JP6592029B2 - Copper foil with carrier and manufacturing method thereof, ultrathin copper layer, manufacturing method of copper clad laminate, and manufacturing method of printed wiring board - Google Patents

Description

  The present invention relates to a carrier-attached copper foil and a method for producing the same, an ultrathin copper layer, and a printed wiring board. In more detail, this invention relates to the copper foil with a carrier used as a material of the printed wiring board of a fine pattern use, its manufacturing method, an ultra-thin copper layer, and a printed wiring board.

  In recent years, with the high integration of semiconductor circuits, fine circuits are also required for printed wiring boards. A general method for forming a fine circuit is to form a wiring circuit on an ultrathin copper layer and then remove the ultrathin copper layer by etching with a sulfuric acid-hydrogen peroxide etchant (MSAP: Modified-Semi-Additive-Process). ). Therefore, it is preferable that the ultrathin copper layer has a uniform thickness.

  Here, the foil thickness accuracy of electrolytic plating is greatly influenced by the distance between the anode and the cathode. A general method for forming an ultrathin copper layer is to form a release layer on a copper foil carrier (12 to 70 μm), and further form an ultrathin copper layer (0.5 to 10.0 μm) and roughened particles on the surface. To do. Regarding the processes after the formation of the copper foil carrier, conventionally, it has been carried out using a ninety-fold folding method that does not support the copper foil carrier with a drum as shown in FIG. 1 (Patent Document 1).

JP 2000-309898 A

However, the thickness accuracy of the ultra-thin copper layer formed by electrolytic plating is greatly affected by the distance between the anode and the cathode. When the method is used, it is difficult to make the distance between the electrodes constant due to the influence of the electrolytic solution, the foil carrying tension, and the like, and there is a problem that the variation in thickness is increased.
Then, this invention makes it the subject to provide the copper foil with a carrier which improved the thickness precision of the ultra-thin copper layer on a copper foil carrier.

  In order to achieve the above object, the present inventor conducted extensive research and paid attention to the foil handling method of the process after the copper foil carrier. It was found that the distance between the electrodes can be ensured and the thickness accuracy of the ultrathin copper layer can be improved.

The present invention has been completed on the basis of the above knowledge. In one aspect, the present invention includes a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the release layer. A copper foil with a carrier,
Using the ultrathin copper layer as a 15 mm (MD direction) × 150 mm (TD direction) sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight-thickness accuracy obtained by the average value of weight thickness measurement values is 6.15% or less copper foil with carrier.

In another aspect, the present invention is a copper foil with a carrier comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the release layer,
Using the ultrathin copper layer as a 15 mm (TD direction) × 150 mm (MD direction) sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight-thickness accuracy determined by the average value of weight thickness measurement values is 9.30% or less copper foil with carrier.

In yet another aspect, the present invention is a copper foil with a carrier comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the release layer,
Using the ultrathin copper layer as a 5 cm square sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight-thickness accuracy determined by an average value of weight thickness measurement values is 2.90% or less copper foil with carrier.

In yet another aspect, the present invention is a copper foil with a carrier comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the release layer,
Using the ultrathin copper layer as a 15 mm (MD direction) × 150 mm (TD direction) sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight thickness accuracy determined by the average value of weight thickness measurement values is 6.15% or less,
Using the ultrathin copper layer as a 15 mm (TD direction) × 150 mm (MD direction) sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight-thickness accuracy determined by the average value of weight thickness measurement values is 9.30% or less copper foil with carrier.

In yet another aspect, the present invention is a copper foil with a carrier comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the release layer,
Using the ultrathin copper layer as a 15 mm (MD direction) × 150 mm (TD direction) sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight thickness accuracy determined by the average value of weight thickness measurement values is 6.15% or less,
Using the ultrathin copper layer as a 15 mm (TD direction) × 150 mm (MD direction) sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight-thickness accuracy determined by an average value of measured thickness values is 9.30% or less,
Using the ultrathin copper layer as a 5 cm square sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight-thickness accuracy determined by an average value of weight thickness measurement values is 2.90% or less copper foil with carrier.

In yet another aspect, the present invention is a copper foil with a carrier comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the release layer,
Using the ultrathin copper layer as a 15 mm (TD direction) × 150 mm (MD direction) sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight-thickness accuracy determined by an average value of measured thickness values is 9.30% or less,
Using the ultrathin copper layer as a 5 cm square sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight-thickness accuracy determined by an average value of weight thickness measurement values is 2.90% or less copper foil with carrier.

  In another aspect of the present invention, a copper foil carrier and a copper foil carrier are treated by treating the surface of a long copper foil carrier conveyed in the length direction by a roll-to-roll conveyance system. This is a method for producing a copper foil with a carrier comprising a laminated release layer and an ultrathin copper layer laminated on the release layer, and the release layer is formed on the surface of the copper foil carrier conveyed by a conveyance roll. With the carrier of the present invention, including a step and a step of forming an ultrathin copper layer on the surface of the release layer by electrolytic plating while supporting the copper foil carrier on which the release layer transported by a transport roll is formed with a drum It is a manufacturing method of copper foil.

In another aspect of the present invention, an electrode made of electrolytic copper foil is laminated on a release layer laminated on a copper foil carrier, and constitutes a copper foil with a carrier together with the copper foil carrier and the release layer. A thin copper layer,
Using the ultrathin copper layer as a 15 mm (MD direction) × 150 mm (TD direction) sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight This is an ultra-thin copper layer having a weight-thickness accuracy of 6.15% or less determined by an average value of measured thickness values.

In another aspect of the present invention, an electrode made of electrolytic copper foil is laminated on a release layer laminated on a copper foil carrier, and constitutes a copper foil with a carrier together with the copper foil carrier and the release layer. A thin copper layer,
Using the ultrathin copper layer as a 15 mm (TD direction) × 150 mm (MD direction) sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight This is an ultra-thin copper layer having a weight-thickness accuracy of 9.30% or less determined by an average value of measured thickness values.

In another aspect of the present invention, an electrode made of electrolytic copper foil is laminated on a release layer laminated on a copper foil carrier, and constitutes a copper foil with a carrier together with the copper foil carrier and the release layer. A thin copper layer,
Using the ultrathin copper layer as a 5 cm square sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight Ultrathin copper layer having a weight-thickness accuracy of 2.90% or less determined by an average value of measured thickness values.

In another aspect of the present invention, an electrode made of electrolytic copper foil is laminated on a release layer laminated on a copper foil carrier, and constitutes a copper foil with a carrier together with the copper foil carrier and the release layer. A thin copper layer,
Using the ultrathin copper layer as a 15 mm (MD direction) × 150 mm (TD direction) sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight thickness accuracy determined by the average value of weight thickness measurement values is 6.15% or less,
Using the ultrathin copper layer as a 15 mm (TD direction) × 150 mm (MD direction) sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight This is an ultra-thin copper layer having a weight-thickness accuracy of 9.30% or less determined by an average value of measured thickness values.

In another aspect of the present invention, an electrode made of electrolytic copper foil is laminated on a release layer laminated on a copper foil carrier, and constitutes a copper foil with a carrier together with the copper foil carrier and the release layer. A thin copper layer,
Using the ultrathin copper layer as a 15 mm (MD direction) × 150 mm (TD direction) sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight thickness accuracy determined by the average value of weight thickness measurement values is 6.15% or less,
Using the ultrathin copper layer as a 15 mm (TD direction) × 150 mm (MD direction) sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight-thickness accuracy determined by an average value of measured thickness values is 9.30% or less,
Using the ultrathin copper layer as a 5 cm square sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight Ultrathin copper layer having a weight-thickness accuracy of 2.90% or less determined by an average value of measured thickness values.

In another aspect of the present invention, an electrode made of electrolytic copper foil is laminated on a release layer laminated on a copper foil carrier, and constitutes a copper foil with a carrier together with the copper foil carrier and the release layer. A thin copper layer,
Using the ultrathin copper layer as a 15 mm (TD direction) × 150 mm (MD direction) sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight-thickness accuracy determined by an average value of measured thickness values is 9.30% or less,
Using the ultrathin copper layer as a 5 cm square sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by a weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight Ultrathin copper layer having a weight-thickness accuracy of 2.90% or less determined by an average value of measured thickness values.

  In yet another aspect, the present invention is a printed wiring board manufactured using the carrier-attached copper foil of the present invention.

  In still another aspect, the present invention is a printed wiring board using the ultrathin copper layer of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the copper foil with a carrier which improved the thickness precision of the ultra-thin copper layer on a copper foil carrier can be provided.

It is a schematic diagram which shows the conventional ninety-fold folding method. It is a schematic diagram which shows the carrying method based on the manufacturing method of the copper foil with a carrier which concerns on Embodiment 1 of this invention. It is a schematic diagram which shows the carrying method based on the manufacturing method of the copper foil with a carrier which concerns on Embodiment 2 of this invention. It is a schematic diagram which shows the conveyance method based on the manufacturing method of the copper foil with a carrier which concerns on Embodiment 3 of this invention. It is the schematic of the cross section of the width direction of the circuit pattern in an Example, and the outline of the calculation method of the etching factor (EF) using this schematic diagram.

<1. Copper foil carrier>
The copper foil carrier that can be used in the present invention 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. In addition to high-purity copper such as tough pitch copper and oxygen-free copper, the copper foil material is, for example, Sn-containing copper, Ag-containing copper, copper alloy added with Cr, Zr, Mg, etc., and Corson-based 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.

  Although there is no restriction | limiting in particular also about the thickness of the copper foil carrier which can be used for this invention, What is necessary is just to adjust suitably to the thickness suitable for fulfill | performing the role as a copper foil carrier, for example, it can be 12 micrometers or more. . However, if it is too thick, the production cost becomes high, so generally it is preferably 35 μm or less. Accordingly, the thickness of the copper foil carrier is typically 12-70 μm, more typically 18-35 μm.

<2. Release layer>
A release layer is provided on the copper foil carrier. The release layer can be formed using nickel, a nickel-phosphorus alloy, a nickel-cobalt alloy, chromium, or the like. The peeling layer is the part that peels when the copper foil carrier is peeled off from the ultrathin copper layer, but it can also have a barrier effect that prevents the copper component from diffusing from the copper foil carrier into the ultrathin copper layer. it can.
When using an electrolytic copper foil as the copper foil carrier, it is preferable to provide a release layer on the low roughness surface from the viewpoint of reducing pinholes. The release layer can be provided using a method such as plating, sputtering, CVD, or physical vapor deposition.
Moreover, as a peeling layer, it can be set as the arbitrary peeling layers known to those skilled in the art in copper foil with a carrier. For example, the release layer is any one of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or an alloy thereof, a hydrate thereof, an oxide thereof, or an organic material. It is preferable to form a layer including the above. The release layer may be composed of a plurality of layers. Note that the release layer can have a diffusion preventing function. Here, the diffusion preventing layer is a layer having a function of preventing the element from the base material from diffusing to the ultrathin copper layer side.

In one embodiment of the present invention, the release layer is a single metal composed of one element selected from the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn from the carrier side. A layer, or an alloy layer made of one or more elements selected from the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn (these have a diffusion preventing function); A layer made of a hydrate or oxide of one or more elements selected from the group of elements of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn laminated thereon Consists of In addition, the total adhesion amount of each element can be 1-6000 microgram / dm < ² >, for example.

  The release layer is preferably composed of two layers of Ni and Cr. In this case, the Ni layer is preferably laminated so as to be 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. Moreover, Zn may be contained in two layers of Ni and Cr.

  The release layer can be obtained by wet plating such as electroplating, electroless plating and immersion plating, or dry plating such as sputtering, CVD and PDV. Electroplating is preferable from the viewpoint of cost.

<3. Ultrathin copper layer>
An ultrathin copper layer is provided on the release layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and is used in general electrolytic copper foil with high current density. Since a copper foil can be formed, a copper sulfate bath is preferable. The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the copper foil carrier, for example, 12 μm or less. Typically, it is 0.5 to 10 μm, and more typically 1 to 5 μm.

<4. Roughening>
A roughening treatment layer may be provided on the surface of the ultrathin copper layer by performing a roughening treatment, for example, in order to improve the adhesion to the insulating substrate. The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening process may be fine. The roughening treatment layer may be any single element selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc, or a layer made of an alloy containing at least one of them. Good. Moreover, after forming the roughened particles with copper or a copper alloy, a roughening treatment can be performed in which secondary particles or tertiary particles are further formed of nickel, cobalt, copper, zinc alone or an alloy. Thereafter, a heat-resistant layer or a rust-preventing layer may be formed of nickel, cobalt, copper, zinc alone or an alloy, and the surface thereof may be further subjected to a treatment such as a chromate treatment or a silane coupling treatment. Alternatively, a heat-resistant layer or a rust-preventing layer may be formed from nickel, cobalt, copper, zinc alone or an alloy without roughening, and the surface may be subjected to a treatment such as chromate treatment or silane coupling treatment. Good. That is, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer. One or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface. In addition, the above-mentioned heat-resistant layer, rust prevention layer, chromate treatment layer, and silane coupling treatment layer may each be formed of a plurality of layers (for example, two or more layers, three or more layers, etc.).

<5. Copper foil with carrier>
The copper foil with a carrier includes a copper foil carrier, a release layer formed on the copper foil carrier, and an ultrathin copper layer laminated on the release layer. 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 peeling layer and the ultrathin copper layer.

Further, the carrier-attached copper foil comprising a carrier and an ultra-thin copper layer laminated on the intermediate layer on the carrier comprises a roughening treatment layer on the ultra-thin copper layer. Alternatively, one or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be provided on the roughening treatment layer.
Further, a roughening treatment layer may be provided on the ultrathin copper layer, a heat resistant layer and a rust prevention layer may be provided on the roughening treatment layer, and a chromate treatment is performed on the heat resistance layer and the rust prevention layer. A layer may be provided, and a silane coupling treatment layer may be provided on the chromate treatment layer.
The carrier-attached copper foil includes a resin layer on the ultrathin copper layer, the roughened layer, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the silane coupling-treated layer. May be. The resin layer may be an insulating resin layer.

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

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. Although the type is not particularly limited, for example, a resin including an epoxy resin, a polyimide resin, a polyfunctional cyanate ester compound, a maleimide compound, a polyvinyl acetal resin, a urethane resin, and the like can be preferably used. .

  These resins are dissolved in a solvent such as methyl ethyl ketone (MEK) or toluene to obtain a resin solution, which is used on the ultrathin copper layer, the heat-resistant layer, the rust-proof layer, the chromate film layer, or the silane cup. On the ring agent layer, for example, it is applied by a roll coater method or the like, and then heat-dried as necessary to remove the solvent to obtain a B-stage state. For example, a hot air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C.

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

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

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

  The thickness of this resin layer is preferably 0.1 to 80 μm.

  When the thickness of the resin layer is less than 0.1 μm, the adhesive strength is reduced, and when this copper foil with a carrier with a resin is laminated on a base material provided with an inner layer material without interposing a prepreg material, the circuit of the inner layer material It may be difficult to ensure interlayer insulation between the two.

  On the other hand, if the thickness of the resin layer is greater than 80 μm, it is difficult to form a resin layer having a target thickness in a single coating process, which is economically disadvantageous because of extra material costs and man-hours. Furthermore, since the formed resin layer is inferior in flexibility, cracks are likely to occur during handling, and excessive resin flow occurs during thermocompression bonding with the inner layer material, making smooth lamination difficult. There is.

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

  Furthermore, a printed circuit board is completed by mounting electronic components on the printed wiring board. Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier which concerns on this invention are shown.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<6. Manufacturing method of copper foil with carrier>
Next, the manufacturing method of the copper foil with a carrier which concerns on this invention is demonstrated. FIG. 2 is a schematic diagram illustrating a foil handling method according to the method of manufacturing the copper foil with a carrier according to the first embodiment of the present invention. The manufacturing method of the copper foil with a carrier which concerns on Embodiment 1 of this invention is a copper foil carrier by processing the surface of the elongate copper foil carrier conveyed in a length direction by a roll-to-roll conveyance system. And a copper foil with a carrier comprising a release layer laminated on a copper foil carrier and an ultrathin copper layer laminated on the release layer. The manufacturing method of the copper foil with a carrier which concerns on Embodiment 1 of this invention is the process of forming an ultra-thin copper layer on the copper foil carrier surface by electrolytic plating, supporting the copper foil carrier conveyed with a conveyance roll with a drum, The process of forming an ultrathin copper layer on the surface of the release layer by electrolytic plating while supporting the copper foil carrier on which the release layer is formed with a drum, and the ultrathin copper by electrolytic plating while supporting the copper foil carrier with a drum Forming a roughened layer on the surface of the layer. In each process, the treated surface of the copper foil carrier supported by the drum also serves as the cathode, and each electrolytic plating is performed in a plating solution between this drum and the anode provided to face the drum. Is called.

  In the present invention, in order to convey a long copper foil carrier by a roll-to-roll conveyance system, the copper foil carrier is conveyed while applying tension in the length direction of the copper foil carrier. The tension can be adjusted by applying torque by connecting each transport roll to a drive motor or the like. The conveyance tension of the copper foil carrier is preferably 0.01 to 0.2 kg / mm. When the conveyance tension is less than 0.01 kg / mm, the adhesion with the drum is weak, and it is difficult to form each layer in a desired thickness. Moreover, although it depends on the structure of the apparatus, problems such as slip are likely to occur, and the winding of the copper foil carrier becomes loose, and problems such as winding deviation are likely to occur. On the other hand, if the transport tension is more than 0.2 kg / mm, wrinkles are likely to occur even with a slight displacement of the copper foil carrier, which is not preferable from the viewpoint of device management. In addition, the winding is hard, and winding wrinkles are likely to occur. The conveyance tension of the copper foil carrier is more preferably 0.02 to 0.1 kg / mm.

  In Embodiment 1, the release layer and the roughening layer are both formed by electrolytic plating while supporting the copper foil carrier with a drum, but the present invention is not limited to this. For example, as Embodiment 2, as shown in FIG. 3, the roughened layer is formed by electrolytic plating using a ninety-fold folding method without a drum support to a conventional copper foil carrier. Also good. In addition, as Embodiment 3, as shown in FIG. 4, the formation of the release layer and the roughening treatment layer was performed using a ninety-nine-fold folding method that does not support a conventional copper foil carrier by a drum. You may form by electroplating. However, since Embodiments 2 and 3 do not perform all the steps by a foil carrying method using a drum as in Embodiment 1, compared with Embodiment 1, the distance between electrodes at the time of electrolytic plating is made constant. It is difficult to do, and the thickness accuracy of a peeling layer and / or a roughening process layer is inferior. In addition, in the case of electrolytic plating using a 99-fold folding method, the distance between the conveying rolls is shortened, the guide rolls are used to prevent the foil from shaking, and the conveying tension is set to the usual 3 By making it 5 times, the plate-thickness accuracy can be improved by stabilizing the distance between the anode and the cathode in electrolytic plating.

  In the present invention, as described above, the distance between the anode and the cathode in electrolytic plating is stabilized by supporting the copper foil carrier with a drum. For this reason, the variation in the thickness of the layer to form is suppressed favorably, and it becomes possible to produce a copper foil with a carrier having an extremely thin copper layer with high thickness accuracy. In addition, by adjusting the linear flow rate (m / sec) in the plating process when forming the release layer, the ultrathin copper layer, and the roughening layer, the carrier with an ultrathin copper layer with better thickness accuracy is provided. Copper foil can be produced.

An embodiment of the weight-thickness method used in the present invention will be described (Evaluation D). First, after measuring the weight of the copper foil with carrier (total weight of the copper foil carrier, release layer, ultrathin copper layer, and surface treatment layer (roughening layer, etc.) on the ultrathin copper layer), ultrathin copper The layer is peeled off, the weight of the copper foil carrier is measured again, and the difference between the former and the latter is defined as the weight of the ultrathin copper layer. The carrier-attached copper foil piece to be measured is a 15 mm (MD direction) × 150 mm (TD direction) sheet cut out by a precision cutter. In order to investigate the weight-thickness accuracy, the average value and the standard deviation (σ of the weight-thickness measurement value of the ultra-thin copper layer pieces of 3 points at equal intervals in the width direction, 5 points in the length direction (40 mm interval), and 15 points in total. ) In addition, the calculation formula of weight thickness accuracy shall be the following formula.
Thickness accuracy (%) = average of 3σ × 100 / weight thickness measurement value The repeatability of this measurement method is 0.2%.
The MD direction indicates a direction parallel to the foil-making direction of the copper foil with carrier (the foil passing direction in the manufacturing apparatus of the copper foil with carrier), and the TD direction is a direction perpendicular to the MD direction, that is, the copper foil with carrier. The direction perpendicular to the foil making direction (width direction of the copper foil with carrier) is shown.
The copper foil with a carrier or the ultrathin copper layer according to the present invention has, on one side surface, a thickness accuracy (%) measured by measuring the ultrathin copper layer as a sample in the above-described region (15 mm (MD direction) × 150 mm (TD direction)) ) Is 6.15% or less, preferably 4% or less, more preferably 3% or less, still more preferably 2.5% or less, and further preferably 2.0% or less. Even more preferably. The lower limit is not particularly limited, but is, for example, 0.01% or more, 0.05% or more, 0.1% or more, or 0.2% or more.

Another embodiment of the weight-thickness method used in the present invention will be described (Evaluation E). First, after measuring the weight of the copper foil with carrier (total weight of the copper foil carrier, release layer, ultrathin copper layer, and surface treatment layer (roughening layer, etc.) on the ultrathin copper layer), ultrathin copper The layer is peeled off, the weight of the copper foil carrier is measured again, and the difference between the former and the latter is defined as the weight of the ultrathin copper layer. The carrier-attached copper foil piece to be measured is a 15 mm (TD direction) × 150 mm (MD direction) sheet cut out by a precision cutter. In order to investigate the weight-thickness accuracy, the average value and standard deviation (σ of the weight-thickness measurement values of the ultrathin copper layer pieces of 10 points at equal intervals in the width direction, 2 points in the length direction (10 mm intervals), and 20 points in total. ) In addition, the calculation formula of weight thickness accuracy shall be the following formula.
Thickness accuracy (%) = average of 3σ × 100 / weight thickness measurement value The repeatability of this measurement method is 0.2%.
In another aspect, the copper foil with carrier or the ultrathin copper layer according to the present invention is a thickness accuracy (15 mm (TD direction) × 150 mm (MD direction)) measured for the ultrathin copper layer used as a sample. %) Is 9.30% or less, preferably 7% or less, more preferably 5% or less, still more preferably 4% or less, and further preferably 3.5% or less. Is still more preferable, and it is still more preferable that it is 3% or less. The lower limit is not particularly limited, but is, for example, 0.01% or more, 0.05% or more, 0.1% or more, or 0.2% or more.

Further, another embodiment of the weight-thickness method used in the present invention will be described (Evaluation C). First, after measuring the weight of the copper foil with carrier (total weight of the copper foil carrier, release layer, ultrathin copper layer, and surface treatment layer (roughening layer, etc.) on the ultrathin copper layer), ultrathin copper The layer is peeled off, the weight of the copper foil carrier is measured again, and the difference between the former and the latter is defined as the weight of the ultrathin copper layer. The copper foil piece with a carrier to be measured is a 5 cm square sheet punched out by a press. In order to investigate the weight-thickness accuracy, the average value and the standard deviation (σ of the weight-thickness measurement values of ultra-thin copper layer pieces of 5 points at equal intervals in the width direction, 3 points in the length direction (40 mm intervals), and a total of 15 points. ) In addition, the calculation formula of weight thickness accuracy shall be the following formula.
Thickness accuracy (%) = average of 3σ × 100 / weight thickness measurement value The repeatability of this measurement method is 0.2%.
In another aspect of the carrier-attached copper foil or ultrathin copper layer according to the present invention, the thickness accuracy (%) measured for the ultrathin copper layer as a sample in the above-described region (5 cm square) is 2.90% or less. It is preferably 2% or less, more preferably 1.5% or less, still more preferably 1.3% or less, and even more preferably 1.1% or less. . The lower limit is not particularly limited, but is, for example, 0.01% or more, 0.05% or more, 0.1% or more, or 0.2% or more.

  EXAMPLES The present invention will be described in more detail below with reference to examples of the present invention, but the present invention is not limited to these examples.

1. Manufacture of copper foil with carrier First, a long copper foil carrier having a thickness shown in Table 1 was prepared. The copper foils of Examples 1, 3, 5 to 7, 10, 13, 15, 16 and Comparative Examples 1 and 2 were electrolytic copper foils (JTC manufactured by JX Nippon Mining & Metals), and Examples 2, 4, As the copper foils of 8, 9, 11, 12, 14, 17 to 21, and Comparative Examples 3 and 4, rolled copper foil (Tough pitch copper foil (JIS-H3100-C1100) manufactured by JIS Nippon Mining & Metals) was used. With respect to the shiny surface of this copper foil, each forming treatment of the peeling layer, the ultrathin copper layer and the roughening treatment layer described in Table 1 under the following conditions in a roll-to-roll type continuous line under the following conditions: went. Here, Examples 1 to 3 and 17 are manufactured by the method according to the third embodiment shown in FIG. 4 described above, and Examples 4 to 9 are methods according to the second embodiment shown in FIG. 3 described above. Examples 10 to 16 and 19 to 21 are manufactured by the method according to Embodiment 1 shown in FIG. Further, Comparative Examples 1 to 4 are manufactured by the conventional method shown in FIG. Moreover, Example 18 was produced by the method shown in FIG. Here, in all of an intermediate | middle layer formation process, an ultra-thin copper layer formation process, and a roughening process layer formation process, Comparative Examples 1-4 are the conveyance roll above the plating bath shown in FIG. 1, and conveyance in a plating bath. Whereas the distance from the roll (dip roll) (that is, the height of the upper transport roll with respect to the dip roll) was 2500 mm, in Example 18, the distance was as short as 1700 mm. Furthermore, in all of the intermediate layer forming step, the ultrathin copper layer forming step, and the roughening treatment layer forming step, in Example 18, the conveyance tension was made three times higher than those of Comparative Examples 1 to 4.

(Peeling layer formation)
(A) Carrying foil method by 99-fold ・ Anode: Insoluble electrode ・ Cathode: Copper foil carrier treated surface ・ Distance between electrodes (shown in Table 1)
-Electrolytic plating solution composition (NiSO ₄ : 100 g / L)
Electrolytic plating solution pH: 6.7
-Electroplating bath temperature: 40 ° C
-Current density of electroplating: 5 A / dm ²
Electrolytic plating time: 10 seconds Copper foil carrier transport tension: 0.05 kg / mm (Example 18 is 0.15 kg / mm)
(B) Foil handling system using drums ・ Anode: Insoluble electrode ・ Cathode: Copper foil carrier surface supported by drum of 100 cm in diameter ・ Distance between electrodes (shown in Table 1)
-Electrolytic plating solution composition (NiSO ₄ : 100 g / L)
Electrolytic plating solution pH: 6.7
-Electroplating bath temperature: 40 ° C
-Current density of electroplating: 5 A / dm ²
Electrolytic plating time: 10 seconds Copper foil carrier transport tension: 0.05 kg / mm

(Ultra-thin copper layer formation)
(A) Carrying foil method by 99-fold ・ Anode: Insoluble electrode ・ Cathode: Copper foil carrier treated surface ・ Distance between electrodes (shown in Table 1)
Electrolytic plating solution composition (Cu: 50 g / L, H ₂ SO ₄ : 50 g / L, Cl: 60 ppm)
-Electroplating bath temperature: 45 ° C
-Current density of electrolytic plating: 30 A / dm ²
Copper foil carrier transport tension: 0.05 kg / mm (Example 18 is 0.15 kg / mm)
(B) Foil handling system using drums ・ Anode: Insoluble electrode ・ Cathode: Copper foil carrier surface supported by drum of 100 cm in diameter ・ Distance between electrodes (shown in Table 1)
・ Linear flow velocity (shown in Table 1)
Electrolytic plating solution composition (Cu: 100 g / L, H ₂ SO ₄ : 80 g / L, Cl: 60 ppm
-Electroplating bath temperature: 55 ° C
-Current density of electrolytic plating: 30 A / dm ²
-Copper foil carrier transport tension: 0.05 kg / mm

(Roughening treatment layer formation)
(A) Carrying foil method by 99-fold ・ Anode: Insoluble electrode ・ Cathode: Copper foil carrier treated surface ・ Distance between electrodes (shown in Table 1)
・ Linear flow velocity (shown in Table 1)
Electrolytic plating solution composition (Cu: 10 g / L, H ₂ SO ₄ : 50 g / L)
-Electroplating bath temperature: 40 ° C
-Current density of electrolytic plating: 30 A / dm ²
Copper foil carrier transport tension: 0.05 kg / mm (Example 18 is 0.15 kg / mm)
(B) Foil handling system using drums ・ Anode: Insoluble electrode ・ Cathode: Copper foil carrier surface supported by drum of 100 cm in diameter ・ Distance between electrodes (shown in Table 1)
・ Linear flow velocity (shown in Table 1)
Electrolytic plating solution composition (Cu: 20 g / L, H ₂ SO ₄ : 50 g / L)
-Electroplating bath temperature: 40 ° C
-Current density of electrolytic plating: 30 A / dm ²
-Copper foil carrier transport tension: 0.05 kg / mm

2. Evaluation of copper foil with carrier The copper foil with carrier obtained as described above was evaluated for thickness accuracy by the following method. The results are shown in Table 1.

<Evaluation of thickness accuracy by weight thickness method C>
First, after measuring the weight of the copper foil with carrier (total weight of the copper foil carrier, release layer, ultrathin copper layer, and surface treatment layer (roughening layer, etc.) on the ultrathin copper layer), ultrathin copper The layer was peeled off, the weight of the copper foil carrier was measured again, and the difference between the former and the latter was defined as the weight of the ultrathin copper layer. The copper foil piece with a carrier to be measured was a 5 cm square sheet punched out with a press. In order to investigate the weight-thickness accuracy, the weight-thickness measurement values of the ultra-thin copper layer pieces of 15 points in total in each example and comparative example, 5 points at equal intervals in the width direction and 3 points in the length direction (40 mm intervals). The average value and standard deviation (σ) were determined. The formula for calculating the weight thickness accuracy was as follows.
Thickness accuracy (%) = average value of 3σ × 100 / weight thickness measurement value The repeatability of this measurement method was 0.2%.
Moreover, HF-400 by A & D Co., Ltd. was used for the weight scale, and HAP-12 by Noguchi Press Co., Ltd. was used for the press machine.

<Evaluation D of thickness accuracy by weight-thickness method>
First, after measuring the weight of the copper foil with carrier (total weight of the copper foil carrier, release layer, ultrathin copper layer, and surface treatment layer (roughening layer, etc.) on the ultrathin copper layer), ultrathin copper The layer was peeled off, the weight of the copper foil carrier was measured again, and the difference between the former and the latter was defined as the weight of the ultrathin copper layer. The ultra-thin copper foil piece to be measured was cut with a cutter to a length of 150 mm in the TD direction after cutting a 15 mm wide sample in the MD direction with JDC PRECISION SAMPLE CUTTER (MODEL JDC 5-10) manufactured by THWIN-ALBERT INSTRUMENT COMPANY. By doing so, a 15 mm (MD direction) × 150 mm (TD direction) sheet was obtained. In order to investigate the weight-thickness accuracy, the weight-thickness measurement values of the ultra-thin copper layer pieces of 3 points at equal intervals in the width direction and 5 points in the length direction (40 mm intervals), a total of 15 points in each example and comparative example. The average value and standard deviation (σ) were determined. The formula for calculating the weight thickness accuracy was as follows.
Thickness accuracy (%) = average value of 3σ × 100 / weight thickness measurement value The repeatability of this measurement method was 0.2%.
The weighing scale used was HF-400 manufactured by A & D Corporation.

<Evaluation of thickness accuracy by weight-thickness method E>
First, after measuring the weight of the copper foil carrier and the copper foil with carrier (total weight of the copper foil carrier, the release layer, the ultrathin copper layer, and the surface treatment layer (such as the roughened layer) on the ultrathin copper layer) Then, the ultrathin copper layer was peeled off, the weight of the copper foil carrier was measured again, and the difference between the former and the latter was defined as the weight of the ultrathin copper layer. A thin copper foil piece to be measured is cut with a cutter to a length of 150 mm in the MD direction after cutting a 15 mm wide sample in the TD direction with JDC PRECISION SAMPLE CUTTER (MODEL JDC 5-10) manufactured by THWIN-ALBERT INSTRUMENT COMPANY. By doing so, a 15 mm (TD direction) × 150 mm (MD direction) sheet was obtained. In order to investigate the weight-thickness accuracy, the average value of the weight-thickness measurement values of ultra-thin copper layer pieces of 20 points in total, that is, 10 points at equal intervals in the width direction, 2 points in the length direction (10 mm intervals), and Standard deviation (σ) was determined. The formula for calculating the weight thickness accuracy was as follows.
Thickness accuracy (%) = average value of 3σ × 100 / weight thickness measurement value The repeatability of this measurement method was 0.2%.
The weighing scale used was HF-400 manufactured by A & D Corporation.

<Evaluation of circuit width variation>
For an ultra-thin copper layer, a circuit with L (line) / S (space) = 20 μm / 20 μm and a length of 200 μm was created, and a 10-point circuit width was measured at intervals of 10 μm. Values and standard deviations (σ circuit width) were determined, and circuit width variation was calculated by the following formula:
Circuit width variation (% / μm) = 3σ circuit width (μm) × 100 / (average circuit width (μm) × thickness of ultrathin copper layer (μm))
It is considered that the etching time varies depending on the thickness of the ultra-thin copper layer, and thereby the circuit width variation also varies. Therefore, in order to reduce the influence of the thickness of the ultrathin copper layer, the average value of 3σ circuit width (μm) × 100 / circuit width (μm) is divided by the value of the thickness (μm) of the ultrathin copper layer. ing.
The calculation results of the circuit width variation were evaluated as a to g based on the following criteria.
a: Circuit width variation (% / μm) is less than 0.15% / μm b: Circuit width variation (% / μm) is 0.15% / μm or more and less than 0.20% / μm c: Circuit width variation (% / Μm) is 0.20% / μm or more and less than 0.25% / μm d: Circuit width variation (% / μm) is 0.25% / μm or more and less than 0.26% / μm e: Circuit width variation (% / Μm) is 0.26% / μm or more and less than 0.28% / μm f: Circuit width variation (% / μm) is 0.28% / μm or more and less than 0.30% / μm g: Circuit width variation (% / Μm) is 0.30% / μm or more

<Etching property>
A copper foil with a carrier was attached to a polyimide substrate and heat-pressed at 220 ° C. for 2 hours, and then the ultrathin copper layer was peeled off from the carrier. Subsequently, after applying a photosensitive resist to the surface of the ultra-thin copper layer on the polyimide substrate, 50 L / S = 5 μm / 5 μm wide circuits are printed by an exposure process to remove unnecessary portions of the copper layer. The etching process was performed under the following spray etching conditions.
(Spray etching conditions)
Etching solution: Ferric chloride aqueous solution (Baume degree: 40 degrees)
Liquid temperature: 60 ° C
Spray pressure: 2.0 MPa
Etching was continued, the time until the circuit top width reached 4 μm was measured, and the circuit bottom width (the length of the base X) and the etching factor at that time were evaluated. The etching factor is the distance of the length of sagging from the intersection of the vertical line from the upper surface of the copper foil and the resin substrate, assuming that the circuit is etched vertically when sagging at the end (when sagging occurs) Is a ratio of a to the thickness b of the copper foil: b / a, and the larger the value, the larger the inclination angle, and the etching residue does not remain and the sagging is small. It means to become. FIG. 5 shows a schematic diagram of a cross section in the width direction of a circuit pattern and an outline of a method for calculating an etching factor using the schematic diagram. This X was measured by SEM observation from above the circuit, and the etching factor (EF = b / a) was calculated. In addition, it calculated by a = (X (μm) −4 (μm)) / 2. The etching factor is obtained by measuring 12 points in the circuit and taking an average value. Thereby, the quality of etching property can be determined easily. Also, by calculating the standard deviation of the 12 etching factors, it is possible to determine whether the linearity of the circuit formed by etching is good or bad. In addition, the circuit pattern was formed in both MD direction and TD direction of the ultra-thin copper layer, and each etching property was evaluated.
In the present invention, an etching factor of 4 or more is etching property: ◯, 2.5 or more and less than 4 are etching property: Δ, less than 2.5 or calculation is impossible or circuit formation is impossible. -Evaluated. Moreover, it can be said that the smaller the standard deviation of the etching factor, the better the linearity of the circuit. When the standard deviation of the etching factor was less than 0.8, the linearity was evaluated as ◯, when 0.8 to 1.2 or less was determined as the linearity: Δ, and 1.2 or more was determined as the linearity: x.
Table 1 shows the test conditions and test results.

(Evaluation results)
In Examples 1 to 21, the thickness accuracy by the weight-thickness method (Evaluation C) is 2.90% or less and the thickness accuracy by the weight-thickness method (Evaluation D) is 6.15% or less for the ultrathin copper layer. The thickness accuracy by the weight thickness method (Evaluation E) was 9.30% or less, the circuit width variation was small, and the etching property was also good.
In Comparative Examples 1 to 4, the thickness accuracy by the weight thickness method (Evaluation C) exceeds 2.90%, the thickness accuracy by the weight thickness method (Evaluation D) exceeds 6.15%, The thickness accuracy by the thickness method (Evaluation E) exceeded 9.30%, the thickness variation was large, and the etching property was poor.
Further, from the results of Table 1, regarding the circuit width variations a to g, the thickness accuracy of the evaluations C to D by the weight-thickness method gradually becomes poor as the best a goes to the bad g. Admitted. Therefore, it can be seen that there is a close correlation between the thickness accuracy of the ultra-thin copper layer and the variation in the width of the circuit fabricated using the copper layer.

Claims (11)

A copper foil with a carrier comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the release layer and thinner than the copper foil carrier, the ultrathin copper The thickness of the layer is 0.5 μm or more and 12 μm or less. Using the ultrathin copper layer as a 5 cm square sheet, the average value and standard deviation (σ) of the weight thickness measurement values are measured by the following weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight-thickness accuracy determined by the average value of weight thickness measured values is 2.90% or less copper foil with carrier.
(The above weight thickness method:
First, after measuring the weight of the copper foil with carrier, the ultrathin copper layer is peeled off, the weight of the copper foil carrier is measured again, and the difference between the former and the latter is defined as the weight of the ultrathin copper layer. The copper foil piece with a carrier to be measured is a 5 cm square sheet. In order to investigate the weight-thickness accuracy, 5 points at equal intervals in the width direction, 3 points in the length direction (40 mm interval), a total of 15 points of the weight-thickness measurement value of the ultrathin copper layer piece of the carrier-attached copper foil piece The average value and standard deviation (σ) are obtained. In addition, the calculation formula of weight thickness accuracy shall be the following formula.
Thickness accuracy (%) = 3σ × 100 / weight thickness average value) The copper foil with a carrier of Claim 1 which satisfy | fills the following (C) .
( C) Using the ultrathin copper layer as a 5 cm square sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by the following weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight-thickness accuracy determined by the average value of measured thickness values is 2% or less.
(Weight thickness method in (C) above:
First, after measuring the weight of the copper foil with carrier, the ultrathin copper layer is peeled off, the weight of the copper foil carrier is measured again, and the difference between the former and the latter is defined as the weight of the ultrathin copper layer. The copper foil piece with a carrier to be measured is a 5 cm square sheet. In order to investigate the weight-thickness accuracy, 5 points at equal intervals in the width direction, 3 points in the length direction (40 mm interval), a total of 15 points of the weight-thickness measurement value of the ultrathin copper layer piece of the carrier-attached copper foil piece The average value and standard deviation (σ) are obtained. In addition, the calculation formula of weight thickness accuracy shall be the following formula.
Thickness accuracy (%) = 3σ × 100 / weight thickness average value) The copper foil with a carrier according to claim 1 or 2 satisfying any one of the following (D)-(F).
(D) having a roughened layer on the surface of the ultrathin copper layer,
(E) From the group which has a roughening process layer on the surface of the said ultra-thin copper layer, and the surface of the said roughening process layer consists of a heat-resistant layer, a rust prevention layer, a chromate process layer, and a silane coupling process layer Having one or more selected layers,
(F) One or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer are provided on the surface of the ultrathin copper layer.   A resin layer is provided on the ultrathin copper layer or on the roughening treatment layer or on one or more layers selected from the group consisting of the heat-resistant layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer. The copper foil with a carrier in any one of Claims 1-3. By treating the surface of the long copper foil carrier conveyed in the length direction by the roll-to-roll conveyance method, the copper foil carrier, the release layer laminated on the copper foil carrier, and the release layer Is a method of manufacturing a copper foil with a carrier provided with an ultrathin copper layer laminated on
Forming a release layer on the surface of the copper foil carrier transported by the transport roll;
A step of forming an ultrathin copper layer on the surface of the release layer by electrolytic plating while supporting the copper foil carrier on which the release layer is conveyed by a transfer roll with a drum;
The manufacturing method of the copper foil with a carrier in any one of Claims 1-4 containing this. It is an ultrathin copper layer thinner than a copper foil carrier by an electrolytic copper foil, which is laminated on a peeling layer laminated on a copper foil carrier and constitutes a copper foil with a carrier together with the copper foil carrier and the peeling layer. The thickness of the ultrathin copper layer is not less than 0.5 μm and not more than 12 μm. Using the ultrathin copper layer as a 5 cm square sheet, the average value and standard deviation (σ) of the weight thickness measurement values are measured by the following weight thickness method. And the following formula:
Thickness accuracy (%) = 3σ × 100 / ultra-thin copper layer having a weight-thickness accuracy of 2.90% or less determined by an average value of measured thickness values.
(The above weight thickness method:
First, after measuring the weight of the copper foil with carrier, the ultrathin copper layer is peeled off, the weight of the copper foil carrier is measured again, and the difference between the former and the latter is defined as the weight of the ultrathin copper layer. The copper foil piece with a carrier to be measured is a 5 cm square sheet. In order to investigate the weight-thickness accuracy, 5 points at equal intervals in the width direction, 3 points in the length direction (40 mm interval), a total of 15 points of the weight-thickness measurement value of the ultrathin copper layer piece of the carrier-attached copper foil piece The average value and standard deviation (σ) are obtained. In addition, the calculation formula of weight thickness accuracy shall be the following formula.
Thickness accuracy (%) = 3σ × 100 / weight thickness average value) The ultrathin copper layer according to claim 6 satisfying the following (I) .
( I) Using the ultrathin copper layer as a 5 cm square sheet, an average value and a standard deviation (σ) of weight thickness measurement values were measured by the following weight thickness method, and the following formula:
Thickness accuracy (%) = 3σ × 100 / weight-thickness accuracy determined by the average value of measured thickness values is 2% or less.
(Weight thickness method in (I) above:
First, after measuring the weight of the copper foil with carrier, the ultrathin copper layer is peeled off, the weight of the copper foil carrier is measured again, and the difference between the former and the latter is defined as the weight of the ultrathin copper layer. The copper foil piece with a carrier to be measured is a 5 cm square sheet. In order to investigate the weight-thickness accuracy, 5 points at equal intervals in the width direction, 3 points in the length direction (40 mm interval), a total of 15 points of the weight-thickness measurement value of the ultrathin copper layer piece of the carrier-attached copper foil piece The average value and standard deviation (σ) are obtained. In addition, the calculation formula of weight thickness accuracy shall be the following formula.
Thickness accuracy (%) = 3σ × 100 / weight thickness average value) An ultra-thin copper layer made of electrolytic copper foil, which is laminated on a release layer laminated on a copper foil carrier and constitutes a copper foil with a carrier together with the copper foil carrier and the release layer,
The ultrathin copper layer according to claim 6 or 7 having a roughened layer on the surface.   The copper foil with a carrier according to any one of claims 1 to 4, the copper foil with a carrier produced by the method for producing a copper foil with a carrier according to claim 5, or the copper foil with a carrier according to claim 6 or 7. A method of manufacturing a printed wiring board using an ultrathin copper layer.   The copper foil with a carrier according to any one of claims 1 to 4, the copper foil with a carrier produced by the method for producing a copper foil with a carrier according to claim 5, or the copper foil with a carrier according to claim 6 or 7. A method for producing a copper clad laminate using an ultrathin copper layer. The copper foil with a carrier according to any one of claims 1 to 4, the copper foil with a carrier produced by the method for producing a copper foil with a carrier according to claim 5, or the copper foil according to claim 6 or 7. Preparing an ultra-thin copper layer and an insulating substrate;
A step of laminating the copper foil with carrier and an insulating substrate; and
After laminating the copper foil with carrier and the insulating substrate, a copper clad laminate is formed through a step of peeling the copper foil carrier of the copper foil with carrier,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.