KR102015838B1 - Copper foil with carrier - Google Patents

Abstract

The copper foil with a carrier suitable for fine pitch formation is provided. Copper foil with a carrier provided with a carrier, a peeling layer, an ultrathin copper layer, and a voluntary resin layer in this order, wherein the average value of Rz on the surface of the ultrathin copper layer was measured in accordance with JIS B0601-1982 with a contact roughness meter, and was determined to be 1.5. Copper foil with a carrier which is micrometer or less and whose standard deviation of Rz is 0.1 micrometer or less.

Description

Copper foil with suitcase {COPPER FOIL WITH CARRIER}

This invention relates to the copper foil with a carrier. More specifically, this invention relates to the copper foil with a carrier used as a material of a printed wiring board.

A printed wiring board is generally manufactured by adhering an insulated substrate to copper foil, making it a copper clad laminated board, and forming a conductor pattern on the copper foil surface by etching. In recent years, with the increase in the demand for miniaturization and high performance of electronic devices, high-density mounting of high-frequency components and high frequency of signals have been advanced, and the printed circuit board has been required to have finer conductor patterns (fine pitch) and higher frequency.

In response to fine pitching, copper foils having a thickness of 9 μm or less, and even 5 μm or less in recent years have been required. However, such ultra-thin copper foils have low mechanical strength and are cracked or wrinkled during manufacture of printed wiring boards. Since it is easy to carry out, the copper foil with a carrier which electrodeposited the ultra-thin copper layer through the peeling layer using the metal foil with a thickness as a carrier has emerged. After bonding the surface of an ultra-thin copper layer to an insulated substrate, and carrying out thermocompression bonding, the carrier is peeled off through a peeling layer. After forming a circuit pattern with a resist on the exposed ultrathin copper layer, a microcircuit is formed by the method (MSAP: Modified-Semi-Additive-Process) which etches away an ultrathin copper layer with the etchant of sulfuric acid-hydrogen peroxide system.

Here, about the surface of the ultra-thin copper layer of the copper foil with a carrier used as the adhesive surface with resin, the thing with sufficient peeling strength of an ultrathin copper layer and a resin base material, and the peeling strength are high temperature heating, a wet process, soldering, chemicals It is desired to be sufficiently maintained even after the treatment or the like. As a method of increasing the peeling strength between an ultra-thin copper layer and a resin base material, generally, the method of attaching a large amount of roughening particle | grains on the ultra-thin copper layer which enlarged the surface profile (unevenness | corrugation, roughness) is typical. .

However, when the ultra-thin copper layer with such a large profile (concave-convex, roughness) is used for the semiconductor package substrate which needs to form especially a fine circuit pattern among printed wiring boards, an unnecessary copper particle remains at the time of circuit etching, and a circuit pattern Problems such as poor insulation between them occur.

For this reason, in WO2004 / 005588 (Patent Document 1), as a copper foil with a carrier for fine circuit applications including a semiconductor package substrate, it has been attempted to use a copper foil with a carrier which has not been subjected to a roughening treatment on the surface of an ultrathin copper layer. . The adhesiveness (peel strength) of the ultrathin copper layer and the resin which has not been subjected to such a roughening treatment tends to be lowered compared to a general copper foil for a printed wiring board under the influence of its low profile (unevenness, roughness, roughness). Therefore, further improvement is calculated | required about the copper foil with a carrier.

Thus, Japanese Unexamined Patent Publication No. 2007-007937 (Patent Document 2) and Japanese Unexamined Patent Publication

In 2010-1006071 (Patent Document 3), forming a Ni layer or a Ni alloy layer and a chromate layer on a surface in contact with (polyadhesive) of a polyimide resin substrate of an ultrathin copper foil with a carrier. To form a Cr layer or / and Cr alloy layer, to form a Ni layer and a chromate layer, and to form a Ni layer and a Cr layer are described. By providing these surface treatment layers, the desired adhesive strength is obtained, without adjusting the adhesion strength of a polyimide-type resin substrate and the ultra-thin copper foil with a carrier, without reducing roughening process (fineness). Moreover, it also describes surface-treating with a silane coupling agent, or performing antirust process.

WO2004 / 005588 Japanese Unexamined Patent Publication No. 2007-007937 Japanese Unexamined Patent Publication No. 2010-006071

In the development of the copper foil with a carrier, the emphasis has been placed on securing the peel strength of the ultra-thin copper layer and the resin substrate until now. For this reason, the fine pitch has not been sufficiently studied yet, and there is still room for improvement. Then, this invention makes it a subject to provide the copper foil with a carrier suitable for fine pitch formation. Specifically, the object of the present invention is to provide a copper foil with a carrier capable of forming a finer wiring than L / S = 20 μm / 20 μm, which is considered to be a limit that can be formed by conventional MSAP.

In order to achieve the above object, the present inventors earnestly studied, and as a result, the surface of the ultrathin copper layer was reduced, and the finely roughened particles were formed uniformly in the surface of the ultrathin copper layer, thereby achieving a uniform and low roughness roughening surface. Found out that it becomes possible to form And it discovered that the said copper foil with a carrier was very effective for fine pitch formation.

This invention was completed based on the said knowledge, In one side, it is an ultra-thin copper foil with a carrier provided with a carrier, a peeling layer, an ultra-thin copper layer, and a voluntary resin layer in this order. The average value of Rz of the surface of a copper layer is copper foil with a carrier which is 1.5 micrometers or less measured by the contact roughness meter based on JISB0601-1982, and the standard deviation of Rz is 0.1 micrometer or less.

In another aspect, the present invention is a copper foil with a carrier provided with a carrier, a peeling layer, an ultrathin copper layer, and a voluntary resin layer in this order, wherein the average value of Rt on the surface of the ultrathin copper layer is JIS based on a contact roughness meter. It is copper foil with a carrier measured in accordance with B0601-2001 and is 2.0 micrometers or less, and the standard deviation of Rt is 0.1 micrometer or less.

In yet another aspect, the present invention is a copper foil with a carrier provided with a carrier, a peeling layer, an ultrathin copper layer, and a voluntary resin layer in this order, wherein the average value of Ra on the ultrathin copper layer surface is a contact roughness meter. It is the copper foil with a carrier measured in accordance with JIS B0601-1982 and is 0.2 micrometer or less, and the standard deviation of Ra is 0.03 micrometer or less.

In one embodiment of the copper foil with a carrier according to the present invention, the ultrathin copper layer is roughened.

This invention is another one side. WHEREIN: It is the printed wiring board manufactured using the copper foil with a carrier which concerns on this invention.

This invention is another one side. WHEREIN: It is the printed circuit board manufactured using the copper foil with a carrier which concerns on this invention.

This invention is another one side. WHEREIN: It is the copper clad laminated board manufactured using the copper foil with a carrier which concerns on this invention.

The copper foil with a carrier which concerns on this invention is suitable for fine pitch formation, For example, wiring finer than L / S = 20 micrometer / 20 micrometer which was considered the limit which can be formed by MSAP process, for example, L / S It is possible to form a fine wiring of = 15 µm / 15 µm. In particular, in the present invention, since the in-plane uniformity of the surface roughness in the ultrathin copper layer is high, the in-plane uniformity in the flash etching at the time of forming the circuit by the MSAP method becomes good, so that a yield improvement is expected.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the crumb system using a drum.
Figure 2 is a schematic diagram showing the rhythm system by the gujeoljang.
FIG. 3: shows from step A to C about the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention.
It shows from step D to F about the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention.
It shows from step G to I about the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention.
FIG. 6: shows from step J to K about the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention.

[1] The present invention is a copper foil with a carrier provided with a carrier, a peeling layer, an ultrathin copper layer, and a voluntary resin layer in this order, wherein an average value of 100 points of Rz on the surface of the ultrathin copper layer is JIS based on a contact roughness meter. It is copper foil with a carrier which is 1.4 micrometers or less measured based on B0601-1982, and the standard deviation of Rz measured at 100 points is 0.1 micrometer or less.

[2] The present invention provides the above-mentioned [1], wherein the average value of 100 points of Rt on the surface of the ultrathin copper layer is 2.0 µm or less measured in accordance with JIS B0601-2001 with a contact roughness meter and measured at 100 points. It is the copper foil with a carrier whose standard deviation of is 0.1 micrometer or less.

[3] The present invention is the above-mentioned [1], in which the average value of 100 points of Ra on the surface of the ultrathin copper layer is 0.2 µm or less measured in accordance with JIS B0601-1982 with a contact roughness meter and measured at 100 points. It is a copper foil with a carrier whose standard deviation is 0.03 µm or less.

[4] The present invention is the above-mentioned [2], wherein the average value of 100 points of Ra on the surface of the ultrathin copper layer is 0.2 µm or less measured in accordance with JIS B0601-1982 with a contact roughness meter and measured at 100 points. It is a copper foil with a carrier whose standard deviation is 0.03 µm or less.

[5] The present invention is the copper foil with a carrier according to any one of the above [1] to [4], wherein an average value of 100 points of Rz on the surface of the ultrathin copper layer is 1.3 µm or less.

[6] The present invention is the copper foil with a carrier according to any one of the above [1] to [4], wherein an average value of 100 points of Rz on the surface of the ultrathin copper layer is 1.0 µm or less.

[7] The present invention is the copper foil with a carrier according to any one of the above [1] to [4], wherein an average value of 100 points of Rz on the surface of the ultrathin copper layer is 0.5 µm or less.

[8] The present invention is a copper foil with a carrier provided with a carrier, a peeling layer, an ultrathin copper layer, and a voluntary resin layer in this order, wherein an average value of 100 points of Rz on the surface of the ultrathin copper layer is JIS based on a contact roughness meter. Copper foil with a carrier which measures 1.4 micrometers or less based on B0601-1982, and the standard deviation of Rz measured at 100 points is 0.1 micrometer or less, and satisfy | fills one or more of the following items.

1: The average value of 100 points of Rz of the surface of an ultra-thin copper layer is 1.3 micrometers or less measured in accordance with JIS B0601-1982 with a contact roughness meter.

2: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 1.2 micrometers or less measured according to JIS B0601-1982 with a contact roughness meter.

3: The average value of 100 points of Rz of the ultra-thin copper layer surface is 1.0 micrometer or less by measuring based on JIS B0601-1982 with a contact roughness meter.

4: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 0.8 micrometer or less measured by the contact roughness meter based on JISB0601-1982.

5: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 0.5 micrometer or less measured by the contact roughness meter based on JISB0601-1982.

6: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 0.01 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

7: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 0.1 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

8: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 0.3 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

9: Standard deviation of Rz measured at 100 points on the ultrathin copper layer surface is 0.068 µm or less

10: The standard deviation of Rz measured at 100 points on the surface of the ultrathin copper layer is 0.05 µm or less.

11: The standard deviation of Rz measured at 100 points on the surface of the ultrathin copper layer is 0.01 μm or more.

12: The average value of 100 points | pieces of Rt on the surface of an ultra-thin copper layer is 2.0 micrometers or less measured in accordance with JIS B0601-2001 by a contact roughness meter.

13: The average value of 100 points of Rt on the surface of an ultra-thin copper layer is 1.8 micrometers or less measured according to JIS B0601-2001 by a contact roughness meter.

14: The average value of 100 points of Rt on the surface of an ultra-thin copper layer is 1.5 micrometers or less measured according to JIS B0601-2001 with a contact roughness meter.

15: The average value of 100 points of Rt on the surface of an ultrathin copper layer is 1.3 micrometers or less measured according to JIS B0601-2001 with a contact roughness meter.

16: The average value of 100 points | pieces of Rt on the surface of an ultra-thin copper layer is 1.1 micrometers or less measured in accordance with JIS B0601-2001 by a contact roughness meter.

17: The average value of 100 points | pieces of Rt on the surface of an ultra-thin copper layer is 1.0 micrometer or less as measured based on JIS B0601-2001 with a contact roughness meter.

18: The average value of 100 points of Rt on the surface of an ultra-thin copper layer is 0.5 micrometer or more as measured based on JIS B0601-2001 with a contact roughness meter.

19: The average value of 100 points of Rt on the surface of an ultra-thin copper layer is 0.6 micrometer or more as measured based on JIS B0601-2001 with a contact roughness meter.

20: The average value of 100 points of Rt on the surface of an ultra-thin copper layer is 0.8 micrometer or more as measured based on JIS B0601-2001 with a contact roughness meter.

21: The standard deviation of Rt measured at 100 points on the surface of the ultrathin copper layer is 0.1 μm or less.

22: The standard deviation of Rt measured at 100 points on the surface of the ultrathin copper layer is 0.060 µm or less.

23: The standard deviation of Rt measured at 100 points on the surface of the ultrathin copper layer is 0.05 µm or less.

24: The standard deviation of Rt measured at 100 points on the surface of the ultrathin copper layer is 0.01 µm or more.

25: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.2 micrometer or less as measured based on JISB0601-1982 by a contact roughness meter.

26: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.18 micrometer or less measured in accordance with JIS B0601-1982 with a contact roughness meter.

27: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.15 micrometer or less measured in accordance with JIS B0601-1982 with a contact roughness meter.

28: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.01 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

29: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.05 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

30: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.12 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

31: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.13 micrometer or more by measuring in accordance with JIS B0601-1982 with a contact roughness meter.

32: The standard deviation of Ra measured at 100 points on the ultrathin copper layer surface is 0.03 µm or less.

33: The standard deviation of Ra measured at 100 points on the surface of the ultrathin copper layer is 0.026 µm or less.

34: The standard deviation of Ra measured at 100 points on the ultrathin copper layer surface is 0.02 µm or less.

35: The standard deviation of Ra measured at 100 points on the ultrathin copper layer surface is 0.001 µm or more .

[9] The present invention is a copper foil with a carrier provided with a carrier, a peeling layer, an ultrathin copper layer, and a voluntary resin layer in this order, wherein an average value of 100 points of Rt on the surface of the ultrathin copper layer is JIS based on a contact roughness meter. It is copper foil with a carrier which is 1.8 micrometers or less measured based on B0601-2001, and the standard deviation of Rt measured at 100 points is 0.1 micrometer or less.

[10] The present invention is the aforementioned [9], wherein the average value of 100 points of Rz on the surface of the ultrathin copper layer is 1.5 µm or less measured in accordance with JIS B0601-1982 with a contact roughness meter, and Rz measured at 100 points. Is a copper foil with a carrier having a standard deviation of 0.1 μm or less.

[11] The present invention is the above-mentioned [9], wherein the average value of 100 points of Ra on the surface of the ultrathin copper layer is 0.2 µm or less measured in accordance with JIS B0601-1982 with a contact roughness meter and measured at 100 points. It is a copper foil with a carrier whose standard deviation is 0.03 µm or less.

[12] The present invention is the above-mentioned [10], wherein the average value of 100 points of Ra on the surface of the ultrathin copper layer is 0.2 µm or less measured in accordance with JIS B0601-1982 using a contact roughness meter, and Ra measured at 100 points. It is a copper foil with a carrier whose standard deviation is 0.03 µm or less.

[13] The present invention is the copper foil with a carrier according to any one of the above [9] to [12], wherein the average value of 100 points of Rt on the ultrathin copper layer surface is 1.0 µm or less.

[14] The present invention is a copper foil with a carrier provided with a carrier, a peeling layer, an ultrathin copper layer, and a voluntary resin layer in this order, wherein an average value of 100 points of Rt on the surface of the ultrathin copper layer is JIS based on a contact roughness meter. Copper foil with a carrier which measures 1.8 m or less based on B0601-2001, and the standard deviation of Rt measured at 100 points is 0.1 micrometer or less, and satisfy | fills one or more of the following items.

1: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 1.5 micrometers or less measured according to JIS B0601-1982 with a contact roughness meter.

2: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 1.4 micrometers or less measured in accordance with JIS B0601-1982 with a contact roughness meter.

3: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 1.3 micrometers or less measured according to JIS B0601-1982 with a contact roughness meter.

4: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 1.2 micrometers or less measured by the contact roughness meter based on JIS B0601-1982.

5: The average value of 100 points of Rz of the ultra-thin copper layer surface is 1.0 micrometer or less by measuring based on JIS B0601-1982 with a contact roughness meter.

6: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 0.8 micrometer or less measured by the contact roughness meter based on JIS B0601-1982.

7: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 0.5 micrometer or less measured by the contact roughness meter based on JISB0601-1982.

8: The average value of 100 points of Rz of the ultra-thin copper layer surface is 0.01 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

9: Average value of 100 points of Rz on the surface of ultra-thin copper layer is 0.1 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

10: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 0.3 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

11: Standard deviation of Rz measured at 100 points on the ultrathin copper layer surface is 0.1 m or less.

12: The standard deviation of Rz measured at 100 points on the surface of the ultrathin copper layer is 0.068 µm or less.

13: The standard deviation of Rz measured at 100 points on the surface of the ultrathin copper layer is 0.05 µm or less.

14: The standard deviation of Rz measured at 100 points on the surface of the ultrathin copper layer is 0.01 µm or more.

15: The average value of 100 points | pieces of Rt on the surface of an ultra-thin copper layer is 1.5 micrometers or less measured according to JIS B0601-2001 with a contact roughness meter.

16: The average value of 100 points | pieces of Rt on the surface of an ultra-thin copper layer is 1.3 micrometers or less measured according to JIS B0601-2001 with a contact roughness meter.

17: The average value of 100 points of Rt on the surface of an ultra-thin copper layer is 1.1 micrometers or less measured according to JIS B0601-2001 with a contact roughness meter.

18: The average value of 100 points | pieces of Rt on the surface of an ultra-thin copper layer is 1.0 micrometer or less as measured based on JIS B0601-2001 with a contact roughness meter.

19: The average value of 100 points | pieces of Rt on the surface of an ultra-thin copper layer is 0.5 micrometer or more as measured based on JIS B0601-2001 with a contact roughness meter.

20: The average value of 100 points | pieces of Rt on the surface of an ultra-thin copper layer is 0.6 micrometer or more as measured based on JIS B0601-2001 with a contact roughness meter.

21: The average value of 100 points | pieces of Rt on the surface of an ultra-thin copper layer is 0.8 micrometer or more as measured based on JIS B0601-2001 with a contact roughness meter.

22: The standard deviation of Rt measured at 100 points on the surface of the ultrathin copper layer is 0.060 µm or less.

23: The standard deviation of Rt measured at 100 points on the surface of the ultrathin copper layer is 0.05 µm or less.

24: The standard deviation of Rt measured at 100 points on the surface of the ultrathin copper layer is 0.01 µm or more.

25: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.2 micrometer or less as measured based on JISB0601-1982 by a contact roughness meter.

26: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.18 micrometer or less measured in accordance with JIS B0601-1982 with a contact roughness meter.

27: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.15 micrometer or less measured in accordance with JIS B0601-1982 with a contact roughness meter.

28: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.01 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

29: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.05 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

30: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.12 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

31: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.13 micrometer or more by measuring in accordance with JIS B0601-1982 with a contact roughness meter.

32: The standard deviation of Ra measured at 100 points on the ultrathin copper layer surface is 0.03 µm or less.

33: The standard deviation of Ra measured at 100 points on the surface of the ultrathin copper layer is 0.026 µm or less.

34: The standard deviation of Ra measured at 100 points on the ultrathin copper layer surface is 0.02 µm or less.

35: The standard deviation of Ra measured at 100 points on the ultrathin copper layer surface is 0.001 µm or more.

[15] The present invention is a copper foil with a carrier provided with a carrier, a peeling layer, an ultrathin copper layer, and a voluntary resin layer in this order, wherein an average value of 100 points of Ra on the surface of the ultrathin copper layer is JIS based on a contact roughness meter. It is copper foil with a carrier which is 0.2 micrometers or less measured based on B0601-1982, and the standard deviation of Ra measured at 100 points is 0.03 micrometer or less.

[16] The present invention provides the above-mentioned [15], wherein the average value of 100 points of Rz on the surface of the ultrathin copper layer is 1.5 µm or less measured according to JIS B0601-1982 using a contact roughness meter, and Rz measured at 100 points. It is the copper foil with a carrier whose standard deviation of is 0.1 micrometer or less.

[17] The present invention provides the above-mentioned [15], wherein the average value of 100 points of Rt on the surface of the ultrathin copper layer is 2.0 µm or less measured in accordance with JIS B0601-2001 with a contact roughness meter and measured at 100 points. It is the copper foil with a carrier whose standard deviation of is 0.1 micrometer or less.

[18] The present invention provides the above-mentioned [16], wherein the average value of 100 points of Rt on the surface of the ultrathin copper layer is 2.0 µm or less measured in accordance with JIS B0601-2001 with a contact roughness meter and measured at 100 points. It is the copper foil with a carrier whose standard deviation of is 0.1 micrometer or less.

[19] The present invention is the copper foil with a carrier according to any one of the above [15] to [18], wherein the average value of 100 points of Ra on the ultrathin copper layer surface is 0.15 µm or less.

[20] The present invention is a copper foil with a carrier provided with a carrier, a peeling layer, an ultrathin copper layer, and a voluntary resin layer in this order, wherein an average value of 100 points of Ra on the surface of the ultrathin copper layer is JIS based on a contact roughness meter. Copper foil with a carrier measured according to B0601-1982 and 0.2 micrometer or less and the standard deviation of Ra measured at 100 points | pieces is 0.03 micrometer or less, and satisfy | fills one or more of the following items.

1: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 1.5 micrometers or less measured according to JIS B0601-1982 with a contact roughness meter.

2: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 1.4 micrometers or less measured in accordance with JIS B0601-1982 with a contact roughness meter.

3: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 1.3 micrometers or less measured according to JIS B0601-1982 with a contact roughness meter.

4: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 1.2 micrometers or less measured by the contact roughness meter based on JIS B0601-1982.

5: The average value of 100 points of Rz of the ultra-thin copper layer surface is 1.0 micrometer or less by measuring based on JIS B0601-1982 with a contact roughness meter.

6: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 0.8 micrometer or less measured by the contact roughness meter based on JIS B0601-1982.

7: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 0.5 micrometer or less measured by the contact roughness meter based on JISB0601-1982.

8: The average value of 100 points of Rz of the ultra-thin copper layer surface is 0.01 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

9: Average value of 100 points of Rz on the surface of ultra-thin copper layer is 0.1 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

10: The average value of 100 points of Rz on the surface of an ultra-thin copper layer is 0.3 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

11: Standard deviation of Rz measured at 100 points on the ultrathin copper layer surface is 0.1 m or less.

12: The standard deviation of Rz measured at 100 points on the surface of the ultrathin copper layer is 0.068 µm or less.

13: The standard deviation of Rz measured at 100 points on the surface of the ultrathin copper layer is 0.05 µm or less.

14: The standard deviation of Rz measured at 100 points on the surface of the ultrathin copper layer is 0.01 µm or more.

15: The average value of 100 points of Rt on the surface of an ultra-thin copper layer is 2.0 micrometers or less measured according to JIS B0601-2001 with a contact roughness meter.

16: The average value of 100 points | pieces of Rt on the surface of an ultra-thin copper layer is 1.8 micrometers or less measured by the contact roughness meter based on JISB0601-2001.

17: The average value of 100 points of Rt on the surface of an ultra-thin copper layer is 1.5 micrometers or less measured according to JIS B0601-2001 with a contact roughness meter.

18: The average value of 100 points of Rt on the surface of an ultra-thin copper layer is 1.3 micrometers or less measured according to JIS B0601-2001 with a contact roughness meter.

19: The average value of 100 points of Rt on the surface of an ultra-thin copper layer is 1.1 micrometers or less measured according to JIS B0601-2001 with a contact roughness meter.

20: The average value of 100 points | pieces of Rt on the surface of an ultra-thin copper layer is 1.0 micrometer or less by measuring based on JIS B0601-2001 with a contact roughness meter.

21: The average value of 100 points of Rt on the surface of an ultra-thin copper layer is 0.5 micrometer or more as measured based on JIS B0601-2001 with a contact roughness meter.

22: The average value of 100 points | pieces of Rt on the surface of an ultra-thin copper layer is 0.6 micrometer or more as measured based on JIS B0601-2001 with a contact roughness meter.

23: The average value of 100 points | pieces of Rt on the surface of an ultra-thin copper layer is 0.8 micrometer or more as measured based on JIS B0601-2001 with a contact roughness meter.

24: The standard deviation of Rt measured at 100 points on the surface of the ultrathin copper layer is 0.1 μm or less.

25: The standard deviation of Rt measured at 100 points on the ultrathin copper layer surface is 0.060 µm or less.

26: The standard deviation of Rt measured at 100 points on the surface of the ultrathin copper layer is 0.05 µm or less.

27: The standard deviation of Rt measured at 100 points on the surface of the ultrathin copper layer is 0.01 µm or more.

28: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.18 micrometer or less measured in accordance with JIS B0601-1982 with a contact roughness meter.

29: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.15 micrometer or less by measuring in accordance with JIS B0601-1982 with a contact roughness meter.

30: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.01 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

31: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.05 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

32: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.12 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

33: The average value of 100 points | pieces of Ra of the ultra-thin copper layer surface is 0.13 micrometer or more as measured based on JIS B0601-1982 with a contact roughness meter.

34: The standard deviation of Ra measured at 100 points on the surface of the ultrathin copper layer is 0.026 µm or less.

35: The standard deviation of Ra measured at 100 points on the ultrathin copper layer surface is 0.02 µm or less.

36: The standard deviation of Ra measured at 100 points on the surface of the ultrathin copper layer is at least 0.001 µm.

[21] The present invention is any one of the above [1] to [4], [8] to [12], [14] to [18], and [20], wherein the ultrathin copper layer is roughened. Copper foil with a carrier.

[22] The present invention is a print produced by using the copper foil with a carrier according to any one of the above [1] to [4], [8] to [12], [14] to [18], and [20]. It is a wiring board.

[23] The present invention is a print produced by using the copper foil with a carrier according to any one of the above [1] to [4], [8] to [12], [14] to [18], and [20]. It is a circuit board.

[24] The invention as described in [22], wherein the insulating substrate,

Having a copper circuit formed on the insulating substrate,

It is a printed wiring board whose circuit width of the said copper circuit is less than 20 micrometers, and the width | variety of the space between adjacent copper circuits is less than 20 micrometers.

[25] The present invention provides the above-mentioned [22], wherein the insulating substrate and

Having a copper circuit formed on the insulating substrate,

It is a printed wiring board whose circuit width of the said copper circuit is 17 micrometers or less, and the width | variety of the space between adjacent copper circuits is 17 micrometers or less.

[26] The invention as described in [23], wherein the insulating substrate,

Having a copper circuit formed on the insulating substrate,

It is a printed circuit board whose circuit width of the said copper circuit is less than 20 micrometers, and the width | variety of the space between adjacent copper circuits is less than 20 micrometers.

[27] The present invention provides the above-mentioned [23], wherein the insulating substrate and

Having a copper circuit formed on the insulating substrate,

It is a printed circuit board whose circuit width of the said copper circuit is 17 micrometers or less, and the width | variety of the space between adjacent copper circuits is 17 micrometers or less.

[28] The present invention is a printed wiring board according to the above [22], wherein the pitch of the line and space is less than 40 µm.

[29] The present invention is a printed wiring board according to the above [22], wherein the pitch of the line and space is less than 34 m.

[30] The present invention is a printed wiring board according to the above [23], wherein the pitch of the line and space is less than 40 µm.

[31] The present invention is a printed wiring board according to the above [23], wherein the pitch of the line and space is less than 34 m.

[32] The present invention is a copper sheet produced by using the copper plate with a carrier according to any one of the above [1] to [4], [8] to [12], [14] to [18], and [20]. Coated laminate.

[33] The present invention provides a process for preparing a copper foil with a carrier and an insulating substrate according to any one of [1] to [4], [8] to [12], [14] to [18], and [20],

Laminating the copper foil with a carrier and an insulating substrate;

After laminating | stacking the said copper foil with a carrier and an insulated substrate, a copper clad laminated board is formed through the process of peeling the carrier of the said copper foil with a carrier,

Then, it is a manufacturing method of the printed wiring board containing the process of forming a circuit by any method of the semiadditive method, the subtractive method, the partly additive method, or the modified semiadditive method.

[34] The present invention provides a circuit on the ultrathin copper layer side surface of the copper foil with a carrier according to any one of [1] to [4], [8] to [12], [14] to [18], and [20]. Forming process,

Forming a resin layer on the ultrathin copper layer side surface of the copper foil with a carrier such that the circuit is buried;

Forming a circuit on the resin layer,

After forming a circuit on the resin layer, the step of peeling the carrier, and

It is a manufacturing method of the printed wiring board including the process of exposing the circuit embedded in the said resin layer formed in the said ultra-thin copper layer side surface by removing the said ultra-thin copper layer after peeling the said carrier.

[35] The invention of [34],

The process of forming a circuit on the said resin layer is a process of bonding the other copper foil with a carrier on the said resin layer from the ultra-thin copper layer side, and forming the said circuit using the copper foil with a carrier bonded to the said resin layer. It is a manufacturing method of a wiring board.

[36] The present invention is the ultra-thin copper layer side of the copper foil with a carrier according to any one of [1] to [4], [8] to [12], [14] to [18], and [20]. Forming circuits on the surface,

Forming a resin layer on the ultrathin copper layer side surface of the copper foil with a carrier such that the circuit is buried;

Forming a circuit on the resin layer,

After forming a circuit on the resin layer, the step of peeling the carrier, and

After exfoliating the carrier, by removing the ultrathin copper layer, exposing a circuit buried in the resin layer formed on the ultrathin copper layer side surface;

The process of forming a circuit on the said resin layer is a process of bonding the other copper foil with a carrier on the said resin layer from the ultra-thin copper layer side, and forming the said circuit using the copper foil with a carrier bonded to the said resin layer,

The other copper foil with a carrier bonded together on the said resin layer is copper foil with a carrier in any one of [1]-[4], [8]-[12], [14]-[18], and [20]. , A method for producing a printed wiring board.

[37] The present invention is the above-mentioned [34].

The process of forming a circuit on the said resin layer is a manufacturing method of the printed wiring board performed by any method of the semiadditive method, the subtractive method, the partly additive method, or the modified semiadditive method.

[38] The invention as in [34],

It is a manufacturing method of the printed wiring board which further includes the process of forming a board | substrate in the carrier side surface of the copper foil with a carrier before peeling a carrier.

<1. Carrier>

The carrier which can be used for the present invention is typically a metal foil or a resin film, for example, copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum alloy foil, insulation It is provided in the form of a resin film (for example, a polyimide film, a liquid crystal polymer (LCP) film, a polyethylene terephthalate (PET) film, a polyamide film, a polyester film, a fluororesin film, etc.).

It is preferable to use copper foil as a carrier which can be used for this invention. The carrier is typically provided in the form of a rolled copper foil or an electrolytic copper foil. Generally, an electrolytic copper foil is manufactured by electrolytically depositing copper on a titanium or stainless steel drum from a copper sulfate plating bath, and a rolled copper foil is manufactured by repeating plastic working and heat processing by a rolling roll. As the material of the copper foil, in addition to high-purity copper such as tough pitch copper or oxygen-free copper, for example, a copper alloy containing Sn-containing copper, Ag-containing copper, Cr, Zr, or Mg, or a Coulson-based copper containing Ni and Si, etc. Copper alloys such as copper alloys may also be used. In addition, when using the term "copper foil" independently in this specification, copper alloy foil shall also be included.

Although there is no restriction | limiting in particular also about the thickness of the carrier which can be used for this invention, What is necessary is just to adjust suitably to a suitable thickness in fulfilling responsibility as a carrier, for example, it can be 12 micrometers or more. However, when it is too thick, since production cost will become high, it is generally preferable to set it as 70 micrometers or less. Therefore, the thickness of a carrier is typically 12-70 micrometers, More typically, it is 18-35 micrometers.

<2. Peeling Layer>

The release layer is formed on the carrier. You may form another layer between a copper foil carrier and a peeling layer. As a peeling layer, it can be set as the arbitrary peeling layer known to a person skilled in the art in copper foil with a carrier. For example, the release layer may be any one or more of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, or organic matters. It is preferable to form in the layer which contains or consists of any 1 or more types of such. The release layer may be composed of a plurality of layers. In addition, the release layer may have a diffusion preventing function. The diffusion preventing function has a function of preventing diffusion of an element from the base material to the ultrathin copper layer side.

In one embodiment of this invention, a peeling layer is a single metal layer which consists of any 1 type of elements from the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from a carrier side, Or an alloy layer containing one or more elements selected from the group of elements of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn or consisting of one or more selected elements (these are diffusion preventing functions Or a hydrate or oxide or organic substance of one or more elements selected from the group of elements of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn stacked thereon; It consists of a layer consisting of a hydrate or an oxide or an organic substance.

For example, a peeling layer is a single metal layer which consists of any 1 type of elements from the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from a carrier side, or Cr, An alloy layer containing one or more elements selected from the group of elements Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn or consisting of one or more selected elements, followed by Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn a single metal layer composed of any one element of the group, or Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, The alloy layer may contain one or more elements selected from the group of elements Al and Zn, or may be composed of one or more selected elements. In addition, the total adhesion amount of each element can be 1-6000 microgram / dm <2>, for example. Moreover, you may use the laminated constitution which can be used as a peeling layer for another layer.

It is preferable that a peeling layer consists of two layers, Ni and Cr. In this case, the Ni layer is laminated so as to be in contact with the interface with the copper foil carrier and the Cr layer is in contact with the interface with the ultrathin copper layer, respectively.

The release layer can be obtained, for example, by wet plating such as electroplating, electroless plating and immersion plating, or by dry plating such as sputtering, CVD and PDV. Electroplating is preferable from the viewpoint of cost.

For example, a peeling layer can be comprised by carrying out nickel, nickel-phosphorus alloy, or nickel-cobalt alloy, and chromium in this order on a carrier. Since the adhesive force of nickel and copper is higher than the adhesive force of chromium and copper, when peeling an ultrathin copper layer, it will peel at the interface of an ultrathin copper layer and chromium. Moreover, the nickel effect of the peeling layer is expected to have a barrier effect of preventing the copper component from diffusing into the ultrathin copper layer from the carrier. The adhesion amount of nickel in the release layer is preferably 100 µg / dm 2 or more and 40000 µg / dm 2 or less, more preferably 100 µg / dm 2 or more and 4000 µg / dm 2 or less, and more preferably 100 µg / d It is preferable that it is 2 m <2> or more and 2500 microgram / dm <2>, More preferably, it is 100 microgram / dm <2> or more and less than 1000 microgram / dm <2>, and the adhesion amount of chromium in a peeling layer is 5 microgram / dm <2> or more and 100 microgram / dm <2> or less. Do. In the case where the release layer is formed only on one side, it is preferable to form a rust preventive layer such as a Ni plating layer on the opposite side of the carrier.

In addition, you may form a peeling layer on both surfaces of a carrier.

<3. Ultrathin Copper Layer>

An ultrathin copper layer is formed on the release layer. You may form another layer between a peeling layer and an ultra-thin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrolate, copper sulfamate, copper cyanide, etc., and is used in general electrolytic copper foil, and copper sulfate bath can be formed at high current density. This is preferable. Although the thickness of an ultra-thin copper layer does not have a restriction | limiting in particular, Usually, it is thinner than a carrier and is 12 micrometers or less, for example. Typically, it is 0.5-12 micrometers, More typically, it is 2-5 micrometers. In addition, you may form an ultra-thin copper layer on both surfaces of a carrier. Moreover, you may use the laminated constitution which can be used as a peeling layer for another layer.

<4. Coordination treatment>

You may form a roughening process layer on the surface of an ultra-thin copper layer, for example, by performing a roughening process, for example, to improve adhesiveness with an insulated substrate. A roughening process can be performed by forming roughening particle | grains with copper or a copper alloy, for example. It is preferable that a roughening process layer is comprised from fine particle from a viewpoint of fine pitch formation. Regarding the electroplating conditions when forming the roughened particles, when the current density is high, the copper concentration in the plating liquid is low, or the amount of coulomb is increased, the particles tend to be fine.

The roughened layer can be composed of electrodeposited grains composed of any one selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc or an alloy containing any one or more of them. have.

In order to improve the in-plane uniformity of surface roughness on the surface-treated surface, it is effective to maintain the anode-cathode distance at the time of forming the roughened layer. Although not limiting, a method of securing a constant gap distance is effective from the viewpoint of industrial production by means of a transportation system using a drum or the like as a support medium. 1 is a schematic diagram showing the hail system. The roughening particle layer is formed in the ultrathin copper layer surface by electrolytic plating, supporting the carrier copper foil conveyed by a conveyance roll with a drum. The process surface of the carrier copper foil supported by the drum doubles as a cathode, and each electroplating is performed in the plating liquid between the drum and the anode formed to face the drum. In addition, FIG. 2 has shown the schematic diagram which shows the crumb system by the conventional type | mold guanjiang. In this system, there is a problem that it is difficult to keep the distance between the anode and the cathode constant under the influence of the electrolyte solution and the pulsation tension. In addition, in order to keep the anode-cathode distance at the time of formation of a roughening process layer by the crumb system by a sectional dressing, it is effective to make the tension for cruising high and to shorten the distance between conveyance rolls conventionally.

As shown in FIG. 1, the crumb system with a drum can be utilized not only for a roughening process but also for formation of a peeling layer and formation of an ultra-thin copper layer. It is because it is possible to improve the thickness precision of a peeling layer or an ultra-thin copper layer by employ | adopting the crumb system by a drum. Moreover, in order to keep the anode-cathode distance at the time of forming a peeling layer or an ultra-thin copper layer by the pulsation system by a sectional dressing, it is effective to make tension more crumb than before, and to shorten the distance between conveyance rolls. Do.

The distance between the poles is not limited, but if it is too long, the production cost increases, while if it is too short, the in-plane variation tends to be large, so that generally 3 to 100 mm is preferable, and 5 to 80 mm is more preferable.

After the roughening treatment, secondary particles, tertiary particles and / or rust-preventing layers are formed of a single element or an alloy of nickel, cobalt, copper, zinc, or the like, and further, chromate treatment, silane coupling treatment, or the like on the surface thereof. May be processed. That is, at least 1 type of layer chosen from the group which consists of a rustproof layer, a chromate treated layer, and a silane coupling process layer may be formed on the surface of a roughening process layer, and a rustproof layer is not given to the surface of an ultra-thin copper layer, Or at least one layer selected from the group consisting of chromate treated layers and silane coupling treated layers. In addition, these surface treatments hardly affect the surface roughness of the ultrathin copper layer.

The ultrathin copper layer surface (when various surface treatments, such as a roughening process, is indicated, the surface of the ultrathin copper layer after surface treatment (also called a "surface treatment surface")) is a contact roughness meter to JIS B0601-1982. Based on the measurement, the average value of Rz (10 point average roughness) of 1.5 µm or less is very advantageous from the viewpoint of fine pitch formation. The average value of Rz becomes like this. Preferably it is 1.4 micrometers or less, More preferably, it is 1.3 micrometers or less, More preferably, it is 1.2 micrometers or less, More preferably, it is 1.0 micrometers or less, More preferably, it is 0.8 micrometers or less. However, when the average value of Rz becomes too small, the adhesive force with resin falls, it is preferable that it is 0.01 micrometer or more, It is more preferable that it is 0.1 micrometer or more, More preferably, 0.3 micrometer or more, Most preferably 0.5 micrometer or more Do. In this invention, the average value of Rz employ | adopts the average value of each Rz obtained when obtaining the standard deviation of Rz by the method described below.

In the present invention, the standard deviation of Rz on the surface of the ultrathin copper layer can also be 0.1 µm or less, preferably 0.05 µm or less, for example, 0.01 to 0.7 µm. The standard deviation of Rz on the surface of the ultrathin copper layer is obtained from in-plane 100 point measurement data. In addition, the measurement data of 100 in-plane points is obtained by dividing 10 sheets of 550 mm in length and length in the vertical direction and the horizontal direction, respectively, and measuring each center part of 100 division areas. Although this method used this method in order to maintain in-plane uniformity, a verification method is not limited to this. For example, the same data can be collected even if a sample having a size of 550 mm × 440 mm to 400 mm × 200 mm, which is generally used, is divided into 100 planes (10 divisions vertically).

The ultra-thin copper layer surface has a mean value of Rt (maximum cross-sectional height) of 2.0 μm or less, preferably 1.8 μm or less, preferably 1.5 μm or less, as measured in accordance with JIS B0601-2001 with a contact roughness meter. Preferably it is 1.3 micrometers or less, Preferably it is 1.1 micrometers or less from a viewpoint of fine pitch formation. However, when the average value of Rt becomes too small, the adhesive force with resin falls, Preferably it is 0.5 micrometer or more, More preferably, it is 0.6 micrometer or more, More preferably, it is 0.8 micrometer or more. In this invention, the average value of Rt employ | adopts the average value of each Rt obtained when the standard deviation of Rt is calculated | required by the method described below.

In this invention, the standard deviation of Rt in the ultra-thin copper layer surface can also be 0.1 micrometer or less, Preferably it can be 0.05 micrometer or less, For example, it can be 0.01-0.6 micrometer. The standard deviation of Rt on the surface of the ultrathin copper layer is obtained from the measurement data of 100 in-plane points in the same manner as Rz.

In addition, it is preferable from the viewpoint of fine pitch formation that the surface of the ultra-thin copper layer has a mean value of Ra (arithmetic mean roughness) of 0.2 μm or less when measured according to JIS B0601-1982 with a contact roughness meter, and is 0.18 μm or less. It is more preferable to set it as 0.15 micrometer or less. However, when the average value of Ra becomes small too much, adhesive force with resin falls, Preferably it is 0.01 micrometer or more, More preferably, it is 0.05 micrometer or more, More preferably, it is 0.12 micrometer or more, Most preferably, 0.13 micrometers or more. In the present invention, the average value of Ra adopts the average value of each Ra obtained when the standard deviation of Ra is obtained by the method described below.

In the present invention, the standard deviation of Ra on the ultrathin copper layer surface can also be 0.03 µm or less, preferably 0.02 µm or less, for example, 0.001 to 0.03 µm. The standard deviation of Ra on the surface of the ultrathin copper layer is obtained from the measurement data of 100 in-plane points, similarly to Rz.

In addition, in the case where an insulating substrate such as a resin or a resin layer is adhered to the surface of an ultrathin copper layer such as a copper foil with a carrier, a printed wiring board or a copper clad laminate plate with a resin layer, the insulating substrate is melted and removed to remove the copper circuit or the like. The surface roughness (Ra, Rt, Rz) mentioned above can be measured about the copper foil surface.

<5. Other Surface Treatments>

After the roughening treatment, a heat-resistant layer or a rust-preventing layer may be formed of a single substance, an alloy, or the like of nickel, cobalt, copper, or zinc, or may be further subjected to treatment such as chromate treatment, silane coupling treatment, or the like. Alternatively, the heat-resistant layer or the rust-preventing layer may be formed of a single element, an alloy, or the like of nickel, cobalt, copper, or zinc, and the surface may be subjected to a chromate treatment or a silane coupling treatment. That is, one or more layers selected from the group consisting of a heat resistant layer, an rustproof layer, a chromate treated layer and a silane coupling treatment layer may be formed on the surface of the roughened layer, and the heat resistant layer and the rustproof layer are formed on the surface of the ultrathin copper layer. Or at least one layer selected from the group consisting of chromate treated layers and silane coupling treated layers. In addition, the heat-resistant layer, the rustproof layer, the chromate treatment layer, and the silane coupling treatment layer described above may be each formed of a plurality of layers such as two or more layers, three or more layers, and the like.

As a heat resistant layer and a rustproof layer, a well-known heat resistant layer and a rustproof layer can be used. For example, the heat resistant layer and / or rustproof layer may be nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum The layer containing at least one element selected from may be nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum The metal layer or the alloy layer which consists of 1 or more types of elements chosen from the group of may be sufficient. The heat-resistant layer and / or rust-proof layer may be selected from the group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron and tantalum. You may contain the oxide, nitride, and silicide containing 1 or more types of elements which become. In addition, the heat resistant layer and / or rustproof layer may be a layer containing a nickel-zinc alloy. The heat-resistant layer and / or rustproof layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% of nickel and 50 wt% to 1 wt% of zinc except for unavoidable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg / m 2, preferably 10 to 500 mg / m 2, preferably 20 to 100 mg / m 2. Moreover, it is preferable that ratio (= adhesion amount of nickel / adhesion amount of zinc) of the adhesion amount of nickel and the adhesion amount of zinc of the layer containing the said nickel- zinc alloy or the said nickel- zinc alloy layer is 1.5-10. Moreover, it is preferable that it is 0.5 mg / m <2> -500 mg / m <2>, and, as for the adhesion amount of nickel of the layer containing the said nickel- zinc alloy or the said nickel-zinc alloy layer, it is more preferable that it is 1 mg / m <2> -50 mg / m <2>. Do. In the case where the heat-resistant layer and / or the rust-preventing layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate is not easily eroded by the desmear liquid when inner wall portions such as through holes and via holes contact with the desmear liquid, And the adhesiveness of the resin substrate are improved.

For example, the heat-resistant layer and / or the rust-preventing layer include a nickel or nickel alloy layer having an adhesion amount of 1 mg / m 2 to 100 mg / m 2, preferably 5 mg / m 2 to 50 mg / m 2, and an adhesion amount of 1 mg / m 2. It may be a laminate of tin layers of from 80 mg / m 2, preferably 5 mg / m 2 to 40 mg / m 2, and the nickel alloy layer may be any one of nickel-molybdenum, nickel-zinc and nickel-molybdenum-cobalt. You may be comprised by a bell. Moreover, it is preferable that the total adhesion amount of nickel or a nickel alloy and tin is 2 mg / m <2> -150 mg / m <2>, and, as for a heat resistant layer and / or a rustproof layer, it is more preferable that they are 10 mg / m <2> -70 mg / m <2>. Moreover, it is preferable that [the nickel adhesion amount in nickel or a nickel alloy] / [tin adhesion amount] = 0.25-10, and, as for a heat-resistant layer and / or an rustproof layer, it is more preferable that it is 0.33-3. When the said heat resistant layer and / or an rustproof layer are used, the peeling strength of the circuit after processing the copper foil with a carrier to a printed wiring board, the chemical-resistance deterioration rate of the said peeling strength, etc. will become favorable.

In addition, a well-known silane coupling agent may be used for the silane coupling agent used for a silane coupling process, for example, an amino silane coupling agent, an epoxy silane coupling agent, or a mercapto silane coupling agent may be used. In addition, the silane coupling agent includes vinyltrimethoxysilane, vinylphenyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and 4-glycidylbutyltrimethoxysilane. , γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) methoxy) propyl-3-aminopropyltri You may use a methoxysilane, imidazole silane, a triazine silane, (gamma)-mercaptopropyl trimethoxysilane.

The silane coupling treatment layer may be formed using a silane coupling agent such as epoxy silane, amino silane, methacryloxy silane, mercapto silane, or the like. In addition, you may mix and use 2 or more types of such silane coupling agents. Especially, it is preferable to form using an amino-type silane coupling agent or an epoxy-type silane coupling agent.

The amino silane coupling agent here is N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxy Silane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- ( 2-aminoethyl-3-aminopropyl) trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane, 6- (aminohexylaminopropyl) trimethoxysilane , Aminophenyltrimethoxysilane, 3- (1-aminopropoxy) -3,3-dimethyl-1-propenyltrimethoxysilane, 3-aminopropyl S (methoxyethoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminoundecyltrimethoxysilane, 3- (2-N-benzylaminoethylamino Propyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, (N, N-dimethyl- 3-aminopropyl) trimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane , γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) methoxy) propyl-3-aminopropyltri It may be selected from the group consisting of methoxysilane.

The silane coupling treatment layer is in the range of 0.05 mg / m 2 to 200 mg / m 2, preferably 0.15 mg / m 2 to 20 mg / m 2, preferably 0.3 mg / m 2 to 2.0 mg / m 2 in terms of silicon atoms. It is preferable that it is formed. In the case of the above-mentioned range, the adhesiveness of base resin and surface treatment copper foil can be improved more.

Moreover, on the surface of an ultra-thin copper layer, a roughening process layer, a heat-resistant layer, a rustproof layer, a silane coupling process layer, or a chromate treatment layer, International Publication No. WO2008 / 053878, Unexamined-Japanese-Patent No. 2008-111169, Japanese Patent No. 5014930. International Publication No. WO2006 / 028207, Japanese Patent Publication No. 4482827, International Publication No. WO2006 / 134868, Japanese Patent Publication No. 5046927, International Publication No. WO2007 / 105635, Japanese Patent Publication No. 5180815, or Japan Patent Publication 2013 The surface treatment of -19056 can be performed.

[Resin Layer on Ultra-thin Copper Layer]

You may provide a resin layer on the ultra-thin copper layer (when an ultra-thin copper layer is surface-treated, the surface treatment layer formed on the ultra-thin copper layer by the said surface treatment) of the copper foil with a carrier of this invention. The resin layer may be an insulated resin layer.

The resin layer may be an adhesive resin, that is, an adhesive, or an insulating resin layer in a semi-cured state (B stage state) for adhesion. The semi-cured state (B stage state) does not have a tack even when the surface is touched by a finger, and the insulating resin layer can be superimposed and stored, and includes a state in which a curing reaction occurs when subjected to heat treatment.

Moreover, the said resin layer may contain thermosetting resin, and a thermoplastic resin may be sufficient as it. Moreover, the said resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton, and the like. The resin layer is, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, Japanese Patent Application Laid-Open No. 11-5828, Japanese Patent Application Laid-Open No. 11-140281. , Japanese Patent Publication No. 3184485, International Publication No. WO97 / 02728, Japanese Patent Publication No. 376375, Japanese Patent Application Publication No. 2000-43188, Japanese Patent Publication No. 3612594, Japanese Patent Application Publication No. 2002-179772, Japanese Patent Application Publication Japanese Unexamined Patent Publication No. 2002-359444, Japanese Unexamined Patent Publication No. 2003-304068, Japanese Patent No. 3992225, Japanese Unexamined Patent Publication No. 2003-249739, Japanese Patent No. 4136509, Japanese Unexamined Patent Publication No. 2004-82687 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent Publication No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent Publication No. 4570070, Japanese Patent Application Laid-Open No. 2005-53218, Japanese Patent Publication No. 3949676 , Japanese Patent Publication No. 4178415, International Publication WO2004 / 005588, Japanese Unexamined Patent Publication No. 2006-257153, Japanese Unexamined Patent Publication No. 2007-326923, Japanese Unexamined Patent Publication No. 2008-111169, Japanese Patent No. 5014930, International Publication No. WO2006 / 028207, Japanese Patent Publication No. 4828427, Japanese Patent Application Laid-Open No. 2009-67029, International Publication No. WO2006 / 134868, Japanese Patent Publication No. 5046927, Japanese Patent Application Publication No. 2009-173017, International Publication No. WO2007 / 105635, Japanese Patent Publication No. 5180815, International Publication No. WO2008 / 114858, International Publication No. WO2009 / 008471, Japanese Laid-Open Patent Publication 2011-14727, International Publication No. WO2009 / 001850, International Publication No. WO2009 / 145179, International Publication No. WO2011 / 068157, Japanese Laid-Open Patent Publication 2013-19056 You may form using the material (resin, resin hardening | curing agent, compound, hardening accelerator, dielectric, reaction catalyst, crosslinking agent, a polymer, a prepreg, a framework | skeletal material, etc.) and / or the formation method of a resin layer, and the formation apparatus which are described in the heading. .

Moreover, the kind of the said resin layer is not specifically limited, For example, an epoxy resin, a polyimide resin, a polyfunctional cyanate ester compound, a maleimide compound, a polymaleimide compound, a maleimide-type resin, aromatic maleim Mid resin, polyvinyl acetal resin, urethane resin, polyethersulfone (also called polyethersulfone, polyethersulfone), polyethersulfone (also called polyethersulfone, polyethersulfone) resin, aromatic polyamide resin, aromatic polyamide Resin polymer, rubbery resin, polyamine, aromatic polyamine, polyamideimide resin, rubber modified epoxy resin, phenoxy resin, carboxyl modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine resin, thermosetting poly Phenylene oxide resin, cyanate ester resin, carboxylic acid Anhydrides, anhydrides of polyhydric carboxylic acids, linear polymers having crosslinkable functional groups, polyphenylene ether resins, 2,2-bis (4-cyanatophenyl) propane, phosphorus-containing phenolic compounds, manganese naphthenate, 2,2- Bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, siloxane modified polyamideimide resin, cyanoester resin, phosphazene resin, rubber modified polyamideimide resin, isoprene, hydrogenated poly Resin containing 1 or more types chosen from the group of butadiene, polyvinyl butyral, phenoxy, high molecular weight epoxy, aromatic polyamide, fluorine resin, bisphenol, a block copolymerization polyimide resin, and a cyano ester resin is mentioned as a preferable thing. .

Moreover, if the said epoxy resin has two or more epoxy groups in a molecule | numerator, and can be used for an electrical / electronic material use, it can use without a problem especially. Moreover, the epoxy resin which the said epoxy resin epoxidized using the compound which has 2 or more glycidyl group in a molecule | numerator is preferable. In addition, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, brominated (cancelled) epoxy Resin, phenol novolak type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolak type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanate Glycidyl amine compounds, such as anurate and N, N- diglycidyl aniline, glycidyl ester compounds, such as tetrahydrophthalic acid diglycidyl ester, phosphorus containing epoxy resin, biphenyl type epoxy resin, and biphenyl furnace 1 type selected from the group of a volac type epoxy resin, a tris hydroxyphenylmethane type epoxy resin, and a tetraphenyl ethane type epoxy resin It may may be used by mixing two or more kinds, or to use a halogenated material chena hydrogenation of the epoxy resin.

As said phosphorus containing epoxy resin, the epoxy resin containing well-known phosphorus can be used. The phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in a molecule thereof. desirable.

The epoxy resin obtained as a derivative from this 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10. Naphthoquinone or hydroquinone was reacted with -oxide to form a compound represented by the following Chemical Formula 1 (HCA-NQ) or Chemical Formula 2 (HCA-HQ), and then an epoxy resin was reacted with a portion of the OH group to contain phosphorus. It was made with epoxy resin.

[Formula 1]

[Formula 2]

It is preferable that the phosphorus containing epoxy resin which is the said E component obtained using the above-mentioned compound as a raw material mixes 1 type or 2 types of the compound which has a structural formula shown in any of the following formula (3)-(5). This is because the stability of the resin quality in the semi-cured state is excellent and at the same time the flame retardant effect is high.

[Formula 3]

[Formula 4]

[Formula 5]

As the brominated (cancelled) epoxy resin, a known brominated (canceled) epoxy resin can be used. For example, the said brominated (cancelled) epoxy resin is a brominated epoxy resin provided with the structural formula shown in Formula 6 obtained as a derivative from tetrabromobisphenol A which has two or more epoxy groups in a molecule | numerator, and is shown by following formula (7) It is preferable to use 1 type or 2 types of brominated epoxy resins which have a structural formula.

[Formula 6]

[Formula 7]

As said maleimide resin, aromatic maleimide resin, a maleimide compound, or a polymaleimide compound, well-known maleimide resin, aromatic maleimide resin, a maleimide compound, or a polymaleimide compound can be used. For example, as maleimide resin, aromatic maleimide resin, maleimide compound, or polymaleimide compound, 4,4'- diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyletherbismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 4 , 4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonbismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, 1,3-bis (4-maleimidephenoxy ) Benzene and the compound and the polymer which polymerized the said compound or another compound, etc. can be used. The maleimide resin may be an aromatic maleimide resin having two or more maleimide groups in a molecule, or may be a polymerization adduct obtained by polymerizing an aromatic maleimide resin having two or more maleimide groups in a molecule, and a polyamine or an aromatic polyamine. do.

As said polyamine or aromatic polyamine, a well-known polyamine or aromatic polyamine can be used. For example, as a polyamine or an aromatic polyamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine , 4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylether, 4,4'-diamino-3-methyldiphenylether , 4,4'-diaminodiphenylsulphide, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulphone, bis (4-aminophenyl) phenylamine, m-xylenediamine, p-xylenediamine, 1,3-bis [4-aminophenoxy] benzene, 3-methyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diamino Diphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2 ', 5,5'-tetrachloro-4,4'-diaminodiphenylmethane, 2,2- Bis (3-methyl-4-aminophenyl) propane, 2,2-bis (3-ethyl-4-aminophenyl) propane, 2,2-bis (2,3-dichloro-4-aminophenyl) propane, bis (2,3-dimethyl-4-aminophenyl ) Phenyl ethane, ethylenediamine and hexamethylenediamine, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, and a polymer obtained by polymerizing the compound with the compound or the like can be used. Moreover, 1 type, or 2 or more types of well-known polyamine and / or aromatic polyamine or the above-mentioned polyamine or aromatic polyamine can be used.

A well-known phenoxy resin can be used as said phenoxy resin. Moreover, what is synthesize | combined by reaction of bisphenol and a bivalent epoxy resin can be used as said phenoxy resin. As an epoxy resin, a well-known epoxy resin and / or the above-mentioned epoxy resin can be used.

As said bisphenol, well-known bisphenol can be used, and bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4'- dihydroxy biphenyl, HCA (9,10-Dihydro-9- Bisphenol etc. which are obtained as an adduct of quinones, such as Oxa-10-Phosphaphenanthrene-10-Oxide), hydroquinone and a naphthoquinone, can be used.

As a linear polymer which has the said crosslinkable functional group, the linear polymer which has a well-known crosslinkable functional group can be used. For example, it is preferable that the linear polymer which has the said crosslinkable functional group is equipped with the functional group which contributes to hardening reaction of epoxy resins, such as a hydroxyl group and a carboxyl group. And it is preferable that the linear polymer which has this crosslinkable functional group is soluble in the organic solvent whose boiling point is 50 degreeC-200 degreeC temperature. Specific examples of the linear polymer having a functional group include polyvinyl acetal resin, phenoxy resin, polyether sulfone resin, polyamideimide resin and the like.

The said resin layer may also contain a crosslinking agent. As a crosslinking agent, a well-known crosslinking agent can be used. As a crosslinking agent, urethane type resin can be used, for example.

The rubbery resin may be a known rubbery resin. For example, the rubbery resin is described as a concept including natural rubber and synthetic rubber, and the latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, acrylonitrile butadiene rubber, Acrylic rubber (acrylic acid ester copolymer), polybutadiene rubber, isoprene rubber and the like. Moreover, when securing the heat resistance of the resin layer to form, it is also useful to select and use the synthetic rubber provided with heat resistance, such as a nitrile rubber, a chloroprene rubber, a silicone rubber, and a urethane rubber. About these rubbery resins, in order to produce a copolymer by reacting with an aromatic polyamide resin or a polyamideimide resin, it is preferable to provide various functional groups at both ends. In particular, it is useful to use CTBN (carboxyl terminal butadienenitrile). Moreover, in an acrylonitrile butadiene rubber, if it is a carboxyl modified body, it can take a crosslinked structure with an epoxy resin, and can improve the flexibility of the resin layer after hardening. As a carboxyl modified body, a carboxyl terminal nitrile butadiene rubber (CTBN), a carboxyl terminal butadiene rubber (CTB), and a carboxy modified nitrile butadiene rubber (C-NBR) can be used.

As said polyamideimide resin, a well-known polyimideamide resin can be used. Moreover, as said polyimide amide resin, trimellitic anhydride, benzophenone tetracarboxylic anhydride, and bitolylene diisocyanate are N-methyl- 2-pyrrolidone or / and N, N- dimethylacetamide, for example. N-methyl-2-pyrrolidone or / and N, N-dimethylacetamide and the like obtained by heating in a solvent such as resin, trimellitic anhydride, diphenylmethane diisocyanate and carboxyl terminal acrylonitrile-butadiene rubber What is obtained by heating in the solvent of can be used.

As the rubber-modified polyamideimide resin, a known rubber-modified polyamideimide resin can be used. Rubber modified polyamideimide resin is obtained by making polyamideimide resin and rubbery resin react. The reaction of the polyamideimide resin with the rubbery resin is carried out for the purpose of improving the flexibility of the polyamideimide resin itself. That is, a polyamideimide resin and a rubbery resin are made to react, and a part of acid components (cyclohexane dicarboxylic acid etc.) of a polyamideimide resin are substituted by a rubber component. As the polyamideimide resin, a known polyamideimide resin can be used. Moreover, well-known rubbery resin or the above-mentioned rubbery resin can be used for rubbery resin. When the rubber-modified polyamideimide resin is polymerized, solvents used for dissolving the polyamideimide resin and the rubbery resin include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and nitro. It is preferable to use 1 type, or 2 or more types of methane, nitroethane, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, acetonitrile, (gamma) -butyrolactone, etc. used.

As the phosphazene-based resin, a known phosphazene-based resin can be used. The phosphazene-based resin is a resin containing phosphazene having a double bond containing phosphorus and nitrogen as constituent elements. The phosphazene-based resin can significantly improve the flame retardant performance by synergistic effects of nitrogen and phosphorus in the molecule. In addition, unlike the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, the resin is stably present in the resin and an effect of preventing migration from occurring is obtained.

As said fluororesin, a well-known fluororesin can be used. Moreover, as a fluororesin, PTFE (polytetrafluoroethylene (tetrafluoride)), PFA (tetrafluoroethylene perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene hexafluoropropylene, for example) Copolymer (4.6 fluoride)), ETFE (tetrafluoroethylene-ethylene copolymer), PVDF (polyvinylidene fluoride (bifluoride)), PCTFE (polychlorotrifluoroethylene (trifluoride)), polyallyl sulfone Or a fluororesin comprising at least one thermoplastic resin and a fluororesin selected from aromatic polysulfides and aromatic polyethers.

Moreover, the said resin layer may also contain the resin hardening | curing agent. As a resin hardener, a well-known resin hardener can be used. For example, as a resin hardening | curing agent, amines, such as dicyandiamide, imidazole, aromatic amine, phenols, such as bisphenol A, brominated bisphenol A, novolaks, such as a phenol novolak resin and cresol novolak resin, phthalic anhydride, etc. Acid anhydride, biphenyl type phenol resin, phenol aralkyl type phenol resin, etc. can be used. Moreover, the said resin layer may also contain 1 type (s) or 2 or more types of the above-mentioned resin hardening | curing agent. These curing agents are particularly effective for epoxy resins.

The specific example of the said biphenyl type phenol resin is shown in General formula (8).

[Formula 8]

Moreover, the specific example of the said phenol aralkyl type phenol resin is shown in General formula (9).

[Formula 9]

As imidazole, a well-known thing can be used, For example, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-ethyl-4- methylimidazole, 2-phenyl-4- Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2 -Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. can be mentioned, These can be used individually or in mixture.

Moreover, it is preferable to use the imidazole provided with the structural formula shown by following formula (10) especially. By using the imidazole of the structural formula shown in this formula (10), the hygroscopicity of the semi-cured resin layer can be remarkably improved, and the long-term storage stability is excellent. It is because imidazole performs a catalytic action at the time of hardening of an epoxy resin, and contributes as a reaction initiator which causes the self-polymerization reaction of an epoxy resin in the initial stage of a hardening reaction.

[Formula 10]

As the resin curing agent of the amines, known amines can be used. Moreover, as the resin curing agent of the said amines, the above-mentioned polyamine and aromatic polyamine can be used, for example, Moreover, aromatic polyamine, polyamide, and the amine adduct obtained by superposing | polymerizing or condensing these with an epoxy resin or polyhydric carboxylic acid, You may use 1 type, or 2 or more types chosen from the group of. Moreover, as a resin hardening | curing agent of the said amines, 4,4'- diamino diphenylene sulfone, 3,3'- diamino diphenylene sulfone, 4, 4- diamino diphenyrel, 2, 2-bis [ It is preferable to use any one or more of 4- (4-aminophenoxy) phenyl] propane or bis [4- (4-aminophenoxy) phenyl] sulfone.

The said resin layer may also contain a hardening accelerator. As a hardening accelerator, a well-known hardening accelerator can be used. For example, tertiary amine, imidazole, urea-type hardening accelerator, etc. can be used as a hardening accelerator.

The said resin layer may also contain a reaction catalyst. As a reaction catalyst, a well-known reaction catalyst can be used. For example, finely divided silica, antimony trioxide, or the like can be used as the reaction catalyst.

It is preferable that the anhydride of the said polyhydric carboxylic acid is a component which contributes as a hardening | curing agent of an epoxy resin. Moreover, the anhydride of the said polyhydric carboxylic acid is phthalic anhydride, maleic anhydride, trimellitic anhydride, a pyromellitic dianhydride, tetrahydroxy phthalic anhydride, hexahydroxy phthalic anhydride, methylhexahydroxy phthalic anhydride, nadine acid, It is preferable that it is methylnadic acid.

The thermoplastic resin may be a thermoplastic resin having a functional group other than the epoxy resin and the alcoholic hydroxyl group polymerizable.

The polyvinyl acetal resin may have a functional group polymerizable with an epoxy resin or maleimide compound other than an acid group and a hydroxyl group. Moreover, the polyvinyl acetal resin may introduce | transduce a carboxyl group, an amino group, or an unsaturated double bond in the molecule | numerator.

As said aromatic polyamide resin polymer, what is obtained by making an aromatic polyamide resin and rubbery resin react is mentioned. Here, an aromatic polyamide resin is synthesize | combined by polycondensation of aromatic diamine and dicarboxylic acid. 4,4'- diamino diphenylmethane, 3,3'- diamino diphenyl sulfone, m-xylenediamine, 3,3'- oxydianiline, etc. are used for aromatic diamine at this time. And phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, etc. are used for dicarboxylic acid.

As the rubbery resin to be reacted with the aromatic polyamide resin, a known rubbery resin or the above-mentioned rubbery resin can be used.

This aromatic polyamide resin polymer is used for the purpose of not being damaged by under etching by etching liquid, when etching the copper foil after processing with the copper clad laminated board.

In addition, the said resin layer sequentially turns a cured resin layer (a "cured resin layer shall mean a hardened resin layer) and a semi-hardened resin layer in order from the copper foil side (namely, the ultra-thin copper layer side of the copper foil with a carrier). The formed resin layer may be sufficient. The cured resin layer may be composed of a polyimide resin having a thermal expansion coefficient of 0 ppm / ° C to 25 ppm / ° C, a polyamideimide resin, or a resin component of any of these composite resins.

Moreover, you may form the semi-hardened resin layer whose thermal expansion coefficient after hardening is 0 ppm / degreeC-50 ppm / degreeC on the said cured resin layer. Moreover, the thermal expansion coefficient of the whole resin layer after hardening of the said cured resin layer and the said semi-hardened resin layer may be 40 ppm / degrees C or less. 300 degreeC or more of glass transition temperature may be sufficient as the said cured resin layer. The semi-cured resin layer may be formed by using a maleimide resin or an aromatic maleimide resin. It is preferable that the resin composition for forming the said semi-hardened resin layer contains maleimide resin, an epoxy resin, and the linear polymer which has a crosslinkable functional group. The epoxy resin can use a well-known epoxy resin or the epoxy resin described in this specification. Moreover, as a linear polymer which has a maleimide resin, an aromatic maleimide resin, and a crosslinkable functional group, a well-known maleimide resin, aromatic maleimide resin, the linear polymer which has a crosslinkable functional group, or the above-mentioned maleimide type resin, aromatic maleim The linear resin which has a mid resin and a crosslinkable functional group can be used.

Moreover, when providing the copper foil with a carrier which has a resin layer suitable for the use for manufacture of a three-dimensionally molded printed wiring board, it is preferable that the said cured resin layer is a high polymer polymer layer which has hardened flexibility. It is preferable that the said high molecular polymer layer consists of resin which has a glass transition temperature of 150 degreeC or more so that a solder mounting process can be endured. It is preferable that the said high molecular polymer layer consists of any 1 type, or 2 or more types of mixed resin of a polyamide resin, a polyether sulfone resin, an aramid resin, a phenoxy resin, a polyimide resin, a polyvinyl acetal resin, and a polyamideimide resin. . Moreover, it is preferable that the thickness of the said high molecular polymer layer is 3 micrometers-10 micrometers.

Moreover, it is preferable that the said high molecular polymer layer contains any 1 type, or 2 or more types of an epoxy resin, a maleimide-type resin, a phenol resin, and a urethane resin. Moreover, it is preferable that the said semi-hardened resin layer is comprised from the epoxy resin composition whose thickness is 10 micrometers-50 micrometers.

Moreover, it is preferable that the said epoxy resin composition contains each component of the following A component-E component.

A component: The epoxy resin whose epoxy equivalent is 200 or less and consists of 1 type (s) or 2 or more types chosen from the group of liquid bisphenol-A epoxy resin, bisphenol F-type epoxy resin, and bisphenol AD-type epoxy resin at room temperature.

B component: High heat resistant epoxy resin.

C component: Phosphorus containing flame-retardant resin which is any 1 type of phosphorus containing epoxy resin and phosphazene resin or resin which mixed these.

D component: Rubber modified polyamideimide resin modified | denatured by the liquid rubber component which has a boiling point in the solvent in the range of 50 degreeC-200 degreeC.

E component: resin curing agent.

B component is "high heat resistant epoxy resin" with high so-called glass transition point Tg. It is preferable that "high heat resistant epoxy resin" here is polyfunctional epoxy resins, such as a novolak-type epoxy resin, a cresol novolak-type epoxy resin, a phenol novolak-type epoxy resin, and a naphthalene type epoxy resin.

As a phosphorus containing epoxy resin of C component, the above-mentioned phosphorus containing epoxy resin can be used. Moreover, the phosphazene-type resin mentioned above can be used as C component phosphazene-type resin.

As the rubber-modified polyamideimide resin of the D component, the rubber-modified polyamideimide resin described above can be used. As the resin curing agent of the E component, the above-mentioned resin curing agent can be used.

A solvent is added to the resin composition shown above and used as a resin varnish, and a thermosetting resin layer is formed as an adhesive layer of a printed wiring board. Resin when the said resin varnish adds a solvent to the resin composition mentioned above, it is prepared in the range whose resin solid content is 30 wt%-70 wt%, and measured based on MIL-P-13949G in MIL specification. Formation of the semi-hardened resin film in which a flow is 5 to 35% of range is possible. A well-known solvent or the solvent mentioned above can be used for a solvent.

The said resin layer is a resin layer which has a 1st thermosetting resin layer and the 2nd thermosetting resin layer located in the surface of the said 1st thermosetting resin layer in order from a copper foil side, and a 1st thermosetting resin layer is a wiring board It is formed with the resin component which does not melt | dissolve in the chemical | medical agent at the time of the desmear process in a manufacturing process, The 2nd thermosetting resin layer uses resin which melt | dissolves and wash | cleans and removes the chemical | medical agent at the time of desmear process in a wiring board manufacturing process. And may be formed. The said 1st thermosetting resin layer may be formed using the resin component which mixed any 1 type or 2 or more types of polyimide resin, polyether sulfone, and polyphenylene oxide. The second thermosetting resin layer may be formed by using an epoxy resin component. When thickness t1 (micrometer) of a said 1st thermosetting resin layer makes rough surface roughness of copper foil with a carrier Rz (micrometer), and makes thickness of a 2nd thermosetting resin layer t2 (micrometer), t1 is Rz It is preferable that it is thickness which satisfy | fills the conditions of <t1 <t2.

The resin layer may be a prepreg in which the skeleton is impregnated with a resin. It is preferable that resin impregnated to the said skeleton material is a thermosetting resin. The prepreg may be a known prepreg or a prepreg used for manufacturing a printed wiring board.

The framework may include aramid fibers or glass fibers or wholly aromatic polyester fibers. It is preferable that the said framework material is a nonwoven fabric or a woven fabric of aramid fiber or glass fiber, or a wholly aromatic polyester fiber. Moreover, it is preferable that the said total aromatic polyester fiber is a wholly aromatic polyester fiber whose melting | fusing point is 300 degreeC or more. The said all aromatic polyester fiber whose melting point is 300 degreeC or more is a fiber manufactured using resin called what is called a liquid crystal polymer, The said liquid crystal polymer is a polymer of 2-hydroxy-6-naphthoic acid and p-hydroxybenzoic acid. It is a main ingredient. Since this all aromatic polyester fiber has a low dielectric constant and low dielectric loss tangent, it has the outstanding performance as a component of an electrical insulation layer, and can use it like a glass fiber and an aramid fiber.

Moreover, in order to improve the wettability with resin of the surface, the fiber which comprises the said nonwoven fabric and a woven fabric is preferable to process a silane coupling agent. The silane coupling agent at this time can use a well-known silane coupling agent, such as an amino type and an epoxy type, or the silane coupling agent mentioned above according to a use purpose.

The prepreg may be a prepreg impregnated with a thermosetting resin in a nonwoven fabric using aramid fibers or glass fibers having a nominal thickness of 70 μm or less, or a skeleton made of glass cross having a nominal thickness of 30 μm or less.

(When the resin layer contains a dielectric (dielectric filler))

The resin layer may contain a dielectric (dielectric filler).

In the case where the dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, the capacitance of the capacitor circuit can be increased for use in forming a capacitor layer. The dielectric (dielectric filler) includes a dielectric powder of a composite oxide having a pebroseite structure such as BaTiO 3, SrTiO 3, Pb (Zr-Ti) O 3 (common name PZT), PbLaTiO 3 · PbLaZrO (common name PLZT), and SrBi2Ta2O9 (common name SBT). Use

The dielectric (dielectric filler) may be powdery. In the case where the dielectric (dielectric filler) is powdery, the powder characteristics of the dielectric (dielectric filler) need to be in the range of 0.01 µm to 3.0 µm, preferably 0.02 µm to 2.0 µm, in particle size. The particle diameter used here is used because the granules form a certain secondary agglomerated state, and thus the precision is inferior in the indirect measurement of estimating the average particle diameter from measured values such as laser diffraction scattering particle size distribution measurement method or BET method. It refers to an average particle diameter obtained by directly observing a dielectric (dielectric filler) with a scanning electron microscope (SEM) and image analysis of the SEM image. In this specification, the particle diameter at this time is represented by DIA. In addition, the image analysis of the powder of the dielectric (dielectric filler) observed using the scanning electron microscope (SEM) in this specification uses the Asahi Engineering Co., Ltd. IP-1000PC, and is a roundness threshold. Circular particle analysis was performed with the value 10 and the overlap degree 20, and the average particle diameter DIA was calculated | required.

By the above-mentioned embodiment, the carrier which has a resin layer containing the dielectric material for improving the adhesiveness of the inner-layer circuit surface of the said inner-layer core material, and the resin layer containing a dielectric material, and forming a capacitor circuit layer with low dielectric tangent. Attached copper foil can be provided.

Resin and / or resin composition and / or compound contained in the above-mentioned resin layer are, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol , Ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylform It melt | dissolves in solvents, such as an amide, and makes it resin resin (resin varnish), and rolls it on the said ultra-thin copper layer, or the said heat-resistant layer, a rustproof layer, or the said chromate treatment layer, or the said silane coupling agent layer, for example. Coating is carried out by a coater method or the like, followed by heating and drying as necessary to remove the solvent to obtain a B stage state. For drying, for example, a hot air drying furnace may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the said resin layer is melt | dissolved using a solvent, The resin solid content is 3 wt%-70 wt%, Preferably it is 3 wt%-60 wt%, Preferably it is 10 wt%-40 wt%, More preferably, It is good also as a resin liquid of 25 wt%-40 wt%. In addition, dissolution using a mixed solvent of methyl ethyl ketone and cyclopentanone is most preferable at this stage from an environmental point of view. Moreover, it is preferable to use the solvent whose boiling point is a range of 50 degreeC-200 degreeC for a solvent.

Moreover, it is preferable that the said resin layer is a semi-hardened resin film whose resin flow at the time of measuring based on MIL-P-13949G in MIL specification exists in 5 to 35% of range.

In this specification, with resin resin, based on MIL-P-13949G in MIL specification, four samples of 10 cm in width and width were sampled from the copper foil with resin which made resin thickness 55 micrometers, and these four pieces The sample was laminated under the condition of a press temperature of 171 ° C, a press pressure of 14 kgf / cm 2, and a press time of 10 minutes in a stacked state (laminate), and the resin outflow weight at that time was measured based on Equation (1). It is the calculated value.

The copper foil with a carrier (copper foil with a carrier with a resin) with the said resin layer superimposes the resin layer, and heat-presses the whole, thermosets the resin layer, and then peels a carrier and makes an ultra-thin copper layer It is used in the aspect which expresses (the natural thing is surface of the intermediate | middle layer side of the ultra-thin copper layer), and forms a predetermined wiring pattern there.

When the copper foil with a carrier with this resin is used, the number of sheets of prepreg material at the time of manufacture of a multilayer printed wiring board can be reduced. Moreover, the thickness of a resin layer can be made into the thickness which can ensure interlayer insulation, or a copper clad laminated board can be manufactured, without using a prepreg material at all. At this time, the surface of the substrate can be undercoated with an insulating resin to further improve the smoothness of the surface.

In addition, when the prepreg material is not used, the material cost of the prepreg material is reduced, and the lamination process is simplified, which is economically advantageous, and the thickness of the multilayer printed wiring board manufactured by the thickness of the prepreg material is There is an advantage that it can be made thin and an ultra-thin multilayer printed wiring board having a thickness of one layer of 100 µm or less can be produced.

It is preferable that the thickness of this resin layer is 0.1-120 micrometers.

When the thickness of the resin layer becomes thinner than 0.1 µm, the adhesive force decreases, and when the copper foil with a carrier with this resin is laminated on a substrate having an inner layer material without interposing a prepreg material, the interlayer insulation between the circuits of the inner layer material It may be difficult to secure. On the other hand, when the thickness of a resin layer is thicker than 120 micrometers, it becomes difficult to form the resin layer of the target thickness in one application | coating process, and it may become disadvantageous economically because extra material cost and process number are needed.

Moreover, when the copper foil with a carrier which has a resin layer is used for manufacturing an ultra-thin multilayer printed wiring board, the thickness of the said resin layer is 0.1 micrometer-5 micrometers, More preferably, 0.5 micrometer-5 micrometers, More preferably, It is preferable to set it as 1 micrometer-5 micrometers in order to make thickness of a multilayer printed wiring board small.

Moreover, when a resin layer contains a dielectric material, it is preferable that the thickness of a resin layer is 0.1-50 micrometers, It is preferable that it is 0.5 micrometer-25 micrometers, It is more preferable that it is 1.0 micrometer-15 micrometers.

The total resin layer thickness of the cured resin layer and the semi-cured resin layer is preferably 0.1 µm to 120 µm, preferably 5 µm to 120 µm, preferably 10 µm to 120 µm, and 10 µm. It is more preferable that it is-60 micrometers. The thickness of the cured resin layer is preferably 2 µm to 30 µm, preferably 3 µm to 30 µm, and more preferably 5 µm to 20 µm. Moreover, it is preferable that the thickness of a semi-hardened resin layer is 3 micrometers-55 micrometers, It is preferable that it is 7 micrometers-55 micrometers, It is more preferable that it is 15 micrometers-115 micrometers. When the total resin layer thickness exceeds 120 µm, it may be difficult to manufacture a thin multilayer printed wiring board, and when it is less than 5 µm, it becomes easy to form a thin multilayer printed wiring board, but between circuits of the inner layer This is because the resin layer, which is an insulating layer of, may become too thin and a tendency to destabilize the insulation between circuits of the inner layer may occur. Moreover, when the cured resin layer thickness is less than 2 micrometers, the surface roughness of a copper foil roughening surface may arise. On the contrary, when the thickness of cured resin layer exceeds 20 micrometers, the effect by the hardened resin layer may not improve especially, and the total insulation layer thickness will become thick.

Moreover, when setting the thickness of the said resin layer to 0.1 micrometer-5 micrometers, in order to improve the adhesiveness of a resin layer and copper foil with a carrier, a heat-resistant layer and / or an rustproof layer, and / or a chromate treatment layer on an ultra-thin copper layer, and After forming a silane coupling process layer, it is preferable to form a resin layer on the said heat-resistant layer, a rustproof layer, a chromate treatment layer, or a silane coupling process layer.

In addition, the thickness of the above-mentioned resin layer says the average value of the thickness measured by cross-sectional observation in arbitrary ten points.

Moreover, as another product form of the copper foil with a carrier with this resin, a resin layer is on the said ultra-thin copper layer, or on the said heat-resistant layer, a rustproof layer, or the said chromate treatment layer, or the said silane coupling process layer. It is also possible to coat | cover with and to make it semi-hardened, and then peeling a carrier and manufacturing it in the form of the copper foil with resin which carrier does not exist.

<6. Printed Wiring Boards>

Below, some examples of the manufacturing process of the printed wiring board using the surface-treated copper foil which concerns on this invention or the copper foil with a carrier are shown. Moreover, a printed circuit board is completed by mounting electronic components in a printed wiring board.

The copper foil with a carrier provided with the copper foil carrier, a peeling layer, and an ultra-thin copper layer in this order is manufactured through the process mentioned above. Although the usage method of the copper foil with a carrier itself is well-known to those skilled in the art, For example, the surface of an ultra-thin copper layer is made into a paper base phenol resin, a paper base epoxy resin, a synthetic fiber cloth base epoxy resin, a glass cloth, a paper composite base material epoxy resin, and a glass cloth. Ultra-thin copper layer bonded to an insulating substrate after forming a copper clad laminated board by bonding together to an insulating substrate, such as a glass nonwoven composite base material epoxy resin, a glass cloth base epoxy resin, a polyester film, and a polyimide film, and peeling a carrier after thermocompression bonding. It can be etched by a conductor pattern for the purpose of manufacturing the printed wiring board finally.

The copper foil with a carrier which concerns on this invention is suitable for formation of the printed wiring board of fine pitch. For example, by using the copper foil with a carrier which concerns on this invention, it has an insulated substrate and the copper circuit formed on the said insulated substrate, The circuit width of the said copper circuit is less than 20 micrometers, and the width of the space between adjacent copper circuits. The printed wiring board of less than 20 micrometers can be manufactured. Furthermore, the printed wiring board of which the circuit width of the said copper circuit is 17 micrometers or less, and the width of the space between adjacent copper circuits is 17 micrometers or less can also be manufactured. Furthermore, the printed wiring board of 15 micrometers or less in circuit width of the said copper circuit, and the width | variety of the space between adjacent copper circuits can also be manufactured. Furthermore, the printed wiring board of 5-10 micrometers in the circuit width of the said copper circuit, and the width of the space between adjacent copper circuits can also be manufactured.

Moreover, a printed circuit board is completed by mounting electronic components in a printed wiring board. By using the copper foil with a carrier which concerns on this invention, for example, it has an insulated substrate and the copper circuit formed on the said insulated substrate, The circuit width of the said copper circuit is less than 20 micrometers, and the width of the space between adjacent copper circuits. A printed circuit board of less than 20 μm can be produced. Furthermore, the printed circuit board of 17 micrometers or less in the circuit width of the said copper circuit, and the width | variety of the space between adjacent copper circuits can also be manufactured. Furthermore, the printed wiring board of which the circuit width of the said copper circuit is 17 micrometers or less, and the width of the space between adjacent copper circuits is 17 micrometers or less can also be manufactured. Furthermore, the printed circuit board of 15 micrometers or less in the circuit width of the said copper circuit, and the width | variety of the space between adjacent copper circuits can also be manufactured. Furthermore, the circuit width of the said copper circuit is 5-10 micrometers, Preferably it is 5-9 micrometers, More preferably, it is 5-8 micrometers, The width of the space between adjacent copper circuits is 5-10 micrometers, Preferably You may manufacture the printed circuit board of 5-9 micrometers, More preferably, it is 5-8 micrometers. Moreover, the pitch of line and space becomes like this. Preferably it is less than 40 micrometers, More preferably, it is 34 micrometers or less, More preferably, it is 30 micrometers or less, More preferably, it is 20 micrometers or less, More preferably, it is 15 micrometers or less. In addition, the lower limit of a line and space does not need to be specifically defined, For example, it is 6 micrometers or more, or 8 micrometers or more, or 10 micrometers or more.

The pitch of the line and space is the distance from the center of the width of the copper circuit to the center of the width of the adjacent copper circuit.

Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier which concerns on this invention are shown.

In one Embodiment of the manufacturing method of the printed wiring board which concerns on this invention, the process of preparing the copper foil with a carrier and an insulated substrate concerning this invention, the process of laminating the said copper foil with a carrier, and an insulated substrate, the said copper foil with a carrier, and an insulated substrate After lamination | stacking so that an ultra-thin copper layer side may face an insulated substrate, a copper clad laminated board is formed through the process of peeling the carrier of the said copper foil with a carrier, and the semiadditive process, the modified semiadditive process, and a partly The process of forming a circuit by any of an additive method and a subtractive method is included. It is also possible for the insulating substrate to have an inner layer circuit inserted therein.

In the present invention, the semi-additive method refers to a method of forming a conductive pattern using electroplating and etching after forming a pattern on a thin electroless plating on an insulating substrate or a copper foil seed layer.

Therefore, in one Embodiment of the manufacturing method of the printed wiring board which concerns on this invention using the semiadditive process, the process of preparing the copper foil with a carrier which concerns on this invention, and an insulated substrate,

Laminating the copper foil with a carrier and an insulating substrate;

After laminating | stacking the said copper foil with a carrier and an insulated substrate, the process of peeling the carrier of the said copper foil with a carrier,

Removing all of the ultra-thin copper layers exposed by peeling the carrier by a method such as etching or plasma using a corrosion solution such as an acid,

Forming a through hole or / and a blind via in the exposed resin layer and the insulating substrate by removing the ultrathin copper layer by etching;

Performing a desmear treatment on the region including the through hole and / or the blind via,

Forming an electroless plating layer on a region comprising said resin and said through hole or / and blind via,

Forming a plating resist on the electroless plating layer,

Exposing to the plating resist and then removing the plating resist in the region where the circuit is formed;

Forming an electroplating layer in a region where the circuit from which the plating resist is removed is formed;

Removing the plating resist,

Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like,

It includes.

In another embodiment of the manufacturing method of the printed wiring board which concerns on this invention using the semiadditive process, the process of preparing the copper foil with a carrier which concerns on this invention, and an insulated substrate,

Laminating the copper foil with a carrier and an insulating substrate;

After laminating | stacking the said copper foil with a carrier and an insulated substrate, the process of peeling the carrier of the said copper foil with a carrier,

Removing all of the ultra-thin copper layers exposed by peeling the carrier by a method such as etching or plasma using a corrosion solution such as an acid,

Forming an electroless plating layer on the surface of the exposed resin layer by removing the ultrathin copper layer by etching;

Forming a plating resist on the electroless plating layer,

Exposing to the plating resist and then removing the plating resist in the region where the circuit is formed;

Forming an electroplating layer in a region where the circuit from which the plating resist is removed is formed;

Removing the plating resist,

Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like,

It includes.

In the present invention, the modified semi-additive method is to remove a resist after laminating a metal foil on an insulating layer, protecting the non-circuit forming portion by a plating resist, and forming the copper thickness of the circuit forming portion by electroplating. And the method of forming a circuit on an insulating layer by removing metal foils other than the said circuit formation part by (flash) etching is pointed out.

Therefore, in one Embodiment of the manufacturing method of the printed wiring board which concerns on this invention using the Modified semiadditive process, the process of preparing the copper foil with a carrier which concerns on this invention, and an insulated substrate,

Laminating the copper foil with a carrier and an insulating substrate;

After laminating | stacking the said copper foil with a carrier and an insulated substrate, the process of peeling the carrier of the said copper foil with a carrier,

Forming a through hole or / and a blind via in the ultrathin copper layer and the insulating substrate exposed by peeling the carrier;

Performing a desmear treatment on the region including the through hole and / or the blind via,

Forming an electroless plating layer on the region including the through hole and / or the blind via,

Forming a plating resist on the surface of the ultrathin copper layer exposed by peeling the carrier;

After forming the plating resist, forming a circuit by electroplating,

Removing the plating resist,

Removing the ultrathin copper layer exposed by removing the plating resist by flash etching;

It includes.

In another embodiment of the manufacturing method of the printed wiring board which concerns on this invention using the modified semiadditive process, the process of preparing the copper foil with a carrier which concerns on this invention, and an insulated substrate,

Laminating the copper foil with a carrier and an insulating substrate;

After laminating | stacking the said copper foil with a carrier and an insulated substrate, the process of peeling the carrier of the said copper foil with a carrier,

Peeling the carrier to form a plating resist on the exposed ultrathin copper layer,

Exposing to the plating resist and then removing the plating resist in the region where the circuit is formed;

Forming an electroplating layer in a region where the circuit from which the plating resist is removed is formed;

Removing the plating resist,

Removing the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like,

It includes.

In the present invention, the partly additive method is provided with a catalyst nucleus on a substrate formed by forming a conductor layer and a substrate formed through holes for through holes and via holes, if necessary, to form a conductor circuit, After forming a soldering resist or plating resist as needed, the method of manufacturing a printed wiring board is performed by forming thickness by electroless-plating process on the said conductor circuit, a through hole, a via hole, etc.

Therefore, in one Embodiment of the manufacturing method of the printed wiring board which concerns on this invention using a partly additive method, the process of preparing the copper foil with a carrier which concerns on this invention, and an insulated substrate,

Laminating the copper foil with a carrier and an insulating substrate;

After laminating | stacking the said copper foil with a carrier and an insulated substrate, the process of peeling the carrier of the said copper foil with a carrier,

Forming a through hole or / and a blind via in the ultrathin copper layer and the insulating substrate exposed by peeling the carrier;

Performing a desmear treatment on the region including the through hole and / or the blind via,

Applying a catalyst nucleus to a region comprising said through hole or / and blind via,

Forming an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier;

Exposing the etching resist and forming a circuit pattern;

Removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosion solution such as an acid to form a circuit,

Removing the etching resist,

Removing the ultrathin copper layer and the catalyst nucleus by etching or plasma using a corrosion solution such as an acid to form a solder resist or a plating resist on the exposed surface of the insulating substrate,

Forming an electroless plating layer in a region where the solder resist or the plating resist is not formed,

It includes.

In the present invention, the subtractive method refers to a method of selectively removing unnecessary portions of copper foil on a copper clad laminate by etching or the like to form a conductor pattern.

Therefore, in one Embodiment of the manufacturing method of the printed wiring board which concerns on this invention using the subtractive method, the process of preparing the copper foil with a carrier which concerns on this invention, and an insulated substrate,

Laminating the copper foil with a carrier and an insulating substrate;

After laminating | stacking the said copper foil with a carrier and an insulated substrate, the process of peeling the carrier of the said copper foil with a carrier,

Forming a through hole or / and a blind via in the ultrathin copper layer and the insulating substrate exposed by peeling the carrier;

Performing a desmear treatment on the region including the through hole and / or the blind via,

Forming an electroless plating layer on the region including the through hole and / or the blind via,

Forming an electroplating layer on the surface of the electroless plating layer,

Forming an etching resist on the surface of the electroplating layer and / or the ultrathin copper layer,

Exposing the etching resist and forming a circuit pattern;

Removing the ultrathin copper layer, the electroless plating layer, and the electroplating layer by a method such as etching or plasma using a corrosion solution such as an acid to form a circuit,

Removing the etching resist,

It includes.

In another embodiment of the manufacturing method of the printed wiring board which concerns on this invention using the subtractive method, the process of preparing the copper foil with a carrier which concerns on this invention, and an insulated substrate,

Laminating the copper foil with a carrier and an insulating substrate;

After laminating | stacking the said copper foil with a carrier and an insulated substrate, the process of peeling the carrier of the said copper foil with a carrier,

Forming a through hole or / and a blind via in the ultrathin copper layer and the insulating substrate exposed by peeling the carrier;

Performing a desmear treatment on the region including the through hole and / or the blind via,

Forming an electroless plating layer on the region including the through hole and / or the blind via,

Forming a mask on the surface of the electroless plating layer,

Forming an electroplating layer on the surface of the electroless plating layer on which no mask is formed;

Forming an etching resist on the surface of the electroplating layer and / or the ultrathin copper layer,

Exposing the etching resist and forming a circuit pattern;

Removing the ultrathin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosion solution such as an acid to form a circuit,

Removing the etching resist,

It includes.

The step of forming the through hole or / and the blind via and the subsequent desmear step need not be performed.

Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing. In addition, although the copper foil with a carrier which has the ultra-thin copper layer in which the roughening process layer was formed here is demonstrated to an example, it is not limited to this, The same print is also performed using the copper foil with a carrier which has the ultra-thin copper layer in which the roughening process layer is not formed. The manufacturing method of a wiring board can be implemented.

First, as shown to FIG. 3-A, the copper foil with a carrier (1st layer) which has the ultra-thin copper layer in which the roughening process layer was formed in the surface is prepared.

Next, as shown to FIG. 3-B, a resist is apply | coated on the roughening process layer of an ultra-thin copper layer, exposure and development are performed, and a resist is etched to a predetermined shape.

Next, as shown to FIG. 3-C, after forming metal plating for circuits, circuit plating of a predetermined shape is formed by removing a resist.

Next, as shown to FIG. 4-D, embedding resin is formed on an ultra-thin copper layer so that circuit plating may be covered (so that circuit plating may be buried), a resin layer is laminated | stacked, and copper foil with another carrier (2nd layer) is then continued. Is bonded from the ultrathin copper layer side.

Next, as shown to FIG. 4-E, a carrier is peeled off from the copper foil with a carrier of a 2nd layer.

Next, as shown to FIG. 4-F, a laser hole is formed in the predetermined position of a resin layer, and circuit plating is exposed and a blind via is formed.

Next, as shown to FIG. 5-G, copper is embedded in a blind via and a via fill is formed.

Next, as shown to FIG. 5-H, circuit plating is formed on a via fill like FIG. 3-B and FIG. 3-C.

Next, as shown to FIG. 5-I, a carrier is peeled off from the copper foil with a carrier of a 1st layer.

Next, as shown to FIG. 6-J, the ultra-thin copper layer of both surfaces is removed by flash etching, and the surface of the circuit plating in a resin layer is exposed.

Next, as shown to FIG. 6-K, bump is formed on the circuit plating in a resin layer, and a copper filler is formed on the said solder. Thus, the printed wiring board using the copper foil with a carrier of this invention is manufactured.

The said other copper foil with a carrier (2nd layer) may use the copper foil with a carrier of this invention, you may use the conventional copper foil with a carrier, and may use a normal copper foil. In addition, one or more circuits may be formed on the circuit of the second layer shown in Fig. 5-H, and the circuit formation may be formed by a semiadditive method, a subtractive method, a partly additive method, or a modifier. You may implement by any method of the semiadditive process.

Moreover, the copper foil with a carrier used for the said 1st layer may have a board | substrate on the carrier side surface of the said copper foil with a carrier. By having the said board | substrate or the resin layer, the copper foil with a carrier used for 1st layer is supported, and since a wrinkle becomes hard to enter, there exists an advantage that productivity improves. Moreover, as long as there is an effect which supports the copper foil with a carrier used for the said 1st layer, all the board | substrates can be used for the said board | substrate. For example, as said board | substrate, the carrier, prepreg, resin layer, a well-known carrier, prepreg, resin layer, a metal plate, metal foil, the plate of an inorganic compound, the foil of an inorganic compound, the plate of an organic compound, the organic compound which are described in this specification Park can be used.

Although there is no restriction | limiting in particular about the timing which forms a board | substrate on a carrier side surface, It is necessary to form before peeling a carrier. It is preferable to form before a process of forming a resin layer in the said ultra-thin copper layer side surface of the said copper foil with a carrier especially, and to form before a process of forming a circuit in the said ultra-thin copper layer side surface of the copper foil with a carrier.

It is preferable that the copper foil with a carrier which concerns on this invention is controlled so that the color difference of the ultra-thin copper layer surface may satisfy the following (1). In this invention, when the color difference of the surface of an ultra-thin copper layer, or various surface treatments, such as a roughening process, is given, the color difference of the surface of the surface treatment layer shows. That is, it is preferable that the copper foil with a carrier which concerns on this invention is controlled so that the color difference of the surface of an ultra-thin copper layer or a roughening process layer, a heat resistant layer, or a rustproof layer, or a chromate treatment layer, or a silane coupling layer may satisfy the following (1). .

(1) Color difference (DELTA) E * ab based on JISZ8730 of the surface of an ultra-thin copper layer or a roughening process layer, a heat resistant layer, or a rustproof layer, or a chromate treatment layer, or a silane coupling process layer is 45 or more.

Here, color difference (DELTA) L, (D) a, (DELTA) b is a comprehensive index measured with a color difference meter, respectively, and adds black / white / red / green / yellow / blue, and shows it using the L * a * b colorimeter based on JIS Z8730, ΔL: black and white, Δa: red green, Δb: cyan. Moreover, (DELTA) E * ab is represented by a following formula using these color differences.

The color difference mentioned above can be adjusted by making the current density at the time of ultra-thin copper layer formation high, making copper concentration low in a plating liquid, and making high the line flow velocity of a plating liquid.

Moreover, the color difference mentioned above can also be adjusted by performing a roughening process on the surface of an ultra-thin copper layer, and forming a roughening process layer. In the case of forming the roughened layer, the current density is higher than the conventional one (for example, 40 to 60 A) by using an electric field solution containing at least one element selected from the group consisting of copper and nickel, cobalt, tungsten, and molybdenum. / dm 2) and can be adjusted by shortening the treatment time (for example, 0.1 to 1.3 seconds). When the roughening layer is not formed on the surface of the ultrathin copper layer, an ultrathin copper layer or a heat resistant layer or an rustproof layer or a chromate treated layer or a silane coupler is used by using a plating bath having a concentration of Ni 2 times or more of other elements. Ni alloy plating (for example, Ni-W alloy plating, Ni-Co-P alloy plating, and Ni-Zn alloy plating) is treated on the surface of the ring treatment layer at a lower current density (0.1 to 1.3 A / dm 2) than before. It can achieve by setting time (20 second-40 second) and processing.

When the color difference ΔE * ab based on JIS Z8730 on the ultrathin copper layer surface is 45 or more, for example, when forming a circuit on the ultrathin copper layer surface of the copper foil with a carrier, the contrast between the ultrathin copper layer and the circuit becomes clear, and As a result, visibility is good and the circuit can be aligned with good precision. The color difference ΔE * ab based on JIS Z8730 on the surface of the ultrathin copper layer is preferably 50 or more, more preferably 55 or more, still more preferably 60 or more.

When the color difference of the surface of an ultra-thin copper layer or a roughening process layer, a heat resistant layer, a rustproof layer, or a chromate treatment layer, or a silane coupling layer is controlled as mentioned above, contrast with circuit plating becomes clear and visibility is favorable. Therefore, in the manufacturing process as shown in FIG. 3-C, for example of the printed wiring board mentioned above, it becomes possible to form circuit plating in a predetermined position with favorable precision. Moreover, according to the manufacturing method of the printed wiring board mentioned above, since the circuit plating is a structure embedded in the resin layer, when removing the ultra-thin copper layer by flash etching as shown to FIG. 6-J, for example, In this way, the circuit plating is protected by the resin layer, and the shape thereof is maintained, thereby facilitating formation of a fine circuit. Moreover, since circuit plating is protected by a resin layer, migration resistance improves and the conduction of the wiring of a circuit is suppressed favorably. For this reason, formation of a fine circuit becomes easy. Moreover, when the ultra-thin copper layer is removed by flash etching as shown to FIG. 6-J and 6-K, since the exposed surface of circuit plating turns into a recessed shape from the resin layer, bumps are formed on the said circuit plating, Moreover, a copper filler becomes easy to form on it, respectively, and manufacturing efficiency improves.

In addition, well-known resin and prepreg can be used for embedding resin (resin). For example, prepreg which is glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, ABF film and ABF made by Ajinomoto Fine Techno Co., Ltd. can be used. Moreover, the resin layer and / or resin and / or prepreg described in this specification can be used for the said embedded resin (resin).

Example

Hereinafter, although an Example of this invention demonstrates this invention further in detail, this invention is not limited at all by these Examples.

1. Manufacture of Copper Foil with Carrier

<Example 1>

As the copper foil carrier, a long electrolytic copper foil (JTC manufactured by JX Nikko Niseki Kinzoku Co., Ltd.) having a thickness of 35 µm was prepared. 4000 g / dm 2 of electrolytic plating was performed on the shiny surface of the copper foil (Rz: 1.2 to 1.4 µm) with a roll-to-roll type continuous plating line (adopted the sectional dressing method shown in Fig. 2) under the following conditions. An adhesion layer of Ni layer was formed.

Ni layer

Nickel sulfate: 250 to 300 g / l

Nickel chloride: 35 to 45 g / l

Nickel acetate: 10 to 20 g / l

Trisodium citrate: 15 to 30 g / l

Polishes: Saccharin, Butyndiol, etc.

Sodium dodecyl sulfate: 30-100 ppm

pH: 4-6

Bath temperature: 50-70 ℃

Current density: 3 to 15 A / dm 2

After washing and pickling, a Cr layer having an adhesion amount of 11 µg / dm 2 was deposited on the Ni layer on the following conditions on a roll-to-roll type continuous plating line (adopted the sectional dressing method shown in Fig. 2). It adhered by chromate treatment.

Electrolytic Chromate Treatment

Liquid composition: potassium dichromate 1-10 g / l, zinc 0-5 g / l

pH: 3-4

Liquid temperature: 50 to 60 ℃

Current density: 0.1 to 2.6 A / dm 2

Coulomb amount: 0.5 to 30 As / dm 2

Subsequently, on the roll-to-roll type continuous plating line (the drum system shown in FIG. 1 is employed), an ultra-thin copper layer having a thickness of 3 µm is formed on the Cr layer by electroplating under the following conditions, thereby forming copper foil with a carrier. Was prepared. In addition, in the present Example, it manufactured also about the copper foil with a carrier whose thickness of the ultra-thin copper layer was 1, 2, 5, and 10 micrometers, and evaluated similarly to the Example whose thickness of an ultra-thin copper layer is 3 micrometers. The results were the same regardless of the thickness.

Ultrathin copper layer

Copper concentration: 30 to 120 g / l

H ₂ SO ₄ concentration: 20 ~ 120 g / ℓ

Electrolytic solution temperature: 20 to 80 ℃

Current density: 10 to 100 A / dm 2

Subsequently, the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and silane coupling treatment were performed on the ultrathin copper layer surface in this order. The roughening process 1 and the roughening process 2 employ | adopt the crumb system (the inter-distance distance is 50 mm) using the drum shown in FIG. 1, and the verse-length dressing system shown in FIG. 2 about antirust process, chromate process, and silane coupling process. Adopted.

Harmonization processing 1

(Solution composition 1)

Cu: 10 to 30 g / l

H ₂ SO ₄ : 10 to 150 g / l

W: 0 (except 0) to 50 mg / l

Sodium dodecyl sulfate: 0 (excluding 0) to 50 mg / l

As: 0 (except 0) to 200 mg / l

(Electroplating condition 1)

Temperature: 30-70 ℃

Current density: 25 to 110 A / dm

Harmonic coulomb amount: 50 to 500 As / dm

Plating time: 0.5-20 seconds

Harmony treatment 2

(Liquid Composition 2)

Cu: 20 to 80 g / l

H ₂ SO ₄ : 50 to 200 g / l

(Electroplating condition 2)

Temperature: 30-70 ℃

Current density: 5 to 50 A / dm 2

Harmonic coulomb amount: 50 to 300 As / dm

Plating time: 1 to 60 seconds

Antirust treatment

(Liquid composition)

NaOH: 40-200 g / l

NaCN: 70-250 g / l

CuCN: 50 to 200 g / l

Zn (CN) ₂ : 2-100 g / l

As ₂ O ₃ : 0.01-1 g / l

(Solution temperature)

40-90 degreeC

(Current condition)

Current density: 1 to 50 A / dm 2

Plating time: 1-20 seconds

Chromate treatment

K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / ℓ

NaOH or KOH: 10-50 g / l

ZnOH or ZnSO ₄ 7H ₂ O: 0.05 to 10 g / l

pH: 7-13

Bath temperature: 20 to 80 ℃

Current density: 0.05 to 5 A / dm 2

Time: 5-30 seconds

Silane coupling treatment

After spray-coating 0.1 vol%-0.3 vol% of 3-glycidoxy propyl trimethoxysilane aqueous solution, it dries and heats for 0.1 to 10 second in 100-200 degreeC air.

After the said surface treatment, the resin layer of "A" mentioned later was formed in the ultrathin copper layer side.

<Example 2>

After the ultrathin copper layer was formed on the copper foil carrier on the same conditions as in Example 1, the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and silane coupling treatment were performed in this order. The roughening process 1 and the roughening process 2 employ | adopt the crumb system (the inter-distance distance is 50 mm) using the drum shown in FIG. 1, and the verse-length dressing system shown in FIG. Adopted. In addition, the thickness of ultra-thin copper foil was 3 micrometers.

Harmonization processing 1

Liquid composition: Copper 10-20 g / l, Sulfuric acid 50-100 g / l

Liquid temperature: 25-50 ℃

Current density: 1 to 58 A / dm 2

Coulomb amount: 4 to 81 As / dm 2

Harmony treatment 2

Liquid composition: copper 10-20 g / l, nickel 5-15 g / l, cobalt 5-15 g / l

pH: 2-3

Liquid temperature: 30-50 ℃

Current density: 24 to 50 A / dm 2

Coulomb amount: 34 to 48 As / dm

Antirust treatment

Liquid composition: nickel 5-20 g / l, cobalt 1-8 g / l

pH: 2-3

Liquid temperature: 40 to 60 ℃

Current density: 5 to 20 A / dm 2

Coulomb amount: 10-20 As / d㎡

Chromate treatment

Liquid composition: potassium dichromate 1-10 g / l, zinc 0-5 g / l

pH: 3-4

Liquid temperature: 50 to 60 ℃

Current density: 0 to 2 A / dm 2 (Also available in electroless for immersion chromate treatment)

Coulomb amount: 0 to 2 As / dm 2 (Also available in electroless for immersion chromate treatment)

Silane coupling treatment

Application of Diaminosilane Aqueous Solution (Diaminosilane Concentration: 0.1-0.5 wt%)

After the said surface treatment, the resin layer of "B" mentioned later was formed in the ultra-thin copper layer side.

<Example 3>

As the copper foil carrier, a long electrolytic copper foil (HLP manufactured by JX Nikko Niseki Kinzoku Co., Ltd.) having a thickness of 35 µm was prepared, and the carrier was attached in the same procedure as in Example 1 for the shiny surface (Rz: 0.1 to 0.3 µm) of the copper foil. Copper foil was manufactured. However, the resin layer formed "C" mentioned later.

<Example 4>

As the copper foil carrier, a long electrolytic copper foil (HLP manufactured by JX Nikko Niseki Kinzoku Co., Ltd.) having a thickness of 35 µm was prepared, and the carrier was attached in the same procedure as in Example 2 to the shiny surface (Rz: 0.1 to 0.3 µm) of the copper foil. Copper foil was manufactured. However, the resin layer formed "D" mentioned later.

Example 5

As the copper foil carrier, a long electrolytic copper foil (HLP of JX Nikko Niseki Kinzoku Co., Ltd.) having a thickness of 35 µm was prepared. About the shiny surface (Rz: 0.1-0.3 micrometer) of this copper foil, the Ni layer of the adhesion amount of 4000 microgram / dm <2> is formed by electroplating with a roll-to-roll type continuous plating line on the conditions similar to Example 1, Subsequently, after forming an ultra-thin copper layer in the same procedure as Example 1, the following rust prevention process (adopted the gusset dressing method) was implemented, without performing a roughening process.

Antirust treatment

Liquid composition: nickel 5-20 g / l, cobalt 1-8 g / l

pH: 2-3

Liquid temperature: 40 to 60 ℃

Current density: 5 to 20 A / dm 2

Coulomb amount: 10-20 As / d㎡

After the said surface treatment, the resin layer of "E" mentioned later was formed in the ultra-thin copper layer side.

Comparative Example 1

After the ultrathin copper layer was formed on the copper foil carrier under the same conditions as in Example 1, the following roughening treatment 1, roughening treatment 2, rust preventing treatment, chromate treatment, and silane coupling treatment were performed on the ultrathin copper layer surface in this order. Was carried out. The roughening process 1 and the roughening process 2 employ | adopt the crumb system (the inter-distance distance is 50 mm) using the drum shown in FIG. 1, and the verse-length dressing system shown in FIG. 2 about antirust process, chromate process, and silane coupling process. Adopted. In addition, the thickness of ultra-thin copper foil was 3 micrometers.

Harmonization processing 1

(Solution composition 1)

Cu: 31-45 g / l

H ₂ SO ₄ : 10 to 150 g / l

As: 0.1-200 mg / l

(Electroplating condition 1)

Temperature: 30-70 ℃

Current density: 25 to 110 A / dm

Harmonic coulomb amount: 50 to 500 As / dm

Plating time: 0.5-20 seconds

Harmony treatment 2

(Liquid Composition 2)

Cu: 20 to 80 g / l

H ₂ SO ₄ : 50 to 200 g / l

(Electroplating condition 2)

Temperature: 30-70 ℃

Current density: 5 to 50 A / dm 2

Harmonic coulomb amount: 50 to 300 As / dm

Plating time: 1 to 60 seconds

Antirust treatment

(Liquid composition)

NaOH: 40-200 g / l

NaCN: 70-250 g / l

CuCN: 50 to 200 g / l

Zn (CN) ₂ : 2-100 g / l

As ₂ O ₃ : 0.01-1 g / l

(Solution temperature)

40-90 degreeC

(Current condition)

Current density: 1 to 50 A / dm 2

Plating time: 1-20 seconds

Chromate treatment

K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / ℓ

NaOH or KOH: 10-50 g / l

ZnOH or ZnSO ₄ 7H ₂ O: 0.05 to 10 g / l

pH: 7-13

Bath temperature: 20 to 80 ℃

Current density: 0.05 to 5 A / dm 2

Time: 5-30 seconds

Silane coupling treatment

After spray-coating 0.1 vol%-0.3 vol% of 3-glycidoxy propyl trimethoxysilane aqueous solution, it dries and heats for 0.1 to 10 second in 100-200 degreeC air.

After the said surface treatment, the resin layer was not formed.

Comparative Example 2

About the roughening process 1 and the roughening process 2, the copper foil with a carrier was manufactured in the same procedure as Example 1 except having adopted the crumb system by the passage head shown in FIG. However, the resin layer was not formed.

Comparative Example 3

About the roughening process 1 and the roughening process 2, the copper foil with a carrier was manufactured in the same procedure as Example 2 except having adopted the crumb system by the passage head shown in FIG. However, the resin layer was not formed.

<Comparative Example 4>

Resin layer "A" mentioned later was formed in the ultrathin copper layer side of the copper foil with a carrier of Comparative Example 1.

Comparative Example 5

Resin layer "B" mentioned later was formed in the ultrathin copper layer side of the copper foil with a carrier of Comparative Example 2.

Comparative Example 6

Resin layer "C" mentioned later was formed in the ultrathin copper layer side of the copper foil with a carrier of Comparative Example 3.

<Example 6>

Copper foil with a carrier was manufactured in the same procedure as in Example 1, except that the resin layer was not formed.

<Example 7>

Copper foil with a carrier was manufactured in the same procedure as in Example 2, except that the resin layer was not formed.

<Example 8>

The copper foil with a carrier was manufactured in the same procedure as in Example 3, except that the resin layer was not formed.

Example 9

The copper foil with a carrier was manufactured in the same procedure as in Example 4 except that the resin layer was not formed.

<Example 10>

A copper foil with a carrier was produced in the same manner as in Example 5 except that the resin layer was not formed.

<Formation of Resin Layer>

Formation of the resin layer was performed as follows.

`` A ''

(Resin synthesis example)

3,4,3 ', 4 in a 2-liter three-necked flask equipped with a reflux condenser equipped with a bead-attached cooling tube on a stainless stir bar, a nitrogen inlet tube and a stopcock attached trap. 117.68 g (400 mmol) of '-biphenyltetracarboxylic dianhydride, 87.7 g (300 mmol) of 1,3-bis (3-aminophenoxy) benzene, 4.0 g (40 mmol) of γ-valerolactone ), Pyridine 4.8 g (60 mmol), 300 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of toluene were added thereto, and the mixture was heated at 180 ° C for 1 hour and then cooled to room temperature. Then, 29.42 g (100 mmol) of 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride, 82.12 g (2,2-bis {4- (4-aminophenoxy) phenyl} propane mmol), NMP 200g, and toluene 40g were added, and after mixing at room temperature for 1 hour, it heated at 180 degreeC for 3 hours, and obtained the block copolymerization polyimide of solid content 38%. This block copolymerized polyimide was General formula (1): General formula (2) = 3: 2 shown below, was number average molecular weight: 70000, and weight average molecular weight: 150000.

[Formula 11]

The block copolymerized polyimide solution obtained by the synthesis example was further diluted with NMP, and it was set as the block copolymerized polyimide solution of 10% of solid content. In this block copolymerized polyimide solution, bis (4-maleimide phenyl) methane (BMI-H, K-Id) was made into solid content weight ratio 35 and solid content weight ratio 65 of block copolymerization polyimide (that is, it contains in resin solution). Bis (4-maleimidephenyl) methane solid content weight: Block copolymerized polyimide solid content weight in a resin solution = 35:65) It melt | dissolved and mixed for 60 minutes and 60 minutes to make a resin solution. Then, the said resin solution is coated on the ultra-thin copper layer side surface of the copper foil with a carrier before forming a resin layer using a reverse roll coating machine, and after drying process for 3 minutes at 120 degreeC, and 3 minutes at 160 degreeC in nitrogen atmosphere, Finally, heat processing was performed at 300 degreeC for 2 minutes, and the copper foil with a carrier was manufactured. In addition, the thickness of the resin layer was 2 micrometers.

`` B ''

In B, the resin composition of 69 weight part of epoxy resins, 11 weight part of hardening agents, 0.25 weight part of hardening accelerators, 15 weight part of polymer components, 3 weight part of crosslinking agents, and 3 weight part of rubbery resins was adjusted. Specifically, it is shown below.

[Composition of Resin Composition]

Component / specific component / specific chemical name (manufacturer) / composition (parts by weight) epoxy resin / bisphenol A type / YD-907 (manufactured by Toto Kasei) / 15 epoxy resin / bisphenol A type / YD-011 (manufactured by Toto Kasei ) / 54 curing agent / aromatic amine / 4,41-diaminodiphenyl sulfone (made by Wakayama purification) / 12

Curing accelerator / imidazole / 2E4MZ (manufactured by Shikoku Chemical Co., Ltd.) / 0.4

Polymer component / polyvinyl acetal resin / 5000A (Denki Chemical Industry Co., Ltd.) / 15

Crosslinking agent / urethane resin / AP-Stable (Nippon polyurethane production) / 3

Rubber component / core shell type nitrile rubber / XER-91 (manufactured by JSR) / 3

And the resin composition shown above was made into the resin composition solution for resin layer formation by adjusting resin solid content to 30 weight% using methyl ethyl ketone and dimethylacetamide. And the resin composition solution for this resin layer formation was apply | coated to the surface of the ultra-thin copper layer side of the copper foil with a carrier before forming a resin layer using the gravure coater. And air drying for 5 minutes is performed, and drying processing is performed for 3 minutes in the heating atmosphere of 140 degreeC after that, the semi-hardened resin layer (adhesive layer) of 1.5 micrometer thickness of a semi-hardened state is formed, and copper foil with a carrier is Prepared. The measurement of the resin flow of the semi-hardened resin layer (adhesive layer) obtained at this time manufactures what formed the semi-hardened resin layer of 40 micrometers thickness on the single side | surface of copper foil of 18 micrometers thickness with the resin composition solution for the said resin layer formation, This was used as the sample for resin flow measurement. Then, four samples of 10 cm in length and width were collected from the sample for measuring the resin flow, and the resin flow was measured in accordance with MIL-P-13949G described above. As a result, the resin flow was 1.5%.

`` C ''

The resin solution which comprises a resin layer was manufactured. In preparing this resin solution, epoxy resin (EPPN-502 manufactured by Nippon Kayaku Co., Ltd.) and polyether sulfone resin (Sumika Excel PES-5003P manufactured by Sumitomo Chemical Co., Ltd.) were used as raw materials. And imidazole type 2E4MZ (made by Shikoku Chemical Co., Ltd.) was added to this as a hardening accelerator, and it was set as the resin composition.

Resin composition: 50 parts by weight of epoxy resin

50 parts by weight of polyether sulfone resin

1 part by weight of a curing accelerator

This resin composition was further obtained as the resin solution by adjusting resin solid content to 30 wt% using dimethylformamide. The resin solution produced as mentioned above was apply | coated to the surface of the ultra-thin copper layer side of copper foil with a carrier before forming a resin layer using the gravure coater. Then, the drying process was performed for 3 minutes in the heating atmosphere of 140 degreeC after that, the resin layer of the 1.5 micrometer thickness of the semi-hardened state was formed, and the copper foil with a carrier which concerns on this invention was obtained. On the other hand, for the measurement of resin flow, copper foil (18 micrometers of copper foil thickness) with resin which made the primer resin layer 40 micrometers thick was manufactured (henceforth "a sample for resin flow measurement"). Then, four samples of 10 cm in length and width were collected from the sample for measuring the resin flow, and the resin flow was measured in accordance with MIL-P-13949G described above. As a result, the resin flow was 1.4%.

`` D ''

The polyimide resin layer is formed as a cured resin layer on the ultra-thin copper layer side surface of the copper foil with a carrier before forming a resin layer, and it is an example of the copper foil with a carrier which used maleimide-type resin for formation of a semi-hardened resin layer.

Preparation of polyamic acid varnish: The polyamic acid varnish for forming a cured resin layer by the casting method is demonstrated. 1 mol of pyromellitic dianhydride and 1 mol of 4,4'- diamino diphenyl ether were dissolved and mixed in N-methylpyrrolidone as a solvent. The reaction temperature at this time was 25 degreeC, and was made to react for 10 hours. And the polyamic-acid varnish whose resin solid content is 20 mass% was obtained.

Formation of cured resin layer: Next, using the obtained polyamic acid varnish, the cured resin layer was formed by the casting method. The polyamic acid varnish is apply | coated to the ultra-thin copper layer side surface of the copper foil with a carrier before forming a resin layer by the multicoater (made by Hirano Texide Co., Ltd.), and it is the conditions of 110 degreeC x 6 minutes in hot-air dryer. Dried. The resin thickness of the cured resin layer after drying was 35 micrometers, and the solvent residual ratio in this step was 32 wt% with respect to the total amount of the resin layer. The composite of the electrolytic copper foil to which this polyamic-acid varnish was apply | coated was put into the hot air oven substituted with nitrogen, it heated up over 15 minutes to room temperature-400 degreeC, and after holding at 400 degreeC for 8 minutes, it cooled. Thereby, the copper coating of the state in which the cured resin layer was laminated | stacked on the ultra-thin copper layer side surface of the copper foil with a carrier by the imide reaction which remove | eliminates a residual solvent from the composite of the copper foil with a carrier with which polyamic acid was apply | coated, and dehydrating and ring-closing a polyamic acid. It was set as the polyimide resin base material. The solvent residual ratio of the copper clad polyimide resin base material obtained by this final heat processing was 0.5 wt% with respect to the resin total amount adhering to the copper foil with a carrier.

Next, the copper foil with a carrier (copper coating polyimide resin base material) in which the cured resin layer was laminated was subjected to corona treatment, and surface modification of the cured resin layer was performed. The corona treatment was performed under conditions of an electric power of 210 W, a speed of 2 m / min, a discharge amount of 300 W · min / m 2, and an irradiation distance of 1.5 mm from the electrode. And in order to measure the thermal expansion coefficient of a cured resin layer, the copper foil with a carrier is removed by peeling and etching from the copper foil with a carrier (corona-treated copper clad polyimide resin base material) in which the cured resin layer after surface modification treatment was laminated | stacked. It was. As a result, the resin thickness of the cured resin layer (polyimide film) obtained by removing the copper foil with a carrier was 27 µm, and the thermal expansion coefficient was 25 ppm / ° C.

Formation of semi-cured resin layer: Here, a semi-cured resin layer is formed on the cured resin layer of the corona-treated copper clad polyimide resin base material. First, the resin composition shown below was melt | dissolved using N, N'- dimethylacetamide as a solvent, and it prepared so that resin solid content might be 30 wt% of a resin varnish.

[Resin Composition to Form Semi-Cured Resin Layer]

Maleimide resin: 4,4'-diphenylmethane bismaleimide (trade name: BMI-1000, manufactured by Daiwa Chemical Industry Co., Ltd.) / 30 parts by weight

Aromatic polyamine resin: 1,3-bis [4-aminophenoxy] benzene (trade name: TPE-R, manufactured by Wakayama Purification Industry Co., Ltd.) / 35 parts by weight

Epoxy resin: Bisphenol A type epoxy resin (brand name: Epikron 850S, Dainippon Ink Chemical Co., Ltd.) / 20 parts by weight

Linear polymer having a crosslinkable functional group: polyvinyl acetal resin (trade name: Denkabutyral 5000A, manufactured by Denki Chemical Industries, Ltd.) / 15 parts by weight

The resin varnish mentioned above is apply | coated to the polyimide resin surface of the corona-treated copper clad polyimide resin base material, air-dried for 5 minutes at room temperature, heat-dried on conditions for 160 degreeCx 5 minutes, and semi-hardened resin layer Was laminated. The resin thickness of the semi-hardened resin layer at this time was 20 micrometers.

And in order to measure the thermal expansion coefficient after hardening of a semi-hardened resin layer, the above-mentioned resin varnish used for formation of a semi-hardened resin layer is apply | coated to the fluorine-type heat resistant film by the same method as the above-mentioned, and it is for 5 minutes at room temperature. It air-dried, it heat-dried on the conditions of 160 degreeCx 5 minutes, and further hardened heating of 200 degreeC * 2 hours, and set it as the cured resin layer for tests of thickness 20micrometer. That is, this cured resin layer for a test corresponds to the case where the semi-hardened resin layer of the copper foil with a carrier which concerns on this invention hardened | cured. The thermal expansion coefficient of this test cured resin layer was 45 ppm / degreeC.

The thickness of the whole resin layer of the copper foil with a carrier obtained as mentioned above was 47 micrometers. And by the method mentioned later, copper foil is etched away from this copper foil with resin, the resin layer which consists of a cured resin layer and a semi-hardened resin layer is used, this is hardened and heated at 200 degreeC x 2 hours, The thermal expansion coefficient of the whole resin layer after hardening the said semi-hardened resin layer was measured. As a result, the coefficient of thermal expansion was 35 ppm / 占 폚. Moreover, peeling strength was 1.0 kgf / cm.

`` E ''

First, the 1st resin composition which comprises a resin layer was manufactured. In manufacturing this 1st resin composition, it is marketed as a mixing varnish with o-cresol novolak-type epoxy resin (YDCN-704 by Toto Chemical Co., Ltd.), the aromatic polyamide resin polymer soluble in a solvent, and cyclopentanone as a solvent. Nippon Gunpowder Co., Ltd. product BP3225-50P was used as a raw material. And in this mixing varnish, 2E4MZ by Shikoku Chemical Co., Ltd. was added as VH-4170 by Dainippon Ink Corporation and a hardening accelerator to the phenol resin as a hardening | curing agent, and it was set as the 1st resin composition which has the compounding ratio shown below.

38 parts by weight of o-cresol novolac epoxy resin

50 parts by weight of aromatic polyamide resin polymer

Phenolic resin 18 parts by weight

0.1 part by weight of a curing accelerator

This 1st resin composition was made into the resin solution by further adjusting resin solid content to 30 weight% using methyl ethyl ketone.

Γ-glycidoxy at a concentration of 5 g / L in ion-exchanged water on the ultrathin copper layer side surface of the copper foil with a carrier before the resin layer formation (the surface treated if the ultrathin copper layer is subjected to surface treatment). It was immersed in the solution which added propyl trimethoxysilane, and it adsorbed. And moisture was blown over 4 second in the furnace adjusted to 180 degreeC atmosphere with the heater, the condensation reaction of the silane coupling agent was performed, and the silane coupling agent layer was formed.

The resin solution produced as mentioned above was apply | coated to the surface in which the silane coupling agent layer of the copper foil with a carrier was formed using the gravure coater. Then, air drying was performed for 5 minutes, drying treatment was then performed for 3 minutes in a heating atmosphere at 140 ° C., a resin layer having a thickness of 1.5 μm in a semi-cured state was formed, and a copper foil with a carrier according to the present invention was obtained. will be. Moreover, the copper foil (henceforth "a sample for resin flow measurement") with resin which made the primer resin layer 40 micrometers thick was manufactured for the measurement of resin flow.

Then, four samples of 10 cm in length and width were collected from the sample for measuring the resin flow, and the resin flow was measured in accordance with MIL-P-13949G described above. As a result, the resin flow was 1.5%.

2. Evaluation of characteristics of copper foil with carrier

About the copper foil with a carrier obtained by making it above, the characteristic evaluation was performed with the following method. The results are shown in Table 1. Further, the "standard deviation (㎛) is""3.91E-16" in "Ra" in Table 1 refers to 3.91 × 10 ^-16 (㎛), and "1.30E-02" is 1.30 × 10 ^-2 ( Μm).

(Surface roughness)

From each copper foil with a carrier (550 mm x 550 mm square) before forming a resin layer, a straight line was drawn vertically and horizontally by 55 mm pitch, and 100 points of the area | regions of 55 mm x 55 mm were allocated per piece. For each area, using a contact roughness measuring instrument (contact illuminometer Surfcorder SE-3C manufactured by Kosaka Research Institute, Inc.), ultra-thin under the following measurement conditions in accordance with JIS B0601-1982 (Ra, Rz) and JIS B0601-2001 (Rt). The surface roughness (Ra, Rt, Rz) of the copper layer was measured, and the average value and standard deviation were measured.

<Measurement conditions>

Cutoff: 0.25 mm

Reference length: 0.8 mm

Measurement environmental temperature: 23-25 ℃

(Migration)

Each copper foil with a carrier (550 mm x 550 mm square) before forming a resin layer was adhere | attached on bismuth type resin, and carrier foil was peeled off then ,. The thickness of the exposed ultrathin copper layer was 1.5 micrometers by soft etching. Then, after washing and drying, DF (Hitachi Chemical Co., Ltd. make, brand name RY-3625) was laminated | stacked on the ultra-thin copper layer. It exposed on the conditions of 15 mJ / cm <2>, liquid-liquid oscillation for 1 minute at 38 degreeC using the developing solution (sodium carbonate), and formed the resist pattern in line and space (L / S) = 15 micrometer / 15 micrometers. Subsequently, after 15 micrometers plating UP using copper sulfate plating (CUBRITE21 by Ebara Udylite), DF was peeled off with the peeling liquid (sodium hydroxide). Thereafter, the ultrathin copper layer was etched away with an sulfuric acid-hydrogen peroxide-based etchant to form a wiring of L / S = 15 μm / 15 μm. From the obtained wiring board, 100 wiring boards were cut out according to the area | region of the size of 55 mm x 55 mm per piece mentioned above.

About each obtained wiring board, the presence or absence of insulation deterioration between wiring patterns was evaluated on the following measurement conditions using the migration measuring device (IMV MIG-9000). For 100 wiring boards, the number of boards in which migration occurred was evaluated.

In addition, about Example 2, the pitch of a line and space is 20 micrometers (L / S = 8micrometer / 12micrometer, L / S = 10micrometer / 10micrometer, L / S = 12micrometer / 8micrometer) The wiring was formed and the migration mentioned above was evaluated. In addition, for Example 3, the pitch of the line and space was 20 µm (L / S = 8 µm / 12 µm, L / S = 10 µm / 10 µm, L / S = 12 µm / 8 µm), The wiring whose pitch of line and space was 15 micrometers (L / S = 5micrometer / 10micrometer, L / S = 8micrometer / 7micrometer) was formed, and the migration mentioned above was evaluated. In addition, when the pitch of the line and space was 15 µm, the thickness of the plating UP was 10 µm. As a result, when the wiring of L / S = 8micrometer / 12micrometer, L / S = 10micrometer / 10micrometer, L / S = 12micrometer / 8micrometer is formed using the copper foil with a carrier of Example 2, Migration rates were 2/100, 2/100, and 3/100, respectively. Moreover, L / S = 8micrometer / 12micrometer, L / S = 10micrometer / 10micrometer, L / S = 12micrometer / 8micrometer, L / S = 5micrometer / 10 using the copper foil with a carrier of Example 3 When the wirings having a thickness of µm and L / S = 8 µm / 7 µm were formed, the in-plane migration rate was 1/100, 1/100, 2/100, 1/100, and 3/100, respectively.

<Measurement conditions>

Threshold: 60% initial resistance down

Measurement time: 1000 h

Voltage: 60 V

Temperature: 85 ℃

Relative Humidity: 85% RH

(Peel strength)

It measured about the peeling strength from the resin base material of the ultra-thin copper layer about the copper foil with a carrier with a manufactured resin layer (but without a resin layer, when not forming a resin layer). Using a BT base material (bismaleimide triazine resin, Mitsubishi Gas Chemical Co., Ltd. product GHPL-830MBT) as a resin base material, this is laminated | stacked on the resin layer side of copper foil with a carrier, and Mitsubishi Gas Chemical Co., Ltd. recommends It was heated and pressed under the conditions to produce a copper clad laminate. Then, after peeling a carrier, the circuit of width 10mm was manufactured by wet etching, and ten measurement samples were produced for every Example / comparative example. Thereafter, the ultrathin copper layer forming the circuit was peeled off, and the 90 degree peel strength was measured for 10 samples, and the average value, the maximum value, the minimum value, and the deviation of the peel strength ((maximum value-minimum value) / Average value x 100 (%)) was calculated | required. The BT substrate is a representative substrate for a semiconductor package substrate. It is preferable that the peeling strength of the ultra-thin copper layer from a BT base material at the time of laminating | stacking a BT base material is 0.70 kN / m or more, and it is more preferable that it is 0.85 kN / m or more.

Claims (2)

As a copper foil with a carrier provided with a carrier, a peeling layer, an ultrathin copper layer, and a voluntary resin layer in this order, the average value of 100 points of Rz on the surface of the ultrathin copper layer is a contact roughness meter based on JIS B0601-1982. Copper foil with a carrier which is 1.15 micrometers or less in measurement, and whose standard deviation of Rz measured at 100 points is 0.1 micrometer or less. The copper foil with a carrier according to claim 1, wherein the ultrathin copper layer is roughened.

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