WO2018110579A1 - 表面処理銅箔および銅張積層板 - Google Patents
表面処理銅箔および銅張積層板 Download PDFInfo
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- WO2018110579A1 WO2018110579A1 PCT/JP2017/044647 JP2017044647W WO2018110579A1 WO 2018110579 A1 WO2018110579 A1 WO 2018110579A1 JP 2017044647 W JP2017044647 W JP 2017044647W WO 2018110579 A1 WO2018110579 A1 WO 2018110579A1
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- WIPO (PCT)
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- copper foil
- layer
- silane coupling
- treated copper
- treatment layer
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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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
Definitions
- the present invention relates to a surface-treated copper foil and a copper-clad laminate, and particularly, when used in a high frequency band exceeding several GHz, constitutes a printed wiring board that has low transmission loss of high frequency electrical signals and has excellent reflow heat resistance.
- the present invention relates to a surface-treated copper foil and a copper-clad laminate that are suitable for use as a member.
- High frequency printed wiring boards are becoming multi-layered with higher functionality, and high multi-layer printed wiring boards having 30 or more layers are often used.
- a peeling phenomenon between layers tends to occur when a thermal load is applied.
- the printed wiring board is subjected to a high-temperature heat load that causes a rapid temperature rise in a short time.
- reflow heat resistance As a result of organic gasification and volume expansion, which tends to cause swelling, the risk of delamination failure tends to increase. For this reason, it is regarded as important from the viewpoint of reliability that the adhesiveness during reflow soldering (hereinafter referred to as “reflow heat resistance”) is good.
- Patent Document 1 discloses that a diameter of 0.05 to 1 is provided on at least one surface of the copper foil.
- a heat treatment comprising a roughening treatment layer composed of spherical fine roughening particles having a diameter of 0.0 ⁇ m and comprising at least one of molybdenum, nickel, tungsten, phosphorus, cobalt, and germanium on the roughening treatment layer.
- a copper foil for a high-frequency printed wiring board having a rust prevention layer, a chromate film layer on the heat and rust prevention layer, and a silane coupling agent layer on the chromate film layer Is disclosed.
- Patent Document 1 by reducing the coarse particles formed on the copper foil, the peel strength of the copper foil from the resin base material is strong, and the circuit pattern is formed by etching the copper foil. It is disclosed that the linearity of the bottom line is high and transmission loss can be reduced.
- Patent Document 1 does not focus on the reflow heat resistance, which is the adhesion during reflow soldering, and also examines the effect of reducing the transmission characteristics due to the specific surface roughening shape and skin effect. Not done.
- the adhesion surface to be bonded to the insulating resin substrate has a surface roughness (Rzjis) of 2.5 ⁇ m or less and a two-dimensional surface area of 6550 ⁇ m 2 measured by a laser method.
- Surface having a surface area ratio (B) of 1.2 to 2.5, which is the ratio [(A) / (6550)] of the three-dimensional surface area (A) ⁇ m 2 to the two-dimensional surface area A treated copper foil is disclosed.
- this surface-treated copper foil when this surface-treated copper foil is used, good linearity is obtained at the edge of the wiring circuit formed on the printed wiring board, and the chemical resistance as well as the adhesion to the insulating resin substrate is obtained.
- Patent Document 2 adopts a configuration in which the surface roughness (Rzjis) and the surface area ratio (B) are limited to appropriate ranges, but only by limiting the surface roughness and the surface area ratio, an accurate surface property can be obtained. It cannot be specified.
- FIG. 4 (a) and FIG. 4 (b) conceptually show two surface states having the same surface area but different surface roughness when viewed geometrically. As is clear from the comparison of the states, the height and width of the mountain are greatly different between the two, and it is difficult to consider that the transmission characteristics and the adhesion to the resin are the same.
- Patent Document 2 does not pay attention to the reflow heat resistance, and in addition, does not examine the effect of reducing the transmission characteristics due to the specific surface roughening shape and the skin effect.
- Patent Document 3 a roughened copper foil having a roughened surface that is formed by depositing fine copper particles on the surface of the copper foil, the roughened surface is a fine protrusion having a top angle of 85 ° or less.
- a roughened copper foil characterized by containing copper particles is disclosed.
- Patent Document 3 discloses that this roughened copper foil is a resin excellent in high heat resistance and high frequency characteristics such as liquid crystal polymer, polyphenylene oxide resin (PPO), polyphenylene ether resin (PPE), and cycloolefin polymer (COP). It is disclosed that it has sufficient adhesiveness and can reduce transmission characteristics.
- Patent Document 3 defines only the top angle of the fine copper particles constituting the roughened surface, and does not limit the shape other than the top.
- Patent Document 3 indirectly quantifies the shape of roughening using the L * value, a * value, and b * value of the L * a * b * color system, but L * , A *, b * are chromaticity parameters. Therefore, if a colored plating film is formed on the copper foil surface by Ni, Co, Cr, etc., or if the surface of the copper foil is oxidized and discolored, these values are greatly affected. It is technically very difficult to accurately grasp and manage the surface shape of the surface.
- Patent Document 4 is a surface-treated copper foil in which a surface treatment layer is formed on at least one surface, the surface treatment layer includes a roughening treatment layer, and Co, Ni, and Fe in the surface treatment layer
- the total adhesion amount is 300 ⁇ g / dm 2 or less
- the surface treatment layer has a Zn metal layer or an alloy treatment layer containing Zn
- the three-dimensional surface area relative to the two-dimensional surface area measured by a laser microscope on the surface treatment layer surface Is a surface-treated copper foil in which the surface roughness Rzjis of at least one surface is 2.2 ⁇ m or less.
- Patent Document 4 discloses that this surface-treated copper foil controls the total adhesion amount of metals (Co, Ni, Fe) exhibiting ferromagnetism at room temperature in the surface treatment layer to a predetermined amount or less, and exhibits ferromagnetism at room temperature.
- metals Co, Ni, Fe
- the high-frequency transmission loss is reduced, and the ratio of the three-dimensional surface area to the two-dimensional surface area that accurately represents the surface roughness Rz and the contact area with the resin (dielectric) is controlled within an appropriate range.
- transmission characteristics can be improved.
- Patent Document 4 As described above, it is very difficult to specify the surface shape and characteristics of the surface-treated copper foil by the surface area ratio and Rz, and the surface that significantly affects the transmission characteristics is clearly defined. Can not. In general, in the process of producing a printed wiring board, an etching process and a reflow soldering process for forming a circuit are essential, and chemical resistance and reflow heat resistance are required. On the other hand, when a configuration that improves the transmission characteristics by reducing the ferromagnetic metal in the surface treatment layer as in the surface-treated copper foil described in Patent Document 4, the surface treatment layer containing Zn is used for etching.
- a copper foil for a high-frequency printed wiring board with a small transmission loss As described above, as a copper foil for a high-frequency printed wiring board with a small transmission loss, a copper foil having a surface shape with a small surface roughness is generally required, but when the copper foil becomes smooth, it adheres to the resin. This causes problems such as deterioration in heat resistance and reflow heat resistance.
- the copper foil surface is treated with a silane coupling agent to increase the chemical adhesion with the resin base material.
- the resin needs to have a substituent having a certain degree of polarity.
- a resin having a low dielectric constant or dielectric loss tangent does not have a substituent having a large polarity or has a small content even if it has a substituent having a large polarity. Therefore, the chemical adhesion with a silane coupling agent is low. Decreases, and it becomes difficult to ensure sufficient adhesion between the copper foil and the resin base material.
- the surface roughness of the copper foil is increased in order to improve adhesion and reflow heat resistance, there arises a problem that transmission characteristics are deteriorated.
- a copper foil capable of satisfying such trade-off characteristics that is, a copper foil having sufficient adhesion strength and reflow heat resistance and excellent in transmission characteristics is required. .
- any of the surface-treated copper foils described in Patent Documents 1 to 4 has transmission characteristics and reflow characteristics when used as a copper foil for a high-frequency printed wiring board used in a high-frequency band exceeding several GHz, for example. It was difficult to provide a printed wiring board satisfying both of the heat resistance at a high level, and further improvement of the surface properties of the surface-treated copper foil was required.
- An object of the present invention is to provide a printed wiring that has low transmission loss of high-frequency electrical signals and has excellent reflow heat resistance even when used as a copper foil for a high-frequency printed wiring board used in a high-frequency band exceeding several GHz, for example.
- An object of the present invention is to provide a surface-treated copper foil and a copper clad laminate capable of producing a plate.
- the present inventors have succeeded in providing a printed wiring board that satisfies both transmission characteristics and reflow heat resistance at a high level.
- the surface properties of the roughened layer are strictly controlled using an optical interference microscope, which is different from conventional optimization of the surface properties.
- the inventors have obtained the knowledge that a surface-treated copper foil capable of exhibiting excellent characteristics can be stably provided by defining a new composite parameter of three-dimensional surface properties.
- the gist configuration of the present invention is as follows. (1) A surface-treated copper foil in which a roughening treatment layer, a rust prevention treatment layer and a silane coupling layer are laminated in this order on the basis of the copper foil on at least one surface of the copper foil, and the silane A surface-treated copper foil characterized in that the value of the developed area ratio Sdr of the interface, which is a composite parameter of the three-dimensional surface properties measured from the surface of the coupling layer, is in the range of 8 to 140%.
- the value of the root mean square surface gradient Sdq which is a composite parameter of a three-dimensional surface property measured from the surface of the silane coupling layer, is in the range of 25 to 70 °, as described in (1) above Surface treated copper foil.
- the aspect ratio Str of the surface texture which is a spatial parameter of the three-dimensional surface texture measured from the surface of the silane coupling layer, is 0.25 to 1, and is described in (1) or (2) above Surface treated copper foil.
- the total content of metals other than copper and oxides of the metals in the roughening treatment layer and the rust prevention treatment layer is 0.15 to 0.50 mg / dm 2 in terms of metal elements.
- the above (1) to (5), wherein the contents of Ni and Zn in the roughening treatment layer and the rust prevention treatment layer are 0.05 to 0.30 mg / dm 2 , respectively.
- the surface-treated copper foil as described in any one of these.
- the copper foil is an electrolytic copper foil, and has the roughening treatment layer only on the M-plane of the electrolytic copper foil, as described in any one of (1) to (6) above Surface treated copper foil.
- a surface-treated copper foil in which a roughening treatment layer, a rust prevention treatment layer, and a silane coupling layer are laminated in this order on the basis of the copper foil on at least one surface of the copper foil.
- the surface area and surface roughness are conventionally used by the range of 8 to 140% of the developed area ratio Sdr of the interface, which is a composite parameter of the three-dimensional surface properties measured from the surface of the silane coupling layer. It becomes possible to stably manufacture a surface-treated copper foil having a roughened surface, which has been difficult to control with the indices (parameters) that have been used, and for example, for high-frequency printed wiring boards used in a high-frequency band exceeding several GHz.
- a surface-treated copper foil and a copper clad laminate that enable the manufacture of printed wiring boards that have low reflow heat resistance and low transmission loss of high-frequency electrical signals even when used as copper foil It can be provided. Further, by using a three-dimensional optical interference microscope, it is possible to appropriately control the degree of unevenness (surface gradient) and the development area of the surface of the surface-treated copper foil.
- FIG. 1 shows the apparent conductivity measured on the surface of various surface-treated copper foils divided into a plurality of regions with respect to the height h and width w of the roughened particles normalized by the skin depth d.
- FIGS. 2A and 2B are conceptual diagrams showing a high-frequency conduction current density on a copper foil cross section when a high-frequency electric field is applied in the horizontal direction on the paper surface in electromagnetic field analysis,
- FIG. 2 (b) shows a case having roughened particles having a relatively small width w on the surface of the copper foil.
- 3A to 3C show the surface states of various copper foils (original foils).
- FIG. 3A is a surface SEM photograph (magnification: 1000) on the M-plane of the original foil A.
- FIG. 3 3) is a surface SEM photograph (magnification: 1000 times) on the M surface of the original foil B
- FIG. 3 (c) is a surface SEM photograph (magnification: 1000 times) on the S surface of the original foil B.
- 4 (a) and 4 (b) are conceptual diagrams of two surface states having the same surface area but different surface roughness when viewed geometrically.
- FIG. FIG. 4B shows a surface state where the height and width are relatively large
- FIG. 4B shows a surface state where the height and width of the mountain are relatively small.
- a roughening treatment layer, a rust prevention treatment layer and a silane coupling layer are laminated in this order on at least one surface of the copper foil based on the copper foil. That is, a roughening treatment layer is formed on at least one surface of the copper foil, a rust prevention treatment layer is formed on the roughening treatment layer, and a silane coupling layer is formed on the rust prevention treatment layer.
- the value of the developed area ratio Sdr of the interface which is a composite parameter of the three-dimensional surface property measured from the surface of the silane coupling layer Is controlled in the range of 8 to 140%.
- a three-dimensional optical interference microscope can be used.
- Light interference is a phenomenon that occurs when there is a difference in the distance (light path) of light from a surface of an object to a certain point.
- An optical interferometer uses this phenomenon to measure irregularities on the surface of an object.
- the resolution in the Z direction can be measured with a very high sensitivity of about 0.1 nm, and the resolution in the Z direction changes even if the measurement magnification is changed.
- a confocal laser microscope that has been widely used conventionally performs biaxial scanning in the X and Y directions, so the resolution in the Z direction is as large as 10 nm to 300 nm. It is not suitable for identifying the very fine surface properties of the surface-treated copper foil. Further, this confocal method is not suitable for quantitatively expressing the rough shape because the resolution in the Z direction varies greatly depending on the magnification to be measured.
- the present inventors examined using a three-dimensional optical interference microscope in order to obtain a copper foil with low transmission loss and good reflow heat resistance.
- the value of the developed area ratio Sdr of the interface which is a composite parameter of the three-dimensional surface properties measured from the surface of the silane coupling layer, there is little transmission loss and good reflow heat resistance.
- a surface-treated copper foil was obtained.
- Sdr represents the development area ratio of the interface (surface) of the roughening treatment layer.
- the value of Sdr is measured from the surface of the silane coupling layer which is the outermost layer of the surface-treated copper foil.
- the surface shape of the roughened layer constituting the surface-treated copper foil is It has been confirmed that the surface shape of the silane coupling layer after the rust prevention treatment layer and the silane coupling layer are further formed on the roughening treatment layer is almost the same. Therefore, in the present invention, the value of Sdr measured from the surface of the silane coupling layer is defined as being the same as the value of Sdr measured from the surface of the roughening treatment layer.
- Sdr indicates the developed area ratio of the interface and is expressed by the following equation.
- the characteristic of Sdr is that it is possible to distinguish the shape of a surface having a similar arithmetic average height Sa. Since the arithmetic average height Sa represents the average of the absolute values of the height difference of each point with respect to the average surface, it is suitable for determining information on the average height of the unevenness. However, the complexity of the irregularities in the surface shape cannot be determined.
- the value of Sdr is affected by both the amplitude and the interval of the unevenness of the surface shape, and shows a higher value as the amplitude is larger and the interval is narrower.
- Sa is often low, and when Sdr is large, Sa tends to be large.
- Sa is a parameter representing height, the amplitude and interval of unevenness Do not depend. That is, Sdr can identify the complexity of irregularities in the surface shape that cannot be represented by Sa. When the value of Sdr is small, the surface shape is almost flat, whereas when the value of Sdr is large, the surface shape has many irregularities.
- the inventors made a plurality of surface-treated copper foils having different values of Sdr and made extensive studies on the relationship between transmission characteristics and reflow heat resistance.
- the value of Sdr was limited to a range of 8 to 140%.
- the complexity of the unevenness of the roughened particles present on the surface of the roughened layer was appropriately controlled, and as a result, both transmission characteristics and reflow heat resistance were excellent.
- the value of Sdr was less than 8%, the reflow heat resistance tended to decrease. This is presumed to be due to insufficient adhesion with the resin due to wide or uneven growth of the roughened particles.
- the value of Sdr was larger than 140%, the transmission characteristics tended to deteriorate. It is presumed that the roughness of the roughened particles is increased due to the increase in Sdr and the transmission loss is increased.
- the value of Sdr is preferably in the range of 20 to 120%, and more preferably in the range of 40 to 100%.
- the development area ratio is low, cracks are easily connected and spread between adjacent roughened particles, and it is thought that continuous cracking occurs at the interface due to the propagation of cracks, resulting in blistering. It is done.
- the contact area between the roughened particles and the resin base material increases, and the frictional force acting between the roughening treatment layer and the resin base material increases. Therefore, the frictional force acting between the roughening treatment layer and the resin base material is larger than the expansion force that is generated when the low molecular weight component in the resin base material volatilizes as a gas. It is thought that there is an effect of suppressing propagation. As a result, it is presumed that the propagation of cracks is difficult to proceed, continuous peeling at the interface between the roughening treatment layer and the resin base material is suppressed, and swelling is less likely to occur.
- the value of the root mean square surface gradient Sdq which is a composite parameter of the three-dimensional surface properties measured from the surface of the silane coupling layer, is preferably in the range of 25 to 70 °.
- the value of Sdq is the same as the value of Sdr, and the surface shape of the roughened layer constituting the surface-treated copper foil is further provided with a rust preventive layer and a silane coupling layer on the roughened layer. It has been confirmed that the surface shape of the silane coupling layer after the lamination is almost the same. Therefore, also in Sdq, the value of Sdq measured from the surface of the silane coupling layer is defined as being the same as the value of Sdq measured from the surface of the roughening treatment layer.
- Sdq means the surface gradient (gradient) of the roughened layer, specifically, the root mean square (rms) surface gradient composed of the surfaces evaluated in all directions, and is represented by the following equation: Value.
- x and y are plane coordinates
- Z is a coordinate in the height direction.
- Z (x, y) indicates the coordinates of a certain point, and the slope at that coordinate is obtained by differentiating this.
- the above equation is obtained by adding the squares of the x-direction gradient and the y-direction gradient of all points (A) to obtain the square root.
- the feature of Sdq is that it is possible to distinguish the shape of a surface having a similar arithmetic average height Sa. Since the arithmetic average height Sa represents the average of the absolute values of the height difference of each point with respect to the average surface, it is suitable for determining information on the average height of the unevenness. However, the degree of sharpness (inclination) of the surface shape cannot be determined.
- the value of Sdq is affected by both the amplitude and spacing of the surface shape.
- the value of Sdq is small, it has a gentle surface shape, whereas when Sdq is large, it has a sharp surface shape.
- the inventors made a plurality of surface-treated copper foils having different values of Sdq, and conducted intensive studies on the relationship between transmission characteristics and reflow heat resistance. As a result, the value of Sdq was limited to a range of 25 to 70 °. As a result, the sharpness of the roughened particles existing on the surface of the roughened layer is more appropriately controlled, and as a result, a surface-treated copper foil having good transmission characteristics and reflow heat resistance can be obtained.
- the value of Sdq ranges from 25 to 70 °. It is preferably controlled within the range of 30 to 65 °, more preferably within the range of 40 to 60 °.
- the resin has a base (concave) position of the surface unevenness of the surface-treated copper foil when the surface-treated copper foil and the resin are laminated. It becomes difficult to fill up to. As a result, it is considered that blistering tends to occur during heating during reflow soldering and the reflow heat resistance tends to deteriorate.
- FIG. 1 is disclosed in International Publication No. 2016/035876, and when the height of the roughened particles is h and the width of the roughened particles at the height of h / 2 is w, The normalized particle height h and width w are normalized by the skin depth d, and the calculation result of the equivalent conductivity in each roughened surface shape is shown.
- FIG. 1 shows the result of calculating the equivalent conductivity distribution with h / d normalized by the skin depth d as the vertical axis and w / d as the horizontal axis.
- FIG. 2A shows the case of roughened particles having a relatively large value of the normalized width w / d
- FIG. 2B shows the width w / d of the normalized roughened particles. The case where the value is relatively small is shown.
- point A is a point where the current density is low
- point B is a point where the current density is high
- point E is a point with a low current density
- point F is a point with a high current density.
- the skin effect becomes remarkable as the conduction current increases in frequency, and the current is interpreted to flow more concentrated on the copper foil surface.
- Such a phenomenon is based on the premise that the copper foil has a surface smooth structure, and the current density state when the surface has a roughened shape as in the present invention is that the surface is smooth. It is very special compared to the case. Specifically, in both FIGS. 2 (a) and 2 (b), it is confirmed that the current hardly flows on the front side of the roughened particles, which can be said to be on the surface side (A point, E point). At this time, it is considered that what is occurring at the tip portion of the roughened particles is cancellation of the conduction current.
- the width w of the roughened particles is narrower than that in FIG. 2A, and the current density in the roughened particles is relatively small.
- the surface position (point D) of the roughened particle that has a current density equivalent to the current density of the inner central point (point C) connecting both side bases of the roughened particle is the roughened particle. It is on the tip side of the height position of 1/2 of the height h.
- the current density on the surface at a height position that is 1 ⁇ 2 of the height h of the roughened particles is equivalent to the current density at the internal center point (point C) of the roughened particles. Therefore, in FIG. 2 (a), the current tends to flow up to a height close to the tip of the roughened particle, so that there is a large amount of current flowing through the tip side, and the current flowing through the base side of the roughened particle tends to decrease. It is thought that there is.
- the surface position (point I) of the roughened particles which has a current density equivalent to the current density of the internal center point (point G) connecting both side bases of the roughened particles, is rough. It exists in the base part side rather than the height position of 1/2 of the height h of a chemical particle. That is, the current density on the surface of the height position of 1/2 of the height h of the roughened particles is lower than the current density at the internal center point (point G) of the roughened particles. From this, in FIG. 2B, it is considered that the current flowing through the tip side of the roughened particles is small and the current flowing through the base side of the roughened particles tends to increase.
- a surface roughening structure that reduces the amount of current flowing to the tip side of the roughened particle (particularly the tip side from the projection height h / 2) relative to the current flowing near the base of the roughened particle is provided. It is considered that current loss can be reduced by selecting.
- the present invention it is possible to reduce transmission loss by setting the Sdr value in the range of 8 to 140% based on such an action and applying a roughening having an appropriate roughening shape to the copper foil surface. It was.
- the value of the developed area ratio Sdr of the interface which is a composite parameter of the three-dimensional surface property measured from the surface of the silane coupling layer, is in the range of 8 to 140%, preferably further squared.
- the value of the mean square root surface gradient Sdq was in the range of 25 to 70 °.
- the surface texture aspect ratio Str which is a spatial parameter of the three-dimensional surface texture measured from the surface of the silane coupling layer, is preferably 0.25 to 1, more preferably 0.30 or more. Is more preferably 0.50 or more. Str is a parameter indicating the isotropy of the surface shape in the vertical and horizontal directions. The value of Str is completely isotropic when 1 is 1 at the maximum. In general, when the value of Str is 0.5 or more, strong isotropy is exhibited, and when it is less than 0.30, anisotropy is exhibited. In general, the circuit of the printed wiring board is optionally formed in a vertical direction, a horizontal direction, and an oblique direction.
- Str is preferably close to 1, and conversely, the smaller the value of Str, the greater the variation in transmission loss depending on the measurement position and measurement direction within the copper foil surface.
- the ten-point average roughness Rzjis measured from the surface of the silane coupling layer is preferably in the range of 0.9 to 1.5 ⁇ m. If the ten-point average roughness Rzjis is less than 0.9 ⁇ m, adhesion and reflow heat resistance may be insufficient, and if Rzjiis exceeds 1.5 ⁇ m, transmission loss may increase. It is.
- the values of Str and Rzjis are the same as the value of Sdr, and the surface shape of the roughened layer constituting the surface-treated copper foil is further provided with a rust preventive layer and a silane coupling layer on the roughened layer. It has been confirmed that the surface shape of the silane coupling layer after forming the layers is almost the same. Therefore, also in Str and Rzjis, the values of Str and Rzjis measured from the surface of the silane coupling layer are defined as being the same as the values of Str and Rzjis measured from the surface of the roughened layer. .
- the total content of the metal other than copper and the oxide of the metal in the roughening treatment layer and the rust prevention treatment layer is 0.15 to 0.50 mg / dm 2 in terms of metal elements.
- the surface shape of the roughened layer can be controlled by adding metal ions other than copper, for example, metal ions such as Mo, Fe, Ni, Co, and W, to the roughened plating solution for forming the roughened layer. Widely known. On the other hand, these metals have a higher electrical resistance than copper and easily form oxides. Therefore, if the metal is excessively contained in the roughening treatment layer or the rust prevention treatment layer, the transmission characteristics are adversely affected. May cause effects.
- the total content of the metal other than copper and the oxide of the metal in the roughened layer and the rust preventive layer is less than 0.15 mg / dm 2 in terms of metal elements, the roughened layer There is a risk that the control of the surface shape of the film becomes difficult to work, and if it exceeds 0.50 mg / dm 2 , the electrical resistance tends to increase and the transmission characteristics tend to deteriorate. Therefore, the total content of the metal other than copper and the oxide of the metal in the roughening treatment layer and the rust prevention treatment layer is preferably 0.15 to 0.50 mg / dm 2 in terms of a metal element. .
- the contents of Ni and Zn in the roughening treatment layer and the rust prevention treatment layer are 0.05 to 0.30 mg / dm 2 , respectively.
- the contents of Ni and Zn in the roughening treatment layer and the rust prevention treatment layer are each less than 0.05 mg / dm 2 , the reflow heat resistance may be insufficient, and each 0.30 mg
- an increase in the Ni content leads to an increase in transmission loss
- an increase in the Zn content leads to over-etching, and as a result, the adhesion at the interface between the copper foil and the resin substrate decreases. It is because reflow heat resistance may fall.
- the copper foil constituting the surface-treated copper foil of the present invention includes a rolled copper foil and an electrolytic copper foil.
- an electrolytic copper foil copper is deposited on the surface of a metal drum for foil production by electrolytic plating, the drum surface side is referred to as the S surface, and the opposite surface side is referred to as the M surface.
- the roughening treatment layer is provided only on the M surface of the electrolytic copper foil in terms of suppressing an increase in transmission loss.
- this invention has the surface-treated copper foil mentioned above and resin laminated
- the dielectric constant in the frequency of 10 GHz of this resin is 3.5 or less.
- the resin constituting the copper clad laminate is limited to a resin having a dielectric constant of 3.5 or less at a frequency of 10 GHz and a dielectric loss tangent of 0.006 or less is because the effect of reducing transmission loss is great. It is.
- any of a copper foil having a smooth surface and a copper foil having minute irregularities on the surface may be used.
- the surface shape of the M surface of the original foil A (the surface that was in contact with the electrolytic solution at the time of foil production) is shown in FIG. 3A, and the M surface and S surface of the original foil B (which was in contact with the electrolytic drum at the time of foil production). 3 (b) and FIG. 3 (c), respectively.
- the roughening layer formed on the surface of the copper foil is a two-step roughening process: a roughening plating process for forming fine copper particles and a capsule plating process for preventing the fine particles from falling off. To do.
- a copper-sulfuric acid aqueous solution with metal ions added is used as the rough plating solution.
- Preferable plating conditions are as follows as an example.
- an aqueous copper-sulfuric acid solution is used as the capsule plating solution.
- Preferable plating conditions are as follows as an example.
- the chloride ion concentration in the above roughening plating solution and capsule plating solution is preferably 0.3 mass ppm or less.
- a raw material for the electrolytic copper foil generally crushed wire scraps are used. This wire scrap contains oil, and if used as it is, defective plating such as pinholes occurs. Therefore, a technique using activated carbon to remove oil from the plating solution (electrolyte) is widely known, but activated carbon adsorbs chloride ions because it is treated with hydrochloric acid in the regeneration process. Therefore, chloride ions are inevitably mixed in the electrolytic solution and contained in the order of several ppm.
- the chloride ion concentration is more than 0.3 ppm by mass, the action of metal ions such as Mo, Fe, Ni, Co, W, etc. cannot be fully exerted, and a uniform and fine surface shape cannot be obtained.
- a substance that traps chloride ions and is finally removed from the plating solution is added to the plating solution, for example, in the plating solution. It is preferable to add about 0.01 to 0.2 mass ppm of Ag ions to By adding Ag ions to the plating solution, the Ag ions react with the chloride ions and precipitate as silver chloride, so that the chloride ions can be removed from the plating solution. Precipitated silver chloride is removed from the plating solution by a filter, so it does not affect the roughening shape. Incidentally, ion chromatography was used for analysis of chloride ions.
- the formation of the roughening treatment layer constituting the surface-treated copper foil of the present invention is preferably carried out by balancing both the roughening plating conditions and the capsule plating conditions, for example, the current density and the processing time. Is set appropriately between the roughening plating conditions and the capsule plating conditions. In addition to the current density and processing time, it is preferable to appropriately select the type and amount of metal ions added to the roughening plating solution in order to exhibit the effect of making the roughened particles fine and uniform. . Specifically, when the current density is increased, the concentration of metal ions to be added may be increased. That is, by increasing the current density, the coarse particles are likely to grow non-uniformly, but by adding a large amount of metal ions, fine and uniform rough particles can be obtained.
- the anti-rust treatment layer examples include a case where it is composed of one or more of various metal or alloy-containing layers.
- three layers of a Ni plating layer, a Zn plating layer, and a chromate treatment layer are sequentially formed. The case where it forms by laminating
- an alloy plating layer such as Ni—Zn, Zn—Cr, Ni—Cr or the like may be used. Good.
- Typical examples of the plating bath composition and plating conditions for forming the Ni plating layer, Zn plating layer, Ni—Zn alloy plating layer, and chromate treatment layer are shown below.
- silane coupling layer is laminated and formed on the above-mentioned antirust treatment layer in order to improve adhesion with the resin.
- the silane coupling agent to be used include silane coupling agents having an epoxy group, a vinyl group, an amino group, an acrylic group, a methacryl group, and the like. Since these silane coupling agents have different effects due to the action of the functional group having reactivity in the resin, it is necessary to appropriately select the silane coupling agent to be used depending on the compatibility with the resin.
- silane coupling agent examples include aminoalkyltrimethoxysilane (eg, 3-aminopropyltrimethoxysilane), aminoalkyltriethoxysilane (eg, 3-aminopropyltriethoxysilane), vinyltrimethoxysilane, vinyl Triethoxysilane, (3- (meth) acryloyloxypropyl) trimethoxysilane, (3- (meth) acryloyloxypropyl) triethoxysilane, (meth) acryloylpropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, styrylpropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Run, 3-but-but-
- the solution concentration of the silane coupling agent when the silane coupling agent is applied to the surface of the metal treatment layer is such that a sufficient amount of the silane coupling agent is applied to the (outermost) surface of the antirust treatment layer, and In order to achieve higher adhesion, the content is preferably 0.01 to 15% by volume, more preferably 0.1 to 10% by volume. It is preferable to use water as the solvent of the solution.
- Example 1 to 42 and Comparative Examples 1 to 4 As the copper foil (original foil), original foil A and original foil B each having a thickness of 18 ⁇ m were obtained under the above-described manufacturing (electrolysis) conditions of the two original foils.
- the surface roughness Rzjis of the original foil A was 1.5 ⁇ m on the S surface (the surface that was in contact with the electrolytic drum at the time of foil production), and 0.8 ⁇ m on the M surface (the surface that was in contact with the electrolytic solution at the time of foil production).
- the surface roughness Rzjis of the original foil B was 1.5 ⁇ m on the S surface and 3.3 ⁇ m on the M surface.
- the rust prevention process layer comprised by laminating
- Table 2 shows the adhesion amount of each layer constituting the antirust treatment layer.
- a silane coupling layer having a silicon (Si) adhesion amount shown in Table 2 is formed on the rust-proofing layer of the copper foil.
- a coupling treatment was performed to produce a surface-treated copper foil.
- Comparative Examples 5 and 6 In Comparative Examples 5 and 6, except that the formation of the roughening treatment layer was performed in the roughening treatment II shown in Table 1, the surface treatment copper foil was produced under the same conditions as in Examples 1 and 12, respectively. .
- the concentration of chloride ions in the roughening plating solution and capsule plating solution used in the roughening treatment II shown in Table 1 is high because only activated carbon is added and the chloride ions are precipitated and removed as silver chloride.
- the concentration of chloride ions in the roughening plating solution and the capsule plating solution used in the roughening treatment I shown in Table 1 is low because of the addition of Ag ions along with activated carbon. This is because chloride ions were precipitated and removed as silver chloride.
- Comparative Example 7 In Comparative Example 7, Cu 20 g / L (copper sulfate pentahydrate 50 g / L), 3-mercapto-1-propane-on the M surface of the original foil A in the same manner as in Example 9 of Patent Document 1. A roughened layer is formed under the conditions of sodium sulfonate 0.25 g / L, cobalt ion 5.2 g / L, nickel ion 2.2 g / L, bath temperature 40 ° C., current density 10 A / dm 2 , and electrolysis time 10 seconds.
- each surface-treated copper foil obtained above is a commercially available high-frequency insulating resin with a thickness of 250 ⁇ m, with the roughened surface facing the resin substrate.
- a base material Movable Markup Language 6 manufactured by Panasonic Corporation
- a press temperature 200 ° C.
- a press pressure 3 MPa
- a press time 120 minutes is laminated under a general press condition to produce a copper-clad laminate
- a circuit board was processed as necessary to prepare a measurement board.
- Measurement of metal adhesion amount Measurement of metal adhesion amount in the roughened layer and the rust preventive layer was performed by masking the surface of the sample not subjected to the roughening treatment with a paint, cutting into 10 cm square, and 80 ° C. After the surface of the copper foil roughened with a mixed acid (nitric acid 1: hydrochloric acid 1 (volume ratio)) heated to about 3 to 5 ⁇ m was dissolved, the mass of the metal in the resulting solution was changed to atoms. It was determined by quantitative analysis by atomic absorption spectrometry using an absorptiometer (Z-2300 manufactured by Hitachi High-Tech Science Co., Ltd.).
- the evaluation of reflow heat resistance was obtained from the above copper-clad laminate in accordance with IPC TM-650 2.44.24.1 “Delamination time measurement using TMA”. Using a substrate for reflow heat resistance measurement, the time until swelling at 288 ° C. (blowing time) was evaluated.
- the reflow heat resistance is “ ⁇ ”when the swelling time is 60 minutes or more,“ ⁇ ”when the swelling time is 45 minutes or more and less than 60 minutes,“ ⁇ ”when the swelling time is 30 minutes or more and less than 45 minutes, and 30 minutes.
- “ ⁇ ”, “ ⁇ ”, and “ ⁇ ” were regarded as acceptable levels.
- the transmission characteristics were obtained by forming a pattern by UV exposure using a pattern film with a resist width of 300 ⁇ m on the copper-clad laminate and further etching to form a microstrip line with a strip line length of 200 mm.
- a transmission characteristic measurement substrate (size: length 210 mm, width 30 mm) was obtained.
- the transmission characteristic measurement substrate 21 was measured for the transmission characteristic S21 at a frequency of 40 GHz with a characteristic impedance of 50 ⁇ using a network analyzer (Keysight Technology N5247A).
- the transmission characteristics are “ ⁇ ” when the pass characteristic S21 is ⁇ 28 dB or more, “ ⁇ ” when the pass characteristic S21 is ⁇ 30 dB or more and less than ⁇ 28 dB, “ ⁇ ” when the pass characteristic S21 is ⁇ 33 dB or more and less than ⁇ 30 dB, ⁇
- the case of less than 33 dB was evaluated as “x”, and in the present invention, “ ⁇ ”, “ ⁇ ”, and “ ⁇ ” were regarded as acceptable levels.
- a surface-treated copper foil having a surface roughened shape which has been difficult to control with conventionally used indices (parameters) such as surface area and surface roughness.
- indices such as surface area and surface roughness.
- a treated copper foil and a copper clad laminate can be provided. Further, by using a three-dimensional optical interference microscope, it is possible to appropriately control the degree of unevenness (surface gradient) and the development area of the surface of the surface-treated copper foil.
- the surface-treated copper foil of the present invention can realize transmission characteristics, resin adhesion, and reflow heat resistance at a high level, and is used for routers and servers that are required to be used in a high frequency band exceeding several tens of GHz.
- a high multilayer printed wiring board can be realized and is extremely useful industrially.
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Abstract
Description
(1)銅箔の少なくとも片方の面に、粗化処理層、防錆処理層及びシランカップリング層が前記銅箔を基準にしてこの順で積層されている表面処理銅箔であり、前記シランカップリング層の表面から測定された三次元表面性状の複合パラメータである、界面の展開面積率Sdrの値が8~140%の範囲であることを特徴する表面処理銅箔。
(2)前記シランカップリング層の表面から測定された三次元表面性状の複合パラメータである、二乗平均平方根表面勾配Sdqの値が25~70°の範囲であること特徴する上記(1)に記載の表面処理銅箔。
(3)前記シランカップリング層の表面から測定された三次元表面性状の空間パラメータである、表面性状のアスペクト比Strの値が0.25~1である上記(1)または(2)に記載の表面処理銅箔。
(4)前記シランカップリング層の表面から測定された十点平均粗さRzjisが0.9~1.5μmの範囲であることを特徴とする上記(1)~(3)のいずれか1つに記載の表面処理銅箔。
(5)前記粗化処理層及び前記防錆処理層中の銅以外の金属及び該金属の酸化物の合計含有量が、金属元素に換算して0.15~0.50mg/dm2であること特徴する上記(1)~(4)のいずれか1つに記載の表面処理銅箔。
(6)前記粗化処理層及び前記防錆処理層中のNi及びZnの含有量が、それぞれ0.05~0.30mg/dm2であることを特徴とする上記(1)~(5)のいずれか1つに記載の表面処理銅箔。
(7)前記銅箔が電解銅箔であり、該電解銅箔のM面のみに前記粗化処理層を有することを特徴とする上記(1)~(6)のいずれか1つに記載の表面処理銅箔。
(8)上記(1)~(7)のいずれか1つに記載の表面処理銅箔と、該表面処理銅箔の前記シランカップリング層上に積層された樹脂とを有し、該樹脂の周波数10GHzにおける誘電率が3.5以下でありかつ誘電正接が0.006以下であることを特徴とする銅張積層板。
表面処理銅箔と樹脂基材を熱プレスなどの方法によって張り付けた銅張積層板では、表面処理銅箔の粗化処理層と樹脂基材との界面に、熱プレス時に出来た欠陥などが元で微細な空隙が存在する(以後、この様な空隙を「亀裂」と称する)。銅張積層板がリフローはんだ付けの際に加熱されると、樹脂基材中の低分子量の成分がガスとして揮発し、亀裂に溜って膨張力を生じさせる。この時、展開面積率が低い場合には、隣接する粗化粒子の間で亀裂が連結されて広がりやすく、亀裂が伝播していくことによって界面における連続的な剥離が生じて膨れが発生すると考えられる。一方で、展開面積率がある程度高くなると、粗化粒子と樹脂基材との接触面積が大きくなり、粗化処理層と樹脂基材との間に作用する摩擦力が大きくなる。そのため、樹脂基材中の低分子量の成分がガスとして揮発した際に亀裂に溜まって生じる膨張力よりも粗化処理層と樹脂基材との間に働く摩擦力が大きくなることで、亀裂の伝播を抑制する効果を奏すると考えられる。この結果、亀裂の伝播が進行しにくくなって、粗化処理層と樹脂基材との界面における連続的な剥離が抑制され、膨れが発生しにくくなると推察される。
図2(a)及び(b)は、電磁界解析上において紙面水平方向に高周波電界を印加し、その際に流れた高周波伝導電流密度を銅箔断面上に示した概念図であり、図中の点線は、等電流密度線である。図2(a)は、規格化された幅w/dの値が相対的に大きい粗化粒子の場合を示し、図2(b)は、規格化された粗化粒子の幅w/dの値が相対的に小さい場合を示している。なお、図2(a)において、A点は、電流密度が小さい点であり、B点は電流密度が高い点である。また、図2(b)において、E点は、電流密度が小さい点であり、F点は電流密度が高い点である。
本発明の表面処理銅箔を構成する銅箔(元箔)としては、表面の平滑な銅箔、および表面に微小凹凸のある銅箔のいずれを用いてもよい。元箔AのM面(製箔時に電解液に接していた面)の表面形状を図3(a)に、また、元箔BのM面およびS面(製箔時に電解ドラムに接していた面)の表面性状をそれぞれ図3(b)および図3(c)に示す。
Cu :60~120g/L
H2SO4 :70~150g/L
浴温 :50~70℃
3-メルカプト-1-プロパンスルホン酸ナトリウム :1~10ppm
ヒドロキシエチルセルロース(HEC:分子量400)濃度 :5~30ppm
膠濃度 :20~50ppm
塩素濃度 :10~40ppm
電流密度 :30~60A/dm2
Cu :60~120g/L
H2SO4 :70~150g/L
浴温 :50~70℃
HEC(分子量400)濃度 :1~20ppm
塩素濃度 :10~40ppm
電流密度 :30~60A/dm2
銅箔表面に形成される粗化処理層は、微細な銅粒子を形成するための粗化めっき工程と、この微細粒子の脱落を防止するためのカプセルめっき工程の2段階の粗化処理で実施する。粗化めっき工程では、銅-硫酸水溶液に金属イオンを添加したものを粗化めっき液として用いる。好ましいめっき条件は、一例として以下の通りである。
Cu :10~30g/L
H2SO4 :100~200g/L
Mo濃度 :0.2~0.5g/L
Fe濃度 :1.0~10g/L
浴温 :20~30℃
電流密度 :20~40A/dm2
処理時間 :3.0~10.0秒
Cu :40~60g/L
H2SO4 :80~120g/L
浴温 :45~60℃
電流密度 :0.5~10A/dm2
処理時間 :3.0~10秒
Ni :10~100g/L
H3BO3 :10~40g/L
PO2 :0~10g/L
浴温 :10~40℃
電流密度 :0.2~10A/dm2
処理時間 :1秒~20秒
pH :2.0~4.0
Zn :1~30g/L
NaOH :10~100g/L
浴温 :5~60℃
電流密度 :0.1~10A/dm2
処理時間 :1秒~20秒
Ni :1~4.0g/L
Zn :0.1~2.0g/L
ピロリン酸カリウム:70~280g/L
浴温 :15~50℃
電流密度 :0.2~10A/dm2
処理時間 :1秒~20秒
Cr :0.5~20g/L
NaOH :10~100g/L
浴温 :20~70℃
電流密度 :0.1~10A/dm2
処理時間 :1秒~20秒
pH :13.0以上
(実施例1~42並びに比較例1~4)
銅箔(元箔)は、上述した2つの元箔の製造(電解)条件により、それぞれ厚さ18μmの元箔A及び元箔Bを得た。元箔Aの表面粗さRzjisは、S面(製箔時に電解ドラムに接していた面)が1.5μm、M面(製箔時に電解液に接していた面)が0.8μmであった。元箔Bの表面粗さRzjisは、S面が1.5μm、M面が3.3μmであった。
<ニッケルめっき浴組成及びめっき条件>
Ni :40g/L
H3BO3 :25g/L
浴温 :20℃
電流密度 :0.2~10A/dm2
処理時間 :1秒~20秒
pH :3.5
Zn :3g/L
NaOH :40g/L
浴温 :20℃
電流密度 :0.1~10A/dm2
処理時間 :1秒~20秒
Cr :2.5g/L
NaOH :20g/L
浴温 :40℃
電流密度 :0.1~10A/dm2
処理時間 :1秒~20秒
pH :13.0以上
比較例5及び6は、粗化処理層の形成を、表1に示す粗化処理IIで行ったこと以外は、それぞれ実施例1及び12と同様な条件で行い、表面処理銅箔を製造した。なお、表1に示す粗化処理IIで用いた粗化めっき液及びカプセルめっき液中の塩化物イオンの濃度が高いのは、活性炭のみを加え、塩化物イオンを塩化銀として沈殿させて除去するためのAgイオンを添加しなかったものであり、表1に示す粗化処理Iで用いた粗化めっき液及びカプセルめっき液中の塩化物イオンの濃度が低いのは、活性炭とともにAgイオンを添加して、塩化物イオンを塩化銀として沈殿させて除去したためである。
比較例7は、元箔AのM面に、特許文献1の実施例9と同様の方法で、Cu 20g/L(硫酸銅五水和物50g/L)、3-メルカプト-1-プロパン-スルホン酸ナトリウム0.25g/L、コバルトイオン5.2g/L、ニッケルイオン2.2g/L、浴温40℃、電流密度10A/dm2、電解時間10秒の条件で粗化処理層を形成した後、硫酸ニッケル(II)六水和物30g/L、モリブデン(VI)酸二ナトリウム二水和物60g/L、クエン酸三ナトリウム二水和物50g/L、pH10.5の液組成で電流密度4A/dm2、電解時間6秒で処理を行った後に、特許文献1に開示されている方法でクロメート処理層を積層して防錆処理層を形成したものである。その後、アミノプロピルトリエトキシシランを用いてシランカップリング処理を行い、表面処理銅箔を製造した。
高周波伝送特性および特にリフロー耐熱性の評価をするため、上記で得られた各表面処理銅箔を粗化処理面側が樹脂基材に対向するようにして、厚さ250μmの市販の高周波対応絶縁樹脂基材(パナソニック株式会社製メグトロン6)と重ね合わせ、一例としてプレス温度:200℃、プレス圧力:3MPa、プレス時間:120分の一般的なプレス条件で積層して銅張積層板を作製し、必要に応じて回路配線の加工などを実施して測定基板を準備した。
(1)金属付着量の測定
粗化処理層及び防錆処理層中の金属付着量の測定は、試料の粗化処理を行っていない面を塗料でマスキングした後、10cm角に切り出し、80℃に加温した混合酸(硝酸1:塩酸1(体積比))で銅箔の粗化処理を施した面の表面を3~5μm程度を溶解した後、得られた溶液中の金属質量を原子吸光光度計(日立ハイテクサイエンス株式会社製Z-2300)を用いて原子吸光分析法により定量分析を行って求めた。
接触式表面粗さ測定機(株式会社小坂研究所製SE1700型)を用い、JIS B0601:2001に準拠して十点平均粗さRzjisを測定した。表面粗さを接触式の表面粗さ測定機で測定するのは、今回の実験で得られた銅箔のマクロな表面粗さを評価するためであり、ミクロな領域を観察することを目的とした3次元白色干渉型顕微鏡ではマクロな表面粗さの違いを正確に測定出来なかったためである。
Sdr、Sdq及びStrの値は、Bruker社製の3次元白色干渉型顕微鏡Wyko(Contour GT-KハイレゾCCD仕様:1280×960画素)を用いて垂直走査型白色干渉方式(VSI)で10倍の倍率にて、表面処理銅箔を構成するシランカップリング層の表面から異なる3カ所において477μm×357μmの面積に対して測定し、それらの平均値を算出した。なお、測定に際してフィルターはかけていない。
リフロー耐熱性の評価は、IPC TM-650 2.4.24.1「TMAを用いたデラミネーションの時間測定」に準拠して、上記銅張積層板から得たリフロー耐熱性測定用基板を用い、288℃での膨れが発生するまでの時間(膨れ時間)にて評価した。リフロー耐熱性は、膨れ時間が、60分以上である場合を「◎」、45分以上60分未満である場合を「○」、30分以上45分未満である場合を「△」、30分未満である場合を「×」として評価し、本発明では、「◎」、「○」および「△」を合格レベルとした。
伝送特性は、上記銅張積層板にレジスト幅300μm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、ストリップライン長200mmのマイクロストリップラインを形成し伝送特性測定用基板(サイズ:長さ210mm、幅30mm)を得た。この伝送特性測定用基板をネットワークアナライザ(キーサイトテクノロジN5247A)を用いて50Ωの特性インピーダンスで40GHzの周波数での通過特性S21の測定を行った。伝送特性は、通過特性S21が、-28dB以上の場合を「◎」、通過特性S21が-30dB以上-28dB未満の場合を「○」、-33dB以上-30dB未満の場合を「△」、-33dB未満の場合を「×」として評価し、本発明では、「◎」、「○」および「△」を合格レベルとした。
これに対し、比較例1~7はいずれも、Sdrの値が本発明の適正範囲外であるため、リフロー耐熱性及び伝送特性の少なくとも一方が合格レベルにはなく劣っていた。
Claims (8)
- 銅箔の少なくとも片方の面に、粗化処理層、防錆処理層及びシランカップリング層が前記銅箔を基準にしてこの順で積層されている表面処理銅箔であり、前記シランカップリング層の表面から測定された三次元表面性状の複合パラメータである、界面の展開面積率Sdrの値が8~140%の範囲であることを特徴とする表面処理銅箔。
- 前記シランカップリング層の表面から測定された三次元表面性状の複合パラメータである、二乗平均平方根表面勾配Sdqの値が25~70°の範囲であることを特徴とする、請求項1に記載の表面処理銅箔。
- 前記シランカップリング層の表面から測定された三次元表面性状の空間パラメータである、表面性状のアスペクト比Strの値が0.25~1である、請求項1又は2に記載の表面処理銅箔。
- 前記シランカップリング層の表面から測定された十点平均粗さRzjisが0.9~1.5μmの範囲であることを特徴とする、請求項1~3のいずれか1項に記載の表面処理銅箔。
- 前記粗化処理層及び前記防錆処理層中の銅以外の金属及び該金属の酸化物の合計含有量が、金属元素に換算して0.15~0.50mg/dm2であること特徴する、請求項1~4のいずれか1項に記載の表面処理銅箔。
- 前記粗化処理層及び前記防錆処理層中のNi及びZnの含有量が、それぞれ0.05~0.30mg/dm2であることを特徴とする、請求項1~5のいずれか1項に記載の表面処理銅箔。
- 前記銅箔が電解銅箔であり、該電解銅箔のM面のみに前記粗化処理層を有することを特徴とする、請求項1~6のいずれか1項に記載の表面処理銅箔。
- 請求項1~7のいずれか1項に記載の表面処理銅箔と、該表面処理銅箔の前記シランカップリング層上に積層された樹脂とを有し、前記樹脂の周波数10GHzにおける誘電率が3.5以下でありかつ誘電正接が0.006以下であることを特徴とする銅張積層板。
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CN110088361B (zh) | 2021-07-16 |
CN110088361A (zh) | 2019-08-02 |
KR20190075054A (ko) | 2019-06-28 |
TWI749123B (zh) | 2021-12-11 |
TW201839178A (zh) | 2018-11-01 |
JP6462961B2 (ja) | 2019-01-30 |
KR102268478B1 (ko) | 2021-06-22 |
JPWO2018110579A1 (ja) | 2018-12-20 |
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