KR20190121327A - Roughened copper foil, copper foil with carrier, copper clad laminate and printed wiring board - Google Patents

Abstract

The roughening copper foil of the low roughness suitable for forming a thin wire circuit, and when used in the SAP method, can be provided with a laminate having a surface profile excellent in not only etching properties and dry film resolution to electroless copper plating but also circuit adhesion. Treated copper foil is provided. The roughening process copper foil of this invention has a roughening process surface in at least one side, is provided with the some primary roughening particle | grains which have a roughened part, and the surface which the primary roughened particle contains the constricted part. Has a plurality of secondary roughened particles smaller than the primary roughened particles, and the secondary roughened particle density, which is the value obtained by dividing the number of secondary roughened particles in the narrowed portion by the surface area of the narrowed portion, is 9 to 30 / μm ² , and is roughened Ten point average roughness Rz of a process surface is 0.7-1.7 micrometers.

Description

Roughened copper foil, copper foil with carrier, copper clad laminate and printed wiring board

This invention relates to roughening process copper foil, copper foil with a carrier, a copper clad laminated board, and a printed wiring board.

In recent years, the SAP (semi additive process) method is widely adopted as a manufacturing method of the printed wiring board suitable for refine | miniaturization of a circuit. The SAP method is a method suitable for forming a very fine circuit and is performed using a roughened copper foil provided with a carrier as one example. For example, as shown in FIG. 1 and FIG. 2, the prepreg 112 has the roughened copper foil 110 on the insulated resin substrate 111 provided with the lower layer circuit 111b in the base substrate 111a. ) And the primer layer 113 are pressed in close contact (step (a)), and the carrier (not shown) is peeled off, and then the via hole 114 is formed by laser drilling as needed (step (b)). ). Next, the roughened copper foil 110 is removed by etching to expose the primer layer 113 provided with the roughened surface profile (step (c)). After performing electroless copper plating 115 on this roughening surface (step (d)), it masks in a predetermined pattern by exposure and image development using the dry film 116 (step (e)), and electroplating ( 117) is carried out (step (f)). After removing the dry film 116 to form the wiring portion 117a (step (g)), the unnecessary electroless copper plating 115 between the adjacent wiring portions 117a and 117a is removed by etching ( Step (h)), the wiring 118 formed in a predetermined pattern is obtained.

As described above, in the SAP method using the roughened copper foil, the roughened copper foil itself is removed by etching after laser drilling (step (c)). And since the uneven | corrugated shape of the roughening process surface of a roughening process copper foil is transcribe | transferred on the laminated body surface from which the roughening process copper foil was removed, in a subsequent process, an insulation layer (for example, the primer layer 113 or a prepreg when it is absent) (112) and the plating circuit (for example, the wiring 118) can be secured. However, since the surface profile suitable for improving adhesiveness with a plating circuit tends to be rough roughness generally, the etching property with respect to an electroless copper plating in a process (h) falls easily. That is, as electroless copper plating penetrates rough roughness, more etching is required in order to remove residual copper.

Thus, a method has been proposed in which the roughened particles can be made smaller and the shrinkage portion shape can be used to achieve satisfactory etching property while securing necessary plating circuit adhesion when used in the SAP method. For example, Patent Document 1 (International Publication No. 2016/158775) is a roughened copper foil having a roughened surface on at least one side, and the roughened surface is provided with a plurality of roughly spherical protrusions made of copper particles. It is disclosed that the average height of the substantially spherical protrusions is 2.60 µm or less.

International Publication No. 2016/158775

With the miniaturization of the further layer of the circuit required by the SAP method in recent years, further miniaturization of the further layer of the roughened particle in roughening process copper foil is desired in order to implement | achieve more excellent etching property. However, the method of patent document 1 has a limit in small-hardening a roughening particle, ensuring circuit adhesiveness, and it is difficult to small-harden a roughened particle so that ten point average roughness Rz may be less than 1.7 micrometers. This is because, in the SAP method, when the roughened particles are made small in order to refine the circuit, the circuit adhesion deteriorates.

MEANS TO SOLVE THE PROBLEM This inventor provided the secondary roughening particle | grains smaller than a primary roughening particle in the surface (especially a narrow part) of the primary roughening particle which has a constricted part in sufficient density, and makes it possible to realize sufficient circuit adhesiveness, but it is ten point average. The knowledge that the roughening particle | grains can be small-hardened to the level suitable for thin line circuit formation of roughness Rz 1.7 micrometers or less was acquired. That is, when the roughness-treated copper foil of low roughness suitable for forming a thin wire circuit is used in the SAP method, it is found that the laminate can be provided with a surface profile excellent in not only the excellent etching property against the electroless copper plating but also the circuit adhesion. Got. Moreover, the knowledge that the very fine dry film resolution can be implement | achieved in the dry film developing process in SAP method by using the said roughening process copper foil was also acquired.

Accordingly, an object of the present invention is a low roughness roughened copper foil suitable for thin wire circuit formation, and when used in the SAP method, not only the etching property and dry film resolution for electroless copper plating, but also the surface profile excellent in circuit adhesion. It is providing the roughening process copper foil which can provide | coat to a laminated body. Moreover, another object of this invention is to provide the copper foil provided with the carrier provided with such roughening process copper foil.

According to 1 aspect of this invention, it is a roughening process copper foil which has a roughening process surface on at least one side, Comprising: The said roughening process surface is provided with the some primary roughening particle which has a narrow part, The said primary roughening particle Has a plurality of secondary roughened particles smaller than the primary roughened particles on the surface including the concave portions,

The second roughened particle density, which is the value obtained by dividing the number of the second roughened particles of the concave portion by the surface area of the concave portion, is 9 to 30 / m ^2, and the ten-point average roughness Rz of the roughened surface is 0.7 to 1.7 μm. Phosphorus, roughening process copper foil is provided.

According to another aspect of the present invention, there is provided a carrier, a peeling layer provided on the carrier, and a copper foil provided with a carrier provided with the roughening treatment copper foil provided on the peeling layer with the roughening treatment surface outside. Is provided.

According to another aspect of the present invention, a copper clad laminate obtained by using the roughened copper foil or the copper foil provided with the carrier is provided.

According to another aspect of the present invention, a printed wiring board obtained by using the roughened copper foil or the copper foil provided with the carrier is provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a process flowchart for demonstrating SAP method, and is a figure which shows the process (process (a)-(d)) of the first half.
FIG. 2 is a process flowchart for explaining the SAP method, and is a diagram showing the second process (steps (e) to (h)).
It is a schematic cross section which shows the roughening process surface containing primary roughening particle | grains and secondary roughening particle | grains in the roughening process copper foil of this invention.
It is a schematic cross section which shows the concave part of secondary roughening particle | grains in the roughening process copper foil of this invention.
It is a figure which shows the x-axis, y-axis, z-axis, and slice surface S in 3D-SEM observation in relationship with a roughening process copper foil.

Justice

Definitions of terms and parameters used to specify the present invention are shown below.

In this specification, "primary roughening particle" means roughness of the size exceeding 150 nm which is directly formed in the base surface 10a of the roughening process copper foil 10, as shown to FIG. 3 and FIG. It is the particle | grains 12, and typically has a form of "a roughly spherical protrusion." In this specification, an "approximately spherical protrusion" is a protrusion which has a substantially spherical round shape, and is distinguished from anisotropic protrusions or particles such as acicular, columnar and elongated shapes. As shown in FIG. 3 and FIG. 4 as the primary roughening particles 12, the roughly spherical projections are connected to the base surface 10a of the copper foil at the cut-off source portion, but cannot be a perfect sphere. The part other than a root part should just be spherical. Therefore, as long as the substantially spherical protrusion is maintained in the shape of a substantially spherical round shape, the existence of some irregularities, deformations, and the like is permitted. In addition, although the said processus | protrusion may be called only a spherical process, as mentioned above, since it cannot become a complete sphere, it should be understood as meaning the above-mentioned roughly processus | protrusion. The primary roughened particle 12 and its particle diameter can be specified by analyzing the cross-sectional image acquired by SEM observation using commercially available software. For example, three-dimensional analysis software Amira (manufactured by Thermo Fisher SCIENTIFIC Co., Ltd.) can be used, and image processing can be performed according to various conditions described in the examples of the present specification.

In this specification, "secondary roughening particle" is the surface of the base surface 10a and the primary roughening particle 12 of the roughening process copper foil 10, as shown typically in FIG.3 and FIG.4. Means the roughened particle 14 of the size smaller than the primary roughened particle 12, ie, 150 nm or less. The secondary roughened particles 14 may also be substantially granular projections such as spherical projections. The secondary roughened particle 14 and its particle diameter can be specified by analyzing the cross-sectional image acquired by SEM observation using commercially available software. For example, three-dimensional analysis software Amira (manufactured by Thermo Fisher SCIENTIFIC Co., Ltd.) can be used, and image processing can be performed according to various conditions described in the examples of the present specification.

In the present specification, the "small part" means a part 12a that is hidden by itself when viewed from directly above, as shown schematically in FIG. 4. . That is, it means the part which has the neck diameter of less than the maximum neck diameter of the primary roughening particle 12, and means the part 12a by the base surface 10a side rather than the said maximum neck diameter. The narrow part can be determined by analyzing the cross-sectional image acquired by SEM observation using commercially available software. For example, three-dimensional analysis software Amira (manufactured by Thermo Fisher SCIENTIFIC Co., Ltd.) can be used, and image processing can be performed according to various conditions described in the examples of the present specification.

In this specification, an "electrode surface" refers to the surface of the side which contacted the cathode when the metal was electrolytically precipitated.

In the present specification, the "precipitation surface" refers to the surface on the side where the metal is electrolytically deposited, that is, the surface on the side not in contact with the cathode.

Conditioning Treatment Copper Foil

The copper foil which concerns on this invention is a roughening process copper foil. This roughening process copper foil has a roughening process surface on at least one side. The roughening process surface is provided with the some primary roughening particle | grains 12 which have the constricted part 12a as shown typically in FIG. The primary roughened particles 12 have a plurality of secondary roughened particles 14 smaller than the primary roughened particles 12 on the surface including the concave portions 12a. The secondary roughened particle density, which is the value obtained by dividing the number of secondary roughened particles 14 in the concave portion 12a by the surface area of the concave portion 12a, is 9 to 30 particles / μm ² . In addition, the ten point average roughness Rz of a roughening process surface is 0.7-1.7 micrometers. Thus, by providing the secondary roughened particles 14 smaller than the primary roughened particles 12 on the surface of the primary roughened particles 12 having the concave portions 12a (particularly the concave portions 12a) with sufficient density. In the case of using the SAP method, the roughened particles can be reduced in size to a level suitable for forming a thin wire circuit of 10 points average roughness Rz of 1.7 µm or less while enabling sufficient circuit adhesion. That is, when used for the SAP method while being the roughening copper foil of low roughness suitable for thin wire circuit formation, the surface profile excellent not only the outstanding etching property to electroless copper plating but also the circuit adhesiveness can be provided to a laminated body. Moreover, by using the said roughening process copper foil, very fine dry film resolution can be implement | achieved in the dry film developing process in SAP method.

Plating circuit adhesion and etching resistance to electroless copper plating are inherently difficult to be compatible. That is, as mentioned above, since the surface profile suitable for improving adhesiveness with a plating circuit tends to become rough roughness generally, the etching property of electroless copper plating in a process (h) of FIG. 2 tends to fall. That is, as electroless copper plating penetrates rough roughness, more etching is required in order to remove residual copper. In this respect, according to the roughening process copper foil of patent document 1, it is supposed that the outstanding plating circuit adhesiveness can be ensured, realizing reduction of the etching amount. However, in recent years, since the further miniaturization of the circuit required by the SAP method is required, the roughening of the roughened particles is desired, and according to the method of Patent Document 1, it is difficult to small-harden the roughened particles so that the ten-point average roughness Rz is less than 1.7 µm. . In contrast, in the present invention, the primary roughened particles 12 are provided with the concave portions 12a, and the secondary roughened particles 14 having a sufficient density are formed in the concave portions 12a, thereby forming Without degrading the adhesiveness, it is possible to significantly reduce the size of the roughened particles to a level suitable for forming a thin wire circuit of ten point average roughness Rz of 1.7 µm or less. That is, although the circuit adhesiveness may fall originally by the small hardening of the primary roughening particle | grains 12 represented by Rz within the said range, in this invention, the surface (especially a concave part () of the primary roughening particle | grains 12 By providing the secondary roughened particles 14 at a density sufficient for 12a)), excellent circuit adhesion can be realized. And it can be considered that very fine dry film resolution can be achieved in the dry film developing process in SAP method by making it compatible with such excellent adhesiveness and the outstanding etching property with respect to an electroless copper plating. Therefore, it is preferable that the roughening process copper foil of this invention is used for preparation of the printed wiring board by a semiadditive process (SAP). In other words, it can also be said that the roughening process copper foil of this invention is used to transfer an uneven shape to the insulated resin layer for printed wiring boards.

The roughening process copper foil 10 of this invention has a roughening process surface on at least one side. That is, a roughening process copper foil may have a roughening process surface at both sides, and may have a roughening process surface only at one side. In the case where the roughening treatment surfaces are provided on both sides, the surface on the laser irradiation side (the surface opposite to the surface to be in close contact with the insulating resin) is also harmonized when used in the SAP method, so that the laser absorbency is increased, thereby improving the laser perforation properties. Can be.

The roughening process surface is provided with the some primary roughening particle | grains 12 and the some secondary roughening particle | grains 14 in the surface, These several primary roughening particle | grains 12 and secondary roughening particle | grains ( It is preferable that 14) consists of copper particles, respectively. That is, each primary roughening particle 12 and the secondary roughening particle 14 are each comprised from one copper particle fundamentally. The copper particles may be made of metallic copper, or may be made of copper alloy. However, when a copper particle is a copper alloy, since the solubility with respect to a copper etching liquid may fall, or the lifetime of an etching liquid may fall by mixing an alloy component into a copper etching liquid, it is preferable that a copper particle consists of metal copper.

The secondary roughened particle density, which is the value obtained by dividing the number of secondary roughened particles 14 of the concave portion 12a by the surface area of the concave portion 12a, is 9-30 pieces / μm ² , and preferably 9-25 pieces / μm. ² , More preferably, it is 9-20 pieces / micrometer <^2> . If it is in these ranges, circuit adhesiveness can be improved further, preventing the fall of secondary roughening particle | grains effectively.

Ten-point average roughness Rz of a roughening process surface is 0.7-1.7 micrometers, Preferably it is 0.7-1.6 micrometers, More preferably, it is 0.8-1.6 micrometers, More preferably, it is 0.8-1.5 micrometers. If it is in these ranges, circuit adhesiveness and a thin wire formation property can be improved further. Rz is determined based on JIS B0601-1994.

As for the roughening process copper foil 10 of this invention, it is preferable that the number of the secondary roughening particles 14 per unit plane area of a roughening process surface is 50-500 piece / micrometer <^2> , More preferably, it is 50-400 Pieces / µm ² , more preferably 50 to 300 pieces / µm ² . If it is in these ranges, circuit adhesiveness can be improved further, preventing the fall of secondary roughening particle | grains effectively.

As for the roughening process copper foil 10 of this invention, it is preferable that the ratio of the surface area of the narrow part which occupies for the whole surface area of the roughening process surface is 0.3-0.5, More preferably, it is 0.3-0.45. If it is in these ranges, circuit adhesiveness can be improved further, preventing the fall of secondary roughening particle | grains effectively.

Although the thickness of the roughening process copper foil 10 of this invention is not specifically limited, 0.1-18 micrometers is preferable, More preferably, it is 0.5-10 micrometers, More preferably, it is 0.5-7 micrometers, Especially preferably, it is 0.5- 5 micrometers, Most preferably, it is 0.5-3 micrometers. This thickness is the thickness containing the primary roughening particle 12 and the secondary roughening particle 14. In addition, the roughening process copper foil of this invention is not limited to what carried out the roughening process on the surface of normal copper foil, The roughening process of the copper foil surface of the copper foil with a carrier may be performed.

Manufacturing method of roughening process copper foil

Although an example of the preferable manufacturing method of the roughening process copper foil by this invention is demonstrated, the roughening process copper foil by this invention is not limited to the method demonstrated below, The surface profile of the roughening process copper foil of this invention can be realized. As long as it is manufactured by what kind of method.

(1) Preparation of copper foil

As copper foil used for manufacture of roughening process copper foil, both use of an electrolytic copper foil and a rolled copper foil is possible. Although the thickness of a copper foil is not specifically limited, 0.1-18 micrometers is preferable, More preferably, it is 0.5-7 micrometers, More preferably, it is 0.5-5 micrometers, Especially preferably, it is 0.5-3 micrometers. When the copper foil is prepared in the form of a copper foil with a carrier, the copper foil is formed by a wet film formation method such as an electroless copper plating method and an electrolytic copper plating method, a dry film formation method such as sputtering and chemical vapor deposition, or a combination thereof. It may be one.

(2) coordination treatment

Copper particles are used to roughen at least one surface of the copper foil. This roughening is performed by electrolysis using the copper electrolytic solution for roughening processes. This electrolysis is preferably performed through a three-step plating process. In the first plating process, using a copper sulfate solution containing 5 to 20 g / L copper concentration, 30 to 200 g / L sulfuric acid concentration, 20 to 100 ppm chlorine concentration and 20 to 100 ppm 9-phenylacridine 9PA concentration, It is preferable to perform electrodeposition on the plating conditions of 20-40 degreeC of liquid temperature, 5-25 A / dm <^{2> of} current density, and 2-10 second of time. In the second plating process, using a copper sulfate solution containing a copper concentration of 65 to 80 g / L and a sulfuric acid concentration of 200 to 280 g / L, a liquid temperature of 45 to 55 ℃ and a current density of 1 to 10 A / dm ² , time 2 to It is preferable to perform electrodeposition on the plating condition of 25 second. In the plating process of the 3rd step, the liquid temperature is 20-40 degreeC, using the copper sulfate solution containing 10-20 g / L of copper concentrations, 30-130 g / L sulfuric acid concentrations, 20-100 ppm of chlorine concentrations, and 100-200 ppm of 9PA concentrations. It is preferable to perform electrodeposition on the plating conditions of current density of 10-40 A / dm <^2> , time 0.3-1.0 second. Electric charge in the plating process of the second step 1 second and the second step, ratio (Q ₁ to the stored electricity quantity Q ₂ in the plating process of the second second stage of the electricity quantity Q ₁ in the plating process of the second step 1 / Q ₂ ) Is preferably set to 3.0 or more. The plating process of the second step is carried out using additives such as 9PA, also it is possible to form the first blend particles 12 having a constricted portion (12a) by satisfying the Q ₁ / Q ₂ ≥3.0. And by performing the 3rd plating process using additives, such as 9PA, the secondary roughening particle | grains 14 smaller than that can be formed in the surface of the primary roughening particle | grains 12. FIG. In particular, it is preferable that the first plating process is carried out using an additive such as 9PA or the like, and the plating processes of the _first and second stages are satisfied to satisfy Q ₁ + Q ₂ ≤ 100 C / dm ² . . By doing in this way, while the surface profile of comparatively low roughness which satisfy | fills ten point average roughness Rz <1.7 micrometer is formed, plating of a 3rd step is widely spread | diffused on the whole surface of the primary roughening particle 12, and the primary roughening particle ( Secondary roughened particles 14 are also formed at high density in the concave portion 12a of 12).

(3) antirust treatment

As needed, you may perform antirust process to the copper foil after a roughening process. It is preferable that a rust prevention process includes the plating process using zinc. The plating treatment using zinc may be either a zinc plating treatment or a zinc alloy plating treatment, and the zinc alloy plating treatment is particularly preferably a zinc-nickel alloy treatment. The zinc-nickel alloy treatment may be a plating treatment containing at least Ni and Zn, and may further include other elements such as Sn, Cr, and Co. As for the Ni / Zn adhesion ratio in zinc-nickel alloy plating, 1.2-10 are preferable by mass ratio, More preferably, it is 2-7, More preferably, it is 2.7-4. Moreover, it is preferable that an antirust process further includes a chromate treatment, and this chromate treatment is more preferably performed on the surface of the plating containing zinc after the plating process using zinc. By doing in this way, rust prevention property can be improved further. Particularly preferred antirust treatment is a combination of zinc-nickel alloy plating treatment and subsequent chromate treatment.

(4) silane coupling agent treatment

As needed, you may process a silane coupling agent to copper foil, and may form a silane coupling agent layer. Thereby, moisture resistance, chemical resistance, adhesiveness with an adhesive agent, etc. can be improved. The silane coupling agent layer can be formed by appropriately diluting and applying the silane coupling agent, and drying. As an example of a silane coupling agent, Epoxy functional silane coupling agents, such as 4-glycidyl butyl trimethoxysilane and 3-glycidoxy propyl trimethoxysilane, or 3-aminopropyl triethoxy silane, N-2 ( Aminoethyl) 3-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) butoxy) propyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimeth Amino functional silane coupling agents, such as oxysilane, or mercapto functional silane coupling agents, such as 3-mercaptopropyl trimethoxysilane, or olefin functional silane couplers, such as vinyltrimethoxysilane and vinylphenyl trimethoxysilane. Acrylic functional silane coupling agents, such as a ring agent or 3-methacryloxypropyl trimethoxysilane, or imidazole functional silane coupling agents, such as imidazolesilane, or triazine functional silane coupling agents, such as triazinesilane, etc. Can be mentioned.

Copper foil with carrier

The roughening process copper foil of this invention can be provided in the form of the copper foil provided with a carrier. In this case, the copper foil provided with a carrier is provided with the carrier, the peeling layer provided on this carrier, and the roughening process copper foil of this invention provided on this peeling layer with the roughening process surface outside. However, the well-known laminated constitution can be employ | adopted for the copper foil provided with a carrier except using the roughening process copper foil of this invention.

A carrier is a layer (typically foil) for supporting roughening process copper foil, and improving the handling property. As an example of a carrier, aluminum foil, copper foil, the resin film which coated metal on the surface with copper, etc., a glass plate, etc. are mentioned, Preferably it is copper foil. The copper foil may be either rolled copper foil or electrolytic copper foil. The thickness of the carrier is typically 200 µm or less, preferably 12 µm to 35 µm.

It is preferable that the surface on the peeling layer side of a carrier has ten-point surface roughness Rz of 0.5-1.5 micrometers, More preferably, it is 0.6-1.0 micrometer. Rz can be determined based on JIS B0601-1994. By providing such a ten-point surface roughness Rz to the surface on the peeling layer side of a carrier, it can make it easy to provide a preferable surface profile to the roughening process copper foil of this invention produced through the peeling layer on it.

A peeling layer is a layer which has a function which weakens the peeling strength of a carrier, ensures the stability of the said strength, and suppresses the interdiffusion which can arise between a carrier and copper foil at the time of press molding at high temperature. The release layer is generally formed on one side of the carrier, but may be formed on both sides. The peeling layer may be either an organic peeling layer or an inorganic peeling layer. As an example of the organic component used for an organic peeling layer, a nitrogen containing organic compound, a sulfur containing organic compound, a carboxylic acid, etc. are mentioned. A triazole compound, an imidazole compound, etc. are mentioned as an example of a nitrogen containing organic compound, Especially, a triazole compound is preferable at the point that peelability becomes easy to be stabilized. Examples of the triazole compound include 1,2,3-benzotriazole, carboxybenzotriazole, N ', N'-bis (benzotriazolylmethyl) urea, 1H-1,2,4-triazole and 3-amino -1H-1,2,4-triazole etc. are mentioned. Examples of the sulfur-containing organic compound include mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazole thiol and the like. Monocarboxylic acid, dicarboxylic acid, etc. are mentioned as an example of carboxylic acid. On the other hand, examples of the inorganic component used for the inorganic release layer include Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, chromate treated films, and the like. In addition, what is necessary is just to form a peeling layer by making a peeling layer component containing solution contact the at least one surface of a carrier, and fixing a peeling layer component to the surface of a carrier. The contact of the carrier to the release layer component-containing solution may be performed by immersion in the release layer component-containing solution, spraying of the release layer component-containing solution, or the dropping of the release layer component-containing solution. In addition, the fixing of the release layer component to the carrier surface may be performed by adsorption or drying of the release layer component-containing solution, or electrodeposition of the release layer component in the release layer component-containing solution. The thickness of a peeling layer is typically 1 nm-1 micrometer, Preferably it is 5 nm-500 nm.

As roughening process copper foil, the roughening process copper foil of this invention mentioned above is used. Although the roughening process of this invention was what performed the roughening using copper particle, as a procedure, a copper layer is first formed as copper foil on the surface of a peeling layer, and what is necessary is just to at least roughen after that. Details of the harmony are as described above. Moreover, in order to utilize the advantage as a copper foil with a carrier, it is preferable to be comprised in the form of ultra-thin copper foil. Preferable thickness as ultra-thin copper foil is 0.1 micrometer-7 micrometers, More preferably, they are 0.5 micrometer-5 micrometers, More preferably, they are 0.5 micrometer-3 micrometers.

You may provide another functional layer between a peeling layer and copper foil. An example of such another functional layer is an auxiliary metal layer. The auxiliary metal layer preferably consists of nickel and / or cobalt. It is preferable that the thickness of an auxiliary metal layer shall be 0.001-3 micrometers.

Copper Clad Laminate

It is preferable that the copper foil provided with the roughening process copper foil or carrier of this invention is used for preparation of the copper clad laminated board for printed wiring boards. That is, according to the preferable aspect of this invention, the copper clad laminated board obtained using the said roughening process copper foil or the copper foil provided with the said carrier is provided. The copper clad laminated board which is especially suitable for SAP method can be provided by using the roughening process copper foil of this invention, and copper foil provided with a carrier. This copper clad laminated board is provided with the roughening process copper foil of this invention, the resin layer provided in close contact with the roughening process surface of this roughening process copper foil, or the copper foil provided with the carrier of this invention, and this carrier It comprises the resin layer provided in close contact with the roughening process surface of the roughening process copper foil in the copper foil provided with the following. The copper foil provided with roughening process copper foil or a carrier may be provided in the single side | surface of a resin layer, and may be provided in both surfaces. The resin layer comprises a resin, preferably an insulating resin. It is preferable that a resin layer is a prepreg and / or a resin sheet. The prepreg is a generic term for a composite material in which synthetic resin is impregnated into a base such as a synthetic resin plate, glass plate, glass woven fabric, glass nonwoven fabric, paper, or the like. Preferable examples of the insulating resin include epoxy resins, cyanate resins, bismaleimide triazine resins (BT resins), polyphenylene ether resins, and phenol resins. Moreover, the insulating resin, such as an epoxy resin, a polyimide resin, and a polyester resin, is mentioned as an example of the insulating resin which comprises a resin sheet. Moreover, the filler layer etc. which consist of various inorganic particles, such as a silica and an alumina, may contain in the resin layer from a viewpoint of improving insulation. Although the thickness of a resin layer is not specifically limited, 1-1000 micrometers is preferable, More preferably, it is 2-400 micrometers, More preferably, it is 3-200 micrometers. The resin layer may be composed of a plurality of layers. Resin layers, such as a prepreg and / or a resin sheet, may be provided in the roughening process copper foil or the copper foil provided with a carrier through the primer resin layer previously apply | coated to the copper foil surface.

Printed wiring board

It is preferable to be used for preparation of a printed wiring board, and the copper foil provided with the roughening process copper foil or carrier of this invention is especially used for preparation of the printed wiring board by a semiadditive process (SAP). That is, according to the preferable aspect of this invention, the printed wiring board obtained using the roughening process copper foil mentioned above or the copper foil provided with the said carrier is provided. By using the roughening process copper foil or the copper foil provided with carrier of this invention, in manufacture of a printed wiring board, not only the outstanding plating circuit adhesiveness but the surface profile excellent also in the etching property with respect to electroless copper plating can be given to a laminated body. . Moreover, by using the said roughening process copper foil, very fine dry film resolution can be implement | achieved in the dry film developing process in SAP method. Therefore, the printed wiring board in which the very fine circuit formation was performed can be provided. The printed wiring board according to this aspect includes a layer structure in which a resin layer and a copper layer are laminated in this order. In the case of SAP method, since the roughening process copper foil of this invention is removed in process (c) of FIG. 1, the printed wiring board produced by SAP method does not contain the roughening process copper foil of this invention anymore, and is a roughening process copper foil Only the surface profile transferred from the roughening process surface of remains. In addition, about a resin layer, it is as having mentioned above regarding the copper clad laminated board. Anyway, a well-known layer structure can be employ | adopted for a printed wiring board. As a specific example regarding a printed wiring board, the single-sided or double-sided printed wiring board which circuit-formed after these were made into the laminated body which adhered and hardened the copper foil with roughening process copper foil or carrier of this invention to one side or both sides of a prepreg, and multilayered these. A multilayer printed wiring board etc. are mentioned. Moreover, as another specific example, the flexible printed wiring board, COF, TAB tape, etc. which form the circuit by forming the copper foil provided with the roughening process copper foil or carrier of this invention on a resin film are mentioned. As another specific example, the copper foil with resin which apply | coated the resin layer mentioned above is formed in the roughening process copper foil or the copper foil with a carrier of this invention, and a resin layer is used for the above-mentioned printed circuit board as an insulation adhesive material layer. After lamination | stacking, the semiconducting semi-additive (MSAP) method, the subtractive method, etc. formed the circuit by the roughening process copper foil as a whole or a part of wiring layer, and the build-up wiring board, and the roughening process copper foil were removed, and the semi The build-up wiring board which formed the circuit by the additive (SAP) method, the direct build-up wafer which alternately repeats lamination | stacking and circuit formation of copper foil with resin on a semiconductor integrated circuit, etc. are mentioned. As a further developmental example, an electronic device for panel display or an electronic material for window glass, in which a copper foil with the resin is laminated on a substrate, and the circuit element is formed by laminating it on glass or a resin film through an adhesive layer and forming a pattern. And the electromagnetic wave shield film which apply | coated the electrically conductive adhesive agent to the roughening process copper foil of this invention, etc. are mentioned. In particular, the copper foil provided with the roughening process copper foil or carrier of this invention is suitable for SAP method. For example, when the circuit is formed by the SAP method, the configuration as shown in Figs. 1 and 2 can be adopted.

Example

This invention is demonstrated further more concretely by the following example.

Examples 1 to 4

Preparation and evaluation of the roughening process copper foil were performed as follows.

(1) production of carriers

As a cathode, a titanium electrode whose surface was polished with a # 2000 buff was prepared. In addition, DSA (dimension stable anode) was prepared as an anode. Using these electrodes, the copper sulfate solution was immersed in a copper sulfate solution having a copper concentration of 80 g / L and a sulfuric acid concentration of 260 g / L, and electrolyzed at a solution temperature of 45 ° C. and a current density of 55 A / dm ² to obtain an electrolytic copper foil having a thickness of 18 μm as a carrier. .

(2) Formation of Peeling Layer

The electrode surface side of the pickled carrier was immersed in a CBTA aqueous solution of 1 g / L CBTA (carboxybenzotriazole) concentration, 150 g / L sulfuric acid concentration and 10 g / L copper concentration for 30 seconds at a liquid temperature of 30 ° C. Was adsorbed on the electrode surface. In this way, a CBTA layer was formed on the surface of the electrode surface of the carrier as an organic release layer.

(3) formation of auxiliary metal layer

The carrier is an organic release layer is formed, is immersed in a solution of a nickel concentration of 20g / L produced by using the nickel sulfate, at a liquid temperature of 45 ℃, pH3, the conditions of a current density of 5A / dm ^2, the amount of deposition of nickel with a thickness equivalent 0.001㎛ Was deposited on an organic release layer. In this manner, a nickel layer was formed on the organic release layer as an auxiliary metal layer.

(4) ultra-thin copper foil formation

The carrier on which the auxiliary metal layer was formed was immersed in a copper sulfate solution having a copper concentration of 60 g / L and a sulfuric acid concentration of 200 g / L, electrolytic at a solution temperature of 50 ° C. and a current density of 5 to 30 A / dm ² , and an ultrathin copper foil having a thickness of 1.2 μm. It was formed on the auxiliary metal layer.

(5) coordination treatment

The roughening process was performed about the precipitation surface of the ultra-thin copper foil mentioned above. This roughening process was performed by the following three steps of plating, but the plating of the 1st step was divided into 2 times. In the plating process of each step, the current shown in Table 2 at the liquid temperature shown in Table 1 using the copper sulfate solution having the copper concentration, sulfuric acid concentration, chlorine concentration and 9-phenylacridine (9PA) concentration shown in Table 1 Electrodeposition was performed at the density. The energization time in the plating of the 1st stage and the 2nd stage was 4.4 second per time, and the electricity supply time in the plating of the 3rd stage was 0.6 second. Thus, four types of roughening process copper foils of Examples 1-4 were produced.

(6) antirust treatment

The antirust process which consists of a zinc- nickel-alloy plating process and the chromate process was performed to the surface of the roughening process layer of the copper foil provided with the obtained carrier. First, the surface of the roughening process layer and the carrier under the conditions of a liquid temperature of 40 ° C. and a current density of 0.5 A / dm ² using an electrolyte solution of zinc concentration 0.2 g / L, nickel concentration 2 g / L and potassium pyrophosphate concentration 300 g / L. The zinc-nickel alloy plating process was performed to it. Next, using a 1 g / L aqueous solution of chromic acid, chromate treatment was performed on the surface subjected to zinc-nickel alloy plating under conditions of pH 11, a liquid temperature of 25 ° C., and a current density of 1 A / dm ² .

(7) silane coupling agent treatment

The aqueous solution containing 3 g / L of 3-aminopropyl trimethoxysilane was adsorb | sucked to the surface of the copper foil side of the copper foil with a carrier, and the silane coupling agent process was performed by evaporating water with an electric heater. At this time, the silane coupling agent process was not performed to the carrier side.

(8) Evaluation of roughened copper foil surface

About the obtained roughening process copper foil, the various characteristics of the surface profile containing a primary roughening particle and a secondary roughening particle were evaluated as follows.

(8-1) Evaluation of three-dimensional shape by 3D-SEM

Various surface profile data was obtained by 3D-SEM observation of the roughening process surface of the obtained roughening process copper foil. Using the obtained data, three parameters for evaluating the three-dimensional shape of the roughened surface (the secondary roughened particle density of the narrowed portion, the number of secondary roughened particles per plane area and the ratio of the surface area of the narrowed portion) were calculated. . Specifically, it is as follows.

(8-1-1) 3D-SEM Observation

Using a FIB-SEM apparatus (SMF-1000 manufactured by Hitachi High-Tech Science Co., Ltd. or Crossbeam540 manufactured by Carl Zeiss, both models equipped with a GEMINI column), the measurement area of 10 μm × 10 μm (= 100 μm ² ) of the roughened surface , Three-dimensional shape data was acquired under the following measurement conditions. Acquisition of this three-dimensional shape data, as shown in FIG. 5, makes x-axis and z-axis the in-plane direction of the roughening copper foil 10, and y-axis is the thickness direction of the roughening copper foil 10. FIG. After the definition, the cross-sectional image of the roughened copper foil 10 in the slice plane S parallel to the xy plane is obtained, and the slice plane is moved in parallel in the z-axis direction by 10 nm in the measurement area. It carried out by acquiring 900 cross-sectional images in total.

<SEM condition>

Acceleration voltage: 0.5 mA

Aperture: 30 μm

-Scan time: 20 seconds / field of view

Detector: Inlens-SE

Image Scale: 10㎛ (x direction length)

<FIB condition>

Acceleration voltage: 30 mA

-3nA irradiation current

Feed: 10 nm (spacing of the slice plane S)

Depth: 15-30 μm (set according to sample shape)

(8-1-2) 3D-SEM Image Analysis

Various data about the roughening process surface were acquired by analyzing 900 slice images of the three-dimensional shape data of the roughening process copper foil obtained by 3D-SEM using three-dimensional analysis software Amira (made by Thermo Fisher SCIENTIFIC). Specifically, it is as follows.

Dictionary Interpretation: Determination of the Negatives

According to the definition mentioned above in this specification, the narrow part of primary roughening particle | grains was determined.

<Plane area A of the measurement area>

Planar area A of the measurement area was 9.9 μm (X direction) × 9 μm (Z direction) = 89.1 μm ² .

<Surface area B of the measurement area>

The surface area B of the measurement area was calculated | required by the surface area calculation function in Amira.

<Surface area C of the narrowed part>

In surface area B of a measurement area | region, the surface area corresponded to the narrow part was made into the surface area C of the narrow part.

<Total number of secondary harmonic particles D>

The function "Remove Island" of Amira was applied to each direction of XY plane, YZ plane, and ZX plane, and the primary roughening particle and the secondary roughening particle were isolate | separated. At this time, the size was set to 15 pixels (150 nm) or less on each plane, and the fraction set value was 0.25. After removing the thing of volume 20000nm <^3> or less from the obtained secondary roughening particle | grains, the number of secondary roughening particle | grains was counted and the total number was made into the total number D of secondary roughening particle | grains.

<Number of Secondary Harmonic Particles in Cutouts E>

Of the secondary roughened particles obtained by D, those present in the narrowed portions were separated, the number thereof was counted, and the number of secondary roughened particles E in the narrowed portions was set.

(8-1-3) Calculation of Evaluation Parameter

The secondary roughened particle density of the narrowed portion was calculated by dividing the number of secondary roughened particles E of the narrowed portion by the surface area C of the narrowed portion. The number of secondary roughened particles per plane area was calculated by dividing the total number D of secondary roughened particles by the plane area A of the measurement area. The ratio which the surface area of a narrow part occupies was computed by dividing the surface area C of a narrow part by the surface area B of a measurement area.

(8-2) Measurement of Ten Point Average Roughness Rz

The roughening process surface was observed using the laser microscope (VK-9510 made from Keyence Co., Ltd.) provided with the objective lens of 150 times, and the visual image of 6550.11 micrometer <^2> was acquired. From the obtained field-of-view image, 10 places of 10 micrometers x 10 micrometers were arbitrarily selected in the range which does not overlap with each other, and ten point average roughness Rz was measured based on JISB0601-1994, respectively. The average value of ten Rz was employ | adopted as Rz of this sample.

(9) Production of copper clad laminate

The copper clad laminated board was produced using the copper foil provided with a carrier. First, the roughening process copper foil of the copper foil with a carrier was laminated | stacked on the surface of an inner layer board through a prepreg (Mitsubishi Gas Chemical Co., Ltd. make, GHPL-830NSF, thickness 0.1mm), and pressure 4.0 Mpa, temperature After thermocompression bonding at 220 degreeC for 90 minutes, the carrier was peeled off and the copper clad laminated board was produced.

(10) Preparation of the laminate for SAP evaluation

Subsequently, after removing all copper foil on the surface with sulfuric acid and a hydrogen peroxide etching liquid, degreasing, Pd type catalyst provision, and activation process were performed. Thus, the electroless copper plating (thickness: 1 micrometer) was performed to the activated surface, and the laminated body immediately before a dry film adheres in the SAP method (henceforth a laminated body for SAP evaluation) was obtained. These processes were performed in accordance with well-known conditions of the SAP method.

(11) Evaluation of Laminate for SAP Evaluation

About the said laminated body for SAP evaluation, evaluation of various characteristics was performed as follows.

Plating Circuit Adhesion (Peeling Strength)

The dry film was stuck to the laminated body for SAP evaluation, and exposure and development were performed. After depositing a 19-micrometer-thick copper layer on the laminated body masked with the developed dry film by pattern plating, the dry film was peeled off. The electroless copper plating expressed by the sulfuric acid and hydrogen peroxide etching liquid was removed, and the sample for peeling strength measurement of 20 micrometers in height, and width 10mm was produced. Peeling strength at the time of peeling a copper layer from the sample for evaluation was measured based on JISC6481 (1996).

<Etchability>

The laminate for SAP evaluation was etched by 0.2 µm each with sulfuric acid and hydrogen peroxide etching solution, and the amount (depth) until the surface copper completely disappeared was measured. This measurement was performed by confirming with an optical microscope (500 times). In more detail, each time 0.2 micrometer etching was carried out, the operation | work which checked the presence or absence of copper with an optical microscope was repeated, and the value (micrometer) obtained by (number of etchings) x 0.2 micrometer was used as an index of etching property. For example, that the etching property is 1.2 µm means that the residual copper is not detected by the optical microscope at the time of performing 0.2 µm etching six times (that is, 0.2 µm x 6 times = 1.2 µm). That is, the smaller this value is, the smaller the number of etching means that the copper on the surface can be removed. That is, the smaller this value, the better the etching property.

<Dry Film Resolution (Minimum L / S)>

A dry film having a thickness of 25 µm was attached to the surface of the laminate for SAP evaluation, and exposure and development were performed using a mask in which a line / space (L / S) pattern was formed from 2 µm / 2 µm to 15 µm / 15 µm. Was performed. The exposure amount at this time was 125 mJ. The sample surface after development was observed with an optical microscope (magnification: 500 times), and the minimum (that is, the finest) L / S in the L / S that could be developed without a problem was employed as an index of dry film resolution. . For example, the minimum L / S = 10 μm / 10 μm, which is an index of dry film resolution evaluation, means that resolution was possible from L / S = 15 μm / 15 μm to 10 μm / 10 μm without any problem. do. For example, when the resolution can be solved without problems, sharp contrast is observed between the dry film patterns, whereas when resolution is not performed well, blackish portions are observed between the dry film patterns, and no sharp contrast is observed. .

result

The evaluation result obtained in Examples 1-4 was as showing in Table 3 and Table 4.

As shown in Table 4, all of Examples 1 and 2 were good either in plating circuit adhesiveness, etching property, or dry film resolution. On the other hand, Example 3 (comparative) was inferior in plating circuit adhesiveness. In addition, Example 4 (comparative) was inferior to etching property and dry film resolution.

Claims (8)

It is a roughening process copper foil which has a roughening process surface in at least one side, Comprising: The said roughening process surface is equipped with the some primary roughening particle which has a narrow part, and the said primary roughening particle is included in the surface containing the said narrow part. Has a plurality of secondary roughened particles smaller than the primary roughened particles,
The second roughened particle density, which is the value obtained by dividing the number of the second roughened particles of the concave portion by the surface area of the concave portion, is 9 to 30 / m ^2, and the ten-point average roughness Rz of the roughened surface is 0.7 to 1.7 μm. Phosphorus, Conditioning Treatment Copper Foil. The method of claim 1,
The roughening process copper foil whose number of the said 2nd roughening particles per unit plane area of the said roughening process surface is 50-500 piece / micrometer <^2> . The method according to claim 1 or 2,
The roughening process copper foil whose ratio of the surface area of the said constricted part which occupies for the whole surface area of the said roughening process surface is 0.3-0.5. The method according to any one of claims 1 to 3,
Roughening process copper foil used for transferring an uneven | corrugated shape to the insulated resin layer for printed wiring boards. The method according to any one of claims 1 to 4,
The roughening process copper foil used for manufacture of the printed wiring board by the semiadditive process (SAP). The carrier provided with the carrier, the peeling layer provided on the said carrier, and the roughening process copper foil in any one of Claims 1-5 provided on the said peeling layer with the said roughening process surface outside. One copper foil. The copper clad laminated board obtained using the roughening process copper foil of any one of Claims 1-5, or the copper foil provided with the carrier of Claim 6. The printed wiring board obtained using the roughening process copper foil of any one of Claims 1-5, or the copper foil provided with the carrier of Claim 6.

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