JP2005048277A - Electrolytic copper foil with carrier foil, and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrolytic copper foil with a carrier foil, which imparts an improved boring property with a laser of low energy to a copper-clad laminate, and contains a little amount of elements different from copper, which places few loads on the environment. <P>SOLUTION: The peelable type of an electrolytic copper foil with the carrier foil comprises the first roughened layer 3 made of the first fine copper grains 4 formed on one side of the carrier foil 2, an organic layer 5 formed on the first roughened layer 3, a bulky copper layer 6 formed on the organic layer 5 through an electrolytic process, the second roughened layer 7 made of the second fine copper grains 8 on the bulky copper layer 6 as needed, and a surface-treated layer such as a rust-prevention layer. In the electrolytic copper foil 1 with the carrier foil, the first fine copper grains 4 constituting the first roughening treatment layer 3 in the above electrolytic copper foil are embedded in the bulky copper layer 6 together with the organic layer 5, so that when the carrier foil 2 is peeled off, all or one of the first fine copper grains 4 are also ripped and peeled while leaving the rest on the surface of the bulky copper layer 6 side in a bonding state.The manufacturing method therefor is also provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The invention according to the present application relates to a peelable type electrolytic copper foil with a carrier foil and a method for producing the electrolytic copper foil with a carrier foil. In particular, a copper-clad laminate is manufactured using the electrolytic copper foil with carrier foil, and the electrolytic copper foil layer exposed after peeling the carrier foil is easily punched using a carbon dioxide laser. It provides.

  The present inventors, when viewed as a layer configuration of the electrolytic copper foil with a carrier foil, has a product having the same configuration disclosed in Patent Document 1 by drilling using a carbon dioxide laser similar to the present invention. It has been widely advocated to have very good effects.

  If the cross section of the electrolytic copper foil with carrier foil disclosed in Patent Document 1 at this time is illustrated, the same layer configuration as the electrolytic copper foil with carrier foil according to the present invention shown in FIG. That is, “provided with a roughened layer made of fine copper particles (corresponding to“ first fine copper particles ”in the present specification) on one side of the carrier foil, with an organic layer on the roughened layer, A bulk copper layer formed by an electrolytic method is provided on the organic layer, and a roughening treatment layer by fine copper grains (corresponding to “second fine copper grains” in the present specification) is provided on the bulk copper layer. This is a peelable type electrolytic copper foil with a carrier foil provided with a surface treatment layer such as a rust prevention treatment as required.

  And the function which the electrolytic copper foil with a carrier foil disclosed in this Patent Document 1 constitutes a roughened layer between the carrier foil and the bulk copper layer when the carrier foil is peeled off from the bulk copper layer. The fine copper particles to be adhered to the carrier foil side hardly remained on the bulk copper layer side and were removed together with the carrier foil. Therefore, at this time, the peeled surface of the bulk copper layer was obtained by transferring the uneven shape of the first fine copper grains in a replica shape.

  Certainly, as disclosed in Patent Document 2 and Patent Document 3, if many documents have a certain roughness on the surface of the copper foil, the absorption efficiency of the laser beam is increased, and the hole using the carbon dioxide laser is increased. This suggests that the finishing process is easy. As this suggestion, the electrolytic copper foil with carrier foil disclosed in Patent Document 1 has also exerted a great effect in securing good drilling workability with a carbon dioxide laser.

JP 2001-62955 A Japanese Patent Application No. 2000-143325 Special Table 2002-540609

  However, since the electrolytic copper foil with carrier foil disclosed in Patent Document 1 is obtained by transferring the replica shape of the first fine copper particles to the bulk copper layer, the shape, density, transfer level, etc. of the first fine copper particles In other words, the processing level by the carbon dioxide laser tends to fluctuate, and the roundness of the hole tends to vary, resulting in poor quality stability.

  In addition, in response to the recent trend toward high-density wiring, the shape of via holes and the like can be processed with low energy using a carbon dioxide laser, and the variation in roundness of the shape of the via holes formed in the copper-clad laminate is also reduced. With respect to control, demands at a level exceeding conventional levels have increased. Moreover, since the copper-clad laminate is usually formed by etching, the etching wastewater does not contain any elements other than copper, and the copper component can be easily recovered, and wastewater treatment with less environmental impact has been demanded. . Therefore, products that exclude foreign elements as much as possible have been desired for copper foil.

  Thus, as a result of earnest research, the present inventors have the same layer structure as the electrolytic copper foil with carrier foil disclosed in Patent Document 1, but the peeling mechanism when the carrier foil is peeled off is completely different. As a result, a stable low energy processing performance far exceeding the electrolytic copper foil with carrier foil disclosed in Patent Document 1 is provided. Hereinafter, the description will be divided into “an electrolytic copper foil with a carrier foil” and “a method for producing the electrolytic copper foil with a carrier foil” according to the present invention.

<Electrolytic copper foil with carrier foil>
The basic layer configuration of the electrolytic copper foil with carrier foil according to the present invention can be expressed as follows: “A first roughening treatment layer comprising first fine copper grains is provided on one surface of the carrier foil, and an organic layer is formed on the first roughening treatment. A bulk copper layer formed by an electrolytic method on the organic layer, a second roughening treatment layer, a surface treatment layer such as a rust prevention treatment, a rust prevention treatment, etc., if necessary, on the bulk copper layer "Peelable type electrolytic copper foil with carrier foil" having a surface treatment layer. This electrolytic copper foil with a carrier foil is a product as if the carrier foil and the electrolytic copper foil were bonded together. As an example, the cross-sectional schematic diagram of FIG. 1 schematically shows the cross-sectional layer configuration of the electrolytic copper foil with carrier foil according to the present invention. In terms of the layer structure that can be seen from FIG. 1, it can be said that there is no difference from the invention disclosed in Patent Document 1 described above. However, the peeling mechanism when the carrier foil is peeled off is completely different. In the present specification, the state in which the carrier foil is removed is referred to as an electrolytic copper foil or an electrolytic copper foil layer. In addition, the thing used in the state which described the 2nd roughening process layer is used for drawing used for description of this invention.

  In the case of the electrolytic copper foil with a carrier foil according to the present invention, as schematically shown in FIG. 2, the first fine copper particles constituting the first roughening treatment layer are embedded in the bulk copper layer together with the organic layer. When the carrier foil and the bulk copper layer are peeled off, all or a part of the first fine copper grains are torn off, and the residual copper adheres to the surface on the bulk copper layer side. The state when the carrier foil is peeled off can be considered by classifying into two modes.

  In one mode, as shown in FIG. 2A, when the carrier foil is peeled off, the first fine copper grains 4 constituting the first roughening treatment layer 3 are torn off, and the first fine copper This is a case where the grain fragments 9 and the residual organic layer 10 which is a part of the organic layer 5 remain on the surface of the carrier foil 2. As schematically shown in FIG. 2B, the other mode is that the first fine copper grains 4 constituting the first roughening treatment layer 3 are not torn off when the carrier foil is peeled off. This is a case where all of the first fine copper grains 4 remain on the surface side of the bulk copper layer 6 and hardly remain on the surface of the carrier foil 2. Regardless of which peeling mode is achieved, the shape of the first fine copper particles 4 constituting the first roughening treatment layer 3 is very important, and the conventional substantially spherical fine copper particles have the shape of the present invention. The peeling mechanism is difficult to achieve. Therefore, in the present invention, the shape of the first fine copper particles 3 is substantially a spindle shape or a dendritic shape, and it is preferable that the side of the first fine copper particles in contact with the carrier foil is as thin as possible. is there. The first fine copper constituting the first roughening treatment layer 3 on the bulk copper layer 6 side when lightly controlling the bonding strength between the carrier foil 2 and the first roughening treatment layer 3 and peeling off from the electrolytic copper foil layer This is because the grains 4 remain.

  Carrier foil said here is metal foil, such as aluminum foil and copper foil, and the organic film etc. which have electroconductivity. The reason why the electrical conductivity is required is to adopt a manufacturing method in which the carrier foil itself is cathodically polarized and the first fine copper particles are deposited on the surface thereof. The thickness of the carrier foil is not particularly limited, but the presence of the carrier foil makes it possible to make the bulk copper layer very thin, and is particularly useful when the bulk copper layer is 9 μm or less. It is.

  The organic layer 5 located on the 1st roughening process layer 3 does not fulfill | perform the function as a peeling layer exclusively so that the positional relationship may become clear. As can be understood from the schematic cross-sectional view of FIG. 1, it is considered that a part of the organic layer 5 is in contact with the surface of the carrier foil through the gap between the first fine copper grains 4 constituting the first roughening treatment layer 3. This is reasonable and partly serves as a release layer. At the same time, the organic layer 5 functions as described below. That is, the organic layer 5 is embedded in the surface of the bulk copper layer 6 together with the first fine copper grains 4 constituting the first roughening treatment layer 3. And it is also considered that the void shape is formed after the organic layer 5 is hot-pressed in the state where it is embedded in the bulk copper layer 6, and due to the component and physical shape, the laser beam is used. It is thought that it acts to improve the laser workability by the carbon dioxide gas laser because it inhibits the diffusion conduction of the supplied heat and causes heat concentration.

  As the organic agent that forms the organic layer 5, it is preferable to use one or two or more selected from nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids. It is also preferable to use the organic layer 5 in a state where an organic agent and copper particles are mixed. The state in which the organic agent and the copper particles are mixed is obtained by adopting a specific method in the formation of the organic layer, and the thickness of the organic layer can be increased. The auxiliary role for further improving the dawn workability is more effectively fulfilled.

  More specific examples of the organic agent include nitrogen-containing organic compounds such as 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolyl), which are triazole compounds having a substituent. Rumethyl) urea, 1H-1,2,4-triazole, 3-amino-1H-1,2,4-triazole and the like are preferably used. As the sulfur-containing organic compound, it is preferable to use mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol, or the like. Further, as the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid, or the like. However, in adopting the production method described later, it is most preferable to use carboxybenzotriazole from the viewpoint of process stability.

  The bulk copper layer 6 produced by electrolysis completely covers the first fine copper grains 4 and the organic layer 5 constituting the first roughening treatment layer 3 so as to enclose the first fine copper grains 4. It must be formed. By doing in this way, when the said 1st fine copper grain 4 will be in the state which digged into the bulk copper layer 6 in the shape of an anchor, and peeled off the carrier foil 2, the said 1st fine copper grain 4 and the organic layer 5 Tends to remain on the surface side of the bulk copper layer 6. FIG. 3 shows a scanning ion microscope image in which the state in which the first fine copper grains 4 have digged into the bulk copper layer 6 is captured from a cross section. It can be seen that the crystal grains with black dots in FIG. 3 are the first fine copper grains 4 grown substantially in a spindle shape, and are firmly biting into the bulk copper layer 6.

  On the surface of the bulk copper layer 6, a second roughening treatment layer 7 made of second fine copper grains 8 is further provided. However, this 2nd roughening process layer 7 is not always required, and is formed as needed. Unlike the first fine copper grains 4 constituting the first roughening treatment layer 3, the second fine copper grains 8 constituting the second roughening treatment layer 7 may employ substantially spherical fine copper grains. It doesn't matter. The second fine copper grains 8 constituting the second roughening treatment layer 7 are hot-pressed on the electrolytic copper foil 1 with a carrier foil and bonded to the resin base material. This is to ensure good adhesion. Accordingly, the adhesive strength can be kept higher as the fine copper particles have a reasonably large particle size and have sufficient hardness and are not deformed.

  Furthermore, it is possible to provide a surface treatment layer such as a rust prevention treatment on the second roughening treatment layer 8 as necessary. The surface treatment layer in the present specification is a silane coupling agent treatment for improving the adhesion with the base resin, an organic rust prevention by benzotriazole, imidazole or the like for ensuring long-term storage as a copper foil, It is described as a concept including a technique generally applied to rust prevention of copper foil such as inorganic rust prevention using zinc alloy such as zinc and brass. Moreover, according to the usage method of the electrolytic copper foil 1 with carrier foil which concerns on this invention, such a surface treatment may be unnecessary and it is also given as needed. In each drawing, the description of the surface treatment layer is omitted.

  The above-described electrolytic copper foil with carrier foil 1 has a surface on which the second roughening treatment layer 7 is located, which is hot-pressed and bonded to a resin base material, and the carrier foil 2 is peeled off. When the carrier foil 2 is peeled in this way, the first fine copper grains 4 constituting the first roughening treatment layer 3 are exposed on the peeled surface on the electrolytic copper foil layer side. When the first fine copper particles 4 are torn off by peeling off the carrier foil, a finer fracture surface is exposed. FIG. 4 shows the peeled surface observed. FIG. 4 (a) shows a scanning ion microscope image viewed in plan from above, and FIG. 4 (b) shows a scanning electron microscope image observed by tilting the sample by 45 °. As is apparent from this figure, the peeled surface does not have large unevenness, but has extremely fine unevenness.

Furthermore, as a result of intensive studies by the present inventors, in order to secure further laser drilling workability, the first fine copper grains 4 constituting the first roughening treatment layer 3 are made to have a high carbon content. It has been found desirable to be composed of copper (referred to above and below as “high carbon containing copper”). Copper forming normal fine copper grains is composed of so-called pure copper having a purity of 99.99 wt% or more, and the amount of carbon contained therein is about 0.005 wt%. On the other hand, the said 1st fine copper grain 4 is comprised with the high carbon content copper whose carbon content is 0.03 wt%-0.40 wt%. Thus, by increasing the carbon content in copper, the thermal conductivity of copper is reduced. Although the thermal conductivity of pure copper is a good conductor of heat of 354 W · m ⁻¹ · K ^{−1 at} 700 ° C., the carbon content is 0.03 to 0.40 wt% by containing the organic matter according to the present invention. The thermal conductivity of the high carbon-containing copper is about 100 to 180 W · m ⁻¹ · K ⁻¹ and the thermal conductivity is lowered.

  That is, high carbon content copper transfers heat only at a rate of about 1/2 to 1/3 of the thermal conductivity of pure copper. Therefore, when the laser beam is irradiated onto the first fine copper grains 4 made of high carbon-containing copper, the diffusion rate of heat is slower than that of pure copper, and the effect of supplying thermal energy by the laser beam is high. It is considered that the thermal energy concentrates on the surface, and the laser irradiation site easily reaches the boiling point of copper. Then, the thermal energy accumulated in the first fine copper grains 4 composed of the high carbon content copper is transferred to the bulk copper layer, and is easily dissolved together with the supply of thermal energy by continuous laser light irradiation. It is considered that the temperature rise exceeding the temperature continuously occurs, and the electrolytic copper foil layer can be easily removed by laser light.

  Moreover, although it is thought that it becomes a fault in the point that a different element is not included, between 0.001 micrometer-0.2 micrometer thickness of nickel, cobalt, or these alloys between the organic layer 5 and the bulk copper layer 6 Providing a thin film layer is also very effective. Such nickel, cobalt, or these nickel-based alloys and cobalt-based alloys are known as elements having high laser light absorption efficiency. When the thickness of the thin film layer is less than 0.001 μm, it is not possible to obtain the effect of improving the laser drilling workability. On the other hand, even if the thickness of the thin film layer exceeds 0.2 μm, the thickness is dramatically increased. The effect of improving the laser drillability cannot be obtained. In the drawing, the thin film layer is not displayed. This is because it is difficult to display extremely thin and is not an essential element in the present invention.

  In the above description, the case where a carbon dioxide laser is used has been described. However, the type of laser used when laser processing a copper clad laminate is not particularly limited, and the type of laser is not limited. However, it is considered that the absorptance is improved as the wavelength is shorter, and the effect is further improved. The laser irradiation conditions may be selected and used as appropriate in consideration of the base material, thickness, and the like.

<Method for producing electrolytic copper foil with carrier foil>
The method for producing an electrolytic copper foil with a carrier foil according to the present invention comprises at least the following a. ~ E. It is characterized by comprising the steps shown in FIG. Therefore, the order of the steps will be described in accordance with the basic flow shown in FIGS.

Step a. Step a. Is a cleaning process for cleaning the surface of the carrier foil. In this cleaning step, so-called pickling, alkali degreasing, and the like are meant. Accordingly, the purpose is to remove the fat and oil components attached to the carrier foil and to remove the surface oxide film when the metal foil is used. By passing the carrier foil through the pickling solution or the alkaline degreasing solution, the carrier foil is cleaned and uniform electrodeposition in the following steps is ensured. For example, various solutions such as a hydrochloric acid solution, a sulfuric acid solution, and a sulfuric acid-hydrogen peroxide solution can be used for the pickling treatment, and there is no particular limitation. In FIG. However, there is no particular physical change in the carrier foil itself.

Step b. Step b. Is a first roughening step of cathodic polarization of the cleaned carrier foil 2 in a copper sulfate electrolyte, depositing and forming the first fine copper grains 4 on one side, and forming the first roughening treatment layer 3 It is. This is schematically shown by step b. In FIG. It is. In the first roughening treatment step, the condition of burnt plating is adopted as the electrolysis condition. Therefore, a low-concentration copper electrolyte is used so as to easily create the burnt plating condition. The burn plating conditions are determined in consideration of the characteristics of the production line so that the first fine copper grains 4 have a substantially spindle shape or dendritic shape. For example, if a copper sulfate solution is used, a copper concentration of 1 to 20 g / l, a sulfuric acid concentration of 50 to 200 g / l, a liquid temperature of 15 to 40 ° C., and a current density of 10 to 50 A / dm ² are used. And so on.

  However, in order to efficiently make the shape of the first fine copper grains 4 into a substantially spindle shape or dendritic shape, copper sulfate having a copper concentration of 1 g / l to 20 g / l, a sulfuric acid concentration of 50 to 200 g / l, and a chlorine concentration of 200 ppm or less. It is most preferable to use a solution in which any one or a combination of 9-phenylacridine, carboxybenzotriazole and arsenic is added to the solution. At this time, the amount added when any one or two or more of 9-phenylacridine, carboxybenzotriazole and arsenic is combined should be determined in consideration of operating conditions such as current density to be employed, and is particularly limited. I don't think it is necessary.

  If the chlorine concentration is not 200 ppm or less, the shape control effect of the first fine copper grains 4 cannot be obtained. Chlorine serves to promote the growth of the grain size of the first fine copper grains 4 in the vertical direction. If the chlorine concentration is not appropriate, abnormal growth will occur. That is, when the chlorine concentration exceeds 200 ppm, the first fine copper particles themselves are pulverized and easily fall off. The chlorine concentration should be determined in relation to the amount of additive such as 9-phenylacridine, carboxybenzotriazole, etc., and an optimum amount according to the operating conditions may be adopted. Therefore, even when the chlorine concentration is “0 ppm” as defined as “200 ppm or less”, the concentration control of 9-phenylacridine, carboxybenzotriazole, and arsenic as additives is good. Thus, first spindle-shaped or dendritic first fine copper grains 4 are obtained.

  And in order to make the 1st fine copper grain 4 which comprises this 1st roughening process layer 3 into a high carbon copper composition, it is by adding various organic agents in electrolyte solution. For example, it is possible to use 9-phenylacridine, carboxybenzotriazole, or the like of the present invention as an additive. However, in order to achieve a high carbon copper composition with a stable carbon content, electrolysis is performed under the condition of burnt plating using a copper sulfate solution containing 100 ppm to 3000 ppm of one or more of glue, gelatin, and collagen peptide. It is preferable to do. That is, by adopting a concentration range such as glue of 100 ppm or more, the carbon content concentration in the high carbon content copper can be 0.05 wt%. This is because if the carbon content in the high carbon-containing copper layer does not exceed 0.05 wt%, it does not contribute to the improvement of laser drillability. On the other hand, the upper limit of the carbon content is 0.40 wt%. This is because even if the carbon content is higher than this, the laser drillability is not further improved.

In order to prevent the first fine copper grains 4 once attached from falling off, it is also preferable to additionally provide a covering plating step. By performing the covering plating, the first fine copper particles 4 are prevented from falling off, and the laser drilling property tends to be improved. Cover plating is to uniformly deposit a thin copper layer so as to cover the first fine copper particles 4 under smooth plating conditions in order to prevent the first fine copper particles 4 deposited and adhered to the surface of the carrier foil from falling off. Is. Therefore, when a covering plating process is provided, smooth copper plating conditions are adopted. The smooth plating conditions are not particularly limited and are determined in consideration of the characteristics of the production line. For example, if a copper sulfate-based solution is used, the conditions are copper 50 to 80 g / l, sulfuric acid 50 to 150 g / l, liquid temperature 40 to 80 ° C., and current density 10 to 50 A / dm ^2. .

Step c. Step c. Is an organic layer forming step of forming the organic layer 5 on the surface of the first roughening treatment layer 3, and this state is schematically shown in the step c. It is. The organic layer 5 is formed by: i) filling the tank with a solution containing an organic agent, and immersing the carrier foil 2 in which the first roughening layer 3 is formed therein; ii) forming the organic layer 5 A method of showering or dripping a solution containing an organic agent on the first roughening treatment layer 3, iii) anodic polarization of the carrier foil 2 on which the first roughening treatment layer 3 is formed in a tank, A method of electrodeposition can be employed. When the method described above is employed, there is no particular limitation on the concentration of the organic agent in the solution.

  However, when the organic layer 5 is in a state where the organic agent and the metal particles are mixed, it is preferable to employ the following method. That is, a solution in which an organic agent to be adsorbed in the pickling solution is mixed is used. By using the pickling solution, compared with the case where the organic agent is adsorbed without dissolution of the carrier foil, the rate of precipitation of the organic agent on the carrier foil is improved, and at the same time the adsorption uniformity is improved. is there. In this case, the organic layer 5 is formed in a pickling solution in which metal ions from which the metal constituting the carrier foil 2 is eluted exist, so that the metal ions in the pickling solution react with the organic agent to form a complex. In order to perform the formation, metal ions are included in the organic coating, and are present in the form of metal particles. This state can be observed using a transmission electron microscope.

  The pickling solution used here has a slightly different composition depending on the type of the carrier foil 2 and may be varied depending on the type of the carrier foil and the pickling time. It is preferable to use a solution. Correspondingly, the carrier foil 2 inevitably uses a metal foil such as copper and copper alloy that can be pickled with a sulfuric acid solution, a resin film having a metal coating layer such as copper and copper alloy, and the like. become.

  And when adding an organic agent in this pickling solution, it is preferable to add so that the density | concentration of an organic agent may become the range of 50 ppm-2000 ppm. When the concentration is less than 50 ppm, the adsorption rate of the organic agent is slow, and the thickness of the formed pickled adsorption organic coating tends to be uneven. On the other hand, the concentration of 2000 ppm, which is the upper limit, can actually dissolve the organic agent even if this concentration is exceeded. However, it is because it is not necessary to employ an excessive amount of dissolution in consideration of the quality stability of the solution and the economic efficiency in actual operation.

  In addition, the temperature of the pickling solution at this time is not particularly limited because it can be appropriately selected in consideration of the speed of the pickling treatment and the speed of the pickling adsorption organic coating forming process. However, at this time, since the organic agent coexists in the pickling solution, when raising the liquid temperature, it is necessary to select a temperature at which the organic agent does not decompose depending on the type of the organic agent used. It needs to be noted.

  In this case, the organic agent is 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, which is a triazole compound having a substituent among nitrogen-containing organic compounds. 1H-1,2,4-triazole, 3-amino-1H-1,2,4-triazole and the like are preferable because of high stability in an acid solution.

  Here, it should be mentioned also about an additional process in the case where a thin film layer having a thickness of 0.001 μm to 0.2 μm made of nickel, cobalt, or an alloy thereof is provided between the organic layer 5 and the bulk copper layer 6. To do. This thin film layer is formed by performing smooth short-time plating of nickel, cobalt or the like on the carrier foil in which the organic layer has been formed. The plating method may be electroless plating or electrolytic plating. When employing electrolytic plating, the following conditions can be used.

When a nickel thin film layer is formed, a solution used as a nickel plating solution can be widely used. For example, i) nickel sulfate is used and the nickel concentration is 5 to 30 g / l, the liquid temperature is 20 to 50 ° C., the pH is ^{2 to} 4, the current density is 0.3 to 10 A / dm ² , and the nickel concentration is nickel sulfate. 5 to 30 g / l, potassium pyrophosphate 50 to 500 g / l, liquid temperature 20 to 50 ° C., pH 8 to 11, current density 0.3 to 10 A / dm ² , iii) nickel concentration of 10 to 10 using nickel sulfate 70 g / l, boric acid 20 to 60 g / l, liquid temperature 20 to 50 ° C., pH ^{2 to} 4, current density 1 to 50 A / dm ² , and other general Watt bath conditions.

When a cobalt thin film layer is formed, a solution used as a cobalt plating solution can be used. For example, i) Conditions using cobalt sulfate and a cobalt concentration of 5-30 g / l, trisodium citrate 50-500 g / l, liquid temperature 20-50 ° C., pH 2-4, current density 0.3-10 A / dm ² Ii) Using cobalt sulfate, the cobalt concentration is 5-30 g / l, potassium pyrophosphate 50-500 g / l, liquid temperature 20-50 ° C., pH 8-11, current density 0.3-10 A / dm ² , iii ) Using cobalt sulfate, the cobalt concentration is 10 to 70 g / l, boric acid 20 to 60 g / l, liquid temperature 20 to 50 ° C., pH ^{2 to} 4 and current density 1 to 50 A / dm ² .

In the case of forming a nickel-zinc alloy thin film layer, for example, nickel sulfate is used and the nickel concentration is 1 to 2.5 g / l, and zinc pyrophosphate is used and the zinc concentration is 0.1 to 1 g / l. The conditions are 50 to 500 g / l, the liquid temperature is 20 to 50 ° C., the pH is 8 to 11, and the current density is 0.3 to 10 A / dm ² .

When forming a nickel-cobalt alloy thin film layer, for example, cobalt sulfate 80-180 g / l, nickel sulfate 80-120 g / l, boric acid 20-40 g / l, potassium chloride 10-15 g / l, phosphoric acid 2 The conditions are sodium hydride 0.1 to 15 g / l, liquid temperature 30 to 50 ° C., pH 3.5 to 4.5, and current density 1 to 10 A / dm ² .

In the case of nickel, nickel-phosphorus alloy plating can be obtained by using a phosphoric acid solution. In this case, nickel sulfate 120-180 g / l, nickel chloride 35-55 g / l, H ₃ PO ₄ 30-50 g / l, H ₃ PO ₃ 20-40 g / l, liquid temperature 70-95 ° C., pH 0.5- The conditions are 1.5, the current density is 5 to 50 A / dm ² , and the like.

Step d. Step d. Is a bulk copper layer forming step in which a bulk copper layer 6 is formed on the surface of the organic layer 5 by an electrolytic reaction using a copper electrolyte. This is schematically shown by step d. In FIG. It is. The bulk copper layer 6 is formed using a solution that can be used as a copper ion supply source such as a copper sulfate-based solution or a copper pyrophosphate-based solution, and the solution composition is not particularly limited. For example, in the case of a copper sulfate-based solution, the concentration is copper 30-100 g / l, sulfuric acid 50-200 g / l, liquid temperature 30-80 ° C., current density 1-100 A / dm ² , copper pyrophosphate-based solution. If present, the conditions are such that the concentration is copper 10-50 g / l, potassium pyrophosphate 100-700 g / l, liquid temperature 30-60 ° C., pH 8-12, current density 1-10 A / dm ² . Here, the copper component forming the bulk copper layer 6 is converted to the organic layer 5 (or the thin film layer) by cathodic polarization of the carrier foil in which the formation of the organic layer 5 (or the thin film layer) is completed in the solution. It deposits uniformly and smoothly on the top.

  For the formation of the bulk copper layer 6, smooth copper plating conditions are applied. There is no need to place strict restrictions on the smooth plating conditions. However, the initial deposition thickness of 0.3 μm to 2 μm of smooth plating is precisely electrolyzed at a low current density, and then the current density is increased in consideration of productivity to make the bulk copper layer 6 have a predetermined thickness. This is preferable from the viewpoint of growing the bulk copper layer 6 so as to enclose the fine copper grains 4. Here, when the low current electrolysis is completed with an initial deposition thickness of less than 0.3 μm of the smooth plating, the residual stability of the first fine copper grains 4 on the surface of the bulk copper layer 6 when the carrier foil is peeled off is improved. It cannot be done. On the other hand, if the initial deposition thickness of smooth plating by low current electrolysis is 2.0 μm, the bulk copper layer 6 usually wraps around the first fine copper grains 4. That is, if the first fine copper particles 4 are encased, the purpose is achieved. Therefore, it is preferable to adopt a technique of increasing the current density and performing electrolysis in consideration of industrial productivity.

Here, the term “low current density” or “high current density” simply refers to the smooth plating conditions depending on the type of solution used for electrolysis, the copper concentration, etc., so abstract expressions must be adopted. It is for not getting. However, according to the study by the present inventors, a current density that is 1/3 or less of the limit current density that can be smooth-plated, which is determined according to the composition and type of the solution, is a low current density, and 1/3 of the limit current density is It has been obtained that the current density exceeding the high current density may be considered. For example, in the case of electrolysis using the above-described copper sulfate solution, the low current density is regarded as a range of 1 to 3 A / dm ² , and the high current density is regarded as a range of 4 to 10 A / dm ² . Moreover, the precipitation thickness said here is the apparent conversion thickness calculated from the conversion weight when it assumes that it plated on the plane.

Step e. Step e. First, it is clearly stated that the process is performed as necessary. This step e. Then, the carrier foil 2 that has been subjected to the above-described steps is cathodic polarized in a copper sulfate electrolyte, and the second fine copper grains 8 are formed on the surface of the bulk copper layer 6 to form the second roughened layer 7. This is the second roughening step. This is shown schematically in step e. It is. As described above, the second fine copper grains 8 constituting the second roughening treatment layer 7 are different from the first fine copper grains 4 constituting the first roughening treatment layer 3 in the form of substantially spherical fine copper grains. Adhesion strength can be kept high as the fine copper particles have a reasonably large particle size, sufficient hardness, large deformation resistance, and no powder falling off.

Thus, step b. The same discoloration conditions as described above are used. However, α-naphthoquinoline, dextrin, glue, thiol in the electrolyte solution is obtained in order to obtain second fine copper particles having a moderately large particle size and sufficient hardness to improve adhesion to the base resin. It is also possible to use a copper sulfate solution to which an additive such as urea is added. For example, if a copper sulfate-based solution is used, the copper concentration is 5 to 20 g / l, the sulfuric acid concentration is 50 to 200 g / l, and other additives as necessary (α-naphthoquinoline, dextrin, glue, thiourea, etc.) , And the liquid temperature is 15 to 40 ° C. and the current density is 10 to 50 A / dm ² . And normally with respect to this 2nd roughening process layer, process b. Thus, the same plating process as described above is performed.

  After the above steps, generally, after the second roughening treatment step, there is a rust prevention treatment step for applying a rust prevention treatment to the surface of the second roughening treatment layer 7 as necessary. A silane coupling treatment step is performed in which the coupling agent is adsorbed and stabilized by a drying treatment, whereby the electrolytic copper foil 1 with a carrier foil as a product is obtained.

<Method for producing electrolytic copper foil with carrier foil>
The copper-clad laminate obtained using the electrolytic copper foil with carrier foil according to the present invention described above is obtained by using the electrolytic copper foil with carrier foil according to the present invention instead of a normal copper foil. The manufacturing method and the layer structure of the copper clad laminate are not particularly different. However, when the electrolytic copper foil with a carrier foil according to the present invention is used instead of the copper foil and subjected to hot press bonding to a prepreg or an inner layer circuit board, the carrier of the electrolytic copper foil with a carrier foil according to the present invention The organic layer located between the first roughening treatment layer and the bulk copper layer provided on one side of the foil has a void shape. The cross-sectional observation by the secondary electron beam image shown in FIG. 7 captures that the organic layer 5 after being subjected to this hot press processing has become a void. In FIG. 7, an arrow is attached to a representative portion that looks like the void shape 11.

  In such a secondary electron beam image, it can be determined at this stage whether the portion that can be observed as the void shape 11 is actually a cavity or whether the organic layer is decomposed by heating and the organic matter is spheroidized. Is not done. For reference, in the analysis by the Auger electron analysis method, comparing the signal intensity of the carbon spectrum between the area where the void is concentrated and the area where the void is not present implies the presence of the organic substance from the area where the void is concentrated. Thus, the signal of the carbon spectrum is detected high.

  As described above, the copper clad laminate in which the void shape is confirmed in the organic layer exhibits extremely good laser processing performance when the carrier foil is removed and processing is performed with laser light.

  In the electrolytic copper foil with carrier foil according to the present invention, the shape of the first fine copper grains constituting the first roughening treatment layer remaining on the surface of the copper foil layer after peeling off the carrier foil is very dense and uniform. Since the organic layer remains in the vicinity of the surface with a void shape, it is difficult to cause thermal diffusion by inhibiting thermal conductivity, making low-energy processing unprecedented and easy. , With stable laser drilling performance.

  Moreover, it becomes possible to further improve laser processing performance by making the 1st fine copper grain which comprises a 1st roughening process layer into high carbon copper. Such a copper foil layer surface contributes to ensuring good adhesion with an etching resist and ensuring good exposure by preventing exposure blur. Therefore, if the adhesion with the etching resist is improved, the intrusion of the etching solution into the bonding interface between the copper foil and the etching resist can be prevented, and a circuit cross section having a good aspect ratio can be formed. This makes it easy to form a fine circuit. Moreover, the manufacturing method of the electrolytic copper foil with carrier foil according to the present invention increases the production efficiency of the electrolytic copper foil with carrier foil, and enables stable supply to the market of inexpensive and high-quality products.

  Hereinafter, the best mode for carrying out the present invention will be described through examples. Hereinafter, examples and comparative examples will be shown in order to understand the superiority of the present invention.

  Here, untreated foil (electrolytic copper foil not subjected to roughening treatment and surface treatment) classified as grade 3 having a thickness of 35 μm is used as the carrier foil, and an electrolytic copper foil layer having a thickness of 3 μm is formed on the glossy surface side. It was. The glossy surface is inevitably formed on the electrolytic copper foil as follows. An electrolytic copper foil manufacturing apparatus is a method in which a copper sulfate solution is passed between a drum-shaped rotating cathode and an insoluble anode facing the rotating cathode, and copper is rotated using an electrolytic reaction. The copper deposited on the surface of the drum is in the form of a foil, which is continuously peeled off from the rotating cathode and wound up. The surface of the untreated foil peeled off from the state in contact with the rotating cathode is a transfer of the mirror-finished surface shape of the rotating cathode, and is a glossy and smooth surface. On the other hand, the surface shape of the separating / separating foil, which was the precipitation side, shows a mountain-shaped uneven shape because the crystal growth rate of the deposited copper differs for each crystal surface, and this is called a rough surface.

Step a. The carrier foil was immersed in a dilute sulfuric acid solution having a concentration of 150 g / l and a liquid temperature of 30 ° C. for 30 seconds to remove oil components and excess surface oxide film attached to the carrier foil and washed with water.

Step b. After the pickling treatment, the carrier foil is put in a solution having a copper concentration of 7.0 g / l, a sulfuric acid concentration of 100 g / l, a 9-phenylacridine concentration of 150 ppm, a chlorine concentration of 50 ppm, and a liquid temperature of 25 ° C. Dendritic fine copper grains were deposited on one side of the carrier foil under the conditions of a density of 15 A / dm ² and an electrolysis time of 15 seconds. And the 1st roughening process layer was formed by carrying out the covering plating in order to prevent this fine copper grain from falling off. This covering plating is a copper sulfate solution, which is electrolyzed for 5 seconds under smooth plating conditions with a sulfuric acid concentration of 70 g / l, a copper concentration of 64 g / l, a liquid temperature of 40 ° C., and a current density of 10 A / dm ^2. The first fine copper particles were washed with water.

Step c. The carrier foil on which the first roughening treatment layer is formed forms an organic layer on the surface thereof. The organic layer at this time was formed by immersing the carrier foil for 30 seconds in an aqueous solution containing CBTA having a concentration of 3.5 g / l and adjusted to pH 5 using sulfuric acid with a liquid temperature of 40 ° C.

Step d. When the organic layer was formed, a bulk copper layer was subsequently formed on the organic layer. Bulk copper formation is performed by using a copper sulfate solution having a sulfuric acid concentration of 70 g / l, a copper concentration of 64 g / l, and a liquid temperature of 40 ° C., and cathodic polarization of the carrier foil in this solution to achieve a smooth current density of 5 A / dm ² . The electrolysis was performed for 30 seconds under plating conditions, and then for 38 seconds under smooth plating conditions with a current density of 20 A / dm ² .

Step e. When the formation of the bulk copper layer was completed, next, the second fine copper grains were adhered and formed on the surface of the bulk copper layer to form the second roughening treatment layer. In the formation of the second roughening treatment layer, the second fine copper particles were deposited on the bulk copper layer, and further, covering plating was performed to prevent the second fine copper particles from falling off.

When depositing and adhering the second fine copper particles on the bulk copper layer, it is a copper sulfate solution having a sulfuric acid concentration of 150 g / l, a copper concentration of 13.7 g / l, a liquid temperature of 30 ° C., and a current density of 30 A. Electrolysis was performed for 5 seconds under the condition of / dm ² burnt plating.

The overlay plating for preventing the second fine copper particles from falling off is a copper sulfate solution similar to that used for forming the bulk copper layer described above, and has a sulfuric acid concentration of 70 g / l and a copper concentration of 64 g / l. This was carried out by electrolysis for 10 seconds under smooth plating conditions with a liquid temperature of 48 ° C. and a current density of 20 A / dm ² .

Step f. Further, as a rust prevention treatment, rust prevention treatment was performed using zinc as a rust prevention element. Here, a zinc sulfate bath was used, and a zinc concentration of 20 g / l, a liquid temperature of 40 ° C., and a current density of 15 A / dm ² were adopted.

  When the rust prevention treatment was completed, it was finally washed with water and dried for 20 seconds in a furnace heated to an atmospheric temperature of 180 ° C. by an electric heater to obtain a finished electrolytic copper foil with carrier foil.

Evaluation of Laser Workability A 70 μm-thick resin layer is formed on the surface of the electrolytic copper foil subjected to rust prevention of the electrolytic copper foil 1 with carrier foil obtained as described above, and the electrolytic copper foil with carrier foil with resin is formed. It was. Then, this resin-coated electrolytic copper foil with carrier foil was placed on each surface of the core material having the inner layer circuit formed on both sides, and hot-pressed to produce a four-layer copper-clad laminate. Then, the carrier foil was peeled off to expose the electrolytic copper foil surface, and a via hole was formed using a carbon dioxide laser. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.94 to 0.97. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

  In addition, in the evaluation of the workability by the carbon dioxide laser in this specification, it is considered that it is very important to compare the processing energy as to whether or not it can be easily processed. However, in actual printed wiring boards, the laser processing conditions that are considered to be optimal differ from product to product, so that processing energy is not compared, and processing is performed with the roundness of processing holes as important as processing energy. The finish of the hole was evaluated. In this specification, the carbon dioxide laser processing conditions employ pulse energy with a processing energy of 20 mJ. Other laser irradiation conditions were a frequency of 2000 Hz, a mask diameter of 7.0 mm, and a pulse width of 23 μsec. Based on the conditions of an offset of 0.0 and a laser beam diameter of 140 μm, optimum conditions were determined for each copper-clad laminate, and 400 holes with a processing diameter of 125 μm were planned to be formed. Therefore, the inventors of the present invention determined that the processing was performed well within the range in which the hole diameter after processing was 115 to 135 μm, and determined the roundness variation.

  In this example, as in Example 1, an electrolytic copper foil that was not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 35 μm was used for the carrier foil. Hereinafter, the description should be made according to the order of the steps, but the flow is basically the same as that described in the first embodiment. Therefore, step c. We will only explain

Step c. The carrier foil on which the first roughening treatment layer is formed forms an organic layer on the surface thereof. The organic layer at this time was formed by immersing the carrier foil in an aqueous solution having a carboxybenzotriazole concentration of 1000 ppm, a sulfuric acid concentration of 150 g / l, a copper concentration of 10 g / l, and a liquid temperature of 40 ° C. for 30 seconds. . Hereinafter, the completed electrolytic copper foil with carrier foil was obtained by the same process as in Example 1.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.95 to 0.98. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

  In this example, as in Example 1, an electrolytic copper foil that was not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 35 μm was used for the carrier foil. Hereinafter, the description should be made according to the order of the steps, but the flow is basically the same as that described in the first embodiment. Therefore, the step b. We will only explain

Step b. After the pickling treatment, the carrier foil is put in a solution having a copper concentration of 7.0 g / l, a sulfuric acid concentration of 100 g / l, a 9-phenylacridine concentration of 150 ppm, a chlorine concentration of 50 ppm, and a liquid temperature of 25 ° C. Dendritic first fine copper grains were deposited on one side of the carrier foil under the conditions of a density of 15 A / dm ² and an electrolysis time of 15 seconds. That is, the covering plating for preventing the first fine copper particles from falling off in Example 1 is omitted.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.93 to 0.97. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

  In this example, as in Example 1, an electrolytic copper foil that was not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 35 μm was used for the carrier foil. Hereinafter, the description should be made according to the order of the steps, but the flow is basically the same as that described in the first embodiment. Therefore, the step b. And step c. We will only explain

Step b. After the pickling treatment, the carrier foil is put in a solution having a copper concentration of 7.0 g / l, a sulfuric acid concentration of 100 g / l, a 9-phenylacridine concentration of 150 ppm, a chlorine concentration of 50 ppm, and a liquid temperature of 25 ° C. Dendritic first fine copper grains were deposited on one side of the carrier foil under the conditions of a density of 15 A / dm ² and an electrolysis time of 15 seconds. That is, the covering plating for preventing the first fine copper particles from falling off in Example 1 is omitted.

Step c. The carrier foil on which the first roughening treatment layer is formed forms an organic layer on the surface thereof. The organic layer at this time was formed by immersing the carrier foil in an aqueous solution having a carboxybenzotriazole concentration of 1000 ppm, a sulfuric acid concentration of 150 g / l, a copper concentration of 10 g / l, and a liquid temperature of 40 ° C. for 30 seconds. . Hereinafter, the completed electrolytic copper foil with carrier foil was obtained by the same process as in Example 1.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.93 to 0.97. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

  In this example, as in Example 1, an electrolytic copper foil that was not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 35 μm was used for the carrier foil. Hereinafter, the description should be made according to the order of the steps, but the flow is basically the same as that described in the first embodiment. Therefore, the step b. We will only explain

Step b. After the pickling treatment, the carrier foil is placed in a solution having a copper concentration of 7.0 g / l, a sulfuric acid concentration of 100 g / l, a carboxybenzotriazole concentration of 75 ppm, a chlorine concentration of 10 ppm, and a liquid temperature of 25 ° C. Dendritic fine copper grains were deposited and formed on one surface of the carrier foil under the conditions of 15 A / dm ² and electrolysis time of 15 seconds. And the 1st roughening process layer was formed by carrying out the covering plating in order to prevent this fine copper grain from falling off. This covering plating is a copper sulfate solution, and is formed into a spindle shape by electrolysis for 5 seconds under smooth plating conditions of a sulfuric acid concentration of 70 g / l, a copper concentration of 64 g / l, a liquid temperature of 40 ° C., and a current density of 10 A / dm ^2. The first fine copper particles were washed with water.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.92 to 0.96. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

  In this example, as in Example 1, an electrolytic copper foil that was not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 35 μm was used for the carrier foil. Hereinafter, the description should be made according to the order of the steps, but the flow is basically the same as that described in the first embodiment. Moreover, it can be said that the manufacturing flow based on Example 5 is employ | adopted. Therefore, step c. We will only explain

Step b. After the pickling treatment, the carrier foil is placed in a solution having a copper concentration of 7.0 g / l, a sulfuric acid concentration of 100 g / l, a carboxybenzotriazole concentration of 75 ppm, a chlorine concentration of 0 ppm, and a liquid temperature of 25 ° C. Dendritic fine copper grains were deposited on one side of the carrier foil under the conditions of 20 A / dm ² and electrolysis time of 15 seconds. And the 1st roughening process layer was formed by carrying out the covering plating in order to prevent this fine copper grain from falling off. This covering plating is a copper sulfate solution, and is formed into a spindle shape by electrolysis for 5 seconds under smooth plating conditions of a sulfuric acid concentration of 70 g / l, a copper concentration of 64 g / l, a liquid temperature of 40 ° C., and a current density of 10 A / dm ^2. The first fine copper particles were washed with water.

Step c. The carrier foil on which the first roughening treatment layer is formed forms an organic layer on the surface thereof. The organic layer at this time was formed by immersing the carrier foil in an aqueous solution having a carboxybenzotriazole concentration of 1000 ppm, a sulfuric acid concentration of 150 g / l, a copper concentration of 10 g / l, and a liquid temperature of 40 ° C. for 30 seconds. . Hereinafter, the completed electrolytic copper foil with carrier foil was obtained by the same process as in Example 1.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.93 to 0.97. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

  In this example, as in Example 1, an electrolytic copper foil that was not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 35 μm was used for the carrier foil. Hereinafter, the description should be made according to the order of the steps, but the flow is basically the same as that described in the first embodiment. Moreover, it can be said that the manufacturing flow based on Example 5 is employ | adopted. Therefore, the step b. We will only explain

Step b. After the pickling treatment, the carrier foil is placed in a solution having a copper concentration of 7.0 g / l, a sulfuric acid concentration of 100 g / l, a carboxybenzotriazole concentration of 75 ppm, a chlorine concentration of 10 ppm, and a liquid temperature of 25 ° C. Dendritic first fine copper grains were deposited on one surface of the carrier foil under the conditions of 15 A / dm ² and electrolysis time of 15 seconds. That is, the cover plating for preventing the first fine copper particles from falling off in Example 5 is omitted.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.92 to 0.96. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

  In this example, as in Example 1, an electrolytic copper foil that was not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 35 μm was used for the carrier foil. Hereinafter, the description should be made according to the order of the steps, but the flow is basically the same as that described in the first embodiment. Moreover, it can be said that the manufacturing flow based on Example 5 is employ | adopted. Therefore, the step b. And step c. We will only explain

Step b. After the pickling treatment, the carrier foil is placed in a solution having a copper concentration of 7.0 g / l, a sulfuric acid concentration of 100 g / l, a carboxybenzotriazole concentration of 75 ppm, a chlorine concentration of 0 ppm, and a liquid temperature of 25 ° C. Dendritic first fine copper grains were deposited on one side of the carrier foil under the conditions of 20 A / dm ² and electrolysis time of 15 seconds. That is, the covering plating for preventing the first fine copper particles from falling off in Example 5 is omitted.

Step c. The carrier foil on which the first roughening treatment layer is formed forms an organic layer on the surface thereof. The organic layer at this time was formed by immersing the carrier foil in an aqueous solution having a carboxybenzotriazole concentration of 1000 ppm, a sulfuric acid concentration of 150 g / l, a copper concentration of 10 g / l, and a liquid temperature of 40 ° C. for 30 seconds. . Hereinafter, the completed electrolytic copper foil with carrier foil was obtained by the same process as in Example 1.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.92 to 0.96. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

  In this example, as in Example 1, an electrolytic copper foil that was not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 35 μm was used for the carrier foil. Hereinafter, the description should be made according to the order of the steps, but the flow is basically the same as that described in the first embodiment. Therefore, the step b. We will only explain

Step b. After the pickling treatment, the carrier foil is placed in a solution having a copper concentration of 7.0 g / l, a sulfuric acid concentration of 100 g / l, a glue concentration of 1000 ppm, a chlorine concentration of 10 ppm, and a liquid temperature of 25 ° C. Dendritic fine copper grains were deposited on one side of the carrier foil under the conditions of dm ² and electrolysis time of 15 seconds. And the 1st roughening process layer was formed by carrying out the covering plating in order to prevent this fine copper grain from falling off. This covering plating is a copper sulfate solution, and is performed by electrolysis for 5 seconds under smooth plating conditions of a sulfuric acid concentration of 70 g / l, a copper concentration of 64 g / l, a liquid temperature of 40 ° C., and a current density of 10 A / dm ^2. The first fine copper particles were washed with water.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.93 to 0.96. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

  In this example, as in Example 1, an electrolytic copper foil that was not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 35 μm was used for the carrier foil. Hereinafter, the description should be made according to the order of the steps, but the flow is basically the same as that described in the first embodiment. Moreover, it can be said that the manufacturing flow based on Example 9 is employ | adopted. Therefore, step c. We will only explain

Step c. The carrier foil on which the first roughening treatment layer is formed forms an organic layer on the surface thereof. The organic layer at this time was formed by immersing the carrier foil in an aqueous solution having a carboxybenzotriazole concentration of 1000 ppm, a sulfuric acid concentration of 150 g / l, a copper concentration of 10 g / l, and a liquid temperature of 40 ° C. for 30 seconds. . Hereinafter, the completed electrolytic copper foil with carrier foil was obtained by the same process as in Example 1.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.93 to 0.98. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

  In this example, as in Example 1, an electrolytic copper foil that was not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 35 μm was used for the carrier foil. Hereinafter, the description should be made according to the order of the steps, but the flow is basically the same as that described in the first embodiment. Moreover, it can be said that the manufacturing flow based on Example 9 is employ | adopted. Therefore, the step b. We will only explain

Step b. After the pickling treatment, the carrier foil is placed in a solution having a copper concentration of 7.0 g / l, a sulfuric acid concentration of 100 g / l, a glue concentration of 1000 ppm, a chlorine concentration of 10 ppm, and a liquid temperature of 25 ° C. Dendritic first fine copper grains were deposited on one side of the carrier foil under the conditions of dm ² and electrolysis time of 15 seconds. That is, the cover plating for preventing the first fine copper particles from falling off in Example 9 was omitted.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.92 to 0.97. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

  In this example, as in Example 1, an electrolytic copper foil that was not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 35 μm was used for the carrier foil. Hereinafter, the description should be made according to the order of the steps, but the flow is basically the same as that described in the first embodiment. Moreover, it can be said that the manufacturing flow based on Example 9 is employ | adopted. Therefore, the step b. And step c. We will only explain

Step b. After the pickling treatment, the carrier foil is placed in a solution having a copper concentration of 7.0 g / l, a sulfuric acid concentration of 100 g / l, a glue concentration of 1000 ppm, a chlorine concentration of 10 ppm, and a liquid temperature of 25 ° C. Dendritic first fine copper grains were deposited on one side of the carrier foil under the conditions of dm ² and electrolysis time of 15 seconds. That is, the covering plating for preventing the first fine copper particles from falling off in Example 9 is omitted.

Step c. The carrier foil on which the first roughening treatment layer is formed forms an organic layer on the surface thereof. The organic layer at this time was formed by immersing the carrier foil in an aqueous solution having a carboxybenzotriazole concentration of 1000 ppm, a sulfuric acid concentration of 150 g / l, a copper concentration of 10 g / l, and a liquid temperature of 40 ° C. for 30 seconds. . Hereinafter, the completed electrolytic copper foil with carrier foil was obtained by the same process as in Example 1.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.93 to 0.97. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

  In this example, as in Example 1, an electrolytic copper foil that was not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 35 μm was used for the carrier foil. Hereinafter, the description should be made according to the order of the steps, but the flow is basically the same as that described in the first embodiment. Therefore, the step b. We will only explain

Step b. After the pickling treatment, the carrier foil is placed in a solution having a copper concentration of 7.0 g / l, a sulfuric acid concentration of 100 g / l, a chlorine concentration of 50 ppm, and a liquid temperature of 25 ° C., and is cathode-polarized to have a current density of 15 A / dm ² , Dendritic fine copper grains were deposited and formed on one surface of the carrier foil under the condition of time 15 seconds. And the 1st roughening process layer was formed by carrying out the covering plating in order to prevent this fine copper grain from falling off. This overplating is a copper sulfate solution, which has a spindle shape by electrolysis for 5 seconds under smooth plating conditions with a sulfuric acid concentration of 70 g / l, a copper concentration of 64 g / l, a liquid temperature of 48 ° C., and a current density of 20 A / dm ^2. The first fine copper particles were washed with water.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.92 to 0.96. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

  In this example, as in Example 1, an electrolytic copper foil that was not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 35 μm was used for the carrier foil. Hereinafter, the description should be made according to the order of the steps, but the flow is basically the same as that described in the first embodiment. Moreover, it can be said that the manufacturing flow based on Example 13 is employ | adopted. Therefore, step c. We will only explain

Step c. The carrier foil on which the first roughening treatment layer is formed forms an organic layer on the surface thereof. The organic layer at this time was formed by immersing the carrier foil in an aqueous solution having a carboxybenzotriazole concentration of 1000 ppm, a sulfuric acid concentration of 150 g / l, a copper concentration of 10 g / l, and a liquid temperature of 40 ° C. for 30 seconds. . Hereinafter, the completed electrolytic copper foil with carrier foil was obtained by the same process as in Example 1.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.91 to 0.96. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

  In this example, as in Example 1, an electrolytic copper foil that was not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 35 μm was used for the carrier foil. Hereinafter, the description should be made according to the order of the steps, but the flow is basically the same as that described in the first embodiment. Moreover, it can be said that the manufacturing flow based on Example 13 is employ | adopted. Therefore, the step b. We will only explain

Step b. After the pickling treatment, the carrier foil is placed in a solution having a copper concentration of 7.0 g / l, a sulfuric acid concentration of 100 g / l, a chlorine concentration of 50 ppm, and a liquid temperature of 25 ° C., and is cathode-polarized to have a current density of 15 A / dm ² , electrolysis Dendritic first fine copper grains were adhered and formed on one surface of the carrier foil under the condition of time 15 seconds. That is, the cover plating for preventing the first fine copper particles from falling off in Example 13 was omitted.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.91 to 0.95. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

  In this example, as in Example 1, an electrolytic copper foil that was not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 35 μm was used for the carrier foil. Hereinafter, the description should be made according to the order of the steps, but the flow is basically the same as that described in the first embodiment. Moreover, it can be said that the manufacturing flow based on Example 13 is employ | adopted. Therefore, the step b. And step c. We will only explain

Step b. After the pickling treatment, the carrier foil is placed in a solution having a copper concentration of 7.0 g / l, a sulfuric acid concentration of 100 g / l, a chlorine concentration of 50 ppm, and a liquid temperature of 25 ° C., and is cathode-polarized to have a current density of 15 A / dm ² , Dendritic first fine copper grains were adhered and formed on one surface of the carrier foil under the condition of time 15 seconds. That is, the covering plating for preventing the first fine copper particles from falling off in Example 13 was omitted.

Step c. The carrier foil on which the first roughening treatment layer is formed forms an organic layer on the surface thereof. The organic layer at this time was formed by immersing the carrier foil in an aqueous solution having a carboxybenzotriazole concentration of 1000 ppm, a sulfuric acid concentration of 150 g / l, a copper concentration of 10 g / l, and a liquid temperature of 40 ° C. for 30 seconds. . Hereinafter, the completed electrolytic copper foil with carrier foil was obtained by the same process as in Example 1.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.91 to 0.96. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

  In the present embodiment, the same manufacturing flow as in the second embodiment is basically employed, but the process c. After forming the organic layer of step d. In this case, a nickel thin film layer is formed on the surface of the organic layer as an additional step before forming the bulk copper layer. Therefore, in order to avoid redundant description, only the formation of a thin film layer, which is an additional step not in Example 2, will be described.

Step c. Using nickel sulfate as the nickel plating solution on the surface on which the organic layer was formed with the conditions of nickel concentration 60 g / l, boric acid concentration 30 g / l, liquid temperature 30 ° C., pH 3, and current density 5 A / dm ² Then, a thin film layer was formed. Hereinafter, the completed electrolytic copper foil with carrier foil was obtained by the same process as in Example 1.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. As a result, it was possible to form a beautiful via hole with little variation in the roundness range of 0.96 to 0.99. Further, the surface of the electrolytic copper foil from which the carrier foil has been peeled is present in a state where the first fine copper particles constituting the first roughening treatment layer are considered to be torn off, and the first fine copper particles are also present on the carrier foil. The torn residue remained. In addition, the organic layer 5 after receiving the hot press processing was in a void shape that can be confirmed in the secondary electron beam image shown in FIG.

Comparative Example 1

  In this comparative example, the same process as in Example 1 is adopted, and the process b. The electrolytic copper foil with a normal carrier foil was manufactured by omitting. Therefore, detailed description regarding each step is omitted to avoid redundant description. In the case of this copper foil with carrier foil, the organic layer itself functions as a release layer when the carrier foil is peeled off. The following evaluation was performed using the electrolytic copper foil with a carrier foil thus obtained.

Laser Workability Evaluation And laser workability was evaluated in the same manner as in Example 1. Then, the via hole shape could not be formed at all with a processing energy of 20 mJ, and could only be slightly processed with a processing energy of 30 mJ. Therefore, the roundness could not be observed at all. In the case of the copper foil with carrier foil according to Comparative Example 2, when the copper foil is processed into a copper foil and the carrier foil is peeled off, the organic layer functions as a release layer, and the first roughening treatment layer does not exist. Therefore, the surface of the electrolytic copper foil layer is a completely glossy surface.

  The electrolytic copper foil with a carrier foil according to the present invention has a stable laser drilling performance and good adhesion to an etching resist as never before, so the processing cost of a printed wiring board with a fine wiring circuit This makes it possible to supply inexpensive and high-quality products to the market. In addition, the method for producing an electrolytic copper foil with a carrier foil according to the present invention enables the production of the electrolytic copper foil with a carrier foil having very high process stability and little quality variation. Therefore, stable supply to the market of high-quality electrolytic copper foil with a carrier foil as a basic material of a printed wiring board is enabled.

The schematic cross section showing the layer constitution of the electrolytic copper foil with carrier foil according to the present invention. The schematic cross section showing the typical peeling state when the carrier foil of the electrolytic copper foil with carrier foil according to the present invention is peeled off. The scanning ion microscope image which looked at the state which the 1st fine copper grain digged into the bulk copper layer from the section. The scanning ion microscope image of the surface of the bulk copper layer after peeling off carrier foil, and the observation image from the 45 degrees diagonal direction by a scanning electron microscope. The schematic diagram showing the basic manufacturing flow of the electrolytic copper foil with carrier foil which concerns on this invention. The schematic diagram showing the basic manufacturing flow of the electrolytic copper foil with carrier foil which concerns on this invention. The observation by the secondary electron beam image of the void shape which generate | occur | produced in the organic layer after hot-pressing using the electrolytic copper foil with a carrier foil which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrolytic copper foil with carrier foil 2 Carrier foil 3 1st roughening process layer 4 1st fine copper grain 5 Organic layer 6 Bulk copper layer 7 2nd roughening process layer 8 2nd fine copper grain 9 First fine copper grain of Fragment 10 Residual organic layer 11 Void shape

Claims (12)

Provided with a first roughening treatment layer with first fine copper grains on one side of the carrier foil, with an organic layer on the first roughening treatment, with a bulk copper layer formed by electrolytic method on the organic layer, In the electrolytic copper foil with a peelable type carrier foil provided with a surface treatment layer such as a second roughening treatment layer and a rust prevention treatment on the bulk copper layer, if necessary,
The first fine copper grains constituting the first roughened layer are embedded in the bulk copper layer together with the organic layer. When the carrier foil and the bulk copper layer are peeled off, all or one of the first fine copper grains is removed. Electrolytic copper foil with carrier foil, characterized in that the portion is torn off and remains attached to the surface on the bulk copper layer side. 2. The electrolytic copper foil with a carrier foil according to claim 1, further comprising a thin film metal layer made of nickel, cobalt, or an alloy thereof between the organic layer and the bulk copper layer. 3. The electrolytic copper foil with carrier foil according to claim 1, wherein the first fine copper grains constituting the first roughening treatment layer are substantially spindle-shaped or dendritic. The electrolytic copper foil with a carrier foil according to any one of claims 1 to 3, wherein the first fine copper grains constituting the first roughening treatment layer are high carbon-containing copper. The carrier foil is a copper foil. The electrolytic copper foil with a carrier foil according to any one of claims 1 to 4. The electrolytic copper foil with carrier foil according to any one of claims 1 to 5, wherein the organic layer is a mixture of an organic agent and copper particles. It is a manufacturing method of the electrolytic copper foil with a carrier foil in any one of Claims 1-6, Comprising: At least the following a. ~ E. A method for producing an electrolytic copper foil with a carrier foil, comprising the steps shown in FIG.
a. A cleaning process to clean the surface of the carrier foil.
b. A first roughening step in which the carrier foil is cathode-polarized in a copper sulfate-based electrolyte, and first fine copper particles are adhered and formed on one surface to form a first roughening treatment layer.
c. An organic layer forming step of forming an organic layer on the surface of the first roughening treatment layer.
d. A bulk copper layer forming step of forming a bulk copper layer by an electrolytic reaction using a copper electrolyte on the surface of the organic layer.
e. The carrier foil that has been subjected to the above-described process is cathodically polarized in a copper sulfate-based electrolyte as necessary, and second fine copper particles are formed on the surface of the bulk copper layer to form a second roughened layer. Second roughening process Step b. The copper sulfate-based solution used in the first roughening step is a copper sulfate solution having a copper concentration of 1 g / l to 20 g / l, containing 200 ppm or less of chlorine, 9-phenylacridine, carboxybenzotriazole, glue, The method for producing an electrolytic copper foil with a carrier foil according to claim 7, wherein any one or a combination of two or more arsenic is added. Step c. The formation of the organic layer in the organic layer forming step uses an aqueous solution containing carboxyl benzotriazole at 50 ppm to 2000 ppm, a copper concentration of 1 g / l to 20 g / l, and sulfuric acid of 50 g / l to 200 g / l. The manufacturing method of the electrolytic copper foil with a carrier foil of Claim 7 or Claim 8. Step d. The bulk layer is formed by copper electrolysis with a thickness of 0.3 μm to 2.0 μm at a low current density of 1/3 or less of the limit current density that can be smooth plated, which is determined according to the type of solution used for electrolysis, copper concentration, etc. The copper foil with a carrier foil according to any one of claims 7 to 9, wherein the copper electrolysis at a high current density exceeding 1/3 of the limit current density is performed to obtain a predetermined thickness. Manufacturing method. After the second roughening treatment step, the surface of the second roughening treatment layer is subjected to a rust prevention treatment step and / or a silane coupling treatment for adsorbing and stabilizing the silane coupling agent. The manufacturing method of the electrolytic copper foil with a carrier foil in any one of Claims 7-10 provided with the process. A copper-clad laminate obtained using the electrolytic copper foil with a carrier foil according to any one of claims 1 to 6,
The copper clad laminated board characterized by the organic layer located between the 1st roughening process layer of one side of carrier foil, and a bulk copper layer having a void shape.