KR20170077280A - Copper foil provided with carrier, and copper-clad laminate using said copper foil provided with carrier - Google Patents

Abstract

A harmful treatment layer formed by subjecting a copper foil or a copper alloy foil to a harm treatment (try treatment), a heat-resistant layer comprising a Ni-Co layer formed on the roughened treatment layer, and Zn, Ni and Cr formed on the heat- (Total Zn amount + total Ni amount) in the surface treatment layer is 0.02 or more and 0.35 or less, and the total amount of Ni in the surface treatment layer is 1600 占 퐂 / dm2 or less. A copper clad laminate using a copper foil for a printed circuit which has been subjected to a silane coupling treatment after a roughening treatment is formed on the surface of the copper foil and a heat resistant layer and a rust preventive layer are formed thereon, It is possible to improve the suppression of decrease in adhesion due to permeation of acid to the interface between the copper foil circuit and the substrate resin when the acid treatment or the chemical etching is carried out and to provide a copper foil with a carrier excellent in acid- to provide.

Description

TECHNICAL FIELD [0001] The present invention relates to a copper-clad laminated board using a copper foil with a carrier and a copper foil with a carrier,

The present invention relates to a copper foil with a carrier. More particularly, the present invention relates to a copper foil with a carrier used as a material for a printed wiring board or a shield member.

Copper and a copper alloy foil (hereinafter referred to as a copper foil) have contributed greatly to the development of the electric and electronic industry, and are indispensable as a printed circuit board. The copper foil for a printed circuit is generally produced by laminating and bonding a substrate such as a synthetic resin board or a polyimide film with an adhesive or without using an adhesive under high temperature and high pressure or by applying a polyimide precursor, A copper clad laminate is manufactured, and then a necessary circuit is printed through a resist coating and an exposing process in order to form a desired circuit, and then an etching process for removing unnecessary portions is performed.

Finally, the necessary elements are soldered to form various printed circuit boards for electronics devices. The copper foil for a printed circuit board differs in the surface (roughened surface) to be adhered to the resin base material and the non-adhered surface (glossy surface), and many methods are proposed respectively.

For example, the demand for roughened surfaces formed on the copper foil is mainly caused by: 1) there is no oxidation discoloration during storage; 2) the peeling strength with the substrate is high temperature heating, wet processing, brazing, (3) lamination with the substrate, and no so-called stacking fault after etching.

The roughening treatment of the copper foil plays a large role in determining the adhesion between the copper foil and the substrate. In this roughening treatment, copper roughening treatment for electrodepositing copper at first is adopted, but various techniques have been developed thereafter. For the purpose of improving heat-resisting peel strength, hydrochloric acid resistance and oxidation resistance, copper- And became a representative processing method.

The applicant of the present application proposed a copper-nickel coarsening treatment (see Patent Document 1), and has achieved results. The copper-nickel-treated surface exhibited black color, and in the case of the rolled treated foil for a flexible substrate in particular, the copper-nickel-treated black color was recognized as a commodity as a commodity.

However, copper-nickel plating treatment is excellent in heat peel strength, oxidation resistance and hydrochloric acid resistance, while etching with an alkaline etching solution, which has recently become important as a treatment for fine patterning, is difficult and fine pattern formation The treatment layer becomes the etch residue.

Thus, as the treatment for the fine pattern, the Applicant has developed Cu-Co treatment (see Patent Document 2 and Patent Document 3) and Cu-Co-Ni treatment (see Patent Document 4).

These coarsening treatments were good in terms of the etching property, the alkali etching property and the hydrochloric acid resistance, but it was again proved that the heat peeling strength was lowered when the acrylic adhesive was used, and the oxidation resistance was not sufficient in the expected period And color tone did not reach to black, and it was brown to dark brown.

According to this demand, the present applicant has found that by forming a cobalt plated layer or a cobalt-nickel alloy plated layer on the surface of a copper foil after roughening treatment by copper-cobalt-nickel alloy plating, A copper foil having an excellent oxidation resistance and a black color on the surface of the copper foil, which does not deteriorate the heat peel strength when the acrylic adhesive is used, and which has the above- (See Patent Document 5).

In addition, since the demand for improvement of the heat peelability of the copper foil circuit board has become stricter in the progress of the development of electronic devices, the present applicant has found that after the copper foil surface is roughened by copper-cobalt-nickel alloy plating, (Refer to Patent Document 6), which is excellent in heat resistance, in which a zinc-nickel alloy plating layer is formed, and further a zinc-nickel alloy plating layer is formed. This is a very effective invention and today it is one of the main products of copper foil circuit material.

Since then, miniaturization and high integration of semiconductor devices have progressed owing to the development of electronic devices, and the technology of multi-layer substrate of FPC has progressed rapidly. In the manufacturing process of the FPC multi-layer substrate, an etching solution containing sulfuric acid and hydrogen peroxide, or an etching solution containing sulfuric acid and hydrogen peroxide as a pretreatment for cleaning the copper foil circuit board in the resist film pressing step or the metal plating step after formation of a fine pattern circuit with a copper- A plurality of surface etching processes using a solution using an aqueous solution of sulfuric acid or the like have been used.

However, in the surface etching treatment in the FPC multilayered plate manufacturing process, the surface of the copper foil referred to in Patent Document 6 is subjected to a roughening treatment by copper-cobalt-nickel alloy plating, a cobalt-nickel alloy plating layer is formed, In the fine pattern circuit of the copper clad laminate using the printing-use copper foil for forming the zinc-nickel alloy plating layer, the surface etchant is eroded at the interface between the copper foil circuit and the substrate resin and the adhesion between the copper foil circuit and the substrate resin is lowered, It is required to solve this problem.

The applicant of the present invention has disclosed in Patent Document 7 the following Patent Document 7 discloses a method for manufacturing a copper-chromium-nickel alloy plating layer, , A zinc-nickel alloy plating layer is formed on a copper foil for a printed circuit, and the total amount of the zinc-nickel alloy plating layer, the amount of nickel, and the ratio of nickel are defined.

Although this technique is effective, since Ni can be contained not only in the zinc-nickel alloy layer but also in the roughened layer, the heat resistant layer and the inner layer, it is possible to prevent circuit erosion in surface etching, In order to obtain a copper foil for a printed circuit that can exert its effect, it has been found that it is necessary to further examine the total amount of Ni in both the coarsened layer, the heat resistant layer and the inner layer.

Since Zn can be contained not only in the zinc-nickel alloy layer but also in both the inner layer and the rust-preventive layer, the ratio of the total amount of Ni to the total amount of Zn in both the inner layer and the rust- I knew I needed to do it.

The printed wiring board is generally manufactured through a step of bonding an insulating substrate to a copper foil to form a copper clad laminate, and then forming a conductor pattern on the copper foil surface by etching. In recent years, along with an increase in the demand for miniaturization and high performance of electronic devices, mounting of high-density mounting parts and high frequency signals have progressed, and a printed circuit board has been required to have finer conductor patterns (fine pitch) and high frequency response.

In response to the fine pitching, a copper foil having a thickness of 9 占 퐉 or less and further having a thickness of 5 占 퐉 or less is required in recent years. However, such a copper foil with a very thin foil has low mechanical strength and is cracked, wrinkled A copper foil with a carrier in which a thin metal foil is used as a carrier and an extremely thin copper layer is electrodeposited with a release layer interposed therebetween has appeared. The surface of the ultra-thin copper layer is bonded to an insulating substrate, and after the thermocompression bonding, the carrier is peeled off through the peeling layer.

Here, regarding the surface of the ultra-thin copper layer of the copper foil with a carrier to be bonded to the resin, the peeling strength between the ultra-thin copper layer and the resin substrate is sufficient, and the peel strength thereof is high temperature heating, wet processing, It is required to be sufficiently retained even after treatment or the like.

As a method of increasing the peeling strength between the ultra-thin copper layer and the resin substrate, a method of attaching a large amount of coarse particles on the ultra-thin copper layer having a generally increased profile (unevenness and roughness) of the surface is typical.

However, when a very thin copper layer having such a profile (irregularity and roughness) is used for a semiconductor package substrate which needs to form a particularly fine circuit pattern among printed wiring boards, unnecessary copper particles remain in circuit etching, And the like.

For this reason, it has been attempted to use a copper foil with a carrier not subjected to a roughening treatment on the surface of the ultra-thin copper layer as a copper foil with a carrier for use in a fine circuit including a semiconductor package substrate. The adhesion (peel strength) between the ultra-thin copper layer and the resin not subjected to such roughening treatment tends to be lowered as compared with a general copper foil for a printed wiring board due to its low profile (unevenness, roughness and roughness). (Patent Document 8)

Therefore, further improvement is required for the copper foil with a carrier.

Japanese Laid-Open Patent Publication No. 52-145769 Japanese Patent Publication No. 63-2158 Japanese Patent Application Laid-Open No. 2-292895 Japanese Patent Application Laid-Open No. 2-292894 Japanese Patent Publication No. 6-54831 Japanese Patent Publication No. 9-87889 WO2009 / 041292 WO2004 / 005588

The present invention relates to a copper foil with a carrier and a copper clad laminate, and more particularly to a copper foil with a carrier and a copper clad laminate having a copper foil coated with a carrier to which a silane coupling treatment has been applied after forming a heat resistant layer, It is possible to improve the suppression of the decrease in adhesion due to " penetration " of the acid at the interface between the copper foil circuit and the substrate resin when the substrate is subjected to the acid treatment or the chemical etching after the formation of the fine pattern printed circuit To a copper foil with a carrier excellent in acid resistance and excellent in alkali etching property.

As the development of electronic devices progresses, miniaturization and high integration of semiconductor devices are further advanced, and processing performed in the manufacturing process of these printed circuits is more strictly demanded. It is an object of the present invention to provide a technique that meets these needs.

From the above, the present invention provides the following invention.

1) A heat-resistant layer comprising a roughened treatment layer formed by subjecting a copper foil or a copper alloy foil to a treatment (treatment), a Ni-Co layer formed on the roughened treatment layer, Cr and a rust preventive layer, wherein the total amount of Zn / (total amount of Zn + total amount of Ni) in the surface treatment layer is 0.02 or more and 0.35 or less, and the total amount of Ni in the surface- 1600 占 퐂 / dm2 or less.

2) The method according to 1), wherein the total amount of Zn in the surface-treated layer / total Zn amount + total Ni amount is 0.02 or more and 0.23 or less, and the total amount of Ni in the surface treatment layer is 1150 占 퐂 / Copper with a carrier.

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 占 퐂 / dm2.

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 占 퐂 / dm2.

(5) The method according to any one of (1) to (4) above, which is characterized in that the total amount of Co in the surface treatment layer is 770 to 3200 쨉 g / dm 2 and the total amount of Co / (total amount of Zn + total amount of Ni) Copper with a carrier.

6) The method according to any one of 1) to 5) above, wherein the total amount of Co in the surface treatment layer is 770 to 2500 占 퐂 / dm2 and the total amount of Co / (total amount of Zn + total amount of Ni) ≪ / RTI >

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 占 퐂 / dm2.

The present invention also provides the following invention.

8) The copper foil with a carrier according to any one of 1) to 7) above, wherein the coarsened layer has Ni of 50 to 550 占 퐂 / dm2.

(9) The copper foil with a carrier according to any one of (1) to (8) above, wherein the roughening treatment layer is a roughened treatment layer made of elements of Co, Cu and Ni.

10) The copper foil with a carrier according to any one of 1) to 9), wherein the roughening treatment layer is composed of fine particles having an average particle diameter of 0.05 to 0.60 μm.

(11) The copper foil with a carrier according to any one of (1) to (10) above, wherein the roughening treatment layer is composed of fine particles of a ternary alloy comprising Cu, Co and Ni having an average particle size of 0.05 to 0.60 μm.

(12) The method according to any one of (1) to (11), wherein the harmonizing 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 ≪ / RTI >

(13) The method according to any one of the above items (1) to (3), wherein the roughening treatment layer comprises a primary particle layer of Cu having an average particle diameter of 0.25 to 0.45 탆 and a secondary particle layer composed of a ternary alloy composed of Cu, Co and Ni having an average particle diameter of 0.05 to 0.25 탆 The copper foil with a carrier according to any one of 1) to 12) above,

14) A copper foil for a printed circuit comprising the ultra-thin copper layer of the copper foil with a carrier according to any one of 1) to 13) above.

15) The copper foil with a carrier according to any one of 1) to 13), which has a resin layer on the surface treatment layer.

16) A copper clad laminate according to item 14), wherein the copper foil for a printed circuit is laminated and bonded to a resin substrate.

(17) A printed wiring board produced by using the copper foil with a carrier according to any one of (1) to (13).

(18) A printed circuit board manufactured by using the copper foil with a carrier according to any one of (1) to (13).

(19) A copper clad laminate produced by using the copper foil with a carrier according to any one of (1) to (13).

20) A method for manufacturing a semiconductor device, comprising the steps of: preparing the copper foil with a carrier and the insulating substrate according to any one of 1) to 13)

A step of laminating the copper foil with a carrier and an insulating substrate,

After the step of laminating the carrier-bonded copper foil with the insulating substrate and the step of peeling the carrier of the carrier-coated copper foil, a copper clad laminate is formed,

Thereafter, a step of forming a circuit by any one of the semi-additive method, the subtractive method, the protein additive method, and the modified semi-

Wherein the step of forming the printed wiring board comprises the steps of:

(21) a step of forming a circuit on the surface of the ultra-thin copper layer side of the copper foil with a carrier according to any one of (1) to (13)

A step of forming a resin layer on the surface of the ultra thin copper layer side of the copper foil with a carrier so that the circuit is buried,

A step of forming a circuit on the resin layer,

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

Exposing a circuit buried in the resin layer formed on the extremely thin copper layer side surface by removing the extremely thin copper layer after peeling the carrier.

22) A process for forming a circuit on the resin layer,

And the other copper-coated copper foil on the resin layer is laminated from the ultra-thin copper layer side, and the circuit is formed by using the copper foil with a carrier bonded to the resin layer.

(23) A copper foil with a carrier to be bonded onto the resin layer, wherein the copper foil is a copper foil with a carrier according to any one of (1) to (13).

(24) The process for producing a circuit according to any one of (21) to (23), wherein the step of forming a circuit on the resin layer is carried out by any one of a semiadditive method, a subtractive method, a patelly additive method and a modified semi- A method for producing a printed wiring board according to any one of claims 1 to 5.

(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 copper foil with a carrier 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 more particularly to a copper foil with a carrier, an intermediate layer and an ultra-thin copper layer laminated in this order, In which a heat resistant layer, an inner layer and an anticorrosion layer are formed thereon, and then a silane coupling treatment is applied to the copper clad laminate, It is possible to improve the suppression of the adhesion deterioration due to " permeation " of the acid to the interface between the copper foil circuit and the substrate resin, and to provide a copper foil with a carrier excellent in acid- .

As the development of electronic devices progresses, miniaturization and high integration of semiconductor devices are further advanced, and processing performed in the manufacturing process of these printed circuits is more strictly demanded. The present invention is an excellent technique to meet these demands.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is an explanatory view showing a state in which an etchant is eroded from the periphery of a copper foil circuit when surface etching is performed using a hydrogen peroxide and a sulfuric acid solution; FIG.
2 is a view showing the result of observing " penetration " of an etching solution to an interface between a copper foil circuit and a substrate resin when a substrate is etched by surface etching (by a solution of hydrogen peroxide and sulfuric acid) after forming a fine pattern printed circuit Photo). In the case where the above drawing (photograph) does not have "seeping", the following drawing (photograph) has "seeping".
Fig. 3 is a schematic view showing a state in which a copper foil with a carrier (A) having an ultra-thin copper layer having a surface roughening treatment layer formed thereon is formed by applying a resist on a roughened treatment layer of an ultra-thin copper layer, performing exposure and development, (B), forming a circuit plating, removing the resist, and forming a circuit plating of a predetermined shape (C).
Fig. 4 is a cross-sectional view showing a state in which a buried resin is formed on the extremely thin copper layer to cover the circuit plating, the resin layers are laminated, and then another carrier-adhered copper foil (second layer) (E) peeling the carrier from the attached copper foil, forming a laser hole at a predetermined position of the resin layer, and exposing the circuit plating to form a blind via (F).
Fig. 5 explains (I) that copper is buried 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- Fig.
Fig. 6 is a plan view showing a state in which the extremely thin copper layer on both surfaces is removed by flash etching, the surface of the circuit plating in the resin layer is exposed (J), the bumps are formed on the circuit plating in the resin layer, (K) to illustrate the production of a printed wiring board using the copper foil with a carrier according to the present invention.

The main object of the present invention is to prevent circuit erosion which occurs during the surface etching in the pre-treatment step in the manufacturing process of the FPC multilayer substrate.

The copper foil with a carrier according to the present invention is characterized by comprising a roughened treatment layer formed by subjecting a copper foil or a copper alloy foil to a roughening treatment, a heat-resistant layer comprising a Ni-Co layer formed on the roughened treatment layer, And a plurality of surface treatment layers composed of an inner layer and an anti-rust layer containing Zn, Ni, and Cr formed on the substrate. 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.

This is the main condition that can effectively prevent " permeation " occurring during surface etching. Zn is a constituent component of the inner layer and the rust preventive layer in the surface treatment layer of the copper foil and Ni is a constituent component of the roughened layer, the heat resistant layer and the inner layer, and Zn and Ni are important components Component.

However, although Zn is a component effective for weather resistance, it is an undesirable component for the characteristics of the chemical resistance in the fine pattern circuit forming step, and is liable to be "permeated" in etching of circuit formation.

On the other hand, Ni is a component effective for "seeping", but if it is excessively large, it lowers the alkaline etching property and becomes unsuitable for a printed circuit.

Thus, it is the present invention that the balance between Zn and Ni becomes 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 0.23 or less.

When it is less than 0.02, there are cases where Zn is excessively small and cases where Ni is excessively large. In cases where Zn is too small, weatherability is poor. In cases where Ni is excessively large, etchability becomes a problem. On the other hand, if it exceeds 0.35, the acid resistance tends to be deteriorated, so that " permeation " tends to occur at the time of etching, which is not preferable.

The total amount of Zn is defined as " the total amount of Zn contained in the roughened treatment layer, heat-resistant layer, inner layer and rust-preventive layer on the copper foil. &Quot; In the case where Zn is not contained in the harmony treatment layer or the heat resistant layer, the total amount of Zn is the sum of the amount of Zn contained in the two layers of the inner layer and the rust preventive layer. When Zn is contained in the intermediate layer, the ultra-thin copper layer is peeled from the carrier. Thereafter, the surface of the ultra-thin copper layer on the side of the roughened layer is masked with a resin or the like, and then the surface of the ultra-thin copper layer on the side of the intermediate layer is pickled to remove Zn contained in the surface of the ultra- Thereafter, the amount of Zn may be measured with respect to the extremely thin copper layer. The acid pickling on the surface of the intermediate layer side of the ultra-thin copper layer may be performed with a nitric acid aqueous solution mixed in a 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 coarsened layer, the heat resistant layer, the inner layer, and the rust-preventive layer on the copper foil (the ultra-thin copper layer of the copper foil with a carrier)". When Ni is not contained in the anticorrosive layer, the total amount of Ni is the sum of the amounts of Ni in the coarsened layer, the heat resistant layer and the inner layer. When Ni is contained in the intermediate layer, the ultra-thin copper layer is peeled off from the carrier. Thereafter, the surface of the ultra-thin copper layer on the side of the roughened layer is masked with a resin or the like, and then the surface of the ultra-thin copper layer on the side of the intermediate layer is pickled to remove Ni contained in the surface of the ultra- Thereafter, the amount of Ni may be measured with respect to the extremely thin copper layer. The acid pickling on the surface of the intermediate layer side of the ultra-thin copper layer may be performed with a nitric acid aqueous solution mixed in a ratio of nitric acid: water = 1: 2 (volume).

The definition of the amount of Ni deposited in the coarsening treatment step is the " amount of Ni contained in the coarsened layer on the copper foil (the ultra-thin copper layer of the copper foil with a carrier) ". The amount of Ni adhered to the roughening treatment step was the same as in each of the Examples and Comparative Examples except that the copper foil with a carrier was produced and then only the roughening treatment layer was formed under the same conditions as in the respective Examples and Comparative Examples, And the Ni deposition amount was measured 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 the coarsened layer, heat-resistant layer, inner layer, and rust-preventive layer on the copper foil (extremely copper layer of the copper foil with a carrier)". When Co is not contained in the rust-preventive layer, the total amount of Co is the sum of Co in the roughening treatment layer, heat-resistant layer and inner layer. When Co is contained in the intermediate layer, the ultra-thin copper layer is peeled from the carrier. Thereafter, the surface of the ultra-thin copper layer on the side of the roughened layer is masked with a resin or the like, and then the surface of the ultra-thin copper layer is pickled to remove Co contained in the surface of the ultra-thin copper layer. Thereafter, the amount of Co may be measured with respect to the extremely thin copper layer. The acid pickling on the surface of the intermediate layer side of the ultra-thin copper layer may be performed with a nitric acid aqueous solution mixed in a ratio of nitric acid: water = 1: 2 (volume).

Similarly, the definition of the total amount of Cr is "the amount of Cr contained in the roughened layer, heat-resistant layer, inner layer, and rust-preventive layer on the copper foil (the ultra-thin copper layer of the copper foil with a carrier)". Generally, when Cr is not contained in the heat-resistant layer and the inner layer, the total amount of Cr is the sum of the amounts of Cr in the roughened layer and the rust-preventive layer. When Cr is contained in the intermediate layer, the ultra-thin copper layer is peeled off from the carrier. Thereafter, the surface of the ultra-thin copper layer on the side of the coarsened layer is masked with a resin or the like, and then the surface of the ultra-thin copper layer on the side of the intermediate layer is pickled to remove Cr contained in the surface of the ultra- Thereafter, the amount of Cr may be measured for the extremely thin copper layer. The acid pickling on the surface of the intermediate layer side of the ultra-thin copper layer may be performed with a nitric acid aqueous solution mixed in a ratio of nitric acid: water = 1: 2 (volume).

In the present invention, the above-mentioned total amount of Ni and total amount of Co are determined by dissolving the sample in a nitric acid aqueous solution mixed with nitric acid: water = 1: 2 (volume) and measuring by atomic absorption spectrometry. And the total amount of Zn is determined by self-dissolving the sample in an aqueous hydrochloric acid solution mixed with a ratio of hydrochloric acid: water = 1: 4 (volume) and quantitatively analyzing it by atomic absorption spectrometry. The Ni deposition amount, the total Ni amount, the total Co amount, the total Cr amount, and the total Zn amount in the coarsening treatment step are set such that the adhesion mass (쨉 g) of Ni, Co, Cr and Zn per unit area (d m2) .

Refers to the case where surface etching is performed using a solution of hydrogen peroxide and sulfuric acid or etching is performed using an etching solution composed of a cupric chloride solution, ferric chloride solution or the like Refers to a phenomenon in which the etching liquid penetrates the interface between the copper foil and the resin.

The left side of Fig. 1 is a conceptual diagram showing a state in which a resin surface and a circuit surface of a copper foil having a surface treatment layer adhere closely to each other (tentative section). The right side of Fig. 1 is a conceptual diagram showing a state where a seal is formed at both edges of a circuit and a little adhesion is reduced (tentative).

2 shows the result of observation of "penetration" of the acid at the interface between the copper foil circuit and the substrate resin when the substrate is soft-etched (by using a solution of hydrogen peroxide and sulfuric acid) after the formation of the fine pattern printed circuit (Photo). In the case where the above drawing (photograph) does not permeate the edge portion of the straight line circuit, the following drawing (photograph) shows "seepage". It can be observed that disturbance is generated in the edge portion of the straight line circuit.

Ni is a component contained in the roughened layer, the heat resistant layer, the inner layer and the rust-preventive layer of the surface treatment layer as described above, and is a very important component in the surface treatment layer of the ultra-thin copper layer. It is a component effective for "permeating" the problem to be solved by the present invention.

Therefore, in the carrier-coated copper foil of the present invention, the total amount of Ni in the surface treatment layer is 1600 占 퐂 / dm2 or less, preferably 1150 占 퐂 / dm2 or less. The total amount of Ni in the surface treatment layer is preferably 350 to 1350 占 퐂 / dm2, more preferably 450 to 1100 占 퐂 / dm2.

Further, Ni contained in the roughening treatment layer needs to have the surface of the surface-treated copper foil to be black, so it is sometimes necessary to include Ni at 50 占 퐂 / dm2 or more.

Further, since Ni is contained in the heat-resistant layer and the inner layer, there is a case that the total amount of Ni is required to be 350 占 퐂 / dm2 or more, and more preferably 450 占 퐂 / dm2 or more. However, if the total amount of Ni exceeds 1350 占 퐂 / dm2 or 1100 占 퐂 / dm2, the alkaline etching property may be lowered, but the coarse particles may remain on the surface of the substrate resin during circuit etching, It can be said that there is a case where 1350 占 퐂 / dm2 or less is preferable, and 1100 占 퐂 / dm2 or less is more preferable.

Further, Co is a component used in the surface treatment layer of the copper foil and is an important component contributing to heat resistance, and the amount of Co is larger than other components. However, it is an undesirable component for "permeation". Therefore, in the copper foil to which the surface treatment layer of the present invention is adhered, it is preferable that the total amount of Co in the surface treatment layer is 770 to 3200 占 퐂 / dm2. In a preferred embodiment, the total amount of Co in the surface treatment layer can be 770 to 2500 占 퐂 / dm2, and more preferably 940 to 2500 占 퐂 / dm2.

On the other hand, when it is less than 770 占 퐂 / dm 2, sufficient heat resistance may not be obtained, and when it exceeds 3200 占 퐂 / dm 2, May occur. Therefore, the above-mentioned numerical range is used. In order to increase the heat resistance, it is particularly preferable that the total amount of Co in the surface treatment layer is 940 占 퐂 / dm2 or more. The total amount of Co / (total amount of Zn + total amount of Ni) is preferably 3.0 or less. Even if the total amount of Co is within the above range, there is a case that the "permeation" tends to deteriorate when the total amount of Co is large relative to the total of the total amount of Zn and the total amount of Ni as the other main component.

In the copper foil to which the surface treatment layer of the present invention is adhered, the total amount of Cr in the surface treatment layer is preferably 50 to 120 占 퐂 / dm2. The total amount of Cr in this range has the effect of suppressing the smudging amount as well.

The Ni of the roughening treatment layer of the copper foil to which the surface treatment layer of the present invention is adhered is effective at 50 to 550 占 퐂 / dm2.

As for the above-mentioned roughening treatment layer, a roughened layer made of elements of Co, Cu, and Ni is effective. The roughened layer is preferably fine particles having an average particle diameter of 0.05 to 0.60 mu m and may be an aggregate of fine particles of a ternary alloy made of Cu, Co and Ni having an average particle diameter of 0.05 to 0.60 mu m. The fine particles having an average particle diameter of 0.05 to 0.60 占 퐉 can be formed by a carbon plating (coarsening plating treatment) of an alloy plating containing copper.

The above-mentioned roughening treatment layer is preferably made of a primary particle layer having an average particle diameter of 0.25 to 0.45 mu m and a secondary particle layer having an average particle diameter of 0.05 to 0.25 mu m formed thereon. The above-mentioned roughening treatment layer is a secondary particle layer composed of a primary particle layer of Cu having an average particle diameter of 0.25 to 0.45 탆 and a ternary alloy composed of Cu, Co and Ni having an average particle diameter of 0.05 to 0.25 탆 formed thereon can do. It is preferable that the primary particle layer is plated with copper (coarsened plating). Further, the secondary particle layer can be formed by a carbon plating (coarsening plating treatment) of an alloy plating containing copper.

A heat-resistant layer made of a Ni-Co layer, an inner layer containing Zn, Ni, Cr, and a rust-preventive layer can be formed by using the following electrolytic plating conditions.

(Condition of harmonization treatment)

When the harmonic treatment of a fine roughening particle aggregate of a ternary alloy consisting of Cu, Co and Ni with an average particle diameter of 0.05 to 0.60 mu m is carried out

Liquid composition: Cu 10 to 20 g / liter, Co 1 to 10 g / liter, Ni 1 to 15 g / liter

pH: 1-4

Temperature: 30 ~ 50 ℃

Current density (D _k ): 20 to 50 A / dm 2

Time: 1 to 5 seconds

When a harmony treatment is carried out comprising a primary grain layer of Cu having an average grain size of 0.25 to 0.45 탆 and a secondary grain layer composed of a ternary alloy composed of Cu, Co and Ni having an average grain size of 0.05 to 0.25 탆 formed thereon

(A) Primary particle layer formation of Cu

Solution composition: Cu 10 to 20 g / liter, sulfuric acid 50 to 100 g / liter

pH: 1-3

Temperature: 25 ~ 50 ℃

Current density (D _k ): 1 to 60 A / dm 2

Time: 1 to 5 seconds

(B) Formation of a secondary particle layer made of a ternary alloy made of Cu, Co, and Ni

Solution composition: Cu 10 to 20 g / liter, Co 1 to 15 g / liter, Ni 1 to 15 g / liter

pH: 1-3

Temperature: 30 ~ 50 ℃

Current density (D _k ): 10 to 50 A / dm 2

Time: 1 to 5 seconds

Before forming the primary particles, a metal layer may be plated between the copper foil and the primary particles. As the metal plating layer, a copper plating layer and a copper alloy plating layer are typically considered. In the case of carrying out the copper plating layer, it is possible to use only an aqueous solution of copper sulfate containing mainly copper sulfate and sulfuric acid as a main component, a surfactant such as an organic sulfur compound having sulfuric acid or a mercapto group, polyethylene glycol or the like, , And a copper plating layer is formed by electroplating.

(Conditions for forming the heat resistant layer)

Liquid composition: Co 1 ~ 20 g / liter, Ni 1 ~ 20 g / liter

pH: 1-4

Temperature: 30 ~ 60 ℃

Current density (D _k ): 1 to 20 A / dm 2

Time: 1 to 5 seconds

(Condition 1 for forming the inner layer and the anti-rust layer)

Solution composition: Ni 1 to 30 g / liter, Zn 1 to 30 g / liter

pH: 2 to 5

Temperature: 30 ~ 50 ℃

Current density (D _k ): 1 to 3 A / dm 2

Time: 1 to 5 seconds

(Condition 2 for forming the inner layer and the anti-rust layer)

Liquid composition: K ₂ Cr ₂ O ₇ : 1 to 10 g / liter, Zn: 0 to 10 g / liter

pH: 2 to 5

Temperature: 30 ~ 50 ℃

Current density (D _k ): 0.01 to 5 A / dm 2

Time: 0.01 to 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 carried out.

Examples of the silane coupling agent include olefin silanes, epoxy silanes, acrylic silanes, amino silanes, and mercapto silanes, and these can be appropriately selected and used.

As the silane coupling agent used for the silane coupling treatment, a known silane coupling agent may be used. For example, an amino silane coupling agent, an epoxy silane coupling agent, or a mercapto silane coupling agent may be used. Examples of the silane coupling agent include vinyltrimethoxysilane, vinylphenyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxy Aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) propoxy) propyl-3-aminopropyl Trimethoxysilane, imidazole silane, triazinilane, gamma-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. Two or more such silane coupling agents may be used in combination. Among them, it is preferable to use an amino-based silane coupling agent or an epoxy-based silane coupling agent.

Examples of the amino-based silane coupling agent include N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxy Silane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- Aminopropyl) trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane, 6- (aminohexylaminopropyl) , Aminophenyltrimethoxysilane, 3- (1-aminopropoxy) -3,3-dimethyl-1-propenyltrimethoxysilane, 3- 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, omega -aminoundecyltrimethoxysilane, 3- (2-N-benzylaminoethylamino Propyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl- Aminopropyl) trimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) Methoxysilane, and methoxysilane.

The silane coupling treatment layer is preferably used in a range of 0.05 mg / m 2 to 200 mg / m 2, preferably 0.15 mg / m 2 to 20 mg / m 2, preferably 0.3 mg / m 2 to 2.0 mg / . In the above-mentioned range, the adhesion between the base resin and the surface-treated copper foil can be further improved.

The coating method may be spraying, coating, dipping, flowing, or the like of the silane coupling agent solution. Since these techniques are already known (see, for example, Japanese Patent Application Laid-open No. 60-15654), detailed description thereof will be omitted.

(carrier)

The carrier of the copper foil with a carrier of the present invention may be a foil such as a copper foil, an aluminum foil, an aluminum alloy foil or an iron alloy, stainless steel, nickel, or a nickel alloy. Further, in consideration of easiness of lamination of the intermediate layer on the carrier, it is preferable that the carrier is a copper foil. The copper foil used in the carrier is typically provided in the form of rolled copper foil or electrolytic copper foil.

Generally, the electrolytic copper foil is produced by electrolytically depositing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel. The rolled copper foil is manufactured by repeating plastic working and heat treatment by a rolling roll. Examples of the material of the copper foil include high-purity copper such as tough pitch copper (JIS H3100 C1100) and oxygen free copper (JIS H3100 C1020), copper such as Sn-containing copper, Ag-containing copper, , A copper alloy such as a Colson type copper alloy to which Ni and Si are added. In the present specification, when the term " copper foil " is used singly, copper alloy foil is also included.

The thickness of the carrier which can be used in the present invention is not particularly limited, but may be suitably adjusted to a suitable thickness for fulfilling its role as a carrier. For example, it may be 12 占 퐉 or more. However, if it is excessively thick, the production cost is increased, and therefore, it is generally preferable to be 35 mu m or less. Thus, the thickness of the carrier is typically 12 to 70 占 퐉, and more typically 18 to 35 占 퐉.

(Middle layer)

An intermediate layer is formed on the carrier. Another layer may be formed between the carrier and the intermediate layer. The intermediate layer of the copper foil with a carrier of the present invention may be any one of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, It is preferable to form a layer containing at least one species. The intermediate layer may be a plurality of layers.

For example, the intermediate layer may be formed of a single metal layer made of any one of the elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Ni, Co, Fe, Mo, Ti, W, P, Cu, and at least one element selected from the group consisting of Fe, Mo, Ti, W, P, Cu, Al, , Al, and Zn, and is composed of a layer composed of a hydrate or an oxide of at least one element selected from the group consisting of Al and Zn.

In addition, for example, the intermediate layer can be composed of two layers of Ni and Cr. The Ni layer is laminated on the interface with the copper foil carrier and the Cr layer is brought into contact with the interface with the ultra-thin copper layer. The adhesion amount of Cr in the intermediate layer may be set to 10 to 100 占 퐂 / dm2, and the adhesion amount of Ni to 1000 to 40000 占 퐂 / dm2. The intermediate layer may contain Zn.

(Strike plating)

And an ultra-thin copper layer is formed on the intermediate layer. Strike plating using a copper-phosphorus alloy may be performed to reduce the pinholes of the ultra-thin copper layer. Strike plating includes copper pyrophosphate plating solution and the like.

(Ultra-thin copper layer)

And an ultra-thin copper layer is formed on the intermediate layer. Another layer may be formed between the intermediate layer and the ultra-thin copper layer. The ultra-thin 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 sulfide or copper cyanide, and is used in a general electrolytic copper foil, A copper sulfate bath is preferable in view of formation.

The thickness of the ultra-thin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. Typically from 0.1 to 12 microns, more typically from 0.5 to 12 microns, and more typically from 2 to 5 microns.

(Copper foil with carrier)

In this manner, a carrier-attached copper foil having a carrier and an ultra-thin copper layer laminated on the carrier and an intermediate layer laminated on the carrier is produced. The method of using the copper foil with a carrier itself is well known to those skilled in the art. For example, the surface of the ultra-thin copper layer may be coated with paper phenol resin, paper base epoxy resin, synthetic fiber base epoxy resin, A glass fiber nonwoven fabric composite epoxy resin, a glass fiber substrate epoxy resin, a polyester film, a polyimide film or the like, peeling the carrier after thermocompression bonding, and forming a very thin copper layer adhered to the insulating substrate And finally, a printed wiring board can be manufactured.

In the case of the copper foil with a carrier according to the present invention, the peeling point is mainly the interface between the carrier and the intermediate layer or the interface between the intermediate layer and the ultra-thin copper layer. When the intermediate layer is composed of a plurality of layers, peeling may occur at the interface between the layers.

(Resin layer)

The carrier-coated copper foil of the present invention may have a resin layer on the surface treatment layer. The resin layer may be an insulating resin layer.

The order of forming the heat resistant layer, the rust prevention layer, the chromate treatment layer and the silane coupling treatment layer is not limited to each other, and the layers may be formed on the extremely thin copper layer or the roughened layer in any order .

The resin layer may be an adhesive resin, that is, an adhesive, or an insulating resin layer in a semi-cured state (B-stage state) for bonding. The semi-cured state (B-stage state) includes a state in which the insulating resin layer can be stacked and stored without being tacky even when the surface is touched with a finger, and a curing reaction occurs when subjected to heat treatment.

The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton or the like. In addition, the resin layer may be formed, for example, in International Publication Nos. WO2008 / 004399, WO2008 / 053878, WO2009 / 084533, JP- , Japanese Patent Publication No. 3184485, International Publication No. WO97 / 02728, Japanese Patent Publication No. 3676375, Japanese Patent Application Laid-Open No. 2000-43188, Japanese Patent Publication No. 3612594, Japanese Patent Application Laid-Open No. 2002-179772, JP-A-2002-359444, JP-A-2003-304068, JP-A-3992225, JP-A-2003-249739, JP-A-4136509, JP-A- 2004-82687, 4025177, 2004-349654, 4286060, 2005-262506, 4570070, 2005-53218, and 3949676, Japanese Patent Application Laid- , Japanese Patent Publication No. 4178415, International Publication Japanese Patent Application Laid-Open Nos. WO2004 / 005588, JP-A-2006-257153, JP-A-2007-326923, JP-A-2008-111169, JP-A-5024930, WO2006 / 028207, Japanese Patent Application Laid-Open No. 2009-71817, International Publication No. WO2007 / 105635, Japanese Patent Publication No. 5180815, International Patent Publication No. International Publication Nos. WO2008 / 114858, WO2009 / 008471, JP-A-2011-14727, WO009 / 001850, WO2009 / 145179, WO2011 / 068157, JP-A-2013-19056 (A resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, etc.) and / or a method of forming a resin layer and a forming apparatus .

The type of the resin layer is not particularly limited, and examples thereof include epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleic acid resin, (Also referred to as polyether sulfone) resin, an aromatic polyamide resin, an aromatic polyamide resin polymer, a rubber resin, a polyamide resin, a polyamide resin, a polyamide resin, , Aromatic polyamines, polyamideimide resins, rubber modified epoxy resins, phenoxy resins, carboxyl group modified acrylonitrile-butadiene resins, polyphenylene oxides, bismaleimide triazine resins, thermosetting polyphenylene oxide resins, cyanate esters Based resin, anhydride of carboxylic acid, anhydride of polycarboxylic acid Water, a linear polymer having a crosslinkable functional group, a polyphenylene ether resin, 2,2-bis (4-cyanatophenyl) propane, a phosphorus-containing phenol compound, manganese naphthenate, 2,2- Phenylene) propane, polyphenylene ether-cyanate resin, siloxane-modified polyamideimide resin, cyanoester resin, phosphazene resin, rubber modified polyamideimide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, A resin containing at least one member selected from the group consisting of phenoxy, polymer epoxy, aromatic polyamide, fluorine resin, bisphenol, block copolymerized polyimide resin and cyanoester resin is preferably used.

The above-mentioned epoxy resin can be used without particular problems, as long as it has two or more epoxy groups in the molecule and can be used for electric and electronic materials. The epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. In addition, epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD type epoxy resins, novolak type epoxy resins, cresol novolak type epoxy resins, alicyclic epoxy resins, Resin, phenol novolak type epoxy resin, naphthalene type epoxy resin, canceled bisphenol A type epoxy resin, orthocresol novolak type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl Glycidyl amine compounds such as isocyanurate and N, N-diglycidyl aniline, glycidyl ester compounds such as tetrahydrophthalic acid diglycidyl ester, phosphorus-containing epoxy resins, biphenyl type epoxy resins, biphenyl A novolak type epoxy resin, a trishydroxyphenylmethane type epoxy resin, and a tetraphenyl ethane type epoxy resin. It may may be used by mixing two or more kinds, or to use a halogenated material chena hydrogenation of the epoxy resin.

As the phosphorus-containing epoxy resin, a known phosphorus-containing epoxy resin 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 desirable.

The epoxy resin obtained as a derivative from this 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 (HCA-NQ) or (2) (HCA-HQ) by reacting naphthoquinone or hydroquinone in the presence of a phosphorus compound Epoxy resin.

[Chemical Formula 1]

(2)

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

(3)

[Chemical Formula 4]

[Chemical Formula 5]

As the brominated (canceled) epoxy resin, a known brominated (canceled) epoxy resin can be used. For example, the brominated (canceled) epoxy resin is a canceled epoxy resin having a structure represented by the formula (6) obtained as a derivative from tetrabromobisphenol A having two or more epoxy groups in the molecule, It is preferable to use one or two kinds of cancelable epoxy resins each having a structural formula representing the formula

[Chemical Formula 6]

(7)

As the maleimide resin or aromatic maleimide resin or the maleimide compound or the polymaleimide compound, known maleimide resin or aromatic maleimide resin or maleimide compound or polymaleimide compound can be used. Examples of the maleimide resin or aromatic maleimide resin or the maleimide compound or the polymaleimide compound include 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'-diphenyl sulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis Benzene, a polymer prepared by polymerizing the compound and the compound or other compounds, and the like. The maleimide-based resin may be an aromatic maleimide resin having two or more maleimide groups in the molecule, or may be a polymerized adduct obtained by polymerizing an aromatic maleimide resin having two or more maleimide groups in the molecule and a polyamine or aromatic polyamine do.

As the polyamines or aromatic polyamines, known polyamines or aromatic polyamines can be used. For example, as the polyamine or aromatic polyamine, there may be mentioned m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6- , 4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenyl ether, 4,4'-diamino- , 4,4'-diaminodiphenylsulfide, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, bis (4-aminophenyl) phenylamine, m- p-xylylenediamine, 1,3-bis [4-aminophenoxy] benzene, 3-methyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'- Diphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2 ', 5,5'-tetrachloro-4,4'-diaminodiphenylmethane, 2,2- Propane, 2,2-bis (3-methyl-4-aminophenyl) propane, (2,3-dimethyl-4-aminophenyl Bis (4- (4-aminophenoxy) phenyl) propane, and polymers obtained by polymerizing the above compounds and other compounds, or the like can be used. The known polyamines and / or aromatic polyamines or the above-mentioned polyamines or aromatic polyamines may be used alone or in combination.

As the phenoxy resin, a known phenoxy resin can be used. As the phenoxy resin, those synthesized by the reaction of a bisphenol and a divalent epoxy resin can be used. As the epoxy resin, a known epoxy resin and / or the above-mentioned epoxy resin can be used.

The bisphenol can be a known bisphenol and can be bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4'-dihydroxybiphenyl, HCA (9,10-Dihydro- Oxa-10-Phosphaphenanthrene-10-Oxide) and bisphenols obtained as adducts of quinones such as hydroquinone and naphthoquinone.

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 contributing to a curing reaction of an epoxy resin such as a hydroxyl group or a carboxyl group. The linear polymer having a crosslinkable functional group is preferably soluble in an organic solvent having a boiling point of 50 ° C to 200 ° C. Specific examples of the linear polymer having a functional group as referred to herein include a polyvinyl acetal resin, a phenoxy resin, a polyether sulfone resin, and a polyamideimide resin.

The resin layer may contain a crosslinking agent. As the crosslinking agent, known crosslinking agents may be used. As the crosslinking agent, for example, a urethane resin can be used.

As the rubbery resin, a known rubbery resin may be used. 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 acid ester copolymer), polybutadiene rubber, and isoprene rubber. In order to secure the heat resistance of the resin layer to be formed, it is also useful to selectively use heat-resistant synthetic rubbers such as nitrile rubber, chloroprene rubber, silicone rubber and urethane rubber. In order to produce a copolymer by reacting with the aromatic polyamide resin or polyamideimide resin, it is preferable that these rubbery resins are provided with various functional groups at both ends. In particular, it is useful to use CTBN (carboxyl-terminated butadiene nitrile). Among acrylonitrile butadiene rubbers, if it is a carboxyl modified product, it can take a crosslinked structure with an epoxy resin and improve the flexibility of the resin layer after curing. As the carboxyl-modified product, a carboxyl-terminated nitrile-butadiene rubber (CTBN), a carboxyl-terminated butadiene rubber (CTB) and a carboxy-modified nitrile-butadiene rubber (C-NBR) can be used.

As the polyamide-imide resin, a known polyimide-amide resin may be used. As the polyimide amide resin, for example, trimellitic anhydride, benzophenonetetracarboxylic acid anhydride and non-tolylene diisocyanate are mixed with N-methyl-2-pyrrolidone and / or N, N-dimethylacetate Amide or the like, or a resin obtained by heating trimellitic acid anhydride, diphenylmethane diisocyanate and carboxyl-terminated acrylonitrile-butadiene rubber with N-methyl-2-pyrrolidone and / or N, N-dimethylacetamide Or the like can be used.

As the rubber-modified polyamide-imide resin, a known rubber-modified polyamide-imide resin can be used. The rubber-modified polyamide-imide resin is obtained by reacting a polyamide-imide resin with a rubber-based resin. The use of a polyamide-imide resin in reaction with a rubber-like resin is carried out for the purpose of improving the flexibility of the polyamide-imide resin itself. That is, a polyamide-imide resin is reacted with a rubber-like resin to replace part of the acid component (cyclohexanedicarboxylic acid, etc.) of the polyamide-imide resin with a rubber component. For the polyamide-imide resin, a known polyamide-imide resin can be used. As the rubbery resin, known rubbery resins or the aforementioned rubbery resins can be used. Examples of the solvent used for dissolving the polyamide-imide resin and the rubber-like resin in the polymerization of the rubber-modified polyamide-imide resin include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, Methane, nitroethane, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, acetonitrile, gamma -butyrolactone, and the like are preferably used in combination.

As the phosphazene resin, a known phosphazene resin can be used. The phosphazene-based resin is a resin containing phosphazene having a double bond containing phosphorus and nitrogen as constituent elements. The phosphazene resin can dramatically improve the flame retardancy by the synergistic effect of nitrogen and phosphorus in the molecule. Further, unlike the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, it is stably present in the resin, and the effect of preventing the occurrence of migration is obtained.

As the fluororesin, a known fluororesin can be used. As the fluororesin, for example, PTFE (polytetrafluoroethylene (tetrafluoro)), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene / hexafluoropropylene (Tetrafluoroethylene-ethylene copolymer), PVDF (polyvinylidene fluoride (difluoride)), PCTFE (polychlorotrifluoroethylene (trifluoromethyl)), polyallyl sulfone , An aromatic polysulfide, and an aromatic polyether, and a fluororesin comprising a fluororesin may be used.

The resin layer may contain a resin curing agent. As the resin curing agent, known resin curing agents may be used. Examples of the resin curing agent include amines such as dicyandiamide, imidazoles and aromatic amines, phenols such as bisphenol A and brominated bisphenol A, novolacs such as phenol novolac resin and cresol novolac resin, phthalic anhydride Acid anhydrides, biphenyl-type phenol resins, phenol aralkyl type phenol resins, and the like. The resin layer may contain one or more of the above-mentioned resin curing agents. These curing agents are particularly effective for epoxy resins.

Specific examples of the biphenyl-type phenol resin are shown in Formula (8).

[Chemical Formula 8]

Specific examples of the phenol aralkyl type phenol resin are shown in the formula (9).

[Chemical Formula 9]

As the imidazoles, known ones can be used, for example, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, -Phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. These may be used alone or in combination.

Among them, it is preferable to use imidazoles having the following structural formula (10). By using the imidazoles of the structural formula (10), the moisture absorption of the resin layer in the semi-cured state can be remarkably improved, and the long-term storage stability is excellent. The imidazoles perform catalytic action upon curing of the epoxy resin and contribute to the polymerization initiator of the epoxy resin in the initial stage of the curing reaction.

[Chemical formula 10]

As the resin curing agent for the amines, known amines can be used. As the resin curing agent for the amines, there can be used, for example, the above-mentioned polyamines or aromatic polyamines, and also aromatic polyamines and polyamides, and amine adducts obtained by polymerizing or condensing them with epoxy resins or polyvalent carboxylic acids May be used alone or in combination of two or more. Examples of the resin curing agent for the amines include 4,4'-diaminodiphenylene sulfone, 3,3'-diaminodiphenylene sulfone, 4,4-diaminodiphenyl, 2,2-bis [4 - (4-aminophenoxy) phenyl] propane or bis [4- (4-aminophenoxy) phenyl] sulfone.

The resin layer may contain a curing accelerator. As the curing accelerator, known curing accelerators may be used. As the curing accelerator, for example, tertiary amines, imidazoles, urea curing accelerators and the like can be used.

The resin layer may include a reaction catalyst. As the reaction catalyst, a known reaction catalyst may be used. For example, fine particles of silica, antimony trioxide or the like can be used as a reaction catalyst.

The anhydride of the polyvalent carboxylic acid is preferably a component contributing as a curing agent for the epoxy resin. The anhydride of the polyvalent carboxylic acid may be at least one selected from phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydroxyphthalic anhydride, hexahydroxyphthalic anhydride, methylhexahydroxyphthalic anhydride, Methylnadic acid is preferable.

The thermoplastic resin may be a thermoplastic resin having a functional group other than the alcoholic hydroxyl group polymerizable with the 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. In addition, the polyvinyl acetal resin may be obtained by introducing a carboxyl group, an amino group or an unsaturated double bond into the molecule.

Examples of the aromatic polyamide resin polymer include those obtained by reacting an aromatic polyamide resin with a rubbery 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-xylene diamine, 3,3'-oxydianiline and the like are used. As the dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid and the like are used.

The rubbery resin to be reacted with the aromatic polyamide resin may be a known rubbery resin or the aforementioned rubbery resin.

This aromatic polyamide resin polymer is used for the purpose of not subjecting to damage by under etching by an etching liquid when the copper foil after being processed into the copper clad laminate is etched.

The resin layer is formed by sequentially laminating a cured resin layer (the term "cured resin layer" means a cured resin layer) and a cured resin layer in this order from the copper foil side (ie, the ultra-thin copper layer side of the copper foil with a carrier) Or a resin layer formed thereon. The cured resin layer may be composed of a resin component of any of a polyimide resin, a polyamide-imide resin, and a composite resin thereof having a thermal expansion coefficient of 0 ppm / ° C to 25 ppm / ° C.

A semi-cured resin layer having a thermal expansion coefficient of 0 ppm / ° C to 50 ppm / ° C after curing may be formed on the cured resin layer. The thermal expansion coefficient of the entire resin layer after curing of the cured resin layer and the semi-cured resin layer may be 40 ppm / 占 폚 or less. The cured resin layer may have a glass transition temperature of 300 캜 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 includes a maleimide resin, an epoxy resin, and a linear polymer having a crosslinkable functional group. The epoxy resin may be a known epoxy resin or the epoxy resin described in this specification. Examples of the maleimide resin, the aromatic maleimide resin, and the linear polymer having a crosslinkable functional group include known maleimide resins, aromatic maleimide resins, linear polymers having a crosslinkable functional group, or the aforementioned maleimide resins, aromatic A maleimide resin, and a linear polymer having a crosslinkable functional group can be used.

In the case of providing a copper foil with a carrier having a resin layer, which is suitable for use in the production of a molded molded printed circuit board, it is preferable that the cured resin layer is a hardened polymeric polymer layer having flexibility. The polymer polymer layer is preferably made of a resin having a glass transition temperature of 150 DEG C or more so as to withstand the solder packaging step. The polymer polymer layer is preferably composed of a mixed resin of at least one 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 . It is preferable that the thickness of the polymer polymer layer is 3 mu m to 10 mu m.

It is preferable that the polymer polymer layer contains at least one of epoxy resin, maleimide resin, phenol resin and urethane resin. The semi-cured resin layer is preferably composed of an epoxy resin composition having a thickness of 10 mu m to 50 mu m.

It is preferable that the epoxy resin composition contains the following components A to E, respectively.

Component A: an epoxy resin comprising at least one epoxy group selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol AD type epoxy resin having an epoxy equivalent of 200 or less and being liquid at room temperature.

Component B: High heat resistant epoxy resin.

Component C: phosphorus-containing flame retardant resin which is a resin obtained by mixing any one of phosphorus-containing epoxy resin and phosphazene resin or a mixture thereof.

Component D: a rubber-modified polyamide-imide resin modified with a liquid rubber component having properties soluble in a solvent having a boiling point in the range of 50 to 200 ° C.

Component E: Resin curing agent.

The component B is a " high heat resistant epoxy resin " having a so-called glass transition point Tg. The "heat-resistant epoxy resin" referred to herein is preferably a polyfunctional epoxy resin such as novolak type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, and naphthalene type epoxy resin.

As the phosphorus-containing epoxy resin of component C, the above-mentioned phosphorus-containing epoxy resin can be used. As the C-component phosphazene-based resin, the above-mentioned phosphazene-based resin can be used.

As the rubber-modified polyamide-imide resin of component D, the above-mentioned rubber-modified polyamide-imide resin can be used. As the resin curing agent for the component E, the aforementioned resin curing agent can be used.

A solvent is added to the resin composition as described above and used as a resin varnish to form a thermosetting resin layer as an adhesive layer of a printed wiring board. The resin varnish is prepared by adding a solvent to the above-mentioned resin composition to prepare a resin having a solid content of 30 wt% to 70 wt% and measuring the resin as measured according to MIL-P-13949G in MIL specification It is possible to form a semi-cured resin film having a flow in the range of 5% to 35%. For the solvent, a known solvent or the above-mentioned solvent may be used.

Wherein the resin layer is a resin layer having a first thermosetting resin layer sequentially from the copper foil side and a second thermosetting resin layer positioned on the surface of the first thermosetting resin layer, And the second thermosetting resin layer is formed of a resin component which is dissolved in a drug used in the desmear treatment in the process of producing a wiring board and is made of a resin that can be cleaned and removed Or the like. The first thermosetting resin layer may be formed using a resin component in which one or more of polyimide resin, polyethersulfone, and polyphenylene oxide are mixed. The second thermosetting resin layer may be formed using an epoxy resin component. The thickness t1 (占 퐉) of the first thermosetting resin layer is represented by Rz (占 퐉) and the thickness of the second thermosetting resin layer is t2 (占 퐉) It is preferable that the thickness satisfies the condition of < t1 < t2.

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

The skeletal material may comprise aramid fibers or glass fibers or wholly aromatic polyester fibers. The skeleton material is preferably a nonwoven fabric or woven fabric of aramid fiber, glass fiber, or all aromatic polyester fiber. The total aromatic polyester fiber is preferably a wholly aromatic polyester fiber having a melting point of 300 캜 or higher. The above all-aromatic polyester fiber having a melting point of 300 ° C or higher is a fiber produced by using a resin called a liquid crystal polymer. The liquid crystal polymer is a polymer of 2-hydroxyl-6-naphthoic acid and p-hydroxybenzoic acid It is the main component. This whole aromatic polyester fiber has a low dielectric constant and a low dielectric loss tangent, and therefore has excellent performance as a constituent material of the electrically insulating layer and can be used in the same manner as glass fibers and aramid fibers.

The fibers constituting the nonwoven fabric and the woven fabric are preferably subjected to a silane coupling agent treatment in order to improve the wettability of the surface of the nonwoven fabric and the woven fabric with the resin. As the silane coupling agent at this time, there may be used known silane coupling agents such as amino and epoxy coupling agents or silane coupling agents described above depending on the purpose of use.

The prepreg may be a nonwoven fabric using aramid fibers or glass fibers having a nominal thickness of 70 μm or less or a prepreg obtained by impregnating a skeletal material made of a glass cloth having a nominal thickness of 30 μm or less with a thermosetting resin.

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

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

When a dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, it can be used for forming a capacitor layer, thereby increasing the capacitance of the capacitor circuit. The dielectric material (dielectric filler) includes a ferroelectric material such as BaTiO ₃ , SrTiO ₃ , Pb (Zr-Ti) O ₃ (commonly referred to as PZT), PbLaTiO ₃ .PbLaZrO (commonly referred to as PLZT), and SrBi ₂ Ta ₂ O ₉ A dielectric powder of a composite oxide having a kite structure is used.

The dielectric (dielectric filler) may be in powder form. When the dielectric (dielectric filler) is in the form of powder, it is necessary that the particle size of the dielectric (dielectric filler) is firstly in the range of 0.01 탆 to 3.0 탆, preferably 0.02 탆 to 2.0 탆. Since the particle diameters referred to herein form a certain degree of secondary agglomeration among the granules, the precision is inferior in the indirect measurement in which the average particle diameter is estimated from the measurement values such as the laser diffraction scattering type particle size distribution measurement method and the BET method, And refers to an average particle size obtained by directly observing a dielectric (dielectric filler) with a scanning electron microscope (SEM) and analyzing the SEM image. In this specification, the particle size at this time is denoted by DIA. The image analysis of the powder of the dielectric (dielectric filler) observed using a scanning electron microscope (SEM) in the present specification was carried out using IP-1000PC manufactured by Asahi Engineering Co., Ltd., A value of 10 and an overlapping degree of 20, and the average particle diameter DIA was obtained.

According to the above-described embodiment, a carrier having a resin layer including a dielectric for improving the adhesion between the inner layer circuit surface of the inner layer core material and the resin layer including the dielectric and for forming the capacitor circuit layer having low dielectric tangent It is possible to provide an attached copper foil.

The resin and / or the resin composition and / or the compound contained in the resin layer described above may be dissolved in a solvent such as methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, , Ethanol, propylene glycol monomethyl ether, dimethyl formamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, (Resin varnish) by dissolving it in a solvent such as an amide or the like to form a resin solution (resin varnish) on the extremely thin copper layer or the heat resistant layer, the rust prevention layer, or the chromate treatment layer or the silane coupling agent layer, Coater method or the like, and then, if necessary, heated and dried to remove the solvent to obtain a B-stage state. For drying, for example, a hot-air drying furnace may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the resin layer is dissolved by 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% resin solution may be used. Further, it is most preferable to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone from the environmental viewpoint at the present stage. It is preferable to use a solvent having a boiling point in the range of 50 ° C to 200 ° C.

It is preferable that the resin layer is a semi-cured resin film having a resin flow in a range of 5% to 35% when measured according to MIL-P-13949G in the MIL standard.

In the present specification, the resin flow is a method in which four samples of 10 cm in length and 10 cm length are sampled from a resin-coated copper foil having a resin thickness of 55 탆 in accordance with MIL-P-13949G in the MIL standard, At a press temperature of 171 DEG C, a press pressure of 14 kgf / cm < 2 >, and a press time of 10 minutes, and the value calculated based on the formula (1) from the result of measuring the resin outflow weight at that time to be.

The resin-coated copper foil with the resin layer (resin-coated copper foil with a carrier) having the resin layer is superimposed on the base material and then thermally pressed to thermally cure the resin layer. Subsequently, the carrier is peeled, (Of course, the surface to be exposed is the surface of the intermediate layer side of the extremely thin copper layer), and is used as an embodiment of forming a predetermined wiring pattern there.

The use of the copper foil with a carrier to which the resin is adhered can reduce the number of prepreg materials used in manufacturing a multilayer printed wiring board. Furthermore, the thickness of the resin layer can be set to a sufficient thickness to ensure interlayer insulation, or a copper clad laminate can be manufactured without using any prepreg material. At this time, the surface of the substrate may be undercoated with an insulating resin to further improve the smoothness of the surface.

In addition, when the prepreg material is not used, the material cost of the prepreg material is reduced, and the lamination step is simplified, which is economically advantageous. Further, the thickness of the multilayer printed wiring board manufactured by the thickness of the prepreg material is It is possible to produce an ultra-thin multilayer printed circuit board having a thickness of 100 m or less in one layer.

The thickness of the resin layer is preferably 0.1 to 120 탆.

When the thickness of the resin layer is smaller than 0.1 占 퐉, the adhesive force is lowered, and when the copper foil with a carrier on which the resin is adhered is laminated on a base material provided with the inner layer material without interposing the prepreg material, It may be difficult to secure a certain amount of time. On the other hand, if the thickness of the resin layer is made larger than 120 占 퐉, it is difficult to form the resin layer having the desired thickness in one coating step, resulting in economical disadvantage because extra material cost and number of steps are involved.

When the copper foil with a carrier having a resin layer is used for producing an ultra-thin multilayered printed circuit board, the thickness of the resin layer is preferably 0.1 to 5 mu m, more preferably 0.5 to 5 mu m, It is preferable that the thickness is 1 占 퐉 to 5 占 퐉 in order to reduce the thickness of the multilayer printed wiring board.

When the resin layer contains a dielectric, the thickness of the resin layer is preferably 0.1 to 50 탆, more preferably 0.5 to 25 탆, and more preferably 1.0 to 15 탆.

The thickness of the total resin layer with respect to the cured resin layer and the semi-cured resin layer is preferably 0.1 mu m to 120 mu m, more preferably 5 mu m to 120 mu m, more preferably 10 mu m to 120 mu m, And more preferably from 60 to 60 mu m. The thickness of the cured resin layer is preferably 2 to 30 탆, more preferably 3 to 30 탆, and more preferably 5 to 20 탆. The thickness of the semi-cured resin layer is preferably in the range of 3 탆 to 55 탆, more preferably in the range of 7 탆 to 55 탆, and more preferably in the range of 15 탆 to 115 탆. If the thickness of the total resin layer exceeds 120 탆, it may be difficult to produce a multilayer printed wiring board having a thin thickness. If the total resin layer thickness is less than 5 탆, it is easy to form a multilayer printed wiring board having a thin thickness. However, The resin layer which is the insulating layer of the inner layer becomes too thin, and there is a tendency that the insulation between the circuits of the inner layer becomes unstable. If the thickness of the cured resin layer is less than 2 占 퐉, it may be necessary to consider the surface roughness of the copper foil roughened surface. On the other hand, if the thickness of the cured resin layer exceeds 20 占 퐉, the effect of the cured resin layer may not be particularly improved, and the total thickness of the insulating layer becomes thick.

When the thickness of the resin layer is from 0.1 to 5 占 퐉, it is preferable that the heat-resistant layer and / or the anticorrosion layer and / or the chromate treatment layer and / or the antireflection layer are formed on the ultra-thin copper layer in order to improve the adhesion between the resin layer and the copper- It is preferable to form a resin layer on the heat resistant layer or rustproof layer, the chromate treatment layer or the silane coupling treatment layer after the silane coupling treatment layer is formed.

The thickness of the resin layer mentioned above refers to an average value of the thickness measured at any 10 points by cross-sectional observation.

Further, as another product form of the copper foil with a carrier on which the resin is adhered, it is preferable that the resin layer is formed on the extremely thin copper layer or on the heat resistant layer, rustproofing layer or the chromate treatment layer, It is possible to produce the resin in the form of a resin-coated copper foil free from carriers by peeling the carrier after it is semi-cured.

Hereinafter, several examples of the production process of a printed wiring board using the copper foil with a carrier according to the present invention are shown.

In one embodiment of the method for manufacturing a printed wiring board according to the present invention, there is provided a method for manufacturing a printed wiring board, comprising the steps of: preparing a copper foil with a carrier and an insulating substrate according to the present invention; laminating the copper foil with a carrier and an insulating substrate; Is laminated so that the extremely thin copper layer side faces the insulating substrate and then the carrier of the copper foil with a carrier is peeled off to form a copper clad laminate. Thereafter, a semi-additive process, a modified semi-additive process, An additive method, and a subtractive method. It is also possible that the insulating substrate has an inner layer circuit inserted therein.

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 to form a pattern, and then a conductive pattern is formed using electroplating and etching.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the semi-additive method,

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,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of removing all of the extremely thin copper layer exposed by peeling off the carrier by a method such as etching or plasma using a corrosive solution such as an acid,

A step of forming a through hole and / or a blind via in the exposed resin by removing the extremely thin copper layer by etching,

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

A step of forming an electroless plating layer on a region including the resin and the through hole and / or the blind via,

A step of forming a plating resist on the electroless plating layer,

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

A step of forming an electroplating layer in a region where the plating resist is removed,

A step of removing the plating resist,

A step of removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like,

.

In another embodiment of the method for producing a printed wiring board according to the present invention using the semi-additive method,

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,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of removing all of the extremely thin copper layer exposed by peeling off the carrier by a method such as etching or plasma using a corrosive solution such as an acid,

A step of forming an electroless plating layer on the exposed surface of the resin by removing the extremely thin copper layer by etching,

A step of forming a plating resist on the electroless plating layer,

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

A step of forming an electroplating layer in a region where the plating resist is removed,

A step of removing the plating resist,

A step of removing the electroless plating layer and the ultra-thin copper layer in regions other than the region where the circuit is formed by flash etching or the like,

.

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, a copper thickness is formed in the circuit forming portion by electrolytic plating, And a metal foil other than the circuit forming portion is removed by (flash) etching to form a circuit on the insulating layer.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a modified semi-additive method,

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,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of forming a through hole and / or a blind via in the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier,

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

A step of forming an electroless plating layer on a region including the through hole and / or the blind via,

A step of forming a plating resist on the surface of the ultra-thin copper layer exposed by peeling the carrier,

A step of forming a circuit by electrolytic plating after the plating resist is formed,

A step of removing the plating resist,

A step of removing the exposed ultra-thin copper layer by removing the plating resist by flash etching,

.

In another embodiment of the method for producing a printed wiring board according to the present invention using a modified semi-additive method,

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,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of forming a plating resist on the extremely thin copper layer exposed by peeling off the carrier,

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

A step of forming an electroplating layer in a region where the plating resist is removed,

A step of removing the plating resist,

A step of removing the electroless plating layer and the ultra-thin copper layer in regions other than the region where the circuit is formed by flash etching or the like,

.

In the present invention, the palladium additive method is a method in which a catalyst core is provided on a substrate on which conductor layers are formed and, if necessary, punched holes for through-holes or via holes, etched to form conductor circuits, Refers to a method for producing a printed wiring board by forming a solder resist or a plating resist as necessary and then forming a thickness on the conductor circuit by through an electroless plating process on a through hole or a via hole or the like.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the palladium additive method,

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,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of forming a through hole and / or a blind via in the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier,

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

Providing a catalyst nucleus to a region including the through hole and / or the blind via,

A step of forming an etching resist on the surface of the ultra-thin copper layer exposed by peeling the carrier,

A step of exposing the etching resist to a circuit pattern,

Removing the ultra-thin copper layer and the catalyst core by a method such as etching or plasma using a corrosion solution such as an acid to form a circuit;

A step of removing the etching resist,

A step of forming a solder resist or a plating resist on the exposed surface of the insulating substrate by removing the extremely thin copper layer and the catalyst core by a method such as etching or plasma using a corrosive solution such as an acid,

A step of forming an electroless plating layer in a region where the solder resist or the plating resist is not formed,

.

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

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the subtractive method,

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,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of forming a through hole and / or a blind via in the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier,

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

A step of forming an electroless plating layer on a region including the through hole and / or the blind via,

A step of forming an electroplating layer on the surface of the electroless plating layer,

A step of forming an etching resist on the surface of the electrolytic plating layer and / or the ultra-thin copper layer,

A step of exposing the etching resist to a circuit pattern,

Removing the extremely thin copper layer, 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,

A step of removing the etching resist,

.

In another embodiment of the method for producing a printed wiring board according to the present invention using the subtractive method,

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,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of forming a through hole and / or a blind via in the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier,

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

A step of forming an electroless plating layer on a region including the through hole and / or the blind via,

A step of forming a mask on the surface of the electroless plating layer,

A step of forming an electroplating layer on the surface of the electroless plating layer where no mask is formed,

A step of forming an etching resist on the surface of the electrolytic plating layer and / or the ultra-thin copper layer,

A step of exposing the etching resist to a circuit pattern,

Removing the extremely 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,

A step of removing the etching resist,

.

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

Here, specific examples of the method for producing a printed wiring board using the copper foil with a carrier according to the present invention will be described in detail with reference to the drawings. Although the copper foil with a carrier having an ultra-thin copper layer formed with a roughened treatment layer is described here as an example, the present invention is not limited to this, and a copper foil with a carrier having an ultra- A manufacturing method of a wiring board can be carried out.

First, as shown in Fig. 3-A, a copper foil with a carrier (first layer) having an ultra-thin copper layer having a roughened treatment layer formed on its surface is prepared.

Next, as shown in Fig. 3-B, a resist is coated on the roughened layer of the ultra-thin copper layer, exposure and development are performed, and the resist is etched into a predetermined shape.

Next, as shown in Fig. 3-C, circuit plating is formed, and then the resist is removed to form circuit plating of a predetermined shape.

Next, as shown in Fig. 4-D, a resin layer is formed on the extremely thin copper layer so as to cover the circuit plating (so that the circuit plating is buried) to laminate the resin layer, Is bonded from the ultra-thin copper layer side.

Next, as shown in Fig. 4-E, the carrier is peeled from the second-layered copper foil with a carrier.

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

Next, as shown in FIG. 5-G, copper is buried 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 in Fig. 5-I, the carrier is peeled from the first-layer copper foil with a carrier.

Next, as shown in Fig. 6-J, the extremely thin copper layer on both surfaces is removed by flash etching to expose the surface of the circuit plating in the resin layer.

Next, as shown in Fig. 6-K, a bump is formed on the circuit plating in the resin layer by solder or the like, and a copper filler is formed on the bump. Thus, a printed wiring board using the copper foil with a carrier of the present invention is produced.

The copper foil with a carrier of the present invention may be used for the other copper foil with a carrier (second layer), or a conventional copper foil with a carrier may be used, or a conventional copper foil may be used. In addition, one or more layers may be further formed on the second layer circuit shown in Fig. 5-H, and the circuit formation may be performed by a semi-additive method, a subtractive method, a pattern additive method, And a semi-additive method.

The carrier-coated copper foil used for the first layer may have a substrate on the carrier-side surface of the carrier-coated copper foil. By having such a substrate or a resin layer, the copper foil with a carrier used in the first layer is supported, and wrinkles are hard to enter, so that productivity is improved. In addition, all the substrates can be used as long as they have the effect of supporting the copper foil with a carrier used for the first layer. For example, the substrate may be a carrier, a prepreg, a resin layer or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a foil of an inorganic compound, You can use pak.

The timing for forming the substrate on the carrier-side surface is not particularly limited, but it is necessary to form the carrier before peeling off. Particularly, it is preferable to form it before the step of forming the resin layer on the surface of the ultra-thin copper layer side of the carrier-coated copper foil, and it is more preferable to form it before the step of forming the circuit on the ultra-thin copper layer side surface of the carrier-

In the copper foil with a carrier according to the present invention, it is preferable that the color difference of the surface of the ultra-thin copper layer be controlled so as to satisfy the following (1). In the present invention, the term " color difference on the surface of the ultra-thin copper layer " refers to the color difference on the surface of the ultra-thin copper layer or the color difference of the surface treatment layer surface when various surface treatments such as roughening treatment are performed. That is, in the copper foil with a carrier according to the present invention, it is preferable that the color difference of the surface of the extremely thin copper layer, the roughened layer, the heat resistant layer, the rustproof layer, the chromate treated layer or the silane coupling layer is controlled to satisfy the following (1) .

(1) The color difference? E * ab based on JIS Z8730 on the surface of the ultra-thin copper layer, the roughened layer, the heat resistant layer, the rust-preventive layer, the chromate treatment layer or the silane coupling treatment layer is 45 or more.

Here, the color differences DELTA L, DELTA a and DELTA b are aggregate indices measured by the colorimeter and represented by using the L * a * b colorimetric system based on JIS Z8730 in consideration of black / white / red / green / ? L: black and white,? A: red color, and? B: white color. Further,? E * ab is expressed by the following equation (2) using these color differences.

The above-described color difference can be adjusted by increasing the current density at the time of formation of the ultra-thin copper layer, lowering the copper concentration in the plating liquid, and increasing the line flow rate of the plating liquid.

The above-described color difference may be adjusted by forming a roughened treatment layer on the surface of the ultra-thin copper layer. In the case of forming the roughened layer, it is preferable to use an electric field solution containing copper and at least one element selected from the group consisting of nickel, cobalt, tungsten, and molybdenum to increase the current density (for example, 40 to 60 A / dm < 2 >) and the treatment time is shortened (for example, 0.1 to 1.3 seconds). When the roughening treatment layer is not formed on the surface of the ultra-thin copper layer, a plating bath in which the concentration of Ni is set to twice or more of the other elements is used to form an ultra-thin copper layer or heat resistant layer or rust- (For example, Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating) on the surface of the ring treatment layer at a lower current density (0.1 to 1.3 A / (20 seconds to 40 seconds) for a long period of time.

When the color difference? E * ab based on JIS Z8730 on the surface of the ultra-thin copper layer is 45 or more, for example, when a circuit is formed on the surface of the ultra-thin copper layer of the copper foil with a carrier, the contrast of the circuit with the ultra-thin copper layer becomes clear, , Visibility is improved, and alignment of the circuit can be performed with good precision. The color difference? E * ab based on JIS Z8730 on the surface of the ultra-thin copper layer is preferably 50 or more, more preferably 55 or more, still more preferably 60 or more.

When the color difference of the surface of the ultra-thin copper layer, the roughened layer, the heat resistant layer, the rust-preventive layer, the chromate treatment layer or the silane coupling layer is controlled as described above, the contrast with the circuit plating becomes clear and the visibility becomes good. Therefore, for example, in the case of the above-described printed wiring board, it is possible to form the circuit plating at a predetermined position with good precision in the manufacturing process as shown in Fig. 3-C. According to the above-described method of manufacturing a printed wiring board, since the circuit plating is embedded in the resin layer, when the ultra-thin copper layer is removed by flash etching as shown in, for example, , The circuit plating is protected by the resin layer and the shape thereof is maintained, thereby facilitating formation of a fine circuit. Further, since the circuit plating is protected by the resin layer, migration resistance is improved and conduction of the circuit wiring is well suppressed. Therefore, formation of a fine circuit is facilitated. As shown in Figs. 6-J and 6-K, when the ultra-thin copper layer is removed by flash etching, the exposed surface of the circuit plating becomes depressed from the resin layer, The copper filler is easily formed thereon, and the production efficiency is improved.

Known resins and prepregs can be used for the buried resin (resin). For example, glass poison prepreg impregnated with BT (bismaleimide triazine) resin or BT resin, ABF film manufactured by Ajinomoto Fine Techno Co., Ltd. or ABF can be used. The resin layer and / or the resin and / or the prepreg described in this specification can be used for the above-mentioned embedding resin (resin).

Example

Next, examples (and comparative examples) will be described. It should be noted that the present invention is not limited to the following examples and that the technical idea of the present invention should be grasped from the entirety described in the present specification It will be easy to understand.

As the carrier, a long electrolytic copper foil having a thickness of 35 mu m (JTC manufactured by JX Nikkisseski Metal Co., Ltd.) was prepared. The shiny side of the copper foil was electroplated with a roll-to-roll type continuous plating line under the following conditions to form a Ni layer having an adhesion amount of 4000 탆 / dm 2.

Ni layer

Nickel sulfate: 250 to 300 g / l

Nickel chloride: 35 to 45 g / l

Nickel acetate: 10 to 20 g / l

Sodium citrate: 15-30 g / l

Polishing agents: saccharin, butynediol, etc.

Decyl sodium sulfate: 30 to 100 ppm

pH: 4 to 6

Bath temperature: 50 to 70 ° C

Current density: 3 ~ 15 A / dm2

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 to 10 g / l, zinc 0 to 5 g / l

pH: 3-4

Liquid temperature: 50 ~ 60 ℃

Current density: 0.1 to 2.6 A / dm 2

Culm amount: 0.5 to 30 As / dm 2

Subsequently, on the roll-to-roll type continuous plating line, an extremely thin copper layer having a thickness of 2 to 10 탆 was formed on the Cr layer by electroplating under the following conditions to prepare a copper foil with a carrier.

· Ultra-thin copper layer

Copper concentration: 30 ~ 120 g / ℓ

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

Electrolyte temperature: 20 ~ 80 ℃

Current density: 10 to 100 A / dm 2

For the examples (and comparative examples), the electrolytic copper foil of 35 mu m was used as the carrier. However, the thickness and type of the copper foil are not limited to the thicknesses of the known copper foil and the copper alloy foil, Applicable. In addition, the known copper foil and the copper alloy foil may be an electrolytic copper foil or a rolled copper foil.

(Example 1 - Common to Examples 5, 8, 9 and 12)

The surface of the extremely thin copper layer of the copper foil with a carrier described above was subjected to a roughening treatment under the following conditions.

(A) Primary particle layer formation of Cu

Liquid composition: Cu 15 g / liter, sulfuric acid 75 g / liter

pH: 1-3

Temperature: 35 ℃

Current density (D _k ): 40 to 60 A / dm 2

Time: 0.05 to 3 seconds

(B) Formation of a secondary particle layer made of a ternary alloy made of Cu, Co, and Ni

Liquid composition: Cu 15 g / liter, Co 8 g / liter, Ni 8 g / liter

pH: 1-3

Temperature: 40 ° C

Current density (D _k ): 20 to 40 A / dm 2

Time: 0.05 to 3 seconds

A secondary particle layer composed of a primary particle layer of Cu having an average particle size of 0.25 to 0.45 占 퐉 and a tertiary alloy layer made of Cu, Co and Ni having an average particle diameter of 0.05 to 0.25 占 퐉 formed thereon was formed in the above roughening treatment.

The coarsely grained particles of the surface-treated copper foil were observed at a magnification of 30000 times that of an electron microscope (SEM (scanning electron microscope)) to evaluate the coarsened particle size (particle size). Further, in the present invention, when a straight line is drawn on a particle of a scanning electron microscopic photograph, the length of the longest straight line across the particle is defined as the particle diameter of the particle. Then, the arithmetic average of the particle diameters of the respective particles measured in the observation field was calculated, and the value of the arithmetic average was taken as the average particle diameter.

The adhesion amount of Ni in the harmony treatment step was 50 to 250 占 퐂 / dm2. The results are shown in Table 1 below.

(Conditions of Example 1)

The heat-resistant layer made of the Ni-Co layer, the inner layer and the rust-preventive layer containing Zn, Ni, and Cr, and the silane coupling treatment were performed under the above-described conditions. The conditions for forming the heat-resistant layer, the inner layer and the rust-preventive layer are shown below. The thickness of the extremely thin copper layer was set to 2 탆.

1) Heat-resistant layer (Ni-Co layer)

Liquid composition: Co 1 to 8 g / liter, Ni 10 to 20 g / liter

pH: 2-3

Temperature: 40 ~ 60 ℃

Current density (D _k ): 8 to 10 A / dm 2

Time: 0.05 to 3.0 seconds

2) inner layer (Zn-Ni layer)

Solution composition: Ni 15-30 g / liter, Zn 1-10 g / liter

pH: 2 to 4

Temperature: 30 ~ 50 ℃

Current density (D _k ): 0.5 to 1.5 A / dm 2

Time: 0.05 to 3.0 seconds

3) Anti-rusting layer (Cr-Zn layer)

Liquid composition: K ₂ Cr ₂ O ₇ : 1 to 10 g / liter, Zn: 0 to 5 g / liter

pH: 2 to 4

Temperature: 40 ~ 50 ℃

Current density (D _k ): 1 to 3 A / dm 2

Time: 0.05 to 3.0 seconds

The plating treatment was carried out so that the total amount of Ni adhered (total Ni amount) in the coarsened layer, the heat resistant layer, the inner layer and the anti-rust layer was 1093 쨉 g / dm 2. (Total amount of Ni + total amount of Zn) = 0.13 from the amount of Zn deposited (total amount of Zn) in all of the coarsened layer, heat resistant layer, inner layer and rustproof layer.

The total Co amount / (total Ni amount + total Zn amount) = 1.6 was found from the Co deposition amount (total Co amount) in the coarsened layer, the heat resistant layer, the inner layer and the anti-

As described above, when two or more layers of the coarsened layer, the heat resistant layer, the inner layer and the rust preventive layer are laminated, the amounts of Ni deposition, Zn deposition, Co deposition and Cr deposition indicate the total amount of deposition of each element.

With respect to Tables 1 and 2, corresponding points of the examples and comparative examples were described as necessary.

Polyamic acid (U varnish A manufactured by Ube Industries, Ltd.) was applied to the surface-treated copper foil manufactured as described above, dried at 100 占 폚 and cured at 315 占 폚 to form a copper clad laminate made of a polyimide resin substrate.

Next, the copper clad laminate was formed into a fine pattern circuit by a general copper chloride-hydrochloric acid etching solution. The fine patterned circuit board was immersed in an aqueous solution containing 10 wt% of sulfuric acid and 2 wt% of 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 swelling.

As a result of the impregnation evaluation, the impregnation width was 3 3 탆, which was good (O).

The ultra thin copper layer side of the carrier-coated copper foil is laminated and bonded to the glass cloth base epoxy resin plate, and then the ultra thin copper layer is peeled off from the carrier and then the state (normal state) (room temperature) After measuring the peel strength (kg / cm), the deterioration resistance of hydrochloric acid was measured by peeling strength after immersing in 18% hydrochloric acid aqueous solution for 1 hour by a 0.2 mm wide circuit.

The state peel strength was 0.99 kg / cm and the hydrochloric acid deterioration resistance was 8 (Loss%) or less (O).

In order to investigate an alkaline etching, after preparing the sample covering the roughened surface of the surface-treated copper foil to the plastic tape, NH ₄ OH: 6 moles / liter, NH ₄ Cl: 5 moles / liter, CuCl ₂ · 2H ₂ O: 2 moles / liter, and a temperature of 50 deg. C for 7 minutes, and then the remaining condition of the coarse particles on the vinyl tape was confirmed.

As a result of the evaluation of the alkali etching, the remaining of the coarsened particles was not observed, and the alkali etching property was also good (O).

Table 1 shows the above results. In addition, the amount of Cr deposited (total Cr amount) is 89 ㎍ / dm 2 as a whole, the amount of deposited Co (total amount of Co) is 2010 ㎍ / d㎡ as a whole and the amount of Zn deposited (total amount of Zn) is 163 ㎍ / Respectively.

The measurement of each metal deposition amount (Ni deposition amount in the harmonization treatment step, total Ni amount, total amount of Co, total amount of Zn, total amount of Cr) is carried out by dissolving the surface-treated surface of the surface-treated copper foil in an acid solution, It was evaluated by atomic absorption analysis (manufactured by VARIAN, AA240FS). The amount of Ni adhered to the roughening treatment step was obtained by preparing a copper foil with a carrier under the same conditions as in each of the examples and comparative examples, forming only a roughened treatment layer, collecting a sample, .

(Example 2)

The Ni deposition amount in the harmonic phase was 50 to 250 占 퐂 / dm 2 as described above. The heat-resistant layer made of the Ni-Co layer, the inner layer and the rust-preventive layer containing Zn, Ni, and Cr, and the silane coupling treatment were performed under the above-described conditions. The conditions for forming the heat-resistant layer, the inner layer and the rust-preventive layer are shown below. The thickness of the ultra-thin copper layer was set to 10 탆.

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) inner layer (Zn-Ni layer)

Current density (D _k ): 0.05 to 0.7 A / dm 2

Time: 0.05 to 3.0 seconds

3) Anti-rusting layer (Cr-Zn layer)

Current density (D _k ): 1 to 3 A / dm 2

Time: 0.05 to 3.0 seconds

The amount of Ni adhering to all of the coarsened layer, the heat resistant layer, the inner layer and the rust preventive layer was 451 쨉 g / dm 2 as a whole (total amount of Ni) The total amount of Zn / (total amount of Ni + total amount of Zn) = 0.18 from the amount of Zn adhered (total amount of Zn). From the amount of Co deposited (total amount of Co) in all of the coarsened layer, heat resistant layer, The total amount of Co / (total Ni amount + total Zn amount) = 2.7.

As a result of the impregnation evaluation, the impregnation width was good (?) Of? 3 占 퐉.

As a result of the adhesion strength evaluation, the state fill strength was 1.00 kg / cm and the hydrochloric acid degradation resistance was 11 (Loss%) and was good (O). Residual particles were not observed in the evaluation of the alkali etching, and were good (O).

Table 1 shows the above results. In addition, the amount of Cr adhered was 84 μg / dm 2 as a whole (amount of Cr), the Co adhered amount (total amount of Co) was 1487 μg / dm 2 as a whole, and the Zn adhered amount (total amount of Zn) was 100 μg / Respectively.

(Example 3)

The Ni deposition amount in the harmonic phase was 50 to 250 占 퐂 / dm 2 as described above. The heat-resistant layer made of the Ni-Co layer, the inner layer and the rust-preventive layer containing Zn, Ni, and Cr, and the silane coupling treatment were performed under the above-described conditions. The conditions for forming the heat-resistant layer, the inner layer and the rust-preventive layer are shown below. The thickness of the extremely thin copper layer was set to 5 탆.

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) inner layer (Zn-Ni layer)

Current density (D _k ): 0.05 to 0.7 A / dm 2

Time: 0.05 to 3.0 seconds

3) Anti-rusting layer (Cr-Zn layer)

Current density (D _k ): 2 to 4 A / dm 2

Time: 0.05 to 3.0 seconds

The amount of Ni adhering to all of the roughened layer, heat-resistant layer, inner layer and rust-preventive layer was 680 占 퐂 / dm2 as a whole (total amount of Ni) The total amount of Zn / (total amount of Ni + total amount of Zn) = 0.19 from the amount of Zn deposited (total amount of Zn), and the amount of Co deposition (total amount of Co) in all of the coarsened layer, heat resistant layer, The total amount of Co / (total Ni amount + total Zn amount) = 2.1. As a result of the impregnation evaluation, the impregnation width was good: ≤ 3 μm.

As a result of the adhesion strength evaluation, the state peel strength was 0.99 kg / cm, and the hydrochloric acid deterioration resistance was 25 (Loss%). Alkali etchability was also good (O) without observing remaining particles.

Table 1 shows the above results. In addition, the Cr adhered amount was 89 ㎍ / dm 2 as a whole (total Cr amount), the Co adherence amount was 1763 ㎍ / dm 2 as a whole (total amount of Co), and the Zn adhered amount (total Zn amount) was 157 ㎍ / Respectively.

(Example 4)

The Ni deposition amount in the harmonic phase was 50 to 250 占 퐂 / dm 2 as described above. The heat-resistant layer made of the Ni-Co layer, the inner layer and the rust-preventive layer containing Zn, Ni, and Cr, and the silane coupling treatment were performed under the above-described conditions. The conditions for forming the heat-resistant layer, the inner layer and the rust-preventive layer are shown below. The thickness of the ultra-thin copper layer was set to 3 탆.

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) inner layer (Zn-Ni layer)

Current density (D _k ): 1 to 3 A / dm 2

Time: 0.05 to 3.0 seconds

3) Anti-rusting layer (Cr-Zn layer)

Current density (D _k ): 0.05 to 1.0 A / dm 2

Time: 0.05 to 3.0 seconds

(Total amount of Ni) in all of the roughened layer, heat-resistant layer, inner layer and rust-preventive layer was 759 쨉 g / dm 2 as a whole, and the amount of Ni adhering to the roughening layer, heat- The total amount of Zn / (total amount of Ni + total amount of Zn) = 0.23 from the amount of Zn deposited (total amount of Zn). From the amount of Co deposition (total amount of Co) in all of the coarsened layer, heat resistant layer, The total amount of Co / (total Ni amount + total Zn amount) = 1.8. As a result of the impregnation evaluation, the impregnation width was very good, 0 탆.

As a result of the adhesion strength evaluation, the state peel strength was 0.99 kg / cm and the hydrochloric acid deterioration resistance was 22 (Loss%). Alkali etching property was also good (O).

Table 1 shows the above results. In addition, the amount of Cr deposited was 90 ㎍ / dm 2 as a whole (amount of Cr), the amount of deposited Co (total amount of Co) was 1774 / / dm 2 as a whole, and the amount of Zn deposited (total amount of Zn) was 223 ㎍ / Respectively.

(Example 5)

The Ni deposition amount in the harmonic phase was 50 to 250 占 퐂 / dm 2 as described above. The heat-resistant layer made of the Ni-Co layer, the inner layer and the rust-preventive layer containing Zn, Ni, and Cr, and the silane coupling treatment were performed under the above-described conditions. The conditions for forming the heat-resistant layer, the inner layer and the rust-preventive layer are shown below. The thickness of the ultra-thin copper layer was set to 7 탆.

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) inner layer (Zn-Ni layer)

Current density (D _k ): 0.6 to 1.5 A / dm 2

Time: 0.05 to 3.0 seconds

3) Anti-rusting layer (Cr-Zn layer)

Current density (D _k ): 1.0 to 3.0 A / dm 2

Time: 0.05 to 3.0 seconds

(Total amount of Ni) in all of the roughened layer, heat-resistant layer, inner layer and rust-preventive layer was 816 쨉 g / dm 2 as a whole, and the amount of Ni adhering to the roughened layer, heat- The total amount of Zn / (total amount of Ni + total amount of Zn) = 0.22 from the amount of Zn deposited (total amount of Zn). From the amount of Co deposition (total amount of Co) in all of the coarsened layer, heat resistant layer, The total amount of Co / (total Ni amount + total Zn amount) = 1.8. As a result of the impregnation evaluation, the impregnation width was very good, 0 탆.

As a result of the adhesion strength evaluation, the state fill strength was 0.99 kg / cm and the hydrochloric acid degradation resistance was 12 (Loss%). Alkali etching property was also good (O).

Table 1 shows the above results. In addition, the amount of Cr adhered was 115 μg / dm 2 as a whole (amount of Cr), Co deposition amount was 1857 μg / dm 2 as a whole (total amount of Co) and Zn deposition amount (total amount of Zn) was 235 μg / Respectively.

(Example 6)

The copper foil with a carrier described above was subjected to a roughening treatment under the following conditions. The thickness of the ultra-thin copper layer was set to 3 탆.

Liquid composition: Cu 10 to 20 g / liter, Co 5 to 10 g / liter, Ni 5 to 15 g / liter

pH: 2 to 4

Temperature: 30 ~ 50 ℃

Current density (D _k ): 20 to 60 A / dm 2

Time: 0.5 to 5 seconds

By coarsening treatment under the above-mentioned conditions, fine aggregation particles of a ternary alloy consisting of Cu, Co and Ni having an average particle size of 0.10 to 0.60 mu m were formed. The coarsely grained particles of the surface-treated copper foil were observed at a magnification of 30000 times that of the electron microscope (SEM), and the coarsened particle size was evaluated.

The Ni deposition amount in the harmonic phase was 200 to 400 / / dm 2.

The heat-resistant layer made of the Ni-Co layer, the inner layer and the rust-preventive layer containing Zn, Ni, and Cr, and the silane coupling treatment were performed under the above-described conditions. The conditions for forming the heat-resistant layer, the inner layer and the rust-preventive 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) inner layer (Zn-Ni layer)

Current density (D _k ): 2.0 to 4.0 A / dm 2

Time: 0.05 to 3.0 seconds

3) Anti-rusting layer (Cr-Zn layer)

Current density (D _k ): 0 A / dm 2

Time: 0.05 to 3 seconds (immersion chromate treatment)

The amount of Ni adhering to all of the roughened layer, heat-resistant layer, inner layer and rust-preventive layer was 1091 쨉 g / dm 2 as a whole (total amount of Ni) The total amount of Zn / (total amount of Ni + total amount of Zn) = 0.18 from the amount of Zn adhered (total amount of Zn). From the amount of Co deposited (total amount of Co) in all of the coarsened layer, heat resistant layer, The total amount of Co / (total Ni amount + total Zn amount) = 1.9. As a result of the impregnation evaluation, the impregnation width was very good, 0 탆.

As a result of the adhesion strength evaluation, the state peel strength was 0.97 kg / cm and the hydrochloric acid thermal decomposition resistance:? 10 (Loss%) or less. Alkali etching property was also good (O).

Table 1 shows the above results. In addition, Cr deposition amount is 110 ㎍ / dm 2 as a whole (total amount of Cr), Co deposition amount is 2475 ㎍ / dm 2 as a whole (total amount of Co), Zn deposition amount is 240 ㎍ / Respectively.

(Example 7)

The above-mentioned copper foil with a carrier was subjected to a roughening treatment under the following conditions. The thickness of the ultra-thin copper layer was set to 3 탆.

Liquid composition: Cu 10 to 20 g / liter, Co 5 to 10 g / liter, Ni 8 to 20 g / liter

pH: 2 to 4

Temperature: 30 ~ 50 ℃

Current density (D _k ): 20 to 60 A / dm 2

Time: 0.5 to 5 seconds

By coarsening treatment under the above-mentioned conditions, an aggregate of fine roughening particles of a ternary alloy consisting of Cu, Co and Ni having an average particle diameter of 0.05 to 0.35 mu m was formed. The coarsely grained particles of the surface-treated copper foil were observed at a magnification of 30000 times that of the electron microscope (SEM), and the coarsened particle size was evaluated.

The Ni deposition amount in the harmonic phase was 300 ~ 550 ㎍ / dm2.

The heat-resistant layer made of the Ni-Co layer, the inner layer and the rust-preventive layer containing Zn, Ni, and Cr, and the silane coupling treatment were performed under the above-described conditions. The conditions for forming the heat-resistant layer, the inner layer and the rust-preventive 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) inner layer (Zn-Ni layer)

Current density (D _k ): 1.5 to 3.5 A / dm 2

Time: 0.05 to 3.0 seconds

3) Anti-rusting layer (Cr-Zn layer)

Current density (D _k ): 0 A / dm 2

Time: 0.05 to 3 seconds (immersion chromate treatment)

(Total amount of Ni) in all of the roughened layer, heat-resistant layer, inner layer and rust-preventive layer was 789 쨉 g / dm 2 as a whole, and the amount of Ni adhering to the roughened layer, heat- The total amount of Zn / (total amount of Ni + total amount of Zn) = 0.22 from the amount of Zn deposited (total amount of Zn). From the amount of Co deposition (total amount of Co) in all of the coarsened layer, heat resistant layer, The total amount of Co / (total Ni amount + total Zn amount) = 2.2. As a result of the impregnation evaluation, the impregnation width was very good, 0 탆.

As a result of the adhesion strength evaluation, the state fill strength was 0.94 kg / cm and the hydrochloric acid thermal decomposition resistance:? 10 (Loss%) or less. Alkali etching property was also good (O).

Table 1 shows the above results. In addition, the amount of Cr adhered was 55 μg / dm 2 as a whole (amount of Cr), the amount of Co adhered was 2167 μg / dm 2 as a whole (total amount of Co), the amount of Zn adhered was 217 μg / Respectively.

(Example 8)

In the same roughening treatment as in Example 1, a primary particle layer of Cu having an average particle size of 0.25 to 0.45 占 퐉 and a secondary particle layer made of a ternary alloy made of Cu, Co and Ni having an average particle diameter of 0.05 to 0.25 占 퐉 formed thereon .

The coarsely grained particles of the surface-treated copper foil were observed at a magnification of 30000 times that of the electron microscope (SEM), and the coarsened particle size was evaluated.

The adhesion amount of Ni in the harmony treatment step was 50 to 250 占 퐂 / dm2.

The conditions for forming the heat-resistant layer, the inner layer and the rust-preventive layer are shown below. The thickness of the ultra-thin copper layer was set to 3 탆.

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) inner layer (Zn-Ni layer)

Current density (D _k ): 0 to 1.0 A / dm 2

Time: 0 to 2.0 seconds

3) Anti-rusting layer (Cr-Zn layer)

Current density (D _k ): 1 to 3 A / dm 2

Time: 0.05 to 3.0 seconds

The coating amount of Ni in all of the roughened layer, heat-resistant layer, inner layer and rust-preventive layer was plated to be 741 쨉 g / dm 2 as a whole (total amount of Ni). (Total amount of Ni + total amount of Zn) = 0.02 from the amount of Zn deposited (total amount of Zn) in all of the coarsened layer, heat resistant layer, inner layer and anti-rust layer.

The total Co amount / (total Ni amount + total Zn amount) = 1.9 from the Co deposition amount (total Co amount) in the coarsened layer, the heat resistant layer, the inner layer and the anti-

For the following Examples 8, 9, and 21 to 26, the surface-treated copper foil was laminated on the following resin, and the penetration evaluation was evaluated by the above-mentioned impregnation evaluation method.

GHPL-830NX (Type A, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was laminated on the surface-treated copper foil at 220 占 폚 for 2 hours under a hot press condition to form a copper clad laminate.

Next, the copper clad laminate was formed into a fine pattern circuit by a general copper chloride-hydrochloric acid etching solution. The fine patterned circuit board was immersed in an aqueous solution containing 10 wt% of sulfuric acid and 2 wt% of 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 swelling. As a result of the impregnation evaluation, the impregnation width was very good, 0 탆.

As a result of the adhesion strength evaluation, the state peel strength was 0.99 kg / cm and the hydrochloric acid thermal decomposition resistance was 5 (Loss%). Alkali etching property was also good (O).

Table 1 shows the above results. In addition, the amount of Cr deposited is 90 ㎍ / dm 2 as a whole (total amount of Cr), the amount of deposited Co is 1437 ㎍ / dm 2 as a whole (total amount of Co), and the amount of Zn deposited (total amount of Zn) Respectively.

(Example 9)

In the same roughening treatment as in Example 1, a primary particle layer of Cu having an average particle size of 0.25 to 0.45 占 퐉 and a secondary particle layer made of a ternary alloy made of Cu, Co and Ni having an average particle diameter of 0.05 to 0.25 占 퐉 formed thereon .

The coarsely grained particles of the surface-treated copper foil were observed at a magnification of 30000 times that of the electron microscope (SEM), and the coarsened particle size was evaluated.

The adhesion amount of Ni in the harmony treatment step was 50 to 250 占 퐂 / dm2.

The conditions for forming the heat-resistant layer, the inner layer and the rust-preventive layer are shown below. The thickness of the ultra-thin copper layer was set to 3 탆.

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) inner layer (Zn-Ni layer)

Current density (D _k ): 0.5 to 1.0 A / dm 2

Time: 0 to 2.0 seconds

3) Anti-rusting layer (Cr-Zn layer)

Current density (D _k ): 1 to 3 A / dm 2

Time: 0.05 to 3.0 seconds

The coating amount of Ni in all of the coarsened layer, the heat resistant layer, the inner layer and the anti-rust layer was plated so as to be 771 쨉 g / dm 2 as a whole (total amount of Ni). (Total amount of Ni + total amount of Zn) = 0.06 from the amount of Zn adhered (total amount of Zn) in all of the roughened layer, heat-resistant layer, inner layer and rust-preventive layer.

(Total amount of Co) / (total amount of Ni) + total amount of Zn) = 1.8 from the amount of Co deposition (total amount of Co) in all of the coarsened layer, heat resistant layer,

As a result of the impregnation evaluation as in Example 8, it was found that the impregnation width was as good as 0 占 퐉. As a result of the adhesion strength evaluation, the state peel strength was 1.01 kg / cm, and the hydrochloric acid thermal decomposition resistance was 6 (Loss%). Alkali etching property was also good (O).

Table 1 shows the above results. In addition, the amount of Cr deposited is 90 ㎍ / dm 2 as a whole (total amount of Cr), the Co deposition amount is 1476 ㎍ / dm 2 as a whole (total amount of Co), and the amount of Zn deposited (total amount of Zn) is 49 ㎍ / Respectively.

(Example 10)

A roughened treatment layer was formed on the above-described copper foil with a carrier under the same conditions as in Example 6. [ By coarsening treatment under the above-mentioned conditions, fine aggregation particles of a ternary alloy consisting of Cu, Co and Ni having an average particle size of 0.10 to 0.60 mu m were formed.

The Ni deposition amount in the harmonic phase was 200 to 400 / / dm 2.

The heat-resistant layer made of the Ni-Co layer, the inner layer and the rust-preventive layer containing Zn, Ni, and Cr, and the silane coupling treatment were performed under the above-described conditions. The conditions for forming the heat-resistant layer, the inner layer and the rust-preventive layer are shown below. The thickness of the ultra-thin copper layer was set to 3 탆.

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 ℃

Current density (D _k ): 6 to 8 A / dm 2

Time: 0.05 to 3.0 seconds

2) inner layer (Zn-Ni layer)

Current density (D _k ): 1.0 to 3.0 A / dm 2

Time: 0.05 to 3.0 seconds

3) Anti-rusting layer (Cr-Zn layer)

Current density (D _k ): 0 A / dm 2

Time: 0.05 to 3 seconds (immersion chromate treatment)

The amount of Ni adhering to all of the roughened layer, heat-resistant layer, inner layer and rust-preventive layer was 815 占 퐂 / dm2 as a whole (total amount of Ni), and the amount of Ni adhering to both the roughened layer, The total amount of Zn / (total amount of Ni + total amount of Zn) = 0.13 from the amount of Zn adhered (total amount of Zn). From the amount of Co adhered (total amount of Co) in all of the coarsened layer, heat resistant layer, The total amount of Co / (total Ni amount + total Zn amount) = 3.2. As a result of the impregnation evaluation, the impregnation width was as good as? 5 占 퐉.

As a result of the adhesion strength evaluation, the state peel strength was 0.99 kg / cm and the hydrochloric acid thermal decomposition resistance was 8 (Loss%). Alkali etchability was good (O). Table 1 shows the above results. In addition, the amount of Cr adhered was 90 μg / dm 2 as a whole (amount of Cr), the amount of deposited Co was 2978 μg / dm 2 as a whole (total amount of Co), and the amount of Zn adhered was 117 μg / Respectively.

(Example 11)

In the same roughening treatment as in Example 1, a primary particle layer of Cu having an average particle size of 0.2 to 0.45 占 퐉 and a secondary particle layer made of a ternary alloy made of Cu, Co and Ni having an average particle diameter of 0.05 to 0.25 占 퐉 formed thereon .

The coarsely grained particles of the surface-treated copper foil were observed at a magnification of 30000 times that of the electron microscope (SEM), and the coarsened particle size was evaluated.

The Ni deposition amount in the harmonic treatment step was 300 to 550 占 퐂 / dm2.

The conditions for forming the heat-resistant layer, the inner layer and the rust-preventive layer are shown below. The thickness of the ultra-thin copper layer was set to 3 탆.

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) inner layer (Zn-Ni layer)

Current density (D _k ): 0.5 to 1.0 A / dm 2

Time: 0 to 2.0 seconds

3) Anti-rusting layer (Cr-Zn layer)

Current density (D _k ): 1 to 3 A / dm 2

Time: 0.05 to 3.0 seconds

The plating amount was 1590 占 퐂 / dm2 in terms of the total amount of Ni (total amount of Ni) in both the coarsened layer, the heat resistant layer, the inner layer and the rust prevention layer. (Total amount of Ni + total amount of Zn) = 0.10 from the amount of Zn deposited (total amount of Zn) in all of the coarsened layer, heat resistant layer, inner layer and anti-rust layer.

(Total amount of Co) / (total amount of Ni) + total amount of Zn) = 1.6 was found from Co deposition amount (total amount of Co) in all of the coarsened layer, heat resistant layer,

As a result of the impregnation evaluation as in Example 1, it was good that the impregnation width was 5 mu m or less. As a result of the adhesion strength evaluation, the state peel strength was 1.02 kg / cm and the hydrochloric acid thermal decomposition resistance was 18 (Loss%). Alkali etching property was also good (O).

Table 1 shows the above results. In addition, the amount of Cr adhered was 90 μg / dm 2 as a whole (amount of Cr), the amount of Co adhered was 2762 μg / dm 2 as a whole (total amount of Co), and the amount of Zn adhered (total amount of Zn) was 177 μg / Respectively.

(Example 12)

In the same roughening treatment as in Example 1, a primary particle layer of Cu having an average particle size of 0.2 to 0.45 占 퐉 and a secondary particle layer made of a ternary alloy made of Cu, Co and Ni having an average particle diameter of 0.05 to 0.25 占 퐉 formed thereon .

The coarsely grained particles of the surface-treated copper foil were observed at a magnification of 30000 times that of the electron microscope (SEM), and the coarsened particle size was evaluated.

The adhesion amount of Ni in the harmony treatment step was 50 to 250 占 퐂 / dm2.

The conditions for forming the heat-resistant layer, the inner layer and the rust-preventive layer are shown below. The thickness of the ultra-thin copper layer was set to 3 탆.

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) inner layer (Zn-Ni layer)

Current density (D _k ): 0.5 to 1.0 A / dm 2

Time: 0 to 2.0 seconds

3) Anti-rusting layer (Cr-Zn layer)

Current density (D _k ): 1 to 3 A / dm 2

Time: 0.05 to 3.0 seconds

The coating amount of Ni in all of the coarsened layer, the heat resistant layer, the inner layer and the anti-rust layer was plated to be 360 쨉 g / dm 2 as a whole (total amount of Ni). (Total amount of Ni + total amount of Zn) = 0.35 from the amount of Zn adhered (total amount of Zn) in all of the coarsened layer, heat resistant layer, inner layer and rustproof layer.

(Total amount of Co) / (total amount of Ni) + total amount of Zn) = 1.4 from the amount of Co deposition (total amount of Co) in the coarsened layer, heat resistant layer, inner layer and anti-

As a result of the impregnation evaluation as in Example 1, it was found that the impregnation width was as good as 0 占 퐉. As a result of the adhesion strength evaluation, the state fill strength was 0.96 kg / cm and the hydrochloric acid thermal decomposition resistance was 5 (Loss%). Alkali etching property was also good (O).

Table 1 shows the above results. In addition, the amount of Cr deposited is 90 ㎍ / dm 2 as a whole (amount of Cr), the amount of deposited Co is 790 / / dm 2 as a whole (total amount of Co), and the amount of Zn deposited (total amount of Zn) is 194 / / Respectively.

(Comparative Example 1)

A roughened treatment layer was formed on the above-described copper foil with a carrier under the same conditions as in Example 1-5. The Ni deposition amount in the harmonic phase was 50 ~ 250 ㎍ / dm2.

The heat-resistant layer made of the Ni-Co layer, the inner layer and the rust-preventive layer containing Zn, Ni, and Cr, and the silane coupling treatment were performed under the above-described conditions. The conditions for forming the heat-resistant layer, the inner layer and the rust-preventive layer are shown below. The thickness of the ultra-thin copper layer was set to 3 탆.

1) Heat-resistant layer (Ni-Co layer)

Current density (D _k ): 10 to 15 A / dm 2

Time: 0.05 to 3.0 seconds

2) inner layer (Zn-Ni layer)

Current density (D _k ): 0.05 to 0.7 A / dm 2

Time: 0.05 to 3.0 seconds

3) Anti-rusting layer (Cr-Zn layer)

Current density (D _k ): 0.5 to 1.5 A / dm 2

Time: 0.05 to 3.0 seconds

The total amount of Ni adhering to the roughened layer, the heat resistant layer, the inner layer and the rust preventive layer was 1540 占 퐂 / dm2 as a whole (total amount of Ni) The total amount of Zn / (total amount of Ni + total amount of Zn) = 0.01 from the amount of Zn adhered (total amount of Zn) from the amount of Co adhered (total amount of Co) in all of the coarsened layer, heat resistant layer, The total amount of Co / (total Ni amount + total Zn amount) = 3.5. As a result of the impregnation evaluation, the impregnation width was as poor as > 5 mu m.

As a result of the adhesion strength evaluation, the state peel strength was 0.98 kg / cm and the hydrochloric acid deterioration resistance was 6 (Loss%). However, the alkali etchability was poor (x) because the remaining particles were observed. As a result, the overall evaluation was poor. This is considered to be because the total amount of Zn / (total amount of Ni + total amount of Zn) is small.

Table 1 shows the above results. In addition, the amount of Cr deposited is 81 ㎍ / dm 2 as a whole (total amount of Cr), the amount of deposited Co is 5444 ㎍ / dm 2 as a whole (total amount of Co), and the amount of Zn deposited is 10 ㎍ / Respectively.

(Comparative Example 2)

A roughened treatment layer was formed on the above-described copper foil with a carrier under the same conditions as in Example 1-5. The Ni deposition amount in the harmonic phase was 50 ~ 250 ㎍ / dm2.

The heat-resistant layer made of the Ni-Co layer, the inner layer and the rust-preventive layer containing Zn, Ni, and Cr, and the silane coupling treatment were performed under the above-described conditions. The conditions for forming the heat-resistant layer, the inner layer and the rust-preventive layer are shown below. The thickness of the ultra-thin copper layer was set to 3 탆.

1) Heat-resistant layer (Ni-Co layer)

Current density (D _k ): 10 to 15 A / dm 2

Time: 0.05 to 3.0 seconds

2) inner layer (Zn-Ni layer)

Current density (D _k ): 0.1 to 1.0 A / dm 2

Time: 0.05 to 3.0 seconds

3) Anti-rusting layer (Cr-Zn layer)

Current density (D _k ): 0.5 to 1.5 A / dm 2

Time: 0.05 to 3.0 seconds

The amount of Ni adhering to all of the roughened layer, heat-resistant layer, inner layer and rust-preventive layer was 1840 占 퐂 / dm 2 as a whole (total amount of Ni) The total amount of Zn / (total amount of Ni + total amount of Zn) = 0.10 from the amount of Zn adhered (total amount of Zn). From the amount of Co adhered (total amount of Co) in all of the coarsened layer, heat resistant layer, The total amount of Co / (total Ni amount + total Zn amount) = 1.5. As a result of the impregnation evaluation, the impregnation width was good: ≤ 3 μm.

As a result of the adhesion strength evaluation, the state fill strength was 0.99 kg / cm and the hydrochloric acid degradation resistance was 7 (Loss%) or less. However, the alkali etchability was poor (x) because the remaining particles were observed. As a result, the overall evaluation was poor. This is considered to be caused by an excessively large amount of Ni deposited.

Table 1 shows the above results. In addition, the amount of Cr adhered was 84 μg / dm 2 as a whole (amount of Cr), the amount of Co adhered was 3058 μg / dm 2 as a whole (total amount of Co), and the amount of Zn adhered was 199 μg / Respectively.

(Comparative Example 3)

A roughened treatment layer was formed on the above-described copper foil with a carrier under the same conditions as in Example 1-5. The Ni deposition amount in the harmonic phase was 50 ~ 250 ㎍ / dm2.

The heat-resistant layer made of the Ni-Co layer, the inner layer and the rust-preventive layer containing Zn, Ni, and Cr, and the silane coupling treatment were performed under the above-described conditions. The conditions for forming the heat-resistant layer, the inner layer and the rust-preventive layer are shown below. The thickness of the ultra-thin copper layer was set to 3 탆.

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) inner layer (Zn-Ni layer)

Current density (D _k ): 0.05 to 0.7 A / dm 2

Time: 0.05 to 3.0 seconds

3) Anti-rusting layer (Cr-Zn layer)

Current density (D _k ): 0.5 to 1.5 A / dm 2

Time: 0.05 to 3.0 seconds

The total amount of Ni adhering to the roughened layer, the heat-resistant layer, the inner layer and the rust-preventive layer was 310 쨉 g / dm 2 as a whole (total amount of Ni) (Total amount of Co) / (total amount of Zn) from the amount of Zn (total amount of Zn) / (total amount of Ni + total amount of Zn) = 0.40 from the amount of Zn adhered The amount of Ni + the total amount of Zn) = 1.4. As a result of the impregnation evaluation, the impregnation width was good: ≤ 3 μm.

As a result of the adhesion strength evaluation, the state peel strength was good at 0.97 kg / cm, but the hydrochloric acid deterioration resistance was poor at 35 (Loss%). The alkaline etching property was good, but the comprehensive evaluation was poor. This is considered to be caused by a large Zn ratio.

Table 1 shows the above results. In addition, the amount of Cr adhered was 82 μg / dm 2 as a whole (amount of Cr), the amount of Co adhered was 723 μg / dm 2 as a whole (total amount of Co), the amount of Zn adhered was 207 μg / Respectively.

(Comparative Example 4)

A roughened treatment layer was formed on the above-described copper foil with a carrier under the same conditions as in Example 1-5. The Ni deposition amount in the harmonic phase was 50 ~ 250 ㎍ / dm2.

The heat-resistant layer made of the Ni-Co layer, the inner layer and the rust-preventive layer containing Zn, Ni, and Cr, and the silane coupling treatment were performed under the above-described conditions. The conditions for forming the heat-resistant layer, the inner layer and the rust-preventive layer are shown below. The thickness of the ultra-thin copper layer was set to 3 탆.

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) inner layer (Zn-Ni layer)

Current density (D _k ): 0.7 to 2.0 A / dm 2

Time: 0.05 to 3.0 seconds

3) Anti-rusting layer (Cr-Zn layer)

Current density (D _k ): 0.8 to 2.5 A / dm 2

Time: 0.05 to 3.0 seconds

The amount of Ni adhering to all of the roughened layer, heat-resistant layer, inner layer and rust-preventive layer was 600 쨉 g / dm 2 as a whole (total amount of Ni) The total amount of Zn / (total amount of Ni + total amount of Zn) = 0.38 from the amount of Zn adhered (total amount of Zn). From the amount of Co deposition (total amount of Co) in all the coarsened layer, heat resistant layer, The total amount of Co / (total Ni amount + total Zn amount) = 1.6. As a result of the impregnation evaluation, the impregnation width was good at 0 탆.

As a result of the evaluation of the adhesion strength, the state peel strength was good at 0.99 kg / cm, but it was poor due to the hydrochloric acid thermal decomposition resistance: 40 (Loss%). Alkali etchability was good (O). However, the overall evaluation was bad. This is considered to be caused by a large Zn ratio.

Table 1 shows the above results. In addition, the Cr adhered amount was 122 ㎍ / dm 2 as a whole (total Cr amount), Co adhered amount was 1546 ㎍ / d㎡ as a whole (total amount of Co), Zn adhered amount was 361 ㎍ / Respectively.

(Example in which the composition of the intermediate layer was 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 formed by plating in a plating liquid having the following liquid composition. The thickness of the extremely thin copper layer was set to 2 탆.

(Liquid composition) CoSO ₄揃 7H ₂ O: 0.5-100 g / ℓ

Na ₂ MoO ₄ .2H ₂ O: 0.5 to 100 g / l

          Sodium citrate dihydrate: 20 to 300 g / l

(Temperature) 10 to 70 DEG C

(pH) 3 to 5

(Current density) 0.1 to 60 A / dm < 2 >

The amount of Ni adhering to all of the coarsened layer, heat-resistant layer, inner layer and rust-preventive layer was 1090 占 퐂 / dm2 as a whole (total Ni amount) The total amount of Zn / (total amount of Ni + total amount of Zn) = 0.13 from the amount of Zn adhered (total amount of Zn). From the amount of Co adhered (total amount of Co) in all of the coarsened layer, heat resistant layer, The total amount of Co / (total Ni amount + total Zn amount) = 1.6. As a result of the impregnation evaluation, the impregnation width was good: ≤ 3 μm.

As a result of the adhesion strength evaluation, the state peel strength was 0.90 kg / cm and the hydrochloric acid thermal decomposition resistance was 10 (Loss%) or less. Alkali etching property was also good (O).

Table 2 shows the above results. The Co deposition amount was 2005 ㎍ / d㎡ as a whole (total Co amount) and the Zn deposition amount was 163 ㎍ / dm 2 as a whole (total Zn amount).

(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 formed by plating in a plating liquid having the following liquid composition. The thickness of the ultra-thin copper layer was set to 10 탆.

(Liquid composition)

CrO ₃ : 200 to 400 g / l

H ₂ SO ₄ : 1.5 to 4 g / ℓ

(pH) 1 to 4

(Liquid temperature) 45 to 60 DEG C

(Current density) 10 to 40 A / dm 2

The total amount of Ni adhering to the roughened layer, heat-resistant layer, inner layer and rust-preventive layer was 449 / / dm 2 as a whole (total amount of Ni) The total amount of Zn / (total amount of Ni + total amount of Zn) = 0.18 from the amount of Zn adhered (total amount of Zn). From the amount of Co deposited (total amount of Co) in all of the coarsened layer, heat resistant layer, The total amount of Co / (total Ni amount + total Zn amount) = 2.7. As a result of the impregnation evaluation, the impregnation width was good: ≤ 3 μm.

As a result of the adhesion strength evaluation, the state fill strength was 0.91 kg / cm and the hydrochloric acid thermal decomposition resistance was 11 (Loss%). Alkali etching property was also good (O).

Table 2 shows the above results. The Co deposition amount was 1481 / / dm 2 as a whole (total Co amount) and the Zn deposition amount was 99 / / dm 2 as a whole (total Zn amount).

(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 formed by plating in a plating solution having the following liquid composition. The thickness of the extremely thin copper layer was set to 2 탆.

(Liquid composition 1)

CrO ₃ : 200 to 400 g / l

H ₂ SO ₄ : 1.5 to 4 g / ℓ

(pH): 1 to 4

(Liquid temperature): 45 to 60 DEG C

(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 to 60 DEG C

(pH): 8 to 10

(Current density): 0.1 to 1.0 A / dm < 2 >

The amount of Ni adhering to all of the roughened layer, heat-resistant layer, inner layer, and rust-preventive layer was 1089 쨉 g / dm 2 as a whole (total Ni amount), and the amount of Ni adhered to both the roughened layer, The total amount of Zn / (total amount of Ni + total amount of Zn) = 0.13 from the amount of Zn adhered (total amount of Zn). From the amount of Co adhered (total amount of Co) in all of the coarsened layer, heat resistant layer, The total amount of Co / (total Ni amount + total Zn amount) = 1.6. As a result of the impregnation evaluation, the impregnation width was good: ≤ 3 μm.

As a result of the adhesion strength evaluation, the state peel strength was 0.90 kg / cm and the hydrochloric acid thermal decomposition resistance was 10 (Loss%) or less. Alkali etching property was also good (O).

Table 2 shows the above results. In addition, the Co deposition amount was 2003 ㎍ / dm 2 as a whole (total Co amount) and the Zn deposition amount was 163 ㎍ / dm 2 as a whole (total Zn amount).

(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 formed by plating in a plating liquid having the following liquid composition. The thickness of the ultra-thin copper layer was set to 10 탆.

(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 to 50 g / l

(pH): 2 to 6

(Bath temperature): 30 to 70 DEG C

(Current density): 0.1 to 50 A / d < 2 >

(Liquid composition 2)

CrO ₃ : 200 to 400 g / l

H ₂ SO ₄ : 1.5 to 4 g / ℓ

(pH): 1 to 4

(Liquid temperature): 45 to 60 DEG C

(Current density): 10 to 40 A / dm < 2 >

The total amount of Ni adhering to the roughened layer, the heat-resistant layer, the inner layer and the rust-preventive layer was 452 쨉 g / dm 2 as a whole (total amount of Ni) The total amount of Zn / (total amount of Ni + total amount of Zn) = 0.18 from the amount of Zn adhered (total amount of Zn). From the amount of Co deposited (total amount of Co) in all of the coarsened layer, heat resistant layer, The total amount of Co / (total Ni amount + total Zn amount) = 2.7. As a result of the impregnation evaluation, the impregnation width was good: ≤ 3 μm.

As a result of the adhesion strength evaluation, the state fill strength was 0.91 kg / cm and the hydrochloric acid thermal decomposition resistance was 11 (Loss%). Alkali etching property was also good (O). Table 2 shows the above results. The Co deposition amount was 1491 / / dm 2 as a whole (total Co amount), and the amount of Zn adhered was 100 쨉 g / dm 2 as a whole (total Zn amount).

(Example 25)

Next, a copper foil with a carrier was formed under the same conditions as in Example 1, except that a Co / chromate treatment layer was formed as an intermediate layer between the carrier and the copper foil.

In this case, the intermediate layer of the Co / chromate treatment was prepared by plating the plating solution in the following liquid composition. The thickness of the extremely thin copper layer was set to 2 탆.

(Liquid composition 1) CoSO ₄揃 7H ₂ O: 10 to 100 g / ℓ

            Sodium citrate dihydrate: 30 to 200 g / l

(Temperature): 10 to 70 DEG C

(pH): 3 to 5

(Current density): 0.1 to 60 A / d < 2 >

(Liquid composition 2) CrO ₃ : 1 to 10 g / l

(Temperature): 10 to 70 DEG C

(pH): 10-12

(Current density): 0.1 to 1.0 A / dm < 2 >

The amount of Ni adhering to all of the roughened layer, heat-resistant layer, inner layer and rust-preventive layer was 1095 占 퐂 / dm2 as a whole (total amount of Ni) The total amount of Zn / (total amount of Ni + total amount of Zn) = 0.13 from the amount of Zn adhered (total amount of Zn). From the amount of Co adhered (total amount of Co) in all of the coarsened layer, heat resistant layer, The total amount of Co / (total Ni amount + total Zn amount) = 1.6. As a result of the impregnation evaluation, the impregnation width was good: ≤ 3 μm.

As a result of the adhesion strength evaluation, the state peel strength was 0.90 kg / cm and the hydrochloric acid thermal decomposition resistance was 10 (Loss%) or less. Alkali etching property was also good (O).

Table 2 shows the above results. The Co deposition amount was 2014 ㎍ / dm 2 as a whole (total Co amount) and the Zn deposition amount was 164 ㎍ / dm 2 as a whole (total Zn amount).

(Example 26)

Next, a carrier-adhered copper foil was formed under the same conditions as in Example 4 except that an organic material layer was formed as an intermediate layer between the carrier and the copper foil. The thickness of the ultra-thin copper layer was set to 10 탆. In this case, the intermediate layer of the organic material layer was prepared by spraying an aqueous solution of carboxybenzotriazole having a liquid temperature of 40 DEG C, a pH of 5, and a concentration of 1 to 10 g / L for 10 to 60 seconds.

The amount of Ni adhering to all of the coarsened layer, heat-resistant layer, inner layer and rust-preventive layer was 450 쨉 g / dm 2 as a whole (total amount of Ni) The total amount of Zn / (total amount of Ni + total amount of Zn) = 0.18 from the amount of Zn adhered (total amount of Zn). From the amount of Co deposited (total amount of Co) in all of the coarsened layer, heat resistant layer, The total amount of Co / (total Ni amount + total Zn amount) = 2.7. As a result of the impregnation evaluation, the impregnation width was good: ≤ 3 μm.

As a result of the adhesion strength evaluation, the state fill strength was 0.91 kg / cm and the hydrochloric acid thermal decomposition resistance was 11 (Loss%). Alkali etching property was also good (O).

Table 2 shows the above results. The Co deposition amount was 1484 ㎍ / dm 2 as a whole (total Co amount), and the Zn deposition amount was 99 ㎍ / dm 2 as a whole (total Zn amount).

Industrial availability

In the copper clad laminate using the copper foil with a carrier having undergone the silane coupling treatment after the roughening treatment is formed on the surface of the copper foil with a carrier and the heat resistant layer and the rust preventive layer are formed thereon, Is subjected to acid treatment or chemical etching, it is possible to improve the suppression of adhesion deterioration due to penetration of acid to the interface between the copper foil circuit and the substrate resin, and to provide an acid-resistant adhesion strength and an excellent alkali-etching property. As a result, miniaturization and high integration of semiconductor devices are progressing while the development of electronic devices is progressing, and the processes performed in the manufacturing process of these printed circuits are more strictly required. to provide.

Claims (40)

A roughened treatment layer formed by subjecting a surface of the ultra-thin copper layer of a copper foil with a carrier on which a carrier, an intermediate layer and an ultra-thin copper layer are laminated in this order to roughening (try) treatment, And a surface treatment layer having an inner layer and an anti-rust layer formed on the heat resistant layer, wherein the roughened layer is composed of fine particles having an average particle diameter of 0.05 to 0.60 mu m, (Total Zn amount + total Ni amount) in the surface treatment layer is 0.02 or more and 0.35 or less, and the total amount of Ni in the surface treatment layer is 1600 占 퐂 / lt; 2 >
The total amount of Zn is defined as the total amount of Zn contained in the coarsened layer, the heat resistant layer, the inner layer and the rustproof layer,
Wherein the total amount of Ni is defined as a total amount of Ni contained in the roughened treatment layer, the heat resistant layer, the inner layer, and the rust preventive layer. The method according to claim 1,
(Total Zn amount + total Ni amount) in the surface treatment layer is 0.02 or more and 0.23 or less, and the total amount of Ni in the surface treatment layer is 1150 占 퐂 / dm2 or less. The method according to claim 1,
Wherein the total amount of Ni in the surface treatment layer is 350 to 1350 占 퐂 / dm2. 3. The method of claim 2,
Wherein the total amount of Ni in the surface treatment layer is 350 to 1350 占 퐂 / dm2. The method of claim 3,
Wherein the total amount of Ni in the surface treatment layer is 450 to 1100 占 퐂 / dm2. 5. The method of claim 4,
Wherein the total amount of Ni in the surface treatment layer is 450 to 1100 占 퐂 / dm2. The method according to claim 1,
Wherein the total amount of Co in the surface treatment layer is 770 to 3200 占 퐂 / dm2 and the total amount of Co / (total amount of Zn + total amount of Ni) is 3.4 or less. 3. The method of claim 2,
Wherein the total amount of Co in the surface treatment layer is 770 to 3200 占 퐂 / dm2 and the total amount of Co / (total amount of Zn + total amount of Ni) is 3.4 or less. The method of claim 3,
Wherein the total amount of Co in the surface treatment layer is 770 to 3200 占 퐂 / dm2 and the total amount of Co / (total amount of Zn + total amount of Ni) is 3.4 or less. 5. The method of claim 4,
Wherein the total amount of Co in the surface treatment layer is 770 to 3200 占 퐂 / dm2 and the total amount of Co / (total amount of Zn + total amount of Ni) is 3.4 or less. 8. The method of claim 7,
Wherein the total amount of Co in the surface treatment layer is 770 to 2500 占 퐂 / dm2 and the total amount of Co / (total amount of Zn + total amount of Ni) is not more than 3.0. 9. The method of claim 8,
Wherein the total amount of Co in the surface treatment layer is 770 to 2500 占 퐂 / dm2 and the total amount of Co / (total amount of Zn + total amount of Ni) is not more than 3.0. 10. The method of claim 9,
Wherein the total amount of Co in the surface treatment layer is 770 to 2500 占 퐂 / dm2 and the total amount of Co / (total amount of Zn + total amount of Ni) is not more than 3.0. 11. The method of claim 10,
Wherein the total amount of Co in the surface treatment layer is 770 to 2500 占 퐂 / dm2 and the total amount of Co / (total amount of Zn + total amount of Ni) is not more than 3.0. 15. The method according to any one of claims 1 to 14,
Wherein the total amount of Cr in the surface treatment layer is 50 to 130 占 퐂 / dm2. 15. The method according to any one of claims 1 to 14,
Wherein the coarsened layer has an Ni content of 50 to 550 占 퐂 / dm2. 15. The method according to any one of claims 1 to 14,
Wherein the roughening treatment layer is a roughened treatment layer composed of elements of Co, Cu, and Ni. 15. The method according to any one of claims 1 to 14,
Wherein the roughened treatment layer is composed of fine particles of a ternary alloy consisting of Cu, Co and Ni having an average particle diameter of 0.05 to 0.60 mu m. 15. The method according to any one of claims 1 to 14,
Wherein the roughening treatment layer is composed of a primary particle layer having an average particle diameter of 0.25 to 0.45 mu m and a secondary particle layer having an average particle diameter of 0.05 to 0.25 mu m formed thereon. 15. The method according to any one of claims 1 to 14,
Characterized in that the roughening treatment layer is composed of a primary particle layer of Cu having an average particle diameter of 0.25 to 0.45 탆 and a secondary particle layer composed of a ternary alloy composed of Cu, Co and Ni having an average particle diameter of 0.05 to 0.25 탆 formed thereon Wherein the copper foil is a copper foil. A roughened treatment layer formed by subjecting a surface of the ultra-thin copper layer of a copper foil with a carrier on which a carrier, an intermediate layer and an ultra-thin copper layer are laminated in this order to roughening (try) treatment, And a surface treatment layer having an inner layer and an anti-rust layer formed on the heat resistant layer, wherein the roughened layer is composed of fine particles having an average particle diameter of 0.05 to 0.60 mu m, (Total Zn amount + total Ni amount) in the surface treatment layer is 0.02 or more and 0.35 or less, and the total amount of Ni in the surface treatment layer is 1600 占 퐂 / lt; 2 >
The total amount of Zn is defined as the total amount of Zn contained in the coarsened layer, the heat resistant layer, the inner layer and the rustproof layer,
Wherein the total amount of Ni is defined as a total amount of Ni contained in the roughening treatment layer, the heat resistant layer, the inner layer and the rust preventive layer,
A copper foil with a carrier satisfying any one of the following (a) to (l):
(a) the total Zn amount / (total Zn amount + total Ni amount) in the surface treatment layer is 0.02 or more and 0.23 or less, and the total amount of Ni in the surface treatment layer is 1150 占 퐂 / dm2 or less;
(b) the total amount of Ni in the surface treatment layer is 350 to 1350 占 퐂 / dm2;
(c) the total amount of Ni in the surface treatment layer is 450 to 1100 占 퐂 / dm2;
(d) the total amount of Co in the surface treatment layer is 770 to 3200 占 퐂 / dm2, the total amount of Co / (total amount of Zn + total amount of Ni) is not more than 3.4;
(e) the total amount of Co in the surface-treated layer is 770 to 2500 占 퐂 / dm2, the total amount of Co / (total amount of Zn + total amount of Ni) is not more than 3.0;
(f) the total amount of Cr in the surface treatment layer is 50 to 130 占 퐂 / dm2;
(g) the amount of Ni of the roughening treatment layer is 50 to 550 占 퐂 / dm2;
(h) the roughened layer is a roughened layer formed of elements of Co, Cu, and Ni;
(i) the roughening treatment layer is composed of fine particles having an average particle diameter of 0.05 to 0.60 mu m;
(j) the roughening treatment layer is composed of fine particles of a ternary alloy made of Cu, Co and Ni having an average particle diameter of 0.05 to 0.60 mu m;
(k) the roughening treatment layer comprises a primary particle layer having an average particle diameter of 0.25 to 0.45 mu m and a secondary particle layer having an average particle diameter of 0.05 to 0.25 mu m formed thereon;
(1) The process according to any one of the above items (1) to (3), wherein the roughening treatment layer is a secondary particle layer composed of a primary particle layer of Cu having an average particle diameter of 0.25 to 0.45 탆 and a ternary alloy comprising Cu, Co and Ni having an average particle diameter of 0.05 to 0.25 탆 consist of. A copper foil for a printed circuit comprising the ultra-thin copper layer of the copper foil with a carrier according to any one of claims 1 to 14 and 21. 22. The method according to any one of claims 1 to 14 and 21,
And a resin layer on the surface treatment layer. A copper clad laminate obtained by laminating the copper foil for a printed circuit according to claim 22 on a resin substrate. A printed wiring board produced by using the copper foil with a carrier according to any one of claims 1 to 14 and 21. A printed wiring board produced by using the copper foil with a carrier according to claim 23. A printed circuit board manufactured using the copper foil with a carrier according to any one of claims 1 to 14 and 21. A copper clad laminate produced by using the copper foil with a carrier according to any one of claims 1 to 14 and 21. A copper clad laminate produced by using the copper foil with a carrier according to claim 23. A method for manufacturing a semiconductor device, comprising the steps of preparing the copper foil with a carrier and the insulating substrate according to any one of claims 1 to 14 and 21,
A step of laminating the copper foil with a carrier and an insulating substrate,
After the step of laminating the carrier-bonded copper foil with the insulating substrate and the step of peeling the carrier of the carrier-coated copper foil, a copper clad laminate is formed,
And thereafter forming a circuit by any one of a semi-additive method, a subtractive method, a pattern additive method, and a modified semi-additive method. A step of forming a circuit on the surface of the ultra thin copper layer side of the copper foil with a carrier according to any one of claims 1 to 14 and 21,
A step of forming a resin layer on the surface of the ultra thin copper layer side of the copper foil with a carrier so that the circuit is buried,
A step of forming a circuit on the resin layer,
A step of forming a circuit on the resin layer and thereafter peeling the carrier,
Exposing a circuit buried in the resin layer formed on the extremely thin copper layer side surface by removing the extremely thin copper layer after peeling the carrier. 32. The method of claim 31,
Wherein the step of forming a circuit on the resin layer comprises:
Wherein another copper foil with a carrier is laminated on the resin layer from an extremely thin copper layer side and the circuit is formed using the copper foil with a carrier bonded to the resin layer. 33. The method of claim 32,
And the carrier-attached copper foil to be bonded onto the resin layer is the copper foil with a carrier. Using the copper foil with a carrier according to any one of claims 1 to 14 and 21;
Forming a circuit on the surface of the ultra thin copper layer side of the copper foil with a carrier;
Forming a resin layer on the extremely thin copper layer side surface of the copper foil with a carrier so that the circuit is buried;
Forming a circuit on the resin layer;
Peeling the carrier after forming a circuit on the resin layer; And
Exposing a circuit buried in the resin layer formed on the extremely thin copper layer side surface by removing the extremely thin copper layer after peeling the carrier;
Wherein the step of forming a circuit on the resin layer comprises the step of forming a circuit by bonding another copper foil with a carrier on the resin layer from an extremely thin copper layer side and using the copper foil with a carrier bonded to the resin layer Process;
Wherein the copper foil with a carrier to be bonded onto the resin layer further comprises a resin layer on the surface treatment layer. 32. The method of claim 31,
Wherein a step of forming a circuit on the resin layer is carried out by any one of a semiadditive method, a subtractive method, a palladium additive method, and a modified semi additive method. 33. The method of claim 32,
Wherein a step of forming a circuit on the resin layer is carried out by any one of a semiadditive method, a subtractive method, a palladium additive method, and a modified semi additive method. 34. The method of claim 33,
Wherein a step of forming a circuit on the resin layer is carried out by any one of a semiadditive method, a subtractive method, a palladium additive method, and a modified semi additive method. 32. The method of claim 31,
Further comprising a step of forming a substrate on a carrier-side surface of the copper foil with a carrier before peeling off the carrier. 33. The method of claim 32,
Further comprising a step of forming a substrate on a carrier-side surface of the copper foil with a carrier before peeling off the carrier. 34. The method of claim 33,
Further comprising a step of forming a substrate on a carrier-side surface of the copper foil with a carrier before peeling off the carrier.

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