copper clad laminated board whose said insulating resin base material is a resin base material containing a polyimide compound. The manufacturing method of the processed copper foil for copper clad laminates in any one of Claims 1-4 in which the said antioxidant process layer is formed in the alkaline electrolytic bath containing cobalt and molybdenum. 9. The method of claim 8,
The manufacturing method of the treated copper foil for copper clad laminates whose said alkaline electrolytic bath is an electrolytic bath containing pyrophosphoric acid. The method for producing a copper-clad laminate according to claim 5, wherein the treated copper foil for a copper-clad laminate and an insulating resin substrate are pressed while heating and adhered. The printed wiring board formed using the copper clad laminated board of Claim 5.

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