JP6360659B2 - Copper foil with carrier, method of producing a printed wiring board using the copper foil with carrier, method of producing a copper clad laminate using the copper foil with carrier, and method of producing a printed wiring board - Google Patents

Description

  The present invention relates to a copper foil with a carrier. In more detail, this invention relates to the copper foil with a carrier used as a material of a printed wiring board.

  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. 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 through a release layer, since it is easily broken or wrinkled. After bonding the surface of the ultrathin copper layer to an insulating substrate and thermocompression bonding, the carrier is peeled and removed through the peeling layer. After forming a circuit pattern with a resist on the exposed ultrathin copper layer, the ultrathin copper layer is etched away with a sulfuric acid-hydrogen peroxide etchant (MSAP: Modified-Semi-Additive-Process). Is formed.

  Here, for 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 base material 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, in WO2004 / 005588 (Patent Document 1), a copper foil with a carrier that is not subjected to a roughening treatment on the surface of an ultrathin copper layer is used as a copper foil with a carrier for use in a fine circuit including a semiconductor package substrate. It has been tried. 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. Therefore, the further improvement is calculated | required about copper foil with a carrier.

  Therefore, in Japanese Patent Application Laid-Open No. 2007-007937 (Patent Document 2) and Japanese Patent Application Laid-Open No. 2010-006071 (Patent Document 3), the surface of the ultrathin copper foil with carrier that contacts (adheres) the polyimide resin substrate is Ni. It is described that a layer or / and a Ni alloy layer are provided, a chromate layer is provided, a Cr layer or / and a Cr alloy layer are provided, a Ni layer and a chromate layer are provided, and a Ni layer and a Cr layer are provided. Has been. By providing these surface treatment layers, the adhesion strength between the polyimide resin substrate and the ultra-thin copper foil with carrier is not roughened, or the desired adhesive strength is achieved while reducing the degree of the roughening treatment (miniaturization). It has gained. Further, it is described that the surface treatment is performed with a silane coupling agent or the rust prevention treatment is performed.

WO2004 / 005588 JP 2007-007937 A JP 2010-006071 A

  In the development of a copper foil with a carrier, the emphasis has so far been on ensuring the peel strength between the ultrathin copper layer and the resin substrate. For this reason, the fine pitch has not been sufficiently studied yet, and there is still room for improvement. Then, this invention makes it a subject to provide the copper foil with a carrier suitable for fine pitch formation. Specifically, it is an object to provide a copper foil with a carrier capable of forming wiring finer than L / S = 20 μm / 20 μm, which has been considered to be a limit that can be formed by conventional MSAP.

  In order to achieve the above object, the present inventors have intensively researched, increasing the thickness accuracy of the ultrathin copper layer, reducing the surface roughness of the ultrathin copper layer, and ultrathin copper layer. Further, it has been found that a uniform and low roughness roughened surface can be formed by forming finely roughened particles uniformly in the surface. And it discovered that the said copper foil with a carrier was very effective for fine pitch formation.

  The present invention has been completed on the basis of the above knowledge, and in one aspect, includes a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the release layer. The thickness of the ultrathin copper layer measured by the weight-thickness method is 3.0% or less, and the average value of Rz on the surface of the ultrathin copper layer is JIS It is a copper foil with a carrier which is 1.5 μm or less as measured in accordance with B0601-1982 and has a standard deviation of Rz of 0.1 μm or less.

  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, The thickness accuracy of the ultrathin copper layer measured by the four-point probe method is 10.0% or less, and the average value of Rz on the surface of the ultrathin copper layer is a contact roughness meter according to JIS B0601-1982. It is a copper foil with a carrier measured to be 1.5 μm or less and having a standard deviation of Rz of 0.1 μm or less.

  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. The thickness accuracy of the ultrathin copper layer measured by the weight-thickness method is 3.0% or less, and the average value of Rt on the surface of the ultrathin copper layer is measured according to JIS B0601-2001 with a contact type roughness meter. The carrier-attached copper foil has a standard deviation of Rt of not more than 2.0 μm and a standard deviation of Rt of not more than 0.1 μm.

  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. The thickness accuracy of the ultrathin copper layer measured by the four probe method is 10.0% or less, and the average value of Rt on the surface of the ultrathin copper layer is a contact type roughness meter according to JIS B0601-2001. The carrier-attached copper foil having a Rt standard deviation of 0.1 μm or less.

  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. The thickness accuracy of the ultrathin copper layer measured by the weight-thickness method is 3.0% or less, and the average value of Ra on the surface of the ultrathin copper layer is measured according to JIS B0601-1982 with a contact-type roughness meter. The carrier-attached copper foil is 0.2 μm or less and the standard deviation of Ra is 0.03 μm or less.

  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. The thickness accuracy of the ultrathin copper layer measured by the four-probe method is 10.0% or less, and the average value of Ra on the surface of the ultrathin copper layer is a contact type roughness meter according to JIS B0601-1982. The copper foil with a carrier is 0.2 μm or less and the standard deviation of Ra is 0.03 μm or less.

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

  In still another aspect, the present invention is a printed circuit board manufactured using the carrier-attached copper foil according to the present invention.

  In yet another aspect, the present invention is a copper clad laminate produced using the carrier-attached copper foil according to the present invention.

In yet another aspect of the present invention, a process for preparing a copper foil with a carrier and an insulating substrate according to the present invention,
A step of laminating the copper foil with carrier and an insulating substrate; and
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Thereafter, the printed wiring board manufacturing method includes a step of forming a circuit by any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.

  The copper foil with a carrier according to the present invention is suitable for fine pitch formation, for example, a wiring finer than L / S = 20 μm / 20 μm, which is considered to be a limit that can be formed by the MSAP process, for example, L / S = 15 μm / It becomes possible to form fine wiring of 15 μm. In particular, in the present invention, since the in-plane uniformity of the surface roughness in the ultra-thin copper layer is high, the in-plane uniformity is improved in flash etching when forming a circuit by the MSAP method, and therefore, an improvement in yield is expected. Is done.

It is a schematic diagram which shows the conveyance method using a drum. It is a schematic diagram which shows the carrying system by 99 folds. It is a schematic diagram for demonstrating the calculation method of an etching factor.

<1. Career>
A copper foil is used as a carrier that can be used in the present invention. The carrier is typically provided in the form of rolled copper foil or 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.

  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 70 μm or less. Accordingly, the thickness of the carrier is typically 12-70 μm, more typically 18-35 μm.

<2. Release layer>
A release layer is provided on the carrier. 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 may be one or more of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, alloys thereof, hydrates thereof, oxides thereof, or organic substances. It is preferable to form with the layer containing. 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 has a function of preventing diffusion of elements from the base material to the ultrathin copper layer side.

In one embodiment of the present invention, the release layer is a single metal layer made of any one element of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al elements from the carrier side, Or an alloy layer (having a function of preventing diffusion) composed of one or more elements selected from the group of elements of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al, It is comprised from the layer which consists of the hydrate or oxide of the 1 or more element selected from the laminated | stacked element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al. 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 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 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. Ultra-thin 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 carrier, for example, 12 μm or less. It is typically 0.5-12 μm, more typically 2-5 μm.

<4. Roughening>
On the surface of the ultrathin copper layer, a roughening treatment layer is provided by performing a roughening treatment, for example, for improving 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 treatment layer is preferably composed of fine particles from the viewpoint of fine pitch formation. Regarding the electroplating conditions for forming the roughened particles, if the current density is increased, the copper concentration in the plating solution is decreased, or the amount of coulomb is increased, the particles tend to become finer.

  The roughening layer is composed of electrodeposited grains made of any single element selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc, or an alloy containing at least one of them. can do.

  In order to improve the in-plane uniformity of the surface roughness on the surface treatment surface, it is effective to keep the anode-cathode distance constant when the roughening treatment layer is formed. Although not limited, a method of securing a certain distance between the electrodes by a foil carrying method using a drum or the like as a supporting medium is effective from the viewpoint of industrial production. FIG. 1 is a schematic view showing the foil handling method. A roughened particle layer is formed on the surface of the ultrathin copper layer by electrolytic plating while supporting the carrier copper foil conveyed by the conveyance roll with a drum. The treated surface of the carrier copper foil supported by the drum also serves as the cathode, and each electrolytic plating is performed in a plating solution between this drum and an anode provided so as to face the drum. On the other hand, FIG. 2 is a schematic diagram showing a conventional foil handling method using ninety-nine folds. In this method, there is a problem that it is difficult to keep the distance between the anode and the cathode constant due to the influence of the electrolytic solution and the foil carrying tension. However, even with the 99-fold method, the tension applied in the transport direction of the copper foil carrier being transported can be increased by introducing a support roll or shortening the distance between the current-carrying rolls. It is possible to stabilize the distance to a certain extent.

  As shown in FIG. 1, the foil carrying method using a drum can be used not only for roughening treatment but also for forming a release layer and an ultrathin copper layer. This is because it is possible to improve the thickness accuracy of the release layer and the ultrathin copper layer by adopting the drum carrying method. In particular, increasing the thickness accuracy of the ultrathin copper layer is advantageous in that it contributes to an improvement in the etching factor. As will be described later, the thickness accuracy of the ultrathin copper layer can be specified using the weight thickness method or the four-probe method in the present invention.

  In order to convey a long copper foil carrier by a roll-to-roll conveyance system using a drum, it is usually 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.

  The distance between the electrodes is not limited, but if it is too long, the production cost increases. On the other hand, if it is too short, the in-plane variation tends to increase, so generally 3 to 100 mm is preferable, and 5 to 80 mm is more preferable.

  Moreover, after roughening treatment, secondary particles, tertiary particles and / or rust prevention layers are formed with nickel, cobalt, copper, zinc alone or an alloy, etc., and further chromate treatment, silane coupling treatment, etc. on the surface You may perform the process of. That is, on the surface of the roughening treatment layer, one or more layers selected from the group consisting of a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer may be formed, and on the surface of the ultrathin copper layer, You may form 1 or more types of layers selected from the group which consists of a rust prevention layer, a chromate process layer, and a silane coupling process layer, without performing a roughening process. These surface treatments hardly affect the surface roughness of the ultrathin copper layer.

  The ultrathin copper layer after various surface treatments such as roughening treatment has a thickness accuracy of the ultrathin copper layer measured by the weight thickness method of 3.0% or less, preferably 2.0% or less. is there. The lower limit is not particularly limited but is, for example, 0.05% or more, 0.1% or more, or 0.2% or more.

A method for measuring thickness accuracy by the weight thickness method will be described. First, after measuring the weight of the copper foil with a carrier to be measured, the ultrathin copper layer is peeled off, the weight of the copper foil carrier is measured, and the difference between the former and the latter is defined as the weight of the ultrathin copper layer . The size of the copper foil with a carrier to be measured is a 5 cm square sheet punched out with a press. To investigate the weight-thickness accuracy, obtain the average value and standard deviation (σ) of the weight-thickness measurement values for a total of 15 square sheets, 5 points at equal intervals in the width direction and 3 points in the length direction (4 cm intervals). . In addition, the calculation formula of weight thickness accuracy shall be the following formula.
Thickness accuracy (%) = 3σ × 100 / average value The repeatability of this measurement method is 0.2%.

  The thickness of the ultrathin copper layer measured by the four-probe method is 10.0% or less, preferably 6.0% or less, after the surface treatment such as the roughening treatment. It is. The lower limit is not particularly limited, but is, for example, 0.05% or more, 0.5% or more, 0.7% or more, or 1.0% or more.

A method for measuring thickness accuracy by the four-probe method will be described. First, after determining the thickness of the copper foil with a carrier by measuring the thickness resistance with a four-point probe, the ultrathin copper layer was peeled off, the thickness due to the thickness resistance of the copper foil carrier was measured, and the former and the latter The difference is defined as the thickness of the ultrathin copper layer. In order to investigate the thickness accuracy, measurements are made at intervals of 5 mm in the width direction for each level, and an average value and standard deviation (σ) of a total of 280 measurement points are obtained. In addition, the calculation formula of the thickness accuracy by four probes is the following formula.
Thickness accuracy (%) = 3σ × 100 / average value The repeatability of this measurement method is 1.0%.

  The surface of the ultrathin copper layer after various surface treatments such as roughening treatment (also referred to as “surface treated surface”) is Rz when measured according to JIS B0601-1982 with a contact-type roughness meter. An average value of (ten-point average roughness) of 1.5 μm or less is extremely advantageous from the viewpoint of fine pitch formation. The average value of Rz is preferably 1.4 μm or less, and more preferably 1.3 μm or less. However, the average value of Rz is preferably 0.01 μm or more, more preferably 0.1 μm or more, and more preferably 0.3 μm or more because the adhesive strength with the resin decreases if the average value becomes too small. More preferably 0.5 μm or more. In the present invention, the average value of Rz employs the average value of each Rz obtained when the standard deviation of Rz is obtained by the method described below.

  In the present invention, the standard deviation of Rz on the surface-treated surface can be 0.1 μm or less, preferably 0.05 μm or less, for example, 0.01 to 0.7 μm. The standard deviation of Rz on the surface-treated surface is obtained from in-plane 100-point measurement data. In addition, the measurement data of 100 points in the plane can be obtained by dividing a 550 mm square sheet into 10 parts in the vertical direction and the horizontal direction, and measuring each central part of 100 divided areas. In this case, this method is used to maintain in-plane uniformity, but the verification method is not limited to this. For example, the same data can be collected even if a sample having a size of 550 mm × 440 mm to 400 mm × 200 mm, which is generally used, is divided into 100 planes (vertically and horizontally 10 sections).

  The surface treated surface should have an average value of Rt (maximum cross-sectional height) of 2.0 μm or less, preferably 1.8 μm or less when measured according to JIS B0601-2001 with a contact-type roughness meter. Is desirable from the viewpoint of fine pitch formation. However, if the average value of Rt becomes too small, the adhesive strength with the resin is lowered, so that it is preferably 0.5 μm or more, more preferably 0.6 μm or more, and even more preferably 0.8 μm or more. is there. In the present invention, the average value of Rt is the average value of each Rt obtained when the standard deviation of Rt is obtained by the method described below.

  Further, in the present invention, the standard deviation of Rt on the surface-treated surface can be 0.1 μm or less, preferably 0.05 μm or less, for example, 0.01 to 0.6 μm. The standard deviation of Rt on the surface-treated surface is obtained from the measurement data at 100 points in the surface in the same manner as Rz.

  In addition, the surface treated surface has a Ra (arithmetic mean roughness) average value of 0.2 μm or less when measured according to JIS B0601-1982 with a contact-type roughness meter from the viewpoint of fine pitch formation. desirable. However, if the average value of Ra becomes too small, the adhesive strength with the resin is lowered, so that it is preferably 0.01 μm or more, more preferably 0.05 μm or more, and even more preferably 0.12 μm or more. And most preferably 0.13 μm or more. In the present invention, the average value of Ra is adopted as the average value of each Ra obtained when the standard deviation of Ra is obtained by the method described below.

  In the present invention, the standard deviation of Ra on the surface-treated surface can be 0.03 μm or less, preferably 0.02 μm or less, for example, 0.001 to 00.3 μm. The standard deviation of Ra on the surface-treated surface is obtained from measurement data at 100 points in the surface in the same manner as Rz.

  In addition, in the case where an insulating substrate such as a resin is bonded to the surface of an ultrathin copper layer, such as a printed wiring board or a copper clad laminate, by melting and removing the insulating substrate, the copper circuit or copper foil surface, The aforementioned surface roughness (Ra, Rt, Rz) can be measured.

<5. Copper foil with carrier>
Thus, the copper foil with a carrier provided with the copper foil carrier, the peeling layer laminated | stacked on the copper foil carrier, and the ultra-thin copper layer laminated | stacked on the peeling 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. A copper-clad laminate is formed by bonding to an insulating substrate such as a base epoxy resin, glass cloth / glass nonwoven fabric composite base epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc., and peeling the carrier after thermocompression bonding After that, the ultrathin copper layer bonded to the insulating substrate is etched into the intended conductor pattern, and finally a printed wiring board can be manufactured.

  The copper foil with a carrier according to the present invention is suitable for forming a fine-pitch printed wiring board. For example, by using the copper foil with a carrier according to the present invention, it has an insulating substrate and a copper circuit provided on the insulating substrate, the circuit width of the copper circuit is less than 20 μm, and adjacent copper A printed wiring board having a space width between circuits of less than 20 μm can be manufactured. Furthermore, it is also possible to manufacture a printed wiring board in which the circuit width of the copper circuit is 17 μm or less and the width of the space between adjacent copper circuits is 17 μm or less. Furthermore, it is also possible to manufacture a printed wiring board in which the circuit width of the copper circuit is 15 μm or less and the width of the space between adjacent copper circuits is 15 μm or less. Furthermore, it is also possible to manufacture a printed wiring board in which the circuit width of the copper circuit is 5 to 10 μm and the width of the space between adjacent copper circuits is 5 to 10 μm.

Furthermore, a printed circuit board is completed by mounting electronic components on the printed wiring board. By using the copper foil with a carrier according to the present invention, for example, it has an insulating substrate and a copper circuit provided on the insulating substrate, the circuit width of the copper circuit is less than 20 μm, and adjacent copper A printed circuit board having a space width between circuits of less than 20 μm can be manufactured. Furthermore, it is also possible to manufacture a printed circuit board in which the circuit width of the copper circuit is 17 μm or less, and the width of the space between adjacent copper circuits is 17 μm or less. Furthermore, it is also possible to manufacture a printed wiring board in which the circuit width of the copper circuit is 17 μm or less and the width of the space between adjacent copper circuits is 17 μm or less. Furthermore, it is also possible to manufacture a printed circuit board in which the circuit width of the copper circuit is 15 μm or less, and the width of the space between adjacent copper circuits is 15 μm or less. Furthermore, the circuit width of the copper circuit is 5 to 10 μm, preferably 5 to 9 μm, more preferably 5 to 8 μm, and the width of the space between adjacent copper circuits is 5 to 10 μm, preferably 5 to 9 μm. It is also possible to produce printed circuit boards which are preferably 5-8 μm. The line-and-space pitch is preferably less than 40 μm, more preferably 34 μm or less, more preferably 30 μm or less, more preferably 20 μm or less, and more preferably 15 μm or less. The lower limit of the line and space need not be specified, but is, for example, 6 μm or more, 8 μm or more, or 10 μm or more.
The line-and-space pitch is a distance from the center of the width of the copper circuit to the center of the width of the adjacent copper circuit.

Moreover, the copper foil with a carrier provided with a carrier and a peeling layer laminated on the carrier and an ultrathin copper layer laminated on the peeling layer comprises a roughening treatment layer on the ultrathin 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 thermocompression bonded 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 of the ultrathin copper layer on the peeling layer side), 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.

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. In the following examples and comparative examples, when forming surface treatment layers such as a release layer, an ultrathin copper layer, and a roughened particle layer, either the ninety-nine fold method or the drum method is described in Table 1. Adopted according to requirements. The common conditions for the 99-fold method and the drum method are as follows.
<Ninety-nine folding method>
・ Anode: Insoluble electrode ・ Cathode: Copper foil carrier treated surface ・ Copper foil carrier transport tension: 0.05 kg / mm
<Drum system>
・ Anode: Insoluble electrode ・ Cathode: Copper foil carrier treated surface supported by drum of 100 cm in diameter ・ Copper foil carrier transport tension: 0.05 kg / mm

1. Production of copper foil with carrier <Examples 1, 6, 11, 16>
As a copper foil carrier, a long electrolytic copper foil having a thickness of 35 μm (JTC manufactured by JX Nippon Mining & Metals) was prepared. The copper foil's shiny surface (Rz: 1.2 to 1.4 μm) is electroplated with a roll-to-roll continuous plating line under the following conditions to provide an adhesion amount of 4000 μg / dm ^2. A layer was formed.

-Ni layer Nickel sulfate: 250-300 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Trisodium citrate: 15-30 g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 30-100 ppm
pH: 4-6
Bath temperature: 50-70 ° C
Current density: 3-15 A / dm ²

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

Subsequently, on the roll-to-roll type continuous plating line, an ultrathin copper layer having the thickness shown in Table 1 is formed on the Cr layer by electroplating under the following conditions to produce a copper foil with a carrier. did.
-Ultrathin copper layer Copper concentration: 30-120 g / L
H ₂ SO ₄ concentration: 20 to 120 g / L
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm ²

Next, the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and silane coupling treatment were performed in this order on the surface of the ultrathin copper layer.
・ Roughening 1
(Liquid composition 1)
Cu: 10-30 g / L
H ₂ SO _4: 10~150g / L
W: 0 to 50 mg / L
Sodium dodecyl sulfate: 0 to 50 mg / L
As: 0 to 200 mg / L
(Electroplating condition 1)
Temperature: 30-70 ° C
Current density: 25 to 110 A / dm ²
Roughening coulomb amount: 50 to 500 As / dm ²
Plating time: 0.5 to 20 seconds, roughening treatment 2
(Liquid composition 2)
Cu: 20-80 g / L
H ₂ SO ₄ : 50 to 200 g / L
(Electroplating condition 2)
Temperature: 30-70 ° C
Current density: 5 to 50 A / dm ²
Roughening coulomb amount: 50 to 300 As / dm ²
Plating time: 1 to 60 seconds, rust prevention treatment (liquid composition)
NaOH: 40-200 g / L
NaCN: 70 to 250 g / L
CuCN: 50-200 g / L
Zn (CN) ₂ : _{2 to} 100 g / L
As ₂ O ₃ : 0.01 to 1 g / L
(Liquid temperature)
40-90 ° C
(Current condition)
Current density: 1 to 50 A / dm ²
Plating time: 1 to 20 seconds, chromate treatment K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnOH or ZnSO ₄ .7H ₂ O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density: 0.05 to 5 A / dm ²
Time: 5 to 30 seconds. Silane coupling treatment After applying 0.1 vol% to 0.3 vol% of 3-glycidoxypropyltrimethoxysilane aqueous solution, 0.1 to 10 in air at 100 to 200 ° C. Dry and heat for seconds.

<Examples 2, 7, 12, 17>
After forming an ultrathin copper layer on the copper foil carrier under the same conditions as in Example 1, the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and silane coupling treatment were performed in this order. went.
・ Roughening 1
Liquid composition: Copper 10-20 g / L, sulfuric acid 50-100 g / L
Liquid temperature: 25-50 degreeC
Current density: 1 to 58 A / dm ²
Coulomb amount: 4 to 81 As / dm ²
・ Roughening 2
Liquid composition: Copper 10-20 g / L, nickel 5-15 g / L, cobalt 5-15 g / L
pH: 2-3
Liquid temperature: 30-50 degreeC
Current density: 24 to 50 A / dm ²
Coulomb amount: 34 to 48 As / dm ²
・ Rust prevention treatment Liquid composition: Nickel 5-20g / L, Cobalt 1-8g / L
pH: 2-3
Liquid temperature: 40-60 degreeC
Current density: 5 to 20 A / dm ²
Coulomb amount: 10-20 As / dm ²
-Chromate treatment Liquid composition: Potassium dichromate 1-10 g / L, Zinc 0-5 g / L
pH: 3-4
Liquid temperature: 50-60 degreeC
Current density: 0 to ^{2 A} / dm ² (Can also be electroless because of immersion chromate treatment)
Coulomb amount: 0 to ^{2 As} / dm ² (can also be electroless because of immersion chromate treatment)
Silane coupling treatment Application of diaminosilane aqueous solution (diaminosilane concentration: 0.1 to 0.5 wt%)

<Examples 3, 8, 13, 18>
Prepare a long electrolytic copper foil (HLP made by JX Nippon Mining & Metals) with a thickness of 35 μm as the copper foil carrier, and perform it on the shiny surface (Rz: 0.1 to 0.3 μm) of this copper foil A copper foil with a carrier was prepared in the same procedure as in Example 1.

<Examples 4, 9, 14, 19>
Prepare a long electrolytic copper foil (HLP made by JX Nippon Mining & Metals) with a thickness of 35 μm as the copper foil carrier, and perform it on the shiny surface (Rz: 0.1 to 0.3 μm) of this copper foil A copper foil with a carrier was prepared in the same procedure as in Example 2.

<Examples 5, 10, 15, 20>
A long electrolytic copper foil (HLP made by JX Nippon Mining & Metals) having a thickness of 35 μm was prepared as a copper foil carrier. The copper foil shiny surface (Rz: 0.1 to 0.3 μm) was electroplated on a roll-to-roll continuous plating line under the same conditions as in Example 1 to obtain 4000 μg / dm ² . After forming an adhesion amount of Ni layer and then forming an ultrathin copper layer in the same procedure as in Example 1, the following rust prevention treatment was performed without performing the roughening treatment.
・ Rust prevention treatment Liquid composition: Nickel 5-20g / L, Cobalt 1-8g / L
pH: 2-3
Liquid temperature: 40-60 degreeC
Current density: 5 to 20 A / dm ²
Coulomb amount: 10-20 As / dm ²

<Example 21>
A copper foil with a carrier was produced under the same conditions as in Example 19 except that the release layer, the ultrathin copper layer, and the surface treatment layer were all formed by the 99-fold method. However, two pairs of pinch rolls (two transport rolls sandwiching the copper foil from the front side and the back side) are introduced as support rolls between the current roll and the current roll, and the copper foil carrier transport tension is tripled (0. 15 kg / mm), which is higher than Example 19, thereby stabilizing the distance between the electrodes.

<Comparative Example 1>
After forming the ultrathin copper layer on the copper foil carrier under the same conditions as in Example 1, the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and The silane coupling treatment was performed in this order.
・ Roughening 1
(Liquid composition 1)
Cu: 31 to 45 g / L
H ₂ SO _4: 10~150g / L
As: 0.1-200 mg / L
(Electroplating condition 1)
Temperature: 30-70 ° C
Current density: 25 to 110 A / dm ²
Roughening coulomb amount: 50 to 500 As / dm ²
Plating time: 0.5 to 20 seconds, roughening treatment 2
(Liquid composition 2)
Cu: 20-80 g / L
H ₂ SO ₄ : 50 to 200 g / L
(Electroplating condition 2)
Temperature: 30-70 ° C
Current density: 5 to 50 A / dm ²
Roughening coulomb amount: 50 to 300 As / dm ²
Plating time: 1 to 60 seconds, rust prevention treatment (liquid composition)
NaOH: 40-200 g / L
NaCN: 70 to 250 g / L
CuCN: 50-200 g / L
Zn (CN) ₂ : _{2 to} 100 g / L
As ₂ O ₃ : 0.01 to 1 g / L
(Liquid temperature)
40-90 ° C
(Current condition)
Current density: 1 to 50 A / dm ²
Plating time: 1 to 20 seconds, chromate treatment K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnOH or ZnSO ₄ .7H ₂ O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density: 0.05 to 5 A / dm ²
Time: 5 to 30 seconds. Silane coupling treatment After applying 0.1 vol% to 0.3 vol% of 3-glycidoxypropyltrimethoxysilane aqueous solution, 0.1 to 10 in air at 100 to 200 ° C. Dry and heat for seconds.

<Comparative example 2>
A copper foil with a carrier was produced under the same conditions as in Example 3 except that the release layer, the ultrathin copper layer, and the surface treatment layer were all formed by the 99-fold method.

<Comparative Example 3>
A copper foil with a carrier was prepared in the same procedure as in Example 2, except that the release layer, the ultrathin copper layer, and the surface treatment layer were all formed by the 99-fold method.

<Comparative example 4>
A copper foil with a carrier was manufactured under the same conditions as in Example 1 except that the ultrathin copper layer was formed by the 99-fold method.

<Comparative Example 5>
A copper foil with a carrier was produced under the same conditions as in Example 2 except that the ultrathin copper layer was formed by the 99-fold method.

<Comparative Example 6>
A copper foil with a carrier was produced under the same conditions as in Example 3 except that the ultrathin copper layer was formed by the 99-fold method.

<Comparative Example 7>
A copper foil with a carrier was manufactured under the same conditions as in Example 4 except that the ultrathin copper layer was formed by the 99-fold method.

<Comparative Example 8>
A copper foil with a carrier was produced under the same conditions as in Example 5 except that the ultrathin copper layer was formed by the 99-fold method.

2. Evaluation of characteristics of copper foil with carrier The characteristics of the copper foil with carrier obtained as described above were evaluated by the following method. The results are shown in Table 1. In Table 1, “E-16” of “Ra” in the “standard deviation (μm) column” means × 10 ⁻¹⁶ .

(Evaluation of thickness accuracy by weight-thickness method)
The thickness accuracy was measured by the weight thickness method described above. The weighing machine used was HF-400 manufactured by A & D Co., Ltd., and the press used HAP-12 manufactured by Noguchi Press Co., Ltd.

(Evaluation of thickness accuracy by four probe method)
The thickness accuracy was measured by the four-probe method described above. As the four probes, CMI-700 manufactured by OXFORD INSTRUMENTS was used.

(Surface roughness)
A straight line was drawn vertically and horizontally at a pitch of 55 mm from each copper foil with a carrier (550 mm × 550 mm square), and 100 square regions of 55 mm × 55 mm were assigned to each. Conforms to JIS B0601-1982 (Ra, Rz) and JIS B0601-2001 (Rt) using a contact-type roughness measuring machine (contact roughness meter Surfcoder SE-3C manufactured by Kosaka Laboratory Ltd.) for each region. Then, the surface roughness (Ra, Rt, Rz) of the ultrathin copper layer was measured under the following measurement conditions, and the average value and standard deviation were measured.
<Measurement conditions>
Cut-off: 0.25mm
Standard length: 0.8mm
Measurement ambient temperature: 23-25 ° C

(migration)
Each carrier-attached copper foil (550 mm × 550 mm square) was bonded to a bismuth-based resin, and then the carrier foil was peeled off. The thickness of the exposed ultrathin copper layer was set to 1.5 μm by soft etching. Then, after washing and drying, DF (manufactured by Hitachi Chemical Co., Ltd., trade name RY-3625) was laminated on the ultrathin copper layer. Exposure was performed at a condition of 15 mJ / cm ^{2, and} the liquid jet rocking was performed for 1 minute at 38 ° C. using a developer (sodium carbonate) to form a resist pattern with line and space (L / S) = 15 μm / 15 μm. Next, after UP was plated by 15 μm using copper sulfate plating (CUBRITE 21 manufactured by Sugawara Eugeneite), DF was peeled off with a stripping solution (sodium hydroxide). Thereafter, the ultrathin copper layer was removed by etching with a sulfuric acid-hydrogen peroxide etchant to form a wiring of L / S = 15 μm / 15 μm. From the obtained wiring board, 100 wiring boards were cut out according to the above-mentioned area of 55 mm × 55 mm.
With respect to each obtained wiring board, the presence or absence of insulation deterioration between wiring patterns was evaluated using a migration measuring machine (IMV MIG-9000) under the following measurement conditions. The number of substrates on which migration occurred on 100 wiring substrates was evaluated.

  In addition, in Example 17, the above-described migration was performed by forming a wiring with a line and space pitch of 20 μm (L / S = 8 μm / 12 μm, L / S = 10 μm / 10 μm, L / S = 12 μm / 8 μm). Was evaluated. In Example 18, the line and space pitch is 20 μm (L / S = 8 μm / 12 μm, L / S = 10 μm / 10 μm, L / S = 12 μm / 8 μm), and the line and space pitch is 15 μm ( (L / S = 5 μm / 10 μm, L / S = 8 μm / 7 μm) was formed and the above-described migration was evaluated. When the line and space pitch was 15 μm, the thickness of the plating UP was 10 μm. As a result, when the wiring with L / S = 8 μm / 12 μm, L / S = 10 μm / 10 μm, L / S = 12 μm / 8 μm was formed using the copper foil with carrier of Example 17, the in-plane migration occurrence rate was They were 1/100, 1/100, and 2/100, respectively. Moreover, using the copper foil with a carrier of Example 18, L / S = 8 μm / 12 μm, L / S = 10 μm / 10 μm, L / S = 12 μm / 8 μm, L / S = 5 μm / 10 μm, L / S = 8 μm When / 7 μm wiring was formed, the in-plane migration occurrence rates were 1/100, 1/100, 1/100, 0/100, and 2/100, respectively.

<Measurement conditions>
Threshold: Initial resistance 60% down Measurement time: 1000h
Voltage: 60V
Temperature: 85 ° C
Relative humidity: 85% RH

Claims (9)

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 copper foil with a carrier whose thickness accuracy of the ultra-thin copper layer measured by the weight-thickness method is 3.0% or less and 0.1% or more and satisfies the following (A ) .
(A) The average value of Rz on the surface of the ultrathin copper layer is 1.5 μm or less and 0.01 μm or more as measured by a contact roughness meter according to JIS B0601-1982, and the standard deviation of Rz is Ru der below 0.01μm more than 0.1μm.
(Weight thickness method:
First, after measuring the weight of the copper foil with a carrier to be measured, the ultrathin copper layer is peeled off, the weight of the copper foil carrier is measured, and the difference between the former and the latter is defined as the weight of the ultrathin copper layer . The size of the copper foil with a carrier to be measured is a 5 cm square sheet punched out with a press. To investigate the weight-thickness accuracy, obtain the average value and standard deviation (σ) of the weight-thickness measurement values for a total of 15 square sheets, 5 points at equal intervals in the width direction and 3 points in the length direction (4 cm intervals). . In addition, the calculation formula of weight thickness accuracy shall be the following formula.
Thickness accuracy (%) = 3σ × 100 / average value) Furthermore, the copper foil with a carrier of Claim 1 which satisfy | fills any one or more of the following (B) or (C).
(B) The average value of Rt on the surface of the ultrathin copper layer is 2.0 μm or less and 0.5 μm or more as measured according to JIS B0601-2001 with a contact type roughness meter, and the standard deviation of Rt is 0.1 μm or less and 0.01 μm or more.
(C) The average value of Ra on the surface of the ultrathin copper layer is 0.2 μm or less and 0.01 μm or more as measured by a contact roughness meter according to JIS B0601-1982, and the standard deviation of Ra is It is 0.03 μm or less 3.18E-16 μm or more.   The copper foil with a carrier of Claim 1 or 2 which has a roughening process layer on the surface of an ultra-thin copper layer.   The copper foil with a carrier of Claim 3 which has 1 or more types of layers selected from the group which consists of a heat-resistant layer, a rust prevention layer, a chromate processing layer, and a silane coupling processing layer on the surface of the said roughening process layer.   The surface of the said ultra-thin copper layer has 1 or more types of layers selected from the group which consists of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. Copper foil with carrier.   Resin layer on one or more layers selected from the group consisting of the ultrathin copper layer, the roughening treatment layer, or the heat-resistant layer, the rust prevention layer, the chromate treatment layer and the silane coupling treatment layer The copper foil with a carrier as described in any one of Claims 1-5 provided with these. A method for producing a printed wiring board comprising at least one wiring having an L / S of 20 μm / 20 μm or less, using the copper foil with a carrier according to claim 1.   The method to manufacture a copper clad laminated board using the copper foil with a carrier in any one of Claims 1-6. Preparing a copper foil with carrier and an insulating substrate according to any one of claims 1 to 6,
A step of laminating the copper foil with carrier and an insulating substrate; and
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Thereafter, a printed wiring including at least one wiring having an L / S of 20 μm / 20 μm or less, including a step of forming a circuit by any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. A manufacturing method of a board.