JP6396967B2 - Copper foil with carrier and copper clad laminate using copper foil with carrier - Google Patents

Description

  The present invention relates to a copper foil with a carrier. More specifically, the present invention relates to a carrier-attached copper foil used as a material for printed wiring boards and shield materials.

Copper and copper alloy foils (hereinafter referred to as copper foils) have greatly contributed to the development of electrical and electronic industries, and are indispensable particularly as printed circuit materials. Copper foils for printed circuits are generally laminated and bonded to substrates such as synthetic resin boards and polyimide films via adhesives, or without using adhesives at high temperature and high pressure, or by applying polyimide precursors. In order to produce a copper-clad laminate by drying and curing, and then forming the desired circuit, the necessary circuit is printed through a resist coating and exposure process, and then an etching process is performed to remove unnecessary portions. Is done.
Finally, the required elements are soldered to form various printed circuit boards for the electronic device. Although the copper foil for printed circuit boards differs in the surface (roughening surface) adhere | attached with a resin base material, and a non-adhesion surface (glossy surface), many methods are each proposed.

For example, the requirements for the roughened surface formed on the copper foil are as follows: 1) No oxidation discoloration during storage, 2) High peel strength with substrate, high temperature heating, wet processing, soldering, chemicals It is sufficient even after treatment or the like, and 3) that there is no so-called lamination stain that occurs after lamination with the substrate and etching.
The roughening treatment of the copper foil plays a major role as determining the adhesiveness between the copper foil and the base material. As this roughening treatment, a copper roughening treatment in which copper was electrodeposited was initially employed. However, various techniques were proposed thereafter, and copper − was used for the purpose of improving the heat-resistant peel strength, hydrochloric acid resistance and oxidation resistance. Nickel roughening is established as one typical processing method.

  The present applicant has proposed a copper-nickel roughening treatment (see Patent Document 1) and has achieved results. The copper-nickel-treated surface exhibits a black color, and particularly in the rolled foil for flexible substrates, this copper-nickel-treated black color has been recognized as a symbol as a product.

However, while the copper-nickel roughening treatment is excellent in heat-resistant peel strength, oxidation resistance and hydrochloric acid resistance, it is difficult to etch with an alkaline etchant that has recently become important as a fine pattern treatment, and has a pitch of 150 μm. When forming a fine pattern having a circuit width or less, the processing layer becomes an etching residue.
Therefore, the present applicant has previously developed a Cu—Co treatment (see Patent Literature 2 and Patent Literature 3) and a Cu—Co—Ni treatment (see Patent Literature 4) as the fine pattern treatment.

  These roughening treatments were good in terms of etching property, alkali etching property and hydrochloric acid resistance, but again proved that the heat-resistant peel strength was reduced when an acrylic adhesive was used, and oxidation resistance was also improved. It was not enough as expected and the color did not reach black, and it was brown to dark brown.

  In response to these demands, the present applicant has formed a cobalt plating layer or a cobalt-nickel alloy plating layer on the surface of the copper foil, followed by a roughening treatment by copper-cobalt-nickel alloy plating. As a matter of course, it has many of the above-mentioned general characteristics, in particular, has the above-mentioned characteristics comparable to Cu-Ni treatment, and does not reduce the heat-resistant peel strength when an acrylic adhesive is used. In addition, the present inventors have succeeded in developing a copper foil treatment method having excellent oxidation resistance and a black surface color (see Patent Document 5).

  Furthermore, as the development of electronic equipment has progressed, the demand for improving the heat-resistant peelability of the copper foil circuit board has become strict, and the present applicant has applied cobalt-cobalt-nickel alloy plating to the surface of the copper foil, followed by cobalt. -It succeeded in developing the copper foil processing method for printing excellent in heat resistance which forms a nickel alloy plating layer and also forms a zinc-nickel alloy plating layer (refer patent document 6). This is a very effective invention and has become one of the main products of today's copper foil circuit materials.

  Later, with the development of electronic equipment, the miniaturization and high integration of semiconductor devices further progressed, and the FPC multilayer substrate technology advanced rapidly. In the manufacturing process of this FPC multilayer board, sulfuric acid and hydrogen peroxide are used as a pretreatment for cleaning the copper foil circuit board in the resist film crimping process and the metal plating process after the fine pattern circuit is formed with the copper-clad laminate. A plurality of surface etching treatments using an etching solution or a solution using an aqueous sulfuric acid solution has been used.

  However, in the surface etching process in the FPC multilayer board manufacturing process, a cobalt-nickel alloy plating layer is formed on the surface of the copper foil referred to in Patent Document 6 after a roughening process by copper-cobalt-nickel alloy plating. In a fine pattern circuit of a copper clad laminate using a printing copper foil for forming a zinc-nickel alloy plating layer, the surface etchant erodes the interface between the copper foil circuit and the substrate resin, and the copper foil circuit and the substrate resin. This causes a problem that an electric circuit failure occurs as an FPC characteristic, and it is required to solve this problem.

  The present applicant states in Patent Document 7 below that a roughening treatment layer by copper-cobalt-nickel alloy plating, a cobalt-nickel alloy plating layer formed on the roughening treatment layer, and this cobalt- In the copper foil for printed circuits in which the zinc-nickel alloy plating layer is formed on the nickel alloy plating layer, a technique has been proposed in which the total amount of zinc-nickel alloy plating layer, the amount of nickel, and the ratio of nickel are predetermined.

Although this technique is effective, Ni can be contained not only in the zinc-nickel alloy layer but also in the roughened layer, the heat-resistant layer, and the weather-resistant layer. In order to obtain a copper foil for printed circuit that can exert a very excellent effect on the FPC characteristics, it is found that it is necessary to further examine the total amount of Ni in the roughened layer, the heat-resistant layer, and the weather-resistant layer. It was.
Furthermore, since Zn can be contained not only in the zinc-nickel alloy layer but also in the weather resistant layer and the rust preventive layer, the total Zn content of all the weather resistant layer and the rust preventive layer is further compared with the above total Ni content. It turns out that the ratio needs to be considered.

  Generally, a printed wiring board is manufactured through a process in which an insulating substrate is bonded to a copper foil to form a copper-clad laminate, and then a conductor pattern is formed on the copper foil surface by etching. In recent years, with the increasing needs for miniaturization and higher performance of electronic devices, higher density mounting of components and higher frequency of signals have progressed, and conductor patterns have become finer (fine pitch) and higher frequency than printed circuit boards. Response is required.

  Recently, copper foils with a thickness of 9 μm or less and further with a thickness of 5 μm or less have been required in response to the fine pitch, but such ultra-thin copper foils have low mechanical strength and are used in the manufacture of printed wiring boards. Copper foil with a carrier has appeared, in which a thick metal foil is used as a carrier, and an ultrathin copper layer is electrodeposited through a release layer, since it is easily broken or wrinkled. It is a general method of using a copper foil with a carrier that the surface of the ultrathin copper layer is bonded to an insulating substrate and thermocompression bonded, and then the carrier is peeled off via the peeling layer.

Here, with respect to the surface of the ultrathin copper layer of the copper foil with a carrier that becomes the adhesive surface with the resin, the peel strength between the ultrathin copper layer and the resin substrate is mainly sufficient, and the peel strength Is required to be sufficiently retained after high-temperature heating, wet processing, soldering, chemical processing, and the like.
As a method of increasing the peel strength between the ultrathin copper layer and the resin base material, generally, a large amount of roughened particles are adhered on the ultrathin copper layer having a large surface profile (unevenness, roughness). The method is representative.

  However, if a very thin copper layer with such a large profile (irregularity, roughness) is used on a semiconductor package substrate that needs to form a particularly fine circuit pattern among printed wiring boards, unnecessary copper particles during circuit etching Will remain, causing problems such as poor insulation between circuit patterns.

For this reason, as a copper foil with a carrier for use in a fine circuit including a semiconductor package substrate, an attempt has been made to use a copper foil with a carrier in which the surface of an ultrathin copper layer is not roughened. The adhesion (peeling strength) between the ultrathin copper layer not subjected to such roughening treatment and the resin is affected by the low profile (unevenness, roughness, roughness) of the general copper foil for printed wiring boards. There is a tendency to decrease when compared. (Patent Document 8)
Therefore, the further improvement is calculated | required about copper foil with a carrier.

JP-A-52-145769 Japanese Examined Patent Publication No. 63-2158 JP-A-2-292895 JP-A-2-292894 Japanese Patent Publication No. 6-54831 Japanese Patent Publication No. 9-87889 WO2009 / 041292 WO2004 / 005588

The present invention relates to a carrier-attached copper foil and a copper-clad laminate, and in particular, after a roughening treatment is formed on the surface of the copper foil, a heat-resistant layer, a weather-resistant layer, and a rust-proof layer are formed thereon, In copper-clad laminates using ring-treated copper foil with carrier, when the substrate is subjected to acid treatment or chemical etching after fine pattern printed circuit formation, the acid to the interface between the copper foil circuit and the substrate resin It is related with copper foil with a carrier which can improve the suppression of the adhesive fall by "dipping" of this, is excellent in acid-proof adhesion strength, and was excellent in alkali etching property.
Along with the development of electronic devices, the miniaturization and high integration of semiconductor devices have further advanced, and the processing performed in the manufacturing process of these printed circuits has become more severe. It is an object of the present invention to provide a technique that meets these requirements.

As described above, the present application provides the following invention.
1) A roughening treatment layer formed by performing a roughening (treat) treatment on a copper foil or a copper alloy foil, a heat-resistant layer comprising a Ni-Co layer formed on the roughening treatment layer, And a surface treatment layer having a weather resistance layer and a rust prevention layer containing Zn, Ni, Cr formed on the heat-resistant layer, and the total Zn content in the surface treatment layer / (total Zn content + total Ni Amount) is 0.02 or more and 0.35 or less, and the total amount of Ni in the surface treatment layer is 1600 μg / dm ² or less.
2) The total Zn amount in the surface treatment layer / (total Zn amount + total Ni amount) is 0.02 or more and 0.23 or less, and the total Ni amount in the surface treatment layer is 1150 μg / dm ² or less. The copper foil with a carrier as described in 1), wherein
3) The copper foil with a carrier according to 1) or 2), wherein the total amount of Ni in the surface treatment layer is 350 to 1350 μg / dm ² .
4) The copper foil with a carrier according to any one of 1) to 3) above, wherein the total amount of Ni in the surface treatment layer is 450 to 1100 μg / dm ² .
5) The total Co amount in the surface treatment layer is 770 to 3200 μg / dm ² , and the total Co amount / (total Zn amount + total Ni amount) is 3.4 or less. The copper foil with a carrier as described in any one of 1).
6) The total amount of Co in the surface treatment layer is 770 to 2500 μg / dm ² , and the total Co / (total Zn + total Ni) is 3.0 or less. Any of the above 1) to 5) A copper foil with a carrier according to claim 1.
7) The copper foil with a carrier according to any one of 1) to 6) above, wherein the total amount of Cr in the surface treatment layer is 50 to 120 μg / dm ² .

The present application also provides the following invention.
8) The copper foil with a carrier according to any one of 1) to 7) above, wherein Ni in the roughened layer is 50 to 550 μg / dm ² .
9) The copper foil with a carrier according to any one of 1) to 8) above, wherein the roughening treatment layer is a roughening treatment layer composed of elements of Co, Cu, and Ni.
10) The copper foil with a carrier according to any one of 1) to 9), wherein the roughened layer comprises fine particles having an average particle diameter of 0.05 to 0.60 μm.
11) The roughening layer is made of fine particles of a ternary alloy composed of Cu, Co, and Ni having an average particle diameter of 0.05 to 0.60 μm. The copper foil with a carrier according to the item.
12) The roughening treatment layer is composed of a primary particle layer having an average particle diameter of 0.25 to 0.45 μm and a secondary particle layer having an average particle diameter of 0.05 to 0.25 μm formed thereon. The copper foil with a carrier according to any one of 1) to 11).
13) The roughening treatment layer includes a primary particle layer of Cu having an average particle diameter of 0.25 to 0.45 μm, and Cu, Co, Ni having an average particle diameter of 0.05 to 0.25 μm formed thereon. The copper foil with a carrier according to any one of 1) to 12) above, which is composed of a secondary particle layer made of a ternary alloy made of

14) Copper foil for printed circuits which consists of the said ultra-thin copper layer of the copper foil with a carrier as described in any one of said 1) -13).
15) The copper foil with a carrier according to any one of 1) to 13), wherein a resin layer is provided on the surface treatment layer.
16) A copper-clad laminate obtained by laminating and bonding a printed circuit copper foil according to 14) above to a resin substrate.
17) The printed wiring board manufactured using the copper foil with a carrier as described in any one of said 1) -13).
18) The printed circuit board manufactured using the copper foil with a carrier as described in any one of said 1) -13.
19) The copper clad laminated board manufactured using the copper foil with a carrier as described in any one of said 1) -13).
20) A step of preparing the carrier-attached copper foil according to any one of 1) to 13) and an insulating substrate,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.
21) The process of forming a circuit in the said ultra-thin copper layer side surface of the copper foil with a carrier as described in any one of said 1) -13),
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Method.
22) forming a circuit on the resin layer,
It is the process of bonding another 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 together to the said resin layer. Manufacturing method of printed wiring board.
23) The method for producing a printed wiring board according to 22), wherein another copper foil with a carrier to be bonded on the resin layer is the copper foil with a carrier according to any one of 1) to 13).
24) The step of forming a circuit on the resin layer is performed by any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method, 21) to 23) The manufacturing method of the printed wiring board of description.
25) The method for producing a printed wiring board according to any one of 21) to 24), further comprising a step of forming a substrate on the carrier-side surface of the carrier-attached copper foil before peeling off the carrier.

The present invention relates to a copper foil for a printed circuit and a copper foil with a carrier for a copper-clad laminate, and in particular, the ultra-thin copper foil with a carrier in which a carrier, an intermediate layer, and an ultra-thin copper layer are laminated in this order. After forming a roughening treatment on the surface of the copper layer, forming a heat-resistant layer, a weather-resistant layer, and a rust-preventing layer on the copper layer, and then using a copper foil with a carrier with a silane coupling treatment, an ultra-thin copper layer In the tension laminate, when the substrate is subjected to acid treatment or chemical etching after the fine pattern printed circuit is formed, it improves the suppression of deterioration in adhesion due to acid "soaking" into the interface between the copper foil circuit and the substrate resin. The present invention relates to a copper foil with a carrier, which has excellent acid-resistant adhesion strength and excellent alkali etching properties.
Along with the development of electronic devices, the miniaturization and high integration of semiconductor devices have further advanced, and the processing performed in the manufacturing process of these printed circuits has become more severe. The present invention is an excellent technique that meets these requirements.

FIG. 1 is an explanatory view showing a state in which an etching solution is eroded from the periphery of a copper foil circuit when surface etching is performed using a solution of hydrogen peroxide and sulfuric acid. FIG. 2 shows the result of observing “soaking” of the etchant into the interface between the copper foil circuit and the substrate resin when the substrate is subjected to surface etching (by a solution of hydrogen peroxide and sulfuric acid) after the fine pattern printed circuit is formed. FIG. The upper diagram (photo) shows no “stain”, and the lower diagram (photo) shows “stain”. 3 shows a copper foil with carrier (A) having an ultrathin copper layer having a roughened layer formed on the surface, a resist is applied on the roughened layer of the ultrathin copper layer, and exposure and development are performed. FIG. 4B is an explanatory view for explaining that a resist plating is formed by etching a resist into a predetermined shape (B) and then forming a circuit plating having a predetermined shape by removing the resist (C). FIG. 4 shows that an embedded resin is provided on an ultrathin copper layer so as to cover circuit plating, and a resin layer is laminated, and then another carrier-attached copper foil (second layer) is adhered from the ultrathin copper layer side ( D) Explanatory drawing explaining peeling a carrier from the copper foil with a carrier of the second layer (E), performing laser drilling at a predetermined position of the resin layer, exposing circuit plating, and forming a blind via (F) It is. FIG. 5 illustrates that copper is embedded in a blind via to form a via fill (G), circuit plating is formed on the via fill (H), and the carrier is peeled from the first layer of copper foil with carrier (I). It is explanatory drawing. FIG. 6 shows that ultrathin copper layers on both surfaces are removed by flash etching, the surface of the circuit plating in the resin layer is exposed (J), bumps are formed on the circuit plating in the resin layers, and the bumps are formed on the bumps. It is explanatory drawing explaining forming a copper pillar (K) and producing the printed wiring board using the copper foil with a carrier of this invention.

The main object of the present invention is to prevent circuit erosion that occurs during surface etching in the pretreatment process in the manufacturing process of the FPC multilayer substrate.
The copper foil with a carrier of the present invention is a roughened layer formed by subjecting a copper foil or a copper alloy foil to a roughening (treating) treatment, and Ni- formed on the roughened layer. It has a heat-resistant layer made of a Co layer, and a plurality of surface treatment layers made of a weather-resistant layer containing Zn, Ni, and Cr and a rust-proof layer formed on the heat-resistant layer. The total Zn content / (total Zn content + total Ni content) in the surface treatment layer is set to 0.02 or more and 0.35 or less.

This is the main condition that can effectively prevent “soaking” that occurs during surface etching. Zn is a component of a weathering layer and a rust prevention layer in the surface treatment layer of copper foil, Ni is a component of a roughening treatment layer, a heat-resistant layer, and a weathering layer, and Zn and Ni are the surfaces of the copper foil It is an important component as a constituent component of the treatment layer.
However, Zn is a component having an effect on weather resistance, but it is an unfavorable component for chemical resistance characteristics in the fine pattern circuit forming process, and “soaking” easily occurs in etching for circuit formation.
On the other hand, Ni is an effective component for “soaking”, but if it is too much, the alkaline etching property is lowered and it is not suitable for printed circuit.

Thus, the present invention has found that the balance between Zn and Ni is important. That is, the total Zn amount / (total Zn amount + total Ni amount) in the surface treatment layer is 0.02 or more and 0.35 or less. In a preferred embodiment, the total Zn content / (total Zn content + total Ni content) in the surface treatment layer can be 0.02 or more and 0.23 or less, more preferably 0.04 or more and 0.03 or less. 23 or less.
If it is less than 0.02, there are cases where Zn is too little and cases where Ni is too much. In cases where Zn is too little, the weather resistance deteriorates. In cases where Ni is too much, etching properties become a problem. Is also not preferred. On the other hand, if it exceeds 0.35, the acid resistance tends to be deteriorated, so that “soaking” tends to occur during etching, which is not preferable.

  The definition of the total Zn amount is “the total amount of Zn contained in the roughened layer, the heat resistant layer, the weather resistant layer, and the rust preventive layer on the copper foil”. When Zn is not contained in the roughened layer and the heat-resistant layer, the total amount of Zn is the sum of the amounts of Zn contained in the two layers of the weather resistant layer and the rust preventive layer. In addition, when Zn is contained in the intermediate layer, the ultrathin copper layer is peeled from the carrier. Then, after masking the surface of the ultrathin copper layer on the roughened layer side with a resin, etc., pickle the surface of the ultrathin copper layer on the intermediate layer side, and include it in the surface of the ultrathin copper layer on the intermediate layer side Zn to be removed. Then, what is necessary is just to measure Zn amount about the said ultra-thin copper layer. In addition, it is good to perform the pickling of the surface by the side of the intermediate | middle layer of an ultra-thin copper layer with the nitric acid aqueous solution mixed by the ratio of nitric acid: water = 1: 2 (volume).

Similarly, the definition of the total amount of Ni is “the amount of Ni contained in the roughened layer, the heat-resistant layer, the weather-resistant layer, and the rust-proof layer on the copper foil (the ultra-thin copper layer of the copper foil with carrier)”. . When Ni is not contained in the rust prevention layer, the total amount of Ni is the sum of the amounts of Ni in the roughening treatment layer, the heat resistant layer, and the weather resistant layer. When Ni is contained in the intermediate layer, the ultrathin copper layer is peeled from the carrier. Then, after masking the surface of the ultrathin copper layer on the roughened layer side with a resin, etc., pickle the surface of the ultrathin copper layer on the intermediate layer side, and include it in the surface of the ultrathin copper layer on the intermediate layer side Ni is removed. Thereafter, the amount of Ni may be measured for the ultrathin copper layer. In addition, it is good to perform the pickling of the surface by the side of the intermediate | middle layer of an ultra-thin copper layer with the nitric acid aqueous solution mixed by the ratio of nitric acid: water = 1: 2 (volume).
The definition of the Ni adhesion amount at the roughening treatment stage is “the amount of Ni contained in the roughening treatment layer on the copper foil (the ultrathin copper layer of the copper foil with carrier)”. The amount of Ni deposited in the roughening treatment stage was the same as that of each example and each comparative example, and after manufacturing a copper foil with a carrier, only the roughening layer was provided under the same conditions as each example and each comparative example. Thereafter, a sample was taken and measured by measuring the Ni adhesion amount in the same manner as the total Ni amount.

  Similarly, the definition of the total amount of Co is “the amount of Co contained in a roughened layer, a heat-resistant layer, a weather-resistant layer, and a rust-proof layer on a copper foil (an ultra-thin copper layer of a copper foil with a carrier)”. . When Co is not contained in the rust preventive layer, the total amount of Co is the total amount of Co in the roughening treatment layer, the heat resistant layer, and the weather resistant layer. When Co is contained in the intermediate layer, the ultrathin copper layer is peeled from the carrier. Then, after masking the surface of the ultrathin copper layer on the roughened layer side with a resin, etc., pickle the surface of the ultrathin copper layer on the intermediate layer side, and include it in the surface of the ultrathin copper layer on the intermediate layer side Remove Co. Thereafter, the amount of Co may be measured for the ultrathin copper layer. In addition, it is good to perform the pickling of the surface by the side of the intermediate | middle layer of an ultra-thin copper layer with the nitric acid aqueous solution mixed by the ratio of nitric acid: water = 1: 2 (volume).

  Similarly, the definition of the total Cr amount is “the amount of Cr contained in the roughened layer, the heat-resistant layer, the weather-resistant layer, and the rust-proof layer on the copper foil (ultra-thin copper layer of the copper foil with carrier)”. . In general, when Cr is not contained in the heat-resistant layer and the weather-resistant layer, the total Cr amount is the sum of the Cr amounts in the roughened layer and the rust preventive layer. When Cr is contained in the intermediate layer, the ultrathin copper layer is peeled from the carrier. Then, after masking the surface of the ultrathin copper layer on the roughened layer side with a resin, etc., pickle the surface of the ultrathin copper layer on the intermediate layer side, and include it in the surface of the ultrathin copper layer on the intermediate layer side Remove Cr. Thereafter, the Cr amount of the ultrathin copper layer may be measured. In addition, it is good to perform the pickling of the surface by the side of the intermediate | middle layer of an ultra-thin copper layer with the nitric acid aqueous solution mixed by the ratio of nitric acid: water = 1: 2 (volume).

In the present invention, the above-mentioned total Ni amount and total Co amount are measured by atomic absorption analysis after dissolving the sample in a nitric acid aqueous solution mixed at a ratio of nitric acid: water = 1: 2 (volume), and the total Cr amount described above. The total Zn content is measured by boiling and dissolving a sample in a hydrochloric acid aqueous solution mixed at a ratio of hydrochloric acid: water = 1: 4 (volume) and performing quantitative analysis by atomic absorption spectrometry. In addition, the Ni adhesion amount, the total Ni amount, the total Co amount, the total Cr amount, and the total Zn amount at the roughening treatment stage are the adhesion masses of Ni, Co, Cr, and Zn per unit area (dm ² ) of the sample, respectively. Displayed in (μg).

The “soaking” is shown in FIG. 1, but the circuit is formed by etching using a solution of hydrogen peroxide and sulfuric acid, or using an etchant composed of a cupric chloride solution, a ferric chloride solution, or the like. This refers to a phenomenon in which an etchant penetrates into the interface between a copper foil and a resin when the formation is etched.
The left side of FIG. 1 is a conceptual diagram showing a state (▼ portion) in which the circuit surfaces of the resin layer and the copper foil with a surface treatment layer are in close contact with each other. The right side of FIG. 1 is a conceptual diagram showing a state (▼ portion) in which permeation occurs on both edges of the circuit and adhesion is slightly reduced.

  Further, in FIG. 2, after the fine pattern printed circuit was formed, the “soaking” of the acid into the interface between the copper foil circuit and the substrate resin was observed when the substrate was soft-etched (by a solution of hydrogen peroxide and sulfuric acid). The figure (photograph) which shows a result is shown. The upper figure (photo) shows the case where there is no stain at the edge of the linear circuit, and the lower figure (photo) shows the case where there is “stain”. It can be observed that the edge of the linear circuit is disturbed.

Ni is a component contained in the roughened layer, heat resistant layer, weather resistant layer, and rust preventive layer of the surface treatment layer as described above, and is an extremely important component in the surface treatment layer of the ultrathin copper layer. And it is a component effective in "sinking" which is a problem to be solved by the present invention.
Thus, a copper foil with a carrier of the present invention, the total Ni content of the surface treatment layer is at 1600μg / dm ² or less, preferably 1150μg / dm ² or less. The total amount of Ni of the surface treatment layer is preferably set to be 350~1350μg / dm ^2, and more preferably to 450~1100μg / dm ^2.

In addition, since the Ni contained in the roughened layer needs to have the surface of the surface-treated copper foil appear black, Ni may need to be contained in an amount of 50 μg / dm ² or more.
Furthermore, since Ni is also included in the heat-resistant layer and the weather-resistant layer, 350 μg / dm ² or more may be necessary as the total amount of Ni, and 450 μg / dm ² or more may be necessary. However, if the total amount of Ni exceeds 1350 μg / dm ² or 1100 μg / dm ² , there may occur a problem that the alkali etching property is deteriorated or rough particles remain on the substrate resin surface during circuit etching. Ni amount may desirable 1350μg / dm ² or less, it can be said that there is a case 1100μg / dm ² or less is more preferable.

Furthermore, Co is an important component by contributing to heat resistance as a component used for the surface treatment layer of the copper foil, and the amount used is larger than other components. However, it is an unfavorable component for “soaking”. Therefore, in the copper foil with a surface treatment layer of the present invention, it may be desirable that the total amount of Co in the surface treatment layer is 770 to 3200 μg / dm ² . In a preferred embodiment, the total amount of Co in the surface treatment layer can be 770 to 2500 μg / dm ² , more preferably 940 to 2500 μg / dm ² .

On the other hand, there are cases where sufficient heat resistance is less than 770μg / dm ² can not be obtained, sometimes significantly exceeds 3200μg / dm ² is "penetration" occurs when more than 2500 g / dm ² "penetration" In some cases, the above numerical value range is set. In order to improve heat resistance, the total amount of Co in the surface treatment layer is particularly preferably 940 μg / dm ² or more. Further, the total Co amount / (total Zn amount + total Ni amount) is preferably 3.0 or less. Even if the total Co amount is in the above range, the “penetration” tends to deteriorate when the total Co amount is large relative to the total of the total Zn amount and the total Ni amount as other main components. Because there are cases.

Moreover, as for the copper foil with a surface treatment layer of this invention, it is desirable that the total Cr amount in the said surface treatment layer shall be 50-120 microgram / dm < ² >. The total Cr amount within this range has the effect of suppressing the penetration amount similarly.

Moreover, 50-550 microgram / dm < ² > is effective for Ni of the roughening process layer of the copper foil with a surface treatment layer of this invention.
For the roughened layer, a roughened layer made of Co, Cu, or Ni is effective. The roughening layer is preferably fine particles having an average particle size of 0.05 to 0.60 μm, and fine particles of a ternary alloy composed of Cu, Co, and Ni having an average particle size of 0.05 to 0.60 μm. It can also be an aggregate of particles. The fine particles having an average particle diameter of 0.05 to 0.60 μm can be formed by burn plating (roughening plating treatment) of alloy plating containing copper.
About the said roughening process layer, it is set as a primary particle layer with an average particle diameter of 0.25-0.45 micrometer, and a secondary particle layer with an average particle diameter of 0.05-0.25 micrometer formed on it. preferable. Moreover, about the said roughening process layer, Cu primary particle layer with an average particle diameter of 0.25-0.45 micrometer, and Cu, Co with an average particle diameter of 0.05-0.25 micrometer formed on it, A secondary particle layer made of a ternary alloy made of Ni can be formed. The primary particle layer is preferably a copper plating burn plating (roughening plating treatment). Moreover, the said secondary particle layer can be formed by the baking plating (roughening plating process) of the alloy plating containing copper.

  The conditions for forming the roughened layer, the heat-resistant layer made of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr and the rust-preventing layer can be formed using the following conditions for electrolytic plating.

(Roughening conditions)
When roughening a finely roughened particle aggregate of a ternary alloy composed of Cu, Co, and Ni having an average particle size of 0.05 to 0.60 μm Liquid composition: Cu 10 to 20 g / liter, Co 1 to 10 g / liter , Ni 1-15 g / liter pH: 1-4
Temperature: 30-50 ° C
Current density (D _k ): 20 to 50 A / dm ²
Time: 1-5 seconds

  A primary particle layer of Cu having an average particle size of 0.25 to 0.45 μm and a ternary alloy composed of Cu, Co, and Ni having an average particle size of 0.05 to 0.25 μm formed thereon. When a roughening treatment consisting of a secondary particle layer is applied

(A) Cu primary particle layer formation Liquid composition: Cu 10-20 g / liter, sulfuric acid 50-100 g / liter pH: 1-3
Temperature: 25-50 ° C
Current density (D _k ): 1 to 60 A / dm ²
Time: 1-5 seconds

(B) Formation of secondary particle layer composed of ternary alloy composed of Cu, Co, Ni Liquid composition: Cu 10-20 g / liter, Co 1-15 g / liter, Ni 1-15 g / liter pH: 1-3
Temperature: 30-50 ° C
Current density (D _k ): 10 to 50 A / dm ²
Time: 1-5 seconds

  Moreover, you may perform metal layer plating between copper foil and primary particle | grains before said primary particle formation. As the metal plating layer, a copper plating layer and a copper alloy plating layer are typically considered. When performing the copper plating layer, when using only copper sulfate and an aqueous copper sulfate solution mainly composed of sulfuric acid, sulfuric acid, an organic sulfur compound having a mercapto group, a surfactant such as polyethylene glycol, and a chloride ion The method of forming a copper plating layer by electroplating using the copper sulfate aqueous solution which combined these.

(Conditions for forming a heat-resistant layer)
Liquid composition: Co 1-20 g / liter, Ni 1-20 g / liter pH: 1-4
Temperature: 30-60 ° C
Current density (D _k ): 1 to 20 A / dm ²
Time: 1-5 seconds

(Condition 1 for forming a weather resistant layer and a rust preventive layer)
Liquid composition: Ni 1-30 g / liter, Zn 1-30 g / liter pH: 2-5
Temperature: 30-50 ° C
Current density (D _k ): 1 to 3 A / dm ²
Time: 1-5 seconds

(Condition 2 for forming a weather resistant layer and a rust preventive layer)
Solution _{composition: K 2 Cr 2 O 7:} 1~10g / l, Zn: 0 to 10 g / l pH: 2 to 5
Temperature: 30-50 ° C
Current density (D _k ): 0.01 to 5 A / dm ²
Time: 0.01-5 seconds

The immersion chromate treatment can be performed at a plating current density of 0 A / dm ² .

(Silane coupling treatment)
A silane coupling treatment for applying a silane coupling agent to at least the roughened surface on the anticorrosive layer is performed.
Examples of the silane coupling agent include olefin silanes, epoxy silanes, acrylic silanes, amino silanes, and mercapto silanes, which can be appropriately selected and used.

  Moreover, a well-known silane coupling agent may be used for the silane coupling agent used for a silane coupling process, for example, using an amino-type silane coupling agent or an epoxy-type silane coupling agent, a mercapto-type silane coupling agent. Good. Silane coupling agents include vinyltrimethoxysilane, vinylphenyltrimethoxylane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, and γ-aminopropyl. Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, γ-mercaptopropyltrimethoxysilane or the like may be used.

  The silane coupling treatment layer may be formed using a silane coupling agent such as an epoxy silane, an amino silane, a methacryloxy silane, or a mercapto silane. In addition, you may use 2 or more types of such silane coupling agents in mixture. 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 referred to here is N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 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-aminopropyltris (methoxyethoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminoundecyltrimethoxysilane, 3- (2 -N-benzylaminoethylaminopropyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, (N, N- Dimethyl-3-aminopropyl) Limethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N -Β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane Good.

The silane coupling treatment layer is 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 in terms of silicon atoms. / M ² is desirable. In the case of the above-mentioned range, the adhesiveness between the base resin and the surface-treated copper foil can be further improved.

  The application method may be any of spraying a silane coupling agent solution, applying a coater, dipping, pouring and the like. Since these are already known techniques (see, for example, Japanese Patent Publication No. 60-15654), details are omitted.

(Career)
For the carrier of the copper foil with a carrier of the present invention, a foil of copper foil, aluminum foil, aluminum alloy foil or iron alloy, stainless steel, nickel, nickel alloy or the like can be used. In consideration of the ease of stacking the intermediate layer on the carrier, the carrier is preferably a copper foil. The copper foil used for the carrier is typically provided in the form of a rolled copper foil or an electrolytic copper foil.

In general, the electrolytic copper foil is produced by electrolytically depositing copper on a titanium or stainless steel drum from a copper sulfate plating bath. Moreover, a rolled copper foil is manufactured by repeating plastic working and heat treatment with a rolling roll. In addition to high-purity copper such as tough pitch copper (JIS H3100 C1100) and oxygen-free copper (JIS H3100 C1020), for example, copper alloys containing Sn-containing copper, Ag-containing copper, Cr, Zr, Mg, etc. Further, a copper alloy such as a Corson copper alloy to which Ni, Si, or the like is added can also be used. In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.

  The thickness of the carrier that can be used in the present invention is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, for example, 12 μm or more. However, if it is too thick, the production cost becomes high, so generally it is preferably 35 μm or less. Accordingly, the thickness of the carrier is typically 12-70 μm, more typically 18-35 μm.

(Middle layer)
An intermediate layer is provided on the carrier. Another layer may be provided between the carrier and the intermediate layer. The intermediate layer of the carrier-attached copper foil of the present invention is made of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or an alloy thereof, or a hydrate thereof, or an oxide thereof. Or it is preferable to form in the layer containing any 1 or more types of organic substance. The intermediate layer may be a plurality of layers.

  For example, the intermediate layer is a single metal layer made of any one of elements of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side, or Cr, Ni , Co, Fe, Mo, Ti, W, P, Cu, Al, an alloy layer made of one or more elements selected from the element group, and then Cr, Ni, Co, Fe, Mo, Ti, W , P, Cu, Al, Zn A layer composed of a hydrate or oxide of one or more elements selected from the element group.

Further, for example, the intermediate layer can be composed of two layers of Ni and Cr. The Ni layer is laminated 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. The adhesion amount of the intermediate layer of Cr deposition amount of 10~100μg / dm ^2, Ni can be set with 1000~40000μg / dm ^2. The intermediate layer may contain Zn.

(Strike plating)
An ultrathin copper layer is provided on the intermediate layer. Before that, strike plating with a copper-phosphorus alloy may be performed in order to reduce pinholes in the ultrathin copper layer. Examples of the strike plating include a copper pyrophosphate plating solution.

(Ultra-thin copper layer)
An ultrathin copper layer is provided on the intermediate layer. Another layer may be provided between the intermediate layer and the ultrathin copper layer. The ultrathin copper layer of the copper foil with a carrier of the present invention can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc. A copper sulfate bath is preferred because it is possible to form a copper foil at a high current density.
The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. It is typically 0.1 to 12 μm, more typically 0.5 to 12 μm, and more typically 2 to 5 μm.

(Copper foil with carrier)
In this way, a carrier-attached copper foil including a carrier and an intermediate layer laminated on the carrier and an ultrathin copper layer laminated on the intermediate layer is manufactured. The method of using the copper foil with carrier itself is well known to those skilled in the art. For example, the surface of the ultra-thin copper layer is made of paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite. Ultra-thin bonded to an insulating substrate, bonded to an insulating substrate such as a base epoxy resin, glass cloth / glass nonwoven fabric composite epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc. The copper layer can be etched into the intended conductor pattern to finally produce a printed wiring board.
In the case of the copper foil with a carrier according to the present invention, the peeling site is mainly the interface between the carrier and the intermediate layer or the interface between the intermediate layer and the ultrathin copper layer. Further, when the intermediate layer is composed of a plurality of layers, it may be peeled off at the interface between the plurality of layers.

(Resin layer)
Moreover, the copper foil with a carrier of the present invention may include a resin layer on the surface treatment layer. The resin layer may be an insulating resin layer.
Note that the order of forming the heat-resistant layer, the rust-proofing layer, the chromate-treated layer, and the silane coupling-treated layer is not limited to each other, and in any order on the ultrathin copper layer or the roughened layer. These layers may be formed.

  The resin layer may be an adhesive resin, that is, an adhesive, or an adhesive semi-cured (B stage state) insulating resin layer. The semi-cured state (B stage state) is a state in which there is no sticky feeling even if the surface is touched with a finger, the insulating resin layer can be stacked and stored, and a curing reaction occurs when subjected to heat treatment. Including that.

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. The resin layer may contain a known resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, and the like. The resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication. No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179722, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 No. -249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, No. 5-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Application Laid-Open No. 2006-257153, Japanese Patent Application Laid-Open No. 2007-326923, Japanese Patent Application Laid-Open No. 2008-11169, and Japanese Patent No. 5024930. No. WO 2006/028207, Japanese Patent No. 4828427, JP 2009-67029, International Publication No. WO 2006/134868, Japanese Patent No. 5046927, JP 2009-173017, International Publication No. WO 2007/105635, Patent No. 5180815, International Publication Number WO2008 / 114858, International Publication Number WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 / 145179, International Publication Number Nos. WO2011 / 068157, JP-A-2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.

  The type of the resin layer is not particularly limited. For example, epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleimide resin , Polyvinyl acetal resin, urethane resin, polyethersulfone (also referred to as polyethersulfone or polyethersulfone), polyethersulfone (also referred to as polyethersulfone or polyethersulfone) resin, aromatic polyamide resin, aromatic Polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamideimide resin, rubber modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine tree Fat, thermosetting polyphenylene oxide resin, cyanate ester resin, carboxylic acid anhydride, polyvalent carboxylic acid anhydride, linear polymer having crosslinkable functional group, polyphenylene ether resin, 2,2-bis (4 -Cyanatophenyl) propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, siloxane-modified polyamideimide resin, cyanoester resin, phosphazene resin, Select from the group of rubber-modified polyamide-imide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy, polymer epoxy, aromatic polyamide, fluororesin, bisphenol, block copolymerized polyimide resin, and cyanoester resin It can be mentioned resins containing one or more kinds as suitable to be.

The epoxy resin has two or more epoxy groups in the molecule and can be used without any problem as long as it can be used for electric / electronic materials. The epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. Also, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated (brominated) epoxy Resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate, N, N -Glycidyl amine compounds such as diglycidyl aniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl type epoxy resins, One or two or more types selected from the group of phenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin can be used, or a hydrogenated product of the epoxy resin or Halogenated substances can be used.
As the phosphorus-containing epoxy resin, a known epoxy resin containing 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 the molecule. Is preferred.

  The epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is converted to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. After reacting naphthoquinone or hydroquinone to obtain a compound represented by the following chemical formula 1 (HCA-NQ) or chemical formula 2 (HCA-HQ), an epoxy resin is reacted with the OH group portion to obtain a phosphorus-containing epoxy resin. Is.

(Chemical formula 1)

(Chemical formula 2)

  The phosphorus-containing epoxy resin obtained using the above-described compound as a raw material is preferably used by mixing one or two compounds having the structural formula shown in any one of the following chemical formulas 3 to 5. This is because the resin quality in a semi-cured state is excellent in stability, and at the same time, the flame retardant effect is high.

(Chemical formula 3)

(Chemical formula 4)

(Chemical formula 5)

  Further, as the brominated (brominated) epoxy resin, a known brominated (brominated) epoxy resin can be used. For example, the brominated (brominated) epoxy resin is a brominated epoxy resin having the structural formula shown in Chemical Formula 6 obtained as a derivative from tetrabromobisphenol A having two or more epoxy groups in the molecule, Chemical Formula 7 shown below It is preferable to use one or two brominated epoxy resins having the structural formula shown in FIG.

(Chemical formula 6)

(Chemical formula 7)

  As the maleimide resin, aromatic maleimide resin, maleimide compound or polymaleimide compound, known maleimide resins, aromatic maleimide resins, maleimide compounds or polymaleimide compounds can be used. For example, as maleimide resin or aromatic maleimide resin or maleimide compound or polymaleimide compound, 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl -5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1, It is possible to use 3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene and a polymer obtained by polymerizing the above compound with the above compound or other compounds. The maleimide resin may be an aromatic maleimide resin having two or more maleimide groups in the molecule, and an aromatic maleimide resin having two or more maleimide groups in the molecule and a polyamine or aromatic polyamine. Polymerization adducts obtained by polymerizing and may be used.

  As the polyamine or aromatic polyamine, known polyamines or aromatic polyamines can be used. For example, as polyamine or 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′-diaminodiphenyl ether, 4,4′-diamino-3-methyldiphenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylsulfone, bis (4-aminophenyl) phenylamine, m-xylenediamine, p-xylenediamine, 1,3-bis [4-aminophenoxy] benzene, 3-methyl-4,4 ′ -Diaminodiphenylmethane, 3,3'- Ethyl-4,4′-diaminodiphenylmethane, 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) phenylethane, ethylenediamine and hexamethylenediamine, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, the above compound, and the above compound or other compounds A polymer obtained by polymerizing 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 known phenoxy resin can be used as the 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 the bisphenol, known bisphenols can be used, and bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4′-dihydroxybiphenyl, HCA (9,10-Dihydro-9-Oxa- Bisphenol obtained as an adduct of 10-phosphophenanthrene-10-oxide) and quinones such as hydroquinone and naphthoquinone can be used.

  As the linear polymer having a crosslinkable functional group, a known linear polymer having a crosslinkable functional group can be used. For example, the linear polymer having a crosslinkable functional group preferably has a functional group that contributes to the curing reaction of an epoxy resin such as a hydroxyl group or a carboxyl group. And it is preferable that the linear polymer which has this crosslinkable functional group is soluble in the organic solvent of the temperature of 50 to 200 degreeC of boiling points. Specific examples of the linear polymer having a functional group mentioned here include polyvinyl acetal resin, phenoxy resin, polyethersulfone resin, polyamideimide resin and the like.

  The resin layer may contain a crosslinking agent. A known crosslinking agent can be used as the crosslinking agent. For example, a urethane-based resin can be used as the crosslinking agent.

  A known rubber resin can be used as the rubber resin. For example, the rubber resin is described as a concept including natural rubber and synthetic rubber. The latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, acrylonitrile butadiene rubber, acrylic rubber ( Acrylic ester copolymer), polybutadiene rubber, isoprene rubber and the like. Furthermore, when ensuring the heat resistance of the resin layer to be formed, it is also useful to select and use a synthetic rubber having heat resistance such as nitrile rubber, chloroprene rubber, silicon rubber, urethane rubber or the like. Regarding these rubber resins, it is desirable to have various functional groups at both ends in order to produce a copolymer by reacting with an aromatic polyamide resin or a polyamideimide resin. In particular, it is useful to use CTBN (carboxy group-terminated butadiene nitrile). Moreover, among acrylonitrile butadiene rubbers, a carboxyl-modified product can take a crosslinked structure with an epoxy resin and improve the flexibility of the cured resin layer. As the carboxyl-modified product, carboxy group-terminated nitrile butadiene rubber (CTBN), carboxy group-terminated butadiene rubber (CTB), and carboxy-modified nitrile butadiene rubber (C-NBR) can be used.

  A known polyimide amide resin can be used as the polyamide imide resin. In addition, as the polyimide amide resin, for example, trimellitic anhydride, benzophenonetetracarboxylic anhydride and vitorylene diisocyanate are heated in a solvent such as N-methyl-2-pyrrolidone and / or N, N-dimethylacetamide. By heating the resin obtained by doing so, trimellitic anhydride, diphenylmethane diisocyanate and carboxyl group-terminated acrylonitrile-butadiene rubber in a solvent such as N-methyl-2-pyrrolidone and / or N, N-dimethylacetamide What is obtained can be used.

  A known rubber-modified polyamideimide resin can be used as the rubber-modified polyamideimide resin. The rubber-modified polyamideimide resin is obtained by reacting a polyamideimide resin and a rubber resin. The reaction of the polyamide-imide resin and the rubber resin is performed for the purpose of improving the flexibility of the polyamide-imide resin itself. That is, the polyamideimide resin and the rubber resin are reacted to replace a part of the acid component (cyclohexanedicarboxylic acid or the like) of the polyamideimide resin with the rubber component. A known polyamideimide resin can be used as the polyamideimide resin. As the rubber resin, a known rubber resin or the aforementioned rubber resin can be used. Solvents used for dissolving the polyamideimide resin and the rubbery resin when polymerizing the rubber-modified polyamideimide resin include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, nitromethane, nitroethane, tetrahydrofuran , Cyclohexanone, methyl ethyl ketone, acetonitrile, γ-butyrolactone, and the like are preferably used alone or in combination.

  A known phosphazene resin can be used as the phosphazene resin. The phosphazene resin is a resin containing phosphazene having a double bond having phosphorus and nitrogen as constituent elements. The phosphazene resin can dramatically improve the flame retardancy due to the synergistic effect of nitrogen and phosphorus in the molecule. In addition, unlike 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, it exists stably in the resin, and the effect of preventing the occurrence of migration is obtained.

  A known fluororesin can be used as the fluororesin. Examples of the fluororesin include PTFE (polytetrafluoroethylene (tetrafluoroethylene)), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene / hexafluoropropylene copolymer (4.6). Fluoride)), ETFE (tetrafluoroethylene / ethylene copolymer), PVDF (polyvinylidene fluoride (difluoride)), PCTFE (polychlorotrifluoroethylene (trifluoride)), polyallylsulfone, aromatic A fluororesin composed of at least one thermoplastic resin selected from polysulfide and aromatic polyether and a fluororesin may be used.

The resin layer may contain a resin curing agent. A known resin curing agent can be used as the resin curing agent. For example, resin curing agents include amines such as dicyandiamide, imidazoles and aromatic amines, phenols such as bisphenol A and brominated bisphenol A, novolaks such as phenol novolac resins and cresol novolac resins, and acid anhydrides such as phthalic anhydride. Products, biphenyl type phenol resins, phenol aralkyl type phenol resins and the like can be used. The resin layer may contain one or more of the aforementioned resin curing agents. These curing agents are particularly effective for epoxy resins.
A specific example of the biphenyl type phenol resin is shown in Chemical Formula 8.

(Chemical formula 8)

  A specific example of the phenol aralkyl type phenol resin is shown in Chemical Formula 9.

(Chemical formula 9)

  Known imidazoles can be used, for example, 2-undecylimidazole, 2-heptadecylimidazole, 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. are mentioned, These can be used individually or in mixture.

  In particular, it is preferable to use imidazoles having the structural formula shown in Chemical Formula 10 below. By using the imidazole having the structural formula shown in Chemical Formula 10, the moisture absorption resistance of the semi-cured resin layer can be remarkably improved, and the long-term storage stability is excellent. This is because imidazoles function as a catalyst during curing of the epoxy resin and contribute as a reaction initiator that causes a self-polymerization reaction of the epoxy resin in the initial stage of the curing reaction.

(Chemical formula 10)

  As the amine resin curing agent, known amines can be used. As the amine resin curing agent, for example, the above-mentioned polyamines and aromatic polyamines can be used, and aromatic polyamines, polyamides, and these are obtained by polymerizing or condensing with epoxy resins or polyvalent carboxylic acids. One or more selected from the group of amine adducts to be used may be used. Examples of the resin curing agent for amines include 4,4′-diaminodiphenylenesulfone, 3,3′-diaminodiphenylenesulfone, 4,4-diaminodiphenylel, and 2,2-bis [4. It is preferable to use at least one of-(4-aminophenoxy) phenyl] propane and bis [4- (4-aminophenoxy) phenyl] sulfone.

  The resin layer may contain a curing accelerator. A known curing accelerator can be used as the curing accelerator. For example, as the curing accelerator, tertiary amine, imidazole, urea curing accelerator and the like can be used.

  The resin layer may include a reaction catalyst. A known reaction catalyst can be used as the reaction catalyst. For example, finely pulverized silica or antimony trioxide can be used as a reaction catalyst.

  The polyhydric carboxylic acid anhydride is preferably a component that contributes as a curing agent for the epoxy resin. The anhydride of the polyvalent carboxylic acid is phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydroxyphthalic anhydride, hexahydroxyphthalic anhydride, methylhexahydroxyphthalic anhydride, nadine. Acid and methyl nadic acid are preferred.

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

  The polyvinyl acetal resin may have a functional group polymerizable with an epoxy resin or a maleimide compound other than an acid group and a hydroxyl group. The polyvinyl acetal resin may have a carboxyl group, an amino group or an unsaturated double bond introduced into the molecule.

Examples of the aromatic polyamide resin polymer include those obtained by reacting an aromatic polyamide resin and a rubber resin. Here, the aromatic polyamide resin is synthesized by condensation polymerization of an aromatic diamine and a dicarboxylic acid. As the aromatic diamine at this time, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, m-xylenediamine, 3,3′-oxydianiline and the like are used. As the dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid or the like is used.
As the rubber resin to be reacted with the aromatic polyamide resin, a known rubber resin or the aforementioned rubber resin can be used.
This aromatic polyamide resin polymer is used for the purpose of not being damaged by under-etching by an etchant when etching a copper foil after being processed into a copper-clad laminate.

  The resin layer is a cured resin layer (the “cured resin layer” means a cured resin layer) and a half in order from the copper foil side (that is, the ultrathin copper layer side of the copper foil with carrier). The resin layer which formed the cured resin layer sequentially may be sufficient. The cured resin layer may be composed of a resin component of any one of a polyimide resin, a polyamideimide resin, and a composite resin having a thermal expansion coefficient of 0 ppm / ° C. to 25 ppm / ° C.

  Moreover, you may provide the semi-hardened resin layer whose thermal expansion coefficient after hardening is 0 ppm / degrees C-50 ppm / degrees C on the said cured resin layer. In addition, the thermal expansion coefficient of the entire resin layer after the cured resin layer and the semi-cured resin layer are cured may be 40 ppm / ° C. or less. The cured resin layer may have a glass transition temperature of 300 ° C. or higher. The semi-cured resin layer may be formed using a maleimide resin or an aromatic maleimide resin. The resin composition for forming the semi-cured resin layer preferably contains a maleimide resin, an epoxy resin, and a linear polymer having a crosslinkable functional group. As the epoxy resin, a known epoxy resin or an epoxy resin described in this specification can be used. In addition, as maleimide resins, aromatic maleimide resins, linear polymers having crosslinkable functional groups, known maleimide resins, aromatic maleimide resins, linear polymers having crosslinkable functional groups, or the aforementioned maleimide resins. An aromatic maleimide resin or a linear polymer having a crosslinkable functional group can be used.

  Moreover, when providing the copper foil with a carrier which has a resin layer suitable for three-dimensional molded printed wiring board manufacture use, it is preferable that the said cured resin layer is a polymeric polymer layer which has the hardened | cured flexibility. The polymer layer is preferably made of a resin having a glass transition temperature of 150 ° C. or higher so that it can withstand the solder mounting process. The polymer layer is preferably composed of one or a mixture of two or more 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. The thickness of the polymer layer is preferably 3 μm to 10 μm.

  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. The semi-cured resin layer is preferably composed of an epoxy resin composition having a thickness of 10 μm to 50 μm.

Moreover, it is preferable that the said epoxy resin composition contains each component of the following A component-E component.
Component A: An epoxy resin having one or more selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AD type epoxy resin that have an epoxy equivalent of 200 or less and are liquid at room temperature.
B component: High heat resistant epoxy resin.
Component C: Phosphorus-containing flame-retardant resin, which is any one of phosphorus-containing epoxy resin and phosphazene-based resin, or a resin obtained by mixing these.
Component D: A rubber-modified polyamide-imide resin modified with a liquid rubber component having a property that is soluble in a solvent having a boiling point in the range of 50 ° C. to 200 ° C.
E component: Resin curing agent.

The B component is a “high heat resistant epoxy resin” having a high so-called glass transition point Tg. The “high heat-resistant epoxy resin” referred to here is preferably a polyfunctional epoxy resin such as a novolac-type epoxy resin, a cresol novolac-type epoxy resin, a phenol novolac-type epoxy resin, or a naphthalene-type epoxy resin.
As the phosphorus-containing epoxy resin of component C, the aforementioned phosphorus-containing epoxy resin can be used. The phosphazene resin described above can be used as the C component phosphazene resin.
The rubber-modified polyamide-imide resin described above can be used as the rubber-modified polyamide-imide resin of component D. The resin curing agent described above can be used as the E component resin curing agent.

  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. The resin varnish is prepared by adding a solvent to the above resin composition so that the resin solid content is in the range of 30 wt% to 70 wt%, and the resin flow when measured in accordance with MIL-P-13949G in the MIL standard. A semi-cured resin film in the range of 5% to 35% can be formed. As the solvent, a known solvent or the aforementioned solvent can be used.

  The resin layer is a resin layer having a first thermosetting resin layer and a second thermosetting resin layer located on the surface of the first thermosetting resin layer in order from the copper foil side, The curable resin layer is formed of a resin component that does not dissolve in chemicals during desmear processing in the wiring board manufacturing process, and the second thermosetting resin layer dissolves in chemicals during desmear processing in the wiring board manufacturing process. Then, it may be formed using a resin that can be washed and removed. The first thermosetting resin layer may be formed using a resin component obtained by mixing one or more of polyimide resin, polyethersulfone, and polyphenylene oxide. The second thermosetting resin layer may be formed using an epoxy resin component. The thickness t1 (μm) of the first thermosetting resin layer is Rz (μm) of the roughened surface roughness of the copper foil with carrier, and the thickness of the second thermosetting resin layer is t2 (μm). Then, t1 is preferably a thickness that satisfies the condition of Rz <t1 <t2.

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

  The skeleton material may include aramid fibers, glass fibers, or wholly aromatic polyester fibers. The skeleton material is preferably an aramid fiber, a glass fiber, or a nonwoven fabric or woven fabric of wholly aromatic polyester fibers. The wholly aromatic polyester fiber is preferably a wholly aromatic polyester fiber having a melting point of 300 ° C. or higher. The wholly aromatic polyester fiber having a melting point of 300 ° C. or higher is a fiber produced using a resin called a so-called liquid crystal polymer, and the liquid crystal polymer contains 2-hydroxyl-6-naphthoic acid and p-hydroxybenzoic acid. The main component is an acid polymer. Since this wholly aromatic polyester fiber has a low dielectric constant and low dielectric loss tangent, it has excellent performance as a constituent material of an electrically insulating layer and can be used in the same manner as glass fiber and aramid fiber. is there.

  In addition, in order to improve the wettability with the resin of the surface, it is preferable to perform the silane coupling agent process for the fiber which comprises the said nonwoven fabric and woven fabric. As the silane coupling agent at this time, a known amino-based or epoxy-based silane coupling agent or the aforementioned silane coupling agent can be used depending on the purpose of use.

  The prepreg is a prepreg obtained by impregnating a thermosetting resin into a nonwoven fabric using an aramid fiber or glass fiber having a nominal thickness of 70 μm or less, or a skeleton material made of glass cloth having a nominal thickness of 30 μm or less. Also good.

(When the resin layer contains a dielectric (dielectric filler))
The resin layer may include a dielectric (dielectric filler).
In the case where a dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, it can be used for the purpose of forming the capacitor layer and increase the capacitance of the capacitor circuit. The dielectric (dielectric filler) includes a composite oxide having a perovskite structure such as BaTiO3, SrTiO3, Pb (Zr-Ti) O3 (common name PZT), PbLaTiO3 / PbLaZrO (common name PLZT), SrBi2Ta2O9 (common name SBT). Dielectric powder is used.

  The dielectric (dielectric filler) may be powdery. When the dielectric (dielectric filler) is powdery, the powder characteristics of the dielectric (dielectric filler) are as follows. First, the particle size is 0.01 μm to 3.0 μm, preferably 0.02 μm to 2.0 μm. Must be in range. The particle size referred to here is indirect in which the average particle size is estimated from the measured values of the laser diffraction scattering type particle size distribution measurement method and the BET method because the particles form a certain secondary aggregation state. It cannot be used because the accuracy is inferior in measurement, and it refers to the average particle diameter obtained by directly observing a dielectric (dielectric filler) with a scanning electron microscope (SEM) and image analysis of the SEM image. It is. In this specification, the particle size at this time is indicated as DIA. The image analysis of the dielectric (dielectric filler) powder observed using a scanning electron microscope (SEM) in this specification is performed using IP-1000PC manufactured by Asahi Engineering Co., Ltd. Circular particle analysis was performed with a threshold value of 10 and an overlapping degree of 20, and the average particle diameter DIA was obtained.

  According to the above-described embodiment, the resin layer containing the dielectric for forming the capacitor circuit layer having a low dielectric loss tangent is improved by improving the adhesion between the inner layer circuit surface of the inner layer core material and the resin layer containing the dielectric. The copper foil with a carrier which has can be provided.

  Examples of the resin and / or resin composition and / or compound contained in the resin layer include 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-dimethylformamide and the like to obtain a resin liquid (resin varnish). On the ultrathin copper layer, or on the heat-resistant layer, rust-preventing layer, chromate-treated layer, or silane coupling agent layer, for example, it is applied by a roll coater method or the like, and then heat-dried as necessary. Removing the solvent Te and to B-stage. For example, a hot air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the resin layer is dissolved using a solvent, and the resin solid content is 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%. It is good also as a resin liquid. In addition, it is most preferable at this stage from an environmental standpoint to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone. In addition, it is preferable to use the solvent whose boiling point is the range of 50 to 200 degreeC as a solvent.

The resin layer is preferably a semi-cured resin film having a resin flow in the range of 5% to 35% when measured according to MIL-P-13949G in the MIL standard.
In this specification, the resin flow is based on MIL-P-13949G in the MIL standard. Four 10 cm square samples are sampled from a resin-coated copper foil with a resin thickness of 55 μm. It is a value calculated based on Formula 1 from the result of measuring the resin outflow weight at the time of lamination in a stacked state (laminate) under the conditions of a press temperature of 171 ° C., a press pressure of 14 kgf / cm 2, and a press time of 10 minutes.

(Formula 1)

  The copper foil with a carrier provided with the resin layer (copper foil with a carrier with resin) is superposed on the base material, and the whole is thermocompression bonded to thermally cure the resin layer, and then the carrier is peeled off. Thus, the ultrathin copper layer is exposed (which is naturally the surface on the intermediate layer side of the ultrathin copper layer), and a predetermined wiring pattern is formed thereon.

  If this resin-attached copper foil with a carrier is used, the number of prepreg materials used when manufacturing a multilayer printed wiring board can be reduced. In addition, the copper-clad laminate can be manufactured even if the resin layer is made thick enough to ensure interlayer insulation or no prepreg material is used. At this time, the surface smoothness can be further improved by undercoating the surface of the substrate with an insulating resin.

In addition, when the prepreg material is not used, the material cost of the prepreg material is saved, and the lamination process is simplified, which is economically advantageous. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 μm or less can be manufactured.
The thickness of the resin layer is preferably 0.1 to 120 μm.

  When the thickness of the resin layer is less than 0.1 μm, the adhesive strength is reduced, and when the copper foil with a carrier with the resin is laminated on the base material provided with the inner layer material without interposing the prepreg material, the circuit of the inner layer material It may be difficult to ensure interlayer insulation between the two. On the other hand, if the thickness of the resin layer is greater than 120 μm, it is difficult to form a resin layer having a target thickness in a single coating process, which may be economically disadvantageous because of extra material costs and man-hours.

In addition, when the copper foil with a carrier having a resin layer is used for manufacturing an extremely thin multilayer printed wiring board, the thickness of the resin layer is 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, More preferably, the thickness is 1 μm to 5 μm in order to reduce the thickness of the multilayer printed wiring board.
When the resin layer includes a dielectric, the thickness of the resin layer is preferably 0.1 to 50 μm, preferably 0.5 μm to 25 μm, and more preferably 1.0 μm to 15 μm. preferable.
The total resin layer thickness with the cured resin layer and the semi-cured resin layer is preferably 0.1 μm to 120 μm, more preferably 5 μm to 120 μm, and preferably 10 μm to 120 μm, 10 μm to 60 μm. Are more preferred. The thickness of the cured resin layer is preferably 2 μm to 30 μm, preferably 3 μm to 30 μm, and more preferably 5 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 they are 7 micrometers-55 micrometers, and it is more desirable that it is 15-115 micrometers. If the total resin layer thickness exceeds 120 μm, it may be difficult to produce a thin multilayer printed wiring board. If the total resin layer thickness is less than 5 μm, a thin multilayer printed wiring board can be easily formed. This is because the resin layer may become too thin and the insulation between the circuits of the inner layer tends to become unstable. Moreover, when the cured resin layer thickness is less than 2 μm, it may be necessary to consider the surface roughness of the roughened copper foil surface. Conversely, if the cured resin layer thickness exceeds 20 μm, the effect of the cured resin layer may not be particularly improved, and the total insulating layer thickness becomes thick.

When the thickness of the resin layer is 0.1 μm to 5 μm, a heat resistant layer and / or a rust preventive layer is formed on the ultrathin copper layer in order to improve the adhesion between the resin layer and the carrier-attached copper foil. After providing the chromate treatment layer and / or the silane coupling treatment layer, it is preferable to form a resin layer on the heat-resistant layer, rust prevention layer, chromate treatment layer or silane coupling treatment 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 10 points | pieces.

  Furthermore, as another product form of this copper foil with a carrier with a resin, on the ultra-thin copper layer, or on the heat-resistant layer, rust-preventing layer, chromate-treated layer, or silane coupling-treated layer After coating with a resin layer and making it into a semi-cured state, the carrier can then be peeled off and manufactured in the form of a copper foil with resin without the carrier.

  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 a method for producing a printed wiring board according to the present invention, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention, a step of laminating the copper foil with a carrier and an insulating substrate, and with the carrier After laminating the copper foil and the insulating substrate so that the ultrathin copper layer side faces the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the copper foil with carrier, and then a semi-additive method, a modified semi-conductor A step of forming a circuit by any one of an additive method, a partial additive method, and a subtractive method. It is also possible for the insulating substrate to contain an inner layer circuit.

  In the present invention, the semi-additive method refers to a method in which a thin electroless plating is performed on an insulating substrate or a copper foil seed layer, a pattern is formed, and then a conductive pattern is formed using electroplating and etching.

Therefore, in one embodiment of a method for manufacturing a printed wiring board according to the present invention using a semi-additive method,
Preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing a through hole or / and a blind via in the resin exposed by removing the ultrathin copper layer by etching;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the resin and the through hole or / and the blind via;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been 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;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method,
Preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing an electroless plating layer on the surface of the resin exposed by removing the ultrathin copper layer by etching;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

  In the present invention, the modified semi-additive method is a method in which a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, and the copper is thickened in the circuit forming portion by electrolytic plating, and then the resist is removed. Then, a method of forming a circuit on the insulating layer by removing the metal foil other than the circuit forming portion by (flash) etching is indicated.

Therefore, in one embodiment of the method for manufacturing a printed wiring board according to the present invention using the modified semi-additive method,
Preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing a plating resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Forming a circuit by electrolytic plating after providing the plating resist;
Removing the plating resist;
Removing the ultra-thin copper layer exposed by removing the plating resist by flash etching;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method,
Preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a plating resist on the exposed ultrathin copper layer by peeling off the carrier;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

  In the present invention, the partial additive method means that a catalyst circuit is formed on a substrate provided with a conductor layer, and if necessary, a substrate provided with holes for through holes or via holes, and etched to form a conductor circuit. Then, after providing a solder resist or a plating resist as necessary, it refers to a method of manufacturing a printed wiring board by thickening through holes, via holes, etc. on the conductor circuit by electroless plating.

Therefore, in one embodiment of a method for manufacturing a printed wiring board according to the present invention using a partly additive method,
Preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Applying catalyst nuclei to the region containing the through-holes and / or blind vias;
Providing an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
A step of providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultrathin copper layer and the catalyst core by a method such as etching or plasma using a corrosive solution such as an acid;
Providing an electroless plating layer in a region where the solder resist or plating resist is not provided,
including.

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

Therefore, in one embodiment of the printed wiring board manufacturing method according to the present invention using the subtractive method,
Preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing an electroplating layer on the surface of the electroless plating layer;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the electroless plating layer and the electrolytic plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.

In another embodiment of the printed wiring board manufacturing method according to the present invention using the subtractive method,
Preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Forming a mask on the surface of the electroless plating layer;
Providing an electroplating layer on the surface of the electroless plating layer on which no mask is formed;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultra-thin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.

  The process of providing a through hole or / and a blind via and the subsequent desmear process may 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. Here, the carrier-attached copper foil having an ultrathin copper layer on which a roughened layer is formed will be described as an example. However, the present invention is not limited thereto, and the carrier has an ultrathin copper layer on which a roughened layer is not formed. The following method for producing a printed wiring board can be similarly performed using an attached copper foil.
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 on 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 image development are performed, and a resist is etched to a defined shape.
Next, as shown in FIG. 3C, after forming a plating for a circuit, the resist is removed to form a circuit plating having a predetermined shape.
Next, as shown in FIG. 4-D, an embedded resin is provided on the ultrathin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then the resin layer is laminated, and then another carrier is attached. A copper foil (second layer) is bonded from the ultrathin copper layer side.
Next, as shown to FIG. 4-E, a carrier is peeled from the copper foil with a carrier of the 2nd layer.
Next, as shown in FIG. 4-F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating and form a blind via.
Next, as shown in FIG. 5G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 5-H, circuit plating is formed on the via fill as shown in FIGS. 3-B and 3-C.
Next, as shown to FIG. 5-I, a carrier is peeled from the copper foil with a carrier of the 1st layer.
Next, as shown in FIG. 6-J, the ultrathin copper layers on both surfaces are removed by flash etching, and the surface of the circuit plating in the resin layer is exposed.
Next, as shown in FIG. 6-K, bumps are formed on the circuit plating in the resin layer with solder or the like, and copper pillars are formed on the bumps. Thus, the printed wiring board using the copper foil with a carrier of this invention is produced.

  As the another copper foil with a carrier (second layer), the copper foil with a carrier of the present invention may be used, a conventional copper foil with a carrier may be used, and a normal copper foil may be further used. Further, one or more circuits may be formed on the second-layer circuit shown in FIG. 5-H, and these circuits may be formed by a semi-additive method, a subtractive method, a partial additive method, or a modified semi-conductor method. You may carry out by any method of an additive method.

  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 resin layer, since the copper foil with a carrier used for the 1st layer is supported and it becomes difficult to wrinkle, there exists an advantage that productivity improves. As the substrate, any substrate can be used as long as it has an effect of supporting the carrier-attached copper foil used in the first layer. For example, the carrier, prepreg, resin layer or known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate, organic compound A foil can be used.

  Although there is no restriction | limiting in particular about the timing which forms a board | substrate in the carrier side surface, It is necessary to form before peeling a carrier. In particular, it is preferably formed before the step of forming a resin layer on the ultrathin copper layer side surface of the copper foil with carrier, and the step of forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier More preferably, it is formed before.

The copper foil with a carrier according to the present invention is preferably controlled so that the color difference on the surface of the ultrathin copper layer satisfies the following (1). In the present invention, the “color difference on the surface of the ultrathin copper layer” means the color difference on the surface of the ultrathin copper layer, or the color difference on the surface of the surface treatment layer when various surface treatments such as roughening treatment are applied. . That is, in the copper foil with a carrier according to the present invention, the color difference of the surface of the ultrathin copper layer, the roughening treatment layer, the heat resistance layer, the rust prevention layer, the chromate treatment layer or the silane coupling layer satisfies the following (1). It is preferably controlled.
(1) The color difference ΔE * ab based on JISZ8730 on the surface of the ultrathin copper layer, the roughened layer, the heat resistant layer, the rust preventive layer, the chromate layer or the silane coupling layer is 45 or more.

  Here, the color differences ΔL, Δa, and Δb are respectively measured with a color difference meter, and are shown using the L * a * b color system based on JIS Z8730, taking into account black / white / red / green / yellow / blue. It is a comprehensive index and is expressed as ΔL: black and white, Δa: reddish green, Δb: yellow blue. ΔE * ab is expressed by the following formula 2 using these color differences.

(Formula 2)

The above-described color difference can be adjusted by increasing the current density when forming the ultrathin copper layer, decreasing the copper concentration in the plating solution, and increasing the linear flow rate of the plating solution.
Moreover, the above-mentioned color difference can also be adjusted by performing a roughening process on the surface of an ultra-thin copper layer and providing a roughening process layer. In the case of providing the roughened layer, the current density is higher than that of the prior art (for example, 40 to 60 A) using an electrolysis solution containing one or more elements selected from the group consisting of copper and nickel, cobalt, tungsten, and molybdenum. / Dm ² ), and the processing time can be shortened (for example, 0.1 to 1.3 seconds). When a roughening layer is not provided on the surface of the ultrathin copper layer, use a plating bath in which the concentration of Ni is twice or more that of other elements, and use an ultrathin copper layer, heat resistant layer, rust preventive layer or chromate. Ni alloy plating (for example, Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating) is applied to the surface of the treatment layer or the silane coupling treatment layer at a lower current density (0.1 to 1.. 3A / dm ² ), and the processing time can be set long (20 to 40 seconds).

  When the color difference ΔE * ab based on JISZ8730 on the surface of the ultrathin copper layer is 45 or more, for example, when forming a circuit on the surface of the ultrathin copper layer of the copper foil with carrier, the contrast between the ultrathin copper layer and the circuit is As a result, the visibility is improved and the circuit can be accurately aligned. The color difference ΔE * ab based on JISZ8730 on the surface of the ultrathin copper layer is preferably 50 or more, more preferably 55 or more, and even more preferably 60 or more.

  When the color difference on the surface of the ultra-thin copper layer, roughened layer, heat-resistant layer, rust-proof layer, chromate-treated layer or silane coupling layer is controlled as described above, the contrast with the circuit plating becomes clear. , Visibility becomes good. Accordingly, in the manufacturing process of the printed wiring board as described above, for example, as shown in FIG. 3C, it is possible to form the circuit plating at a predetermined position with high accuracy. Further, according to the printed wiring board manufacturing method as described above, since the circuit plating is embedded in the resin layer, for example, removal of the ultrathin copper layer by flash etching as shown in FIG. 6-J. At this time, the circuit plating is protected by the resin layer and the shape thereof is maintained, thereby facilitating the formation of a fine circuit. Further, since the circuit plating is protected by the resin layer, the migration resistance is improved, and the continuity of the circuit wiring is satisfactorily suppressed. For this reason, formation of a fine circuit becomes easy. Also, as shown in FIGS. 6-J and 6-K, when the ultrathin copper layer is removed by flash etching, the exposed surface of the circuit plating is recessed from the resin layer, so that bumps are formed on the circuit plating. In addition, copper pillars can be easily formed thereon, and the production efficiency is improved.

  A known resin or prepreg can be used as the embedding resin (resin). For example, a prepreg that is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, an ABF film or ABF manufactured by Ajinomoto Fine Techno Co., Ltd. can be used. Moreover, the resin layer and / or resin and / or prepreg as described in this specification can be used for the embedding resin (resin).

  Next, examples (and comparative examples) will be described. In addition, about this Example, it creates in order to make an understanding of this invention easy, and this invention is not restrict | limited to the following Examples, It is a technique from the whole described in this specification. It can be easily understood that the idea should be grasped.

A long electrolytic copper foil (JTC made by JX Nippon Mining & Metals) having a thickness of 35 μm was prepared as a carrier. A Ni layer having an adhesion amount of 4000 μm / dm ² was formed on the shiny surface of the copper foil by electroplating using a roll-to-roll type continuous plating line under the following conditions.

-Ni layer Nickel sulfate: 250-300 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Trisodium citrate: 15-30 g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 30-100 ppm
pH: 4-6
Bath temperature: 50-70 ° C
Current density: 3-15 A / dm ²

After washing with water and pickling, a Cr layer having an adhesion amount of 11 μg / dm ² was deposited on the Ni layer by electrolytic chromate treatment under the following conditions on a roll-to-roll type continuous plating line. .
Electrolytic chromate treatment Liquid composition: potassium dichromate 1-10 g / L, zinc 0-5 g / L
pH: 3-4
Liquid temperature: 50-60 degreeC
Current density: 0.1-2.6 A / dm ²
Coulomb amount: 0.5-30 As / dm ²

Subsequently, on a roll-to-roll type continuous plating line, an ultrathin copper layer having a thickness of 2 to 10 μm was formed on the Cr layer by electroplating under the following conditions to produce a copper foil with a carrier.
-Ultrathin copper layer Copper concentration: 30-120 g / L
H ₂ SO ₄ concentration: 20 to 120 g / L
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm ²

  For the examples (and comparative examples), 35 μm electrolytic copper foil was used as the carrier, but regarding the present invention, the thickness and type of the copper foil were known copper foil and copper alloy foil thickness, known copper foil and copper alloy. Applicable to all foils. The known copper foil and copper alloy foil may be electrolytic copper foil or rolled copper foil.

(Common items of Example 1 to Examples 5, 8, 9, and 12)
The surface of the ultrathin copper layer of the copper foil with a carrier described above was subjected to a roughening treatment under the following conditions.
(A) Cu primary particle layer formation Liquid composition: Cu 15 g / liter, sulfuric acid 75 g / liter pH: 1-3
Temperature: 35 ° C
Current density (D _k ): 40-60 A / dm ²
Time: 0.05-3 seconds

(B) Composition of a secondary particle layer formed of a ternary alloy composed of Cu, Co, and Ni: Cu 15 g / liter, Co 8 g / liter, Ni 8 g / liter pH: 1 to 3
Temperature: 40 ° C
Current density (D _k ): 20 to 40 A / dm ²
Time: 0.05-3 seconds

In the above roughening treatment, a primary particle layer of Cu having an average particle diameter of 0.25 to 0.45 μm, and Cu, Co, and Ni having an average particle diameter of 0.05 to 0.25 μm formed thereon are formed. A secondary particle layer made of a ternary alloy was formed.
The roughened particle size (particle diameter) is evaluated by observing the roughened particles of the surface-treated copper foil at a magnification of 30000 times that of an electron microscope (SEM (scanning electron microscope)). did. In the present application, when a straight line is drawn on the particle of the scanning electron micrograph, the length of the particle having the longest length of the straight line across the particle is defined as the particle diameter of the particle. And the value of the arithmetic mean of the particle diameter of each particle | grain measured within the observation visual field was computed, and the value of the said arithmetic mean was made into the average particle diameter.
The amount of Ni deposited at the roughening treatment stage was 50 to 250 μg / dm ² . The results are shown in Table 1 below.

(Conditions of Example 1)
The heat-resistant layer composed of the Ni—Co layer, the weather resistant layer containing Zn, Ni, and Cr, the rust preventive layer, and the silane coupling treatment were performed within the range of the conditions shown above. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 2 μm.
1) Heat-resistant layer (Ni-Co layer)
Liquid composition: Co 1-8 g / liter, Ni 10-20 g / liter pH: 2-3
Temperature: 40-60 ° C
Current density (D _k ): 8 to 10 A / dm ²
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Liquid composition: Ni 15-30 g / liter, Zn 1-10 g / liter pH: 2-4
Temperature: 30-50 ° C
Current density (D _k ): 0.5 to 1.5 A / dm ²
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Solution _{composition: K 2 Cr 2 O 7:} 1~10g / l, Zn: 0 to 5 g / l pH: 2 to 4
Temperature: 40-50 ° C
Current density (D _k ): 1 to 3 A / dm ²
Time: 0.05-3.0 seconds

The plating treatment was performed so that the Ni adhesion amount (total Ni amount) in all of the roughening layer, the heat resistant layer, the weather resistant layer, and the rust preventive layer was 1093 μg / dm ^{2 as a} whole. The total Zn content / (total Ni content + total Zn content) = 0.13 from the Zn adhesion amount (total Zn content) in all of the roughened layer, heat resistant layer, weather resistant layer, and rust prevention layer.
From the Co adhesion amount (total Co amount) in all of the roughening layer, heat-resistant layer, weathering layer, and rust prevention layer, the total Co amount / (total Ni amount + total Zn amount) = 1.6.
As described above, the amount of Ni deposited, Zn deposited, Co deposited, and Cr deposited in the case of laminating two or more layers of a roughened layer, a heat resistant layer, a weather resistant layer, and a rust preventive layer are the amount of each element deposited. It shows the total amount.
About Table 1 and Table 2, these were written together as needed about the location corresponding to an Example and a comparative example.

A polyamic acid (U varnish A manufactured by Ube Industries) was applied onto the surface-treated copper foil produced as described above, dried at 100 ° C. and cured at 315 ° C. to form a copper-clad laminate composed of a polyimide resin substrate.
Next, a fine pattern circuit was formed on the copper-clad laminate using a general copper chloride-hydrochloric acid etching solution. The fine pattern circuit board was immersed in an aqueous solution of 10 wt% sulfuric acid and 2 wt% hydrogen peroxide for 5 minutes, and then the interface between the resin substrate and the copper foil circuit was observed with an optical microscope to evaluate the penetration.
As a result of the soaking evaluation, the soaking width was ≦ 3 μm and good (◯).

After laminating and bonding the ultrathin copper layer side of the copper foil with carrier to the glass cloth base epoxy resin plate, and then peeling off the ultrathin copper layer from the carrier, the normal state from the epoxy resin plate of the ultrathin copper layer (Room temperature) After measuring peel strength (kg / cm), the hydrochloric acid resistance deterioration rate was measured with a 0.2 mm width circuit after being immersed in an 18% aqueous hydrochloric acid solution for 1 hour.
The normal peel strength was 0.99 kg / cm, and the hydrochloric acid degradation resistance was 8 (Loss%) or less (◯), both of which were good.

In order to investigate the alkali etching property, after preparing a sample in which the roughened surface of the copper foil with surface treatment was covered with a vinyl tape, NH ₄ OH: 6 mol / liter, NH ₄ Cl: 5 mol / liter, CuCl ₂ · 2H ₂ O: ₂ moles / liter, after immersion for 7 minutes in an alkaline etching solution consisting of temperature 50 ° C., was confirmed remaining conditions of the roughening particles on the plastic tape.
As a result of the alkali etching evaluation, the remaining coarse particles were not observed, and the alkali etching property was good (◯).

The results are shown in Table 1. In addition, the Cr adhesion amount (total Cr amount) is 89 μg / dm ^{2 as} a whole, the Co adhesion amount (total Co amount) is 2010 μg / dm ^{2 as} a whole, and the Zn adhesion amount (total Zn amount) is 163 μg / dm ^{2 as a} whole. Met.
In addition, measurement of each said metal adhesion amount (Ni adhesion amount of a roughening process stage, total Ni amount, total Co amount, total Zn amount, total Cr amount) measured the surface treatment surface of surface-treated copper foil with an acid solution. And was evaluated by atomic absorption analysis (manufactured by VARIAN, AA240FS). Note that the amount of Ni deposited in the roughening treatment stage was determined by producing a copper foil with a carrier under the same conditions as in each example and each comparative example, and after providing only the roughening treatment layer, collecting a sample, In the same manner as above, the amount of Ni adhesion was measured.

(Example 2)
The amount of Ni deposited in the roughening stage was 50 to 250 μg / dm ^{2 as} described above.
The heat-resistant layer composed of the Ni—Co layer, the weather resistant layer containing Zn, Ni, and Cr, the rust preventive layer, and the silane coupling treatment were performed within the range of the conditions shown above. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 10 μm.

1) Heat-resistant layer (Ni-Co layer)
Current density (D _k ): 4 to 6 A / dm ²
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D _k ): 0.05 to 0.7 A / dm ²
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D _k ): 1 to 3 A / dm ²
Time: 0.05-3.0 seconds

The total amount of Ni (total Ni amount) in the roughened layer, heat-resistant layer, weather-resistant layer, and rust-preventing layer is 451 μg / dm ² , and all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-proof layer From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.18, Co adhesion amount in all of the roughened layer, heat resistant layer, weather resistant layer, and rust preventive layer (total From the (Co amount), the total Co amount / (total Ni amount + total Zn amount) = 2.7.
As a result of the soaking evaluation, the soaking width: ≦ 3 μm was good (◯).

As a result of the adhesion strength evaluation, the normal peel strength was 1.00 kg / cm, and the hydrochloric acid degradation resistance was 11 (Loss%), which was good (◯). Residual particles were not observed even in the alkali etching evaluation, and it was good (◯).
The results are shown in Table 1. In addition, Cr coating weight total 84μg / dm ² at (total Cr content), Co deposition amount (total Co content) 1487μg / dm ^2, Zn deposition amount in overall (total amount of Zn) are total 100 [mu] g / dm ² Met.

(Example 3)
The amount of Ni deposited in the roughening stage was 50 to 250 μg / dm ^{2 as} described above.
The heat-resistant layer composed of the Ni—Co layer, the weather resistant layer containing Zn, Ni, and Cr, the rust preventive layer, and the silane coupling treatment were performed within the range of the conditions shown above. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 5 μm.

1) Heat-resistant layer (Ni-Co layer)
Current density (D _k ): 6 to 8 A / dm ²
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D _k ): 0.05 to 0.7 A / dm ²
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D _k ): ^{2 to} 4 A / dm ²
Time: 0.05-3.0 seconds

The total amount of Ni (total Ni amount) in the roughened layer, heat-resistant layer, weather-resistant layer, and rust-preventing layer is 680 μg / dm ² , and all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-proof layer From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.19, Co deposited amount in all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-preventive layer (total From the Co amount, the total Co amount / (total Ni amount + total Zn amount) = 2.1. As a result of soaking evaluation, the soaking width was good at ≦ 3 μm.

As a result of the adhesion strength evaluation, the normal peel strength was 0.99 kg / cm, and the hydrochloric acid resistance against degradation was 25 (Loss%), indicating that there was no problem. Residual particles were not observed and the alkali etching property was good (◯).
The results are shown in Table 1. In addition, whole Cr adhesion amount (total Cr content) across 89μg / dm ^2, Co deposition amount in (total Co content) at 1763μg / dm ^2, Zn deposition amount (total amount of Zn) is total 157μg / dm ² Met.

(Example 4)
The amount of Ni deposited in the roughening stage was 50 to 250 μg / dm ^{2 as} described above.
The heat-resistant layer composed of the Ni—Co layer, the weather resistant layer containing Zn, Ni, and Cr, the rust preventive layer, and the silane coupling treatment were performed within the range of the conditions shown above. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.

1) Heat-resistant layer (Ni-Co layer)
Current density (D _k ): 6 to 8 A / dm ²
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D _k ): 1 to 3 A / dm ²
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D _k ): 0.05 to 1.0 A / dm ²
Time: 0.05-3.0 seconds

The Ni adhesion amount (total Ni amount) in all of the roughened layer, heat resistant layer, weather resistant layer and rust preventive layer is 759 μg / dm ² in total, and all of the roughened layer, heat resistant layer, weather resistant layer and rust preventive layer From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.23, Co adhesion amount in all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-preventive layer (total From the Co amount, the total Co amount / (total Ni amount + total Zn amount) = 1.8. As a result of the soaking evaluation, the soaking width was 0 μm, which was very good.

As a result of the evaluation of the adhesion strength, the normal peel strength was 0.99 kg / cm, and the hydrochloric acid degradation resistance was 22 (Loss%). Alkali etching property was also good (◯).
The results are shown in Table 1. In addition, the Cr adhesion amount is 90 μg / dm ^{2 as} a whole (total Cr amount), the Co adhesion amount (total Co amount) is 1774 μg / dm ^{2 as} a whole, and the Zn adhesion amount (total Zn amount) is 223 μg / dm ^{2 as a} whole. Met.

(Example 5)
The amount of Ni deposited in the roughening stage was 50 to 250 μg / dm ^{2 as} described above.
The heat-resistant layer composed of the Ni—Co layer, the weather resistant layer containing Zn, Ni, and Cr, the rust preventive layer, and the silane coupling treatment were performed within the range of the conditions shown above. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 7 μm.

1) Heat-resistant layer (Ni-Co layer)
Current density (D _k ): 6 to 8 A / dm ²
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D _k ): 0.6 to 1.5 A / dm ²
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D _k ): 1.0 to 3.0 A / dm ²
Time: 0.05-3.0 seconds

The Ni adhesion amount (total Ni amount) in all of the roughened layer, heat resistant layer, weather resistant layer and rust preventive layer is 816 μg / dm ² in total, and all of the roughened layer, heat resistant layer, weather resistant layer and rust preventive layer From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.22, the amount of Co deposited in all of the roughened layer, the heat-resistant layer, the weather-resistant layer, and the rust-proof layer (total From the Co amount, the total Co amount / (total Ni amount + total Zn amount) = 1.8. As a result of the soaking evaluation, the soaking width was 0 μm, which was very good.

As a result of the adhesion strength evaluation, the normal peel strength was 0.99 kg / cm, and the hydrochloric acid degradation resistance was 12 (Loss%), which was good. Alkali etching property was also good (◯).
The results are shown in Table 1. In addition, whole Cr adhesion amount (total Cr content) across 115μg / dm ^2, Co deposition amount in (total Co content) at 1857μg / dm ^2, Zn deposition amount (total amount of Zn) is total 235μg / dm ² Met.

(Example 6)
The copper foil with a carrier described above was subjected to a roughening treatment under the following conditions. The thickness of the ultrathin copper layer was 3 μm.
Liquid composition: Cu 10-20 g / liter, Co 5-10 g / liter, Ni 5-15 g / liter pH: 2-4
Temperature: 30-50 ° C
Current density (D _k ): 20 to 60 A / dm ²
Time: 0.5-5 seconds

By performing the roughening treatment under the above conditions, an aggregate of finely roughened particles of a ternary alloy composed of Cu, Co, and Ni having an average particle diameter of 0.10 to 0.60 μm was formed. The roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM).
The amount of Ni deposited in the roughening stage was 200 to 400 μg / dm ² .

The heat-resistant layer composed of the Ni—Co layer, the weather resistant layer containing Zn, Ni, and Cr, the rust preventive layer, and the silane coupling treatment were performed within the range of the conditions shown above. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
1) Heat-resistant layer (Ni-Co layer)
Current density (D _k ): 6 to 8 A / dm ²
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D _k ): 2.0 to 4.0 A / dm ²
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D _k ): 0 A / dm ²
Time: 0.05-3 seconds (immersion chromate treatment)

The total amount of Ni (total Ni amount) in all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-proof layer is 1091 μg / dm ² , and all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-proof layer From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.18, Co adhesion amount in all of the roughened layer, heat resistant layer, weather resistant layer, and rust preventive layer (total From the Co amount), the total Co amount / (total Ni amount + total Zn amount) = 1.9. As a result of the soaking evaluation, the soaking width was 0 μm, which was very good.

As a result of the evaluation of the adhesion strength, the normal peel strength was 0.97 kg / cm, hydrochloric acid deterioration resistance: ≦ 10 (Loss%) or less, which was very good. Alkali etching property was also good (◯).
The results are shown in Table 1. In addition, Cr coating weight total (total Cr amount) at 110μg / dm ^2, Co coating weight across the entire 2475μg / dm ^2, Zn deposition amount is (total Co content) (total amount of Zn) at 240 [mu] g / dm ² Met.

(Example 7)
The above-mentioned copper foil with a carrier was roughened under the conditions shown below. The thickness of the ultrathin copper layer was 3 μm.
Liquid composition: Cu 10-20 g / liter, Co 5-10 g / liter, Ni 8-20 g / liter pH: 2-4
Temperature: 30-50 ° C
Current density (D _k ): 20 to 60 A / dm ²
Time: 0.5-5 seconds

By performing the roughening treatment under the above conditions, an aggregate of finely roughened particles of a ternary alloy composed of Cu, Co, and Ni having an average particle diameter of 0.05 to 0.35 μm was formed. The roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM).
The amount of Ni deposited at the roughening stage was 300 to 550 μg / dm ² .

The heat-resistant layer composed of the Ni—Co layer, the weather resistant layer containing Zn, Ni, and Cr, the rust preventive layer, and the silane coupling treatment were performed within the range of the conditions shown above. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
1) Heat-resistant layer (Ni-Co layer)
Current density (D _k ): 4 to 6 A / dm ²
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D _k ): 1.5 to 3.5 A / dm ²
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D _k ): 0 A / dm ²
Time: 0.05-3 seconds (immersion chromate treatment)

The Ni adhesion amount (total Ni amount) in all of the roughened layer, heat resistant layer, weather resistant layer and rust preventive layer is 789 μg / dm ^{2 as a} whole, and all of the roughened layer, heat resistant layer, weather resistant layer and rust preventive layer are present. From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.22, the amount of Co deposited in all of the roughened layer, the heat-resistant layer, the weather-resistant layer, and the rust-proof layer (total From the Co amount, the total Co amount / (total Ni amount + total Zn amount) = 2.2. As a result of the soaking evaluation, the soaking width was 0 μm, which was very good.

As a result of the evaluation of the adhesion strength, the normal peel strength was 0.94 kg / cm, hydrochloric acid deterioration resistance: ≦ 10 (Loss%) or less, which was very good. Alkali etching property was also good (◯).
The results are shown in Table 1. In addition, Cr coating weight total (total amount of Cr) in 55 [mu] g / dm ^2, Co coating weight across the entire 2167μg / dm ^2, Zn deposition amount is (total Co content) (total amount of Zn) at 217μg / dm ² Met.

(Example 8)
In the same roughening treatment as in Example 1, a primary particle layer of Cu having an average particle diameter of 0.25 to 0.45 μm, and Cu and Co having an average particle diameter of 0.05 to 0.25 μm formed thereon. Then, a secondary particle layer made of a ternary alloy made of Ni was formed.
The roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM).
The amount of Ni deposited at the roughening treatment stage was 50 to 250 μg / dm ² .

The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.
1) Heat-resistant layer (Ni-Co layer)
Current density (D _k ): 6 to 8 A / dm ²
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D _k ): 0 to 1.0 A / dm ²
Time: 0 to 2.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D _k ): 1 to 3 A / dm ²
Time: 0.05-3.0 seconds

The plating treatment was performed so that the Ni adhesion amount in all of the roughening layer, the heat resistant layer, the weather resistant layer, and the rust prevention layer was 741 μg / dm ^{2 in} total (total Ni amount). The total Zn content / (total Ni content + total Zn content) = 0.02 from the Zn adhesion amount (total Zn content) in all of the roughened layer, heat resistant layer, weather resistant layer, and rust prevention layer.
From the Co adhesion amount (total Co amount) in all of the roughening layer, the heat-resistant layer, the weathering layer, and the rust prevention layer, the total Co amount / (total Ni amount + total Zn amount) = 1.9.
About the following Examples 8, 9, and 21-26, after surface-treated copper foil was laminated | stacked on the following resin, the penetration was evaluated by said penetration evaluation method.
GHPL-830NX (Mitsubishi Gas Chemical Co., Ltd. Type A) was laminated on a surface-treated copper foil at 220 ° C. for 2 hours to form a copper-clad laminate.

Next, a fine pattern circuit was formed on the copper-clad laminate using a general copper chloride-hydrochloric acid etching solution. The fine pattern circuit board was immersed in an aqueous solution of 10 wt% sulfuric acid and 2 wt% hydrogen peroxide for 5 minutes, and then the interface between the resin substrate and the copper foil circuit was observed with an optical microscope to evaluate the penetration.
As a result of the soaking evaluation, the soaking width was 0 μm, which was very good.

As a result of the evaluation of the adhesion strength, the normal peel strength was 0.99 kg / cm, and the hydrochloric acid resistance was 5 (Loss%), which was very good. Alkali etching property was also good (◯).
The results are shown in Table 1. In addition, whole Cr adhesion amount (total Cr content) total 90 [mu] g / dm ^2, Co deposition amount in (total Co content) at 1437μg / dm ^2, Zn deposition amount (total amount of Zn) is total 15 [mu] g / dm ² Met.

Example 9
In the same roughening treatment as in Example 1, a primary particle layer of Cu having an average particle diameter of 0.25 to 0.45 μm, and Cu and Co having an average particle diameter of 0.05 to 0.25 μm formed thereon. Then, a secondary particle layer made of a ternary alloy made of Ni was formed.
The roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM).
The amount of Ni deposited at the roughening treatment stage was 50 to 250 μg / dm ² .

The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.
1) Heat-resistant layer (Ni-Co layer)
Current density (D _k ): 6 to 8 A / dm ²
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D _k ): 0.5 to 1.0 A / dm ²
Time: 0 to 2.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D _k ): 1 to 3 A / dm ²
Time: 0.05-3.0 seconds

The plating treatment was performed so that the Ni adhesion amount in all of the roughening layer, the heat resistant layer, the weather resistant layer, and the rust preventive layer was 771 μg / dm ^{2 in} total (total Ni amount). The total Zn content / (total Ni content + total Zn content) = 0.06 from the Zn adhesion amount (total Zn content) in all of the roughened layer, heat resistant layer, weather resistant layer, and rust preventive layer.
The total amount of Co / (total Ni amount) + total Zn amount) = 1.8 from the Co adhesion amount (total Co amount) in all of the roughening layer, heat-resistant layer, weathering layer, and rust prevention layer.

As a result of the penetration evaluation similar to that of Example 8, the penetration width was 0 μm, which was very good. As a result of the adhesion strength evaluation, the normal peel strength was 1.01 kg / cm, hydrochloric acid deterioration resistance: 6 (Loss%), which was very good. Alkali etching property was also good (◯).
The results are shown in Table 1. In addition, whole Cr adhesion amount (total Cr content) total 90 [mu] g / dm ^2, Co deposition amount in (total Co content) at 1476μg / dm ^2, Zn deposition amount (total amount of Zn) is total 49μg / dm ² Met.

(Example 10)
A roughening layer was formed on the above-described copper foil with a carrier under the same conditions as in Example 6. By performing the roughening treatment under the above conditions, an aggregate of finely roughened particles of a ternary alloy composed of Cu, Co, and Ni having an average particle diameter of 0.10 to 0.60 μm was formed.
The amount of Ni deposited in the roughening stage was 200 to 400 μg / dm ² .
The heat-resistant layer composed of the Ni—Co layer, the weather resistant layer containing Zn, Ni, and Cr, the rust preventive layer, and the silane coupling treatment were performed within the range of the conditions shown above. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.

1) Heat-resistant layer (Ni-Co layer)
Liquid composition: Co 1-10 g / liter, Ni 1-10 g / liter pH: 2-3
Temperature: 40-60 ° C
Current density (D _k ): 6 to 8 A / dm ²
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D _k ): 1.0 to 3.0 A / dm ²
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D _k ): 0 A / dm ²
Time: 0.05-3 seconds (immersion chromate treatment)

The amount of Ni adhered to all of the roughened layer, heat resistant layer, weather resistant layer, and rust preventive layer is 815 μg / dm ² in total (total Ni amount), and all of the roughened layer, heat resistant layer, weather resistant layer, and rust preventive layer are present. From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.13, the amount of Co deposited in all of the roughened layer, the heat-resistant layer, the weather-resistant layer, and the rust-proof layer (total From the (Co amount), the total Co amount / (total Ni amount + total Zn amount) = 3.2. As a result of the soaking evaluation, the soaking width was good at ≦ 5 μm.

As a result of the adhesion strength evaluation, the normal peel strength was as good as 0.99 kg / cm and hydrochloric acid deterioration resistance: 8 (Loss%). The alkali etching property was good (◯). The results are shown in Table 1. In addition, Cr coating weight total (total amount of Cr) in 90 [mu] g / dm ^2, Co coating weight across the entire 2978μg / dm ^2, Zn deposition amount is (total Co content) (total amount of Zn) at 117μg / dm ² Met.

(Example 11)
In the same roughening treatment as in Example 1, a primary particle layer of Cu having an average particle diameter of 0.2 to 0.45 μm, and Cu and Co having an average particle diameter of 0.05 to 0.25 μm formed thereon. Then, a secondary particle layer made of a ternary alloy made of Ni was formed.
The roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM).
The amount of Ni deposited at the roughening treatment stage was 300 to 550 μg / dm ² .

The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.
1) Heat-resistant layer (Ni-Co layer)
Current density (D _k ): 6 to 8 A / dm ²
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D _k ): 0.5 to 1.0 A / dm ²
Time: 0 to 2.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D _k ): 1 to 3 A / dm ²
Time: 0.05-3.0 seconds

The plating treatment was performed so that the Ni adhesion amount in all of the roughening layer, the heat resistant layer, the weather resistant layer, and the rust preventive layer was 1590 μg / dm ^{2 in} total (total Ni amount). From the Zn adhesion amount (total Zn amount) in all of the roughened layer, heat-resistant layer, weathering layer, and rust prevention layer, the total Zn amount / (total Ni amount + total Zn amount) = 0.10.
The total amount of Co / (total Ni amount) + total Zn amount) = 1.6 from the Co adhesion amount (total Co amount) in all of the roughening layer, heat-resistant layer, weathering layer, and rust prevention layer.

As a result of the infiltration evaluation similar to that in Example 1, the infiltration width was good at 5 μm or less. As a result of the evaluation of the adhesion strength, the normal peel strength was 1.02 kg / cm and the hydrochloric acid resistance against deterioration: 18 (Loss%), which was good. Alkali etching property was also good (◯).
The results are shown in Table 1. In addition, whole Cr adhesion amount (total Cr content) total 90 [mu] g / dm ^2, Co deposition amount in (total Co content) at 2762μg / dm ^2, Zn deposition amount (total amount of Zn) is total 177μg / dm ² Met.

(Example 12)
In the same roughening treatment as in Example 1, a primary particle layer of Cu having an average particle diameter of 0.2 to 0.45 μm, and Cu and Co having an average particle diameter of 0.05 to 0.25 μm formed thereon. Then, a secondary particle layer made of a ternary alloy made of Ni was formed.
The roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM).
The amount of Ni deposited at the roughening treatment stage was 50 to 250 μg / dm ² .

The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.
1) Heat-resistant layer (Ni-Co layer)
Current density (D _k ): 6 to 8 A / dm ²
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D _k ): 0.5 to 1.0 A / dm ²
Time: 0 to 2.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D _k ): 1 to 3 A / dm ²
Time: 0.05-3.0 seconds

The plating treatment was performed so that the Ni adhesion amount in all of the roughening layer, the heat resistant layer, the weather resistant layer, and the rust preventive layer was 360 μg / dm ^{2 in} total (total Ni amount). The total Zn content / (total Ni content + total Zn content) = 0.35 from the Zn adhesion amount (total Zn content) in all of the roughened layer, heat resistant layer, weather resistant layer, and rust prevention layer.
From the Co adhesion amount (total Co amount) in all of the roughening layer, the heat resistant layer, the weathering layer, and the rust prevention layer, the total Co amount / (total Ni amount) + total Zn amount) = 1.4.

As a result of the penetration evaluation similar to that of Example 1, the penetration width was 0 μm, which was very good. As a result of the evaluation of the adhesion strength, the normal peel strength was 0.96 kg / cm, and the hydrochloric acid degradation resistance was 5 (Loss%), which was favorable. Alkali etching property was also good (◯).
The results are shown in Table 1. In addition, whole Cr adhesion amount (total Cr content) total 90 [mu] g / dm ^2, Co deposition amount in (total Co content) at 790μg / dm ^2, Zn deposition amount (total amount of Zn) is total 194μg / dm ² Met.

(Comparative Example 1)
The roughening process layer was formed on the above-mentioned copper foil with a carrier on the conditions similar to Example 1-5. The amount of Ni deposited in the roughening stage was 50 to 250 μg / dm ² .
The heat-resistant layer composed of the Ni—Co layer, the weather resistant layer containing Zn, Ni, and Cr, the rust preventive layer, and the silane coupling treatment were performed within the range of the conditions shown above. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.

1) Heat-resistant layer (Ni-Co layer)
Current density (D _k ): 10-15 A / dm ²
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D _k ): 0.05 to 0.7 A / dm ²
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D _k ): 0.5 to 1.5 A / dm ²
Time: 0.05-3.0 seconds

The total amount of Ni (total Ni amount) in the roughened layer, heat-resistant layer, weather-resistant layer and rust-preventing layer is 1540 μg / dm ² , and all of the roughened layer, heat-resistant layer, weather-resistant layer and rust-proof layer From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.01, the amount of Co deposited in all of the roughened layer, the heat resistant layer, the weather resistant layer, and the rust preventive layer (total From the Co amount, the total Co amount / (total Ni amount + total Zn amount) = 3.5. As a result of the soaking evaluation, the soaking width was poor at> 5 μm.

As a result of the adhesion strength evaluation, the normal peel strength was 0.98 kg / cm, and the hydrochloric acid degradation resistance was 6 (Loss%), which was good. However, the alkali etching property was poor (x) because residual particles were observed. As a result, the overall evaluation was poor. This is considered due to the fact that the total Zn amount / (total Ni amount + total Zn amount) is small.
The results are shown in Table 1. In addition, Cr coating weight total (total Cr amount) at 81μg / dm ^2, Co coating weight across the entire 5444μg / dm ^2, Zn deposition amount is (total Co content) (total amount of Zn) at 10 [mu] g / dm ² Met.

(Comparative Example 2)
The roughening process layer was formed on the above-mentioned copper foil with a carrier on the conditions similar to Example 1-5. The amount of Ni deposited in the roughening stage was 50 to 250 μg / dm ² .
The heat-resistant layer composed of the Ni—Co layer, the weather resistant layer containing Zn, Ni, and Cr, the rust preventive layer, and the silane coupling treatment were performed within the range of the conditions shown above. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.

1) Heat-resistant layer (Ni-Co layer)
Current density (D _k ): 10-15 A / dm ²
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D _k ): 0.1 to 1.0 A / dm ²
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D _k ): 0.5 to 1.5 A / dm ²
Time: 0.05-3.0 seconds

The total amount of Ni (total Ni amount) in the roughened layer, heat-resistant layer, weather-resistant layer, and rust-preventing layer is 1840 μg / dm ² , and all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-proof layer From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.10, the Co deposited amount in all of the roughened layer, the heat resistant layer, the weather resistant layer and the rust preventive layer (total From the (Co amount), the total Co amount / (total Ni amount + total Zn amount) = 1.5. As a result of soaking evaluation, the soaking width was good at ≦ 3 μm.

As a result of the adhesion strength evaluation, the normal peel strength was 0.99 kg / cm, and the hydrochloric acid degradation resistance was 7 (Loss%) or less, which was good. However, the alkali etching property was poor (x) because residual particles were observed. As a result, the overall evaluation was poor. This is considered due to the fact that the total amount of deposited Ni is too large.
The results are shown in Table 1. In addition, Cr coating weight total (total Cr amount) at 84μg / dm ^2, Co coating weight across the entire 3058μg / dm ^2, Zn deposition amount is (total Co content) (total amount of Zn) at 199μg / dm ² Met.

(Comparative Example 3)
The roughening process layer was formed on the above-mentioned copper foil with a carrier on the conditions similar to Example 1-5. The amount of Ni deposited in the roughening stage was 50 to 250 μg / dm ² .
The heat-resistant layer composed of the Ni—Co layer, the weather resistant layer containing Zn, Ni, and Cr, the rust preventive layer, and the silane coupling treatment were performed within the range of the conditions shown above. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.

1) Heat-resistant layer (Ni-Co layer)
Current density (D _k ): 1.0 to 3.0 A / dm ²
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D _k ): 0.05 to 0.7 A / dm ²
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D _k ): 0.5 to 1.5 A / dm ²
Time: 0.05-3.0 seconds

The total amount of Ni (total Ni amount) in the roughened layer, heat-resistant layer, weather-resistant layer, and rust-preventing layer is 310 μg / dm ² , and all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-proof layer From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.40. From the Co deposited amount (total Co amount) in all of the roughened layer and the heat-resistant layer, Amount / (total Ni amount + total Zn amount) = 1.4. As a result of soaking evaluation, the soaking width was good at ≦ 3 μm.

As a result of the adhesion strength evaluation, the normal peel strength was as good as 0.97 kg / cm, but the hydrochloric acid degradation resistance was 35 (Loss%), which was poor. The alkali etching property was good, but the overall evaluation was poor. This is considered to be caused by a large Zn ratio.
The results are shown in Table 1. In addition, Cr coating weight total (total Cr amount) at 82μg / dm ^2, Co coating weight across the entire 723μg / dm ^2, Zn deposition amount is (total Co content) (total amount of Zn) at 207μg / dm ² Met.

(Comparative Example 4)
The roughening process layer was formed on the above-mentioned copper foil with a carrier on the conditions similar to Example 1-5. The amount of Ni deposited in the roughening stage was 50 to 250 μg / dm ² .
The heat-resistant layer composed of the Ni—Co layer, the weather resistant layer containing Zn, Ni, and Cr, the rust preventive layer, and the silane coupling treatment were performed within the range of the conditions shown above. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.

1) Heat-resistant layer (Ni-Co layer)
Current density (D _k ): 1.0 to 3.0 A / dm ²
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D _k ): 0.7 to 2.0 A / dm ²
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D _k ): 0.8 to 2.5 A / dm ²
Time: 0.05-3.0 seconds

The total amount of Ni (total Ni amount) in all of the roughening layer, heat-resistant layer, weathering layer, and rust-preventing layer is 600 μg / dm ² , and all of the roughening layer, heat-resistant layer, weathering layer, and rust-preventing layer From the amount of Zn deposited (total Zn amount), the total amount of Zn / (total Ni amount + total Zn amount) = 0.38, the amount of Co deposited in all of the roughened layer, the heat-resistant layer, the weather-resistant layer, and the rust-proof layer (total From the Co amount, the total Co amount / (total Ni amount + total Zn amount) = 1.6. As a result of the soaking evaluation, the soaking width was good at 0 μm.

As a result of the adhesion strength evaluation, the normal peel strength was as good as 0.99 kg / cm, but the hydrochloric acid resistance against deterioration with hydrochloric acid: 40 (Loss%) was poor. The alkali etching property was good (◯). However, the overall evaluation was poor. This is considered to be caused by a large Zn ratio.
The results are shown in Table 1. In addition, Cr coating weight total (total Cr amount) at 122μg / dm ^2, Co coating weight across the entire 1546μg / dm ^2, Zn deposition amount is (total Co content) (total amount of Zn) at 361μg / dm ² Met.

(Example when the composition of the intermediate layer is changed)
(Example 21)
Next, a copper foil with a carrier was formed under the same conditions as in Example 1 except that a CoMo alloy was formed as an intermediate layer between the carrier and the copper foil. In this case, the CoMo alloy intermediate layer was produced by plating in a plating solution having the following liquid composition. The thickness of the ultrathin copper layer was 2 μm.

(Liquid composition) CoSO ₄ .7H ₂ O: 0.5 to 100 g / l
Na ₂ MoO ₄ .2H ₂ O: 0.5 to 100 g / l
Sodium citrate dihydrate: 20-300 g / l
(Temperature) 10 ~ 70 ℃
(PH) 3-5
(Current density) 0.1-60 A / dm ²

The total amount of Ni (total Ni amount) in all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-proof layer is 1090 μg / dm ² , and all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-proof layer From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.13, the amount of Co deposited in all of the roughened layer, the heat-resistant layer, the weather-resistant layer, and the rust-proof layer (total From the Co amount, the total Co amount / (total Ni amount + total Zn amount) = 1.6. As a result of soaking evaluation, the soaking width was good at ≦ 3 μm.

As a result of the evaluation of the adhesion strength, the normal peel strength was 0.90 kg / cm, and the resistance to hydrochloric acid degradation was 10 (Loss%) or less, which was very good. Alkali etching property was also good (◯).
The results are shown in Table 2. In addition, Ni deposition amount (roughening step) 50~250μg / dm ^2, Co coating weight across the entire 2005μg / dm ^2, Zn deposition amount is (total Co content) (total amount of Zn) at 163μg / dm ² there were.

(Example 22)
Next, a copper foil with a carrier was formed under the same conditions as in Example 2 except that Cr was formed as an intermediate layer between the carrier and the copper foil. In this case, the Cr intermediate layer was produced by plating in a plating solution having the following liquid composition. The thickness of the ultrathin copper layer was 10 μm.

(Liquid composition)
CrO ₃ : 200 to 400 g / l
H ₂ SO _4: 1.5~4g / l
(PH) 1-4
(Liquid temperature) 45-60 ° C
(Current density) 10-40 A / dm ²

The total amount of Ni (total Ni amount) in the roughened layer, heat-resistant layer, weather-resistant layer, and rust-preventing layer is 449 μg / dm ² , and all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-proof layer From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.18, Co adhesion amount in all of the roughened layer, heat resistant layer, weather resistant layer, and rust preventive layer (total From the (Co amount), the total Co amount / (total Ni amount + total Zn amount) = 2.7. As a result of soaking evaluation, the soaking width was good at ≦ 3 μm.

As a result of the evaluation of the adhesion strength, the normal peel strength was 0.91 kg / cm, hydrochloric acid resistance against degradation: 11 (Loss%), and was very good. Alkali etching property was also good (◯).
The results are shown in Table 2. In addition, Ni deposition amount (roughening step) 50~250μg / dm ^2, Co coating weight across the entire 1481μg / dm ^2, Zn deposition amount is (total Co content) (total amount of Zn) at 99 ug / dm ² there were.

(Example 23)
Next, a copper foil with a carrier was formed under the same conditions as in Example 1 except that Cr / CuP was formed as an intermediate layer between the carrier and the copper foil. In this case, the Cr / CuP intermediate layer was produced by plating in a plating solution having the following liquid composition. The thickness of the ultrathin copper layer was 2 μm.

(Liquid composition 1)
CrO ₃ : 200 to 400 g / l
H ₂ SO _4: 1.5~4g / l
(PH): 1-4
(Liquid temperature): 45-60 degreeC
(Current density): 10 to 40 A / dm ²

(Liquid composition 2)
Cu ₂ P ₂ O ₇ : 3H ₂ O: 5 to 50 g / l
K ₄ P ₂ O ₇ : 50 to 300 g / l
(Temperature): 30-60 ° C
(PH): 8 to 10
(Current density): 0.1 to 1.0 A / dm ²

The total amount of Ni (total Ni amount) in the roughened layer, heat-resistant layer, weather-resistant layer, and rust-preventing layer is 1089 μg / dm ² , and all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-proof layer From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.13, the amount of Co deposited in all of the roughened layer, the heat-resistant layer, the weather-resistant layer, and the rust-proof layer (total From the Co amount, the total Co amount / (total Ni amount + total Zn amount) = 1.6. As a result of soaking evaluation, the soaking width was good at ≦ 3 μm.

As a result of the evaluation of the adhesion strength, the normal peel strength was 0.90 kg / cm, and the resistance to hydrochloric acid degradation was 10 (Loss%) or less, which was very good. Alkali etching property was also good (◯).
The results are shown in Table 2. In addition, Ni deposition amount (roughening step) 50~250μg / dm ^2, Co coating weight across the entire 2003μg / dm ^2, Zn deposition amount is (total Co content) (total amount of Zn) at 163μg / dm ² there were.

(Example 24)
Next, a copper foil with a carrier was formed under the same conditions as in Example 2 except that Ni / Cr was formed as an intermediate layer between the carrier and the copper foil. In this case, the Ni / Cr intermediate layer was produced by plating in a plating solution having the following liquid composition. The thickness of the ultrathin copper layer was 10 μm.

(Liquid composition 1)
NiSO ₄ .6H ₂ O: 250 to 300 g / l
NiCl ₂ · 6H ₂ O: 35 to 45 g / l
Boric acid: 10-50 g / l
(PH): 2-6
(Bath temperature): 30-70 ° C
(Current density): 0.1 to 50 A / dm ²

(Liquid composition 2)
CrO ₃ : 200 to 400 g / l
H ₂ SO _4: 1.5~4g / l
(PH): 1-4
(Liquid temperature): 45-60 degreeC
(Current density): 10 to 40 A / dm ²

The total amount of Ni (total Ni content) in the roughened layer, heat-resistant layer, weather-resistant layer, and rust-preventing layer is 452 μg / dm ² , and all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-proof layer From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.18, Co adhesion amount in all of the roughened layer, heat resistant layer, weather resistant layer, and rust preventive layer (total From the (Co amount), the total Co amount / (total Ni amount + total Zn amount) = 2.7. As a result of soaking evaluation, the soaking width was good at ≦ 3 μm.

As a result of the evaluation of the adhesion strength, the normal peel strength was 0.91 kg / cm, hydrochloric acid resistance against degradation: 11 (Loss%), and was very good. Alkali etching property was also good (◯). The results are shown in Table 2. In addition, Ni deposition amount (roughening step) 50~250μg / dm ^2, Co coating weight across the entire 1491μg / dm ^2, Zn deposition amount is (total Co content) (total amount of Zn) at 100 [mu] g / dm ² there were.

(Example 25)
Next, a copper foil with a carrier was formed under the same conditions as in Example 1 except that a Co / chromate-treated layer was formed as an intermediate layer between the carrier and the copper foil.
In this case, the Co / chromate intermediate layer was prepared by plating in a plating solution having the following liquid composition. The thickness of the ultrathin copper layer was 2 μm.

(Liquid composition 1) CoSO ₄ .7H ₂ O: 10 to 100 g / l
Sodium citrate dihydrate: 30-200 g / l
(Temperature): 10-70 ° C
(pH): 3-5
(Current density): 0.1 to 60 A / dm ²

(Liquid composition 2): CrO ₃ : 1 to 10 g / L
(Temperature); 10-70 ° C
(pH): 10-12
(Current density): 0.1 to 1.0 A / dm ²

The total amount of Ni (total Ni amount) in all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-proof layer is 1095 μg / dm ² , and all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-proof layer From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.13, the amount of Co deposited in all of the roughened layer, the heat-resistant layer, the weather-resistant layer, and the rust-proof layer (total From the Co amount, the total Co amount / (total Ni amount + total Zn amount) = 1.6. As a result of soaking evaluation, the soaking width was good at ≦ 3 μm.

As a result of the evaluation of the adhesion strength, the normal peel strength was 0.90 kg / cm, and the resistance to hydrochloric acid degradation was 10 (Loss%) or less, which was very good. Alkali etching property was also good (◯).
The results are shown in Table 2. In addition, Ni adhesion amount (roughening stage) 50-250 μg / dm ² , Co adhesion amount as a whole (total Co amount) is 2014 μg / dm ² , Zn adhesion amount as a whole (total Zn amount) is 164 μg / dm ² . there were.

(Example 26)
Next, a copper foil with a carrier was formed under the same conditions as in Example 4 except that an organic layer was formed as an intermediate layer between the carrier and the copper foil. The thickness of the ultrathin copper layer was 10 μm. In this case, the intermediate layer of the organic layer was prepared by spraying an aqueous carboxybenzotriazole solution having a liquid temperature of 40 ° C., pH 5, and a concentration of 1 to 10 g / l for 10 to 60 seconds.

The total amount of Ni (total Ni content) in the roughened layer, heat-resistant layer, weather-resistant layer, and rust-preventing layer is 450 μg / dm ² , and all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-proof layer From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.18, Co adhesion amount in all of the roughened layer, heat resistant layer, weather resistant layer, and rust preventive layer (total From the (Co amount), the total Co amount / (total Ni amount + total Zn amount) = 2.7. As a result of soaking evaluation, the soaking width was good at ≦ 3 μm.

As a result of the evaluation of the adhesion strength, the normal peel strength was 0.91 kg / cm, hydrochloric acid resistance against degradation: 11 (Loss%), and was very good. Alkali etching property was also good (◯).
The results are shown in Table 2. In addition, Ni deposition amount (roughening step) 50~250μg / dm ^2, Co coating weight across the entire 1484μg / dm ^2, Zn deposition amount is (total Co content) (total amount of Zn) at 99 ug / dm ² there were.

  After forming a roughening treatment on the surface of the copper foil with a carrier, forming a heat-resistant layer and a rust-preventing layer on the surface, and then applying a silane coupling treatment. When the substrate is subjected to acid treatment or chemical etching after the pattern printed circuit is formed, it is possible to improve the suppression of adhesion deterioration due to the infiltration of acid into the interface between the copper foil circuit and the substrate resin. Excellent and alkaline etching property. As a result, the progress of electronic equipment has led to further miniaturization and higher integration of semiconductor devices, and the processing performed in the manufacturing process of these printed circuits has become more severe. Provide useful techniques that can be answered.

Claims (13)

Carrier, intermediate layer, ultrathin copper layer are laminated in this order on the surface of the ultrathin copper layer of the copper foil with carrier, a roughened layer, and a heat-resistant layer comprising a Ni-Co layer on the roughened layer. a layer, and resistance to weathering layer and anticorrosive layer over the heat-resistant layer, a surface treatment layer having,
The weathering layer comprises Zn and Ni;
The rust preventive layer contains Cr or contains Cr and Zn,
The total Zn amount in the surface treatment layer / (total Zn amount + total Ni amount) is 0.02 or more and 0.35 or less,
A copper foil with a carrier, wherein the total amount of Ni in the surface treatment layer is 1600 μg / dm ² or less, and the total amount of Co in the surface treatment layer is 2500 μg / dm ² or less.   The copper foil for printed circuits which consists of the said ultra-thin copper layer of the copper foil with a carrier of Claim 1.   The copper foil with a carrier according to claim 1, further comprising a resin layer on the surface treatment layer.   A copper-clad laminate in which the copper foil for printed circuit according to claim 2 is laminated and adhered to a resin substrate.   A method for producing a printed wiring board using the copper foil with a carrier according to claim 1.   A method for producing a printed circuit board using the copper foil with a carrier according to claim 1.   The method to manufacture a copper clad laminated board using the copper foil with a carrier of Claim 1. Preparing a copper foil with a carrier according to claim 1 and an insulating substrate;
Laminating the copper foil with carrier and an insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. Forming a circuit on the ultrathin copper layer side surface of the copper foil with a carrier according to claim 1;
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Method. Forming a circuit on the resin layer,
It is the process of bonding another copper foil with a carrier on the resin layer from the ultrathin copper layer side, and forming the circuit using the copper foil with a carrier bonded to the resin layer. Manufacturing method of printed wiring board. The method for manufacturing a printed wiring board according to claim 10 , wherein another copper foil with a carrier to be bonded onto the resin layer is the copper foil with a carrier according to claim 1.   The process of forming a circuit on the resin layer is performed according to any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. Manufacturing method of printed wiring board.   The manufacturing method of the printed wiring board as described in any one of Claims 9-12 which further includes the process of forming a board | substrate in the carrier side surface of copper foil with a carrier, before peeling a carrier.