WO2017026490A1 - 高周波回路用銅箔、銅張積層板、プリント配線基板 - Google Patents
高周波回路用銅箔、銅張積層板、プリント配線基板 Download PDFInfo
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- WO2017026490A1 WO2017026490A1 PCT/JP2016/073476 JP2016073476W WO2017026490A1 WO 2017026490 A1 WO2017026490 A1 WO 2017026490A1 JP 2016073476 W JP2016073476 W JP 2016073476W WO 2017026490 A1 WO2017026490 A1 WO 2017026490A1
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- copper foil
- roughening
- roughened
- height
- particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
Definitions
- the present invention relates to a copper foil for a high-frequency circuit that has excellent adhesion to a resin base material and excellent high-frequency signal transmission characteristics.
- Such a printed wiring board is manufactured from a copper clad laminate in which a circuit forming copper foil is disposed and integrated on the surface of an insulating resin base material.
- a circuit pattern is formed by applying a mask pattern to the copper foil and etching the copper-clad laminate.
- the copper foil and the resin base material are integrated by heating and pressurization, but the adhesiveness of a predetermined level or more is required.
- a method of ensuring such adhesion a method of performing a predetermined roughening treatment on the copper foil is common.
- the reduction of the conductor loss largely depends on the uneven shape on the surface of the copper foil, particularly the size and shape of the roughening formed on the adhesive surface with the printed board material. Therefore, in order to reduce the conductor loss, the roughened size of the surface (the surface to be bonded to the printed circuit board material) is reduced (Patent Document 1).
- Patent Documents 2 to 6 When reducing the roughening size, it is considered to increase the adhesion with the resin base material and improve the other characteristics by paying attention to the height and shape of the roughened particles on the copper foil surface. I came. (Patent Documents 2 to 6)
- Patent Documents 7 to 8 disclose copper foil focusing on the height and shape of roughened particles on the surface of the copper foil.
- Japanese Patent No. 5178064 Japanese Patent Laid-Open No. 07-231152 Japanese Patent Application Laid-Open No. 08-222857 JP 2006-210689 A Republished 2010-110092 JP 2013-199082 A JP 2006-103189 A JP 2011-168887 A
- the printed circuit board material is chemically bonded to the silane coupling agent formed on the copper foil surface. Therefore, if the roughened size is simply reduced, there is a problem that the adhesion with the substrate material is remarkably lowered.
- Patent Documents 2 to 8 disclose that the adhesion to the resin base material and other characteristics are improved by giving the roughening height and shape of the roughening particles on the surface of the copper foil. Has been.
- Patent Document 2 a large number of uniform and fine bumps are generated on the smooth surface of a copper foil. Specifically, reverse teardrop-shaped rough particles are formed with a roughening height of 0.6 to 1.0 ⁇ m. By doing so, the adhesiveness with the resin base material is excellent, and the etching property of the fine circuit is enhanced.
- Patent Document 3 a fine and uniform bumping process is performed on the rough surface side of the electrolytic copper foil. Specifically, the roughening height is 0.05 to 0.3 ⁇ m and the needle-like or bump-like roughening is performed. By forming the particles, an etching factor that is excellent in adhesion to the resin substrate and is high is obtained.
- a roughened particle layer composed of fine roughened particles is formed on the surface of a copper foil. Specifically, a spherical roughened particle having a diameter (roughened height) of 0.05 to 1.0 ⁇ m. By forming the particles, the adhesiveness with the resin substrate is excellent, the linearity of the circuit is high, and the transmission loss can be reduced.
- a roughened particle layer composed of fine roughened particles is formed on the surface of a copper foil.
- the diameter (roughened height) is 0.1 to 2.0 ⁇ m, and high
- the adhesiveness with the resin substrate is excellent and the circuit erosion phenomenon is avoided.
- a roughened particle layer composed of fine roughened particles is formed on the surface of a copper foil.
- the diameter (roughened height) is 0.666 to 15 ⁇ m, and the height and width.
- the amount and shape of the roughening treatment to be applied to the surface of the copper foil are set within an appropriate range, specifically, a convex portion with a roughening height of 0.4 to 1.8 ⁇ m and a sharp tip.
- each of the copper foils in Patent Documents 2 to 8 described above is composed of only single-shaped roughened particles, so that both the adhesion to the resin substrate and other characteristics are improved.
- adhesion there is a trade-off relationship with adhesion, and the most important high-frequency transmission characteristics in a high-frequency circuit have not been achieved at a high level.
- thermosetting resin containing a low dielectric loss resin with low transmission loss as a component when used as a printed circuit board material used in a high frequency region, a resin having a high glass transition temperature has a temperature at which the resin fluidity increases. The temperature at which the resin is cured is close, and the resin may be cured before the resin is sufficiently filled in the gaps between the roughened particles of the copper foil. In such a resin, there is a problem that in a state where roughened particles having a low roughened height are arranged without gaps, the resin is difficult to be filled, and adhesion with the substrate material is lowered.
- a method for ensuring the adhesion with the resin base material by increasing the height of the roughened particles does not necessarily sufficiently consider the high-frequency transmission characteristics.
- coherence of transmission characteristics when using a copper-clad laminate is a major issue as well as ensuring adhesion to a resin substrate.
- the present inventors not only specify the height of the roughened particles (surface roughness), but also partially increase the height of the roughened particles or control the shape of the roughened particles. It has been found that the adhesiveness with the resin base material and the high-frequency transmission characteristics can be compatible.
- the height and shape of the roughened particles have a large effect on the filling properties of the resin base material, the resin breaking behavior during pulling, the transmission path of high-frequency signals, etc., and as a result, the main factors that fluctuate adhesion and high-frequency transmission characteristics. It was confirmed that. In this respect, it is important to accurately grasp the entire image of the roughened particles, and the present inventor has also intensively studied the observation method of the roughened particles.
- the present invention has been made in view of such problems, and an object of the present invention is to provide a copper foil or the like that has excellent adhesion to a resin base material and excellent high-frequency transmission characteristics.
- a first invention is a copper foil for transmitting a high-frequency electric signal, and is formed on at least one surface and made of a roughened particle layer, and the roughened particle layer.
- a roughened particle having a roughening height of 0.5 ⁇ m or more and 3 ⁇ m or less is 30 ⁇ m in a cross-section obtained by cutting the copper foil in the width direction.
- the number of the roughened particles having a range of 1 to 10 in a range and a roughening height of 0.1 to 0.4 ⁇ m is 5 or more in a range of 30 ⁇ m Copper foil.
- the roughening particles having a roughening height of 0.5 ⁇ m or more and 3 ⁇ m or less are 1 to 5 in a range of 30 ⁇ m, and the roughening height is It is more desirable that the number of the roughened particles of 0.1 ⁇ m or more and 0.4 ⁇ m or less is 7 or more in the range of 30 ⁇ m.
- the root mean square slope Sdq of the contour curved surface on the surface of the copper foil is 45 or more and 95 or less.
- the root mean square slope Sdq of the contour curved surface on the surface of the copper foil is 55 or more and 95 or less.
- the number of roughening particles having a roughening height of 0.5 ⁇ m or more and 3 ⁇ m or less is 2 or more and 10 or less in a range of 30 ⁇ m, and the roughening height is 0.00. It is desirable that the cross-sectional shape of the roughened particles of 5 ⁇ m or more and 3 ⁇ m or less includes two or more shapes among a backdrop shape, a columnar shape, a needle shape, and a dendritic shape.
- the roughening particles having a roughening height of 0.5 ⁇ m or more and 3 ⁇ m or less are 2 or more and 5 or less in a range of 30 ⁇ m, and the roughening height is It is desirable that the cross-sectional shape of the roughened particles of 0.5 ⁇ m or more and 3 ⁇ m or less includes two or more shapes among a backdrop shape, a column shape, a needle shape, and a dendritic shape.
- the adhesion with the resin base material is improved. Further, high-roughening particles having a roughening height of 0.5 ⁇ m or more and 3 ⁇ m or less and low-roughening particles having a roughening height of 0.1 ⁇ m or more and 0.4 ⁇ m or less are mixed. Therefore, it is possible to partially form a portion having a high roughening height and a portion having a low roughening height.
- the number of roughening particles having a high roughening height is 1 or more and 10 or less, and the number of roughening particles having a low roughening height is 5 or more. Even if the overall roughening height is reduced, the roughening particles having a high roughening height that are partially formed can increase the adhesion and lower the overall roughening height. Thus, good high frequency transmission characteristics can be ensured.
- Such an effect is that, within the range of 30 ⁇ m, the number of roughening particles having a high roughening height is 1 or more and 5 or less, and the number of roughening particles having a low roughening height is 7 or more. Thus, a greater effect can be obtained.
- the root mean square slope Sdq of the contour curved surface on the surface of the copper foil is 45 or more and 95 or less, the shape of the roughened particles becomes appropriate, the adhesion can be improved, and good high-frequency transmission characteristics are ensured. be able to.
- the root mean square slope Sdq of the contour curved surface on the surface of the copper foil is 55 or more and 95 or less, a greater effect can be obtained.
- the number of roughening particles having a roughening height of 0.5 ⁇ m or more and 3 ⁇ m or less is 2 or more and 10 or less in a range of 30 ⁇ m
- the roughening height is By making the cross-sectional shape of the roughened particles of 0.5 ⁇ m or more and 3 ⁇ m or less to include two or more shapes of backdrop, columnar, needle, and dendritic, for example, excellent transmission characteristics, but adhesion
- the presence of backdrop-like and dendritic shapes with excellent adhesion can improve adhesion and provide good high-frequency transmission characteristics. Can be secured.
- the roughening particles having a roughening height of 0.5 ⁇ m or more and 3 ⁇ m or less are 2 or more and 5 or less in the range of 30 ⁇ m, the above effect is great.
- copper or a copper alloy is particularly suitable as the roughened particle layer of the copper foil for high-frequency circuits.
- the high-frequency copper foil according to the first invention is an epoxy, heat-resistant epoxy, bismaleimide / triazine resin, polyimide, polyamideimide, polyetherimide, polyetheretherketone, polyphenylene ether, polyphenylene oxide, cyanate.
- a copper-clad laminate characterized in that it is affixed to one or both sides of a resin substrate made of any resin of ester resins or a mixed resin thereof.
- a copper-clad laminate with low transmission loss can be obtained efficiently. Moreover, sufficient binding force of the copper foil for high frequency circuits and resin can be ensured by applying the copper foil of this invention also to such resin.
- the third invention is a printed wiring board characterized by using the copper clad laminate according to the second invention.
- the present invention it is possible to provide a copper foil or the like that is excellent in adhesion to a resin base material and excellent in high-frequency transmission characteristics.
- FIG. The conceptual diagram which shows an acicular roughening particle
- FIG. 1 is a view showing a printed wiring board 1 according to the present invention.
- the printed wiring board 1 is formed by bonding a copper foil 5 on a resin base material 3.
- the copper foil 5 is patterned by masking and etching to form a circuit not shown.
- the copper-clad laminate 2 is obtained by bonding and integrating the copper foil 5 and the resin base material 3 before etching.
- a known method such as a hot press method, a continuous roll laminating method, a continuous belt pressing method, or the like can be used.
- the copper foil 5 can be appropriately selected from an electrolytic copper foil, an electrolytic copper alloy foil, a rolled copper foil, and a rolled copper alloy foil according to the use of the copper clad laminate 2 and the like. The details of the copper foil 5 will be described later.
- the resin base 3 examples include epoxy, heat-resistant epoxy, bismaleimide / triazine resin, polyimide, polyamideimide, polyetherimide, polyetheretherketone, polyphenylene ether, polyphenylene oxide, and cyanate ester resins. It consists of these mixed resins. A sufficient chemical bonding force between the high-frequency circuit copper foil and the resin can be secured by applying the copper foil of the present invention to such a resin.
- the copper foil 5 and the resin base material 3 can be obtained only by the chemical bonding force by the silane coupling agent treatment layer. Therefore, it is necessary to perform a process for forming appropriate roughened particles. This tendency becomes more prominent as the glass transition temperature becomes higher, and the effect of using the copper foil of the present invention is enhanced in a resin base material having a glass transition temperature exceeding 150 ° C. Furthermore, the effect of using the copper foil of the present invention is remarkably enhanced in a resin base material having a glass transition temperature exceeding 200 ° C.
- the printed wiring board 1 is a high-frequency low transmission loss board. For example, it is used for transmission of high-frequency electrical signals of 5 GHz or higher. As shown in the figure, the printed wiring board 1 is not limited to one in which the resin base material 3 and the copper foil 5 are laminated one layer on each side, and may be a plurality of layers. For example, the copper foil 5 may be laminated on both surfaces of the resin base material 3, and similarly, the resin base material 3 may be laminated on both surfaces of the copper foil 5.
- FIG. 2 is an enlarged cross-sectional view of the resin contact surface of the copper foil 5.
- the copper foil 5 has a plurality of roughened particles 9 formed on a copper base foil 7.
- a layer formed by the roughened particles 9 is referred to as a roughened particle layer 11.
- the copper foil for high-frequency circuits of the present invention is obtained by burning plating on at least one surface of the original foil surface as a metal substrate (the surface roughness is not particularly limited, but Rz is preferably 5.0 ⁇ m or less).
- Roughened particles 9 are provided to form a roughened particle layer 11.
- the roughened particles 9 are preferably made of copper or a copper alloy.
- a rust prevention layer composed of the chromate treatment layer 13 is formed as necessary.
- a silane coupling agent treatment layer 15 is formed on the chromate treatment layer 13.
- the silane coupling agent treatment layer 15 will be described as being formed on the roughened particle layer 11. That is, in the present invention, the formation of the silane coupling agent treated layer 15 on the roughened particle layer 11 means that another layer is formed between the roughened particle layer 11 and the silane coupling agent treated layer 15. Including those that are made.
- a chromate treatment layer 13 is formed thereon, and a silane coupling agent treatment layer 15 is formed on the chromate treatment layer 13, or the roughened particle layer
- a nickel layer is formed on 11
- a zinc layer is formed
- a chromate treatment layer 13 is formed thereon
- a silane coupling agent treatment layer 15 is formed on the chromate treatment layer 13.
- the silane coupling agent treatment layer 15 can be appropriately selected from epoxy, amino, methacrylic, vinyl, acrylic, mercapto and the like according to the resin of the resin base material 3.
- epoxy, amino, and vinyl coupling agents that are particularly excellent in compatibility can be selected.
- the overall height of the roughened particles 9 is not increased, but partially increased, thereby improving the adhesion and suppressing the height of the roughened particles 9 as a whole, It achieves both adhesion to the resin substrate and high frequency transmission characteristics. That is, it has been found that the adhesiveness can be secured without increasing the overall height by partially increasing the roughened particles 9.
- the rough particles 9 partially have a height of 0.5 ⁇ m or more and 3 ⁇ m or less, the effect of improving the adhesion to the resin substrate is great.
- the height of the roughened particles 9 is 0.1 ⁇ m or more and 0.4 ⁇ m or less, the effect of improving the adhesion to the resin substrate is reduced, but the adverse effect on the high-frequency transmission characteristics is small.
- the roughening particle 9 having a roughening height of 0.5 ⁇ m or more and 3 ⁇ m or less is 1 to 10 in a range of 30 ⁇ m
- the number of roughening particles 9 having a roughening height of 0.1 ⁇ m or more and 0.4 ⁇ m or less is 5 or more in the range of 30 ⁇ m.
- the width direction refers to a direction perpendicular to the longitudinal direction of the roll when the electrolytic copper foil or rolled copper foil formed as a copper base material is wound on the roll.
- the reason for limiting to the width direction is that, when the roughening treatment is performed, the unevenness in roughening can be in the tensile direction, and therefore the measurement in the width direction can be stably performed.
- the adhesion to the resin substrate can be improved. it can.
- the number of roughening particles 9 having a high roughening height exceeds 10 in the range of 30 ⁇ m, the influence on the high-frequency transmission characteristics increases, which is not desirable. Therefore, in the present invention, the number of roughened particles 9 having a roughening height of 0.5 ⁇ m or more and 3 ⁇ m or less is required to be 1 or more and 10 or less in the range of 30 ⁇ m, and more preferably 1 or more in the range of 30 ⁇ m. Or less.
- the resin is completely flat compared to the case of flatness.
- the effect of improving the adhesion with the substrate can be obtained.
- the roughened particles 9 having a low roughened height are present.
- the roughened particles 9 having a roughened height of 0.1 ⁇ m or more and 0.4 ⁇ m or less, 5 or more are required in the range of 30 ⁇ m, and more preferably 7 or more in the range of 30 ⁇ m.
- grains 9 whose roughening height is 0.1 to 0.4 micrometer and whose roughening height is low even if the number increases, there is little influence on a high frequency transmission characteristic.
- the lower the roughening height the smaller the transmission loss.
- the roughness height is too low, the contribution to the adhesion becomes small, and therefore it is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more.
- the roughening height of the roughening particle 9 is made high as a whole by mixing the roughening particle 9 with a high roughening height and the roughening particle 9 with a low roughening height. Compared with the case where it does, while suppressing the bad influence to a high frequency transmission characteristic, sufficient adhesiveness with a resin substrate can be ensured.
- the surface roughness of the roughened surface of the original foil can be dealt with by adjusting the roughness of the drum surface when the original foil is made.
- the surface roughness of the roughened surface of the original foil can be increased by polishing the surface of the drum that forms the original foil with a rough buff.
- the concentration of the leveler added to the plating solution at the time of foil making is lowered, or the etching time for chemically dissolving (etching) the surface of the copper foil after the foil making is lengthened. Can also respond.
- the 10-point average roughness Rz of the roughened surface of the original foil is preferably 1.5 ⁇ m or less, more preferably 1.3 ⁇ m or less, and even more preferably 1.1 ⁇ m or less.
- the roughened particles 9 having a high roughening height and the roughening having a low roughening height are obtained without greatly increasing the surface roughness of the original foil. It can be set as the form in which the chemical particle 9 was mixed.
- the current density of the roughening plating after the previous roughening plating is increased when performing roughening plating multiple times. By doing so, the level difference of the roughening particle
- the level difference of the roughened particles can be increased by appropriately selecting an additive element in the roughened plating solution in multiple times of roughening plating.
- capsule plating which is smooth plating
- capsule plating may be applied after burn plating for forming rough particles to prevent the rough particles from falling off.
- the next burn plating can be performed continuously after the burn plating. By performing the burn plating continuously, the level difference of the roughened particles can be effectively expanded.
- the inventors have found that not only the roughening height of the roughened particles 9 but also the shape (tilt) of the roughened particles 9 affects the transmission characteristics and adhesion. That is, by defining not only the distribution of the roughening height of the roughened particles 9 but also the form of the roughened particles 9, both transmission characteristics and adhesion can be achieved at a higher level.
- the present inventor has found that the shape of the roughened particles and the clearance between the roughened particles are affected by the composition of the roughening plating solution and the temperature, and the root mean square slope Sdq of the contour curve on the surface of the copper foil. Found that it was affected by the shape of the roughened particles and the gap between the roughened particles.
- the root mean square slope Sdq of the contour curved surface on the surface of the copper foil is preferably 45 or more and 95 or less, and more preferably, the root mean square slope Sdq is 55 or more and 95 or less.
- the root mean square gradient represents the surface properties of the contour surface in all directions, and is obtained by averaging the roughness height of the roughened particles 9 with the square root. That is, a high value means that the inclination of the roughened particles 9 is high.
- the root mean square slope Sdq is desirably 95 or less.
- the root mean square slope Sdq is desirably 45 or more.
- the root mean square slope Sdq is generally given by the following equation.
- x and y in the formula are plane coordinates, and Z is a coordinate in the height direction.
- Z (x, y) indicates the coordinates of a certain point, and the slope at the coordinate point is obtained by differentiating this.
- the square root is obtained by adding the squares of the x-direction gradient and the y-direction gradient of all points (A).
- the root mean square slope Sdq can be measured at a measurement magnification of 5 times or more using, for example, vertical scanning low coherence interferometry.
- the measurement is preferably a non-contact type surface roughness measuring apparatus having a resolution of 1 ⁇ m or less (for example, 800 nm).
- the condition of rough particles that achieve both high adhesion and transmission characteristics is defined by Sdq, a parameter obtained using an optical interference measurement device that is excellent in height resolution even in a non-contact type. It is possible to do.
- the shape (gradient) of the roughened particles can be adjusted by, for example, an additive element contained in a plating solution used for roughening plating.
- nickel contained in the burn plating solution in the rough plating has an effect on the rough shape, and becomes round when the nickel concentration is high, and becomes thin and sharp when the nickel concentration is low.
- molybdenum contained in the discoloration plating solution affects the clearance of the roughened particles, and when the molybdenum concentration is low, the roughened particles are present sparsely.
- the temperature of the burn plating solution also affects the clearance of the roughened particles, and when the liquid temperature is high, the roughened particles are sparsely distributed.
- the root mean square gradient Sdq can be optimized by optimizing the composition of the burnt plating solution and the plating solution temperature as an example of the roughening plating conditions for forming the roughened particles.
- the Sdq can be increased by lowering the nickel concentration of the burn plating solution, and as another example, the molybdenum concentration of the burn plating solution can be decreased, or the temperature of the burn plating solution can be increased. You can also do it.
- FIGS. 3A to 3E are conceptual diagrams showing classification of the shape of the roughened particles 9, and FIG. 3A shows the needle-like roughened particles 9.
- an ion milling device is used to perform cross-sectional processing in the width direction, and the measurement magnification is 3,000 times or more with an HR-SEM (scanning electron microscope). It can be measured by an image taken at a magnification of.
- the width of the base of the roughened particles 9 is a.
- grains 9 is set to b.
- c be the width at half the height (h / 4) from the half height (h / 2) to the top of the roughened particles 9.
- a> b> c the width changes almost uniformly.
- FIG. 3B is a diagram showing the columnar roughened particles 9.
- a ⁇ b ⁇ c In the columnar roughened particles 9, a ⁇ b ⁇ c, and the widths are almost the same.
- a difference from the acicular roughened particles 9 for example, a difference between a, b, and c is 20% or less.
- FIG. 3C is a diagram showing the backdrop-like roughened particles 9.
- FIG. 3D is a diagram showing spherical roughened particles 9.
- the spherical roughened particles 9 have a substantially spherical shape as a whole, and the widest width d is formed between a height of 0 and h / 2.
- FIG. 3E is a diagram showing dendritic roughening particles 9.
- the dendritic roughening particles 9 have a plurality of branched shapes.
- the cross-sectional shape of the roughened particles 9 having a roughened height of 0.5 ⁇ m or more and 3 ⁇ m or less includes two or more shapes of a backdrop shape, a columnar shape, a needle shape, and a dendritic shape.
- the width of the base of the roughened particles 9 is narrow, the transmission characteristics will be less deteriorated, but will be easily broken from the root of the roughened particles, and the adhesion will be reduced.
- the adhesiveness can be improved by including one or more shapes other than the acicular roughened particles 9.
- two or more roughening particles 9 having a roughening height of 0.5 ⁇ m or more and 3 ⁇ m or less are required in the range of 30 ⁇ m, more preferably 2 or more and 5 in the range of 30 ⁇ m. It is as follows.
- the cross-sectional shape of the roughened particles 9 to include two or more shapes as described above, for example, when the burnt plating is performed a plurality of times, it is possible to use a burned plating solution having a different composition.
- the current density can be changed.
- roughing particles having different shapes can be formed by using different burn plating solutions.
- the overall height of the roughened particles 9 is not increased, but the height of the roughened particles 9 is reduced as a whole by improving the adhesion by partially increasing the height.
- the overall height of the roughened particles 9 is not increased, but the height of the roughened particles 9 is reduced as a whole by improving the adhesion by partially increasing the height.
- both transmission characteristics and adhesion can be further achieved.
- both transmission characteristics and adhesion can be achieved.
- Examples 1 to 7 An untreated smooth copper foil having a thickness of 18 ⁇ m was prepared as a metal substrate, and the untreated copper foil was subjected to burnt plating for forming roughened particles.
- the bath composition of the burnt plating was solution A shown in Table 1.
- Table 2 shows the burn plating conditions and the evaluation results.
- the burn A plating solution A is characterized in that the roughened particles tend to grow sparsely, and as the surface roughness of the roughened surface of the original foil becomes rougher, the roughening height of the roughened particles tends to vary in height.
- capsule plating was performed with the following bath composition and plating conditions in order to obtain a strong and sound roughened particle shape in which roughened particles do not fall off by applying capsule plating to the rough surface of the burnt plating.
- Sulfuric acid concentration 100 g / L
- Copper concentration from copper sulfate 50 g-Cu / L
- Bath temperature 55 ° C
- Current density 15 A / dm 2 by DC rectification
- a rust-proof chromate treatment layer was formed by treatment under the following chrome plating conditions.
- the cross-sectional shape of the copper foil thus produced was subjected to cross-section processing using an ion milling device (IM4000 manufactured by Hitachi High-Tech), and an acceleration voltage of 3 kV (secondary electron image) was obtained using HR-SEM (SU8020 manufactured by Hitachi High-Tech). Is used to observe the cross section at a magnification of 50,000 times, and the number of particles having a roughening height of 0.5 ⁇ m to 3 ⁇ m and the number of particles having a roughening height of 0.1 ⁇ m to 0.4 ⁇ m at an arbitrary 30 ⁇ m in the width direction. I counted.
- the roughened particles having a roughened height of 0.5 ⁇ m or more and 3 ⁇ m or less one kind of roughened shape was designated as “good”, and two kinds or more were designated as “excellent”. Furthermore, using a three-dimensional white light interference microscope (BRUKER Wyko ContourGT-K), the root mean square slope Sdq was measured (measurement conditions were 10 times measurement magnification, using a high-resolution CCD camera, and after applying a special filter) The value between 45 and 95 was “good”, the sample satisfying 55 and 95 was “excellent”, and the others were “bad”.
- BRUKER Wyko ContourGT-K three-dimensional white light interference microscope
- the obtained copper foil with roughened particles is applied to a commercially available high-frequency insulating substrate (Megtron 6 manufactured by Panasonic Corporation: glass transition temperature 185 ° C.), press temperature: 200 ° C., press pressure: 35 kgf / cm 2 , press Time: Laminated under pressing conditions of 160 minutes.
- a pattern was formed on this laminate by UV exposure using a pattern film having a resist width of 300 ⁇ m and a circuit interval of 450 mm, and further etched to obtain a substrate for measuring transmission characteristics having a microstrip line structure.
- the transmission characteristics were evaluated from the measured transmission loss by measuring the transmission loss with a network analyzer.
- the produced microstrip line had a characteristic impedance of 50 ⁇ , and as an example, the thickness of the copper foil was 18 ⁇ m, the thickness of the resin was 0.2 mm, the width was 500 ⁇ m, and the length was 450 mm.
- the adhesion strength was measured by using a Tensilon tester (manufactured by A & D Co., Ltd.), pressing the insulating substrate and the copper foil, etching the test piece into a 10 mm wide circuit pattern, and rotating the circuit pattern in the 90 ° direction. The peel strength when pulled at a speed of 50 mm / min was measured.
- Example 8 For Example 1, capsule plating was performed after the first burn plating, and then capsule plating was performed after the second burn plating. A solution used in the second burn plating was set as Solution B, and the same evaluation was performed as in Example 1 except that the current density was changed. Bake-plating solution B is easy to grow rough, and has the characteristics that it is easy to grow rough particles without changing the difference in the height of the rough particles formed by the first burn-off plating. is there.
- Example 8 (Examples 12 to 15) For Example 8, the capsule plating was not performed after the first burn plating, the capsule plating was performed after the second burn plating, and then the capsule plating was performed after the third burn plating and the current density was changed. Except for the above, it was produced in the same manner as in Example 8, and the same evaluation was performed.
- Example 16 to 22 For Example 8 or Example 12, the solution used in the second and subsequent burn plating was set as Solution C or Solution D, except that the current density was changed. Evaluation was performed.
- the solution C of burnt plating is easy to grow with rounded rough particles, and the solution D has a characteristic that the roughened particles tend to grow in a sharp shape.
- Example 1 or Example 8 was prepared in the same manner as in Example 1 or Example 8 except that a roughening treatment with a commercially available etchant was performed on the surface of the base foil on the surface to be roughened, and the same evaluation was performed. Went.
- a commercially available etching solution (CZ8101: manufactured by Meck Co., Ltd.) was used, and the etching was performed at a liquid temperature of 30 ° C., a spray pressure of 0.25 MPa, and an etching amount of 1 ⁇ m.
- Examples 25 to 27 For Example 4 or Example 9 or Example 13, produced in the same manner as Example 4 or Example 9 or Example 13 except that nickel plating and zinc plating were performed after rough plating and then chromate treatment was performed. The same evaluation was performed. Nickel plating and zinc plating were performed under the following conditions as an example.
- Nickel sulfate Nickel concentration: 5.0 g / L Ammonium persulfate: 40.0 g / L Boric acid: 28.5 g / L Current density: 1.5 A / dm 2 pH: 3.8 Temperature: 28.5 ° C Time: 1 second to 2 minutes
- Zinc sulfate heptahydrate 1-30 g / L Sodium hydroxide: 10 to 300 g / L Current density: 0.1 to 10 A / dm 2 Temperature: 5-60 ° C Time: 1 second to 2 minutes
- Example 1 was prepared in the same manner as in Example 1 except that the roughening treatment was not performed, and the same evaluation was performed.
- Table 2 shows the results of evaluating the copper foils for high-frequency circuits according to the respective examples and comparative examples by the above evaluation methods.
- the transmission characteristics are “excellent” when the transmission loss at 40 GHz is ⁇ 28 dB or more, “good” when the transmission loss is less than ⁇ 28 dB, ⁇ 31 dB or more, and “ ⁇ ” when less than ⁇ 31 dB or ⁇ 33 dB or more. average ”and less than ⁇ 33 dB is indicated as“ bad ”.
- the peel strength is 0.6 kN / m or more
- “excellent” when the peel strength is 0.5 kN / m or more and less than 0.6 kN / m
- “good” indicates a case where the peel strength is less than 0.45 kN / m.
- Roughening particles having a roughening height of 0.5 ⁇ m or more and 3 ⁇ m or less are 1 or more and 10 or less in the range of 30 ⁇ m, and roughening particles having a roughening height of 0.1 ⁇ m or more and 0.4 ⁇ m or less In the example of 5 or more in the range of 30 ⁇ m, it was possible to achieve both sufficient peel strength and good transmission characteristics.
- the peel strength is And 40 GHz transmission loss are both “excellent”.
- Example 21 since the solution C was used for the first burn plating, the roundness of the roughened particles became remarkable, Sdq was less than 45, and the peel strength was slightly reduced. Further, in Example 22, since the solution D was used for the first burn plating, the sharpness of the shape of the roughened particles became remarkable, Sdq was larger than 95, and the transmission loss was slightly increased.
- Comparative Examples 1 to 6 even if one of the peel strength and the transmission characteristic was good, it was not possible to achieve both.
- Comparative Example 1 since the current density of the burnt plating was small, the number of roughening particles having a roughening height of 0.5 ⁇ m or more and 3 ⁇ m or less was less than one, and the peel strength was insufficient.
- Comparative Example 2 since the current density of the burnt plating is large, 10 or more roughening particles with a roughening height of 0.5 ⁇ m or more and 3 ⁇ m or less and a roughening particle with a roughening height of 0.1 ⁇ m or more and 0.4 ⁇ m or less. Is less than 5, and the transmission characteristics deteriorated.
- Comparative Example 3 since the surface roughness of the roughened surface of the original foil is rough, the roughening height is 10 ⁇ m or more and the roughening height is 0.1 ⁇ m or more and 0.1 to 0.03 ⁇ m. The number of roughened particles of 4 ⁇ m or less was less than 5, and the transmission characteristics deteriorated.
- Comparative Example 4 since the solution A was used for the second burn plating, the roughening height was 10 or more and the roughening height was 0.1 to 0.4 ⁇ m. The number of roughened particles was less than 5, and the transmission characteristics deteriorated. In Comparative Example 5, no roughening treatment was performed, and the peel strength was significantly insufficient.
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Abstract
Description
以下、図面を参照しながら、本発明の実施形態について説明する。図1は本発明にかかるプリント配線基板1を示す図である。プリント配線基板1は、樹脂基材3上に、銅箔5が貼り合わされて形成される。銅箔5は、マスキングおよびエッチングによってパターニングされ、図示を省略した回路を形成する。なお、エッチング前の銅箔5と樹脂基材3とが貼り合わさって一体化されたものを銅張積層板2とする。樹脂基材3と銅箔5を貼り合わせて、銅張積層板2を形成する方法としては、公知の方法、例えば熱プレス方式、連続ロールラミネート方式、連続ベルトプレス方式などを用いることができる。
銅箔5は、電解銅箔、電解銅合金箔、圧延銅箔、圧延銅合金箔のうちから、銅張積層板2の用途等に応じて適宜選択することができる。なお、銅箔5の詳細は後述する。
次に、銅箔5について詳細に説明する。図2は、銅箔5の樹脂密着面における断面拡大図である。銅箔5は、銅の元箔7上に複数の粗化粒子9が形成される。粗化粒子9により形成される層を粗化粒子層11とする。本発明の高周波回路用銅箔は、金属基材としての元箔表面の少なくとも一方の面(表面粗さは特に限定されないが、Rzが5.0μm以下であることが好ましい)に、ヤケめっきにより粗化粒子9が設けられて粗化粒子層11が形成される。なお、粗化粒子9は、銅または銅合金からなることが好ましい。
粗化高さは高い方が密着性は良好となるが、必要以上に高くしても密着性は飽和し、伝送損失も増加するため、3μm以下であることが好ましく、2μm以下であることがさらに好ましい。
粗化高さは低い方が伝送損失は小さくなるが、低くなりすぎると密着性への寄与が小さくなるため、0.1μm以上であることが好ましく、0.2μm以上であることがさらに好ましい。
粗化高さの異なる粗化粒子が混在した形態とするには、一例としては、複数回の粗化めっきを行う際に、前の粗化めっきよりも後の粗化めっきの電流密度を大きくすることにより、前の粗化めっきにより形成された粗化粒子の高低差を更に拡大することができる。また、他に一例としては複数回の粗化めっきにおいて、粗化めっき液中の添加元素を適宜選択することにより、粗化粒子の高低差を拡大することも可能である。
金属基材として厚さ18μmの未処理平滑銅箔を用意し、この未処理銅箔に粗化粒子を形成するヤケめっきを施した。ヤケめっきの浴組成は表1の溶液Aとした。また、ヤケめっき条件及び評価結果を表2に示す。
ヤケめっきの溶液Aは粗化粒子がまばらに成長しやすく、元箔の粗化処理面の表面粗さが粗いほど粗化粒子の粗化高さに高低差が生じやすい特徴がある。
硫酸濃度:100g/L
硫酸銅からの銅濃度:50g-Cu/L
浴温:55℃
電流密度:直流整流で15A/dm2
無水クロム酸(CrO3) : 2.5g/L
pH: 2.5
電流密度: 0.5A/dm2
温度: 15~45℃
時間: 1秒~2分
この積層板に、レジスト幅300μm、回路間隔450mmのパターンフィルムを用いてUV露光によってパターンを形成し、さらにエッチングを施し、マイクロストリップライン構造の伝送特性測定用基板を得た。伝送特性は、ネットワークアナライザにより伝送損失を測定し、この測定した伝送損失の数値から評価した。作製したマイクロストリップラインは、特性インピーダンスを50Ωとし、一例として銅箔の厚さ:18μm、樹脂の厚さ:0.2mm、幅:500μm、長さ:450mmとした。
実施例1に対し、1回目のヤケめっき後にカプセルめっきを行い、次いで2回目のヤケめっき後にカプセルめっきを行った。2回目のヤケめっきで用いる溶液を溶液Bとし、電流密度を変更した以外は、実施例1と同様に作製し、同様の評価を行った。
ヤケめっきの溶液Bは粗化が均一に成長しやすく、1回目のヤケめっきにより形成された粗化粒子の粗化高さの高低差をあまり変化させずに粗化粒子を成長させやすい特徴がある。
実施例8に対し、1回目のヤケめっき後にカプセルめっきを施さずに、そのまま2回目のヤケめっき後にカプセルめっきを施し、次いで3回目のヤケめっき後にカプセルめっきを行ったことと電流密度を変更した以外は、実施例8と同様に作製し、同様の評価を行った。
実施例8または実施例12に対し、2回目以降のヤケめっきで用いる溶液を溶液Cまたは溶液Dとして、電流密度を変更した以外は、実施例8または実施例12と同様に作製し、同様の評価を行った。
ヤケめっきの溶液Cは粗化粒子が丸味を帯びて成長しやすく、また溶液Dは粗化粒子が尖った形状に成長しやすい特徴がある。
実施例1または実施例8に対し、元箔の粗化処理面側に市販のエッチング液による粗面化処理を施した以外は、実施例1または実施例8と同様に作製し、同様の評価を行った。
エッチング処理条件としては、一例として市販のエッチング液(CZ8101:メック株式会社製)を用いて、液温30℃、スプレー圧0.25MPa、エッチング量1μmで実施した。
実施例4または実施例9もしくは実施例13に対し、粗化めっき後にニッケルめっきおよび亜鉛めっきを施した後にクロメート処理を施した以外は、実施例4または実施例9または実施例13と同様に作製し、同様の評価を行った。
ニッケルめっきおよび亜鉛めっきについては、一例として下記条件にて行った。
硫酸ニッケル: ニッケル濃度として 5.0g/L
過硫酸アンモニウム: 40.0g/L
ほう酸: 28.5g/L
電流密度: 1.5A/dm2
pH: 3.8
温度: 28.5℃
時間: 1秒~2分
<Znめっき条件>
硫酸亜鉛7水和物: 1~30g/L
水酸化ナトリウム: 10~300g/L
電流密度: 0.1~10A/dm2
温度: 5~60℃
時間: 1秒~2分
実施例1~7に対し、ヤケめっきの電流密度または元箔の粗化処理面の表面粗さを変更した以外は、実施例1~7と同様に作製し、同様の評価を行った。
実施例8~11に対し、2回目のヤケめっきで用いる溶液を溶液Aとした以外は、実施例8~11と同様に作製し、同様の評価を行った。
実施例1に対し、粗化処理を施さなかった以外は、実施例1と同様に作製し、同様の評価を行った。
比較例1ではヤケめっきの電流密度が小さいため粗化高さが0.5μm以上3μm以下の粗化粒子の数が1個未満であり、引き剥がし強さが不足した。比較例2では、ヤケめっきの電流密度が大きいため粗化高さが0.5μm以上3μm以下の粗化粒子が10個以上かつ粗化高さが0.1μm以上0.4μm以下の粗化粒子が5個未満であり、伝送特性が低下した。また、比較例3では元箔の粗化処理面の表面粗さが粗いため粗化高さが0.5μm以上3μm以下の粗化粒子が10以上かつ粗化高さが0.1μm以上0.4μm以下の粗化粒子が5個未満であり、伝送特性が低下した。比較例4では2回目のヤケめっきにも溶液Aを用いたため粗化高さが0.5μm以上3μm以下の粗化粒子が10個以上かつ粗化高さが0.1μm以上0.4μm以下の粗化粒子が5個未満であり、伝送特性が低下した。比較例5では粗化処理を施しておらず、引き剥がし強さが大幅に不足した。
2………銅張積層板
3………樹脂基材
5………銅箔
7………元箔
9………粗化粒子
11………粗化粒子層
13………クロメート処理層
15………シランカップリング剤処理層
Claims (10)
- 高周波電気信号の伝送用の銅箔であって、
少なくとも一方の面に形成され、粗化粒子からなる粗化粒子層と、
前記粗化粒子層の上に形成されるシランカップリング剤処理層と、
を具備し、
前記銅箔を幅方向に切断した断面において、粗化高さが0.5μm以上3μm以下の前記粗化粒子が、30μmの範囲に1個以上10個以下であり、かつ、粗化高さが0.1μm以上0.4μm以下の前記粗化粒子が、30μmの範囲に5個以上であることを特徴とする高周波回路用銅箔。 - 前記銅箔を幅方向に切断した断面において、粗化高さが0.5μm以上3μm以下の前記粗化粒子が、30μmの範囲に1個以上5個以下であり、かつ、粗化高さが0.1μm以上0.4μm以下の前記粗化粒子が、30μmの範囲に7個以上であることを特徴とする請求項1記載の高周波回路用銅箔。
- 前記銅箔の表面における輪郭曲面の二乗平均平方根勾配Sdqが45以上95以下であることを特徴とする請求項1記載の高周波回路用銅箔。
- 前記銅箔の表面における輪郭曲面の二乗平均平方根勾配Sdqが55以上95以下であることを特徴とする請求項3記載の高周波回路用銅箔。
- 前記銅箔を幅方向に切断した断面において、粗化高さが0.5μm以上3μm以下の前記粗化粒子が、30μmの範囲に2個以上10個以下であり、
粗化高さが0.5μm以上3μm以下の前記粗化粒子の断面形状が、逆滴状、柱状、針状、樹枝状のうち2つ以上の形状を含むことを特徴とする請求項1記載の高周波回路用銅箔。 - 前記銅箔を幅方向に切断した断面において、粗化高さが0.5μm以上3μm以下の前記粗化粒子が、30μmの範囲に2個以上5個以下であり、
粗化高さが0.5μm以上3μm以下の前記粗化粒子の断面形状が、逆滴状、柱状、針状、樹枝状のうち2つ以上の形状を含むことを特徴とする請求項1記載の高周波回路用銅箔。 - 前記粗化粒子が、銅又は銅合金からなることを特徴とする請求項1記載の高周波回路用銅箔。
- 前記粗化粒子層と前記シランカップリング剤処理層との間にクロメート処理層を具備することを特徴とする請求項1記載の高周波回路用銅箔。
- 請求項1記載の高周波回路用銅箔が、エポキシ、耐熱エポキシ、ビスマレイミド・トリアジンレジン、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリエーテルエーテルケトン、ポリフェニレンエーテル、ポリフェニレンオキサイド、シアネートエステル系樹脂のいずれかの樹脂またはこれらの混合樹脂からなる樹脂基材の片面または両面に貼り付けられていることを特徴とする銅張積層板。
- 請求項9記載の銅張積層板を有することを特徴とするプリント配線基板。
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Also Published As
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TWI598474B (zh) | 2017-09-11 |
CN107113971B (zh) | 2019-04-26 |
KR101954556B1 (ko) | 2019-03-05 |
TW201718951A (zh) | 2017-06-01 |
JPWO2017026490A1 (ja) | 2017-08-10 |
JP6089160B1 (ja) | 2017-03-01 |
CN107113971A (zh) | 2017-08-29 |
KR20170097054A (ko) | 2017-08-25 |
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