JP5399582B2 - Copper foil with carrier, method for producing copper foil with carrier, copper foil with carrier for printed wiring board and printed wiring board - Google Patents

Description

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

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

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

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

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

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

On the other hand, the copper foil for a semiconductor package substrate is generally referred to as a copper foil for a printed wiring board, but is usually produced by the following process. First, a copper foil is laminated and bonded to a base material such as a synthetic resin under high temperature and pressure. Next, in order to form a target conductive circuit on the substrate, a circuit equivalent to the circuit is printed on the copper foil with a material such as an etching resistant resin.
Then, unnecessary portions of the exposed copper foil are removed by an etching process. After the etching, the printed part made of a material such as resin is removed to form a conductive circuit on the substrate. A predetermined element is finally soldered to the formed conductive circuit to form various printed circuit boards for electronic devices.
Finally, it is joined to a resist or a build-up resin substrate. In general, the quality requirements for copper foil for printed wiring boards differ between an adhesive surface (so-called roughened surface) to be bonded to a resin substrate and a non-adhesive surface (so-called glossy surface), and satisfy both of them simultaneously. is necessary.

The requirements for glossy surfaces are: (1) good appearance and no oxidation discoloration during storage, (2) good solder wettability, (3) no oxidation discoloration when heated at high temperatures, (4 ) Good adhesion to the resist is required.
On the other hand, for the roughened surface, mainly (1) no oxidation discoloration during storage, (2) the peel strength from the substrate is high temperature heating, wet processing, soldering, chemical processing, etc. And (3) lamination with a base material, no so-called lamination spots that occur after etching, and the like.
In recent years, with the refinement of patterns, there has been a demand for low profile copper foil. Accordingly, it is necessary to increase the peel strength of the roughened copper foil surface.

Furthermore, in electronic devices such as personal computers and mobile communications, the frequency of electrical signals has been increasing with the increase in communication speed and capacity, and printed wiring boards and copper foils that can cope with this have been demanded. . When the frequency of the electric signal is 1 GHz or more, the influence of the skin effect in which current flows only on the surface of the conductor becomes significant, and the influence that the current transmission path changes due to the unevenness of the surface and the impedance increases cannot be ignored. Also from this point, it is desired that the surface roughness of the copper foil is small.
Many processing methods have been proposed for copper foils for printed wiring boards in order to meet these demands.

Generally, copper foil for printed wiring boards is processed using rolled copper foil or electrolytic copper foil. First, in order to increase the adhesion (peel strength) between the copper foil and the resin, in general, fine particles composed of copper and copper oxide are used. The roughening process provided to the copper foil surface is performed. Next, a heat-resistant treatment layer (barrier layer) such as brass or zinc is formed in order to impart heat resistance and rust prevention characteristics.
And in order to prevent surface oxidation etc. during conveyance or storage on this, it is made into a product by performing rust prevention treatment such as immersion or electrolytic chromate treatment or electrolytic chromium / zinc treatment.

Among these, the roughening treatment layer plays a major role in increasing the adhesive strength (peel strength) between the copper foil and the resin. Conventionally, it has been considered that this roughening treatment is good for round (spherical) protrusions. This rounded protrusion is achieved by suppressing the development of dendrites. However, this rounded protrusion was peeled off during etching, resulting in a phenomenon of “powder off”. This phenomenon is natural. This is because the contact area between the spherical protrusion and the copper foil is very small compared to the diameter of the round (spherical) protrusion.
In order to avoid this “powder-off” phenomenon, a thin copper plating layer was formed on the protrusions after the roughening treatment to prevent the protrusions from peeling off (see Patent Document 1). This has the effect of preventing “powder falling”, but there are problems that the number of steps increases and the effect of preventing “powder falling” differs depending on the thin copper plating.

Moreover, the technique of forming the acicular nodular coating layer which consists of an alloy of copper and nickel on copper foil is known (patent document 2). Since this nodular coating layer has a needle shape, it is considered that the adhesive strength with the resin is increased as compared with the round (spherical) protrusions disclosed in Patent Document 1, but with the copper foil as the base It is a copper-nickel alloy having different components, and has different etching rates when etching to form a copper circuit. Therefore, there is a problem that it is not suitable for stable circuit design.

When forming the copper foil for printed wiring boards, a heat-resistant / rust-proofing layer is generally formed. As an example of a metal or alloy for forming a heat-resistant treatment layer, many copper foils on which a coating layer such as Zn, Cu—Ni, Cu—Co, and Cu—Zn is formed have been put into practical use (for example, see Patent Document 3). ).
Among these, copper foil with a heat-resistant treatment layer made of Cu-Zn (brass) has no stain on the resin layer when laminated on a printed circuit board made of epoxy resin, etc., and peeling after high-temperature heating Since it has excellent characteristics such as little deterioration in strength, it is widely used industrially.
The method of forming the heat-resistant treatment layer made of brass is described in detail in Patent Document 4 and Patent Document 5.

After roughening the surface of the copper foil, rust-proofing zinc or zinc alloy, and chromating, the surface after chromating is adsorbed with a silane coupling agent containing a small amount of chromium ions to resist hydrochloric acid. There has been a proposal to improve (see Patent Document 7).

JP-A-8-236930 Japanese Patent No. 3449964 Japanese Patent Publication No. 51-35711 Japanese Patent Publication No.54-6701 Japanese Patent No. 3306404 Japanese Patent Application No. 2002-170827 JP-A-3-122298 WO2004 / 005588

The present invention relates to a copper foil for a printed wiring board with a carrier excellent in chemical resistance and adhesiveness, a manufacturing method thereof, a resin substrate for a printed wiring board and a printed wiring board. In particular, it is possible to obtain strong peeling strength against chemical treatment during fine pattern formation, and fine etching is possible for package substrates typified by BT (bismaleimide / triazine) resin-impregnated base materials. A copper foil with a carrier, a method for producing the same, and a printed wiring board are provided.
In particular, a copper foil for a printed wiring board with a carrier capable of improving the roughening treatment and process of the copper foil and enhancing the adhesive strength between the copper foil and the resin, its manufacturing method, the resin substrate for the printed wiring board, and the printed wiring board It is an issue to provide.

In order to solve the above-mentioned problems, the present inventors have conducted intensive studies, and as a result, the following copper foil for a printed wiring board with a carrier, a manufacturing method thereof, and a printed wiring board are provided.

1) On the surface of the ultra-thin copper layer of the carrier-added copper foil in which the carrier, the intermediate layer, and the ultra-thin copper layer are laminated in this order, the average diameter D1 of the particle root at a position of 10% of the particle length is 0.2 μm to A copper foil with a carrier, characterized by having a roughened layer having a ratio L1 / D1 of 1.0 μm and a particle length L1 to an average diameter D1 of the particle root of 15 or less.

2) The ratio D2 / D1 of the average diameter D2 of the particle center at the position of 50% of the particle length to the average diameter D1 of the particle root is 1 to 4 on the surface of the ultrathin copper layer. Item 4. A copper foil with a carrier according to item 1.
3) The copper foil with a carrier according to claim 2, wherein the ratio D2 / D3 of the average diameter D2 at the center of the particle and the particle tip D3 at a position of 90% of the particle length is 0.8 to 1.0.
4) The copper foil with a carrier according to claim 2 or 3, wherein an average diameter of the particle center D2 is 0.7 to 1.5 µm.

5) The copper foil with a carrier according to claim 3 or 4, wherein an average diameter D3 of the particle tip is 0.7 to 1.5 µm.
6) A heat-resistant / rust-proof layer containing at least one element selected from zinc, nickel, copper, phosphorus, and cobalt on the roughened layer, a chromate film layer on the heat-resistant / rust-proof layer, and The copper foil with a carrier according to any one of claims 1 to 5, further comprising a silane coupling agent layer on the chromate film layer.

7) Roughening treatment according to any one of claims 1 to 6, using an electrolytic bath composed of sulfuric acid and copper sulfate containing at least one substance selected from alkyl sulfate salts, tungsten and arsenic. A method for producing a copper foil with a carrier, comprising forming a layer.
8) A heat-resistant / rust-proof layer containing at least one element selected from zinc, nickel, copper, phosphorus, and cobalt is formed on the roughened layer, and then chromate is formed on the heat-resistant / rust-proof layer. The method for producing a copper foil with a carrier according to claim 7, wherein a film layer is formed, and a silane coupling agent layer is further formed on the chromate film layer.

9) After laminating the carrier-added copper foil and the resin layer having a roughened layer on the surface of the ultrathin copper layer of the carrier-added copper foil in which the carrier, the intermediate layer, and the ultrathin copper layer are laminated in this order, the carrier And the total area occupied by the holes in the roughened resin surface is 20% or more on the surface of the resin where the intermediate layer is peeled from the ultrathin copper layer and then the ultrathin copper layer is removed by etching. A copper foil with a carrier for a printed wiring board.
10) After laminating a resin on the copper foil with a carrier having the roughened layer according to any one of claims 1 to 8, the carrier and the intermediate layer are peeled off from the ultrathin copper layer, and then the ultrathin copper In the resin from which the layer has been removed by etching, the total area occupied by the holes in the roughened resin surface having the irregularities transferred to the roughened surface of the ultrathin copper layer is 20% or more. Copper foil with carrier.

11) After laminating a carrier-added copper foil and a resin layer having a roughened layer on the surface of the ultrathin copper layer of the carrier-added copper foil in which a carrier, an intermediate layer, and an ultrathin copper layer are laminated in this order, the carrier And the intermediate layer is peeled from the ultrathin copper layer, and then the surface of the resin from which the ultrathin copper layer has been removed by etching is plated in the order of electroless copper plating / electrolytic plating to form a copper layer, A printed wiring board with a circuit formed by etching.

12) After laminating the copper foil with carrier and the resin layer having the roughened layer according to any one of claims 1 to 8, the carrier and the intermediate layer are peeled off from the ultrathin copper layer, and then the ultrathin A printed wiring board in which the surface of the resin from which the copper layer has been removed by etching is plated in the order of electroless copper plating and electrolytic plating, thereby forming a copper layer and further forming a circuit by etching.
13) The printed wiring board according to claim 11 or 12, wherein five or more acicular particles are present in a circuit width of 10 μm.

As described above, the copper foil for a printed wiring board with a carrier of the present invention is not a rounded (spherical) projection of a roughening treatment that has been conventionally considered good, but on at least one surface of the copper foil, It forms needle-shaped or rod-shaped fine roughened particles.
This copper foil enhances the adhesive strength with the resin, and it is possible to increase the peel strength against chemical treatment when forming a fine pattern on the substrate for the package. It has the outstanding effect that a wiring board can be provided. In addition, this copper foil with carrier removes the entire copper layer by etching once, and the roughened surface is transferred to the resin layer, so that the copper plating layer for the circuit (electroless plating layer) formed on the resin surface thereafter. It is also useful for construction methods that increase adhesion to
In recent years, printed circuit copper foils (semiconductor package substrate copper foil) and semiconductor package substrate copper foils and semiconductor package resins made by bonding semiconductor package resins are becoming increasingly important as printed circuits have become finer and higher in frequency. It is valid.

It is a schematic explanatory drawing of a particle size. It is the SEM photograph (right side) of the resin (replica) surface which removed the copper layer by etching, after laminating | stacking resin on the copper layer and the FIB-SIM photograph (left side) of the roughening process layer of Example 1. FIG. It is the SEM photograph (right side) of the resin (replica) surface which laminated | stacked resin on the FIB-SIM photograph and the copper layer of the roughening process layer of the comparative example 1, and removed the copper layer by the etching.

Next, in order to facilitate understanding of the present invention, the present invention will be described specifically and in detail. The copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil.
As described above, the copper foil for a printed wiring board with a carrier of the present invention is not a rounded (spherical) projection of a roughening treatment, which has been considered good in the past, but on at least one surface of the copper foil, It forms rod-shaped fine copper roughened particles.

The shape is such that the average diameter D1 of the particle root at 10% of the particle length is 0.2 μm to 1.0 μm, and the ratio L1 / D1 between the particle length L1 and the average diameter D1 of the particle root is 15 or less. It has a roughened layer of copper foil. As a more desirable shape, on at least one surface of the copper foil, the ratio D2 / D1 of the average diameter D2 of the particle center at the position of 50% of the particle length and the average diameter D1 of the particle root is 1 to 4. It is.
Further, the ratio D2 / D3 of the average diameter D2 at the particle center to the particle tip D3 at a position of 90% of the particle length can be set to 0.8 to 1.0. In this case, it is desirable that the average diameter of the particle center D2 is 0.7 to 1.5 μm, and the average diameter D3 of the particle tip is 0.7 to 1.5 μm.

  FIG. 1 is a schematic explanatory diagram of particle dimensions. Fig. 1 shows the average diameter D1 of the particle root at the position of 10% of the particle length, the average diameter D2 of the particle center at the position of 50% of the particle length, and the particle tip D3 at the position of 90% of the particle length. Show. Thereby, the shape of the particles can be specified.

Further, on the roughened layer, a heat-resistant / rust-proof layer containing at least one element selected from zinc, nickel, copper, phosphorus, cobalt, a chromate film layer and a heat-resistant / rust-proof layer on the heat-resistant / rust-proof layer A silane coupling agent layer can be formed on the chromate film layer.

These copper foil roughening treatment layers can be formed using an electrolytic bath made of sulfuric acid / copper sulfate containing at least one substance selected from alkyl sulfate salts, tungsten, and arsenic. This can be achieved by arbitrarily setting the electrolytic treatment conditions so as to obtain a shape. Furthermore, a heat / rust preventive layer containing at least one element selected from zinc, nickel, copper, phosphorus, and cobalt is formed on the roughened layer, and then chromate is formed on the heat / rust preventive layer. A film layer can be formed, and a silane coupling agent layer can be formed on the chromate film layer.
The copper foil and resin on which the roughening layer is formed can be formed into a laminate by means of a press method or a laminate method.

Further, when the resin is laminated on the copper foil having the roughened layer as described above and the copper layer is removed by etching, the unevenness of the roughened surface of the copper foil is transferred to the resin from which the copper layer has been removed. The unevenness of the transferred resin indicates the shape and number distribution of roughened particles on the surface of the copper foil, and is important. In the case where the base of the rough surface of the copper foil is thin, the diameter of the hole is small, and the total area occupied by the holes on the resin surface is small.

The so-called reverse teardrop-shaped particles with narrow roots on the rough surface of the copper foil seem to increase the adhesive strength between the copper foil and the resin, but the adhesion width between the copper layer and the roughened particles is narrow. In addition, when the copper layer and the resin layer are peeled off, the roughened particles are easily cut from the roots, and peeled at the interface between the copper layer and the roughened particles or at the roots of the roughened particles, resulting in a decrease in adhesion. The total area occupied by the holes on the resin surface must be 20% or more.

In addition, when the root of the rough surface of the copper foil is thin, the holes on the surface of the resin from which the copper layer has been removed by etching are small, so even when electroless plating is formed on the resin surface, the electroless plating solution Does not enter and electroless plating is incomplete. Naturally, the problem arises that the peel strength of the plating is reduced.
As described above, the roughened surface of the copper foil needs to have a certain diameter and length, and the total area occupied by the holes on the resin surface having the unevenness onto which the rough surface of the copper foil is transferred is important. By making this 20% or more, the peeling strength of the circuit can be improved.

As described above, after laminating a resin layer on a copper foil having a roughened layer, the copper surface is removed by etching, and then the copper layer is formed in the order of electroless copper plating and electrolytic copper plating. In addition, a printed wiring board in which a circuit is formed by etching can be obtained, but the electroless plating / electrolytic plating layer (copper layer) is formed on the rough surface of the resin substrate, and the uneven surface of the resin surface is formed. Reflecting, needle-like particles or rod-like particles are formed.
It is desirable that five or more needle-like particles or rod-like particles are present in a circuit width of 10 μm, which can greatly improve the adhesive strength between the resin and the electroless plating or the circuit layer. The present invention provides a printed wiring board formed as described above.

As described above, the roughening layer made of fine copper roughening particles in the form of needles or rods is an electrolysis made of sulfuric acid / copper sulfate containing at least one substance selected from alkyl sulfate salts, tungsten, and arsenic. It can be manufactured using a bath.
It is desirable that the roughening treatment layer composed of fine needle-like copper particles is covered with an electrolytic bath made of sulfuric acid / copper sulfate to prevent powder falling and to improve peel strength.

Specific processing conditions are as follows.
(Liquid composition 1)
Cu: 10-30g / L
H ₂ SO ₄ : 10 ~ 150g / L
W: 0-50mg / L
Sodium dodecyl sulfate: 0-50mg
As: 0 to 2000 mg / L

(Electroplating condition 1)
Temperature: 30 ~ 70 ℃
(Current condition 1)
Current density: 25 ~ 110A / dm ²
Roughening coulomb amount: 50 to 500 As / dm ²
Plating time: 0.5-20 seconds
(Liquid composition 2)
Cu: 20-80g / L
H ₂ SO ₄ : 50 ~ 200g / L

(Electroplating condition 2)
Temperature: 30 ~ 70 ℃
(Current condition 2)
Current density: 5-50 A / dm ²
Roughening coulomb amount: 50-300 As / dm ²
Plating time: 1-60 seconds

Furthermore, a heat-resistant / rust-proof layer further containing at least one element selected from zinc, nickel, copper, phosphorus and cobalt on the roughened layer, a chromate film layer on the heat-resistant / rust-proof layer And a silane coupling agent layer can be formed on the chromate film layer to obtain a copper foil for printed wiring boards.
The heat and rust preventive layer is not particularly limited, and a conventional heat and rust preventive layer can be used. For example, a conventionally used brass coating layer can be used for a copper foil for a semiconductor package substrate.

Further, a chromate film layer and a silane coupling agent layer are formed on the heat and rust preventive layer to form an adhesive surface of the copper foil with at least the resin. A copper foil having a coating layer composed of a chromate film layer and a silane coupling agent layer is laminated and bonded to a resin, and an etching-resistant printed circuit is formed on the copper foil. Unnecessary portions of the foil are removed by etching to form a conductive circuit.

As the heat-resistant / rust-proof layer, existing treatments can be used. Specifically, for example, the following can be used.
(Liquid composition)
NaOH: 40-200g / L
NaCN: 70-250g / L
CuCN: 50-200g / L
Zn (CN) ₂ : _{2 to} 100 g / L
As ₂ O ₃ : 0.01-1g / L
(Liquid temperature)
40 ~ 90 ° C
(Current condition)
Current density: 1-50A / dm ²
Plating time: 1 to 20 seconds

As the chromate film layer, an electrolytic chromate film layer or an immersion chromate film layer can be used. The chromate film layer preferably has a Cr content of 25-150 μg / dm ² .
When the Cr content is less than 25 μg / dm ² , there is no rust preventive layer effect. In addition, if the Cr amount exceeds 150 μg / dm ² , the effect is saturated and is wasted. Therefore, the Cr content is preferably 25-150 μg / dm ² .
Examples of conditions for forming the chromate film layer are described below. However, as described above, it is not necessary to be limited to this condition, and any known chromate treatment can be used. This rust prevention treatment is one of the factors affecting the acid resistance, and the acid resistance is further improved by the chromate treatment.

(a) Immersion chromate treatment
K ₂ Cr ₂ O ₇ : 1 to 5 g / L, pH: 2.5 to 4.5, Temperature: 40 to 60 ° C, Time: 0.5 to 8 seconds
(b) Electrolytic chromate treatment (chromium / zinc treatment (alkaline bath))
K ₂ Cr ₂ O ₇ : 0.2 to 20 g / L, acid: phosphoric acid, sulfuric acid, organic acid, pH: 1.0 to 3.5, temperature: 20 to 40 ° C, current density: 0.1 to 5 A / dm ² , time: 0.5-8 seconds

(c) Electrolytic chromium / zinc treatment (alkaline bath)
K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L, NaOH or KOH: 10 to 50 g / L, ZnOH or ZnSO ₄ · 7H ₂ O: 0.05 to 10 g / L, pH : 7-13, bath temperature: 20 to 80 ° C, current density: 0.05~5A / dm ^2, time: 5-30 seconds
(d) Electrolytic chromate treatment (chromium / zinc treatment (acid bath))
_{K 2 Cr 2 O 7: 2~10g} / L, Zn: 0~0.5g / L, Na 2 SO 4: 5~20g / L, pH: 3.5~5.0, bath temperature: 20 to 40 ° C, current density : 0.1 ~ 3.0A / dm ² 、 Time: 1 ~ 30sec

As the silane coupling agent layer used for the copper foil for a semiconductor package substrate of the present invention, a silane coupling agent usually used for a copper foil can be used, and there is no particular limitation. For example, specific conditions for the silane treatment are as follows.
After spray application of 0.2 vol% 3-glycidoxypropyltrimethoxysilane aqueous solution, it is dried and heated in air at 100 to 200 ° C. for 0.1 to 10 seconds.
The thing containing 1 or more types of alkoxysilane provided with the functional group which has the reactivity of tetraalkoxysilane and resin can also be used. Although the selection of the silane coupling agent layer is arbitrary, it can be said that the selection considering the adhesiveness with the resin is desirable.

(Career)
For the carrier of the copper foil with a carrier of the present invention, a foil of copper foil, aluminum foil, aluminum alloy foil or iron alloy, stainless steel, nickel, nickel alloy or the like can be used. In consideration of the ease of stacking the intermediate layer on the carrier, the carrier is preferably a copper foil. The copper foil used for the carrier is typically provided in the form of a rolled copper foil or an electrolytic copper foil. In general, the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll.

Copper foil materials include high-purity copper such as tough pitch copper and oxygen-free copper, for example, copper containing Sn, copper containing Ag, copper alloy added with Cr, Zr, Mg, etc., Corson type added with Ni, Si, etc. Copper alloys such as copper alloys can also be used. In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.

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

(Middle layer)
An intermediate layer is provided on the carrier. The intermediate layer of the copper foil with a carrier of the present invention is Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, or an alloy thereof, or a hydrate thereof, or an oxide thereof, or It is preferable to form a layer containing one or more organic substances. The intermediate layer may be a plurality of layers.

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

Further, for example, the intermediate layer can be composed of two layers of Ni and Cr. The Ni layer is laminated in contact with the interface with the copper foil carrier, and the Cr layer is in contact with the interface with the ultrathin copper layer. The adhesion amount of the intermediate layer of Cr deposition amount of 10~100μg / dm ^2, Ni can be set with 1000~40000μg / dm ^2.

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

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

Next, examples and comparative examples will be described. In addition, a present Example shows a suitable example, This invention is not limited to these Examples. Accordingly, all modifications and other examples or aspects included in the technical idea of the present invention are included in the present invention.
In addition, the comparative example was published for contrast with this invention.

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

(Ni layer)
Nickel sulfate: 200-300g / L
Trisodium citrate: 2-10g / L
pH: 2-4
Bath temperature: 40-70 ° C
Current density: 1 ~ 15A / dm ²

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

Subsequently, on a continuous roll-to-roll type plating line, an ultrathin copper layer having a thickness of 2 to 15 μm is formed on the Cr layer by electroplating under the conditions shown in the following examples and comparative examples. A copper foil with a carrier was produced.
・ Ultra-thin copper layer Copper concentration: 30 ~ 120g / L
H ₂ SO ₄ concentration: 20-120 g / L
Electrolyte temperature: 20-80 ° C
Nika: 1-20ppm
Current density: 10-100A / dm ²

Example 1
Using the copper foil with carrier (ultra thin copper layer thickness 5μm, ultra thin copper layer roughening surface roughness: Rz0.6μm) by the above treatment, on the rough surface (matte surface: M surface) of this copper foil The following roughening plating was performed. The processing conditions are shown below. These are all steps for forming a roughened layer on the copper foil of the present invention. The ratio of limiting current density during the formation of coarse particles was 2.50.
(Liquid composition 1)
Cu: 15g / L
H ₂ SO ₄ : 100 g / L
W: 3mg / L
Sodium dodecyl sulfate addition amount: 10ppm
(Electroplating temperature 1) 50 ° C

After the roughening treatment, normal plating shown below was performed. The processing conditions are shown below.
(Liquid composition 2)
Cu: 40g / L
H ₂ SO ₄ : 100 g / L
(Electroplating temperature 1) 40 ° C
(Current condition 1)
Current density: 30 A / dm ²
Roughening coulomb amount: 150 As / dm ²

Next, electrolytic chromate treatment was performed on the heat-resistant / rust-proof layer.
Electrolytic chromate treatment (chromium / zinc treatment (acid bath))
CrO ₃ : 1.5g / L
Zn SO ₄・ 7H ₂ O: 2.0g / L
Na ₂ SO ₄ : 18g / L
pH: 4.6
Bath temperature: 37 ° C
Current density: 2.0A / dm ²
Time: 1 to 30 seconds (PH adjustment is performed with sulfuric acid or potassium hydroxide)
Next, silane treatment (by coating) was performed on the chromate film layer.
The conditions for the silane treatment are as follows.
0.2% 3-Glycidoxypropyltrimethoxysilane

An FIB-SIM photograph of the roughened layer of Example 1 is shown on the left side of FIG. The surface roughness Rz of this roughening treatment layer is 1.17 μm, the average diameter D1 of the particle root at a position of 10% of the particle length is 0.57 μm, the particle length L1 is 2.68, the average diameter D1 of the particle root The ratio L1 / D1 is 4.74, and it can be seen from FIG. 2 that the particles are formed in the shape of needles or rods. The measurement of the diameter of the roughened particles is based on JIS H 0501 item 7 cutting method.

The average diameter D1 of the particle root at a position of 10% of the particle length of the present invention is 0.2 μm to 1.0 μm, and the ratio L1 / D1 between the particle length L1 and the average diameter D1 of the particle root is 15 or less. The conditions of the present invention of the roughened layer of foil were satisfied. This condition is an essential requirement for achieving the present invention. The results are shown in Table 1.

Table 1 shows the average particle diameter (width) D1: 0.57 at the root of the roughened particles, the average diameter D2 at the center, 0.83, the average diameter at the tip D3: 0.68, and the average diameter at the center and the average of the roots. Diameter ratio: D2 / D1 = 1.47, Ratio of tip average diameter to root average diameter: D3 / D1 = 1.21, Ratio of tip average diameter to center average diameter: D3 / D2 = 0.83 However, all of these met the preferable requirements of the present invention.
However, it should be easily understood that these are not primary requirements of the present invention, that is, they are not essential requirements. It just shows more preferable conditions.

Next, using this copper foil, the resin was laminated on the copper foil using GHPL-830MBT as the resin. The SEM photograph of the resin (replica) surface from which the copper layer on which the resin is laminated is removed by etching is shown on the right side of FIG.
The total area occupied by holes on the resin surface with irregularities transferred to the roughened surface of the copper foil is 51%, the density of the holes is 2.10 / μm ² , and the total area occupied by the holes of the present invention is 20% It can be seen that the above conditions are satisfied.

What laminated | stacked resin (GHPL-830MBT) on copper foil as mentioned above was measured as a normal-state peel strength of a laminated body, and the peel strength after a heating, and the result is similarly shown in Table 1. The circuit width of peel strength is 10 mm. The normal peel strength was 1.01 kg / cm, and the peel strength after heating was 0.94 kg / cm. Both peel strengths were improved as compared with Comparative Examples described later.

(Example 2)
Using the copper foil with carrier (ultra thin copper layer thickness 5μm, ultra thin copper layer roughening surface roughness: Rz0.6μm) by the above treatment, on the rough surface (matte surface: M surface) of this copper foil The following rough plating and normal plating similar to Example 1 were performed. The roughening plating treatment conditions are shown below. These are all steps for forming a roughened layer on the copper foil of the present invention. The ratio of the limiting current density during the formation of coarse particles was 3.10.

(Liquid composition 1)
Cu: 15g / L
H ₂ SO ₄ : 100 g / L
W: 3mg / L
Sodium dodecyl sulfate addition amount: 10ppm
(Electroplating temperature 1) 50 ° C

The surface roughness Rz of this roughening treatment layer is 1.51 μm, the average diameter D1 of the particle root at a position of 10% of the particle length is 0.51 μm, the particle length L1 is 2.68 μm, the average diameter of the particle root The ratio L1 / D1 with D1 is 5.21, and it can be seen from FIG. 2 that the particles are formed in the shape of needles or rods. The measurement of the diameter of the roughened particles is based on JIS H 0501 item 7 cutting method.

The average diameter D1 of the particle root at a position of 10% of the particle length of the present invention is 0.2 μm to 1.0 μm, and the ratio L1 / D1 between the particle length L1 and the average diameter D1 of the particle root is 15 or less. The conditions of the present invention of the roughened layer of foil were satisfied. This condition is an essential requirement for achieving the present invention. The results are shown in Table 1.

Table 1 shows the flat particle diameter (width) D1: 0.51 μm at the base of the roughened particles, the average diameter D2 at the center: 0.78 μm, the average diameter at the tip D3: 0.68 μm, and the average diameter at the center. Ratio of root average diameter: D2 / D1 = 1.51 Ratio of tip average diameter to root average diameter: D3 / D1 = 1.32 Ratio of tip average diameter to center average diameter: D3 / D2 = 0.87 was shown, all of which met the preferable requirements of the present invention.
However, it should be easily understood that these are not primary requirements of the present invention, that is, they are not essential requirements. It just shows more preferable conditions.

Next, using this copper foil, using GHPL-830MBT (product name, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as the resin, the resin was laminated on the copper foil, and then the copper layer was removed by etching. The total area occupied by the holes on the resin surface having irregularities transferred to the roughened surface of the copper foil is 29%, the density of the holes is 1.93 holes / μm ² , and the total area occupied by the holes of the present invention is 20% It can be seen that the above conditions are satisfied.

What laminated | stacked resin on copper foil as mentioned above was measured as a normal-state peel strength of the laminated body of a laminated body, and the peel strength after a heating, and the result is similarly shown in Table 1. The circuit width of peel strength is 10mm. The normal peel strength was 0.81 kg / cm, and the peel strength after heating was 0.78 kg / cm. Both peel strengths were improved as compared with Comparative Examples described later.

(Example 3)
Using the copper foil with carrier (ultra thin copper layer thickness 5μm, ultra thin copper layer roughening surface roughness: Rz0.6μm) by the above treatment, on the rough surface (matte surface: M surface) of this copper foil The following rough plating and normal plating similar to Example 1 were performed. The roughening plating treatment conditions are shown below. These are all steps for forming a roughened layer on the copper foil of the present invention. The ratio of the limiting current density when forming coarse particles was 4.30.

(Liquid composition 1)
Cu: 15g / L
H ₂ SO ₄ : 100 g / L
W: 3mg / L
Sodium dodecyl sulfate addition amount: 10ppm
(Electroplating temperature 1) 50 ° C

The surface roughness Rz of this roughening treatment layer is 1.56 μm, the average diameter D1 of the particle root at a position of 10% of the particle length is 0.59 μm, the particle length L1 is 2.68 μm, the average diameter of the particle root The ratio L1 / D1 with D1 is 4.52, and it can be seen from FIG. 2 that the particles are formed in the shape of needles or rods. The measurement of the diameter of the roughened particles is based on JIS H 0501 item 7 cutting method.

The average diameter D1 of the particle root at a position of 10% of the particle length of the present invention is 0.2 μm to 1.0 μm, and the ratio L1 / D1 between the particle length L1 and the average diameter D1 of the particle root is 15 or less. The conditions of the present invention of the roughened layer of foil were satisfied. This condition is an essential requirement for achieving the present invention. The results are shown in Table 1.

In addition to the flat particle diameter (width) D1: 0.51μm at the base of the roughened particles, Table 1 shows the average diameter D2: 0.73μm at the center, average diameter D3: 0.65μm at the tip, and the average diameter at the center. Ratio of root average diameter: D2 / D1 = 1.23 Ratio of tip average diameter to root average diameter: D3 / D1 = 1.10 Ratio of tip average diameter to center average diameter: D3 / D2 = 0.89 was shown, all of which met the preferable requirements of the present invention.
However, it should be easily understood that these are not primary requirements of the present invention, that is, they are not essential requirements. It just shows more preferable conditions.

Next, using this copper foil, using MBT-830 as a resin and laminating the resin on the copper foil, the copper layer was removed by etching.
The total area occupied by the holes on the resin surface having irregularities transferred to the roughened surface of the copper foil is 43%, the density of the holes is 1.77 / μm ² , and the total area occupied by the holes of the present invention is 20% It can be seen that the above conditions are satisfied.

What laminated | stacked resin on copper foil as mentioned above was measured as the normal-state peel strength of a laminated body, and the peel strength after a heating, and the result is similarly shown in Table 1. The circuit width of peel strength is 10mm. The normal peel strength was 0.84 kg / cm, and the peel strength after heating was 0.77 kg / cm. Both peel strengths were improved as compared with Comparative Examples described later.

Example 4
Using the copper foil with carrier (ultra-thin copper layer thickness 3μm, ultra-thin copper layer roughening surface roughness: Rz0.6μm) by the above treatment on the rough surface (matte surface: M surface) of this copper foil The following rough plating and normal plating similar to Example 1 were performed. The roughening plating treatment conditions are shown below. These are all steps for forming a roughened layer on the copper foil of the present invention. The ratio of the limiting current density during the formation of coarse particles was 3.50.

(Liquid composition 1)
Cu: 15g / L
H ₂ SO ₄ : 100 g / L
W: 3mg / L
Sodium dodecyl sulfate addition amount: 10ppm
(Electroplating temperature 1) 50 ° C

The surface roughness Rz of this roughening treatment layer is 1.62 μm, the average diameter D1 of the particle root at the position of 10% of the particle length is 0.89 μm, the particle length L1 is 2.98 μm, the average diameter of the particle root The ratio L1 / D1 with D1 is 3.33, and it can be seen from FIG. 2 that the particles are formed in the shape of needles or rods. The measurement of the diameter of the roughened particles is based on JIS H 0501 item 7 cutting method.

The average diameter D1 of the particle root at a position of 10% of the particle length of the present invention is 0.2 μm to 1.0 μm, and the ratio L1 / D1 between the particle length L1 and the average diameter D1 of the particle root is 15 or less. The conditions of the present invention of the roughened layer of foil were satisfied. This condition is an essential requirement for achieving the present invention. The results are shown in Table 1.

Table 1 shows the flat particle diameter (width) D1: 0.89μm at the base of the roughened particles, the average diameter D2 at the center: 1.65μm, the average diameter at the tip D3: 0.98μm, and the average diameter at the center. Ratio of root average diameter: D2 / D1 = 1.18 Ratio of tip average diameter to root average diameter: D3 / D1 = 1.10 Ratio of tip average diameter to center average diameter: D3 / D2 = 0.93 was shown, all of which met the preferable requirements of the present invention.
However, it should be easily understood that these are not primary requirements of the present invention, that is, they are not essential requirements. It just shows more preferable conditions.

Next, after using this copper foil and laminating the resin on the copper foil using GHPL-830MBT as a resin, the copper layer was removed by etching.
The total area occupied by holes on the resin surface with irregularities transferred to the roughened surface of the copper foil is 78%, the density of the holes is 2.02 / μm ² , and the total area occupied by the holes of the present invention is 20% It can be seen that the above conditions are satisfied.

What laminated | stacked resin on copper foil as mentioned above was measured as the normal-state peel strength of a laminated body, and the peel strength after a heating, and the result is similarly shown in Table 1. The circuit width of peel strength is 10mm. The normal peel strength was 0.90 kg / cm, and the peel strength after heating was 0.86 kg / cm. Both peel strengths were improved as compared with Comparative Examples described later.

(Example 5)
Using the copper foil with carrier (ultra-thin copper layer thickness 2μm, ultra-thin copper layer roughening surface roughness: Rz0.6μm) by the above treatment on the rough surface (matte surface: M surface) of this copper foil The following rough plating and normal plating similar to Example 1 were performed. The roughening plating treatment conditions are shown below. These are all steps for forming a roughened layer on the copper foil of the present invention. The ratio of limiting current density during the formation of coarse particles was 4.80.

(Liquid composition 1)
Cu: 15g / L
H ₂ SO ₄ : 100 g / L
W: 3mg / L
Sodium dodecyl sulfate addition amount: 10ppm
(Electroplating temperature 1) 50 ° C

The surface roughness Rz of this roughening treatment layer is 1.01 μm, the average diameter D1 of the particle root at the position of 10% of the particle length is 0.26 μm, the particle length L1 is 2.68 μm, the average diameter of the particle root The ratio L1 / D1 with D1 is 10.34, and it can be seen from FIG. 2 that the particles are formed in the shape of needles or rods. The measurement of the diameter of the roughened particles is based on JIS H 0501 item 7 cutting method.

The average diameter D1 of the particle root at a position of 10% of the particle length of the present invention is 0.2 μm to 1.0 μm, and the ratio L1 / D1 between the particle length L1 and the average diameter D1 of the particle root is 15 or less. The conditions of the present invention of the roughened layer of foil were satisfied. This condition is an essential requirement for achieving the present invention. The results are shown in Table 1.

In addition to the flat grain diameter (width) D1: 0.26μm at the base of the roughened particles, Table 1 shows the average diameter D2: 0.84μm at the center, the average diameter D3 at the tip D3: 0.79μm, and the average diameter at the center. Ratio of root average diameter: D2 / D1 = 3.23, Ratio of tip average diameter to root average diameter: D3 / D1 = 3.06, Ratio of tip average diameter to center average diameter: D3 / D2 = 0.95 was shown, all of which met the preferable requirements of the present invention.
However, it should be easily understood that these are not primary requirements of the present invention, that is, they are not essential requirements. It just shows more preferable conditions.

Next, using this copper foil, the resin was laminated on the copper foil using GHPL-830MBT as the resin.
The total area occupied by the holes on the resin surface having irregularities to which the roughened surface of the copper foil is transferred is 40%, the density of the holes is 2.65 pieces / μm ² , and the total area occupied by the holes of the present invention is 20% It can be seen that the above conditions are satisfied.

What laminated | stacked resin on copper foil as mentioned above was measured as the normal-state peel strength of a laminated body, and the peel strength after a heating, and the result is similarly shown in Table 1. The circuit width of peel strength is 10mm. The normal peel strength was 0.91 kg / cm, and the peel strength after heating was 0.84 kg / cm. Both peel strengths were improved as compared with Comparative Examples described later.

(Example 6)
Using the copper foil with a carrier (ultra thin copper layer thickness 12μm, ultra thin copper layer roughening surface roughness: Rz0.6μm) by the above treatment, on the rough surface (matte surface: M surface) of this copper foil The following rough plating and normal plating similar to Example 1 were performed. The roughening plating treatment conditions are shown below. These are all steps for forming a roughened layer on the copper foil of the present invention. The ratio of the limiting current density when forming coarse particles was set to 3.20.

(Liquid composition 1)
Cu: 15g / L
H ₂ SO ₄ : 100 g / L
W: 3mg / L
Sodium dodecyl sulfate addition amount: 10ppm
(Electroplating temperature 1) 50 ° C

The surface roughness Rz of this roughening treatment layer is 1.48 μm, the average diameter D1 of the particle root at a position of 10% of the particle length is 0.60 μm, the particle length L1 is 2.68 μm, the average diameter of the particle root The ratio L1 / D1 with respect to D1 is 4.44, and it can be seen from FIG. 2 that the particles are formed in the shape of needles or rods. The measurement of the diameter of the roughened particles is based on JIS H 0501 item 7 cutting method.

The average diameter D1 of the particle root at a position of 10% of the particle length of the present invention is 0.2 μm to 1.0 μm, and the ratio L1 / D1 between the particle length L1 and the average diameter D1 of the particle root is 15 or less. The conditions of the present invention of the roughened layer of foil were satisfied. This condition is an essential requirement for achieving the present invention. The results are shown in Table 1.

In addition to the flat particle diameter (width) D1: 0.60μm at the base of the roughened particles, Table 1 shows the average diameter D2: 0.84μm at the center, average diameter D3: 0.78μm at the tip, and the average diameter at the center. Ratio of root average diameter: D2 / D1 = 1.39 Ratio of tip average diameter to root average diameter: D3 / D1 = 1.30 Ratio of tip average diameter to center average diameter: D3 / D2 = 0.94 was shown, all of which met the preferable requirements of the present invention.
However, it should be easily understood that these are not primary requirements of the present invention, that is, they are not essential requirements. It just shows more preferable conditions.

Next, using this copper foil and using GHPL-830MBT as the resin to form a laminate of the copper foil and the resin, the copper layer was removed by etching.
The total area occupied by the holes on the roughened resin surface having the transferred uneven surface of the copper foil is 93%, the density of the holes is 2.22 holes / μm ² , and the total area occupied by the holes of the present invention is It can be seen that the condition of 20% or more is satisfied.

What laminated | stacked resin on copper foil as mentioned above was measured as the normal-state peel strength of a laminated body, and the peel strength after a heating, and the result is similarly shown in Table 1. The circuit width of peel strength is 10mm. The normal peel strength was 0.91 kg / cm, and the peel strength after heating was 0.91 kg / cm. Both peel strengths were improved as compared with Comparative Examples described later.

(Comparative Example 1)
Using the copper foil with carrier (ultra thin copper layer thickness 5μm, ultra thin copper layer roughening surface roughness: Rz0.6μm) by the above treatment, on the rough surface (matte surface: M surface) of this copper foil The following rough plating and normal plating similar to Example 1 were performed. The roughening plating treatment conditions are shown below. The limiting current density ratio during the formation of roughened particles was 10.50.

(Liquid composition 1)
Cu: 15g / L
H ₂ SO ₄ : 100 g / L
W: 3mg / L
Sodium dodecyl sulfate addition amount: 10ppm
(Electroplating temperature 1) 50 ° C

An SEM photograph of the roughened layer of Comparative Example 1 is shown on the left side of FIG. The surface roughness Rz of this roughened layer is 1.13 μm, the average diameter D1 of the particle root at a position of 10% of the particle length is 0.12 μm, the root width is small, the particle length L1 is 3.87, and the particles The ratio L1 / D1 to the root average diameter D1 is 30.97, and it can be seen from FIG. 3 that the particles are formed in a needle-like or dendrite-like particle shape that is not suitable for the present invention. The measurement of the diameter of the roughened particles is based on JIS H 0501 item 7 cutting method.

As described above, the average diameter D1 of the particle root at a position of 10% of the particle length of the present invention is 0.2 μm to 1.0 μm, and the ratio L1 / D1 between the particle length L1 and the average diameter D1 of the particle root is It did not satisfy the conditions of the invention of the present invention, ie, a roughened layer of copper foil of 15 or less. The results are shown in Table 1.

In addition to the flat particle diameter (width) D1: 0.12μm at the base of the roughened particles, Table 1 shows the average diameter D2 of 0.74μm, the average diameter D3 of the tip D3: 0.74μm, and the average diameter of the center. Ratio of root average diameter: D2 / D1 = 5.93 Ratio of tip average diameter to root average diameter: D3 / D1 = 5.93 Ratio of tip average diameter to center average diameter: D3 / D2 = Although 1.00 was shown, none of them met the preferable requirements of the present invention.

Next, after using this copper foil and laminating the resin on the copper foil using GHPL-830MBT as a resin, the copper layer was removed by etching. An SEM photograph of the resin (replica) surface from which the copper layer has been removed by etching is shown on the right side of FIG. The total area occupied by the holes on the resin surface having irregularities transferred to the roughened surface of the copper foil is 2%, the density of the holes is 1.06 / μm ² , and the total area occupied by the holes of the present invention is 20% It can be seen that the above conditions are not satisfied.

What laminated | stacked resin GHPL-830MBT on copper foil as mentioned above was measured as a normal-state peel strength of a laminated body, and the peel strength after a heating, and the result is similarly shown in Table 1. The circuit width of peel strength is 10mm. The normal peel strength was 0.54 kg / cm, and the peel strength after heating was 0.53 kg / cm, both of which were greatly inferior to the previous examples. When copper foil with roughened particles with thin roots is used as described above, when peeling off the copper foil and resin, peeling occurs at the interface between the copper layer and the roughened particles, so improvement in peel strength cannot be expected. Met.

(Comparative Example 2)
Using the copper foil with carrier (ultra thin copper layer thickness 5μm, ultra thin copper layer roughening surface roughness: Rz0.6μm) by the above treatment, on the rough surface (matte surface: M surface) of this copper foil The following rough plating and normal plating similar to Example 1 were performed. The roughening plating treatment conditions are shown below. The limiting current density ratio during the formation of coarse particles was 9.50.

(Liquid composition 1)
Cu: 15g / L
H ₂ SO ₄ : 100 g / L
W: 3mg / L
Sodium dodecyl sulfate addition amount: 10ppm
(Electroplating temperature 1) 50 ° C

The surface roughness Rz of the roughening treatment layer of Comparative Example 2 is 1.02 μm, the average diameter D1 of the particle root at a position of 10% of the particle length is 0.15 μm, the root width is small, and the particle length L1 is 2.83. The ratio L1 / D1 with respect to the average diameter D1 of the particle root is 18.54, and it can be seen from FIG. 3 that it is formed in a needle-like or dendrite-like particle shape that does not conform to the present invention. The measurement of the diameter of the roughened particles is based on JIS H 0501 item 7 cutting method.

As described above, the average diameter D1 of the particle root at a position of 10% of the particle length of the present invention is 0.2 μm to 1.0 μm, and the ratio L1 / D1 between the particle length L1 and the average diameter D1 of the particle root is It did not satisfy the conditions of the invention of the present invention, ie, a roughened layer of copper foil of 15 or less. The results are shown in Table 1.

In addition to the flat particle diameter (width) D1: 0.15 μm at the base of the roughened particles, Table 1 shows the average diameter D2 of 0.65 μm, the average diameter D3 of the tip D3: 0.65 μm, and the average diameter of the center. Ratio of root average diameter: D2 / D1 = 4.25, Ratio of tip average diameter to root average diameter: D3 / D1 = 4.25, Ratio of tip average diameter to center average diameter: D3 / D2 = Although 1.00 was shown, none of them met the preferable requirements of the present invention.

Next, using this copper foil, using GHPL-830MBT as a resin and laminating the resin on the copper foil, the copper layer was removed by etching.
The total area occupied by the holes on the resin surface having irregularities to which the roughened surface of the copper foil is transferred is 4%, the density of the holes is 2.11 pieces / μm ² , and the total area occupied by the holes of the present invention is 20% It can be seen that the above conditions are not satisfied.

What laminated | stacked resin GHPL-830MBT on copper foil as mentioned above was measured as a normal-state peel strength of a laminated body, and the peel strength after a heating, and the result is similarly shown in Table 1. The circuit width of peel strength is 10mm. The normal peel strength was 0.54 kg / cm, and the peel strength after heating was 0.53 kg / cm, both of which were greatly inferior to the previous examples.
When copper foil with roughened particles with thin roots is used as described above, when peeling off the copper foil and resin, peeling occurs at the interface between the copper layer and the roughened particles, so improvement in peel strength cannot be expected. Met.

(Comparative Example 3)
Using the copper foil with carrier (ultra thin copper layer thickness 5μm, ultra thin copper layer roughening surface roughness: Rz0.6μm) by the above treatment, on the rough surface (matte surface: M surface) of this copper foil The following rough plating and normal plating similar to Example 1 were performed. The roughening plating treatment conditions are shown below. The limiting current density ratio during the formation of roughened particles was 9.80.

(Liquid composition 1)
Cu: 15g / L
H ₂ SO ₄ : 100 g / L
W: 3mg / L
Sodium dodecyl sulfate addition amount: 10ppm
(Electroplating temperature 1) 50 ° C

The surface roughness Rz of the roughened layer of Comparative Example 3 is 0.88 μm, the average diameter D1 of the particle root at a position 10% of the particle length is 0.14 μm, the root width is small, and the particle length L1 is 2.98. The ratio L1 / D1 to the average diameter D1 of the particle root is 20.64, and it can be seen from FIG. 3 that the particles are formed in a needle-like or dendrite-like particle shape that does not conform to the present invention. The measurement of the diameter of the roughened particles is based on JIS H 0501 item 7 cutting method.

As described above, the average diameter D1 of the particle root at a position of 10% of the particle length of the present invention is 0.2 μm to 1.0 μm, and the ratio L1 / D1 between the particle length L1 and the average diameter D1 of the particle root is It did not satisfy the conditions of the invention of the present invention, ie, a roughened layer of copper foil of 15 or less. The results are shown in Table 1.

Table 1 shows the flat particle diameter (width) D1: 0.14 μm at the base of the coarse particles, the average diameter D2 at the center: 0.65 μm, the average diameter at the tip D3: 0.65 μm, and the average diameter at the center. Ratio of root average diameter: D2 / D1 = 4.50, Ratio of tip average diameter to root average diameter: D3 / D1 = 4.50, Ratio of tip average diameter to center average diameter: D3 / D2 = Although 1.00 was shown, none of them met the preferable requirements of the present invention.

Next, using this copper foil and using GHPL-830MBT as the resin to form a laminate of the copper foil and the resin, the copper layer was removed by etching.
The total area occupied by the holes in the roughened resin surface having the transferred irregularities on the copper foil is 14%, the density of the holes is 3.12 holes / μm ² , and the total area occupied by the holes in the present invention is It can be seen that the condition of 20% or more is not satisfied.

What laminated | stacked resin GHPL-830MBT on copper foil as mentioned above was measured as a normal-state peel strength of a laminated body, and the peel strength after a heating, and the result is similarly shown in Table 1. The circuit width of peel strength is 10mm. The normal peel strength was 0.54 kg / cm, and the peel strength after heating was 0.53 kg / cm, both of which were greatly inferior to the previous examples. When copper foil with roughened particles with thin roots is used as described above, when peeling off the copper foil and resin, peeling occurs at the interface between the copper layer and the roughened particles, so improvement in peel strength cannot be expected. Met.

From the above, the copper foil for printed wiring board of the present invention is not a round (spherical) projection or dendrite-like crystal grain size of the roughening treatment, which has been considered good in the past, but on at least one surface of the copper foil. By forming fine needle-like roughened particles, the adhesive strength of the copper foil itself with the resin is increased, and the peeling strength is also improved against chemical treatment during fine pattern formation on the package substrate. It is possible to increase the size of the copper foil, and it can be seen that it has a great effect that it is possible to provide a copper foil that enables fine etching and a manufacturing method thereof.

(Example 21)
Next, a copper layer was formed under the same conditions as in Example 1 except that a CoMo alloy was formed as an intermediate layer between the carrier and the copper foil. In this case, the CoMo alloy intermediate layer was produced by plating in a plating solution having the following liquid composition.
(Liquid composition) CoSO ₄ · 7H ₂ O: 0.5 to 100 g / L
_{Na 2 MoO 4 · 2H 2 O} : 0.5~100g / L
Sodium citrate dihydrate: 20-300 g / L
(Temperature) 10 ~ 70 ℃
(pH) 3-5
(Current density) 0.1-60A / dm ²
And what laminated | stacked resin (GHPL-830MBT) on copper foil as mentioned above was measured as the normal state peel strength of a laminated body, and the peel strength after a heating. The results are shown in Table 2. The circuit width of peel strength is 10 mm.
The normal peel strength was 1.01 kg / cm, and the peel strength after heating was 0.94 kg / cm. Both peel strengths were improved as compared with Comparative Examples described later.

(Example 22)
Next, a copper layer was formed under the same conditions as in Example 2 except that Cr was formed as an intermediate layer between the carrier and the copper foil. In this case, the Cr intermediate layer was produced by plating in a plating solution having the following liquid composition.
(Liquid composition)
CrO ₃ : 200 ~ 400g / L
H ₂ SO ₄ : 1.5-4g / L
(PH) 1-4
(Liquid temperature) 45-60 ℃
(Current density) 10 ~ 40A / dm ²
And what laminated | stacked resin (MBT-830) on copper foil as mentioned above was measured as the normal-state peel strength of a laminated body, and the peel strength after a heating. The results are also shown in Table 2.
The circuit width of peel strength is 10mm. The normal peel strength was 0.81 kg / cm, and the peel strength after heating was 0.78 kg / cm. Both peel strengths were improved as compared with Comparative Examples described later.

(Example 23)
Next, a copper layer was formed under the same conditions as in Example 3 except that Cr / CuP was formed as an intermediate layer between the carrier and the copper foil. In this case, the Cr / CuP intermediate layer was produced by plating in a plating solution having the following liquid composition.
(Liquid composition 1)
CrO ₃ : 200 ~ 400g / L
H ₂ SO ₄ : 1.5-4g / L
(PH): 1-4
(Liquid temperature): 45-60 ° C
(Current density): 10-40A / dm ²
(Liquid composition 2)
Cu ₂ P ₂ O ₇ : 3H ₂ O: 5 to 50 g / L
K ₄ P ₂ O ₇ : 50 to 300 g / L
(Temperature): 30-60 ℃
(pH): 8-10
(Current density): 0.1 to 1.0 A / dm ²
And what laminated | stacked resin (MBT-830) on copper foil as mentioned above was measured as the normal-state peel strength of a laminated body, and the peel strength after a heating. The results are also shown in Table 2.
The circuit width of peel strength is 10mm. The normal peel strength was 0.84 kg / cm, and the peel strength after heating was 0.77 kg / cm. Both peel strengths were improved as compared with Comparative Examples described later.

(Example 24)
Next, a copper layer was formed under the same conditions as in Example 4 except that Ni / Cr was formed as an intermediate layer between the carrier and the copper foil. In this case, the Ni / Cr intermediate layer was produced by plating in a plating solution having the following liquid composition.
(Liquid composition 1)
NiSO ₄ · 6H ₂ O: 250 to 300 g / L
NiCl ₂ · 6H ₂ O: 35 to 45 g / L
Boric acid: 10-50g / L
(PH): 2-6
(Bath temperature): 30-70 ° C
(Current density): 0.1 ~ 50A / dm ²
(Liquid composition 2)
CrO ₃ : 200 ~ 400g / L
H ₂ SO ₄ : 1.5-4g / L
(PH): 1-4
(Liquid temperature): 45-60 ° C
(Current density): 10-40A / dm ²
And what laminated | stacked resin (MBT-830) on copper foil as mentioned above was measured as the normal-state peel strength of a laminated body, and the peel strength after a heating. The results are also shown in Table 2.
The circuit width of peel strength is 10mm. The normal peel strength was 0.90 kg / cm, and the peel strength after heating was 0.86 kg / cm. Both peel strengths were improved as compared with Comparative Examples described later.

(Example 25)
Next, a copper layer was formed under the same conditions as in Example 4 except that a Co / chromate treatment layer was formed as an intermediate layer between the carrier and the copper foil.
In this case, the Co / chromate intermediate layer was prepared by plating in a plating solution having the following liquid composition.
(Liquid composition 1) CoSO4 · 7H ₂ O: 10 to 100 g / L
Sodium citrate dihydrate: 30-200 g / L
(Temperature): 10 ~ 70 ℃
(pH): 3-5
(Current density): 0.1 ~ 60A / dm ²
(Liquid composition 2): CrO ₃ : 1 to 10 g / L
(Temperature); 10 ~ 70 ℃
(pH): 10-12
(Current density): 0.1 to 1.0 A / dm ²
And what laminated | stacked resin (MBT-830) on copper foil as mentioned above was measured as the normal-state peel strength of a laminated body, and the peel strength after a heating. The results are also shown in Table 2.
The circuit width of peel strength is 10mm. The normal peel strength was 0.91 kg / cm, and the peel strength after heating was 0.84 kg / cm. Both peel strengths were improved as compared with Comparative Examples described later.

(Example 26)
Next, a copper layer was formed under the same conditions as in Example 4 except that an organic layer was formed as an intermediate layer between the carrier and the copper foil.
In this case, the intermediate layer of the organic layer was prepared by spraying a carboxybenzotriazole aqueous solution having a liquid temperature of 40 ° C., pH 5, and a concentration of 1 to 10 g / L for 10 to 60 seconds.
And what laminated | stacked resin (MBT-830) on copper foil as mentioned above was measured as the normal-state peel strength of a laminated body, and the peel strength after a heating. The results are also shown in Table 2.
The circuit width of peel strength is 10mm. The normal peel strength was 0.91 kg / cm, and the peel strength after heating was 0.91 kg / cm. Both peel strengths were improved as compared with Comparative Examples described later.

As described above, the present invention increases the adhesive strength between the copper foil itself and the resin by forming fine acicular coarse particles on at least one surface of the carrier-attached copper foil. It is possible to provide a copper foil with a carrier and a manufacturing method thereof capable of increasing the peel strength even for chemical treatment when forming a fine pattern on a substrate, and capable of providing fine etching. Has an effect.
In recent years, printed circuit copper foils (semiconductor package substrate copper foil) and semiconductor package substrate copper foils and semiconductor package resins made by bonding semiconductor package resins are becoming increasingly important as printed circuits have become finer and higher in frequency. It is valid.

Claims (17)

  Carrier, intermediate layer, copper foil with carrier in which ultra-thin copper layers are laminated in this order, the intermediate layer is Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, or these Alloy, or a hydrate thereof, or an oxide thereof, or a layer containing any one or more organic materials, the carrier-attached copper foil has a roughened layer on the surface of the ultrathin copper layer, After laminating the resin on the roughened layer, the carrier and the intermediate layer are peeled off from the ultrathin copper layer, and then the ultrathin copper layer is removed by etching. 20% or more of the total area occupied by the holes in the roughened resin surface having the irregularities transferred to the roughened surface of the roughened layer on the surface of the laminated resin on the roughened layer. The copper foil with a carrier characterized by being.   The intermediate layer is a single metal layer made of any one element of the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al from the carrier side, or Cr, Ni, Co, An alloy layer composed of one or more elements selected from the element group of Fe, Mo, Ti, W, P, Cu, and Al, Cr, Ni, Co, Fe, Mo on the single metal layer or the alloy layer 2. The copper foil with a carrier according to claim 1, comprising a layer made of a hydrate or oxide of one or more elements selected from the group consisting of Ti, W, P, Cu, and Al. Said include an intermediate layer is Ni and Cr, either deposition amount of Cr is 10-100 [mu] g / dm ^2, the amount of deposition of Ni is as claimed in claim 1 or 2, characterized in that a 1000~40000μg / dm ² A copper foil with a carrier according to claim 1.   The surface of the ultrathin copper layer has a roughened layer, and the average diameter D1 of the particle root at a position of 10% of the particle length of the roughened layer is 0.2 μm to 1.0 μm, and the particle length L1 The copper foil with a carrier according to any one of claims 1 to 3, further comprising a roughened layer having a ratio L1 / D1 to an average diameter D1 of the particle root of 15 or less.   The surface of the ultra-thin copper layer has a roughened layer, and the average diameter D1 (μm) of the particle root at the position of 10% of the particle length of the roughened layer, the particle length of the roughened layer The ratio D2 / D1 of the D2 and the D1 is 1 to 4 when the average diameter D2 (μm) at the center of the particle at a position of 50% is set forth. The copper foil with a carrier as described in 2.   6. The ratio D 2 / D 3 between the average diameter D 2 at the center of the particle and the particle tip D 3 at a position of 90% of the particle length is 0.8 to 1.0. 6. Copper foil with carrier.   The carrier-attached copper foil according to any one of claims 4 to 6, wherein an average diameter D2 at the center of the particle is 0.7 to 1.5 µm.   The copper foil with a carrier according to any one of claims 4 to 7, wherein an average diameter D3 of a particle tip at a position of 90% of the particle length is 0.7 to 1.5 µm.   The heat-resistant / rust-proof layer containing at least one element selected from zinc, nickel, copper, phosphorus, and cobalt is provided on the roughened layer. The copper foil with a carrier according to the item.   A heat-resistant / rust-proof layer containing at least one element selected from zinc, nickel, copper, phosphorus, and cobalt is provided on the roughened layer, and a chromate film layer is provided on the heat-resistant / rust-proof layer. The copper foil with a carrier as described in any one of Claims 1-9 characterized by these.   A heat-resistant / rust-proof layer containing at least one element selected from zinc, nickel, copper, phosphorus and cobalt on the roughened layer, a chromate film layer and the chromate on the heat-resistant / rust-proof layer The copper foil with a carrier according to any one of claims 1 to 10, wherein a silane coupling agent layer is provided on the coating layer. It is a method of manufacturing the copper foil with a carrier as described in any one of the said Claims 1-11, Comprising: When forming a roughening process layer in an ultra-thin copper layer surface, a sulfate alkylester salt, tungsten, arsenic The copper with a carrier according to any one of claims 1 to 11, wherein the roughening layer is formed using an electrolytic bath made of sulfuric acid / copper sulfate containing at least one kind of substance selected from the above. Foil manufacturing method.   A heat-resistant / rust-proof layer containing at least one element selected from zinc, nickel, copper, phosphorus and cobalt is formed on the roughened layer, and then a chromate film layer is formed on the heat-resistant / rust-proof layer. The method for producing a copper foil with a carrier according to claim 12, further comprising forming a silane coupling agent layer on the chromate film layer.   After laminating | stacking resin with the copper foil with a carrier as described in any one of the said Claims 1-13, the said carrier and the said intermediate | middle layer are peeled from the said ultra-thin copper layer, and the said ultra-thin copper layer is etched by etching after that. A printed wiring board in which the surface of the removed resin is plated in the order of electroless copper plating and electrolytic plating, a copper layer is formed, and a circuit is formed by etching.   After laminating | stacking resin with the copper foil with a carrier as described in any one of the said Claims 1-13, the said carrier and the said intermediate | middle layer are peeled from the said ultra-thin copper layer, and the said ultra-thin copper layer is etched by etching after that. A printed wiring board with a circuit formed on the surface of the removed resin.   After laminating | stacking resin with the copper foil with a carrier as described in any one of the said Claims 1-13, the said carrier and the said intermediate | middle layer are peeled from the said ultra-thin copper layer, and the said ultra-thin copper layer is etched by etching after that. A printed wiring board in which a circuit is formed by forming a copper layer on the surface of the removed resin.   17. The printed wiring board according to claim 14, wherein five or more acicular particles are present in a circuit width of 10 μm.