TW201706457A - Roughened copper foil and printed wiring board - Google Patents

Abstract

Provided is a copper foil which can exhibit high peel strength with respect to insulating resin substrates from which chemical bonding cannot be expected, such as liquid crystal polymer films, while exhibiting good transmission loss in high frequency applications. This roughened copper foil has a roughened surface having roughened particles on at least one side of the foil, the roughened surface has a ten point average roughness Rzjis of 0.6-1.7 [mu]m, and the half value width is 0.9 [mu]m or less in a frequency distribution of the height of the roughened particles.

Description

Roughening copper foil and printed circuit board

The present invention relates to a roughened copper foil and a printed circuit board, and more particularly to a printed circuit board suitable for high frequency use and a roughened copper foil suitable for the same.

A flexible printed circuit board (FPC) is widely used in electronic devices such as portable electronic devices. In particular, with the high performance of portable electronic devices and the like in recent years, high-speed processing of a large amount of information has entered high-frequency signals, and flexible printed circuit boards suitable for high-frequency applications have been required. Such a high-frequency flexible printed circuit board is preferably transportable so as not to deteriorate the high-frequency signal quality, so that it is preferable to reduce the transmission loss. The flexible printed circuit board has a copper foil and an insulating resin substrate which are processed in a wiring pattern, but the transmission loss is caused by a conductor loss due to the copper foil and a dielectric loss due to the insulating resin substrate. the Lord. The conductor loss is increased by the skin effect of the copper foil which is more pronounced as it becomes higher frequency.

In order to reduce the transmission loss in high-frequency applications, it is proposed to reduce the copper foil loss of the conductor. For example, in Patent Document 1 (Japanese Special Edition) Japanese Patent Publication No. 2014-224313 discloses a copper foil for a high-frequency circuit which is formed on a surface of a copper foil to form a primary particle layer of copper, and then a Cu-Co-Ni alloy is formed on the primary particle layer. The copper foil of the secondary particle layer has an average value of the height of the unevenness of the roughened surface obtained by the laser microscope of 1,500 or more. In the patent document 2 (JP-A-2014-225650), a copper foil for a high-frequency circuit is formed on the surface of a copper foil to form a primary particle layer of copper, and then on the primary particle layer. The copper foil of the secondary particle layer of the Cu-Co-Ni alloy was formed, and the ratio of the three-dimensional surface area to the two-dimensional surface area obtained from the laser microscope in a certain range of the roughened surface was 2.0 or more and less than 2.2. The copper foils described in Patent Documents 1 and 2 are all used for a high-frequency circuit board, and transmission loss can be satisfactorily suppressed.

Further, as another method for reducing the transmission loss in high-frequency applications, an insulating resin substrate capable of reducing dielectric loss has been proposed. An example of such an insulating resin substrate is a liquid crystal polymer (LCP) film. However, the insulating resin substrate suitable for high-frequency use such as a liquid crystal polymer film tends to have a low adhesion to the copper foil, and copper having improved adhesion to such an insulating resin substrate is also proposed. Foil. For example, Patent Document 3 (JP-A-2005-219379) discloses a composite material comprising a surface-treated copper foil having a roughened surface having a surface roughness Rz of 2.5 to 4.0 μm, and 50%. The above is formed of an insulating substrate composed of a thermoplastic liquid crystal polymer. In the patent document 4 (JP-A-2010-236058), a roughened copper foil having a head forming angle of 85° or less is provided. The roughened surface of the fine copper particles in the shape of protrusions.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2014-224313

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2014-225650

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-219379

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-236058

In order to suppress the transmission loss in high-frequency use, from the viewpoint of the skin effect, a copper foil having a flat and narrow surface is required. On the other hand, the flat-necked copper foil reduces the fixing effect with the insulating resin substrate (that is, the physical adhesion improving effect by the unevenness of the surface of the copper foil). Therefore, it is difficult to obtain sufficient peel strength for an insulating resin substrate which cannot be chemically sealed like a liquid crystal polymer film, and for this reason, it is inferior in reliability as a flexible printed circuit board. As described above, the transmission loss and the peeling strength are in a trade-off relationship with respect to the surface profile of the copper foil, so that it is difficult to coexist in the original.

The inventors of the present invention have obtained a knowledge of the present invention, and can provide a copper foil which has a ten-point average roughness Rzjis of 0.6 to 1.7 μm and a half-value width of a frequency distribution at the height of the roughened particles. Roughened surface of 0.9μm or less is given to copper foil for high frequency use The transmission loss is good, and the insulating resin substrate which cannot be expected to be chemically sealed like a liquid crystal polymer film exhibits high peel strength.

Accordingly, an object of the present invention is to provide a copper foil which is excellent in transmission loss at high frequency applications and which exhibits high peel strength for an insulating resin substrate which cannot be expected to be chemically sealed like a liquid crystal polymer film.

According to one aspect of the present invention, there is provided a roughened copper foil which is a roughened copper foil having a roughened surface having roughened particles on at least one side thereof, wherein the roughened surface has 0.6 to 1.7 The ten-point average roughness Rzjis of μm, and the half value width of the frequency distribution at the height of the roughened particles is 0.9 μm or less.

According to still another aspect of the present invention, there is provided a printed circuit board suitable for high-frequency use, comprising: a roughened copper foil having the above-described aspect, and an insulating layer provided in close contact with the roughened surface of the copper foil; Resin layer.

40‧‧‧Insulating resin substrate

42‧‧‧Signal layer

44‧‧‧ Grounding layer

46‧‧‧ Coverage

[Fig. 1] A diagram for explaining the relationship between the frequency distribution of the height of the roughened particles and the half value width.

[Fig. 2] A FIB-SIM image of the cross section of the roughened particles on the roughened surface was observed.

[Fig. 3] An enlarged image (FIB-SIM image) of the head of the roughened particle.

Fig. 4 is a schematic cross-sectional view showing the configuration of a sample for measurement of transmission loss.

definition

The terms or parameters used for specific purposes of the present invention are indicated below.

In the present specification, the "ten-point average roughness Rzjis" is the surface roughness measured in accordance with JIS B0601-2001, and the roughness curve is from the highest peak to the average of the height of the 5th mountain, and the bottom of the valley. Start with the sum of the averages from the depth order to the fifth.

In the present specification, the "half-value width of the frequency distribution at the height of the roughened particles" is defined as the frequency distribution at the height of the roughened particles existing on the roughened surface of the roughened copper foil, as shown in FIG. The full width of the frequency distribution spike as shown by the value of 1/2 of the maximum value of the peak of the frequency distribution. The frequency distribution of the height of the roughened particles is obtained by using a three-dimensional roughness analysis device by roughening the surface profile of the roughened copper foil to a desired magnification in accordance with the size of the roughened particles (for example, 600 to 30,000 times ) measured. The height of the roughened particles can be considered as the grain size of the roughened particles. The height or particle size of the roughened particles is calculated by measuring the surface profile of the electrolytic copper foil (original foil) before the roughening treatment, and the value of the surface profile due to the roughening treatment is used as the background value in the calculation of the particle size. It is best to remove it.

The "specific surface area" in the present specification is a value obtained by dividing the three-dimensional surface area X of the roughened surface of the roughened copper foil by the measurement area Y to obtain the value of X/Y. The three-dimensional surface area X can be calculated by measuring the surface profile of the specific measurement area Y (for example, 14000 μm ² ) of the roughened surface by a commercially available laser microscope.

In the present specification, the "roughened particle cross-sectional area ratio" is an index indicating the unevenness of the surface of the roughened particles (that is, the degree of fine roughening), and a commercially available image processing analyzer and a commercially available concentrated ion beam processing are used. Observing device (FIB), observing the profile of the respective roughened particles in the specific field of view (for example, 8 μm × 8 μm) of the roughened surface, and obtaining the SIM image of the FIB at a magnification of 18,000 times (hereinafter, referred to as FIB-SIM) Image), the FIB-SIM image is image-analyzed, and the closed cross-sectional area and the cross-sectional area are measured, and the ratio of the (closed area of the roughened particles) / (the cross-sectional area of the roughened particles) is set. The value determined by calculating the ratio of the cross-sectional area of the roughened particles is calculated. The specific measurement procedure is as follows. First, as shown in the FIB-SIM image drawing method shown in FIG. 2, a straight line is drawn from the slightly equal position of the roughened particle to the longitudinal direction of the roughened particle (that is, the height direction of the roughened particle). A specific reference point a is separated from the top of the head of the roughened particles on the straight line by a certain distance (for example, 2 μm). From this reference point a, two tangent lines are drawn to the roughened particles, and the joints b and c of the tangent lines and the roughened particles are specified. The cross-sectional area of the cross-section of the line connecting the joints b and c (hereinafter referred to as the bc line) and the cross-sectional contour of the head of the roughened particle is obtained by image analysis, and is referred to as "roughened particle". The sectional area." Next, the "closed sectional area of the roughened particles" is measured in the manner described by the FIB-SIM image as shown in FIG. The area of the range surrounded by the line of the fine convex shape of the roughened particle surface (the front end of the finely roughened particle in the case where the fine roughened particle is present) and the bc line are determined by the image. Calculated by analysis. The position determination of each of the above-described front ends is automatically performed by a software included in a commercially available image processing analyzer. The closed cross-sectional area of the roughened particles is obtained by taking the unevenness of the surface of the roughened particles (i.e., the degree of fine roughening) as a larger cross-sectional area of the roughened particles. Therefore, by dividing the closed cross-sectional area of the roughened particles by the cross-sectional area of the roughened particles, a numerical value indicating the unevenness of the surface of the roughened particles (that is, the degree of fine roughening) can be obtained. That is, the ratio of the cross-sectional area of the roughened particles is calculated from the closed cross-sectional area obtained as described above and the cross-sectional area of the roughened particles. The roughened particle cross-sectional area ratio is preferably calculated for each of the roughened particles observed for each field of view, and the average value of the cross-sectional area ratio of the roughened particles obtained for all the roughened particles of the five fields of view is calculated.

Roughened copper foil

The copper foil of the present invention is a roughened copper foil. The roughened copper foil has a roughened surface having roughened particles on at least one side thereof. The roughened surface has a ten-point average roughness Rzjis of 0.6 to 1.7 μm, and the half value width of the frequency distribution at the height of the roughened particles is 0.9 μm or less. In this manner, a roughened surface having a ten-point average roughness Rzjis of 0.6 to 1.7 μm and a half-value width of 0.9 μm or less in the frequency distribution of the height of the roughened particles can be imparted to the copper foil. The transmission loss in high-frequency applications is good, and at the same time, it is impossible to expect such as liquid crystal polymerization. The chemically-bonded insulating resin substrate having a film thickness also exhibits high peel strength (for example, 1.2 kgf/cm or more in a copper foil having a thickness of 18 μm). As described above, since the transfer loss and the peel strength are in a trade-off relationship with respect to the surface profile of the copper foil, there is a problem that it is difficult to coexist in the original, but a good transfer can be achieved by roughening the copper foil by the present invention. Loss and high peel strength are expected to coexist in the field.

A mechanism for coexisting good transmission loss and high peel strength is not necessarily clear, but it can be considered as follows. First, it can be considered that the ten-point average roughness Rzjis of the roughened surface is in a range of a low value of 0.6 to 1.7 μm, and the skin effect of the copper foil for high-frequency use can be intentionally lowered to reduce the conductor loss. Therefore, the transmission loss is reduced. However, the above-mentioned 10-point average roughness Rzjis of 0.6 to 1.7 μm is reduced, and only the adhesion between these and the insulating resin substrate which is not expected to be chemically sealed like a liquid crystal polymer film may become insufficient. This is considered to be that if the height of the roughened particles is uneven, the adhesion strength becomes unstable. In this regard, in the roughened copper foil of the present invention, the half value width of the frequency distribution at the height of the roughened particles is set to 0.9 μm or less to reduce the unevenness of the height of the roughened particles, which contributes to The adhesion of more roughened particles is improved, and the stability of the adhesion strength can be achieved by these. As a result, the insulating resin substrate which cannot be chemically sealed like a liquid crystal polymer film can exhibit high peel strength (for example, 1.2 kgf/cm or more of copper foil having a thickness of 18 μm).

The ten-point average roughness Rzjis of the roughened surface (measured according to JIS B0601-2001) is 0.6 to 1.7 μm, and ideally 0.7 to 1.6 μm, preferably 0.9 to 1.5 μm. If Rzjis is within this range, it is desirable to reduce the transmission loss in high-frequency applications and also to ensure adhesion to the insulating resin substrate.

The half value width of the frequency distribution at the height of the roughened particles is 0.9 μm or less, preferably 0.2 to 0.9 μm, more preferably 0.2 to 0.7 μm, still more preferably 0.2 to 0.6 μm. If the half value in the range is equal to this, the unevenness of the height of the roughened particles is reduced, which contributes to an increase in the adhesion of more roughened particles, thereby achieving stability of the adhesion strength. Chemical. As a result, the insulating resin substrate which cannot be chemically sealed like a liquid crystal polymer film can exhibit high peel strength (for example, 1.2 kgf/cm or more of copper foil having a thickness of 18 μm).

It is preferable that the roughened copper foil is formed on the roughened particles to have finer coarsened particles which are more finer than the roughened particles. By forming the finely roughened particles on the roughened particles to increase the surface area, the peel strength can be further improved. In this case, the particle size of the finely roughened particles is typically as small as 150 nm or less, and the influence on the transmission loss in the band of 100 GHz or less is extremely low.

It is desirable that the roughened surface has a specific surface area of 1.1 to 2.1, preferably 1.2 to 2.0, more preferably 1.3 to 1.9, and particularly preferably 1.5 to 1.9. The specific surface area is the value of X/Y obtained by dividing the three-dimensional surface area X of the roughened surface by the measurement area Y as described above. The specific surface area is appropriately increased to 1.1 or more to improve the peel strength to the insulating resin substrate. In addition, the specific surface area is not more than 2.1, and it is possible to suppress the peeling of roughened particles due to physical contact which may occur when the specific surface area is excessively large. Falling (so-called powder drop), thereby effectively avoiding the dirt of the peeling strength or the post-step dirt.

It is desirable that the roughened surface has a roughened particle cross-sectional area ratio of 1.10 to 1.50, preferably 1.15 to 1.30, more preferably 1.15 to 1.20. The roughened particle cross-sectional area ratio is an index indicating the unevenness of the surface of the roughened particle (that is, the degree of fine roughening) as described above. Therefore, since the value of the cross-sectional area ratio of the roughened particles becomes larger as the protrusions are formed on the roughened particles, the contact area with the insulating resin substrate changes when the roughened surface is bonded to the insulating resin substrate. Larger, as a result, the physical adhesion is improved more than the roughened particles alone (that is, the case where there is no finely roughened particles). Therefore, if the ratio of the cross-sectional area of the roughened particles is 1.15 or more, the physical adhesion of the roughened particles can be effectively improved. In addition, by setting the ratio of the cross-sectional area of the roughened particles to 1.50 or less, it is possible to suppress peeling of finely roughened particles (so-called powder falling) due to physical contact which may occur when the specific surface area is excessively large, thereby It can effectively avoid the dirt of the peeling strength or the post-step dirt.

The thickness of the roughened copper foil of the present invention is not particularly limited, but is preferably 0.1 to 35 μm, more preferably 0.5 to 18 μm. Further, the roughened copper foil of the present invention is not limited to the roughening treatment on the surface of a normal copper foil, and is also a roughening treatment or a fine roughening treatment of the copper foil surface of the copper foil with the carrier. can.

As described above, the roughened copper foil of the present invention is preferably used in a printed circuit board suitable for high frequency applications. That is, by the ideal aspect of the present invention, a printed circuit suitable for high frequency use can be provided. The board is provided with the roughened copper foil of the present invention and an insulating resin layer provided in contact with the roughened surface of the copper foil. In the case of using a printed circuit board suitable for high-frequency use, the roughened copper foil of the present invention is excellent in transmission loss at high-frequency use, and chemical adhesion such as liquid crystal polymer film cannot be expected. The insulating resin substrate may also exhibit high peel strength (for example, 1.2 kgf/cm or more in a copper foil having a thickness of 18 μm). Therefore, it is preferable that the insulating resin layer contains a liquid crystal polymer (LCP), and is, for example, a liquid crystal polymer (LCP) film. As a preferable example of high-frequency use, high-frequency components such as a liquid crystal display module, a camera module, and an antenna module mounted on a portable electronic device such as a smart phone can be cited.

Production method

An example of an ideal manufacturing method of the roughened copper foil by the present invention will be described. The preferred manufacturing method includes a step of preparing a copper foil having a surface having a ten-point average roughness Rzjis of 1.5 μm or less, and a first roughening step of electrically analyzing the surface with a specific current density J ₁ , and a second roughened electrolytic deposition step ₂ is performed with respect to the surface of a particular current density J, the above-mentioned electrolytic deposition surface at a particular current density _{J. 3} of the third form of the roughened surface roughening The step of desirably, the ratio of the current densities J ₁ , J ₂ , and J ₃ in the first roughening step, the second roughening step, and the third roughening step (ie, J ₁ :J ₂ :J ₃ ) is set to 1.0: 1.4: 1.2~1.0: 1.6:1.5. However, the roughened copper foil by the present invention is not limited to the method described below, and may be produced by any method.

(1) Preparation of copper foil

As the copper foil used for the production of the roughened copper foil, both an electrolytic copper foil and a rolled copper foil can be used, and an electrolytic copper foil is preferable. Further, the copper foil is a copper foil which is not roughened, and may be a roughened person which has been applied. The thickness of the copper foil is not particularly limited, but is preferably 0.1 to 35 μm, and more preferably 0.5 to 18 μm. The copper foil is prepared in the form of a copper foil with a carrier, and the copper foil is dry by a wet film formation method such as an electroless copper plating method or an electrolytic copper plating method, sputtering, or chemical vapor deposition. The film formation method, or a combination formed by these, is preferred.

The surface of the copper foil to be subjected to the roughening treatment is preferably a surface having a ten-point average roughness Rzjis measured in accordance with JIS B0601-2001 having a surface of 1.5 μm or less, more preferably 1.3 μm or less, still more preferably 1.0 μm or less. The lower limit is not particularly limited, but is, for example, 0.1 μm or more. When it is in the above range, it is easy to impart the surface profile required for the roughened copper foil of the present invention, in particular, the ten-point average roughness Rzjis of 0.6 to 1.7 μm to the roughened surface.

(2) roughening treatment

For the surface of the copper foil having an Rzjis of 1.5 μm or less, a three-stage roughening step of applying the first roughening step, the second roughening step, and the third roughening step is desirable. In the first roughening step, a copper sulfate solution having a copper concentration of 8 to 12 g/L and a sulfuric acid concentration of 200 to 280 g/L is preferably formed at a specific current density J ₁ at a temperature of 20 to 40 ° C. This electric analysis system is ideal for 5~20 seconds. In the second roughening step, a copper sulfate solution having a copper concentration of 8 to 12 g/L and a sulfuric acid concentration of 200 to 280 g/L is preferably formed at a specific current density J ₂ at a temperature of 20 to 40 ° C. This electric analysis system is ideal for 5~20 seconds. In the third roughening step, a copper sulfate solution having a copper concentration of 65 to 80 g/L and a sulfuric acid concentration of 200 to 280 g/L is electrically analyzed at a specific current density J ₃ at a temperature of 45 to 55 ° C. The roughened surface is ideal, and the electroanalytical system is ideal for 5 to 25 seconds. Then, the ratio of the current densities J ₁ , J ₂ and J ₃ in the first roughening step, the second roughening step and the third roughening step, that is, J ₁ :J ₂ :J ₃ is 1.0:1.4:1.2 It is ideal in the range of ~1.0:1.6:1.5. If the current density ratio is within this range, it becomes easy to impart the half value width of the surface profile required for the roughened copper foil of the present invention, particularly the height distribution of the roughened particles below 0.9 μm. Roughing the surface. Preferably, the current density J ₁ of the first roughening step is 8-20 A/dm ² , the current density J ₂ of the second roughening step is 12~32 A/dm ² , and the current density J ₃ of the third roughening step is 10 ~30A/dm ² .

(3) Micro-roughening treatment

It is preferable to further perform the fine roughening treatment on the roughened surface formed by the third roughening step. The micro-roughening treatment is carried out in a copper sulfate solution having a copper concentration of 10 to 20 g/L, a sulfuric acid concentration of 30 to 130 g/L, a 9-phenylpyridinium concentration of 100 to 200 mg/L, and a chlorine concentration of 20 to 100 mg/L. It is preferable to carry out the electrolysis of the fine copper particles at a current density of 10 to 40 A/dm ² at a temperature of ~40 ° C, and it is preferable that the electrolysis is carried out for 0.3 to 1.0 second.

(4) Anti-rust treatment

The rust-preventing treatment may be applied to the roughened copper foil as desired. The rustproof treatment is preferably performed by a plating treatment using zinc. Zinc plating treatment and zinc alloy plating treatment may be used for the zinc plating treatment, and the zinc alloy plating treatment is particularly preferable for the zinc-nickel alloy treatment. The zinc-nickel alloy treatment is preferably a plating treatment containing at least Ni and Zn, and may further contain other elements such as Sn, Cr, and Co. The Ni/Zn adhesion ratio of the zinc-nickel alloy plating is preferably 1.2 to 10, more preferably 2 to 7, more preferably 2.7 to 4. Further, it is preferable that the rust-preventing treatment further contains a chromate treatment, and the chromate treatment is preferably carried out on the surface containing zinc plating after the plating treatment using zinc. In such a manner, the rust preventive agent can be further improved. A particularly desirable rust-preventing treatment is a combination of zinc-nickel alloy plating treatment and subsequent chromate treatment.

(5) decane coupling agent treatment

The decane coupling agent layer may be formed by applying a decane coupling agent to the copper foil as expected. Thereby, moisture resistance, chemical resistance, adhesion to an insulating resin substrate, etc. can be improved. The decane coupling agent layer can be formed by coating and drying by appropriately diluting a decane coupling agent. Examples of the decane coupling agent include an epoxy functional decane coupling agent such as 4-glycidyl butyl trimethoxy decane or 3-glycidoxy propyl trimethoxy decane, or a 3-amino group. Propyltriethoxydecane, N-2 (aminoethyl) 3-aminopropyltrimethoxydecane, N-3-(4-(3-aminopropoxy)butoxy)propyl An amino-functional decane coupling agent such as 3-aminopropyltrimethoxydecane or N-phenyl-3-aminopropyltrimethoxydecane, or 3-mercaptopropyltrimethoxydecane a mercapto-functional decane coupling agent or an olefin-functional decane coupling agent such as vinyltrimethoxynonane or vinylphenyltrimethoxynonane or propylene such as 3-methylpropenyloxypropyltrimethoxydecane The hydrazine-functional decane coupling agent is an imidazole-functional decane coupling agent such as imidazolium or a triazine-functional decane coupling agent such as triazine decane.

Copper foil with carrier

The roughened copper foil of the present invention may also be provided in the form of a copper foil with a carrier. In this case, the copper foil with a carrier includes a carrier, a release layer provided on the carrier, and a roughened copper foil of the present invention in which the roughened surface is provided on the release layer. However, the copper foil with a carrier may be formed of a generally known layer in addition to the roughened copper foil of the present invention.

The carrier supports a foil-like or layered member for roughening the copper foil for improving the operability. Examples of the carrier include an aluminum foil, a copper foil, a resin film having a metal surface coated thereon, and the like, and a copper foil is preferable. The copper foil may be either rolled copper foil or electrolytic copper foil. The thickness of the carrier is typically 200 μm or less, and desirably 12 μm to 70 μm.

The peeling layer weakens the peel strength of the carrier, guarantees the stability of the strength, and further has the effect of suppressing at the time of high temperature stamping. A layer of interdiffused function that may be generated between the carrier and the copper foil. The peeling layer is generally formed on one side of the carrier, but may be formed on both sides. The release layer may be either an organic release layer or an inorganic release layer. Examples of the organic component used in the organic release layer include a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid. Examples of the nitrogen-containing organic compound include a triazole compound and an imidazole compound, and the triazole compound is preferably one in which the peelability is easily stabilized. Examples of the triazole compound include 1,2,3-benzotriazole, carboxybenzotriazole, N,N'-bis(benzotriazolylmethyl)urea, and 1H-1,2. 4-triazole and 3-amino-1H-1,2,4-triazole and the like. Examples of the sulfur-containing organic compound include mercaptobenzothiazole, trimeric thiocyanate, and 2-thiol benzimidazole. Examples of the carboxylic acid include a monocarboxylic acid, a dicarboxylic acid, and the like. On the other hand, examples of the inorganic component to be used in the inorganic release layer include Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, and a chromate treatment film. Further, the release layer is formed by bringing the surface of at least one of the carriers into contact with the solution containing the release layer component, and fixing the release layer component to the surface of the carrier or the like. The contact of the carrier to the solution containing the release layer component may be carried out by dipping into a solution containing the release layer component, spraying a solution containing the release layer component, flowing a solution containing the release layer component, or the like. Further, the fixing of the release layer component to the surface of the carrier may be carried out by adsorption or drying of a solution containing a release layer component, electrodeposition of a release layer component in a solution containing a release layer component, or the like. The thickness of the release layer is typically from 1 nm to 1 μm, preferably from 5 nm to 500 μm.

As the roughened copper foil, the above-described roughened copper foil of the present invention is used. The roughened copper foil of the present invention is roughened Although the treatment, the roughening treatment, and the fine roughening treatment are used, the copper layer is first formed on the surface of the release layer as a copper foil, and then at least roughening treatment and/or fine roughening treatment may be performed. The details of the roughening treatment and the fine roughening treatment are as described above. In addition, it is desirable to use a copper foil as a copper foil with a carrier, and it is desirable to form an ultra-thin copper foil. The thickness of the ultra-thin copper foil is preferably 0.1 μm to 7 μm, more preferably 0.5 μm to 5 μm, still more preferably 0.5 μm to 3 μm.

Other functional layers may also be provided between the release layer and the copper foil. An example of such another functional layer is an auxiliary metal layer. It is desirable that the auxiliary metal layer is composed of nickel and/or cobalt. It is preferable that the thickness of the auxiliary metal layer is 0.001 to 3 μm.

[Examples]

The present invention will be more specifically described by way of the following examples.

Example 1~3

The roughened copper foil of the present invention was produced in the following manner.

(1) Production of electrolytic copper foil

A copper sulfate solution having the composition shown below was used as the copper electrolytic solution, and a rotating electrode made of titanium having a surface roughness Ra of 0.20 μm was used for the cathode, and DSA (size stable anode) was used for the anode, and the solution temperature was 45 ° C. Electrolysis was carried out at a current density of 55 A/dm ^{2 to} obtain an electrolytic copper foil having a thickness of 18 μm. The ten-point average roughness Rzjis of the deposition surface of the electrolytic copper foil was measured by a method described later, and was 0.6 μm.

<Composition of sulfuric acid acidic copper sulfate solution>

- copper concentration: 80g / L

- sulfuric acid concentration: 260g / L

- bis(3-sulfopropyl)-disulfide concentration: 30 mg/L

-Diallyldimethylammonium chloride polymer concentration: 50mg/L

- Chlorine concentration: 40mg/L

(2) roughening treatment

In the electrode surface, the deposition surface, and the deposition surface side of the above-mentioned electrolytic copper foil, the following three-stage process is subjected to roughening treatment.

- The first stage of the roughening treatment is a copper electrolytic solution for roughening treatment (copper concentration: 10.8 g/L, sulfuric acid concentration: 240 g/L, concentration of 9-phenylpyridinium: 0 mg/L, chlorine concentration: 0 mg/L) In the above, the conditions shown in Table 1A were carried out by electrolysis and washing with water.

- The second stage of the roughening treatment is a copper electrolytic solution for roughening treatment (copper concentration: 10.8 g/L, sulfuric acid concentration: 240 g/L, concentration of 9-phenylpyridinium: 0 mg/L, chlorine concentration: 0 mg/L) In the above, the conditions shown in Table 1A were carried out by electrolysis and washing with water.

- The third stage of the roughening treatment is a copper electrolytic solution for roughening treatment (copper concentration: 70 g/L, sulfuric acid concentration: 240 g/L, 9-phenyl acridine concentration: In the case of 0 mg/L and chlorine concentration: 0 mg/L, electrolysis and washing with water were carried out under the conditions shown in Table 1A.

(3) Micro-roughening treatment

Electrolysis was carried out under the conditions shown in Table 1 to carry out fine roughening treatment. The fine roughening treatment is a copper electrolytic solution for roughening treatment (copper concentration: 13 g/L, sulfuric acid concentration: 70 g/L, 9-phenylpyridinium concentration: 140 mg/L, chlorine concentration: 35 mg/L), and Table 1B The conditions shown are carried out by electrolysis and washing with water.

(4) Anti-rust treatment

On both sides of the electrolytic copper foil after the fine roughening treatment, an inorganic rustproof treatment and an antirust treatment composed of chromate treatment are performed. First, as an inorganic anti-rust treatment, pyrophosphoric acid was used, and zinc was prepared at a potassium pyrophosphate concentration of 80 g/L, a zinc concentration of 0.2 g/L, a nickel concentration of 2 g/L, a liquid temperature of 40 ° C, and a current density of 0.5 A/dm ² . Nickel alloy anti-rust treatment. Next, as a chromate treatment, a chromate layer is further formed on the zinc-nickel alloy anti-rust treatment. This chromate treatment was carried out at a chromic acid concentration of 1 g/L, a pH of 11, a solution temperature of 25 ° C, and a current density of 1 A/dm ² .

(5) decane coupling agent treatment

The copper foil subjected to the above rust-preventing treatment was washed with water, and immediately after the decane coupling agent treatment, the decane coupling agent was adsorbed on the rust-preventing treatment layer of the roughened surface. The decane coupling agent treatment is carried out by using pure water as a solvent. A solution having a 3-aminopropyltrimethoxydecane concentration of 3 g/L was used, and this solution was subjected to adsorption treatment by rinsing and blowing the roughened surface. After the adsorption of the decane coupling agent, the water was finally evaporated by an electric heater to obtain a roughened copper foil having a thickness of 18 μm.

Example 4

The production of the roughened copper foil was carried out in the same manner as in Example 1 except that i) the fine roughening treatment was omitted and ii) the roughening treatment was carried out under the conditions shown in Table 1A.

Example 5 (comparative)

Except that i) the electrode surface side of the electrodeposited copper foil (ie, the side opposite to the deposition surface side, Rzjis: 1.5 μm) was roughened, and the like, and ii) the roughening treatment and the fine roughening treatment were as shown in Table 1A and The conditions shown in 1B were carried out in the same manner as in Example 1, and the roughened copper foil was produced.

Example 6 (comparative)

The roughening treatment of the copper foil was carried out in the same manner as in Example 1 except that i) was subjected to the roughening treatment in one of the following stages in place of the first, second, and third roughening steps, and ii) the fine roughening treatment was omitted. Production.

(roughening treatment)

The copper electrolytic solution for roughening treatment using the composition shown below was used in the electrode surface, the deposition surface, and the deposition surface side of the above-mentioned electrolytic copper foil, and the solution temperature was 30 ° C, the current density was 50 A/dm ² , and time was used. Electrolysis was carried out under conditions of 4 seconds to carry out roughening treatment.

<Composition of copper electrolytic solution for roughening treatment>

- copper concentration: 13g / L

- sulfuric acid concentration: 70g / L

-9-phenyl acridine concentration: 100mg/L

- Chlorine concentration: 35mg/L

Example 7 (comparative)

Except that i) the electrode surface side of the electrodeposited copper foil (that is, the side opposite to the deposition surface side, Rzjis: 1.5 μm) was subjected to a roughening treatment or the like, and ii) the fine roughening treatment was omitted, and iii) the roughening treatment was performed. The same procedure as in Example 1 was carried out under the conditions shown in Table 1A, and the roughened copper foil was produced.

Example 8 (comparative)

Except that i) the electrode surface side of the electrodeposited copper foil (that is, the side opposite to the deposition surface side, Rzjis: 1.5 μm) is subjected to a roughening treatment or the like, and ii) the second roughening step and the fine roughening treatment are omitted, and Iii) The roughening treatment (that is, the first roughening step and the third roughening step) was carried out in the same manner as in Example 1 except for the conditions shown in Table 1A, and the roughened copper foil was produced.

Evaluation

The roughened copper foils produced in Examples 1 to 8 were subjected to various evaluations as described below.

<10 point average roughness Rzjis>

The ten-point average roughness Rzjis of the roughened surface of the roughened copper foil was measured by a contact surface roughness meter (Korea Institute, SE3500) in accordance with JIS B 0601-2001. In this measurement, a diamond ball having a diameter of 2 μm was used as a stylus, and the reference length was 0.8 mm. Further, the measurement of the Rzjis of the deposition surface or the electrode surface of the electrolytic copper foil before the roughening treatment of each of the above examples was carried out in accordance with the same procedure as described above.

<half-value width of the frequency distribution at the height of the roughened particles>

The surface profile of the roughened surface of the roughened copper foil was measured using a three-dimensional roughness analyzer (ERA-8900, manufactured by ELIONIX Co., Ltd.). The measurement was carried out under the conditions of a magnification of 600 to 30,000 times and an acceleration voltage of 10 kV. The measurement magnification was adjusted within the above range in accordance with the size of the roughened particles. The particle size was calculated from the measured surface profile. At this time, the height of the roughened particles measured per 0.01 μm in the z-axis (foil thickness direction) was regarded as the particle size. The height or particle size of the roughened particles is calculated by measuring the surface profile of the electrolytic copper foil (original foil) before the roughening treatment, and the value of the surface profile caused by the roughening treatment is removed as the background value when the particle size is calculated. And proceed. The frequency distribution of the height of the roughened particles of the height or the particle size calculated according to the above-described operation is as shown in Fig. 1 as the full width of the frequency distribution peak at a value of 1/2 of the maximum value of the peak of the frequency distribution. The half value width (μm) is calculated.

<roughening surface specific surface area>

The surface profile of the roughened surface of the roughened copper foil in the range of 14000 μm ² (100 μm × 140 μm) was measured at a magnification of 2000 times using a laser microscope (VK-X100, manufactured by Keyence Corporation). The three-dimensional surface area X (μm ² ) of the surface profile of the obtained roughened surface was calculated, and the value X/Y obtained by dividing the value of X by the measurement area Y (14000 μm ² ) was defined as the specific surface area.

<peel strength>

A liquid crystal polymer (LCP) film (Vecstar CTZ, manufactured by Kuraray Co., Ltd.) having a thickness of 50 μm was prepared as an insulating resin substrate. The insulating resin substrate is roughened copper foil with the roughened surface and the insulating tree The grease substrate was laminated in such a manner that it was subjected to hot press molding at a pressure of 4 MPa and a temperature of 310 ° C for 10 minutes to prepare a copper clad laminate sample. With respect to this copper clad laminate sample, the normal peel strength (kgf/cm) was measured in accordance with the method A of JIS C 5016-1994, and the surface of the insulating resin substrate was peeled off in the direction of 90°.

<roughened particle cross-sectional area ratio>

The ratio of the cross-sectional area ratio of the roughened particles on the roughened surface of the roughened copper foil was measured. This measurement uses a desktop automatic multi-function image processing analyzer (LUZEX AP, manufactured by NIRECO Corporation) and a concentrated ion beam processing observation device (FIB) to observe a specific field of view on the roughened surface (for example, 8 μm × The profile of each roughened particle of 8 μm) was obtained as a SIM image of FIB at a magnification of 18,000 times (hereinafter referred to as FIB-SIM image), and the FIB-SIM image was subjected to image analysis to measure the closed sectional area. The cross-sectional area is calculated by calculating the ratio of the cross-sectional area of the roughened particles by the ratio of the (closed area of the roughened particles)/the cross-sectional area of the roughened particles. The binarization setting of this image analysis is set to 127. The specific procedures are as follows.

(1) Determination of the sectional area of roughened particles

As shown in Fig. 2, the FIB-SIM image is drawn in a straight line from the slightly equal position of the roughened particle to the longitudinal direction of the roughened particle (i.e., the height direction of the roughened particle). A position of a specific reference point a of 2 μm is left at the top of the head of the roughened particles on the straight line. Reference point a Two tangent lines are drawn for the roughened particles, and the joints b and c of the tangent and the roughened particles are specified. A straight line connecting the joints b and c (hereinafter referred to as a bc straight line) and a cross-sectional area of the cross-sectional area surrounded by the cross-sectional contour of the roughened particle are obtained by image analysis, and are referred to as roughened particles. Sectional area. Further, when the distance of the reference point a from the top of the roughened particle is set to 2 μm, the length of the scale of the FIB-SIM image is considered to be 2 μm, because even if the length of the correlation is slightly changed from the position of the reference point a, the contact point The positions of b and c are substantially uniquely specified, and as a result, the value of the sectional area of the roughened particles can be obtained with high precision.

(2) Determination of the closed sectional area of roughened particles

An enlarged image of the head of the roughened particles is illustrated in Figure 3. The shape of the closed cross-sectional area of the roughened particles is defined as the tip end of the fine convex shape on the surface of the roughened particles in the manner described in the FIB-SIM image of FIG. 3 (in the case where the fine roughened particles are present) The area of the line surrounded by the front end of the finely roughened particles and the line surrounded by the bc line is obtained by image analysis. The position determination of each of the above-described front ends is automatically performed by the software included in the image processing analyzer.

<Determining the ratio of the cross-sectional area of the roughened particles>

The ratio of the cross-sectional area of the roughened particles was calculated from the closed cross-sectional area obtained as described above and the cross-sectional area of the roughened particles. The roughened particle cross-sectional area ratio is calculated for each of the roughened particles observed for each field of view, and the average of the ratio of the cross-sectional area of the roughened particles obtained for all the roughened particles of the five fields of view is calculated. value.

<transmission loss>

A liquid crystal polymer (LCP) film (Vecstar CTZ, manufactured by Kuraray Co., Ltd.) having a thickness of 50 μm was prepared as an insulating resin substrate. On both surfaces of the insulating resin substrate, the roughened copper foil is laminated such that the roughened surface abuts against the insulating resin substrate, and is bonded by batch pressing. As shown in Fig. 4, the roughened copper foil on one side of the insulating resin substrate 40 was etched, and the microstrip line was formed into a signal layer 42 (thickness: 18 μm) so that the characteristic impedance was 50 Ω. On the other hand, the roughened copper foil on the opposite side of the signal layer 42 of the insulating resin substrate 40 is used as the ground layer 44 (having a thickness of 18 μm) without being etched. On the signal layer 42 side of the insulating resin substrate 40 A transfer film having a thickness of 12 μm (CISV-1225, manufactured by NIKKAN Industrial Co., Ltd.) was used as a coating layer 46 to form a transfer loss by applying an adhesive (AY-25KA, manufactured by Tosoh Corporation) to a thickness of 25 μm. For the microstrip line of the obtained sample, a network analyzer (manufactured by KEYSIGHT TECHNOLOGIES, N5247A) and a detection system (manufactured by Cascade Microtech, SUMMIT 9000) were used to determine the transmission loss S ₂₁ at a circuit length of 5 cm. .

result

The evaluation results obtained in Examples 1 to 8 are shown in Table 2.

Claims (8)

A roughened copper foil which is a roughened copper foil having a roughened surface having roughened particles on at least one side thereof, wherein the roughened surface has a ten point average roughness of 0.6 to 1.7 μm The degree Rzjis, and the half value width of the frequency distribution at the height of the roughened particles is 0.9 μm or less. The roughened copper foil according to claim 1, wherein the half value width is 0.2 to 0.9 μm. The roughened copper foil according to claim 1, wherein the roughened surface has a specific surface area of 1.1 to 2.1, and the specific surface area is divided by the measured area Y by the three-dimensional surface area X of the roughened surface. And get the value of X/Y. The roughened copper foil according to claim 1, wherein the roughened particles are further provided with finely roughened particles which are finer than the roughened particles. The roughened copper foil according to claim 1, wherein the roughened surface has a roughened particle cross-sectional area ratio of 1.10 to 1.50. The roughened copper foil of claim 1 is used for a printed circuit board suitable for high frequency use. A printed circuit board suitable for high-frequency use, comprising the roughened copper foil according to any one of claims 1 to 6, and an insulating resin layer provided in close contact with the roughened surface of the copper foil. A printed circuit board suitable for high-frequency use according to claim 7, wherein the insulating resin layer is formed by containing a liquid crystal polymer.