KR101803390B1 - Carrier-equipped ultrathin copper foil, and copper-clad laminate, printed circuit substrate and coreless substrate that are manufactured using same - Google Patents

Carrier-equipped ultrathin copper foil, and copper-clad laminate, printed circuit substrate and coreless substrate that are manufactured using same Download PDF

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KR101803390B1
KR101803390B1 KR1020167000224A KR20167000224A KR101803390B1 KR 101803390 B1 KR101803390 B1 KR 101803390B1 KR 1020167000224 A KR1020167000224 A KR 1020167000224A KR 20167000224 A KR20167000224 A KR 20167000224A KR 101803390 B1 KR101803390 B1 KR 101803390B1
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carrier
ultra
foil
copper foil
thin copper
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KR20160048755A (en
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료타 후지타
타케오 우노
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후루카와 덴키 고교 가부시키가이샤
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/20—Separation of the formed objects from the electrodes with no destruction of said electrodes
    • C25D1/22—Separating compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/20—Separation of the formed objects from the electrodes with no destruction of said electrodes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
    • H05K3/4658—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern characterized by laminating a prefabricated metal foil pattern, e.g. by transfer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/01—Tools for processing; Objects used during processing
    • H05K2203/0147—Carriers and holders
    • H05K2203/0156—Temporary polymeric carrier or foil, e.g. for processing or transferring

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

There is provided an ultra thin copper foil with a carrier which can easily adjust the carrier peel strength. The ultra-thin copper foil 10 with a carrier according to the present invention is formed by sequentially laminating a diffusion preventive layer 12, a release layer 13 and an ultra-thin copper foil 16 on a carrier foil 11, The carrier foil 11 is peeled off from the ultra-thin copper foil 10 and the depth direction composition of the carrier foil 11 peeled off is analyzed by the Auger electron spectroscopy (AES) The maximum value of the proportion of elemental elements of Cu existing from the release face to the depth position within 15 nm when denoted by denominator Mo, Ni, Fe, W, Cr, C and O is in the range of 9 at. .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper clad laminate, a printed wiring board, and a coreless substrate using the same, and a copper clad laminate, a printed wiring board, and a core-

The present invention relates to an ultra-thin copper foil with a carrier, and a copper clad laminate, a printed wiring board and a coreless substrate produced using the same.

BACKGROUND ART [0002] In recent years, a build-up substrate used in a semiconductor package or the like has been replaced with a coreless substrate. With the advancement of miniaturization and thinning of electronic devices, in the circuit board maker, the production of a multilayer laminate using a substrate capable of being thinned, called a coreless substrate, has been studied. However, since the core-less substrate does not have a core layer for supporting the wiring layer, there is a concern that defects such as bending, warpage, and cracks may occur during formation of the wiring layer due to insufficient stiffness. Thus, a build-up circuit board is laminated on the ultra thin copper foil side with the carrier foil constituting the ultra-thin copper foil with carrier as a support, and the carrier foil finally constituting the ultra- The process is under review.

In the build-up substrate, fine wiring layers (build-up layers) are stacked on both sides of a core layer as a support to form high-density wirings. Although a printed circuit board technology using a glass epoxy resin or the like is adopted for the core layer, this core layer causes deterioration of electrical characteristics. Particularly, a large inductance component of the plated-through hole passing through the core layer is a factor for increasing the power supply noise of the semiconductor chip. Therefore, the movement of adopting a coreless substrate in which this core layer does not exist is rapidly proceeding.

A specific manufacturing process of a coreless substrate having a support made of an ultra-thin copper foil with a carrier will be described. The core-less substrate is manufactured by sequentially performing the processes shown in Figs. 1 (a) to 1 (g). First, the prepreg 4 is bonded to the ultra-thin copper foil 2 side of the ultra-thin copper foil 3 with a carrier for a support (Fig. 1 (a)). Next, the ultra-thin copper foil 6 side of the ultra-thin copper foil 7 with a carrier for wiring formation is bonded to the other surface of the prepreg 4 (Fig. 1 (b)). Thereafter, the carrier foil 5 for wiring formation is peeled off from the ultra-thin copper foil 7 with a carrier bonded thereto and the ultra-thin copper foil 6 is etched with a predetermined wiring pattern to form a fine wiring 8 c)). Subsequently, the prepreg 4 is bonded again onto the fine wiring 8, thereby completing the first layer of the coreless substrate (Fig. 1 (d)). 1 (b) to 1 (d) are repeated until the necessary number of fine interconnections 8 are formed, whereby the core-less ultra-thin copper foil 3 with the carrier, which is the support, Thereby forming a substrate 9 (Fig. 1 (e)). Thereafter, the carrier foil 1 of the ultra-thin copper foil 3 with a carrier for a support is peeled off (Fig. 1 (f)), and finally the exposed ultra-thin copper foil 2 is removed by etching or the like, 9) (Fig. 1 (g)).

In the production of the coreless substrate, the peel strength at the time of peeling the carrier foil 1 for support from the ultra-thin copper foil 3 with a carrier is such that the peel strength at the time of forming (laminating) It is necessary to have an adhesive property to such an extent that peeling does not occur in a manufacturing process such as pressing or etching of the layer and also to have an appropriate adhesiveness enough to mechanically peel off after the formation (lamination) of the layer.

Although the copper foil with a carrier is described in, for example, Patent Documents 1 and 2, it is not intended to fabricate a coreless substrate in all cases, and even if these proposals are directly applied to the production of a coreless substrate, The inventors of the present invention have recognized that there is a possibility of occurrence of such a problem. For example, Patent Document 1 is directed to setting the carrier foil and the ultra-thin copper foil so that they can be easily peeled off even when placed in an environment at a high temperature of 300 ° C to 400 ° C in consideration of the temperature to be applied when the multi- , And the peeling interface is made of two layers, and the metal ratio of the two-layer release layer is defined and easily peeled off.

In Patent Document 2, the content of the two kinds of metals A and B constituting the release layer is specified in order to suppress the occurrence of the low peeling strength and the swelling.

The proposals of Patent Documents 1 and 2 are that all of the peel strengths at the time of peeling off the carrier foil from the ultra thin copper foil with a carrier are held low even after the pressing under high temperature (300 ° C. to 400 ° C.) When a laminated board, particularly a coreless board, is manufactured by using the ultra-thin copper foil with a carrier having a low carrier-fill strength as a support, a load (e.g., There is a risk that peeling may occur between the carrier foil to be a support and the ultra-thin copper foil at an unintended stage in the laminating process.

On the other hand, also in the formation (lamination) of the layer constituting the core-less substrate, the ultra-thin copper foil 7 with the same carrier as the ultra-thin copper foil 3 with a carrier serving as a support is used. The peel strength at the time of peeling off the carrier foil 5 for wiring formation from the ultra-thin copper foil 7 with a carrier when the carrier foil 5 for wiring formation is peeled off after the step of Fig. 1 (b) Is lower than the peel strength at which the carrier foil 1 for carrier is peeled off from the carrier foil 3, unintended peeling may occur in the carrier foil 1 used as the carrier during the production of the coreless substrate.

Therefore, when manufacturing a coreless substrate, it is necessary to use two types of ultra-thin copper foil with a carrier having different carrier peel strengths, that is, a carrier with ultra-thin copper foil 3 for use as a support, (7) need to be prepared. However, preparing the ultra-thin copper foil with a carrier having these two different carrier fill strengths is not preferable from the viewpoint of the copper foil manufacturer because it is necessary to switch the production conditions every time, resulting in an increase in manufacturing cost . From the viewpoint of a circuit board maker using the same, a product (ultra-thin copper foil with a carrier) having a low carrier fill strength can be used only for wiring formation, There is a problem in that each of them can be used only for a support for producing a lease substrate, and the applications are each limited. In order to solve these drawbacks, it is assumed that only one type of ultra-thin copper foil with a carrier is used, and that by using a simple method performed by the user, it is possible to change the carrier- Is required.

International Publication No. WO2010 / 27052 Japanese Patent Application Laid-Open No. 2007-186781

As described above, there is a demand for a copper foil with a carrier capable of arbitrarily changing the carrier fill strength on the user side. Particularly, in the production of the core-less substrate, in the layer formation (lamination) step of the fine wiring, the temperature after the heating load at the applied temperature (mostly in the range of 150 ° C to 220 ° C though depending on the type of the prepreg) With regard to the ultra-thin copper foil with a carrier which has a low carrier fill strength and which is used as a support, there is a problem that a carrier peel strength can be set to a high value in a mechanical peelable range, Copper foil is required.

An object of the present invention is to provide an ultra-thin copper foil with a carrier which satisfies such a demand, and a copper clad laminate, a printed wiring board and a coreless substrate produced by using the same.

The ultra-thin copper foil with a carrier according to the present invention is an ultra-thin copper foil with a carrier formed by laminating a diffusion preventive layer, a release layer and an ultra-thin copper foil on a carrier foil in this order. The carrier foil is peeled off from the ultra- (AES) was carried out on the peeling surface of the carrier foil thus obtained to determine the depth direction composition of the carrier foil as a denominator in which Cu, Co, Mo, Ni, Fe, W, Cr, And the maximum value of the element ratio of Cu present to the depth position within 15 nm from the release face is 9 at.% To 91 at.%. More preferably, Cu is contained so as to have such an element ratio at a position within 5 nm from the peeling interface.

The ultra-thin copper foil with a carrier according to the present invention is characterized by having a peel strength T1 of less than 0.02 kN / m when the carrier foil is peeled from the ultra-thin copper foil with a carrier after heat treatment at 220 占 폚 for 1 hour and further heat treatment at 350 占 폚 for 10 minutes The peel strength T2 after heat treatment at 350 占 폚 for 10 minutes and the peel strength T2 after heat treatment at 350 占 폚 for 220 minutes are preferably in the range of 0.02 kN / m to 0.1 kN / (T2-T1) of the peel strength T1 after heat treatment for 1 hour at room temperature is preferably in the range of 0.015 to 0.080 kN / m.

In the present invention, the carrier foil is peeled off from the ultra-thin copper foil with a carrier of unheated heat, and the depth direction composition analysis carried out on the release face of the peeled carrier foil indicates that measured by Auger electron spectroscopy (AES) The maximum value of the proportion of elemental elements of Cu existing from the release face to the depth position within 15 nm when denoted by denominator Mo, Ni, Fe, W, Cr, C and O is in the range of 9 at. . The depth from the peeling surface refers to a value obtained by converting SiO 2 to a speed at the time of sputtering with an Ar ion beam.

The release layer contains Cu and preferably contains at least one kind of element selected from the group consisting of Mo, W, Fe, Co, Ni and Cr. Further, even when the organic release layer such as benzotriazole mainly containing C, N, and O elements contains Cu in the form of a high carrier fill strength after the heat treatment is realized. However, when the carrier foil and the ultra-thin copper foil are peeled off, the constitution of such an organic peelable layer may remain on the surface of the ultra-thin copper foil, which may cause a problem of inhibiting etching of the ultra-thin copper foil.

The diffusion preventive layer is preferably formed of at least one metal or alloy selected from the group consisting of Fe, Ni, Co, and alloys containing these elements.

The carrier foil is preferably copper or a copper alloy.

The ultra-thin copper foil with a carrier according to the present invention is preferably used for producing a copper clad laminate, a printed wiring board and a coreless substrate.

The ultra-thin copper foil with a carrier of the present invention is based on the premise that only one kind of ultra-thin copper foil with a carrier is used, and the ultra-thin copper foil with a carrier used as a support is subjected to heat treatment at a high temperature The strength is increased within a range in which mechanical peeling is possible. On the other hand, for the ultra-thin copper foil with a carrier used for forming a wiring, the temperature is maintained at a temperature (for example, 150 to 220 캜) The carrier peel strength is not increased. By setting the carrier fill strength in such a manner by dividing the application, peeling of the carrier foil and the ultra-thin copper foil at the unintended stage during the laminating process can be prevented as a support for laminating the coreless substrate. That is, the ultra-thin copper foil with a carrier according to the present invention has an epoch-making characteristic that can be used in various cases as one product.

1 (a) to 1 (g) are schematic views for explaining a general process flow for manufacturing a coreless substrate using an ultra-thin copper foil with a carrier.
2 is a cross-sectional view showing one layer structure of the ultra-thin copper foil with a carrier according to the present invention.

(Mode for carrying out the invention)

2 is a representative embodiment of the ultra-thin copper foil with a carrier according to the present invention. 2, the ultra-thin copper foil 10 with a carrier has a carrier foil 11, a diffusion preventing layer 12 formed on the surface of the carrier foil 11, Layer 13 and an ultra-thin copper foil 16 formed on the surface of the release layer 13. As shown in Fig. The peeling layer 13 may be composed of a single layer, but as shown in Fig. 2, the first peeling layer 14 formed on the side of the carrier foil 11 and the second peeling layer 14 formed on the side of the ultra- Layer 15 is preferable. 2, when the peeling layer 13 is composed of two layers of the first peeling layer 14 and the second peeling layer 15, the carrier foil 11 is peeled from the ultra-thin copper foil 10 with the carrier, The first release layer 14 remains on the carrier foil 11 side and the second release layer 15 remains on the ultra-thin copper foil 16 side. Although the peeling layer 13 can achieve the same high carrier filed strength even in the case of a single layer constitution of only the first peeling layer 14, the first peeling layer 14 can be formed in the same manner as the first peeling layer 14 14, it is likely to be dissolved in the plating solution used in the copper strike plating process, which is often performed generally before the formation of the ultra-thin copper foil 16. Thus, in order to prevent the dissolution of the first peeling layer 14, a second peeling layer 15 is formed on the first peeling layer 14 so that the first peeling layer 14 is in direct contact with the copper strike plating solution It is more desirable to avoid the problem.

An aluminum foil, an aluminum alloy foil, a stainless steel foil, a titanium foil, a titanium alloy foil, a copper foil, a copper alloy foil, or the like can be generally used as the carrier foil 11 constituting the ultra- As the carrier foil 11 used for the ultra-thin copper foil or the ultra-thin copper foil (hereinafter, collectively referred to simply as "ultra-thin copper foil" when no need to distinguish between them is simply referred to as "ultra-thin copper foil"), Electrolytic copper alloy foil, rolled copper foil or rolled copper alloy foil is preferable. It is preferable to use a foil having a thickness of 7 mu m to 200 mu m.

When the thickness of the carrier foil 11 is less than 7 占 퐉, the carrier foil 11 has a low mechanical strength. Therefore, when the carrier foil 11 is used for the production of a laminated board, particularly a coreless substrate, And it is liable to cause bending or warpage. As a result, the manufactured coreless substrate may be damaged. If the thickness of the carrier foil 11 is more than 200 mu m, the weight per unit coil (coil unit weight) is increased, which greatly affects the productivity and requires a larger tension on the facility, Which is undesirable. Therefore, it is preferable that the thickness of the carrier foil 11 is 7 mu m to 200 mu m.

The release layer 13 preferably contains Cu and preferably contains at least one kind of element selected from the group consisting of Mo, W, Fe, Co, Ni and Cr.

In the present invention, with regard to the Cu contained in the release layer, the carrier foil 11 is peeled off from the ultra-thin copper foil 10 with the carrier of unheated heat, and the element 11 existing on the peeled side of the peeled carrier foil 11 Co, Mo, Ni, Fe, W (W), or the like) is performed by analyzing the depth direction composition (depth profile) by the Auger electron spectroscopy (AES) , And the maximum value of the proportion of elemental elements of Cu present to the depth position within 15 nm from the release face when Cr, C and O are denominators is preferably 9 at.% To 91 at.%. More preferably, Cu is contained so as to have such an element ratio at a position within 5 nm from the peeling interface.

If the maximum value of the element ratio of Cu is less than 9 at.%, Even if the ultra-thin copper foil with a carrier is subjected to a heat treatment at a high temperature (for example, 350 占 폚), the carrier peel strength can not be increased to an expected extent. That is, when the ultra-thin copper foil with a carrier having the maximum value of the element ratio of Cu less than 9 at.% Is used as a support for the coreless substrate, It is feared that unintended peeling of foil may occur. When the maximum value of the element ratio of Cu is higher than 91 at.%, The carrier peel strength becomes excessively high beyond the range in which peeling can be performed mechanically by performing the heat treatment at a high temperature (for example, 350 ° C.) . That is, when the ultra-thin copper foil with a carrier having a maximum element content of more than 91 at.% Is used as the support of the core-less substrate, after the layer formation (lamination) When the carrier foil is peeled off from the ultra-thin copper foil, a large force acts on the coreless substrate, resulting in a fear of causing defects such as bending and warping on the coreless substrate. Therefore, in the present invention, the maximum value of the element ratio of Cu is set to 9 at.% To 91 at.%.

[Formation of diffusion preventing layer]

In the present invention, the diffusion preventive layer 12 is formed on the surface of the carrier foil 11 in order to stabilize the peeling property of the carrier foil 11 from the ultra-thin copper foil 10 with a carrier. By forming the diffusion preventing layer 12 in this way, the Cu contained in the carrier foil 11 is prevented from being thermally diffused into the peeling layer 13, and the carrier foil 11 and the ultra-thin copper foil 16 can be mechanically peeled The peeling property of the peeling layer 13 can be stabilized. Examples of the material of the diffusion preventing layer 12 include Fe, Ni, Co, or alloys formed by these elements. The thickness of the diffusion preventing layer 12 is preferably 10 to 200 nm in view of preventing diffusion of Cu in the carrier foil. The diffusion preventing layer 12 may be formed by, for example, electrolytic plating such as Ni plating, Fe plating, Co plating, or the like.

[Formation of release layer]

In the manufacturing process of the ultra-thin copper foil 10 with a carrier, in the embodiment shown in Fig. 2, the first peeling layer 14 is formed on the diffusion preventing layer 12 formed on the carrier foil 11, A second release layer 15 is formed. Each of the release layers 14 and 15 may be formed by electrolytic plating, for example, as described later. As a means for changing the Cu ratio contained in the first release layer 14, for example, a method of changing the Cu concentration in the plating bath for forming the first release layer 14 may be mentioned. The above-described method is merely an example, and a method of controlling the deposition amount of Cu by controlling the electric potential at the time of plating of the first release layer 14 may be employed. That is, in the present invention, the method of controlling the Cu ratio in the release layer 13 is not particularly limited, and various methods can be employed. The thickness of the release layer 13 is preferably in the range of about 5 to 15 nm from the viewpoint of achieving peeling of the carrier foil and the ultra-thin copper foil and realizing the carrier fill strength specified in the present invention. The reason is that if the thickness of the release layer 13 is too thin than the above range, the ultra-thin copper foil may not be peelable from the carrier foil, while if it is too thick, the carrier peel strength may be too low It is because. When the peeling layer 13 is composed of two layers of the first peeling layer 14 and the second peeling layer 15, the thickness of the first peeling layer 14 and the thickness of the second peeling layer 15 And the thickness is preferably in the range of about 2: 1 to 4: 1. The composition of the release layer 13 preferably includes, for example, Cu and further includes at least one kind of element selected from the group consisting of Mo, W, Fe, Co, Ni and Cr, , Co-Mo-Cu alloy plating, Fe-Mo-Cu alloy plating, Ni-Mo-Cu alloy plating, Ni-Cu alloy plating and Cr-Cu alloy plating.

[Formation of ultra-thin copper foil]

The ultra-thin copper foil 16 is formed by electrolytic plating on the peeling layer 13 and the second peeling layer 15 in Fig. 2 using a copper sulfate bath, a copper pyrophosphate bath, a copper cyanide bath, or the like . In addition, in forming the ultra-thin copper foil, the second peeling layer 15 is formed by the elements contained in the second peeling layer 15 so that the dip time in the plating solution in the electrolytic plating step for forming the ultra-thin copper foil 16, It is assumed that the plating solution is subjected to damage such as dissolution at the time of drying of the plating solution of plating finishing, at the time of washing with water, and at the pH of the plating solution immediately after the metal plating. Since the occurrence of such a damage is assumed, it is necessary to carefully select the plating bath composition, the plating condition, and the like in the electrolytic plating step for forming the ultra-thin copper foil in relation to the elements constituting the second release layer 15 .

In the present invention, before forming the ultra-thin copper foil 16 on the peeling layer 13 (the second peeling layer 15 in Fig. 2), it is more preferable to perform strike copper plating in a copper pyrophosphate bath or the like . By performing the strike copper plating, a grounded Cu plating layer (not shown) having good adhesion and dense can be formed on the peeling layer 13. That is, by performing copper plating on the underlying Cu plating layer, it is possible to form a uniform ultra thin copper foil 16 on the release layer 13, to reduce the number of pin holes generated in the ultra-thin copper foil 16, It is possible to prevent occurrence of swelling from defects.

The thickness of the underlying Cu plating layer adhered by strike plating is preferably 0.01 탆 to 0.5 탆 from the viewpoint of making the peelability of the peeling layer 13 not to deteriorate. The conditions vary depending on the type of plating bath, but the current density is preferably 0.1 A / dm 2 to 20 A / dm 2, and the plating time is preferably 0.1 second or more. First, when the current density is less than 0.1 A / dm 2, it is difficult to uniformly form the underlying Cu plating layer on the peeling layer 13, and when it exceeds 20 A / dm 2, It should be noted that in the strike plating with a low concentration, plating burning occurs and tends to be difficult to uniformly form the underlying copper plating layer. It should be noted that the plating time tends to become difficult to uniformly form a copper strike plating layer of a predetermined thickness after a short time at less than 0.1 second. After forming the underlying Cu plating layer, Cu plating of a desired thickness is performed to form an ultra-thin copper foil 16.

In the production of the coreless substrate, the thermal history at the time of pressure heating applied in the step of forming (laminating) the layer of the coreless substrate varies depending on the type of the prepreg, but is usually within a range of 150 to 220 캜 In about one hour. The peel strength at the time of peeling off the carrier foil 11 from the ultra-thin copper foil 10 with a carrier is the same as that in the case where the ultra-thin copper foil 10 with a carrier is used as a support, (Lamination) of the core-less substrate, which does not peel off the carrier foil from the ultra-thin copper foil with a carrier for forming a wiring, and which can be mechanically peeled . Specifically, the preferable range is 0.02 kN / m to 0.1 kN / m.

Therefore, in the present invention, it is presumed that one kind of ultra-thin copper foil with a carrier is used, and in the heat treatment for 1 hour at a temperature up to 220 ° C, the workability at the time of peeling of the carrier foil A good low carrier strength is realized. On the other hand, with the ultra-thin copper foil with a carrier used as a support, by carrying out heat treatment in advance at a high temperature (for example, at 350 占 폚 for 10 minutes), a high carrier fill strength suitable for a coreless substrate support is realized. By realizing such a high carrier fill strength, it is possible to reduce the defect that the carrier foil of the support body peels off at an unintended stage even under the load such as the etching treatment at the time of forming a circuit in the coreless substrate production process, Do.

For example, in the ultra-thin copper foil with a carrier of the present invention, when the carrier foil is peeled from the ultra-thin copper foil with a carrier after heat treatment at 220 ° C for 1 hour, the peel strength T1 is less than 0.02 kN / m, It is preferable that the fill strength T2 when the carrier foil is peeled off from the ultra-thin copper foil with a carrier after the heat treatment for 10 minutes is 0.02 kN / m to 0.1 kN / m.

When the fill strength T1 after heat treatment at 220 占 폚 for 1 hour is less than 0.02 kN / m, it is easy to peel off the carrier foil from the ultra-thin copper foil with a carrier for wiring formation. If the fill strength T2 after the heat treatment at 350 占 폚 for 10 minutes is less than 0.02 kN / m, the carrier foil is peeled off from the ultra-thin copper foil with the carrier for wiring formation in the layer formation (lamination) There is a possibility that the carrier foil may be unintentionally peeled off from the ultra-thin copper foil with a carrier used as a support. On the other hand, if the fill strength T2 after the heat treatment at 350 占 폚 for 10 minutes is more than 0.1 kN / m, the carrier foil is removed from the ultra-thin copper foil with the carrier used as the support in the post- It is difficult to mechanically peel off the film and tends to cause bending and warpage, which may cause damage to the produced coreless substrate, which is not preferable.

In particular, the present invention is characterized in that the difference (T2-T1) between the peel strength T2 after heat treatment at 350 deg. C for 10 minutes and the peel strength T1 after heat treatment at 220 deg. C for 1 hour is in the range of 0.015 to 0.080 kN / m Is more suitable. By setting the difference (T2-T1) between the peel strengths T2 and T1 in the range of 0.015 to 0.080 kN / m, it is possible to prevent the carrier (s) from the ultra- It is possible to prevent the carrier foil from being unintentionally peeled off from the ultra thin copper foil with a carrier used as a support when stripping the foil, The carrier foil can be mechanically peeled off from the ultra-thin copper foil.

As described above, the release layer 13 of the present invention is composed of the first release layer 14 and the second release layer 15, and further the outermost layer of the first release layer 14 (The boundary portion between the layer 14 and the second peeling layer 15), a metal oxide layer is preferably formed. The metal oxide layer is liable to be mechanically broken, resulting in a peeling interface. The metal oxide layer can be formed on the outermost layer by adjusting the plating conditions at the time of forming the first release layer 14. When the heat treatment is performed at a high temperature (for example, 350 DEG C), the Cu present in the first release layer 14 is diffused into the above-mentioned metal oxide layer, so that a clear metal oxide layer is lost and consequently the first release layer 14 ) And the second release layer 15 are tightly bonded to each other through the diffused Cu, thereby realizing high carrier film strength. In order to facilitate the diffusion of Cu in the first release layer 14 to the portion to be the release interface, the first release layer 14 has a thickness of 15 nm or less (more preferably 5 (More preferably, within 5 nm) from the peeling surface when a denominator of Cu, Co, Mo, Ni, Fe, W, Cr, , And the maximum value of the element ratio of Cu present up to 9 at.% To 91 at.%.

In addition, as a result of studies by the inventors of the present invention, it has been found that even when the release layer 13 is a single layer of only the first release layer 14, high carrier peel strength is caused by the same phenomenon. The configuration in which the short peeling layer 13 is composed of only the first peeling layer 14 differs depending on the kind of the plating liquid used in the strike plating process in the next step and the extremely thin copper foil 16 The peeling layer 13 is preferably formed of the first peeling layer 14 and the second peeling layer 15 that protects the peeling layer 13 because the peeling layer 13 is not peeled off at all.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The plating conditions described in the following examples are merely examples, and the present invention is not limited thereto.

[Examples 1 to 6]

(Thickness: 18 mu m) having a surface roughness Rz of one side of one side was used as the carrier foil 11 and Ni plating treatment was performed on the carrier foil 11 under the following Ni plating conditions to form a Diffusion preventing layer 12 was formed.

Ni plating condition

  Ni 50.0-200 g / L

H 3 BO 3 5.00 to 100 g / L

  pH 3.0 to 5.0

  Bath temperature 30 ~ 60 ℃

  Current density 10 to 40 A / dm 2

  Plating time 5.00 ~ 30.0s

(Co-Mo-Cu alloy plating bath composition, current density 1.0 to 10 A / dm 2, plating time 1.0 to 10 s) was formed on the carrier foil 11 on which the diffusion preventive layer 12 was formed, A first peeling layer 14 of about 4 to 10 nm was formed.

Co-Mo-Cu alloy plating conditions

  Mo 1.0-20 g / L

  Co 0.50 to 15 g / L

  Cu 0.50 - 10 g / L

  Citric acid 10.0-200 g / L

  pH 4.0 to 7.0

  Bath temperature 20 ~ 40 ℃

After the formation of the first release layer 14, the Co-Mo-Cu alloy plating bath composition as described above was used and immersed in the Co-Mo-Cu alloy plating bath for 5.0 seconds. Thereafter, using the same plating solution, A second peeling layer 15 having a density of 0.1 to 0.9 A / dm 2 and a plating time of 5.0 to 30 s and a thickness of about 1.5 to 3 nm was formed.

Subsequently, Cu strike plating was performed on the second peeling layer 15 under the following underlying Cu plating conditions, and Cu plating was performed thereon under the Cu plating conditions described below. An ultra-thin copper foil 16 of 3 mu m was formed to produce an ultra-thin copper foil 10 with a carrier.

Cu plating conditions

   10 to 50 g / L of copper pyrophosphate

   Potassium pyrophosphate 50.0 - 500 g / L

   pH 8.0 to 10.0

   Bath temperature 30 ~ 50 ℃

   Current density 0.5 to 3.0 A / dm 2

   Plating time 20.0 ~ 100s

Cu plating conditions

  Cu 10-100 g / L

H 2 SO 4 30-200 g / L

  Cl 10 to 50 ppm

  Bath temperature 30 to 70 ℃

  Current density 10 to 50 A / dm 2

  Plating time 20.0 ~ 100.0s

[Example 7]

The same diffusion barrier layer 12 as in Example 1 was formed on the same carrier foil 11 as in Example 1. On the carrier foil 11 on which the diffusion preventing layer 12 was formed, a first peeling layer 14 having a thickness of about 5 nm was formed under the following Fe-Mo-Cu alloy plating condition.

Fe-Mo-Cu alloy plating conditions

  Mo 1.0-20 g / L

  Fe 0.50 to 15 g / L

  Cu 0.60 to 10 g / L

  Citric acid 10.0-200 g / L

  pH 4.0 to 7.0

  Bath temperature 20 ~ 40 ℃

  Current density 1.0 to 10 A / dm 2

  Plating time 1.0-10s

After the first release layer 14 was formed, it was immersed in the Fe-Mo-Cu alloy plating bath for 5.0 seconds using the same Fe-Mo-Cu alloy plating bath composition as described above. After immersing in a plating bath, a second peeling layer 15 having a current density of 0.1 to 0.9 A / dm 2 and a plating time of 5.0 to 30 s and a thickness of about 2 nm was formed. Subsequently, copper strike plating and copper plating were performed on this second peeling layer 15 in the same manner as in Example 1 to form an ultra-thin copper foil 16 having a thickness of 3 占 퐉 including underlying copper plating to form an ultra- 10).

[Example 8]

The same diffusion barrier layer 12 as in Example 1 was formed on the same carrier foil 11 as in Example 1. A first peeling layer 14 having a thickness of about 5 nm was formed on the carrier foil 11 on which the diffusion preventing layer 12 was formed by using a Ni-Mo-Cu alloy plating bath shown below.

Ni-Mo-Cu alloy plating condition

  Mo 1.0-20 g / L

  Ni 0.50 to 15 g / L

  Cu 0.60 to 10 g / L

  Citric acid 10.0-200 g / L

  pH 4.0 to 7.0

  Bath temperature 20 ~ 40 ℃

  Current density 1.0 to 10 A / dm 2

  Plating time 1.0-10s

After the first release layer 14 was formed, it was immersed in the Ni-Mo-Cu alloy plating bath for 5.0 seconds. After immersion in a plating bath, a second peeling layer 15 having a current density of 0.1 to 0.9 A / dm 2 and a plating time of 5.0 to 30 s and a thickness of about 2 nm was formed. Subsequently, copper strike plating and copper plating were performed on this second peeling layer 15 in the same manner as in Example 1 to form an ultra-thin copper foil 16 having a thickness of 3 占 퐉 including underlying copper plating to form an ultra- 10).

[Example 9]

The same diffusion barrier layer 12 as in Example 1 was formed on the same carrier foil 11 as in Example 1. A first peeling layer 14 having a thickness of about 5 nm was formed on the carrier foil 11 on which the diffusion preventing layer 12 was formed under the Ni-W-Cu alloy plating conditions shown below.

Ni-W-Cu alloy plating conditions

  W 1.0 to 20 g / L

  Ni 0.50 to 15 g / L

  Cu 0.60 to 10 g / L

  Citric acid 10.0-200 g / L

  pH 4.0 to 7.0

  Bath temperature 20 ~ 40 ℃

  Current density 1.0 to 10 A / dm 2

  Plating time 1.0-10s

After the first release layer 14 was formed, it was immersed in a Ni-W-Cu alloy plating bath for 5.0 seconds. After immersing in a plating bath, a second peeling layer 15 having a current density of 0.1 to 0.9 A / dm 2 and a plating time of 5.0 to 30 s and a thickness of about 2 nm was formed. Subsequently, copper strike plating and copper plating were performed on this second peeling layer 15 in the same manner as in Example 1 to form an ultra-thin copper foil 16 having a thickness of 3 占 퐉 including underlying copper plating to form an ultra- 10).

[Example 10]

The same diffusion barrier layer 12 as in Example 1 was formed on the same carrier foil 11 as in Example 1. The first release layer 14 having a thickness of about 5 nm was formed on the carrier foil 11 on which the diffusion preventing layer 12 was formed under the following conditions of Cr-Cu alloy plating.

Cr-Cu alloy plating conditions

  Cr 1.0 to 20 g / L

  Cu 0.60 to 10 g / L

  pH 3.5 to 5.0

  Bath temperature 20 ~ 30 ℃

  Current density 1.0 to 10 A / dm 2

  Plating time 1.0-10s

After the first release layer 14 was formed, it was immersed in the Cr-Cu alloy plating bath for 5.0 seconds. After immersing in a plating bath, a second peeling layer 15 having a current density of 0.1 to 0.9 A / dm 2 and a plating time of 5.0 to 30 s and a thickness of about 2 nm was formed. Subsequently, copper strike plating and copper plating were performed on this second peeling layer 15 in the same manner as in Example 1 to form an ultra-thin copper foil 16 having a thickness of 3 占 퐉 including underlying copper plating to form an ultra- 10).

[Example 11]

The same diffusion barrier layer 12 as in Example 1 was formed on the same carrier foil 11 as in Example 1. A first peeling layer 14 having a thickness of about 5 nm was formed on the carrier foil 11 on which the diffusion preventing layer 12 was formed under the Ni-Cu alloy plating conditions shown below.

Ni-Cu alloy plating condition

  Ni 0.50 to 15 g / L

  Cu 0.60 to 10 g / L

  pH 4.0 to 6.0

  Bath temperature 20 ~ 40 ℃

  Current density 1.0 to 10 A / dm 2

  Plating time 1.0-10s

After the first release layer 14 was formed, it was immersed in the Ni-Cu alloy plating bath for 5.0 seconds. After immersing in a plating bath, a second peeling layer 15 having a current density of 0.1 to 0.9 A / dm 2 and a plating time of 5.0 to 30 s and a thickness of about 2 nm was formed. Subsequently, copper strike plating and copper plating were performed on this second peeling layer 15 in the same manner as in Example 1 to form an ultra-thin copper foil 16 having a thickness of 3 占 퐉 including underlying copper plating to form an ultra- 10).

[Comparative Example 1]

The same diffusion barrier layer 12 as in Example 1 was formed on the same carrier foil 11 as in Example 1. Co-Mo (Cu components other than Cu are the same as in Examples 1 to 6) alloy plating bath on the carrier foil 11 on which the diffusion preventive layer 12 was formed were used in Examples 1 to 6, A first peeling layer 14 having a thickness of about 4 nm is formed at the same bath temperature, current density and plating time. After the formation of the first peeling layer 14, a Co-Mo alloy plating bath containing no Cu And then a second peeling layer 15 having a thickness of about 2 nm was formed under the same plating conditions as in Example 1 by using a Co-Mo alloy plating bath not containing Cu.

Subsequently, copper strike plating and copper plating were performed on this second peeling layer 15 in the same manner as in Example 1 to form an ultra-thin copper foil 16 having a thickness of 3 占 퐉 including underlying copper plating to form an ultra- 10).

[Comparative Example 2]

The same diffusion barrier layer 12 as in Example 1 was formed on the same carrier foil 11 as in Example 1. Mo-Cu alloy plating bath having the same composition as those of Examples 1 to 6 except that the Cu concentration was 0.15 g / L on the carrier foil 11 on which the diffusion preventing layer 12 was formed A first peeling layer 14 having a thickness of about 4 nm was formed at the same bath temperature, current density and plating time as in Examples 1 to 6, and after forming the first peeling layer 14, 0.15 g / L of Cu Cu-Al alloy plating bath containing 0.15 g / L of Cu was used for the plating bath of the Co-Mo-Cu alloy for 5.0 seconds, A second release layer 15 was formed.

Subsequently, copper strike plating and copper plating were carried out on this second peeling layer 15 in the same manner as in Example 1 to form an ultra-thin copper foil 16 having a thickness of 3 탆 including underlying copper plating to form an ultra-thin copper foil with a carrier 10).

[Comparative Example 3]

The same diffusion barrier layer 12 as in Example 1 was formed on the same carrier foil 11 as in Example 1. Mo-Cu alloy plating bath having the same composition as in Examples 1 to 6 except that the Cu concentration was 20 g / L on the carrier foil 11 on which the diffusion preventing layer 12 was formed. A first peeling layer 14 having a thickness of about 8 nm was formed at the same bath temperature, current density and plating time as those of the first to sixth peeling layers 1 to 6. After the formation of the first peeling layer 14, a Co- Mo-Cu alloy plating bath for 5.0 seconds and thereafter a Co-Mo-Cu alloy plating bath containing 20 g / L of Cu was used to conduct a second peeling with a thickness of about 3 nm under the same plating conditions as in Example 1 Layer 15 was formed. Subsequently, copper strike plating and copper plating were carried out on this second peeling layer 15 in the same manner as in Example 1 to form an ultra-thin copper foil 16 having a thickness of 3 탆 including underlying copper plating to form an ultra-thin copper foil 10 with a carrier ).

[Comparative Example 4]

The diffusion preventive layer was not formed on the same carrier foil 11 as in Example 1 and Co-Mo (Cu components other than Cu is the same as those in Examples 1 to 6) A first peeling layer 14 having a thickness of about 4 nm is formed at the same bath temperature, current density and plating time as that of the Co-Mo alloy plating bath 14, and after forming the first peeling layer 14, And then a second peeling layer 15 having a thickness of about 2 nm was formed under the same plating conditions as in Example 1 by using a Co-Mo alloy plating bath not containing Cu.

Subsequently, copper strike plating and copper plating were carried out on this second peeling layer 15 in the same manner as in Example 1 to form an ultra-thin copper foil 16 having a thickness of 3 탆 including underlying copper plating to form an ultra-thin copper foil 10 with a carrier ).

[Comparative Example 5]

Mo-Cu alloy plating bath under the same conditions as in Example 1 without forming the diffusion barrier layer on the same carrier foil 11 as in Example 1, the same bath temperature, current density and plating time as in Examples 1 to 6 A first release layer 14 having a thickness of about 4 nm is formed on the first release layer 14 and a Co-Mo-Cu alloy plating bath composition similar to that described above is used to form the first release layer 14. The Co- A second peeling layer 15 having a thickness of about 1.5 to 3 nm was formed at a current density of 0.1 to 0.9 A / dm 2 and a plating time of 5.0 to 30 s using the same plating solution did.

Subsequently, copper strike plating and copper plating were carried out on this second peeling layer 15 in the same manner as in Example 1 to form an ultra-thin copper foil 16 having a thickness of 3 탆 including underlying copper plating to form an ultra-thin copper foil 10 with a carrier ).

The carrier foil 11 was peeled off from the ultra-thin copper foil 10 with a carrier of each sample in the prepared unheated column and the remaining elements in the release face on the side of the carrier foil 11 had a depth profile analysis (depth profile) Was measured by an electronic spectroscopic analyzer (PHI 5400 manufactured by ULVAC PIE Co., Ltd.). The sputter rate was 15.9 nm / min (in terms of SiO 2 ) and the measurement area was 1 mm square (mm square). The element of Cu existing in a depth position within 15 nm from the peeling surface when the denominator is Cu, Co, Mo, Ni, Fe, W, Cr, The maximum value of the ratio was measured. The values are shown in Table 1.

The manufactured ultra-thin copper foil with a carrier was pressed under a condition of a press pressure of 30 kgf / cm 2 at a temperature of 220 ° C for 1 hour or 350 ° C for 10 minutes to bond the ultra-thin copper foil and the prepreg. Thereafter, a circuit having a width of 10 mm was produced, and the carrier foil was peeled in a 90-degree direction using a tensile tester (manufactured by TOYOBALDWIN, UTM-4-100) based on JIS C 6481-1996 . The peel strength T1 after heat treatment at 220 deg. C for one hour and the peel strength T2 after heat treatment at 350 deg. C for 10 minutes were measured when the carrier foil was peeled off from the ultra thin copper foil with a carrier. The measurement results are shown in Table 1.

Figure 112016001059387-pct00001

[Evaluation results]

In Examples 1 to 11, when the carrier foil was peeled off from the ultra-thin copper foil with a carrier, the maximum value of the proportion of elemental Cu present at a depth of 15 nm or less from the release surface of the carrier foil side was 9.6 to 91.0 at.% . After heat treatment at 220 占 폚 for 1 hour, all of them were in the range of 0.002 to 0.015 kN / m, showing a low carrier peel strength of less than 0.02 kN / m. On the other hand, after heat treatment at 350 占 폚 for 10 minutes, all of them were in the range of 0.020 to 0.091 kN / m and exhibited high carrier peel strength in the range of 0.02 to 0.1 kN / m. As is apparent from the above-described measurement results, carrier peel strength suitable for use for fine wiring formation and for use as a support in the production of a coreless substrate is realized according to the difference in heat treatment conditions. In the above embodiment, all of the Ni plating layers are made of the diffusion preventing layer. The inventors of the present invention have also found that the same evaluation as above is made even when the Fe plating layer or the Co plating layer is used as the diffusion preventing layer so as to form the Ni plating layer and the Co plating layer as the diffusion preventing layer, It was confirmed that the same effect was obtained.

On the other hand, in Comparative Example 1, the first peeling layer and the second peeling layer were treated in a Co-Mo alloy plating bath not containing Cu, and the carrier foil was peeled off from the ultra- The maximum value of the elemental proportion of Cu existing up to the depth position within 15 nm from the iridium plane was 0At.%. Therefore, even after the heat treatment at 350 ° C for 10 minutes, the high carrier film strength did not occur. That is, the carrier foil is peeled from the ultra-thin copper foil with a carrier used as a support in an unintended stage during the laminating process at the time of producing the core-less substrate because high carrier peel strength is not caused.

In Comparative Example 2, the first peeling layer and the second peeling layer were treated with a Co-Mo-Cu alloy plating bath. However, when the carrier foil was stripped from the ultra-thin copper foil with a carrier, , The effect of increasing the high carrier film strength after heat treatment at 350 DEG C for 10 minutes was weak and the object of the present invention was not achieved. The carrier peel strength was not obtained. Therefore, the carrier foil peeled from the ultra-thin copper foil with a carrier used as a support in an unintended stage during the laminating process at the time of manufacturing the coreless substrate in the same manner as in Comparative Example 1. [

In Comparative Example 3, the first peeling layer and the second peeling layer were treated with a Co-Mo-Cu alloy plating bath. However, when the carrier foil was stripped from the ultra-thin copper foil with a carrier, , The maximum value of the elemental proportion of Cu existing up to the depth position within the range of the present invention is greater than the appropriate range of the present invention. Thus, the high carrier film strength after heat treatment at 350 캜 for 10 minutes is realized. However, it has been confirmed that when the carrier foil is peeled off, the carrier peel strength becomes too high, and the coreless substrate is damaged, such as warpage or bending.

In Comparative Example 4, the first peeling layer and the second peeling layer were treated with a Co-Mo alloy plating bath not containing Cu in the same manner as in Comparative Example 1, but the diffusion preventing layer was not formed. The maximum value of the proportion of elemental elements of Cu existing up to a depth position within 15 nm from the release face of the carrier foil when the carrier foil was peeled off from the ultra thin copper foil with a carrier did not contain Cu in the release layer, at.%, but it is considered that this is because the signal of the copper foil of the carrier foil is acquired. The carrier peel strength is more than 0.020 kN / m at the time point after the press at 220 ° C, and the carrier peel strength becomes too high, so that when the carrier foil is peeled off, damage such as warpage or breakage occurs in the core- .

In Comparative Example 5, the diffusion preventing layer was removed from Example 1. Diffusion of Cu from the carrier foil proceeded because no diffusion preventing layer was present, and the carrier peel strength exceeded 0.020 kN / m at the time point after the press at 220 ° C. As described above, when the carrier foil was peeled off, it was confirmed that the core-less substrate suffered damage such as warping or bending due to an excessively high carrier peel strength.

As a result of manufacturing the coreless substrate according to the above coreless substrate manufacturing step using the ultra-thin copper foil with carriers prepared in each of Examples 1 to 11, it was possible to peel off without any trouble in the manufacturing process and without any trouble in the peeling step.

The ultra-thin copper foil with a carrier of the present invention is based on the premise that only one kind of ultra-thin copper foil with a carrier is used, and the ultra-thin copper foil with a carrier used as a support is subjected to heat treatment at a high temperature The strength is increased within a range in which mechanical peeling is possible. On the other hand, with respect to the ultra-thin copper foil with a carrier used for forming a wiring, the carrier (copper) is removed at a temperature (for example, 150 to 220 캜) And the peel strength is not increased. By setting the carrier fill strength in such a manner by dividing the application, peeling of the carrier foil and the ultra-thin copper foil at the unintended stage during the laminating process can be prevented as a support for laminating the coreless substrate. That is, the ultra-thin copper foil with a carrier according to the present invention has an epoch-making characteristic that can be used in various cases as one product.

1: carrier foil
2: Ultra-thin copper foil
3: Ultra-thin copper foil with carrier for support
4: prepreg
5: Carrier foil
6: Ultra-thin copper foil
7: Ultra-thin copper foil with carrier for wiring formation
8: Fine wiring
9: Coreless substrate
10: Ultra-thin copper foil with carrier
11: Carrier foil
12: diffusion prevention layer
13: Release layer
14: First release layer
15: Second peeling layer
16: Ultra-thin copper foil

Claims (10)

An ultra-thin copper foil with a carrier formed by laminating a diffusion preventive layer, a release layer and an ultra-thin copper foil on a carrier foil in this order,
Wherein the peeling layer is made of a copper alloy containing Cu and at least one kind of element selected from the group consisting of Mo, W, Fe, Co and Ni, and a carrier foil is formed from the ultra- (AES) was performed on the peeled surface of the peeled and peeled carrier foil to determine the depth direction composition of the carrier foil when Cu, Co, Mo, Ni, Fe, W, C and O were denominators , And the maximum value of the proportion of elemental elements of Cu present to a depth position within 15 nm from the release surface is 9 at.% To 91 at.%,
Treated at 220 DEG C for 1 hour, peeled off the carrier foil from the ultra-thin copper foil with a carrier, and had a peel strength T1 at 20 DEG C of less than 0.02 kN / m and a heat treatment at 350 DEG C for 10 minutes. Wherein a peel strength T2 at 20 占 폚 when the carrier foil is stripped from the ultra-thin copper foil is 0.02 kN / m to 0.1 kN / m. The method according to claim 1,
Wherein the peeling layer is composed of two layers of a first peeling layer and a second peeling layer. The method according to claim 1,
(T2-T1) between the peel strength T2 at 20 占 폚 after heat treatment at 350 占 폚 for 10 minutes and the peel strength T1 at 20 占 폚 after heat treatment at 220 占 폚 for 1 hour is 0.015 to 0.080 kN / lt; RTI ID = 0.0 > m. < / RTI > 4. The method according to any one of claims 1 to 3,
Wherein the diffusion preventing layer is formed of Fe, Ni, Co, or an alloy formed by these elements. A copper clad laminate produced using the ultra-thin copper foil with a carrier according to any one of claims 1 to 3. A printed wiring board manufactured using the ultra-thin copper foil with a carrier according to any one of claims 1 to 3. A coreless substrate produced using the ultra-thin copper foil with a carrier according to any one of claims 1 to 3. A copper clad laminate produced using the ultra-thin copper foil with a carrier according to claim 4. A printed wiring board manufactured using the ultra-thin copper foil with a carrier according to claim 4. A coreless substrate produced using the ultra-thin copper foil with a carrier according to claim 4.
KR1020167000224A 2014-02-14 2015-01-23 Carrier-equipped ultrathin copper foil, and copper-clad laminate, printed circuit substrate and coreless substrate that are manufactured using same KR101803390B1 (en)

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CN105378150B (en) 2018-06-22
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CN105378150A (en) 2016-03-02
KR20160048755A (en) 2016-05-04

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