TWI461576B - Ultra thin copper foil with very low profile copper foil as carrier and its manufacturing method - Google Patents

Description

Ultra-thin copper foil with ultra-low ridge copper foil as carrier and manufacturing method thereof

The invention relates to an ultra-thin copper foil with ultra-low ridge copper foil as a carrier, and more specifically, is composed of a carrier foil, a peeling layer and an ultra-thin copper foil, and is applied to a printed circuit board of high density and fine lines, A substrate such as a multilayer printed circuit board or a flip chip.

The ultra-thin copper foil with carrier is used in the field of electronics industry as a printed circuit board assembly for high-density and fine-line applications. Today, it is light, thin, short, and small, and the precision requirements for circuit lines are also With the trend toward precision, the demand for thinning of copper foil is also increasing. In the current ultra-thin copper foil with a carrier, a carrier (copper foil or aluminum foil) having a thickness of 18 to 35 μm is generally used, and then a very thin electrolytic copper foil having a thickness of 1 to 6 μm is attached via electroplating.

With the high density of various electronic components, the combination of circuit boards and their circuit patterns must be high-density. For example, printed circuit boards used for packaging, the line width and line spacing between circuits need to be high density and fineness of about 30 μm. In the circuit, if the electrolytic copper foil used is thick, the etching time is increased. As a result, the verticality of the side of the circuit pattern is broken, and the circuit having a wide line distance is not generated, but A narrower circuit can cause problems with short circuits or broken wires.

The peeling layer between the carrier foil and the ultra-thin copper foil is usually an organic nitrogen-containing organic compound or an inorganic chromium metal or chromate ternary alloy inorganic film layer. The use of organic organic peeling film defects, not only the plating solution and wastewater discharge treatment, increases the cost and time of processing, and in the high-temperature circuit board process will generate bubbles, causing the manufacturing quality of the circuit board and the electrical test Stability issue. On the other hand, the release film layer is composed of an inorganic two-component alloy, and the film thickness ratio is an important factor for controlling the bonding strength between the carrier foil and the ultra-thin copper foil. When the ratio of the two is poorly controlled, it is easy to have incomplete peeling or It is easily peeled off and causes oxidative discoloration and other defects after the platen.

The ultra-thin copper foil for the fine circuit pattern is formed by directly depositing a peeling layer on the carrier foil, and the optimum thickness is 5 μm or less. Since the surface pattern of the carrier foil directly affects the peeling layer and the ultra-thin copper foil layer, when the surface roughness of the carrier is too high, the ultra-thin copper foil which is subsequently plated is also likely to have a high thickness, thereby affecting the etching property. In addition, when the surface pattern of the carrier foil is not uniform, the thickness uniformity of the ultra-thin copper foil is also affected. At the same time, when the carrier foil has pinholes, the ultra-thin copper foil also has pinholes. Since the carrier foil is the basis of the subsequent release layer and the ultra-thin copper foil, the selection of the carrier copper foil is quite important. The invention used in the past mainly uses a conventional HTE (High Temperature Elongation) copper foil or a rolled copper foil as a carrier copper foil, but the use of the HTE copper foil tends to have problems such as poor surface uniformity and pinholes. On the other hand, the use of rolled copper foil limits the usability of the product due to problems such as width and cost.

In addition, the matte surface of the ultra-thin copper foil is thermocompression bonded to the epoxy resin substrate, and the roughening treatment of the ultra-thin copper foil pressing surface, the anti-rust treatment, and the decane coating treatment are all The adhesion of the substrate is closely related, which obviously affects the quality of the product.

In view of the above-mentioned current ultra-thin copper foil with carrier, the inventors have found that the ultra-low ridge copper foil is used as the carrier, the quaternary alloy peeling layer, and the ultra-thin copper foil after years of work experience and research. An ultra-thin copper foil with an ultra-low ridge copper foil as a carrier is as shown in Fig. 1. The carrier layer uses the ultra-low ridge copper foil of South Asia, which has the characteristics of uniform surface type, smooth surface roughness and no pinhole. In terms of the release layer, the release layer affects the bond strength between the carrier foil and the ultra-thin copper foil. When the release layer is composed of quaternary alloys of molybdenum, nickel, chromium and potassium, it is better than the binary alloy. The anti-oxidation property and the etching property, while at a high temperature and hot pressing environment, the carrier foil and the ultra-thin copper foil still have excellent peeling characteristics, which is an important characteristic of the invention.

1‧‧‧very thin copper foil

2‧‧‧ peeling layer

3‧‧‧Carrier foil

4‧‧‧Etching line type

5‧‧‧ Etching substrate type

Figure 1 is a description of the structure of the copper foil.

Figure 2 shows the Etching line type.

Figure 3 shows the adhesion of the carrier foil to the very thin copper foil applied to different substrates.

The object of the present invention is to provide an ultra-thin copper foil with ultra-low ridge copper foil as a carrier, the ultra-thin copper foil has good oxidation resistance and etching characteristics, and is heated at a high temperature. The download body foil and ultra-thin copper foil still have excellent peeling properties, while the carrier copper foil has a uniform thickness and a very small number of pinholes.

A metal carrier foil generally having a carrier-attached ultra-thin copper foil, such as aluminum foil, copper foil, titanium foil, stainless steel foil, etc., the carrier foil of which is excellent in surface flatness, and has a thickness of 12-70 μm, preferably 18 to 35 μm, carrier foil gloss surface roughness (Surface Roughness; refers to the ten point average roughness value Rz, and in μm) is 1.5 μm or less.

The carrier layer foil which is the basis of the peeling layer and the ultra-thin copper foil is an ultra-low ridge copper foil (VLP copper foil), which is characterized in that the two sides have a bright characteristic, the thickness is low, the thickness is uniform and there is no pinhole. These characteristics are useful for subsequent release layers and very thin copper foils. However, it should be emphasized that, based on the fine peeling layer and the ultra-thin copper foil layer formulation mentioned in the following patent, the ultra-thin copper with the carrier copper foil attached to this patent is used regardless of the type or thickness of the carrier copper foil. The basic characteristics of the foil (such as peeling characteristics, etching characteristics, and high temperature resistance characteristics) are not significantly deteriorated. However, if an excellent VLP copper foil is used, the overall characteristics of the ultra-thin copper foil with the carrier copper foil are improved.

The invention is used as a peeling layer of the structure of the carrier foil and the ultra-thin copper foil, and is an important plating layer which has the greatest influence on the bonding force. When the bonding strength of the peeling layer is too strong, the peeling layer cannot be peeled off, and if it is too weak, the foil and the electrode are pressed at a high temperature. The thin copper foil is easy to separate, causing problems such as oxidative discoloration of the shiny surface of the extremely thin copper foil. How to effectively control the uniformity and thickness of the peeling layer is an important subject that must be overcome at present. In order to overcome the above-mentioned drawbacks, it has been found by the inventors one by one that when the peeling layer is composed of a metal such as molybdenum, nickel, chromium, potassium or the like which is plated with a quaternary alloy having a peeling property, the above-mentioned deficiency can be overcome and the object of the present invention can be attained.

The ultra-thin copper foil of the invention is formed by first using a copper pyrophosphate plating bath of PH=6~10, and then plating a metal carrier foil with a copper sulfate electroplating bath of pH=1~12, which is electroplated to form a coke on the peeling layer. The copper phosphate layer acts as a barrier layer for the release layer to protect the release layer from being washed away by the copper sulfate plating bath, affecting the formation of the subsequent ultra-thin copper foil and the change in peel strength. Then, a very thin copper foil thickness of 1 to 6 μm is formed in the copper sulfate plating bath. In the following, in order to enable the review committee to further understand the technical features, it is proposed to have examples to support the contents of the invention.

According to the invention, the copper foil with excellent flatness is made into a carrier foil and the concentration of nickel sulfate hexahydrate is 10~50g/L, and the concentration of sodium dihydrate molybdate is 0.5~10g/L, K ₄ P ₂ O ₇ : 50 ~ 100g / L, CrO 3: 0.5 ~ 2g / L in the plating bath in a plating peeling layer is formed, and then the release layer was applied on the _{Cu 2 P 2 O 7 .3H 2} O: 10 ~ 60g / L, K ₄ P ₂ O ₇ : 100~400g/L bath electroplating as a protective layer, and then electroplating with copper concentration: 50~100g/L, sulfuric acid: 90~125 g/L to become ultra-thin copper foil of 3μm or less .

In order to obtain a stronger peeling strength between the surface of the ultra-thin copper foil and the substrate, the surface of the ultra-thin copper foil of the present invention is subjected to roughening treatment, and zinc and nickel having anti-rust and heat-resistance effects are attached to the roughened surface. Metals and chromates, in order to improve the peel strength of the ultra-thin copper foil and the substrate, coated with decane to improve the peel strength.

[Example 1]

1. The surface roughness (Surface Roughness: refers to the ten-point average roughness value Rz and in μm) of 1.5 μm or less, and the South Asian VLP copper foil with excellent flatness and thickness of 18 μm is used as the carrier foil.

2. Place nickel sulfate hexahydrate: 10~50g/L, sodium dihydrate molybdate: 0.5~10g/L, K ₄ P ₂ O ₇ : 50~100g/L, CrO ₃ : 0.5~2g/L , PH: 6~10, bath temperature: 10~50°C, current density: 6~15A/dm ² , electrification time: 20 seconds of electroplating bath made of molybdenum, nickel, chromium and potassium quaternary alloys , nickel, chromium, potassium alloy peeling layer.

3. Next, apply Cu ₂ P ₂ O ₇ over the release layer. 3H ₂ O: 10~60g/L, K ₄ P ₂ O ₇ : 100~400g/L, PH: 6~10, bath temperature: 10~60°C, current density: 1~5A/dm ² , power-on time: The 15 second plating was used as a peeling layer protective layer.

4. Further copper concentration: 50~100g/L, sulfuric acid: 90~125g/L, bath temperature: 40~70°C, current density: 25A/dm ² , energization time: 20 seconds, electroplating becomes extremely thin with thickness of 3μm Copper foil.

5. Re-use the conventional roughening treatment technology to perform copper particle treatment on the mat surface, and then apply galvanizing and chromate anti-rust treatment and coating decane to obtain ultra-low ridge copper foil as carrier. The ultra-thin copper foil has been tested and its carrier foil and ultra-thin copper foil cannot be peeled off.

[Example 2]

1. The surface roughness (Surface Roughness: refers to the ten-point average roughness value Rz and in μm) of 1.5 μm or less, and the South Asian VLP copper foil with excellent flatness and thickness of 18 μm is used as the carrier foil.

2. Place nickel sulfate hexahydrate: 10~50g/L, sodium dihydrate molybdate: 0.5~10g/L, K ₄ P ₂ O ₇ : 50~100g/L, CrO ₃ : 0.5~2g/L , PH: 6~10, bath temperature: 10~50°C, current density: 1~2.5A/dm ² , electrification time: 20 seconds of electroplating bath of molybdenum, nickel, chromium and potassium quaternary alloy Molybdenum, nickel, chromium, potassium alloy release layer.

3. Next, apply Cu ₂ P ₂ O ₇ .3H ₂ O: 10~60g/L, K ₄ P ₂ O ₇ : 100~400g/L, PH: 6~10, bath temperature: 10~ above the peeling layer. 60 ° C, current density: 1 ~ 5A / dm ² , power-on time: 15 seconds of plating as a peeling layer protective layer.

4. Further copper concentration: 50~100g/L, sulfuric acid: 90~125g/L, bath temperature: 40~70°C, current density: 25A/dm ² , energization time: 20 seconds, electroplating becomes extremely thin with thickness of 3μm Copper foil.

5. Re-use the conventional roughening treatment technology to perform copper particle treatment on the mat surface, and then apply galvanizing and chromate anti-rust treatment and coating decane to obtain ultra-low ridge copper foil as carrier. The ultra-thin copper foil has been tested and its carrier foil has almost no bonding force with the ultra-thin copper foil.

[Example 3]

1. The surface roughness (Surface Roughness: refers to the ten-point average roughness value Rz and in μm) of 1.5 μm or less, and the South Asian VLP copper foil with excellent flatness and thickness of 18 μm is used as the carrier foil.

2. Place nickel sulfate hexahydrate: 10~50g/L, sodium dihydrate molybdate: 0.5~10g/L, K ₄ P ₂ O ₇ : 50~100g/L, CrO ₃ : 0.5~2g/L , PH: 6~10, bath temperature: 10~50°C, current density: 2.5~6A/dm ² , electrification time: 20 seconds of electroplating bath made of molybdenum, nickel, chromium and potassium quaternary alloys , nickel, chromium, potassium alloy peeling layer.

3. Next, apply Cu ₂ P ₂ O ₇ .3H ₂ O: 10~60g/L, K ₄ P ₂ O ₇ : 100~400g/L, PH: 6~10, bath temperature: 10~ above the peeling layer. 60 ° C, current density: 1 ~ 5A / dm ² , power-on time: 15 seconds of plating as a peeling layer protective layer.

4. Further copper concentration: 50~100g/L, sulfuric acid: 90~125g/L, bath temperature: 40~70°C, current density: 25A/dm ² , energization time: 20 seconds, electroplating becomes extremely thin with thickness of 3μm Copper foil.

5. Re-use the conventional roughening treatment technology to perform copper particle treatment on the mat surface, and then apply galvanizing and chromate anti-rust treatment and coating decane to obtain ultra-low ridge copper foil as carrier. Extremely thin copper foil. The binding force between the carrier foil and the ultra-thin copper foil was measured to be 2.87 g/cm by a tensile tester manufactured by Shimadzu Corporation, Japan.

[Comparative Example 1]

1. A South Asian VLP copper foil having a smooth surface roughness (Surface Roughness: ten point average roughness value Rz and in μm) of 1.5 μm or less and a flatness excellent thickness of 18 μm is used as a carrier foil.

2. Place nickel sulfate hexahydrate: 10~50g/L, sodium dihydrate molybdate: 0.5~10g/L, K ₄ P ₂ O ₇ : 50~100g/L, PH: 6~10, bath temperature : 10~50 °C, current density: 2.5~6A/dm ² , electrification time: 20 seconds of molybdenum, nickel, potassium ternary alloy plating bath made of molybdenum, nickel, potassium alloy peeling layer.

3. Next, apply Cu ₂ P ₂ O ₇ .3H ₂ O: 10~60g/L, K ₄ P ₂ O ₇ : 100~400g/L, PH: 6~10, bath temperature: 10~ above the peeling layer. 60 ° C, current density: 1 ~ 5A / dm ² , power-on time: 15 seconds of plating as a peeling layer protective layer.

4. Further copper concentration: 50~100g/L, sulfuric acid: 90~125g/L, bath temperature: 40~70°C, current density: 25A/dm ² , energization time: 20 seconds, electroplating becomes extremely thin with thickness of 3μm Copper foil.

5. Re-use the conventional roughening treatment technology to perform copper particle treatment on the mat surface, and then apply galvanizing and chromate anti-rust treatment and coating decane to obtain ultra-low ridge copper foil as carrier. The extremely thin copper foil was measured by a tensile tester manufactured by Shimadzu Co., Ltd., Japan, and the binding force between the carrier foil and the ultra-thin copper foil was 5.40 g/cm.

[Comparative Example 2]

1. A South Asian VLP copper foil having a smooth surface roughness (Surface Roughness: ten point average roughness value Rz and in μm) of 1.5 μm or less and a flatness excellent thickness of 18 μm is used as a carrier foil.

2. Inserted sodium dihydrate molybdate: 0.5~10g/L, K ₄ P ₂ O ₇ : 50~100g/L, CrO ₃ : 0.5~2g/L, PH: 6~10, bath temperature: 10~ 50 ° C, current density: 2.5 ~ 6A / dm ² , electrification time: 20 seconds of molybdenum, potassium, chromium ternary alloy plating bath in the plating bath with molybdenum, potassium, chromium alloy peeling layer.

3. Next, apply Cu ₂ P ₂ O ₇ .3H ₂ O: 10~60g/L, K ₄ P ₂ O ₇ : 100~400g/L, PH: 6~10, bath temperature: 10~ above the peeling layer. 60 ° C, current density: 1 ~ 5A / dm ² , power-on time: 15 seconds of plating as a peeling layer protective layer.

4. Further copper concentration: 50~100g/L, sulfuric acid: 90~125g/L, bath temperature: 40~70°C, current density: 25A/dm ² , energization time: 20 seconds, electroplating becomes extremely thin with thickness of 3μm Copper foil.

5. Re-use the conventional roughening treatment technology to perform copper particle treatment on the mat surface, and then apply galvanizing and chromate anti-rust treatment and coating decane to obtain ultra-low ridge copper foil as carrier. Extremely thin copper foil. The carrier foil and the ultra-thin copper foil were tested to be incapable of being peeled off.

[Comparative Example 3]

1. A South Asian VLP copper foil having a smooth surface roughness (Surface Roughness: ten point average roughness value Rz and in μm) of 1.5 μm or less and a flatness excellent thickness of 18 μm is used as a carrier foil.

2. Place nickel sulfate hexahydrate: 10~50g/L, K ₄ P ₂ O ₇ : 50~100g/L, CrO ₃ : 0.5~2g/L, PH: 6~10, bath temperature: 10~50 °C, current density: 2.5~6A/dm ² , energization time: 20 seconds nickel, potassium, chromium ternary alloy plating bath made of nickel, potassium, chromium alloy peeling layer.

3. Next, apply Cu ₂ P ₂ O ₇ .3H ₂ O: 10~60g/L, K ₄ P ₂ O ₇ : 100~400g/L, PH: 6~10, bath temperature: 10~ above the peeling layer. 60 ° C, current density: 1 ~ 5A / dm ² , power-on time: 15 seconds of plating as a peeling layer protective layer.

4. Further copper concentration: 50~100g/L, sulfuric acid: 90~125g/L, bath temperature: 40~70°C, current density: 25A/dm ² , energization time: 20 seconds, electroplating becomes extremely thin with thickness of 3μm Copper foil.

5. Re-use the conventional roughening treatment technology to perform copper particle treatment on the mat surface, and then apply galvanizing and chromate anti-rust treatment and coating decane to obtain ultra-low ridge copper foil as carrier. The ultra-thin copper foil has been tested and its carrier foil and ultra-thin copper foil cannot be peeled off.

[Comparative Example 4]

1. A South Asian VLP copper foil having a smooth surface roughness (Surface Roughness: ten point average roughness value Rz and in μm) of 1.5 μm or less and a flatness excellent thickness of 18 μm is used as a carrier foil.

2. Place nickel sulfate hexahydrate: 10~50g/L, sodium dihydrate molybdate: 0.5~10g/L, CrO ₃ : 0.5~2g/L, PH: 6~10, bath temperature: 10~50 °C, current density: 2.5~6A/dm ² , energization time: 20 seconds of nickel, molybdenum, chromium ternary alloy plating bath made of nickel, molybdenum, chromium alloy peeling layer.

3. Next, apply Cu ₂ P ₂ O ₇ .3H ₂ O: 10~60g/L, K ₄ P ₂ O ₇ : 100~400g/L, PH: 6~10, bath temperature: 10~ above the peeling layer. 60 ° C, current density: 1 ~ 5A / dm ² , power-on time: 15 seconds of plating as a peeling layer protective layer.

4. Further copper concentration: 50~100g/L, sulfuric acid: 90~125g/L, bath temperature: 40~70°C, current density: 25A/dm ² , energization time: 20 seconds, electroplating becomes extremely thin with thickness of 3μm Copper foil.

5. Re-use the conventional roughening treatment technology to perform copper particle treatment on the mat surface, and then apply galvanizing and chromate anti-rust treatment and coating decane to obtain ultra-low ridge copper foil as carrier. Extremely thin copper foil. The bonding force between the carrier foil and the ultra-thin copper foil was measured to be 11.45 g/cm by a tensile tester manufactured by Shimadzu Corporation of Japan.

[Comparative Example 5]

1. A South Asian VLP copper foil having a smooth surface roughness (Surface Roughness: ten point average roughness value Rz and in μm) of 1.5 μm or less and a flatness excellent thickness of 18 μm is used as a carrier foil.

2. Place nickel sulfate hexahydrate: 10~50g/L, sodium dihydrate molybdate: 0.5~10g/L, CrO ₃ : 0.5~2g/L, sodium citrate: 100~350g/L, PH: 6~10, bath temperature: 10~50°C, current density: 2.5~6A/dm ² , energization time: 20 seconds of nickel, molybdenum, chromium, sodium quaternary alloy plating bath made of nickel, molybdenum, chromium , sodium alloy release layer.

3. Next, apply Cu ₂ P ₂ O ₇ .3H ₂ O: 10~60g/L, K ₄ P ₂ O ₇ : 100~400g/L, PH: 6~10, bath temperature: 10~ above the peeling layer. 60 ° C, current density: 1 ~ 5A / dm ² , power-on time: 15 seconds of plating as a peeling layer protective layer.

4. Further copper concentration: 50~100g/L, sulfuric acid: 90~125g/L, bath temperature: 40~70°C, current density: 25A/dm ² , energization time: 20 seconds, electroplating becomes extremely thin with thickness of 3μm Copper foil.

5. Re-use the conventional roughening treatment technology to perform copper particle treatment on the mat surface, and then apply galvanizing and chromate anti-rust treatment and coating decane to obtain ultra-low ridge copper foil as carrier. Extremely thin copper foil. The carrier foil and the ultra-thin copper foil were tested to be incapable of being peeled off.

[Comparative Example 6]

1. The surface roughness (Surface Roughness: refers to the ten-point average roughness value Rz, and in μm) of 1.5 μm or less, and the South Asian HTE copper foil with excellent flatness and thickness of 18 μm is used as the carrier foil.

2. Place nickel sulfate hexahydrate: 10~50g/L, sodium dihydrate molybdate: 0.5~10g/L, K ₄ P ₂ O ₇ : 50~100g/L, CrO ₃ : 0.5~2g/L , PH: 6~10, bath temperature: 10~50°C, current density: 2.5~6A/dm ² , electrification time: 20 seconds of electroplating bath made of molybdenum, nickel, chromium and potassium quaternary alloys , nickel, chromium, potassium alloy peeling layer.

3. Next, apply Cu ₂ P ₂ O ₇ .3H ₂ O: 10~60g/L, K ₄ P ₂ O ₇ : 100~400g/L, PH: 6~10, bath temperature: 10~ above the peeling layer. 60 ° C, current density: 1 ~ 5A / dm ² , power-on time: 15 seconds of plating as a peeling layer protective layer.

4. Further copper concentration: 50~100g/L, sulfuric acid: 90~125g/L, bath temperature: 40~70°C, current density: 25A/dm ² , energization time: 20 seconds, electroplating becomes extremely thin with thickness of 3μm Copper foil.

5. Re-use the conventional roughening treatment technology to perform copper particle treatment on the mat surface, and then apply galvanizing and chromate anti-rust treatment and coating decane to obtain ultra-low ridge copper foil as carrier. Extremely thin copper foil. The bonding strength between the carrier foil and the ultra-thin copper foil was measured to be 10.8 g/cm by a tensile tester manufactured by Shimadzu Corporation, Japan.

From the above examples, comparative examples and Table 1, in Example 1, the plating current density of the quaternary alloy was increased, and the carrier bonding force was too strong to be peeled off. On the contrary, reducing the plating current density of the quaternary alloy weakens the carrier bonding force, resulting in almost no adhesion between the carrier foil and the ultra-thin copper foil, as in Example 2. The carrier bonding force of 5.50 g/cm of the ultra-thin copper foil with the ultra-low ridge copper foil as the carrier of Comparative Example 1 was quite close to 2.87 g/cm of Example 3, and there was no problem of peelability between the carrier foil and the ultra-thin copper foil. However, the extremely thin copper foil of Comparative Example 1 has insufficient anti-oxidation ability on the shiny side, and is slightly oxidized. Elephant.

The ultra-thin copper foil carrier with the ultra-low ridge copper foil as the carrier of Comparative Example 4 has a high bonding force, and there is no problem of peeling property between the carrier foil and the ultra-thin copper foil, but the quaternary alloy plating solution has turbid precipitation. The phenomenon of plating solution management and wastewater discharge will increase the processing time and cost. Although the metals forming the release layers of Comparative Example 1 and Comparative Example 4 all had peeling characteristics, they were insufficient in oxidation resistance and turbid precipitation of the plating solution, and were not optimally selected.

The metals forming the release layer of the other Comparative Examples 2, 3, and 5 all had a problem that the carrier bonding force was too strong to be smoothly peeled off from the extremely thin copper foil. The ultra-thin copper foil with the ultra-low ridge copper foil as the carrier of the quaternary alloy has low carrier bonding force, and there is no problem of peeling property between the carrier foil and the ultra-thin copper foil, compared with the comparative example 1 to the comparative example 5. The quaternary alloy of the third embodiment has the problems of low carrier binding force, no pinhole, no turbid sedimentation of the plating solution and waste water discharge, so the metal forming the quaternary alloy is indispensable. The carrier foil of the ultra-thin copper foil with the ultra-low ridge copper foil as the carrier of the present invention has low bonding force with the ultra-thin copper foil, and the technical scheme of forming the quaternary alloy combination of the peeling layer is not found in the prior art, and belongs to the first technology.

The ultra-thin copper foil with ultra-low ridge copper foil as the carrier of the embodiment of the invention has excellent environmental tolerance, low carrier peeling strength, high temperature resistance, moisture resistance, acid resistance and alkali resistance, and high temperature hot pressing. The environmentally-friendly body foil and the ultra-thin copper foil still have excellent peeling characteristics, for example, high-temperature thermocompression bonding with a resin substrate, peeling off the carrier foil after pressing, and observing the glossy surface of the ultra-thin copper foil without oxidative discoloration, enduring the environment The performance is quite excellent; the normal temperature bonding performance is also excellent as shown in Table 1; it is thermocompression bonded with various high glass transition temperature substrates, and the bonding strength between the carrier foil and the ultra-thin copper foil after pressing is also excellent. As shown in Fig. 2 and Fig. 3, it can be seen that the carrier foil has a good bonding force with the ultra-thin copper foil.

Note: BT = Mitsubishi Gas Company Resin, Bismelaimide Triazene, Bisuccinimide - Triazabenzene resin, trade name BT.

NPG180IA = South Asia company halogen-free resin, glass transition temperature (Tg) 180 ° C, trade name NPG180IA.

NP180 = South Asian company halogen resin, glass transition temperature (Tg) 180 ° C, trade name NP180.

The ultra-thin copper foil with the ultra-low ridge copper foil as the carrier of the present invention has excellent etching characteristics and environmental resistance, and has excellent etching characteristics, and the verticality of the side pattern of the circuit pattern after etching is good, and the circuit pattern is good. There is no residue on the lower edge of the side sill, and there is no problem such as short circuit or disconnection. This feature contributes to the electrical reliability and quality stability of printed circuit boards. See Figure 2 for details.

1‧‧‧Carrier foil

2‧‧‧ peeling layer

3‧‧‧very thin copper foil

Claims (1)

A method for manufacturing an ultra-thin copper foil with a carrier, comprising: (1) taking an ultra-low ridgeline (VLP) copper foil having a gloss surface roughness of 1.5 μm or less and a thickness of 12 to 70 μm as a carrier foil; (2) The carrier foil of the step (1) is placed in a bath of a plating bath composed of the following components a to d and having a pH of 6 to 10, and the plating of the molybdenum-nickel-chromium-potassium quaternary alloy peeling layer is applied at the bath temperature. :0~50°C, current density: 2.5~6A/dm ² and energization time: under the plating condition of 20 seconds, the carrier foil is plated with a quaternary alloy peeling layer with an adsorption amount of 0.05-60 mg/dm ² :a Nickel sulfate hexahydrate: 10~50g/L, b. Naphthyl molybdate dihydrate: 0.5~10g/L, c. K ₄ P ₂ O ₇ : 50~100g/L, d. CrO ₃ :0.5~ 2g/L; (3) using pyrophosphate composed of Cu ₂ P ₂ O ₇ .3H ₂ O: 10~60g/L and K ₄ P ₂ O ₇ : 100~400g/L and having a pH of 6~10 The copper plating bath is applied to the quaternary alloy peeling layer of the carrier foil of the step (2) under the plating conditions of bath temperature: 10 to 60 ° C, current density: 1 to 5 A/dm ² and energization time: 15 seconds. The peeling layer protective layer is electroplated, and the quaternary alloy peeling layer is plated with a peeling layer protective layer; (4) reused with copper : 50 ~ 100g / L and a sulfuric acid concentration: 90 ~ 125g / L configuration and copper sulfate plating bath PH value between 1 to 12, at a bath temperature: 40 ~ 70 ℃, current density: 10 ~ 50A / dm ^2, and energization Time: Under 20 seconds of plating conditions, the peeling protective layer of the carrier foil which completed the step (3) was subjected to ultra-thin copper foil plating, and the peeling protective layer was plated with an extremely thin copper foil having a thickness of 1 to 6 μm.