JP5544444B1 - Resin base material, printed wiring board, printed circuit board, copper-clad laminate, and printed wiring board manufacturing method - Google Patents

Abstract

The present invention provides a resin base material having a surface profile shape that maintains fine wiring formability and realizes good adhesion of an electroless copper plating film.
A resin base material having a surface roughness Sz of 1 to 5 μm.
[Selection] Figure 3

Description

  The present invention relates to a resin substrate, a printed wiring board, a printed circuit board, a copper-clad laminate, and a method for manufacturing a printed wiring board.

  The circuit forming method for the semiconductor package substrate and the printed wiring board is mainly a subtractive method. However, in recent years, with higher integration of semiconductors, miniaturization of circuits of semiconductor package substrates and printed wiring boards used therein has progressed, and it has become difficult to form microcircuits by a subtractive method.

  As a countermeasure for further miniaturization, circuit formation method (1), prepreg and build-up is performed by pattern copper plating using ultra-thin copper foil as a power feeding layer and finally removing the ultra-thin copper layer by flash etching. Circuit formation method (2), copper foil surface profile that forms reliable fine wiring by curing the film with a vacuum press etc., roughening the surface and forming appropriate irregularities on the substrate surface A circuit forming method (3) that forms a reliable fine wiring by transferring to a substrate surface and forming appropriate irregularities on the substrate surface has attracted attention. These methods are generally called the SAP method (semi-additive method).

  The SAP method using the profile of the copper foil surface is described in Patent Document 1, for example. The following is mentioned as an example of the typical SAP method using the profile of such copper foil surface. That is, the entire surface of the copper foil laminated on the resin is etched, the etched substrate surface is perforated, the desmear treatment is applied to the entire surface or part of the perforated portion and the substrate, and the dry film is applied to the etched surface of the perforated portion. Then, the portion of the dry film that does not form a circuit is exposed and developed, the unnecessary portion of the dry film is removed with a chemical solution, and the electroless copper plating is applied to the etching substrate surface to which the copper foil surface profile not covered with the dry film is transferred. Electro copper plating is performed, and finally the electroless copper plating layer is removed by flash etching to form fine wiring.

JP 2006-196863 A

  For fine wiring formation, it is preferable that the profile of the substrate surface is small and smooth, but in this case, the adhesion of the electroless copper plating film is weakened, and the reliability required for the semiconductor package substrate or printed wiring board is reduced. There is a risk of damage. On the other hand, in order to ensure the adhesion of the electroless copper plating film, it is preferable that the profile of the base material surface is large. However, in this case, the fine wiring formability may be impaired.

  With respect to these points, the prior art has not been sufficiently studied, and there is still room for improvement. Then, this invention makes it a subject to provide the resin base material provided with the profile shape of the surface which maintains the fine wiring formation property and implement | achieves the favorable adhesive force of an electroless copper plating film.

  In order to achieve the above-mentioned object, the present inventors have conducted intensive research and have found that when a circuit is formed on the surface of a resin substrate by using a resin substrate whose surface roughness Sz is controlled within a predetermined range. It has been found that the fine wiring formability can be maintained and the good adhesion of the electroless copper plating film can be realized.

The present invention has been completed on the basis of the above knowledge. In one aspect, the present invention is a resin base material having Sz of 1 to 5 μm based on surface roughness ISO25178 .

  In another aspect of the present invention, the resin base material has a ratio B / A of the surface three-dimensional surface area B to the two-dimensional surface area A of 1.01 to 1.5.

  In still another aspect, the present invention is a printed wiring board manufactured using the resin base material of the present invention.

  In still another aspect, the present invention is a printed circuit board manufactured using the resin base material of the present invention.

  In still another aspect, the present invention is a copper clad laminate produced using the resin base material of the present invention.

  In yet another aspect of the present invention, the step of preparing a surface-treated copper foil and a resin base material, the step of laminating the surface-treated copper foil on the resin base material from the surface-treated layer side, on the resin base material It is a manufacturing method of a printed wiring board including the process of removing the surface treatment copper foil, and obtaining the resin base material of the present invention, and the process of forming a circuit on the surface of the resin base material from which the surface treatment copper foil was removed.

  In yet another aspect of the present invention, the carrier, intermediate layer, and ultrathin copper layer are laminated in this order to prepare a carrier-attached copper foil and a resin base material, The step of laminating the resin base material from the ultrathin copper layer side, the step of peeling the carrier of the copper foil with carrier and the resin base material after peeling the carrier after laminating the copper foil with carrier and the resin base material It is the manufacturing method of a printed wiring board including the process of removing the upper ultra-thin copper layer and obtaining the resin base material of this invention, and the process of forming a circuit on the surface of the resin base material from which the ultra-thin copper layer was removed.

  ADVANTAGE OF THE INVENTION According to this invention, the resin base material provided with the profile shape of the surface which maintains the fine wiring formation property and implement | achieves the favorable adhesive force of an electroless copper plating film | membrane can be provided.

A schematic example of a semi-additive construction method using a copper foil profile is shown. The sample preparation flow for obtaining the data of an Example and a comparative example is shown. Resin base material surface SEM images of Examples 1, 2, 3, 5, and 6 are shown in (a), (b), (c), (d), and (e), respectively. (F), (g) shows the resin base material surface SEM images of Comparative Examples 1 and 2, respectively.

[Resin substrate]
The resin base material according to the present invention is not particularly limited as long as the surface form described below can be formed. FG, etc.) and a prepreg (EI-6785TS-F, etc.) manufactured by Sumitomo Bakelite. In the present invention, a prepreg GHPL-830MBT manufactured by Mitsubishi Gas Chemical Company was prepared. The substrate press manufacturer's recommended conditions were used for the temperature, pressure, and time of the lamination press.

  Although it does not specifically limit as thickness of the resin base material which concerns on this invention, For example, it can be set as 750-850 micrometers, 100-200 micrometers, 30-100 micrometers, and is typically 30-200 micrometers (in the case of a double-sided board). is there.

[Surface roughness Sz]
In the SAP method, conventionally, as a method for quantifying the profile shape of the surface of a substrate forming a circuit, roughness measurement using a contact-type roughness meter has been common. On the other hand, in the present invention, the profile shape of the substrate surface in which the surface roughness Sz measured by the laser roughness meter is defined within the appropriate range maintains the fine wiring formability more satisfactorily. It has been found that good adhesion of the electrolytic copper plating film can be realized. From such a viewpoint, the resin base material according to the present invention is controlled to 1 to 5 μm. When the surface roughness Sz of the resin base material surface is less than 1 μm, it is difficult to achieve good adhesion of the electroless copper plating film. Further, when the surface roughness Sz on the surface of the resin substrate is more than 5 μm, the fine wiring formability on the surface of the resin substrate is deteriorated. The surface roughness Sz of the resin substrate surface is preferably 1 to 4 μm, more preferably 1.5 to 3.5 μm, and still more preferably 2 to 3 μm.

[Area ratio B / A]
The profile shape of the surface of the resin base material having the ratio of the three-dimensional surface area to the two-dimensional surface area within a predetermined range provides good fine wiring formability and good adhesion of the electroless copper plating film. From such a viewpoint, it is preferable that the ratio B / A between the three-dimensional surface area B and the two-dimensional surface area A on the surface of the resin substrate according to the present invention is controlled to 1.01 to 1.5. When the ratio B / A between the three-dimensional surface area B and the two-dimensional surface area A on the surface of the resin substrate is less than 1.01, it is difficult to achieve good adhesion of the electroless copper plating film. Further, when the ratio B / A of the three-dimensional surface area B and the two-dimensional surface area A on the resin base material surface is more than 1.5, the fine wiring formability on the resin base material surface is deteriorated. The ratio B / A between the three-dimensional surface area B and the two-dimensional surface area A of the resin substrate surface according to the present invention is preferably 1.03 to 1.4, more preferably 1.05 to 1.35, and still more preferably. 1.1 to 1.3.

[Black area ratio and average hole diameter]
When the degree of unevenness on the surface of the resin base material is indicated by the black area ratio obtained from the SEM observation photograph, the profile shape of the surface of the resin base material having the black area ratio in a predetermined range has good fine wiring formability. In addition, good adhesion of the electroless copper plating film is realized. From such a viewpoint, it is preferable that the black area ratio on the surface of the resin substrate according to the present invention is controlled to be 10 to 50%. Here, as the black area ratio, the SEM image (30 k times) of the substrate surface was subjected to white / black image processing using Photoshop 7.0 software, and the area ratio (%) of the black area was obtained. For the black area ratio (%), a “histogram” of “image” in Photoshop 7.0 was selected, and the ratio at the threshold value 128 was used. The black region indicates that the measurement surface is concave, and the white portion indicates that the measurement surface is convex. If the black area ratio on the surface of the substrate is less than 10%, it is difficult to achieve good adhesion of the electroless copper plating film. If the black area ratio on the surface of the substrate is more than 50%, the fine wiring formability deteriorates.

  At the same time as the black area ratio, the profile shape of the surface of the resin base material having a diameter average value of holes on the surface within a predetermined range has good fine wiring formability and good adhesion of the electroless copper plating film It is a necessary condition to realize. The reason is that the black area ratio alone does not satisfy the profile size and the appropriate distribution on the plane. From such a viewpoint, it is preferable that the average diameter value of the holes on the surface of the resin substrate according to the present invention is controlled to be 0.03 to 1.0 μm. If the average diameter of the holes on the surface of the resin substrate is less than 0.03 μm, it is difficult to achieve good adhesion of the electroless copper plating film. If the average diameter value of the holes on the surface of the resin substrate is more than 1.0 μm, the fine wiring formability deteriorates.

  Thus, the resin base material according to the present invention preferably has a black surface area ratio of 10 to 50% on the base material surface and a diameter average value of the holes of 0.03 to 1.0 μm. More preferably, the area ratio is 15 to 45% and the average diameter of the holes is 0.1 to 0.8 μm, the black area ratio is 20 to 40% and the average diameter of the holes is 0.15. Even more preferably, it is -0.7 μm.

[Method for forming surface profile of resin substrate]
The profile shape of the surface of the resin base material according to the present invention can be formed by laminating the surface-treated copper foil on the resin base material and then removing the surface-treated copper foil by etching or the like on the entire surface. Moreover, the profile shape of the surface of the resin base material which concerns on this invention can be formed by processing the resin base material surface by a predetermined chemical | medical solution.

As a method for forming a surface profile of a resin substrate according to the present invention using a surface-treated copper foil, first, a surface-treated copper foil in which the surface roughness Sz of the surface-treated layer surface is controlled to 2 to 6 μm is prepared. . Next, it bonds together to the resin base material from the surface treatment layer side of the said surface treatment copper foil, and removes surface treatment copper foil by whole surface etching etc. Thereby, the surface roughness Sz of the resin base material surface after surface treatment copper foil removal will be 1-5 micrometers.
In addition, as the surface-treated copper foil, a resin base material is similarly used by using a surface-treated layer whose surface ratio B / A of the three-dimensional surface area B and the two-dimensional surface area A is controlled to 1.05 to 1.8. When the surface-treated copper foil is removed by overall etching or the like, the ratio B / A of the three-dimensional surface area B and the two-dimensional surface area A of the resin base material surface after the surface-treated copper foil is removed is 1.01. 1.5.
Similarly, as the surface-treated copper foil, the surface roughness Sz with a laser roughness meter is 2 to 6 μm, and the ratio B / A of the three-dimensional surface area B to the two-dimensional surface area A is 1.05 to 1.8. In the same manner, when the surface-treated copper foil is removed by overall etching or the like, the black area ratio of the resin substrate surface is 10 to 50%, the resin substrate surface The average diameter of the holes can be controlled to 0.03 to 1.0 μm.
By controlling the current density of the surface treatment and the immersion time in the plating solution after completion of the surface treatment during the surface treatment such as the formation of the roughened particles, the surface state of the copper foil after the surface treatment, the form of the roughened particles, The formation density is determined, whereby the surface roughness Sz, the area ratio B / A, the black area ratio, and the average diameter of the holes of the surface-treated copper foil can be controlled.
Specifically, at the time of surface treatment such as when roughening particles are formed, the surface treatment is performed by controlling the current density of the surface treatment high, and then the surface treatment is performed by controlling the current density of the surface treatment low, The surface state of the copper foil after the surface treatment, the form and formation density of the roughened particles are determined, and the surface roughness Sz, the area ratio B / A, the black area ratio, and the average diameter of the holes can be controlled. . It is also effective to repeatedly perform the surface treatment by controlling the current density of the surface treatment high, and then performing the surface treatment by controlling the current density of the surface treatment low.
Here, when the current density of the surface treatment is increased during the surface treatment such as during the formation of roughened particles, the deposited metal particles tend to grow in a direction perpendicular to the surface of the copper foil. Moreover, when the current density of the surface treatment is lowered during the surface treatment such as the formation of roughened particles, the copper foil surface tends to be smooth (unevenness is reduced).
Therefore, the surface treatment is performed by controlling the current density of the surface treatment high, and then the surface treatment is performed by controlling the current density of the surface treatment low, after the metal particles are grown in the direction perpendicular to the copper foil surface. It is considered that the surface state is controlled by filling the metal particles and the copper foil surface with unevenness and smoothing the surface.
Moreover, when the surface treatment layer of copper foil is easy to melt | dissolve in a plating solution, there exists a tendency for the influence of the immersion time in the plating solution after completion | finish of a surface treatment which acts on the surface form of a surface treatment copper foil to become larger.

  As a method for forming the surface profile of the resin substrate according to the present invention by treatment with a chemical solution (the surface roughness Sz, area ratio B / A, black area ratio, hole diameter average value), It can form by performing a desmear process on the immersion process conditions A or B of No. 1, and performing a neutralization process after that.

(Desmear processing condition A)
Desmear treatment liquid: 40 g / L KMnO ₄ , 20 g / L NaOH
・ Processing temperature: Room temperature ・ Immersion time: 20 minutes ・ Rotating speed of stirring bar: 300 rpm
(Desmear processing condition B)
Desmear treatment solution: 90 g / L KMnO ₄ , 5 g / L HCl
・ Processing temperature: 49 ℃
・ Immersion time: 20 minutes ・ Stirrer rotation speed: 300 rpm
(Neutralization conditions)
・ Neutralization treatment liquid: L-ascorbic acid 80 g / L
・ Processing temperature: Room temperature ・ Immersion time: 3 minutes ・ No stirring

In addition to the immersion treatment, the surface profile of the resin substrate (the surface roughness Sz, the area is the same) by performing shower treatments A and B and neutralization treatment on the resin substrate surface under the following treatment conditions. (B / A ratio, black area ratio, hole diameter average value) can be formed.
(Shower treatment condition A)
Desmear treatment liquid: 40 g / L KMnO ₄ , 20 g / L NaOH
・ Processing temperature: Room temperature ・ Processing time: 20 minutes ・ Shower pressure: 0.2 MPa
(Shower treatment condition B)
Desmear treatment solution: 90 g / L KMnO ₄ , 5 g / L HCl
・ Processing temperature: 49 ℃
・ Processing time: 20 minutes ・ Shower pressure: 0.2 MPa
(Neutralization conditions)
・ Neutralization treatment liquid: L-ascorbic acid 80 g / L
・ Processing temperature: Room temperature ・ Immersion time: 3 minutes ・ No stirring

[Surface treated copper foil]
The copper foil used in the surface-treated copper foil for forming the surface profile of the resin substrate may be either an electrolytic copper foil or a rolled copper foil. The thickness of the copper foil is not particularly limited, but is, for example, 1 μm or more, 2 μm or more, 3 μm or more, 5 μm or more, for example, 3000 μm or less, 1500 μm or less, 800 μm or less, 300 μm or less, 150 μm or less, 100 μm or less, 70 μm or less. , 50 μm or less and 40 μm or less.

  The rolled copper foil used in the present invention contains a copper alloy containing one or more elements such as Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, V, B, and Co. Foil is also included. When the concentration of the above elements increases (for example, 10% by mass or more in total), the conductivity may decrease. The conductivity of the rolled copper foil is preferably 50% IACS or more, more preferably 60% IACS or more, and still more preferably 80% IACS or more. The rolled copper foil includes copper foil produced using tough pitch copper (JIS H3100 C1100) or oxygen-free copper (JIS H3100 C1020). In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.

Moreover, about the electrolytic copper foil which can be used for this invention, it can produce with the following electrolyte solution composition and manufacturing conditions.
・ General electrolytic raw foil:
<Electrolyte composition>
Copper: 80-120 g / L
Sulfuric acid: 80-120 g / L
Chlorine: 30-100ppm
Leveling agent (Nika): 0.1-10ppm
・ Double-sided flat electrolytic foil, carrier copper foil of ultra-thin copper foil with carrier:
<Electrolyte composition>
Copper: 80-120 g / L
Sulfuric acid: 80-120 g / L
Chlorine: 30-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
As the amine compound, an amine compound having the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.)

<Production conditions>
Current density: 70 to 100 A / dm ²
Electrolyte temperature: 50-65 ° C
Electrolyte linear velocity: 1.5-5 m / sec
Electrolysis time: 0.5 to 10 minutes (adjusted according to the thickness of copper to be deposited and current density)

As the roughening treatment, alloy plating such as copper-cobalt-nickel alloy plating, copper-nickel-phosphorus alloy plating, copper-nickel-tungsten alloy plating, copper-cobalt-tungsten alloy plating, and more preferably copper alloy plating is used. it can. Copper as roughening treatment - cobalt - nickel alloy plating, by electrolytic plating, coating weight is to be the 15~40mg / dm ² of copper -100~3000μg / dm ² of cobalt -100~1500μg / dm ² of nickel It can be carried out so as to form a ternary alloy layer. If the amount of deposited Co is less than 100 μg / dm ² , the heat resistance may deteriorate and the etching property may deteriorate. When the amount of Co deposition exceeds 3000 μg / dm ² , it is not preferable when the influence of magnetism must be taken into account, etching spots may occur, and acid resistance and chemical resistance may deteriorate. If the Ni adhesion amount is less than 100 μg / dm ² , the heat resistance may deteriorate. On the other hand, when the Ni adhesion amount exceeds 1500 μg / dm ² , the etching residue may increase. A preferable Co adhesion amount is 1000 to 2500 μg / dm ² , and a preferable nickel adhesion amount is 500 to 1200 μg / dm ² . Here, the etching stain means that Co remains without being dissolved when etched with copper chloride, and the etching residue means that Ni remains without being dissolved when alkaline etching is performed with ammonium chloride. It means that.

The plating bath and plating conditions for forming such ternary copper-cobalt-nickel alloy plating are as follows:
Plating bath composition: Cu 10-20 g / L, Co 1-10 g / L, Ni 1-10 g / L
pH: 1-4
Temperature: 30-50 ° C
Current density D _k : 20 to 30 A / dm ²
Plating time: 1 to 5 seconds The plating solution immersion time after the end of plating: 20 seconds or less (because the particle shape is disturbed when immersed for longer than 20 seconds), preferably 10 seconds or less, more preferably 5 seconds or less Thereafter, if it is normal, it is not particularly quickly removed from the plating solution, but in the present invention, it is necessary to remove from the plating solution within a predetermined time after the completion of the plating. For this reason, as described above, the plating solution immersion time after the completion of the plating is set to 20 seconds or less. If the immersion time exceeds 20 seconds, a part of the roughened particles may be dissolved by the plating solution. It is considered that dissolution of a part of the roughened particles is one of the causes of the disturbance of the particle shape.
By shortening the plating solution immersion time after the completion of the plating to 10 seconds or less, or 5 seconds or less, the particle shape can be made more difficult to disturb, which is effective.
In addition, as with copper-cobalt-nickel alloy plating, alloy plating other than copper-cobalt-nickel alloy plating also has a plating solution immersion time of 20 seconds or less after completion of plating. Therefore, it is important to control to 10 seconds or less, more preferably 5 seconds or less. If the immersion time exceeds 20 seconds, a part of the roughened particles may be dissolved by the plating solution. It is considered that dissolution of a part of the roughened particles is one of the causes of the disturbance of the particle shape. Known conditions can be used for pH, temperature, current density, and plating time of alloy plating other than copper-cobalt-nickel alloy plating.
By shortening the plating solution immersion time after the completion of the plating to 10 seconds or less, or 5 seconds or less, the particle shape can be made more difficult to disturb, which is effective.
Further, copper plating as the following roughening treatment may be performed as the surface treatment. The surface treatment layer formed by copper plating as the following roughening treatment has a high copper concentration, and becomes a roughening treatment layer (plating layer) mostly composed of copper. A roughening layer (plating layer) having a high copper concentration is characterized by being hardly soluble in the plating solution. Copper plating as the following roughening treatment is performed in the order of copper plating 1 and copper plating 2.
・ Copper plating 1
(Liquid composition 1)
Cu concentration: 10-30 g / L
H ₂ SO ₄ concentration: 50 to 150 g / L
Tungsten concentration: 0.5-50 mg / L
Sodium dodecyl sulfate: 0.5-50 mg / L
(Electroplating condition 1)
Temperature: 30-70 ° C
(First stage current condition)
Current density: 18 to 70 A / dm ²
Roughening coulomb amount: 1.8 to 1000 A / dm ^2, preferably 1.8 to 500 A / dm ²
Plating time: 0.1 to 20 seconds (second stage current condition)
Current density: 0.5 to 13 A / dm ²
Roughening Coulomb amount: 0.05~1000A / dm ² preferably 0.05~500A / dm ²
Plating time: 0.1 to 20 seconds Note that the first and second steps may be repeated. Further, after the first stage is performed once or a plurality of times, the second stage may be performed once or a plurality of times. Further, after the first stage is performed once or a plurality of times, the second stage may be repeated once or a plurality of times.
・ Copper plating 2
(Liquid composition 2)
Cu concentration: 20-80 g / L
H ₂ SO ₄ concentration: 50 to 200 g / L
(Electroplating condition 2)
Temperature: 30-70 ° C
(Current condition)
Current density: 5 to 50 A / dm ²
Roughening coulomb amount: 50 to 300 A / dm ²
Plating time: 1 to 60 seconds In addition, the above-described copper plating may be combined with the above-described copper-cobalt-nickel alloy plating alloy plating. It is preferable to perform the alloy plating described above after the copper plating is performed on the copper foil.

  In the present invention, the surface treatment layer formed on the copper foil may be a roughening treatment layer. The roughening treatment is usually performed on the surface of the copper foil after degreasing for the purpose of improving the peel strength of the copper foil after being laminated on the surface of the copper foil to be bonded to the resin substrate, that is, the surface on the surface treatment side. A process for forming a fist-like electrodeposition. Although the electrolytic copper foil has irregularities at the time of manufacture, the irregularities can be further increased by enhancing the convex portions of the electrolytic copper foil by roughening treatment. 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 is a layer made of any single element selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc, or an alloy containing one or more of them. Also 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. Moreover, you may form 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 a roughening processing layer.

In the present invention, the surface treatment layer formed on the copper foil may be 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.
As the heat-resistant layer and the rust-proof layer, known heat-resistant layers and rust-proof layers can be used. For example, the heat-resistant layer and / or the anticorrosive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum A layer containing one or more elements selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements Further, it may be a metal layer or an alloy layer made of one or more elements selected from the group consisting of iron, tantalum and the like. The heat-resistant layer and / or rust preventive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. An oxide, nitride, or silicide containing one or more elements selected from the above may be included. Further, the heat-resistant layer and / or the rust preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and / or the rust preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% nickel and 50 wt% to 1 wt% zinc, excluding inevitable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg / m ² , preferably 10 to 500 mg / m ² , preferably 20 to 100 mg / m ² . Further, the ratio of the nickel adhesion amount and the zinc adhesion amount of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (= nickel adhesion amount / zinc adhesion amount) is 1.5 to 10. It is preferable. Further, the nickel - in adhesion amount of nickel in the zinc alloy layer is preferably from ^{0.5mg / m 2 ~500mg / m 2} , 1mg / m 2 ~50mg / m 2 - zinc alloy layer or the nickel containing More preferably. When the heat-resistant layer and / or rust prevention layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate is eroded by the desmear liquid when the inner wall such as a through hole or via hole comes into contact with the desmear liquid. It is difficult to improve the adhesion between the copper foil and the resin substrate.

For example heat-resistant layer and / or anticorrosive layer has coating weight of 1 mg / m ² -100 mg / m ^2, preferably from 5 mg / m ² and to 50 mg / m ² of nickel or nickel alloy layer, the adhesion amount is 1 mg / m ² to 80 mg / m ^2, preferably it may be obtained by sequentially laminating a tin layer of ^{5mg / m 2 ~40mg / m 2} , wherein the nickel alloy layer of nickel - molybdenum, nickel - zinc, nickel - molybdenum - cobalt You may be comprised by any one of these. The heat-resistant layer and / or anticorrosive layer, it is ^{preferably, 10mg / m 2 ~70mg / m} 2 total deposition amount of nickel or nickel alloy and tin is 2mg / m ² ~150mg / m 2 It is more preferable. Further, the heat-resistant layer and / or the rust preventive layer is preferably [nickel or nickel adhesion amount in nickel or nickel alloy] / [tin adhesion amount] = 0.25 to 10, preferably 0.33 to 3. More preferred. When the heat-resistant layer and / or rust-preventing layer is used, the carrier-clad copper foil is processed into a printed wiring board, and the subsequent circuit peeling strength, the chemical resistance deterioration rate of the peeling strength, and the like are improved.

  In addition, you may use a well-known silane coupling agent for the silane coupling agent used for a silane coupling process, for example, using an amino-type silane coupling agent or an epoxy-type silane coupling agent, a mercapto-type silane coupling agent. Good. Silane coupling agents include vinyltrimethoxysilane, vinylphenyltrimethoxylane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, and γ-aminopropyl. Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, γ-mercaptopropyltrimethoxysilane or the like may be used.

  The silane coupling treatment layer may be formed using a silane coupling agent such as an epoxy silane, an amino silane, a methacryloxy silane, or a mercapto silane. In addition, you may use 2 or more types of such silane coupling agents in mixture. Especially, it is preferable to form using an amino-type silane coupling agent or an epoxy-type silane coupling agent.

  The amino silane coupling agent referred to here is N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (3 -Acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl-3-aminopropyl) Trimethoxysilane, N (2-aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane, 6- (aminohexylaminopropyl) trimethoxysilane, aminophenyltrimethoxysilane, 3- (1-aminopropoxy) -3,3- Dimethyl-1-propenyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminoundecyltrimethoxysilane, 3- (2 -N-benzylaminoethylaminopropyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, (N, N- Dimethyl-3-aminopropyl) Limethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N -Β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane may be selected from the group consisting of Good.

The silane coupling treatment layer is 0.05 mg / m ^{2 to} 200 mg / m ² , preferably 0.15 mg / m ^{2 to} 20 mg / m ² , preferably 0.3 mg / m ^{2 to} 2.0 mg in terms of silicon atoms. / M ² is desirable. In the case of the above-mentioned range, the adhesiveness between the substrate and the surface-treated copper foil can be further improved.

[Copper foil with carrier]
As the surface-treated copper foil for forming the surface profile of the resin substrate, a copper foil with a carrier may be used. The copper foil with a carrier includes a carrier, an intermediate layer laminated on the carrier, and an ultrathin copper layer laminated on the intermediate layer.

<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.

  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 becomes high, so generally it is preferably 35 μm or less. Accordingly, the thickness of the carrier is typically 12-70 μm, more typically 18-35 μm.

<Intermediate layer>
An intermediate layer is provided on the carrier. In the intermediate layer used in the present invention, the ultrathin copper layer is hardly peeled off from the carrier before the copper foil with the carrier is laminated on the insulating substrate, while the ultrathin copper layer is separated from the carrier after the lamination step on the insulating substrate. There is no particular limitation as long as it can be peeled off. For example, the intermediate layer of the copper foil with a carrier of the present invention is Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, One or two or more selected from the group consisting of organic substances may be included. The intermediate layer may be a plurality of layers.
Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, A layer made of a hydrate or oxide of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. It can comprise by forming.
Further, for example, the intermediate layer can be configured by laminating nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy, and chromium in this order on a carrier. Since the adhesive strength between nickel and copper is higher than the adhesive strength between chromium and copper, when the ultrathin copper layer is peeled off, it peels at the interface between the ultrathin copper layer and chromium. Further, the nickel of the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin copper layer. Adhesion amount of nickel in the intermediate layer is preferably 100 [mu] g / dm ² or more 40000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 4000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 2500 g / dm ² or less, more Preferably, it is 100 μg / dm ² or more and less than 1000 μg / dm ² , and the amount of chromium deposited on the intermediate layer is preferably 5 μg / dm ² or more and 100 μg / dm ² or less. When the intermediate layer is provided only on one side, it is preferable to provide a rust preventive layer such as a Ni plating layer on the opposite side of the carrier.

<Ultrathin copper layer>
An ultrathin copper layer is provided on the intermediate layer. The ultrathin copper layer is the surface-treated copper foil of the present invention. The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. Typically, it is 0.5 to 12 μm, and more typically 1.5 to 5 μm. Further, strike plating with a copper-phosphorus alloy may be performed before reducing the pinholes in the ultrathin copper layer before providing the ultrathin copper layer on the intermediate layer. Examples of the strike plating include a copper pyrophosphate plating solution.

[Resin layer on the surface treatment layer]
A resin layer may be provided on the surface treatment layer of the surface-treated copper foil of the present invention. The resin layer may be an insulating resin layer.

  The resin layer may be an adhesive, or an insulating resin layer in a semi-cured state (B stage state) 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. The type is not particularly limited. For example, epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, maleimide resin, polyvinyl acetal resin, urethane resin, polyethersulfone, polyethersulfone Resin, aromatic polyamide resin, polyamideimide resin, rubber-modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine resin, thermosetting polyphenylene oxide resin, cyanate ester resin, polyvalent carboxyl A resin containing an acid anhydride or the like can be mentioned as a preferable one. The resin layer may be a resin layer containing a block copolymerized polyimide resin layer or a resin layer containing a block copolymerized polyimide resin and a polymaleimide compound. The epoxy resin has two or more epoxy groups in the molecule and can be used without any problem as long as it can be used for electric / electronic materials. The epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, glycidylamine Type epoxy resin, triglycidyl isocyanurate, glycidyl amine compound such as N, N-diglycidyl aniline, glycidyl ester compound such as tetrahydrophthalic acid diglycidyl ester, phosphorus-containing epoxy resin, biphenyl type epoxy resin, biphenyl novolac type epoxy resin, One or two or more selected from the group of trishydroxyphenylmethane type epoxy resin and tetraphenylethane type epoxy resin can be used, or the epoxy Resin hydrogenated products and halogenated products can be used.

  The polyhydric carboxylic acid anhydride is preferably a component that contributes as a curing agent for the epoxy resin. The anhydride of the polyvalent carboxylic acid is phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydroxyphthalic anhydride, hexahydroxyphthalic anhydride, methylhexahydroxyphthalic anhydride, nadine. Acid and methyl nadic acid are preferred.

  The resin composition for forming the resin layer may contain an anhydride of polyvalent carboxylic acid, a phenoxy resin, and an epoxy resin. The acid anhydride is preferably contained in an amount of 0.01 mol to 0.5 mol with respect to 1 mol of a hydroxyl group contained in the phenoxy resin. As the phenoxy resin, one synthesized by a reaction between bisphenol and a divalent epoxy resin can be used. The content of the phenoxy resin may be 3 to 30 parts by weight when the total amount of the resin composition is 100 parts by weight. The epoxy resin may be an epoxy resin epoxidized with a compound having two or more glycidyl groups in the molecule. The resin composition can be obtained by reacting a polycarboxylic acid anhydride with a phenoxy resin, ring-opening addition of the polyvalent carboxylic acid to the hydroxyl group of the phenoxy resin, and then adding an epoxy resin. it can.

  As the bisphenol, bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4′-dihydroxybiphenyl, HCA (9,10-Dihydro-9-Oxa-10-Phosphophenanthrene-10-Oxide), hydroquinone, naphthoquinone, etc. Bisphenol obtained as an adduct with quinones can be used.

The thermoplastic resin may be a thermoplastic resin having a functional group other than an alcoholic hydroxyl group polymerizable with an epoxy resin.
The composition of the resin layer contains 50 to 90% by weight of an epoxy resin, 5 to 20% by weight of a polyvinyl acetal resin, and 0.1 to 20% by weight of a urethane resin with respect to the total amount of the resin components. 40% by weight may be a rubber-modified epoxy resin.
The polyvinyl acetal resin may have a functional group polymerizable with an epoxy resin or a maleimide compound other than an acid group and a hydroxyl group. Functionality polymerizable with 40 to 80 parts by weight of an epoxy resin composition, 10 to 50 parts by weight of a maleimide compound, an epoxy resin other than a hydroxyl group and a hydroxyl group, or a maleimide compound with respect to 100 parts by weight of the resin composition used for the resin layer It may be from 5 to 30 parts by weight of a polyvinyl acetal resin having a group. Further, the polyvinyl acetal resin may have a carboxyl group, an amino group or an unsaturated double bond introduced into the molecule.

  The resin layer is 20 to 80 parts by weight of an epoxy resin (including a curing agent), 20 to 80 parts by weight of an aromatic polyamide resin polymer soluble in a solvent, and a curing that is added in an appropriate amount as necessary. It may be formed using a resin composition made of an accelerator. In addition, the resin layer is 5 to 80 parts by weight of an epoxy resin (including a curing agent), 20 to 95 parts by weight of an aromatic polyamide resin polymer soluble in a solvent, and curing that is added in an appropriate amount as necessary. It may be formed using a resin composition made of an accelerator. The aromatic polyamide resin polymer used for the composition of the resin composition used for forming the resin layer may be obtained by reacting an aromatic polyamide with a rubber resin. The resin layer may contain a dielectric filler. The resin layer may contain a skeleton material.

  Here, examples of the aromatic polyamide resin polymer include those obtained by reacting an aromatic polyamide resin and a rubber resin. Here, the aromatic polyamide resin is synthesized by condensation polymerization of an aromatic diamine and a dicarboxylic acid. In this case, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, m-xylenediamine, 3,3'-oxydianiline, or the like is used as the aromatic diamine. As the dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid or the like is used.

  The rubbery resin to be reacted with the aromatic polyamide resin is described as a concept including natural rubber and synthetic rubber, and the latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene. There is rubber. Furthermore, when ensuring the heat resistance of the dielectric layer to be formed, it is also useful to select and use a synthetic rubber having heat resistance such as nitrile rubber, chloroprene rubber, silicon rubber, urethane rubber or the like. Since these rubber resins react with an aromatic polyamide resin to produce a copolymer, it is desirable to have various functional groups at both ends. In particular, it is useful to use CTBN (carboxy group-terminated butadiene nitrile).

  The aromatic polyamide resin and rubber resin that constitute the aromatic polyamide resin polymer are preferably used in a blend of 25 wt% to 75 wt% of the aromatic polyamide resin and the remaining rubber resin. When the aromatic polyamide resin is less than 25 wt%, the abundance ratio of the rubber component is too high and the heat resistance is inferior. On the other hand, when it exceeds 75 wt%, the abundance ratio of the aromatic polyamide resin is too large to be cured. Later hardness becomes too high and becomes brittle. This aromatic polyamide resin polymer is used for the purpose of not being damaged by under-etching by an etchant when etching a copper foil after being processed into a copper-clad laminate.

  The aromatic polyamide resin polymer is required to have a property of being soluble in a solvent. This aromatic polyamide resin polymer is used in a blending ratio of 20 to 80 parts by weight. When the amount of the aromatic polyamide resin polymer is less than 20 parts by weight, it becomes too brittle under general press conditions for producing a copper clad laminate, and becomes microcracked easily on the substrate surface. On the other hand, there is no particular problem even if the aromatic polyamide resin polymer is added in an amount exceeding 80 parts by weight, but the strength after curing is not further improved even if the aromatic polyamide resin polymer is added in an amount exceeding 80 parts by weight. It is. Therefore, if economics are considered, it can be said that 80 weight part is an upper limit.

  “A curing accelerator to be added in an appropriate amount as needed” includes tertiary amines, imidazoles, urea-based curing accelerators, and the like. In the present invention, the mixing ratio of the curing accelerator is not particularly limited. This is because the curing accelerator may be arbitrarily selected by the manufacturer in consideration of production conditions in the process of producing the copper-clad laminate.

The resin composition for forming the resin layer is prepared by dissolving three types of epoxy resins, a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, and a brominated bisphenol A type epoxy resin, in a solvent, and a curing agent and finely pulverizing them. It may be a resin composition to which a reaction catalyst such as silica or antimony trioxide is added. The curing agent at this time is the same as described above. This resin composition also shows good adhesion between the copper foil and the base resin.
The resin composition for forming the resin layer is polyphenylene ether resin, 2,2-bis (4-cyanatophenyl) propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis (4-glycidylphenyl) It may be a polyphenylene ether-cyanate resin composition in which propane is dissolved in a solvent. This resin composition also shows good adhesion between the copper foil and the base resin.
The resin composition for forming the resin layer may be a siloxane-modified polyamideimide resin composition or a siloxane-modified polyamideimide resin composition in which a cresol novolac type epoxy resin is dissolved in a solvent. This resin composition also shows good adhesion between the copper foil and the base resin.

(In the case of a resin layer containing a dielectric (dielectric filler))
When a dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, it can be used for the purpose of forming a capacitor layer and increase the capacitance of the capacitor circuit. Examples of the dielectric (dielectric filler) include BaTiO ₃ , SrTiO ₃ , Pb (Zr—Ti) O ₃ (common name PZT), PbLaTiO ₃ · PbLaZrO (common name PLZT), SrBi ₂ Ta ₂ O ₉ (common name SBT), and the like. A composite oxide dielectric powder having a perovskite structure is used.

  The dielectric (dielectric filler) may be powdery. When the dielectric (dielectric filler) is powdery, the powder characteristics of the dielectric (dielectric filler) are as follows. First, the particle size is 0.01 μm to 3.0 μm, preferably 0.02 μm to 2.0 μm. Must be in range. The particle size referred to here is indirect in which the average particle size is estimated from the measured values of the laser diffraction scattering type particle size distribution measurement method and the BET method because the particles form a certain secondary aggregation state. It cannot be used because the accuracy is inferior in measurement, and it refers to the average particle diameter obtained by directly observing a dielectric (dielectric filler) with a scanning electron microscope (SEM) and image analysis of the SEM image. It is. In this specification, the particle size at this time is indicated as DIA. The image analysis of the dielectric (dielectric filler) powder observed using a scanning electron microscope (SEM) in this specification is performed using IP-1000PC manufactured by Asahi Engineering Co., Ltd. Circular particle analysis was performed with a threshold value of 10 and an overlapping degree of 20, and the average particle diameter DIA was obtained.

  Furthermore, the volume cumulative particle diameter D50 by the laser diffraction scattering particle size distribution measurement method is 0.2 μm to 2.0 μm, and the volume cumulative particle diameter D50 and the average particle diameter DIA obtained by image analysis are used to obtain D50 / It is required to be a dielectric powder having a substantially spherical perovskite structure with a cohesion value represented by DIA of 4.5 or less.

  The volume cumulative particle size D50 by the laser diffraction scattering type particle size distribution measurement method is a particle size at 50% weight cumulative obtained by using the laser diffraction scattering type particle size distribution measurement method, and the value of this volume cumulative particle size D50. The smaller the is, the larger the proportion of fine powder particles in the particle size distribution of the dielectric (dielectric filler) powder. In the present invention, this value is required to be 0.2 μm to 2.0 μm. That is, when the value of the volume cumulative particle diameter D50 is less than 0.2 μm, the progress of aggregation is remarkably satisfied with the degree of aggregation described below regardless of the production method of dielectric (dielectric filler) powder. It is not what you do. On the other hand, when the value of the volume cumulative particle diameter D50 exceeds 2.0 μm, it cannot be used as a dielectric (dielectric filler) for forming a built-in capacitor layer of a printed wiring board, which is an object of the present invention. It becomes. That is, the dielectric layer of the double-sided copper-clad laminate used to form the built-in capacitor layer is usually 10 μm to 25 μm thick, and 2.0 μm to uniformly disperse the dielectric filler therein. Is the upper limit.

  In the present invention, the volume cumulative particle size D50 is measured by mixing and dispersing dielectric (dielectric filler) powder in methyl ethyl ketone, and using this solution as a laser diffraction scattering type particle size distribution measuring device, Micro Trac HRA 9320-X100 (manufactured by Nikkiso Co., Ltd.). ) And then measured.

  Here, the concept of cohesion is used, which is adopted for the following reason. That is, the value of the volume cumulative particle size D50 obtained by using the laser diffraction / scattering particle size distribution measurement method is considered not to be a direct observation of each individual particle size. This is because the powder particles constituting most of the dielectric powder are not so-called monodispersed powders in which individual particles are completely separated, but are in a state where a plurality of powder particles are aggregated and aggregated. This is because the laser diffraction / scattering particle size distribution measurement method regards the aggregated particles as one particle (aggregated particle) and calculates the volume cumulative particle size.

  On the other hand, since the average particle diameter DIA obtained by image processing the observation image of the dielectric powder observed using the scanning electron microscope is obtained directly from the SEM observation image, the primary particles are surely obtained. On the other hand, the presence of the agglomerated state of the particles is not reflected at all.

  Considering the above, the present inventors calculated the value calculated by D50 / DIA using the volume cumulative particle diameter D50 of the laser diffraction scattering particle size distribution measurement method and the average particle diameter DIA obtained by image analysis. Is regarded as the degree of cohesion. That is, assuming that the values of D50 and DIA can be measured with the same accuracy in the same lot of copper powder, considering the above-mentioned theory, the value of D50 that reflects the presence of an agglomerated state is DIA. It is considered that the value is larger than the value of.

  At this time, the value of D50 approaches the value of DIA as much as possible if the state of aggregation of the dielectric (dielectric filler) powder is completely eliminated. The value of D50 / DIA as the degree of aggregation is It approaches 1 It can be said that it is a monodispersed powder in which the agglomeration state of the powder is completely lost when the aggregation degree becomes 1. However, in reality, the degree of aggregation may be less than 1. Theoretically, in the case of a true sphere, it does not become a value less than 1, but in reality, it seems that a cohesion value of less than 1 is obtained because the powder is not a true sphere. is there.

  In this invention, it is preferable that the aggregation degree of this dielectric material (dielectric filler) powder is 4.5 or less. If this degree of aggregation exceeds 4.5, the level of aggregation between the powder particles of the dielectric filler becomes too high, and uniform mixing with the above-described resin composition becomes difficult.

  As a method for producing a dielectric (dielectric filler) powder, a fixed aggregation state is inevitably formed even if any production method such as an alkoxide method, a hydrothermal synthesis method, or an oxalate method is employed. Dielectric filler powder that does not satisfy the degree of aggregation can be generated. In particular, in the case of the hydrothermal synthesis method which is a wet method, the formation of an aggregated state tends to occur. Therefore, the aggregated state of the dielectric filler powder can be set within the above-described aggregation degree range by performing a pulverization process for separating the agglomerated powder into one granular particle. is there.

  If the purpose is simply pulverization, high energy ball mill, high-speed conductor impingement airflow pulverizer, impact pulverizer, gauge mill, medium agitation mill, high water pressure Various things such as a pulverizer can be used. However, in order to ensure the mixing and dispersibility of the dielectric (dielectric filler) powder and the resin composition, it should be considered to reduce the viscosity as a dielectric (dielectric filler) -containing resin solution described below. . In order to reduce the viscosity of the dielectric (dielectric filler) -containing resin solution, the specific surface area of the dielectric particles (dielectric filler) is required to be small and smooth. Therefore, even if granulation is possible, it should not be a granulation technique that damages the surface of the granule during granulation and increases its specific surface area.

  Based on this recognition, the inventors of the present invention diligently researched and found that the two methods are effective. What is common to these two methods is that the powder particles of the dielectric (dielectric filler) are agglomerated while minimizing the contact of the powder with the inner wall of the device, the stirring blade, the grinding media, etc. This is a method capable of sufficiently pulverizing particles by causing the particles to collide with each other. That is, contact with parts such as the inner wall of the apparatus, stirring blades, and grinding media damages the surface of the powder, increases the surface roughness, and deteriorates the sphericity, thereby preventing this. . Then, by causing sufficient collision between the powder particles, it is possible to disaggregate the powder particles in an agglomerated state, and at the same time, it is possible to employ a method capable of smoothing the surface of the powder particles by the collision between the powder particles.

  One of them is a pulverization treatment of dielectric (dielectric filler) powder in an agglomerated state using a jet mill. “Jet mill” as used here refers to the use of a high-speed air current to place dielectric (dielectric filler) powder in this air current, and the particles collide with each other in this high-speed air current to break up the particles. Is done.

  In addition, a slurry in which a dielectric (dielectric filler) powder in an agglomerated state is dispersed in a solvent that does not destroy the stoichiometry is pulverized using a fluid mill using centrifugal force. By using the “fluid mill using centrifugal force”, the slurry is allowed to flow at a high speed so as to draw a circumferential trajectory. And then pulverize. By doing in this way, the dielectric (dielectric filler) powder which finished the granulation work is obtained by washing, filtering, and drying the slurry after the granulation work. By the method described above, the degree of aggregation can be adjusted and the powder surface of the dielectric filler powder can be smoothed.

  The resin composition described above and a dielectric (dielectric filler) are mixed to form a dielectric (dielectric filler) -containing resin for forming a built-in capacitor layer of a printed wiring board. In addition, resin which can be used for the said resin layer can be mentioned as resin used for the resin composition for mixing with a dielectric material (dielectric filler). At this time, the blending ratio of the resin composition and the dielectric (dielectric filler) is preferably such that the content of the dielectric (dielectric filler) is 75 wt% to 85 wt%, and the remaining resin composition.

When the content of the dielectric (dielectric filler) is less than 75 wt%, the relative permittivity of 20 currently required in the market cannot be satisfied, and the content of the dielectric (dielectric filler) exceeds 85 wt%. And the resin composition content is less than 15 wt%, the adhesiveness between the dielectric (dielectric filler) -containing resin and the copper foil laminated thereon is impaired, and the required characteristics for manufacturing a printed wiring board are satisfied. This makes it difficult to produce a copper-clad laminate.
The resin layer containing the dielectric (dielectric filler) may be formed using a resin composition containing a dielectric (dielectric filler), an epoxy resin, an active ester resin, a polyvinyl acetal resin, and a curing accelerator. Good.
Further, the resin layer containing the dielectric (dielectric filler) is 25 parts by weight of epoxy resin when the weight of the resin composition containing epoxy resin, active ester resin, polyvinyl acetal resin, and curing accelerator is 100 parts by weight. It may be formed using a resin composition containing ˜60 parts by weight and a dielectric (dielectric filler).
The resin layer containing the dielectric material (dielectric filler) is 28 weight parts of the active ester resin when the weight of the resin composition containing the epoxy resin, the active ester resin, the polyvinyl acetal resin, and the curing accelerator is 100 parts by weight. It may be formed using a resin composition containing a part to 60 parts by weight and a dielectric (dielectric filler).
Further, the resin layer containing the dielectric (dielectric filler) has an epoxy resin and an active ester resin when the weight of the resin composition containing an epoxy resin, an active ester resin, a polyvinyl acetal resin, and a curing accelerator is 100 parts by weight. May be formed using a resin composition containing 78 parts by weight to 95 parts by weight and a dielectric (dielectric filler).
In addition, the resin layer containing the dielectric (dielectric filler) has 1 weight of polyvinyl acetal resin when the weight of the resin composition containing epoxy resin, active ester resin, polyvinyl acetal resin, and curing accelerator is 100 parts by weight. It may be formed using a resin composition containing 20 parts by weight to 20 parts by weight and a dielectric (dielectric filler).
Further, the resin layer containing the dielectric (dielectric filler) has a curing accelerator of 0.00 when the weight of the resin composition containing epoxy resin, active ester resin, polyvinyl acetal resin, and curing accelerator is 100 parts by weight. It may be formed using a resin composition containing 01 to 2 parts by weight and a dielectric (dielectric filler).

Moreover, the resin layer containing the dielectric (dielectric filler) has an epoxy resin, an active ester resin, and a polyvinyl acetal constituting the resin composition when the weight of the resin composition constituting the resin layer is 100 parts by weight. It may be formed using a resin composition in which the total amount of each component of the resin and the curing accelerator is 70 parts by weight or more and a dielectric (dielectric filler).
The resin layer containing the dielectric contains a dielectric (dielectric filler) in a range of 65 wt% to 85 wt% when the weight of the resin containing the dielectric (dielectric filler) is 100 wt%. It is preferable that
The epoxy resin, active ester resin, polyvinyl acetal resin and curing accelerator include known epoxy resins, active ester resins, polyvinyl acetal resins and curing accelerators, or the epoxy resins, active ester resins and polyvinyl acetals described in the present specification. Resins and cure accelerators can be used.
The resin layer containing the dielectric (dielectric filler) preferably has a resin flow of less than 1% when measured according to MIL-P-13949G in the MIL standard.
In addition, as a hardening accelerator and an epoxy resin, a well-known thing or the hardening accelerator and epoxy resin as described in this-application specification can be used. Moreover, as a hardening accelerator, a well-known imidazole compound or the imidazole compound as described in this-application specification can be used.

  As this dielectric (dielectric filler), it is preferable to use barium titanate among complex oxides having a perovskite structure in consideration of manufacturing accuracy as a powder at the present stage. As the dielectric (dielectric filler) at this time, either calcined barium titanate or uncalcined barium titanate can be used. In order to obtain a high dielectric constant, it is preferable to use calcined barium titanate, but it may be selectively used according to the design quality of the printed wiring board product.

Furthermore, it is most preferable that the dielectric filler of barium titanate has a cubic crystal structure. The crystal structure of barium titanate includes cubic and tetragonal crystals, but the cubic barium titanate dielectric (dielectric filler) has a tetragonal structure only. The value of the dielectric constant of the finally obtained dielectric layer is stabilized as compared with the case where a barium acid dielectric (dielectric filler) is used. Therefore, it can be said that it is necessary to use barium titanate powder having both a cubic crystal structure and a tetragonal crystal structure.
According to the above-described embodiment, the resin layer containing the dielectric for forming the capacitor circuit layer having a low dielectric loss tangent is improved by improving the adhesion between the inner layer circuit surface of the inner layer core material and the resin layer containing the dielectric The surface-treated copper foil which has can be provided.

  The resin layer is a resin layer in which a cured resin layer (“cured resin layer” means a cured resin layer) and a semi-cured resin layer are sequentially formed from the surface treatment layer side. May be. The cured resin layer may be composed of a resin component of any one of a polyimide resin, a polyamideimide resin, and a composite resin having a thermal expansion coefficient of 0 ppm / ° C. to 25 ppm / ° C.

  Moreover, you may provide the semi-hardened resin layer whose thermal expansion coefficient after hardening is 0 ppm / degrees C-50 ppm / degrees C on the said cured resin layer. In addition, the thermal expansion coefficient of the entire resin layer after the cured resin layer and the semi-cured resin layer are cured may be 40 ppm / ° C. or less. The cured resin layer may have a glass transition temperature of 300 ° C. or higher. The semi-cured resin layer may be formed using a maleimide resin, and the maleimide resin may be an aromatic maleimide resin having two or more maleimide groups in the molecule. The maleimide resin may be a polymerized adduct obtained by polymerizing an aromatic maleimide resin having two or more maleimide groups in the molecule and an aromatic polyamine. The semi-cured resin layer may contain 20 to 70 parts by weight of a maleimide resin when the semi-cured resin layer is 100 parts by weight. The resin composition for forming the semi-cured resin layer preferably contains a maleimide resin, an epoxy resin, and a linear polymer having a crosslinkable functional group as an essential component. The maleimide resin may be a polymerization adduct obtained by polymerizing an aromatic maleimide resin and an aromatic polyamine. Moreover, you may add the cyanoester resin and epoxy resin which have reactivity with a maleimide-type resin as needed to a semi-hardened resin layer. As the epoxy resin, a known epoxy resin or an epoxy resin described in the present specification can be used.

  Moreover, it is preferable that the linear polymer which has the said crosslinkable functional group is equipped with the functional group which contributes to hardening reaction of epoxy resins, such as a hydroxyl group and a carboxyl group. And it is preferable that the linear polymer which has this crosslinkable functional group is soluble in the organic solvent of the temperature of 50 to 200 degreeC of boiling points. Specific examples of the linear polymer having a functional group mentioned here include polyvinyl acetal resin, phenoxy resin, polyethersulfone resin, polyamideimide resin and the like. The linear polymer having a crosslinkable functional group is preferably used in a blending ratio of 3 to 30 parts by weight when the resin composition is 100 parts by weight. When the epoxy resin is less than 3 parts by weight, the resin flow may increase. As a result, a large amount of resin powder may be observed from the end of the produced copper-clad laminate, and the moisture absorption resistance of the resin layer in a semi-cured state may not be improved. On the other hand, even if it exceeds 30 parts by weight, the resin flow may be small, and defects such as voids may easily occur in the insulating layer of the produced copper-clad laminate.

  As the maleimide resin here, 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4 , 4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4′-diphenyl ether bismaleimide, 4,4′-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) Benzene, 1,3-bis (4-maleimidophenoxy) benzene and the like can be used. When the content of the maleimide resin is less than 20 parts by weight, the effect of reducing the thermal expansion coefficient of the semi-cured resin layer after curing may not be obtained. On the other hand, if the content of the maleimide resin exceeds 70 parts by weight, the semi-cured resin layer may become a brittle resin layer when cured, and the resin layer may be easily cracked. The reliability as a layer may be reduced.

  When forming a polymerization adduct obtained by polymerizing an aromatic maleimide resin having two or more maleimide groups in the molecule and an aromatic polyamine, examples of the aromatic polyamine include m-phenylenediamine and p-phenylenediamine. 4,4′-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, 4,4′-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4′- Diaminodiphenyl ether, 4,4′-diamino-3-methyldiphenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenyl sulfone, bis (4-aminophenyl) phenylamine , M-xylenediamine, p-xylenediamine 1,3-bis [4-aminophenoxy] benzene, 3-methyl-4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dichloro-4,4 '-Diaminodiphenylmethane, 2,2', 5,5'-tetrachloro-4,4'-diaminodiphenylmethane, 2,2-bis (3-methyl-4-aminophenyl) propane, 2,2-bis (3 -Ethyl-4-aminophenyl) propane, 2,2-bis (2,3-dichloro-4-aminophenyl) propane, bis (2,3-dimethyl-4-aminophenyl) phenylethane, ethylenediamine and hexamethylenediamine Etc. are preferably added to the resin composition to form a resin layer.

  When an epoxy resin curing agent is required, amines such as dicyandiamide, imidazoles and aromatic amines, phenols such as bisphenol A and brominated bisphenol A, novolacs such as phenol novolac resin and cresol novolac resin Acid anhydrides such as phthalic anhydride are used. Since the addition amount of the epoxy resin curing agent with respect to the epoxy resin at this time is naturally derived from the respective equivalents, no special addition amount limitation is performed.

Moreover, when providing the surface-treated copper foil which has a resin layer suitable for a three-dimensional molded printed wiring board manufacture use, it is preferable that the said cured resin layer is a polymeric polymer layer which has hardened | cured flexibility. The polymer layer is preferably made of a resin having a glass transition temperature of 150 ° C. or higher so that it can withstand the solder mounting process. The polymer layer is preferably composed of one or a mixture of two or more of a polyamide resin, a polyether sulfone resin, an aramid resin, a phenoxy resin, a polyimide resin, a polyvinyl acetal resin, and a polyamideimide resin. The thickness of the polymer layer is preferably 3 μm to 10 μm.
Moreover, it is preferable that the said high polymer layer contains any 1 type, or 2 or more types of an epoxy resin, a maleimide resin, a phenol resin, and a urethane resin. The semi-cured resin layer is preferably composed of an epoxy resin composition having a thickness of 10 μm to 50 μm.

Moreover, it is preferable that the said epoxy resin composition contains each component of the following A component-E component.
Component A: An epoxy resin having one or more selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AD type epoxy resin that have an epoxy equivalent of 200 or less and are liquid at room temperature.
B component: High heat resistant epoxy resin.
Component C: Phosphorus-containing flame-retardant resin, which is any one of phosphorus-containing epoxy resin and phosphazene-based resin, or a resin obtained by mixing these.
Component D: A rubber-modified polyamide-imide resin modified with a liquid rubber component having a property that is soluble in a solvent having a boiling point in the range of 50 ° C. to 200 ° C.
E component: Resin curing agent.

  The component A is an epoxy resin composed of one or more selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AD type epoxy resin that have an epoxy equivalent of 200 or less and are liquid at room temperature. Here, the bisphenol-based epoxy resin is selectively used because it has good compatibility with the D component (rubber-modified polyamideimide resin) described later, and it is easy to impart appropriate flexibility to the resin film in a semi-cured state. It is. If the epoxy equivalent exceeds 200, the resin becomes semi-solid at room temperature, and the flexibility in the semi-cured state decreases, which is not preferable. Furthermore, if it is the above-mentioned bisphenol-type epoxy resin, 1 type may be used independently or 2 or more types may be used in mixture. In addition, when two or more kinds are mixed and used, there is no particular limitation with respect to the mixing ratio.

  This epoxy resin is preferably used in a blending ratio of 3 to 30 parts by weight, with 100 parts by weight of the epoxy resin composition constituting the semi-cured resin layer. When the epoxy resin is less than 3 parts by weight, the thermosetting property is not sufficiently exhibited, and the function as a binder with the inner layer flexible printed wiring board and the adhesiveness with the copper foil as the resin-coated copper foil are sufficient. Can't be done. On the other hand, when the amount exceeds 30 parts by weight, the viscosity of the resin varnish increases from the balance with other resin components, and when the resin-coated copper foil is produced, the resin film with a uniform thickness is formed on the copper foil surface. Formation becomes difficult. Moreover, considering the amount of D component (rubber-modified polyamideimide resin) to be described later, sufficient toughness as a cured resin layer cannot be obtained.

  The B component is a “high heat resistant epoxy resin” having a high so-called glass transition point Tg. The “high heat-resistant epoxy resin” referred to here is preferably a polyfunctional epoxy resin such as a novolac-type epoxy resin, a cresol novolac-type epoxy resin, a phenol novolac-type epoxy resin, or a naphthalene-type epoxy resin. And it is preferable to use this B component in the range of 3-30 weight part, when the epoxy resin composition which comprises a semi-hardened resin layer is 100 weight part. When the component B is less than 3 parts by weight, it is not preferable because the Tg of the resin composition tends to be insufficient. On the other hand, if the component B exceeds 30 parts by weight, the cured resin becomes brittle and flexibility is impaired, which is not preferable for flexible printed wiring board applications. More preferably, by using the B component in the range of 10 to 20 parts by weight, it is possible to stably achieve both high Tg of the resin composition and good flexibility of the cured resin.

  The component C is a so-called halogen-free flame-retardant resin, and a phosphorus-containing flame-retardant resin that is any one of a phosphorus-containing epoxy resin and a phosphazene-based resin or a mixture of these is used. First, the phosphorus-containing epoxy resin is a general term for epoxy resins containing phosphorus in an epoxy skeleton. And when the phosphorus atom content of the epoxy resin composition constituting the semi-cured resin layer is 100% by weight of the epoxy resin composition, the phosphorus atom derived from component C is 0.5% by weight to 3.0%. Any phosphorus-containing epoxy resin that can be in the range of% by weight can be used. However, among the phosphorus-containing epoxy resins described above, a phosphorus-containing epoxy resin which is a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative having two or more epoxy groups in the molecule is used. When used, it is preferable because it is excellent in the stability of the resin quality in the semi-cured state and at the same time has a high flame retardant effect. For reference, the structural formula of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is shown below.

  Furthermore, as a specific example of the phosphorus-containing epoxy resin that is a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, a compound having the structural formula shown in Chemical Formula 3 is shown. It is preferable to use a compound having the structural formula shown in Chemical Formula 3 because it is more excellent in the stability of the resin quality in the semi-cured state and at the same time the flame retardancy effect is enhanced.

  Further, as the phosphorus-containing epoxy resin of the C component, a compound having a structural formula shown in Chemical Formula 4 shown below is also preferable. Similar to the phosphorus-containing epoxy resin shown in Chemical Formula 3, it is preferable because it is excellent in the stability of the resin quality in a semi-cured state and at the same time can impart high flame retardancy.

  Further, as the C component phosphorus-containing epoxy resin, a compound having the structural formula shown in Chemical Formula 5 below is also preferable. Like the phosphorus-containing epoxy resin shown in Chemical Formula 3 and Chemical Formula 4, it is preferable because it is excellent in the stability of the resin quality in a semi-cured state, and at the same time it is possible to impart high flame retardancy.

  The epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is converted to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. After making naphthoquinone and hydroquinone react to make a compound shown in the following chemical formula 6 (HCA-NQ) or chemical formula 7 (HCA-HQ), an epoxy resin is reacted with the OH group portion to make a phosphorus-containing flame retardant resin Are listed.

  Here, the resin composition in the case of using a phosphorus-containing epoxy resin as the phosphorus-containing flame retardant resin is not limited to two or more types of phosphorus-containing epoxy resins, even if one kind of phosphorus-containing epoxy resin is used alone. You may mix and use. However, in consideration of the total amount of the phosphorus-containing flame retardant resin as the C component, when the weight of the epoxy resin composition constituting the semi-cured resin layer is 100% by weight, the phosphorus atom derived from the C component is 0.5% by weight. It is preferable to determine the addition amount so as to be in the range of% to 3.0% by weight. The phosphorus-containing epoxy resin has different amounts of phosphorus atoms contained in the epoxy skeleton depending on the type. Therefore, as described above, the phosphorus atom content can be designed with priority over the added amount of the C component.

  Next, a case where a phosphazene resin is used as the phosphorus-containing flame retardant resin will be described. The phosphazene resin is a resin containing phosphazene having a double bond having phosphorus and nitrogen as constituent elements. The phosphazene resin can dramatically improve the flame retardancy due to the synergistic effect of nitrogen and phosphorus in the molecule. In addition, unlike 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, it exists stably in the resin, and the effect of preventing the occurrence of migration is obtained.

  Moreover, the resin composition in the case of using a phosphazene resin as the phosphorus-containing flame retardant resin may be used alone or in combination of two or more phosphazene resins. Absent. However, in consideration of the total amount of the phosphorus-containing flame retardant resin as the C component, when the weight of the phosphazene resin composition constituting the semi-cured resin layer is 100% by weight, the phosphorus atom derived from the C component is 0.5%. It is preferable to determine the addition amount so as to be in the range of wt% to 3.0 wt%. The same applies to the case where a phosphorus-containing epoxy resin and a phosphazene resin are mixed and used as the C component.

  As the phosphorus-containing flame retardant resin as the C component, any one of a phosphorus-containing epoxy resin and a phosphazene resin or a mixture thereof may be used. When the phosphorus-containing epoxy resin is used alone as the phosphorus-containing flame retardant resin, the phosphorus-containing epoxy resin is 5 parts by weight to 50 parts when the epoxy resin composition constituting the semi-cured resin layer is 100 parts by weight. It is preferably used in the range of parts by weight. When the C component comprising the phosphorus-containing epoxy resin is less than 5 parts by weight, considering the blending ratio of other resin components, phosphorus atoms derived from the C component are insufficient, and it becomes difficult to obtain flame retardancy. . On the other hand, even if the C component made of phosphorus-containing epoxy resin exceeds 50 parts by weight, the effect of improving flame retardancy is saturated, and at the same time, the cured resin layer becomes brittle.

  When a phosphazene resin is used alone as the phosphorus-containing flame retardant resin, the phosphazene resin is 2 to 18 parts by weight with respect to 100 parts by weight of the epoxy resin composition constituting the semi-cured resin layer. It is preferably used in the range of parts. When the C component composed of the phosphazene resin is less than 2 parts by weight, the phosphorus atom derived from the C component is insufficient and it becomes difficult to obtain flame retardancy in consideration of the blending ratio of the other resin components. On the other hand, when the C component made of phosphazene resin exceeds 18 parts by weight, the glass transition point Tg, solder heat resistance, and peel strength of the resin composition tend to be insufficient, which is not preferable.

  “High Tg” and “flexibility” of the cured resin described above are generally inversely proportional characteristics. At this time, there are phosphorus-containing flame retardant resins that contribute to the improvement of the flexibility of the cured resin and those that contribute to an increase in Tg. Therefore, rather than using one type of phosphorus-containing flame-retardant epoxy resin, “phosphorus-containing flame-retardant epoxy resin that contributes to higher Tg” and “phosphorus-containing flame-retardant epoxy resin that contributes to improved flexibility” By mixing and using in a well-balanced manner, it is possible to obtain a resin composition suitable for flexible printed wiring board applications.

  Component D is a rubber-modified polyamideimide resin that is soluble in a solvent having a boiling point in the range of 50 ° C. to 200 ° C. and modified with a liquid rubber component. This rubber-modified polyamideimide resin is obtained by reacting a polyamideimide resin and a rubber resin. The rubber-modified polyamide-imide resin and the rubber-like resin used here are reacted for the purpose of improving the flexibility of the polyamide-imide resin itself. That is, the polyamideimide resin and the rubber resin are reacted to replace a part of the acid component (cyclohexanedicarboxylic acid or the like) of the polyamideimide resin with the rubber component. The rubber component includes natural rubber and synthetic rubber. Examples of the latter synthetic rubber include styrene-butadiene rubber, butadiene rubber, butyl rubber, and ethylene-propylene rubber. Furthermore, from the viewpoint of ensuring heat resistance, it is also useful to selectively use a synthetic rubber having heat resistance such as nitrile rubber, chloroprene rubber, silicon rubber, urethane rubber and the like. Since these rubber resins react with the polyamide-imide resin to produce a copolymer, it is desirable to have various functional groups at both ends. In particular, it is useful to use CTBN (carboxy group-terminated butadiene nitrile) having a carboxyl group. In addition, the said rubber component may copolymerize only 1 type or may copolymerize 2 or more types. Further, when a rubber component is used, it is preferable to use a rubber component having a number average molecular weight of 1000 or more from the viewpoint of stabilization of the flexibility.

  Solvents used for dissolving the polyamideimide resin and the rubbery resin when polymerizing the rubber-modified polyamideimide resin include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, nitromethane, nitroethane, tetrahydrofuran , Cyclohexanone, methyl ethyl ketone, acetonitrile, γ-butyrolactone, and the like are preferably used alone or in combination. And in order to raise | generate a polymerization reaction, it is preferable to employ | adopt the polymerization temperature of the range of 80 to 200 degreeC. When a solvent having a boiling point of more than 200 ° C. is used for these polymerizations, it is preferable that the solvent be replaced with a solvent having a boiling point in the range of 50 ° C. to 200 ° C., depending on the application.

  Here, examples of the solvent having a boiling point in the range of 50 ° C. to 200 ° C. include one single solvent or two or more mixed solvents selected from the group of methyl ethyl ketone, dimethylacetamide, dimethylformamide and the like. When the boiling point is lower than 50 ° C., the solvent is greatly diffused by heating, and it is difficult to obtain a good semi-cured state when the resin varnish is changed to a semi-cured resin. On the other hand, when the boiling point exceeds 200 ° C., bubbling is likely to occur when the resin varnish is used as a semi-cured resin, so that it is difficult to obtain a good semi-cured resin film.

  Among the rubber-modified polyamideimide resins used in the epoxy resin composition, when the weight of the rubber-modified polyamideimide resin is 100% by weight, the copolymerization amount of the rubber component is preferably 0.8% by weight or more. When the copolymerization amount is less than 0.8% by weight, the rubber-modified polyamideimide resin lacks flexibility when the resin layer formed using the epoxy resin composition according to the present invention is cured. In addition, the adhesiveness with the copper foil is also lowered, which is not preferable. More preferably, the copolymerization amount of the rubber component is 3% by weight or more, more preferably 5% by weight or more. Empirically, there is no particular problem even if the amount of the rubber component added is increased beyond 40% by weight. However, since the effect of improving the flexibility of the cured resin layer is saturated, resources are wasted, which is not preferable.

  The rubber-modified polyamideimide resin described above is required to be soluble in a solvent. This is because preparation as a resin varnish is difficult unless it is soluble in a solvent. This rubber-modified polyamideimide resin is preferably used in a blending ratio of 10 to 40 parts by weight, when the weight of the resin composition is 100 parts by weight. When the rubber-modified polyamideimide resin is less than 10 parts by weight, the flexibility of the cured resin layer cannot be improved and becomes brittle, and microcracks are easily generated in the resin layer. On the other hand, adding rubber-modified polyamideimide resin in excess of 40 parts by weight has no particular problem, but the flexibility of the cured resin layer is not improved further, and the cured resin can have a higher Tg. Absent. Therefore, considering the economy, it can be said that 40 parts by weight is the upper limit.

  The E component resin curing agent will be described. As the resin curing agent referred to here, it is preferable to use one or more of biphenyl type phenol resin and phenol aralkyl type phenol resin. The addition amount of the resin curing agent is naturally derived from the reaction equivalent to the resin to be cured, and does not require any particular quantitative limitation. However, in the case of the epoxy resin composition used in the present invention, the E component is preferably used in the range of 20 to 35 parts by weight when the epoxy resin composition is 100 parts by weight. When the E component is less than 20 parts by weight, considering the resin composition, a sufficient cured state cannot be obtained, and flexibility as a cured resin cannot be obtained. On the other hand, when the E component exceeds 35 parts by weight, the moisture absorption resistance of the cured resin layer tends to deteriorate, which is not preferable.

A solvent is added to the resin composition shown above and used as a resin varnish, and a thermosetting resin layer is formed as an adhesive layer of a printed wiring board. The resin varnish is prepared by adding a solvent to the above resin composition so that the resin solid content is in the range of 30 wt% to 70 wt%, and the resin flow when measured in accordance with MIL-P-13949G in the MIL standard. A semi-cured resin film in the range of 5% to 35% can be formed. As the solvent, the boiling point is in the range of 50 ° C. to 200 ° C., and it is preferable to use one kind of single solvent or two or more kinds of mixed solvents selected from the group of methyl ethyl ketone, dimethylacetamide, dimethylformamide and the like. This is to obtain a good semi-cured resin film as described above. And the range of the resin solid content shown here is a range in which the film thickness can be controlled to the most accurate one when applied to the surface of the copper foil. When the resin solid content is less than 30 wt%, the viscosity is too low, and it flows immediately after application to the copper foil surface, making it difficult to ensure film thickness uniformity. On the other hand, when the resin solid content exceeds 70 wt%, the viscosity increases and it becomes difficult to form a thin film on the surface of the copper foil. In addition, when the resin flow is less than 5%, it is not preferable because air entrapment or the like occurs in the uneven portions of the inner layer circuit on the surface of the inner layer core material. On the other hand, when the resin flow exceeds 35%, the resin flow becomes too large, and the thickness of the insulating layer formed using the resin layer of the surface-treated copper foil having the resin layer becomes nonuniform.
When the cured resin layer and the semi-cured resin layer are provided on the surface-treated copper foil, it is possible to provide a surface-treated copper foil having a resin layer suitable for three-dimensional molded printed wiring board manufacturing applications.

Moreover, it is preferable that the said resin layer is equipped with the protective film which can be peeled off to the single side | surface of the said semi-hardened insulating layer. A known insulating film or resin film can be used for the protective film. For example, a polyethylene terephthalate film, a polyethylene naphthalate film, a metal foil, or the like can be used for the protective film.
The resin layer may contain a curing agent and / or a curing accelerator.
The resin layer may be a resin layer formed of a resin composition having a resin flow of 5% or less when measured according to MIL-P-13949G in the MIL standard.
The resin layer is 5 parts by weight to 50 parts by weight of an epoxy resin (including a curing agent), 50 parts by weight to 95 parts by weight of a polyether sulfone soluble in a solvent, and curing that is added in an appropriate amount as necessary. What was comprised using the resin composition which consists of an accelerator may be used.

In addition, the resin layer contains the following components A to D in a range of the following content (provided that the resin composition is 100 parts by weight excluding the epoxy resin curing agent). It may be formed of a composition.
Component A: Polyamideimide resin having a tensile strength of 200 MPa or more at 25 ° C. 10 to 20 parts by weight Component B: Polyamideimide resin having a tensile strength of 100 MPa or less at 25 ° C. 20 to 40 parts by weight Component C: Epoxy resin component D: Epoxy resin curing agent The resin layer may be a semi-cured resin layer.

  The component A is a polyamideimide resin having a tensile strength of 200 MPa or more at 25 ° C. Here, “polyamideimide resin having a tensile strength of 200 MPa or more” means, for example, trimellitic acid anhydride, benzophenone tetracarboxylic acid anhydride and vitorylene diisocyanate as N-methyl-2-pyrrolidone or / and N, N— A resin obtained by heating in a solvent such as dimethylacetamide. Here, although the upper limit is not described, the upper limit of the tensile strength of the polyamide-imide resin is about 500 MPa in consideration of the tensile strength of the polyimide amide resin. In addition, the tensile strength of the polyamide-imide resin according to Component A and Component B in the present invention was determined from the polyamide-imide resin solution using a film-shaped No. 2 test piece as defined in JIS K7113 (total length 115 mm, distance between chucks 80 ± 5 mm, parallel part length) The thickness is 33 ± 2 mm, the parallel part width is 6 ± 0.4 mm, and the film thickness is 1 to 3 mm.

The component B is a polyamideimide resin having a tensile strength at 25 ° C. of 100 MPa or less. Here, “polyamideimide resin having a tensile strength of 100 MPa or less” means, for example, trimellitic anhydride, diphenylmethane diisocyanate, and carboxyl group-terminated acrylonitrile-butadiene rubber with N-methyl-2-pyrrolidone and / or N, N-dimethyl. It is obtained by heating in a solvent such as acetamide.
The content of component C (epoxy resin) may be 40 to 70 parts by weight when the resin composition is 100 parts by weight. In addition, the above-mentioned epoxy resin can be used as an epoxy resin. The content of component D (epoxy resin curing agent) is preferably such that the resin composition contains an imidazole compound that can cure the epoxy resin. The semi-cured resin layer is preferably a semi-cured resin layer having a volatile content of less than 1 wt% formed from the resin composition. When the above content is satisfied, even if the surface-treated copper foil having the resin layer is stored or transported in a roll shape, the transfer of the organic solvent from the resin layer of the surface-treated copper foil having the resin layer to the surface-treated copper foil can be performed. In addition, it is possible to obtain a surface-treated copper foil provided with a resin layer having excellent heat resistance and adhesive properties with the surface-treated copper foil.

  Here, as the imidazole compound, known compounds can be used. For example, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1- Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl- 5-hydroxymethylimidazole etc. are mentioned, These can be used individually or in mixture.

The amount of the curing agent to be added is inevitably determined according to the amount of epoxy resin, the curing rate required in the process, and the like. When the addition amount of the imidazole compound as a curing agent is described, when the resin composition is 100 parts by weight (however, in this case, all parts A to D are 100 parts by weight of the resin composition). In the range of 0.01 to 2 parts by weight in the resin composition. And the compounding quantity of an imidazole compound has more preferable 0.02 weight part-1.5 weight part, More preferably, it is 0.03 weight part-1.0 weight part. When the blending amount of the imidazole compound is less than 0.01 parts by weight, the curing may be insufficient in consideration of the content of the epoxy resin, and the resin layers of the surface-treated copper foil having a resin layer may be combined. Adhesive strength at the time of bonding decreases. On the other hand, when the compounding amount of the imidazole compound exceeds 2 parts by weight, the curing reaction of the epoxy resin is accelerated, the resin layer after curing becomes brittle, the strength of the cured resin film, the resin layers of the copper foil with resin, Adhesiveness at the time of pasting may deteriorate.
In addition, the epoxy resin of component C, the epoxy resin curing agent of component D, the known epoxy resin of component C, the epoxy resin curing agent of component D or the epoxy resin of component C described in this specification, the epoxy resin of component D A curing agent can be used.

The resin layer is a resin composition having moisture absorption resistance in a semi-cured state, and the resin composition includes the following components A to E, and contains phosphorus atoms when the resin composition weight is 100% by weight. You may form using the resin composition contained in 0.5 weight%-3.0 weight%.
Component A: One or more selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin having an epoxy equivalent of 200 or less and liquid at 25 ° C.
Component B: A linear polymer having a crosslinkable functional group.
Component C: Crosslinking agent.
D component: Imidazole-based epoxy resin curing agent.
E component: Phosphorus-containing epoxy resin.
The linear polymer having a functional group as the component B is preferably a polymer component soluble in an organic solvent having a boiling point of 50 ° C. to 200 ° C. Specifically, polyvinyl acetal resin, phenoxy resin, polyethersulfone resin, polyamideimide resin, and the like. The linear polymer having a crosslinkable functional group is preferably used in a blending ratio of 3 to 30 parts by weight when the resin composition is 100 parts by weight. When the epoxy resin is less than 3 parts by weight, the resin flow may increase. As a result, a large amount of resin powder may be observed from the end of the produced copper-clad laminate, and the moisture absorption resistance of the resin layer in a semi-cured state may not be improved. On the other hand, even if it exceeds 30 parts by weight, the resin flow may be small, and defects such as voids may easily occur in the insulating layer of the produced copper-clad laminate.

Specific examples of the organic solvent having a boiling point of 50 ° C. to 200 ° C. mentioned here include groups such as methanol, ethanol, methyl ethyl ketone, toluene, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, and ethyl cellosolve. 1 type of single solvent chosen from these, or 2 or more types of mixed solvents. When the boiling point is less than 50 ° C., the solvent is greatly diffused by heating, and it may be difficult to obtain a good semi-cured state from the resin varnish to the semi-cured resin. On the other hand, when the boiling point exceeds 200 ° C., the solvent may easily remain in a semi-cured state. In addition, the normally required volatilization rate may not be satisfied, and industrial productivity may not be satisfied.
The component C is a crosslinking agent for causing a crosslinking reaction between the component B and the epoxy resin. As this crosslinking agent, it is preferable to use a urethane-based resin. This cross-linking agent is added according to the mixing amount of the B component, and it is considered that there is no need to specify the mixing ratio strictly strictly. However, when the resin composition is 100 parts by weight, it is preferably used at a blending ratio of 10 parts by weight or less. If the C component which is a urethane-based resin is present exceeding 10 parts by weight, the moisture absorption resistance of the resin layer in the semi-cured state is deteriorated, and the cured resin layer becomes brittle.

  Component D is an imidazole epoxy resin curing agent. In the resin composition according to the present invention, it is preferable to selectively use an imidazole epoxy resin curing agent from the viewpoint of improving the moisture absorption resistance of the semi-cured resin layer. Among these, it is preferable to use an imidazole-based epoxy resin curing agent having the structural formula shown in Chemical Formula 8 below. By using the imidazole-type epoxy resin curing agent having the structural formula shown in Chemical Formula 8, the moisture absorption resistance of the semi-cured resin layer can be remarkably improved, and the long-term storage stability is excellent. In addition, it is preferable to employ | adopt the optimal amount obtained experimentally as the addition amount of the epoxy resin hardening | curing agent with respect to an epoxy resin rather than calculating from a reaction equivalent. This is because the imidazole-based epoxy resin curing agent performs a catalytic function in curing the epoxy resin and contributes as a reaction initiator that causes a self-polymerization reaction of the epoxy resin in the initial stage of the curing reaction.

The phosphorus-containing epoxy resin as the E component is an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. It is preferable.
The structural formula of 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is as follows.

  The epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is converted to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. After reacting naphthoquinone or hydroquinone to obtain a compound represented by the following chemical formula 10 (HCA-NQ) or chemical formula 11 (HCA-HQ), an epoxy resin is reacted with the OH group portion to obtain a phosphorus-containing epoxy resin. Is.

  The phosphorus-containing epoxy resin, which is the E component obtained using the above-mentioned compound as a raw material, is used by mixing one or two kinds of compounds having the structural formula shown in any one of Chemical Formulas 12 to 14 below. Is preferred. This is because the resin quality in a semi-cured state is excellent in stability, and at the same time, the flame retardant effect is high.

  When the resin composition has a resin composition weight of 100 parts by weight, the A component is 3 parts by weight to 20 parts by weight, the B component is 3 parts by weight to 30 parts by weight, and the resin composition weight is 100% by weight. The resin composition is preferably a resin composition in which parts by weight of the E component are determined so that the phosphorus atom is in the range of 0.5 wt% to 3.0 wt%.

You may form the said resin layer using the resin composition containing each component of the following A component-F component.
Component A: One or more selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin having an epoxy equivalent of 200 or less and liquid at 25 ° C.
Component B: A linear polymer having a crosslinkable functional group.
Component C: Crosslinking agent (provided that the component A can be omitted when the component A functions as a crosslinking agent for the component B). Component D: 4,4′-diaminodiphenylsulfone or 2,2-bis (4- (4-aminophenoxy) phenyl) propane.
E component: Flame retardant epoxy resin.
F component: Polyfunctional epoxy resin.
G component: A curing accelerator.
The linear polymer having a crosslinkable functional group as the component B is preferably a polyvinyl acetal resin or a polyamideimide resin.
It is preferable that the crosslinking agent as the component C is a urethane resin.
The flame retardant epoxy resin as the component E is a brominated epoxy resin having the structural formula shown in Chemical formula 15 obtained as a derivative from tetrabromobisphenol A having two or more epoxy groups in the molecule, and chemical formula 16 shown below. It is preferable to use one or two brominated epoxy resins having the structural formula shown in FIG.

The flame retardant epoxy resin which is the E component uses a phosphorus-containing epoxy resin which is a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative having two or more epoxy groups in the molecule. It is preferable.
The flame retardant epoxy resin as the component E is preferably used by mixing one or two phosphorus-containing epoxy resins having the structural formula shown in any one of the following chemical formulas 17 to 19.

It is preferable to use an ortho cresol novolac type epoxy resin as the polyfunctional epoxy resin of the F component.
When the weight of the resin composition for forming the resin layer is 100 parts by weight, the A component is 3 to 20 parts by weight, the B component is 3 to 30 parts by weight, and the C component is 3 parts by weight. 10 parts by weight (0 to 10 parts by weight when the A component functions as a crosslinking agent for the B component), 5 to 20 parts by weight of the D component, and 3 to 20 parts by weight of the F component When the weight of the resin composition is 100% by weight, it is preferable to determine the weight part of the E component so that the bromine atom derived from the E component is contained in the range of 12% by weight to 18% by weight.
When the weight of the resin composition for forming the resin layer is 100 parts by weight, the A component is 3 to 20 parts by weight, the B component is 3 to 30 parts by weight, and the C component is 3 parts by weight. 10 parts by weight (0 to 10 parts by weight when the A component functions as a crosslinking agent for the B component), 5 to 20 parts by weight of the D component, and 3 to 20 parts by weight of the F component In addition, when the weight of the resin composition is 100% by weight, it is preferable that the part by weight of the E component is determined so that the phosphorus atom derived from the E component is contained in the range of 0.5% by weight to 3.0% by weight. .
The resin composition for forming the resin layer preferably contains a curing accelerator as the G component.
The said resin layer prepares the resin varnish used for formation of a resin layer with the procedure of the following processes a and process b, applies the said resin varnish to the surface of surface-treated copper foil, and is dried, and average thickness of 5 micrometers-100 micrometers It is preferable to form a semi-cured resin film.
Step a: A component to F component among the A component, B component, C component (may be omitted when the A component functions as a crosslinking agent for the B component), D component, E component, F component, G component When the weight of the resin composition containing as an essential component is 100% by weight, the bromine atom derived from the E component is in the range of 12% to 18% by weight or the phosphorus atom is 0.5% to 3.0% by weight. Each component is mixed so that it may be contained in a range to obtain a resin composition.
Process b: The said resin composition is melt | dissolved using an organic solvent, and it is set as the resin varnish whose resin solid content is 25 to 50 weight%.

The resin layer is preferably formed using a resin composition containing the following components A to E.
Component A: An epoxy resin having one or more selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AD type epoxy resin that have an epoxy equivalent of 200 or less and are liquid at room temperature.
B component: High heat resistant epoxy resin.
Component C: Flame retardant epoxy resin containing phosphorus.
Component D: A rubber-modified polyamide-imide resin modified with a liquid rubber component having a property that is soluble in a solvent having a boiling point in the range of 50 ° C. to 200 ° C.
Component E: A resin curing agent comprising one or more of a biphenyl type phenol resin and a phenol aralkyl type phenol resin.
The resin layer is preferably formed using a resin composition containing a phosphorus-containing flame retardant having no reactivity with an epoxy resin as an F component in addition to the components A to E.

  The component A is an epoxy resin composed of one or more selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AD type epoxy resin that have an epoxy equivalent of 200 or less and are liquid at room temperature. Here, the bisphenol-based epoxy resin is selectively used because it has good compatibility with the D component (rubber-modified polyamideimide resin) described later, and it is easy to impart appropriate flexibility to the resin film in a semi-cured state. It is. When the epoxy equivalent exceeds 200, the resin becomes semi-solid at room temperature, and the flexibility in the semi-cured state is decreased, which is not preferable. Furthermore, if it is the above-mentioned bisphenol-type epoxy resin, 1 type may be used independently or 2 or more types may be used in mixture. In addition, when two or more kinds are mixed and used, there is no particular limitation with respect to the mixing ratio.

  This epoxy resin is preferably used in a blending ratio of 3 parts by weight to 20 parts by weight when the resin composition is 100 parts by weight. When the epoxy resin is less than 3 parts by weight, the thermosetting property is not sufficiently exhibited, and the function as a binder with the inner layer flexible printed wiring board and the adhesiveness with the copper foil as the resin-coated copper foil are sufficient. It becomes difficult to do. On the other hand, when the amount exceeds 20 parts by weight, the viscosity of the resin varnish increases from the balance with other resin components, and when the resin-coated copper foil is produced, the resin film with a uniform thickness is formed on the copper foil surface. Formation becomes difficult. In addition, considering the amount of addition with a D component (rubber-modified polyamideimide resin) described later, sufficient toughness as a cured resin layer cannot be obtained.

  The B component is a “high heat resistant epoxy resin” having a high so-called glass transition point. The “high heat-resistant epoxy resin” referred to here is preferably a polyfunctional epoxy resin such as a novolac-type epoxy resin, a cresol novolac-type epoxy resin, a phenol novolac-type epoxy resin, or a naphthalene-type epoxy resin. And it is preferable to use this B component in the range of 3 weight part-30 weight part, when a resin composition is 100 weight part. When the component B is less than 3 parts by weight, the resin composition cannot have a high Tg. On the other hand, when the B component exceeds 30 parts by weight, the cured resin becomes brittle and the flexibility is completely impaired, which is not preferable for flexible printed wiring board applications. More preferably, by using the B component in the range of 10 to 20 parts by weight, it is possible to stably achieve both high Tg of the resin composition and good flexibility of the cured resin.

  The component C is a so-called halogen-free flame-retardant epoxy resin, and a phosphorus-containing flame-retardant epoxy resin is used. The phosphorus-containing flame-retardant epoxy resin is a general term for epoxy resins containing phosphorus in an epoxy skeleton. And when the phosphorus atom content of the resin composition according to the present application is 100% by weight of the resin composition, the phosphorus atom derived from component C can be in the range of 0.5% to 3.0% by weight. Any phosphorus-containing flame-retardant epoxy resin can be used. However, it is possible to use a phosphorus-containing flame-retardant epoxy resin that is a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative having two or more epoxy groups in the molecule in a semi-cured state. It is preferable because of its excellent resin quality stability and high flame retardant effect. For reference, the structural formula of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is shown in Chemical Formula 20.

  A specific example of a phosphorus-containing flame-retardant epoxy resin that is a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative is the use of a compound having the structural formula shown in Chemical Formula 21. preferable. It is preferable because it is excellent in stability of the resin quality in a semi-cured state and at the same time has a high flame retardant effect.

  Moreover, as a C component phosphorus containing flame-retardant epoxy resin, the compound provided with the structural formula shown in the chemical formula 22 shown below is also preferable. Like the phosphorus-containing flame-retardant epoxy resin shown in Chemical formula 21, it is preferable because it is excellent in the stability of the resin quality in a semi-cured state and at the same time imparting high flame retardancy.

  Furthermore, as the phosphorus-containing flame-retardant epoxy resin of component C, a compound having the structural formula shown in Chemical Formula 23 below is also preferable. Like the phosphorus-containing flame-retardant epoxy resin shown in Chemical formula 21 and Chemical formula 22, it is preferable because it is excellent in the stability of the resin quality in the semi-cured state and at the same time imparting high flame retardancy.

  The epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is converted to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. After reacting with naphthoquinone or hydroquinone to obtain a compound shown in the following chemical formula 24 (HCA-NQ) or chemical formula 25 (HCA-HQ), an epoxy resin is reacted with the OH group portion to make a phosphorus-containing flame-retardant epoxy. What was made into resin is mentioned.

  Here, the resin composition in the case of using the phosphorus-containing flame-retardant epoxy resin is not limited to two types of phosphorus-containing flame-retardant epoxy resins even if one of the phosphorus-containing flame-retardant epoxy resins as the C component is used alone. May be used in combination. However, in consideration of the total amount of the phosphorus-containing flame-retardant epoxy resin as the C component, when the weight of the resin composition is 100% by weight, the phosphorus atom derived from the C component is 0.5% to 3.0% by weight. It is preferable to add so that it may become this range. The phosphorus-containing flame-retardant epoxy resin has different amounts of phosphorus atoms contained in the epoxy skeleton depending on the type. Therefore, it is possible to define the phosphorus atom content as described above and replace it with the added amount of the C component. However, the component C is usually used in the range of 5 to 50 parts by weight when the resin composition is 100 parts by weight. In the case where the C component is less than 5 parts by weight, it is difficult to make the phosphorus atom derived from the C component 0.5% by weight or more in consideration of the blending ratio of other resin components, and to obtain flame retardancy. I can't. On the other hand, even if the C component exceeds 50 parts by weight, the effect of improving flame retardancy is saturated, and at the same time, the cured resin layer becomes brittle, which is not preferable.

  “High Tg” and “flexibility” of the cured resin described above are generally inversely proportional characteristics. At this time, there are phosphorus-containing flame-retardant epoxy resins that contribute to improving the flexibility of the cured resin and those that contribute to a higher Tg. Therefore, rather than using one type of phosphorus-containing flame-retardant epoxy resin, “phosphorus-containing flame-retardant epoxy resin that contributes to higher Tg” and “phosphorus-containing flame-retardant epoxy resin that contributes to improved flexibility” By mixing and using in a well-balanced manner, it is possible to obtain a resin composition suitable for flexible printed wiring board applications.

  Component D is a rubber-modified polyamideimide resin that is soluble in a solvent having a boiling point in the range of 50 ° C. to 200 ° C. and modified with a liquid rubber component. This rubber-modified polyamideimide resin is obtained by reacting a polyamideimide resin and a rubber resin. The rubber-modified polyamide-imide resin and the rubber-like resin used here are reacted for the purpose of improving the flexibility of the polyamide-imide resin itself. That is, the polyamideimide resin and the rubber resin are reacted to replace a part of the acid component (cyclohexanedicarboxylic acid or the like) of the polyamideimide resin with the rubber component. The rubber component is described as a concept including natural rubber and synthetic rubber, and the latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber and the like. Furthermore, from the viewpoint of ensuring heat resistance, it is also useful to selectively use a synthetic rubber having heat resistance such as nitrile rubber, chloroprene rubber, silicon rubber, urethane rubber and the like. Since these rubber resins react with the polyamide-imide resin to produce a copolymer, it is desirable to have various functional groups at both ends. In particular, it is useful to use CTBN (carboxy group-terminated butadiene nitrile) having a carboxyl group. In addition, the said rubber component may copolymerize only 1 type or may copolymerize 2 or more types. Further, when a rubber component is used, it is preferable to use a rubber component having a number average molecular weight of 1000 or more from the viewpoint of stabilization of the flexibility.

  Solvents used for dissolving the polyamideimide resin and the rubbery resin when polymerizing the rubber-modified polyamideimide resin include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, nitromethane, nitroethane, tetrahydrofuran , Cyclohexanone, methyl ethyl ketone, acetonitrile, γ-butyrolactone, and the like are preferably used alone or in combination. And in order to raise | generate a polymerization reaction, it is preferable to employ | adopt the polymerization temperature of the range of 80 to 200 degreeC. When a solvent having a boiling point of more than 200 ° C. is used for these polymerizations, it is preferable that the solvent be replaced with a solvent having a boiling point in the range of 50 ° C. to 200 ° C., depending on the application.

  Here, examples of the solvent having a boiling point in the range of 50 ° C. to 200 ° C. include one single solvent or two or more mixed solvents selected from the group of methyl ethyl ketone, dimethylacetamide, dimethylformamide and the like. When the boiling point is lower than 50 ° C., the solvent is greatly diffused by heating, and it is difficult to obtain a good semi-cured state when the resin varnish is changed to a semi-cured resin. On the other hand, when the boiling point exceeds 200 ° C., bubbling is likely to occur when the resin varnish is used as a semi-cured resin, and it is difficult to obtain a good semi-cured resin film.

  Among the rubber-modified polyamideimide resins used in the resin composition according to the present invention, when the weight of the rubber-modified polyamideimide resin is 100% by weight, the copolymerization amount of the rubber component is 0.8% by weight or more. preferable. When the copolymerization amount is less than 0.8% by weight, the rubber-modified polyamide-imide resin lacks flexibility when the resin layer formed using the resin composition according to the present invention is cured, Since the adhesiveness with copper foil also falls, it is not preferable. More preferably, the copolymerization amount of the rubber component is 3% by weight or more, more preferably 5% by weight or more. Empirically, there is no particular problem even if the amount of the rubber component added is increased beyond 40% by weight. However, since the effect of improving the flexibility of the cured resin layer is saturated, resources are wasted, which is not preferable.

  The rubber-modified polyamideimide resin described above is required to be soluble in a solvent. This is because preparation as a resin varnish is difficult unless it is soluble in a solvent. This rubber-modified polyamideimide resin is used in a blending ratio of 10 to 40 parts by weight, when the weight of the resin composition is 100 parts by weight. When the rubber-modified polyamide-imide resin is less than 10 parts by weight, the flexibility of the cured resin layer is difficult to improve, becomes brittle, and tends to cause micro cracks in the resin layer. On the other hand, adding more than 40 parts by weight of the rubber-modified polyamideimide resin will not cause any particular problem, but the flexibility of the cured resin layer will not be further improved, and the cured resin will have a higher Tg. Absent. Therefore, considering the economy, it can be said that 40 parts by weight is the upper limit.

  The E component resin curing agent will be described. The resin hardening | curing agent said here uses 1 type, or 2 or more types of a biphenyl type phenol resin and a phenol aralkyl type phenol resin. Generally, the addition amount of the resin curing agent is naturally derived from the reaction equivalent to the resin to be cured, and does not require any particular quantitative limitation. However, the E component in the case of the resin composition according to the present invention is preferably used in the range of 20 to 35 parts by weight when the resin composition is 100 parts by weight. When the E component is less than 20 parts by weight, considering the resin composition, a sufficient cured state cannot be obtained, and flexibility as a cured resin cannot be obtained. On the other hand, when the E component exceeds 35 parts by weight, the moisture absorption resistance of the cured resin layer tends to deteriorate, which is not preferable.

  The phosphorus-containing flame retardant for the F component will be described. This phosphorus-containing flame retardant is an optional additive component and does not need to contribute to the curing reaction of the resin, and is simply used to greatly improve the flame retardancy. As such a phosphorus-containing flame retardant, it is preferable to use a halogen-free flame retardant of a phosphazene compound. Therefore, this F component is used in the range of 0 to 7 parts by weight. Here, “0 part by weight” is described in order to clarify that the F component may not be used and is an optional additive component. On the other hand, even if the F component exceeds 7 parts by weight, no significant improvement in flame retardancy can be expected.

When the weight of the resin composition is 100 parts by weight, the A component is 3 to 20 parts by weight, the B component is 3 to 30 parts by weight, the C component is 5 to 50 parts by weight, and the D component is 10 parts by weight. Parts by weight to 40 parts by weight, E component from 20 parts by weight to 35 parts by weight, F component from 0 parts by weight to 7 parts by weight, and when the resin composition weight is 100% by weight, the resin composition contains C component The derived phosphorus atom is preferably contained in the range of 0.5 wt% to 3.0 wt%.
The component D is a liquid rubber component having a property soluble in one single solvent or two or more mixed solvents selected from the group of methyl ethyl ketone, dimethylacetamide, and dimethylformamide having a boiling point in the range of 50 ° C to 200 ° C. A rubber-modified polyamide-imide resin modified with
The rubber-modified polyamideimide resin that is the component D is preferably obtained by reacting polyamideimide with a rubber resin.
The resin layer is prepared by adding a solvent to the above-described resin composition so that the resin solid content is in the range of 30% by weight to 70% by weight, and measured according to MIL-P-13949G in the MIL standard. Is preferably formed using a resin composition (resin varnish) capable of forming a semi-cured resin layer in the range of 1% to 30%.
For the resin layer, a resin varnish to be used for forming the resin layer is prepared by the following steps a and b, and the resin varnish is applied to the surface of the copper foil and dried to be half the thickness of 10 μm to 50 μm. It is preferably formed as a cured resin layer.
Step a: A component is 3 to 20 parts by weight, B component is 3 to 30 parts by weight, C component is 5 to 50 parts by weight, D component is 10 to 40 parts by weight, and E component is In the range of 20 parts by weight to 35 parts by weight and F component in the range of 0 part by weight to 7 parts by weight, each component is mixed, and the phosphorus atom derived from the C component is contained in the range of 0.5% by weight to 3.0% by weight. The resin composition is made.
Process b: The said resin composition is melt | dissolved using an organic solvent, and it is set as the resin varnish whose resin solid content amount is 30 weight%-70 weight%.

The resin layer is a resin composition used for forming an adhesive layer for multilayering an inner layer flexible printed wiring board, and is formed of a resin composition containing each of the following components A to E: Is preferred.
A component: Solid high heat-resistant epoxy resin having a softening point of 50 ° C. or higher (excluding biphenyl type epoxy resin).
B component: 1 of biphenyl type phenol resin, phenol aralkyl type phenol resin
Epoxy resin curing agent comprising two or more species.
Component C: A rubber-modified polyamideimide resin soluble in a solvent having a boiling point in the range of 50 ° C to 200 ° C.
D component: An organic phosphorus-containing flame retardant.
E component: Biphenyl type epoxy resin.
The resin composition used for forming the resin layer preferably contains a phosphorus-containing flame-retardant epoxy resin as the F component in addition to the components A to E.
The resin composition used to form the resin layer is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin having an epoxy equivalent of 200 or less and liquid at room temperature as the G component. It is preferable that the epoxy resin which consists of 1 type (s) or 2 or more types is further included.
It is preferable that the resin composition used for forming the resin layer further contains a low-elasticity material made of a thermoplastic resin and / or a synthetic rubber as the H component.
The solid high heat resistant epoxy resin in which the softening point of the component A is 50 ° C. or higher is one or more of cresol novolac type epoxy resin, phenol novolac type epoxy resin, and naphthalene type epoxy resin. Is preferred.
Resin further including a high heat-resistant epoxy resin composed of one or more of a novolak type epoxy resin, a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, and a naphthalene type epoxy resin that is liquid at room temperature as the component A The resin layer is preferably formed using a composition.
When the weight of the resin composition for forming the resin layer is 100 parts by weight, the A component is 3 to 30 parts by weight, the B component is 13 to 35 parts by weight, and the C component is 10 parts by weight. It is preferable that 50 parts by weight, the D component is 3 to 16 parts by weight, and the E component is 5 to 35 parts by weight.

  A resin varnish prepared by adding a solvent to the resin composition so that the resin solid content is in the range of 30 wt% to 70 wt%. When a semi-cured resin layer is formed, the MIL-P-13949G in the MIL standard In conformity, it is preferable to form the resin layer using a resin varnish characterized by having a resin flow in a range of 0% to 10% when measured at a resin thickness of 55 μm.

The resin layer has a thickness of 10 μm to 80 μm by preparing a resin varnish used for forming the resin layer in the following steps a and b, applying the resin varnish to the surface of the surface-treated copper foil, and drying the resin varnish. The semi-cured resin layer is preferably formed.
Step a: When the weight of the resin composition is 100 parts by weight, the A component is 3 to 30 parts by weight, the B component is 13 to 35 parts by weight, the C component is 10 to 50 parts by weight, and the D component Is a resin composition containing each component in the range of 3 to 16 parts by weight and E component in the range of 5 to 35 parts by weight.
Process b: The said resin composition is melt | dissolved using an organic solvent, and it is set as the resin varnish whose resin solid content amount is 30 weight%-70 weight%.

The component A is a solid high heat resistant epoxy resin having a softening point of 50 ° C. or higher. Component A is an epoxy resin having a high so-called glass transition temperature Tg. The reason why a solid high heat resistant epoxy resin having a softening point of 50 ° C. or higher among the epoxy resins is used is that the glass transition temperature Tg is high, and a high heat resistance effect can be obtained by adding a small amount.

The “solid high heat resistant epoxy resin having a softening point of 50 ° C. or higher” mentioned here is one or more of cresol novolac type epoxy resin, phenol novolac type epoxy resin, and naphthalene type epoxy resin. It is preferable.

  In addition to the solid high heat-resistant epoxy resin having a softening point of 50 ° C. or higher, the component A further includes a novolac type epoxy resin, a cresol novolac type epoxy resin, a phenol novolak type epoxy resin, and a naphthalene type. It is good also as what contains the highly heat-resistant epoxy resin which consists of any 1 type or 2 types or more of an epoxy resin. As described above, as the component A, a high heat-resistant epoxy composed of one or more of a novolak type epoxy resin, a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, and a naphthalene type epoxy resin that is liquid at room temperature. If the resin is contained, the effect of further improving the glass transition temperature Tg and improving the B stage cracking can be enhanced.

  The component A is preferably used in the range of 3 to 30 parts by weight when the resin composition is 100 parts by weight. When the component A is less than 3 parts by weight, it is difficult to increase the Tg of the resin composition. On the other hand, when the component A exceeds 30 parts by weight, the cured resin layer becomes brittle and the flexibility is completely impaired, which is not preferable for use as a flexible printed wiring board. More preferably, the component A is used in the range of 10 to 25 parts by weight, so that both high Tg of the resin composition and good flexibility of the resin layer after curing can be stably achieved.

Component B is an epoxy resin curing agent composed of one or more of a biphenyl type phenol resin and a phenol aralkyl type phenol resin. The addition amount of the epoxy resin curing agent is naturally derived from the reaction equivalent to the resin to be cured, and does not require any particular quantitative limitation. However, in the case of the resin composition according to the present invention, the component B is preferably used in the range of 13 parts by weight to 35 parts by weight when the resin composition is 100 parts by weight. When this B component is less than 13 parts by weight, considering the resin composition of the present invention, it becomes impossible to obtain a sufficiently cured state, and it becomes impossible to obtain the flexibility of the cured resin layer. On the other hand, when the component B exceeds 35 parts by weight, the moisture absorption resistance of the cured resin layer tends to deteriorate, which is not preferable.
A specific example of the biphenyl type phenol resin is shown in Chemical formula 26.

  A specific example of the phenol aralkyl type phenol resin is shown in Chemical Formula 27.

  Component C is a rubber-modified polyamideimide resin that is soluble in a solvent having a boiling point in the range of 50 ° C to 200 ° C. By mix | blending the said C component, while improving a flexible performance, the effect which suppresses a resin flow is acquired. This rubber-modified polyamideimide resin is obtained by reacting a polyamideimide resin and a rubber resin, and is performed for the purpose of improving the flexibility of the polyamideimide resin itself. That is, the polyamideimide resin and the rubber resin are reacted to replace a part of the acid component (cyclohexanedicarboxylic acid or the like) of the polyamideimide resin with the rubber component. The rubber component is described as a concept including natural rubber and synthetic rubber. Examples of the latter synthetic rubber include styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, and acrylonitrile butadiene rubber. Furthermore, from the viewpoint of ensuring heat resistance, it is also useful to selectively use a synthetic rubber having heat resistance such as nitrile rubber, chloroprene rubber, silicon rubber, urethane rubber and the like. Since these rubber-like resins react with the polyamide-imide resin to produce a copolymer, it is desirable to have various functional groups at both ends. In particular, it is useful to use CTBN (carboxy group-terminated butadiene nitrile rubber) having a carboxyl group. In addition, the said rubber component may copolymerize only 1 type or may copolymerize 2 or more types. Further, when a rubber component is used, it is preferable to use a rubber component having a number average molecular weight of 1000 or more from the viewpoint of stabilization of flexibility.

  When polymerizing the rubber-modified polyamideimide resin, the solvents used for dissolving the polyamideimide resin and the rubbery resin include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, nitromethane, nitroethane, and tetrahydrofuran. , Cyclohexanone, methyl ethyl ketone, acetonitrile, γ-butyrolactone, and the like are preferably used alone or in combination. And in order to raise | generate a polymerization reaction, it is preferable to employ | adopt the polymerization temperature of the range of 80 to 200 degreeC. When a solvent having a boiling point of more than 200 ° C. is used for these polymerizations, it is preferable that the solvent be replaced with a solvent having a boiling point in the range of 50 ° C. to 200 ° C., depending on the application.

  Here, examples of the solvent having a boiling point in the range of 50 ° C. to 200 ° C. include one single solvent or two or more mixed solvents selected from the group of methyl ethyl ketone, dimethylacetamide, dimethylformamide and the like. When the boiling point is lower than 50 ° C., the solvent is greatly diffused by heating, and it is difficult to obtain a good semi-cured state when the resin varnish is changed to a semi-cured resin. On the other hand, when the boiling point exceeds 200 ° C., when the semi-cured resin is used from the state of the resin varnish, it is difficult to obtain a good semi-cured resin layer because the solvent is difficult to dry.

  Among the rubber-modified polyamideimide resins used in the resin composition according to the present invention, when the weight of the rubber-modified polyamideimide resin is 100% by weight, the copolymerization amount of the rubber component may be 0.8% by weight or more. preferable. When the copolymerization amount is less than 0.8% by weight, the rubber-modified polyamide-imide resin lacks flexibility when the resin layer formed using the resin composition according to the present invention is cured, Since the adhesiveness with copper foil also falls, it is not preferable. More preferably, the copolymerization amount of the rubber component is 3% by weight or more, more preferably 5% by weight or more. Empirically, there is no particular problem even if the copolymerization amount exceeds 40% by weight. However, since the effect of improving the flexibility of the cured resin layer is saturated, resources are wasted, which is not preferable.

  The rubber-modified polyamide-imide resin described above is required to be soluble in a solvent. This is because preparation as a resin varnish is difficult unless it is soluble in a solvent. The rubber-modified polyamide-imide resin is used in a blending ratio of 10 to 50 parts by weight when the weight of the resin composition is 100 parts by weight. When the rubber-modified polyamideimide resin is less than 10 parts by weight, the resin flow suppressing effect is hardly exhibited. In addition, the cured resin layer becomes brittle and it is difficult to improve flexibility. As a result, there is an effect that microcracks of the resin layer are easily generated. On the other hand, when the rubber-modified polyamide-imide resin is added in an amount exceeding 50 parts by weight, the embedding property in the inner layer circuit is lowered, and as a result, voids are likely to be generated.

  Component D is an organic phosphorus-containing flame retardant and is used to improve flame retardancy. Examples of organic phosphorus-containing flame retardants include phosphorus-containing flame retardants composed of phosphate esters and / or phosphazene compounds. The component D is preferably used in the range of 3 to 16 parts by weight when the resin composition is 100 parts by weight. When the content of the D component is less than 3 parts by weight, the flame retardancy effect cannot be obtained. On the other hand, even if the content of the D component exceeds 16 parts by weight, improvement in flame retardancy cannot be expected. In addition, more preferable content of D component is 5 weight part-14 weight part.

  In addition, when the resin composition according to the present invention is added so that the total content of phosphorus is in the range of 0.5 wt% to 5 wt% when the weight of the resin composition is 100 wt%, it is flame retardant. Is preferable.

  The E component is a biphenyl type epoxy resin. The biphenyl type epoxy resin contributes to improvement of so-called glass transition temperature Tg and flexibility. Examples of the biphenyl type epoxy resin include a biphenyl aralkyl type epoxy resin. The component E is preferably used in the range of 5 to 35 parts by weight when the resin composition is 100 parts by weight. When the content of the E component is less than 5 parts by weight, the effect of increasing the glass transition temperature Tg and the flexibility cannot be obtained. On the other hand, even if the content of the E component exceeds 35 parts by weight, it is not possible to expect a high Tg and an improvement in flexibility. In addition, more preferable content of E component is 7 weight part-25 weight part.

  In addition to the A component to the E component, if the resin composition includes a phosphorus-containing flame-retardant epoxy resin as the F component, the flame retardancy can be further improved. The phosphorus-containing flame-retardant epoxy resin is a general term for epoxy resins containing phosphorus in an epoxy skeleton, and is a so-called halogen-free flame-retardant epoxy resin. And phosphorus content which can make phosphorus atom derived from F component into the range of 0.1 weight%-5 weight% when the resin composition weight is 100 weight% about the phosphorus atom content of the resin composition concerning this application Any flame retardant epoxy resin can be used. However, using a phosphorus-containing flame retardant epoxy resin having two or more epoxy groups in the molecule, which is a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, is a semi-cured state. It is preferable because it has excellent resin quality stability at the same time and has a high flame retardant effect. For reference, the structural formula of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is shown in Chemical Formula 28.

  This 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, a phosphorus-containing flame-retardant epoxy resin having two or more epoxy groups in the molecule, is 9,10-dihydro-9. -Oxa-10-phosphaphenanthrene-10-oxide is reacted with naphthoquinone or hydroquinone to form a compound shown in the following chemical formula 29 or chemical formula 30, and then the epoxy resin is reacted with the OH group portion to make it difficult to contain phosphorus. What was made into the flammable epoxy resin is preferable.

  A specific example of a phosphorus-containing flame-retardant epoxy resin having two or more epoxy groups in the molecule, which is a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, The use of a compound having the structural formula shown in Chemical Formula 31, Chemical Formula 32 or Chemical Formula 33 is preferred.

  Here, when the phosphorus-containing flame-retardant epoxy resin is used, the resin composition may be one of the phosphorus-containing flame-retardant epoxy resins as the F component, or two or more phosphorus-containing flame-retardant epoxy resins. May be used in combination. However, considering the total amount of the phosphorus-containing flame-retardant epoxy resin as the F component, when the resin composition weight is 100% by weight, the phosphorus atom derived from the F component is in the range of 0.1% to 5% by weight. It is preferable to add so that it becomes. The phosphorus-containing flame-retardant epoxy resin has different amounts of phosphorus atoms contained in the epoxy skeleton depending on the type. Therefore, it is possible to define the content of phosphorus atoms as described above and replace it with the addition amount of the F component. However, the component F is usually used in the range of 5 to 50 parts by weight when the resin composition is 100 parts by weight. In the case where the F component is less than 5 parts by weight, it becomes difficult to make the phosphorus atom derived from the F component 0.1% by weight or more in consideration of the blending ratio of the other resin components. Can not get. On the other hand, even if the F component exceeds 50 parts by weight, the effect of improving flame retardancy is saturated, and at the same time, the cured resin layer becomes brittle.

  “High Tg” and “flexibility” of the cured resin layer described above are generally inversely proportional characteristics. At this time, there are phosphorus-containing flame-retardant epoxy resins that contribute to improving the flexibility of the cured resin layer and those that contribute to high Tg. Therefore, rather than using one type of phosphorus-containing flame-retardant epoxy resin, “phosphorus-containing flame-retardant epoxy resin that contributes to higher Tg” and “phosphorus-containing flame-retardant epoxy resin that contributes to improved flexibility” By mixing and using in a well-balanced manner, it is possible to obtain a resin composition suitable for flexible printed wiring board applications.

  The resin composition according to the present invention is further selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin having an epoxy equivalent of 200 or less and being liquid at room temperature as the G component. Or it is good also as what contains the epoxy resin which consists of 2 or more types. Here, the reason why the bisphenol-based epoxy resin is selectively used is that the compatibility with the component C (rubber-modified polyamideimide resin) is good, and it is easy to impart appropriate flexibility to the semi-cured resin layer. If the epoxy equivalent exceeds 200, the resin becomes semi-solid at room temperature, and the flexibility in the semi-cured state decreases, which is not preferable. Furthermore, if it is the above-mentioned bisphenol-type epoxy resin, 1 type may be used independently or 2 or more types may be used in mixture. In addition, when two or more kinds are mixed and used, there is no particular limitation with respect to the mixing ratio.

  This G component epoxy resin, when the resin composition is 100 parts by weight, exhibits a sufficient thermosetting property when used in a blending ratio of 2 to 15 parts by weight. It is preferable because the occurrence of a so-called warp phenomenon can be reduced, and the flexibility of the resin layer in a semi-cured state can be further improved. When the said epoxy resin exceeds 15 weight part, there exists a tendency for a flame retardance to fall from the balance with another resin component, or for the resin layer after hardening to become hard. Moreover, considering the amount of component C (rubber-modified polyamideimide resin) added, sufficient toughness for the cured resin layer cannot be obtained.

  The resin composition according to the present invention may further include a low-elasticity substance made of a thermoplastic resin and / or a synthetic rubber as the H component. By setting it as the resin composition containing H component, the crack in the semi-hardened state of a resin composition can be prevented, and the flexibility after hardening can be improved. Examples of the low-elasticity material as the H component include acrylonitrile butadiene rubber, acrylic rubber (acrylic ester copolymer), polybutadiene rubber, isoprene, hydrogenated polybutadiene, polyvinyl butyral, polyethersulfone, phenoxy, and polymer epoxy. And aromatic polyamides. One of these may be used alone, or two or more may be used in combination. In particular, acrylonitrile butadiene rubber is preferably used. Among the acrylonitrile butadiene rubbers, a carboxyl-modified product can take a crosslinked structure with an epoxy resin and improve the flexibility of the cured resin layer. As a carboxyl modified body, it is preferable to use carboxy group terminal nitrile butadiene rubber (CTBN), carboxy group terminal butadiene rubber (CTB), and carboxy modified nitrile butadiene rubber (C-NBR).

  The H component is preferably used at a blending ratio of 25 parts by weight or less when the resin composition is 100 parts by weight. If an H component in an amount exceeding 25 parts by weight is added, problems such as a decrease in glass transition temperature Tg, a decrease in solder heat resistance, a decrease in peel strength, and an increase in thermal expansion coefficient are undesirable.

  The resin composition according to the present invention can improve the flame retardancy and the glass transition temperature Tg by combining the above-described components A to E, and can prevent the heat resistance of the folding resistance. And sufficient flexibility can be obtained, without adding an inorganic filler like the conventional resin composition for adhesive agents. Furthermore, it is possible to prevent cracking in a semi-cured state and powder falling off during punching.

  Resin varnish according to the present invention: The resin varnish according to the present invention is prepared by adding a solvent to the above resin composition so that the resin solid content is in the range of 30 wt% to 70 wt%. The semi-cured resin layer formed with this resin varnish has a resin flow in the range of 0% to 10% when measured with a resin thickness of 55 μm according to MIL-P-13949G in the MIL standard. Features. As the solvent mentioned here, one kind of single solvent selected from the group of methyl ethyl ketone, dimethylacetamide, dimethylformamide, etc., which is a solvent having a boiling point in the range of 50 ° C. to 200 ° C., or a mixed solvent of two or more kinds is used. It is preferable. This is for obtaining a good semi-cured resin layer as described above. And the range of the resin solid content shown here is a range in which the film thickness can be controlled to the most accurate one when applied to the surface of the copper foil. When the resin solid content is less than 30% by weight, the viscosity is too low and it flows immediately after application to the copper foil surface, making it difficult to ensure film thickness uniformity. On the other hand, when the resin solid content exceeds 70% by weight, the viscosity increases and it becomes difficult to form a thin film on the surface of the copper foil.

  When the resin varnish is used to form a semi-cured resin layer, the measured resin flow is preferably in the range of 0% to 10%. When the resin flow is high, the thickness of the insulating layer formed using the resin layer of the resin-coated copper foil becomes nonuniform. However, the resin varnish according to the present invention can suppress the resin flow to a low value of 10% or less. In addition, since the resin varnish which concerns on this invention can implement | achieve the level which resin flow hardly produces, the lower limit of the said resin flow was made into 0%. In addition, the more preferable range of the resin flow of the resin varnish concerning this invention is 0%-5%.

  In this specification, the resin flow is based on MIL-P-13949G in the MIL standard. Four 10 cm square samples are sampled from a resin-coated copper foil with a resin thickness of 55 μm. It is a value calculated based on Equation 1 from the result of measuring the resin outflow weight at the time of laminating under the conditions of a press temperature of 171 ° C., a press pressure of 14 kgf / cm 2, and a press time of 10 minutes in a stacked state (laminate).

The resin layer is soluble in a solvent and contains 2 to 50 parts by weight of a polymer component having one or more of hydroxyl group, carboxyl group and amino group in the molecule as a functional group, and a boiling point of 200 ° C. or more. You may contain 50 weight part or more of the epoxy resin compound which consists of an epoxy resin and an amine epoxy resin hardening | curing agent with a boiling point of 200 degreeC or more. The resin layer may be a fluororesin substrate or a fluororesin film adhesive resin. The polymer component may be a mixture of one or more selected from the group of polyvinyl acetal resins, phenoxy resins, aromatic polyamide resins, polyether sulfone resins, and polyamideimide resins. The epoxy resin having a boiling point of 200 ° C. or higher is a mixture of one or more selected from the group of bisphenol A type epoxy resin, bisphenol F type epoxy resin, rubber-modified bisphenol A type epoxy resin, and biphenyl type epoxy resin. There may be.
The amine-based epoxy resin curing agent is an aromatic polyamine, a polyamide, and one or more selected from the group of amine adducts obtained by polymerizing or condensing these with an epoxy resin or a polyvalent carboxylic acid. May be.

  The fluororesin substrate or fluororesin film refers to PTFE (polytetrafluoroethylene (tetrafluoroethylene)), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene / hexafluoro). Propylene copolymer (4.6 fluoride)), ETFE (tetrafluoroethylene / ethylene copolymer), PVDF (polyvinylidene fluoride (difluoride)), PCTFE (polychlorotrifluoroethylene (trifluoride)) ), A base material or a film using a fluororesin composed of at least one thermoplastic resin selected from polyallylsulfone, aromatic polysulfide, and aromatic polyether and a fluororesin. . It does not matter whether or not a skeletal material such as glass cloth is included. Moreover, there is no special limitation also about the thickness of this fluororesin base material.

  Further, as the curing agent, for the purpose of merely curing, amines such as dicyandiamide, imidazoles and aromatic amines, phenols such as bisphenol A and brominated bisphenol A, phenol novolac resins and cresol novolacs Any curing agent such as novolaks such as resins and acid anhydrides such as phthalic anhydride can be used. These curing agents are particularly effective for epoxy resins. However, it is most preferable to use an amine epoxy resin curing agent having a boiling point of 200 ° C. or higher from the viewpoint of significantly improving the adhesion between the fluororesin substrate and the metal foil. If the press molding temperature is around 180 ° C. and the boiling point of the curing agent is near the press molding temperature, the epoxy resin curing agent will boil due to the press molding, and bubbles are likely to be generated in the cured insulating resin layer. The most stable adhesion can be obtained when an amine-based epoxy resin curing agent is used to form an adhesive layer between the fluororesin substrate and the metal foil. That is, the “amine epoxy resin curing agent having a boiling point of 200 ° C. or more” is selected from the group of aromatic polyamines, polyamides, and amine adducts obtained by polymerizing or condensing these with epoxy resins or polyvalent carboxylic acids. The case where one kind or two kinds or more are used. More specifically, 4,4′-diaminodiphenylenesulfone, 3,3′-diaminodiphenylenesulfone, 4,4-diaminodiphenylel, 2,2-bis [4- It is preferable to use either (4-aminophenoxy) phenyl] propane or bis [4- (4-aminophenoxy) phenyl] sulfone. Moreover, since the addition amount with respect to the epoxy resin of the said amine epoxy resin hardening | curing agent is derived from each equivalent naturally, it thinks that it is not necessary to specify the compounding ratio strictly strictly. Therefore, in this invention, the addition amount of a hardening | curing agent is not specifically limited.

  It is also preferable to use a curing accelerator that is added in an appropriate amount as required. The curing accelerator referred to here is a tertiary amine, imidazole, urea curing accelerator or the like. In the present invention, the mixing ratio of the curing accelerator is not particularly limited. This is because the amount of the hardening accelerator can be arbitrarily determined by the manufacturer in consideration of heating conditions during press working.

  The resin layer preferably contains a rubbery resin. The rubber resin referred to here is described as a concept including natural rubber and synthetic rubber, and the latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber and the like. Furthermore, when heat resistance is required, it is also useful to selectively use heat-resistant synthetic rubbers such as nitrile rubber, chloroprene rubber, silicon rubber, urethane rubber. Regarding these rubber resins, it is desirable to have various functional groups at both ends so as to react with the polymer component to form a copolymer.

  Furthermore, it is also preferable to add the above-mentioned high-molecular polymer crosslinking agent as necessary. For example, when a polyvinyl acetal resin is used as the polymer, a urethane resin is used as a cross-linking material.

  The components of the resin composition of the resin layer are 50 parts by weight to 80 parts by weight of the epoxy resin, 1 part by weight to 15 parts by weight of the curing agent, and 0 part of the curing accelerator when the resin composition is 100 parts by weight. .01 parts by weight to 1.0 parts by weight, 2 to 50 parts by weight of the polymer component, 1 to 5 parts by weight of the crosslinking agent, and 1 to 10 parts by weight of the rubbery resin are employed. May be. As long as it is included in this composition range, good adhesion between the fluororesin substrate and the metal foil is maintained, and variation in product adhesion is reduced.

  The resin layer is 5 to 50 parts by weight of an epoxy resin (including a curing agent), 50 to 95 parts by weight of a polyethersulfone resin (having a hydroxyl group or an amino group at the terminal and being soluble in a solvent), and What was formed using the resin mixture which consists of a hardening accelerator added suitably as needed, or what made the said resin mixture semi-hardened may be used.

  The resin layer is a resin layer having a first thermosetting resin layer and a second thermosetting resin layer located on the surface of the first thermosetting resin layer in order from the copper foil side, The curable resin layer is formed of a resin component that does not dissolve in chemicals during desmear processing in the wiring board manufacturing process, and the second thermosetting resin layer dissolves in chemicals during desmear processing in the wiring board manufacturing process. Then, it may be formed using a resin that can be washed and removed. The first thermosetting resin layer may be formed using a resin component obtained by mixing one or more of polyimide resin, polyethersulfone, and polyphenylene oxide. The second thermosetting resin layer may be formed using an epoxy resin component. The thickness t1 (μm) of the first thermosetting resin layer is such that the roughened surface roughness of the surface-treated copper foil is Rz (μm), and the thickness of the second thermosetting resin layer is t2 (μm). Then, t1 is preferably a thickness that satisfies the condition of Rz <t1 <t2.

  The resin layer may be a prepreg in which a skeleton material is impregnated with a resin. The resin impregnated in the skeleton material is preferably a thermosetting resin. The prepreg may be a known prepreg or a prepreg used for manufacturing a printed wiring board. The prepreg may be a prepreg manufactured by a manufacturing method having the following steps. 1. A liquid resin film forming step of forming a liquid resin layer as a film having a predetermined thickness on a flat work plane using a liquid thermosetting resin. 2. A preliminary drying step in which the liquid resin layer on the work plane is dried as it is to obtain a dry resin layer. 3. A skeleton material pre-adhesion step in which a skeleton material is superimposed on the surface of the dry resin layer on the work plane, preheated and pressed to form a dry resin layer with a skeleton material. 4). A resin impregnation step in which the resin is heated at a temperature at which the resin can be reflowed while the dry resin layer with the skeleton material is placed on the work plane, and the skeleton material is impregnated with the thermosetting resin component. 5. When the resin impregnation is completed, the cooling step is performed so that the temperature setting operation is immediately performed without completely curing the thermosetting resin, and the semi-cured state of the thermosetting resin impregnated in the skeleton material is maintained to be in the prepreg state. .

The skeleton material may include aramid fibers, glass fibers, or wholly aromatic polyester fibers. The skeleton material is preferably an aramid fiber, a glass fiber, or a nonwoven fabric or woven fabric of wholly aromatic polyester fibers. The wholly aromatic polyester fiber is preferably a wholly aromatic polyester fiber having a melting point of 300 ° C. or higher. The wholly aromatic polyester fiber having a melting point of 300 ° C. or higher is a fiber produced using a resin called a so-called liquid crystal polymer, and the liquid crystal polymer contains 2-hydroxyl-6-naphthoic acid and p-hydroxybenzoic acid. The main component is an acid polymer. Since this wholly aromatic polyester fiber has a low dielectric constant and low dielectric loss tangent, it has excellent performance as a constituent material of an electrically insulating layer and can be used in the same manner as glass fiber and aramid fiber. is there.
In addition, in order to improve the wettability with the resin of the surface, it is preferable to perform the silane coupling agent process for the fiber which comprises the said nonwoven fabric and woven fabric. The silane coupling agent at this time may be an amino or epoxy silane coupling agent depending on the purpose of use.

  The prepreg is a prepreg obtained by impregnating a thermosetting resin into a nonwoven fabric using an aramid fiber or glass fiber having a nominal thickness of 70 μm or less, or a skeleton material made of glass cloth having a nominal thickness of 30 μm or less. Also good.

  These resins are, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl. 2-Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, etc., dissolved in a solvent to give a resin liquid, which is applied to the ultrathin copper layer, the heat-resistant layer, the rust-proof layer, or the chromate On the treatment layer or the silane coupling agent layer, for example, it is applied by a roll coater method or the like, and then heated and 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 resin layer composition may be dissolved using a solvent to obtain a resin liquid having a resin solid content of 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%. In addition, it is most preferable at this stage from an environmental standpoint to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone.

  The surface-treated copper foil provided with the resin layer (surface-treated copper foil with resin) is superposed on the base material, and the whole is thermocompressed to thermally cure the resin layer. This wiring pattern is used in the form of forming. Moreover, about the copper foil with a carrier which used the said surface-treated copper foil as an ultra-thin copper layer, the copper foil with a carrier provided with the resin layer (copper foil with a carrier with a resin) overlapped the resin layer on the base material After that, the entire resin layer is thermocompression-bonded to thermally cure the resin layer, and then the carrier is peeled off to expose the ultrathin copper layer (naturally it is the surface on the intermediate layer side of the ultrathin copper layer) And a predetermined wiring pattern is formed there.

  When this surface-treated copper foil with resin or copper foil with carrier with resin is used, the number of prepreg materials used in the production of the 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 particularly with respect to the copper foil with a carrier with resin, 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 the resin layer is preferably 0.1 to 120 μm.

  When the thickness of the resin layer becomes thinner than 0.1 μm, the adhesive strength is reduced, and the surface-treated copper foil with resin or the copper foil with carrier with resin is laminated on the base material provided with the inner layer material without interposing a prepreg material. In some cases, it may be difficult to ensure interlayer insulation with the circuit of the inner layer material. The total resin layer thickness with the cured resin layer and the semi-cured resin layer is preferably 0.1 μm to 120 μm, and practically preferable is 35 μm to 120 μm. And in that case, as for each thickness, it is desirable that a cured resin layer is 5-20 micrometers, and a semi-hardened resin layer is 15-115 micrometers. If the total resin layer thickness exceeds 120 μm, it may be difficult to produce a thin multilayer printed wiring board. If the total resin layer thickness is less than 35 μm, it is easy to form a thin multilayer printed wiring board. This is because the resin layer may become too thin and the insulation between the circuits of the inner layer tends to become unstable. Moreover, when the cured resin layer thickness is less than 5 μm, it may be necessary to consider the surface roughness of the roughened copper foil surface. Conversely, if the cured resin layer thickness exceeds 20 μm, the effect of the cured resin layer may not be particularly improved, and the total insulating layer thickness becomes thick. The cured resin layer may have a thickness of 3 μm to 30 μm. The semi-cured resin layer may have a thickness of 7 μm to 55 μm. The total thickness of the cured resin layer and the semi-cured resin layer may be 10 μm to 60 μm.

Further, when the surface-treated copper foil with resin or the copper foil with carrier with resin is used for producing an ultra-thin multilayer printed wiring board, the thickness of the resin layer is 0.1 μm to 5 μm, more preferably 0. The thickness is preferably 5 μm to 5 μm, more preferably 1 μm to 5 μm, in order to reduce the thickness of the multilayer printed wiring board. When the thickness of the resin layer is 0.1 μm to 5 μm, in order to improve the adhesion between the resin layer and the copper foil, a heat-resistant layer and / or a rust-proof layer and / or on the surface treatment layer After providing the chromate treatment layer and / or the silane coupling treatment layer, it is preferable to form a resin layer on the heat-resistant layer, rust prevention layer, chromate treatment layer or silane coupling treatment layer.
When the resin layer includes a dielectric, the thickness of the resin layer is preferably 0.1 to 50 μm, preferably 0.5 μm to 25 μm, and more preferably 1.0 μm to 15 μm. preferable. In addition, the thickness of the above-mentioned resin layer says the average value of the thickness measured by cross-sectional observation in arbitrary 10 points | pieces.

  On the other hand, if the thickness of the resin layer is thicker than 120 μm, it becomes difficult to form a resin layer having a desired 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, another product form of the copper foil with a carrier with resin is a resin on the ultrathin copper layer, or on the heat-resistant layer, rust-proof layer, chromate-treated layer, or silane coupling-treated layer. After coating with a 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 in which no carrier is present.

  Below, some examples of the manufacturing process of the printed wiring board using the resin base material which concerns on this invention are shown. Moreover, a printed circuit board is completed by mounting electronic components on the printed wiring board.

  In one 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 surface-treated copper foil and a resin base material, the surface-treated copper foil is formed from the surface-treated layer side with a resin substrate. A step of laminating the material, a step of removing the surface-treated copper foil on the resin base material to obtain the resin base material of the present invention, and a step of forming a circuit on the surface of the resin base material from which the surface-treated copper foil has been removed.

  FIG. 1 shows a schematic example of a semi-additive construction method using a copper foil profile. In this construction method, the surface profile of the copper foil is used for forming the surface profile of the resin base material. Specifically, first, the copper foil of the present invention is laminated on a resin base material to produce a copper clad laminate. Next, the entire surface of the copper foil of the copper clad laminate is etched. Next, electroless copper plating is applied to the surface of the resin substrate (entire etching substrate) to which the copper foil surface profile has been transferred. Then, a portion of the resin base material (entire etching base material) where the circuit is not formed is covered with a dry film or the like, and electroless (electrolytic) copper plating is applied to the surface of the electroless copper plating layer not covered with the dry film. Then, after removing the dry film, a fine circuit is formed by removing the electroless copper plating layer formed in the portion where the circuit is not formed. Since the fine circuit formed in the present invention is in close contact with the etching surface of the resin base material (entire etching base material) to which the copper foil surface profile of the present invention is transferred, the adhesion force (peel strength) is good. It has become.

  The resin base material can also have 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 a resin substrate or a copper foil seed layer, a pattern is formed, and then a conductor pattern is formed using electroplating and etching.

  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 a resin base material, the copper foil with a carrier is resin from the ultrathin copper layer side The process of laminating on the substrate, laminating the carrier-attached copper foil and the resin substrate, removing the carrier of the copper foil with carrier, removing the ultrathin copper layer on the resin substrate after removing the carrier And a step of forming a circuit on the surface of the resin substrate from which the ultrathin copper layer has been removed.

  In one embodiment of the method for producing a printed wiring board according to the present invention, a surface-treated copper foil is laminated on the resin base material of the present invention from the surface-treated layer side to form a copper-clad laminate, and then subtractive Forming a circuit by any one of a method, a partial additive method, or a modified semi-additive method.

  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.

  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.

  In the present invention, the modified semi-additive method is a method of laminating a metal foil on a resin base material, protecting a non-circuit forming portion with a plating resist, thickening the copper of the circuit forming portion by electrolytic plating, It refers to a method of forming a circuit on a resin substrate by removing and removing the metal foil other than the circuit forming part by (flash) etching.

  In one embodiment of the method for producing a printed wiring board according to the present invention, the step of laminating the copper foil with carrier on the resin base material of the present invention from the ultrathin copper layer side, laminating the copper foil with carrier and the resin base material Thereafter, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil, and then a step of forming a circuit by either the partial additive method or the modified semi-additive method is included.

  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 metal foil having a circuit formed on the surface, a resin base material on the surface of the metal foil so that the circuit is buried A step of laminating the surface-treated copper foil on the resin substrate from the surface-treated layer side, a step of removing the surface-treated copper foil on the resin substrate to obtain the resin substrate of the present invention, the surface-treated copper A step of forming a circuit on the surface of the resin base material from which the foil has been removed, and a step of exposing the circuit embedded in the resin base material formed on the surface of the metal foil by removing the metal foil.

  In one embodiment of the method for manufacturing a printed wiring board according to the present invention using the semi-additive method, a step of forming a circuit on the ultrathin copper layer side surface of the first copper foil with carrier so that the circuit is buried Forming a resin base material on the surface of the ultrathin copper layer side of the first copper foil with carrier, preparing a second copper foil with carrier, and forming a resin base from the ultrathin copper layer side of the second copper foil with carrier The step of laminating on the material, the step of peeling the carrier of the second copper foil with carrier after laminating the second copper foil with carrier on the resin substrate, the resin after peeling off the carrier of the second copper foil with carrier The process of obtaining the resin base material of the present invention by removing the ultrathin copper layer on the base material, the step of forming a circuit on the surface of the resin base material from which the ultrathin copper layer was removed, and the circuit was formed on the resin base material Later, the step of peeling the carrier of the first copper foil with carrier, and the first copper with carrier After removing the carrier, the ultrathin copper layer of the first carrier-attached copper foil is removed, so that it is buried in the resin substrate formed on the ultrathin copper layer side surface of the first carrier-attached copper foil. Exposing the active circuit.

  In one embodiment of the method for producing a printed wiring board according to the present invention, a step of preparing a metal foil having a circuit formed on the surface, the resin base material of the present invention is formed on the surface of the metal foil so that the circuit is buried A step of laminating a surface-treated copper foil on a resin base material from the surface-treated layer side, and forming a circuit on the resin layer by any one of a subtractive method, a partial additive method, or a modified semi-additive method; and The process of exposing the circuit embedded in the resin base material formed in the metal foil surface by removing metal foil is included.

  In one embodiment of the method for manufacturing a printed wiring board according to the present invention, a step of forming a circuit on the surface of the first copper foil with carrier on the ultrathin copper layer side, the first copper with carrier so that the circuit is buried The step of forming the resin base material of the present invention on the surface of the ultrathin copper layer of the foil, preparing a second copper foil with carrier, and laminating the resin base material from the ultrathin copper layer side of the second copper foil with carrier And removing the carrier of the copper foil with the second carrier, forming a circuit on the resin substrate by any one of the subtractive method, the partial additive method or the modified semi-additive method, and forming the circuit on the resin substrate. After the formation, the step of peeling the carrier of the first copper foil with carrier, and after peeling the carrier of the first copper foil with carrier, the ultrathin copper layer of the first copper foil with carrier is removed. With that, with the first carrier It formed in the ultrathin copper layer side surface of the foil, comprising the step of exposing the circuit are embedded in the resin substrate.

  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 a resin base material, a step of laminating the copper foil with a carrier and a resin base material, After laminating the copper foil with carrier and the resin base material, the step of peeling the carrier of the copper foil with carrier, the ultrathin copper layer exposed by peeling the carrier is etched using a corrosive solution such as acid or plasma Removing all by a method to obtain the resin base material of the present invention, providing a through hole or / and a blind via in the resin exposed by removing the ultrathin copper layer by etching, the through hole or / and A step of performing a desmear process on a region including the blind via, including the resin and the through hole or / and the blind via; A step of providing an electroless plating layer for a region, a step of providing a plating resist on the electroless plating layer, a step of exposing the plating resist, and then removing the plating resist in a region where a circuit is formed, A step of providing an electrolytic plating layer in a region where the circuit from which the plating resist is removed is formed, a step of removing the plating resist, a flash etching of an electroless plating layer in a region other than the region where the circuit is formed, etc. The step of removing by.

  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 a resin base material, and laminating the copper foil with a carrier and a resin base material A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and a resin base material, etching using a corrosive solution such as an acid on the ultrathin copper layer exposed by peeling the carrier, Removing all by a method such as plasma to obtain the resin substrate of the present invention, providing an electroless plating layer on the surface of the resin exposed by removing the ultrathin copper layer by etching, the electroless plating Providing a plating resist on the layer, exposing the plating resist, and then removing the plating resist in a region where a circuit is formed, the plating A step of providing an electrolytic plating layer in a region where the circuit from which the dies are removed is formed, a step of removing the plating resist, an electroless plating layer and an ultrathin copper layer in a region other than the region where the circuit is formed Is removed by flash etching or the like.

  In one embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, a step of preparing a copper foil with a carrier and a resin base material, and laminating the copper foil with a carrier and a resin base material A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the resin base, a through hole or / and a blind via in the ultrathin copper layer and the resin base exposed by peeling the carrier Providing a surface profile of the resin base material of the present invention by performing a desmear process on the region including the through hole or / and the blind via, and electroless plating layer on 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, After providing the serial plating resist to form a circuit by electroplating, removing the plating resist, comprising the step of removing the ultra-thin copper layer exposed by removing the plating resist by flash etching.

  In another embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, a step of preparing a copper foil with a carrier and a resin base, the copper foil with a carrier and the resin base A step of laminating, a step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and a resin base material, a step of 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 the region where the circuit is formed; providing an electrolytic plating layer in the region where the circuit where the plating resist is removed; and 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, It comprises obtaining the surface profile of the resin substrate of the invention.

  In one embodiment of a method for producing a printed wiring board according to the present invention using a partly additive method, a step of preparing a copper foil with a carrier and a resin base material, a step of laminating the copper foil with a carrier and a resin base material The step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the resin base material, through holes or / and blind vias in the ultrathin copper layer and the resin base material exposed by peeling the carrier A step of performing a desmear process on the region including the through hole or / and the blind via to obtain a surface profile of the resin base material of the present invention, and providing a catalyst nucleus for the region including the through hole or / and the blind via. A step of providing an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier, the etching Exposing the resist to form a circuit pattern, 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 to form a circuit, A step of removing an etching resist, a solder resist or a plating resist on the surface of the resin substrate exposed by removing the ultrathin copper layer and the catalyst core by a method such as etching using a corrosive solution such as acid or plasma. And a step of providing an electroless plating layer in a region where the solder resist or the plating resist is not provided.

  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 a copper foil with a carrier and a resin base material, a step of laminating the copper foil with a carrier and a resin base material The step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the resin base material, through holes or / and blind vias in the ultrathin copper layer and the resin base material exposed by peeling the carrier A step of performing a desmear process on the region including the through hole or / and the blind via to obtain a surface profile of the resin base material of the present invention, and an electroless plating layer on the region including the through hole or / and the blind via. The step of providing, the step of providing an electroplating layer on the surface of the electroless plating layer, the electroplating layer or / and before A step of providing an etching resist on the surface of the ultrathin copper layer, a step of exposing the etching resist to form a circuit pattern, a corrosion of the ultrathin copper layer, the electroless plating layer, and the electrolytic plating layer with an acid or the like It includes a step of forming a circuit by removing it by a method such as etching using a solution or plasma, and a step of removing the etching resist.

  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 a copper foil with a carrier and a resin base material, and laminating the copper foil with a carrier and the resin base material A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the resin base material, a through hole or / and a blind in the ultrathin copper layer and the resin base material exposed by peeling the carrier A step of providing vias, a step of obtaining a surface profile of the resin base material of the present invention by performing desmear treatment on the region including the through hole or / and the blind via, and electroless plating on the region including the through hole or / and the blind via. A step of providing a layer, a step of forming a mask on the surface of the electroless plating layer, and the electroless plating without a mask. A step of providing an electrolytic plating layer on the surface of the coating layer, a step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer, a step of exposing the etching resist to form a circuit pattern, A step of forming a circuit by 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, and a step of removing the etching resist.

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

Examples of the present invention are shown below, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.
In this example, as described below, the surface profile of the resin substrate was formed using a copper foil and the surface profile formed using a chemical solution.

1. Formation of Surface Profile of Resin Base Material Using Copper Foil FIG. 2 shows a sample production flow for obtaining data of examples and comparative examples.
The following copper foil bulk layers (raw foils) were prepared as copper foils for producing the substrate surface profiles of Examples 1-8, 10-12 and Comparative Examples 1-4.

・ General electrolytic green foil Copper concentration of 80 to 120 g / L, sulfuric acid concentration of 80 to 120 g / L, chloride ion concentration of 30 to 100 ppm, glue concentration of 1 to 5 ppm, and electrolytic solution temperature of 57 to 62 ° C. The electrolytic solution flowing between the anode and the cathode (a metal drum for electrodeposition for copper foil) as a plating bath has a linear velocity of 1.5 to 2.5 m / sec, a current density of 70 A / dm ² and a thickness of 12 μm (weight thickness 95 g). / M ² ) general electrolytic green foil was prepared.

-Double-sided flat electrolytic green foil Copper concentration 80-120 g / L, sulfuric acid concentration 80-120 g / L, chloride ion concentration 30-100 ppm, leveling agent 1 (bis (3sulfopropyl) disulfide): 10-30 ppm, leveling agent 2 (Amine compound): The linear velocity of the electrolyte flowing between the anode and the cathode (electrodeposition metal drum for copper foil) using a copper sulfate electrolyte of 10 to 30 ppm and an electrolyte temperature of 57 to 62 ° C. as an electrolytic copper plating bath Was produced at a current density of 70 A / dm ² and a thickness of 12 μm (weight thickness 95 g / m ² ). As the amine compound, an amine compound having the following chemical formula was used.
(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.)

-Ultra-thin raw copper foil with carrier A double-sided flat electrolytic raw foil having a thickness of 18 µm was produced under the above-mentioned double-sided flat electrolytic raw foil manufacturing conditions. Using this as a copper foil carrier, a peeling layer and an ultrathin copper layer were formed by the following method to obtain an ultrathin copper foil with a carrier having a thickness of 1.5, 2, 3, 5 μm.
(1) Ni layer (peeling layer: base plating 1)
An Ni layer having an adhesion amount of 1000 μg / dm ² was formed on the S surface of the copper foil carrier by electroplating with a roll-to-roll type continuous plating line under the following conditions. Specific plating conditions are described below.
Nickel sulfate: 270-280 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Boric acid: 30-40 g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55-75 ppm
pH: 4-6
Bath temperature: 55-65 ° C
Current density: 10 A / dm ²
(2) Cr layer (peeling layer: base plating 2)
Next, after the surface of the Ni layer formed in (1) was washed with water and pickled, a Cr layer having an adhesion amount of 11 μg / dm 2 was subsequently formed on the Ni layer on a roll-to-roll type continuous plating line. It was made to adhere by carrying out the electrolytic chromate process on the conditions of.
Potassium dichromate 1-10g / L, zinc 0g / L
pH: 7-10
Liquid temperature: 40-60 degreeC
Current density: 2 A / dm ²
(3) Ultra-thin copper layer Next, after the surface of the Cr layer formed in (2) was washed with water and pickled, the thickness 1. on the Cr layer on a continuous roll-to-roll type continuous plating line. An ultrathin copper layer of 5, 2, 3, 5 μm was formed by electroplating under the following conditions to produce an ultrathin copper foil with a carrier.
Copper concentration: 80-120 g / L
Sulfuric acid concentration: 80-120 g / L
Chloride ion concentration: 30-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
In addition, the following amine compounds were used for the leveling agent 2. As the amine compound, an amine compound having the following chemical formula was used.
(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.)
Electrolyte temperature: 50-80 ° C
Current density: 100 A / dm ²

  Next, each of roughening treatment, barrier treatment, rust prevention treatment, and silane coupling material application is applied to the M (matte surface) or S surface (shiny surface) which is the surface of the green foil bonded to the resin base material. The surface treatment was applied in this order. Each processing condition is shown below.

[Roughening treatment]
・ Spherical roughening (normal):
The roughening process was performed on the M surface or S surface of the various raw foils described above under the following conditions.
(Electrolytic solution composition)
Cu: 20-30 g / L (added with copper sulfate pentahydrate, the same applies hereinafter)
H ₂ SO ₄ : 80-120 g / L
Arsenic: 1.0-2.0 g / L
(Electrolyte temperature)
35-40 ° C
(Current condition)
Current density: 70 A / dm ²

  Cover the M surface of various copper foils roughened under the above conditions and the surface of the ultrathin copper foil with carrier with a copper electrolytic bath made of sulfuric acid and copper sulfate to prevent the removal of the roughened particles and improve the peel strength. Plating was performed. The covering plating conditions are described below.

(Electrolytic solution composition)
Cu: 40-50 g / L
H ₂ SO ₄ : 80-120 g / L
(Electrolyte temperature)
43-47 ° C
(Current condition)
Current density: 29 A / dm ²

-Fine roughening (1):
The M surface of the various raw foils described above and the surface of the ultrathin raw copper foil with a carrier were subjected to a roughening treatment under the following conditions.
(Electrolytic solution composition)
Cu concentration: 10 to 20 g / L
H ₂ SO ₄ concentration: 80 to 120 g / L
Tungsten concentration: 1 to 10 mg / L (added with sodium tungstate dihydrate)
Sodium dodecyl sulfate concentration: 1 to 10 mg / L
(Electrolyte temperature)
35-45 ° C
(Current condition)
In order to obtain a predetermined hole shape, a current was applied in a four-stage system. The current density was as follows.
First stage: 30 A / dm ²
Second stage: 10 A / dm ²
Third stage: 30 A / dm ²
Fourth stage: 10 A / dm ²

Cover the M surface of various copper foils roughened under the above conditions and the surface of the ultrathin copper foil with carrier with a copper electrolytic bath made of sulfuric acid and copper sulfate to prevent the removal of the roughened particles and improve the peel strength. Plating was performed. The covering plating conditions are described below.
(Electrolytic solution composition)
Cu: 40-50 g / L
H ₂ SO ₄ : 80-120 g / L
(Electrolyte temperature)
43-47 ° C
(Current condition)
Current density: 41 A / dm ²

-Fine roughening (2):
The surface of the ultrathin raw copper foil with a carrier described above was roughened under the following conditions.
(Electrolytic solution composition)
Cu concentration: 10 to 20 g / L
H ₂ SO ₄ concentration: 80 to 120 g / L
Tungsten concentration: 1 to 10 mg / L (added with sodium tungstate dihydrate)
Sodium dodecyl sulfate concentration: 1 to 10 mg / L
(Electrolyte temperature)
35-45 ° C
(Current condition)
A two-stage system was applied to obtain a predetermined hole shape. The current density was as follows.
First stage: 50 A / dm ²
Second stage: 10 A / dm ²

Cover the M surface of various copper foils roughened under the above conditions and the surface of the ultrathin copper foil with carrier with a copper electrolytic bath made of sulfuric acid and copper sulfate to prevent the removal of the roughened particles and improve the peel strength. Plating was performed. The covering plating conditions are described below.
(Electrolytic solution composition)
Cu: 40-50 g / L
H ₂ SO ₄ : 80-120 g / L
(Electrolyte temperature)
43-47 ° C
(Current condition)
Current density: 41 A / dm ²

-Fine roughening (3):
The roughening process was performed on the M surface of the double-sided flat electrolytic raw foil described above and the surface of the ultrathin raw copper foil with a carrier under the following conditions.
(Electrolytic solution composition)
Cu: 10 to 20 g / L
Co: 1-10 g / L
Ni: 1-10g / L
pH: 1-4
(Electrolyte temperature)
40-50 ° C
(Current condition)
Current density: 25 A / dm ²
(Immersion time in plating solution after plating)
In order to obtain a predetermined hole shape, it was within 5 seconds.

Co-Ni plating was performed on the M surface of the double-sided flat copper foil subjected to the roughening treatment under the above conditions and the surface of the ultrathin copper foil with carrier. The covering plating conditions are described below.
(Electrolytic solution composition)
Co: 1-30 g / L
Ni: 1-30 g / L
pH: 1.0-3.5
(Electrolyte temperature)
30-80 ° C
(Current condition)
Current density 5.0A / dm ²

-Fine roughening (4):
The surface of the ultrathin raw copper foil with a carrier described above was subjected to a roughening treatment for forming primary particles and secondary particles under the following conditions.
Primary particle formation:
(Electrolytic solution composition)
Cu concentration: 10 to 20 g / L
H ₂ SO ₄ concentration: 80 to 120 g / L
Tungsten concentration: 1 to 10 mg / L (added with sodium tungstate dihydrate)
Sodium dodecyl sulfate concentration: 1 to 10 mg / L
(Electrolyte temperature)
35-45 ° C
(Current condition)
A two-stage system was applied to obtain a predetermined hole shape. The current density was as follows.
First stage: 50 A / dm ²
Second stage: 10 A / dm ²

The surface of the ultrathin copper foil with carrier on which the primary roughened particles are formed under the above conditions is covered with a copper electrolytic bath composed of sulfuric acid and copper sulfate to prevent the primary roughened particles from falling off and improve the peel strength. Went. The covering plating conditions are described below.
(Electrolytic solution composition)
Cu: 40-50 g / L
H ₂ SO ₄ : 80-120 g / L
(Electrolyte temperature)
43-47 ° C
(Current condition)
Current density: 41 A / dm ²

Secondary particle formation:
Next, the roughening process for forming a secondary coarse particle on the primary coarse particle of the ultra-thin copper foil with a carrier was performed.
(Electrolytic solution composition)
Cu: 10 to 20 g / L
Co: 1-10 g / L
Ni: 1-10g / L
pH: 1-4
(Electrolyte temperature)
40-50 ° C
(Current condition)
Current density: 25 A / dm ²
(Immersion time in plating solution after plating)
In order to obtain a predetermined hole shape, it was within 5 seconds.

Co-Ni covering plating was performed on the surface of the ultrathin copper foil with a carrier that had been subjected to secondary particle roughening treatment under the above conditions. The covering plating conditions are described below.
(Electrolytic solution composition)
Co: 1-30 g / L
Ni: 1-30 g / L
pH: 1.0-3.5
(Electrolyte temperature)
30-80 ° C
(Current condition)
Current density 5.0A / dm ²

-Fine roughening (5):
The surface of the ultrathin raw copper foil with a carrier described above was subjected to a roughening treatment for forming primary particles and secondary particles under the following conditions.
Primary particle formation:
(Electrolytic solution composition)
Cu concentration: 10 to 20 g / L
H ₂ SO ₄ concentration: 80 to 120 g / L
Tungsten concentration: 1 to 10 mg / L (added with sodium tungstate dihydrate)
Sodium dodecyl sulfate concentration: 1 to 10 mg / L
(Electrolyte temperature)
35-45 ° C
(Current condition)
A two-stage system was applied to obtain a predetermined hole shape. The current density was as follows.
First stage: 20 A / dm ²
Second stage: 10 A / dm ²

The surface of the ultrathin copper foil with carrier on which the primary roughened particles are formed under the above conditions is covered with a copper electrolytic bath composed of sulfuric acid and copper sulfate to prevent the primary roughened particles from falling off and improve the peel strength. Went. The covering plating conditions are described below.
(Electrolytic solution composition)
Cu: 40-50 g / L
H ₂ SO ₄ : 80-120 g / L
(Electrolyte temperature)
43-47 ° C
(Current condition)
Current density: 41 A / dm ²

Secondary particle formation:
Next, the roughening process for forming a secondary coarse particle on the primary coarse particle of the ultra-thin copper foil with a carrier was performed.
(Electrolytic solution composition)
Cu: 10 to 20 g / L
Co: 1-10 g / L
Ni: 1-10g / L
pH: 1-4
(Electrolyte temperature)
40-50 ° C
(Current condition)
Current density: 25 A / dm ²
(Immersion time in plating solution after plating)
In order to obtain a predetermined hole shape, it was set to 15 to 20 seconds.

Co-Ni covering plating was performed on the surface of the ultrathin copper foil with a carrier that had been subjected to secondary particle roughening treatment under the above conditions. The covering plating conditions are described below.
(Electrolytic solution composition)
Co: 1-30 g / L
Ni: 1-30 g / L
pH: 1.0-3.5
(Electrolyte temperature)
30-80 ° C
(Current condition)
Current density 5.0A / dm ²

-Fine roughening (6):
The surface of the ultrathin raw copper foil with a carrier described above was roughened under the following conditions.
(Electrolytic solution composition)
Cu concentration: 10 to 20 g / L
H ₂ SO ₄ concentration: 80 to 120 g / L
Tungsten concentration: 1 to 10 mg / L (added with sodium tungstate dihydrate)
Sodium dodecyl sulfate concentration: 1 to 10 mg / L
(Electrolyte temperature)
35-45 ° C
(Current condition)
A four-stage system was applied to obtain a predetermined hole shape. The current density was as follows.
First stage: 50 A / dm ²
Second stage: 10 A / dm ²
Third stage: 50 A / dm ²
Fourth stage: 10 A / dm ²

Cover the M surface of various copper foils roughened under the above conditions and the surface of the ultrathin copper foil with carrier with a copper electrolytic bath made of sulfuric acid and copper sulfate to prevent the removal of the roughened particles and improve the peel strength. Plating was performed. The covering plating conditions are described below.
(Electrolytic solution composition)
Cu: 40-50 g / L
H ₂ SO ₄ : 80-120 g / L
(Electrolyte temperature)
43-47 ° C
(Current condition)
Current density: 41 A / dm ²

-Fine roughening (7):
The surface of the ultrathin raw copper foil with a carrier described above was subjected to a roughening treatment for forming primary particles and secondary particles under the following conditions.
Primary particle formation:
(Electrolytic solution composition)
Cu concentration: 10 to 20 g / L
H ₂ SO ₄ concentration: 80 to 120 g / L
Tungsten concentration: 1 to 10 mg / L (added with sodium tungstate dihydrate)
Sodium dodecyl sulfate concentration: 1 to 10 mg / L
(Electrolyte temperature)
35-45 ° C
(Current condition)
A three-stage system was applied to obtain a predetermined hole shape. The current density was as follows.
First stage: 25 A / dm ²
Second stage: 10 A / dm ²
Third stage: 5 A / dm ²

The surface of the ultrathin copper foil with carrier on which the primary roughened particles are formed under the above conditions is covered with a copper electrolytic bath composed of sulfuric acid and copper sulfate to prevent the primary roughened particles from falling off and improve the peel strength. Went. The covering plating conditions are described below.
(Electrolytic solution composition)
Cu: 40-50 g / L
H ₂ SO ₄ : 80-120 g / L
(Electrolyte temperature)
43-47 ° C
(Current condition)
Current density: 41 A / dm ²

Secondary particle formation:
Next, the roughening process for forming a secondary coarse particle on the primary coarse particle of the ultra-thin copper foil with a carrier was performed.
(Electrolytic solution composition)
Cu: 10 to 20 g / L
Co: 1-10 g / L
Ni: 1-10g / L
pH: 1-4
(Electrolyte temperature)
40-50 ° C
(Current condition)
Current density: 25 A / dm ²
(Immersion time in plating solution after plating)
In order to obtain a predetermined hole shape, it was set to 5 to 10 seconds.

Co-Ni covering plating was performed on the surface of the ultrathin copper foil with a carrier that had been subjected to secondary particle roughening treatment under the above conditions. The covering plating conditions are described below.
(Electrolytic solution composition)
Co: 1-30 g / L
Ni: 1-30 g / L
pH: 1.0-3.5
(Electrolyte temperature)
30-80 ° C
(Current condition)
Current density 5.0A / dm ²

[Barrier (heat resistant) treatment]
A barrier (heat resistant) treatment was performed under the following conditions to form a brass plating layer or a zinc / nickel alloy plating layer.

Barrier layer (brass plating) formation conditions of Example 6 and Comparative Examples 3 and 4:
Using a brass plating bath having a copper concentration of 50 to 80 g / L, a zinc concentration of 2 to 10 g / L, a sodium hydroxide concentration of 50 to 80 g / L, a sodium cyanide concentration of 5 to 30 g / L, and a temperature of 60 to 90 ° C. The plating electric quantity of 30 As / dm ² was applied to the M surface on which the roughening treatment layer was formed by 5 to 10 A / dm ² (multistage treatment).

Conditions for forming the barrier layer (zinc / nickel plating) of Example 3 and Comparative Example 1:
Ni: 10 g / L to 30 g / L, Zn: 1 g / L to 15 g / L, sulfuric acid (H ₂ SO ₄ ): 1 g / L to 12 g / L, chloride ion: 0 g / L to 5 g / L Using a plating bath, a plating electric quantity of 5.5 As / dm ² was applied to the M surface on which the roughening treatment layer was formed at a current density of 1.3 A / dm ² .

[Rust prevention treatment]
Rust prevention treatment (chromate treatment) was performed under the following conditions to form a rust prevention treatment layer.

(Chromate conditions) CrO ₃ : 2.5 g / L, Zn: 0.7 g / L, Na ₂ SO ₄ : 10 g / L, pH 4.8, an electric quantity of 0.7 As / dm ^{2 in} a chromate bath at 54 ° C. Addition. Furthermore, immediately after completion of the rust prevention treatment in the chromate bath, the entire roughened surface was showered using the same chromate bath using a liquid shower pipe.

[Silane coupling material application]
A silane coupling material coating treatment was performed by spraying a solution having a pH of 7 to 8 containing 0.2 to 2% of alkoxysilane on the roughened surface of the copper foil.

About Example 8, the resin layer was formed on the following conditions after the antirust process and silane coupling material application | coating.
(Resin synthesis example)
To a 2-liter three-necked flask equipped with a stainless steel vertical stirring bar, a trap equipped with a nitrogen inlet tube and a stopcock, and a reflux condenser equipped with a ball cooling tube, 3,4, 3 ', 117.68 g (400 mmol) of 4′-biphenyltetracarboxylic dianhydride, 87.7 g (300 mmol) of 1,3-bis (3-aminophenoxy) benzene, 4.0 g (40 mmol) of γ-valerolactone, 4. 8 g (60 mmol), N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 300 g, and toluene 20 g were added, heated at 180 ° C. for 1 hour, cooled to near room temperature, then 3, 4, 3 ′, 4′- Add 29.42 g (100 mmol) of biphenyltetracarboxylic dianhydride, 82.12 g (200 mmol) of 2,2-bis {4- (4-aminophenoxy) phenyl} propane, 200 g of NMP, and 40 g of toluene. After 1 hour mixing at room temperature, and heated for 3 hours at 180 ° C., to obtain a 38% solids polyimide block copolymer. The block copolymerized polyimide had the following general formula (1): general formula (2) = 3: 2, number average molecular weight: 70000, and weight average molecular weight: 150,000.

  The block copolymerized polyimide solution obtained in the synthesis example was further diluted with NMP to obtain a block copolymerized polyimide solution having a solid content of 10%. In this block copolymerized polyimide solution, bis (4-maleimidophenyl) methane (BMI-H, Silica Chemical) is contained in a solid content weight ratio of 35 and a solid content weight ratio of block copolymer polyimide of 65 (that is, included in the resin solution). Bis (4-maleimidophenyl) methane solid content weight: block copolymerized polyimide solid content weight contained in resin solution = 35: 65) A resin solution was prepared by dissolving and mixing at 60 ° C. for 20 minutes. Thereafter, in Example 8, the resin solution was applied to the ultrathin copper surface of the copper foil using a reverse roll coating machine, and after a drying treatment at 120 ° C. for 3 minutes and at 160 ° C. for 3 minutes in a nitrogen atmosphere. Finally, heat treatment was performed at 300 ° C. for 2 minutes to produce a copper foil provided with a resin layer. The thickness of the resin layer was 2 μm.

About the surface-treated copper foil and the copper foil with carrier of each example and comparative example, the following resin base material having a 20 cm square size is prepared, and the surface having the surface treatment layer of the copper foil is prepared with the resin base material and the copper foil. The laminate was pressed so as to contact the resin substrate. The substrate press manufacturer's recommended conditions were used for the temperature, pressure, and time of the lamination press.
Resin used: Mitsubishi Gas Chemical Company, Inc. GHPL-830MBT

Next, the surface-treated copper foil on the resin substrate was removed by whole surface etching under the following etching conditions. Moreover, about the copper foil with a carrier on a resin base material, after peeling a carrier, the ultra-thin copper layer was removed by the whole surface etching on the following etching conditions. Note that “entire surface etching” means that etching is performed until the copper foil is completely removed by a thickness and the resin is exposed on the entire surface.
(Etching conditions) Etching solution: cupric chloride solution, HCl concentration: 3.5 mol / L, temperature: 50 ° C., CuCl ₂ concentration adjusted so as to have a specific gravity of 1.26

2. Formation of Surface Profile of Resin Base Material Using Chemical Solution As Comparative Example 5, two resin base materials GHPL-830MBT having a thickness of 100 μm manufactured by Mitsubishi Gas Chemical Company were prepared. The two resin base materials were overlapped, and a release layer film was bonded to both sides of the two resin base materials, followed by lamination pressing. The substrate press manufacturer's recommended conditions were used for the temperature, pressure, and time of the lamination press. After the lamination press was completed, the release layer film was peeled from the resin substrate, and desmear treatments A and B and neutralization treatment were performed under the following immersion treatment conditions to form a surface profile of the resin substrate.
(Desmear processing condition A)
Desmear treatment liquid: 40 g / L KMnO ₄ , 20 g / L NaOH
・ Processing temperature: Room temperature ・ Immersion time: 20 minutes ・ Rotating speed of stirring bar: 300 rpm
(Desmear processing condition B)
Desmear treatment solution: 90 g / L KMnO ₄ , 5 g / L HCl
・ Processing temperature: 49 ℃
・ Immersion time: 20 minutes ・ Stirrer rotation speed: 300 rpm
(Neutralization conditions)
・ Neutralization treatment liquid: L-ascorbic acid 80 g / L
・ Processing temperature: Room temperature ・ Immersion time: 3 minutes ・ No stirring

As Comparative Example 6, two sheets of a resin base material GHPL-830MBT manufactured by Mitsubishi Gas Chemical Company with a thickness of 100 μm were prepared. The two resin base materials were overlapped, and a release layer film was bonded to both sides of the two resin base materials, followed by lamination pressing. The substrate press manufacturer's recommended conditions were used for the temperature, pressure, and time of the lamination press. After the lamination press was completed, the release layer film was peeled from the resin substrate, and desmear treatments A and B and neutralization treatment were performed under the following immersion treatment conditions to form a surface profile of the resin substrate.
(Desmear processing condition A)
Desmear treatment liquid: 40 g / L KMnO ₄ , 20 g / L NaOH
・ Processing temperature: Room temperature ・ Immersion time: 20 minutes ・ Rotating speed of stirring bar: 300 rpm
(Desmear processing condition B)
Desmear treatment solution: 90 g / L KMnO ₄ , 5 g / L HCl
・ Processing temperature: 49 ℃
・ Immersion time: 30 minutes ・ Rotating speed of stirrer: 300 rpm
(Neutralization conditions)
・ Neutralization treatment liquid: L-ascorbic acid 80 g / L
・ Processing temperature: Room temperature ・ Immersion time: 3 minutes ・ No stirring

As Example 9, two sheets of a resin base material GHPL-830MBT manufactured by Mitsubishi Gas Chemical Company with a thickness of 100 μm were prepared. The two resin base materials were overlapped, and a release layer film was bonded to both sides of the two resin base materials, followed by lamination pressing. The substrate press manufacturer's recommended conditions were used for the temperature, pressure, and time of the lamination press. After the lamination press is completed, the release layer film is peeled from the resin substrate, and the surface profile of the resin substrate is formed by performing shower treatments A and B and neutralization treatment on the resin substrate surface under the following processing conditions. did.
(Shower treatment condition A)
Desmear treatment liquid: 40 g / L KMnO ₄ , 20 g / L NaOH
・ Processing temperature: Room temperature ・ Processing time: 20 minutes ・ Shower pressure: 0.2 MPa
(Shower treatment condition B)
Desmear treatment solution: 90 g / L KMnO ₄ , 5 g / L HCl
・ Processing temperature: 49 ℃
・ Processing time: 20 minutes ・ Shower pressure: 0.2 MPa
(Neutralization conditions)
・ Neutralization treatment liquid: L-ascorbic acid 80 g / L
-Processing temperature: Room temperature-Immersion time: 3 minutes-No stirring In this way, the surface profile of the resin base material was formed using a chemical solution.

-Evaluation of resin substrate-
The following evaluation was performed about the resin base material of the Example and comparative example which have the surface profile produced above.
<Line roughness Rz>
About the etching side surface of the resin base material of each Example and a comparative example, ten-point average roughness was measured based on JIS B0601-1994 using Kosaka Laboratory Co., Ltd. contact roughness meter Surfcorder SE-3C. . The measurement was performed three times under the conditions of a measurement reference length of 0.8 mm, an evaluation length of 4 mm, a cut-off value of 0.25 mm, and a feed rate of 0.1 mm / second, and values obtained by three measurements were obtained.

<Roughness Sz>
Using the Olympus laser microscope (test machine: OLYMPUS LEXT OLS 4000, resolution: XY-0.12 μm, Z-0.0 μm, cut-off: none) for the etching side surface of the resin base material of each example and comparative example , the surface roughness Sz, was measured in accordance with ISO2517 8.

<Area ratio (B / A)>
Using the Olympus laser microscope (test machine: OLYMPUS LEXT OLS 4000, resolution: XY-0.12 μm, Z-0.0 μm, cut-off: none) for the etching side surface of the resin base material of each example and comparative example A three-dimensional surface area B in an area equivalent to 256 μm × 256 μm (surface area obtained when viewed in plan) A (66,524 μm ^{2 in} actual data) is measured, and three-dimensional surface area B ÷ two-dimensional surface area A = area ratio (B / A). In addition, the measurement environmental temperature of the three-dimensional surface area B with a laser microscope was 23-25 degreeC.

<Black area ratio>
About the etching side surface of the resin base material of each Example and a comparative example, the acceleration voltage was set to 15 kV using the scanning electron microscope (SEM), and photography was performed. Note that the contrast and brightness were adjusted so that the outline of the hole in the entire observation field could be clearly seen when taking a picture. The photo was taken while the whole photo was not white or black and the outline of the hole could be observed. If the photo was taken in a state where the entire photo was not white or black and the outline of the hole could be observed, the black area ratio (%) in the photo would be almost the same value. The photograph (SEM image (30k times (30000 times))) was subjected to white / black image processing using Photoshop 7.0 software, and the black area ratio (%) was obtained. The black area ratio (%) is the ratio of the black area to the observation area (the total area of the white area and the black area) when the “image” “histogram” in Photoshop 7.0 is selected and the threshold value is 128. did.

<Average diameter of holes>
For the etching side surface of the resin base material of each example and comparative example, the hole diameter is measured vertically, horizontally and diagonally from the SEM image (x6000 to x30000) by the line segment method, and the average value of these N = 3 is calculated. did.

<Peel strength>
Electroless copper plating was performed under the following conditions using a catalyst application for precipitating electroless copper and a KAP-8 bath manufactured by Kanto Kasei Co., Ltd. on the etching surface of a resin base material (entire etching base material). The thickness of the obtained electroless copper plating was 0.5 μm.
CuSO ₄ concentration: 0.06 mol / L, HCHO concentration: 0.5 mol / L, EDTA concentration: 0.12 mol / L, pH 12.5, additive: 2,2′-dipyridyl, additive concentration: 10 mg / L, Surfactant: REG-1000, Surfactant concentration: 500 mg / L
Next, electrolytic plating was further performed on the electroless copper plating using the following electrolytic solution. The copper thickness (total thickness of electroless plating and electrolytic plating) was 12 μm.
Simple copper sulfate electrolyte: Cu concentration: 100 g / L, H ₂ SO ₄ concentration: 80 g / L
As described above, a copper circuit having a width of 10 mm was prepared by wet etching on a laminated board with plated copper having electroless copper plating and electrolytic copper plating applied to the resin base material (entire etching base material) to a copper layer thickness of 12 μm. . In accordance with JIS-C-6481, the strength when this copper circuit was peeled at 90 degrees was measured and defined as peel strength.

<Fine wiring formability>
As described above, the plated copper is processed by etching on the laminated board with plated copper, in which the electroless copper plating and the electrolytic copper plating are applied to the resin base material (entire etching base material) and the copper layer thickness is 12 μm. ) / S (space) = 15 μm / 15 μm and 10 μm / 10 μm circuits were formed. At this time, the fine wiring formed on the resin substrate was visually observed, and it was determined as OK (◯) if there was no peeling of the circuit, shorting between the circuits (abnormal copper deposition between the circuits), and chipping of the circuit.

In Table 1, the manufacturing conditions of the copper foil used in order to obtain the base material surface profile of Examples 1-12 and Comparative Examples 1-4 by the transfer to the base material surface of the above-mentioned copper foil surface profile are shown. .
Table 2 shows the evaluation results of the substrate surface profile described above.
In Table 3, the evaluation result of the copper foil surface profile which gives the above-mentioned base-material surface profile is shown.

(Evaluation results)
The base materials of Examples 1 to 12 all had good fine wiring formability, and further exhibited good peel strength.
Since all the base materials of Comparative Examples 1 to 6 had a surface roughness Sz outside the range of 1 to 5 μm, the fine wiring formability or peel strength was poor. Moreover, since the base materials of Comparative Examples 1 to 4 all had a ratio B / A of the surface three-dimensional surface area B to the two-dimensional surface area A outside the range of 1.01 to 1.5, the fine wiring formability Or the peel strength was poor. Further, the base materials of Comparative Examples 1 to 6 each had a surface black area ratio of 10 to 50% and a surface hole diameter average value of 0.03 to 1.0 μm, or either of them was out of range. Therefore, the fine wiring formability or peel strength was poor.
In addition, it was confirmed from the evaluation result of an Example and a comparative example that the numerical value of Rz of the resin base-material surface has no relationship in particular with respect to having favorable fine wiring formation property and peel strength.
3 (a), (b), (c), (d), and (e) show resin base material surface SEM images of Examples 1, 2, 3, 5, and 6, respectively.
The resin base material surface SEM image of the comparative examples 1 and 2 is shown to FIG.4 (f), (g), respectively.

Claims (18)

A resin base material having an Sz of 1 to 5 μm based on surface roughness ISO25178 .   2. The resin base material according to claim 1, wherein the ratio B / A of the surface three-dimensional surface area B to the two-dimensional surface area A is 1.01 to 1.5. The resin base material according to claim 1 or 2 , which is for a semi-additive construction method. The printed wiring board manufactured using the resin base material as described in any one of Claims 1-3 . The printed circuit board manufactured using the resin base material as described in any one of Claims 1-3 . The copper clad laminated board manufactured using the resin base material as described in any one of Claims 1-3 . Preparing a surface-treated copper foil and a resin base material,
Laminating the surface-treated copper foil on the resin substrate from the surface-treated layer side,
The process of removing the surface treatment copper foil on the said resin base material, and obtaining the resin base material as described in any one of Claims 1-3 ,
The manufacturing method of a printed wiring board including the process of forming a circuit in the surface of the resin base material which removed the said surface treatment copper foil. A step of preparing a carrier, an intermediate layer, a copper foil with a carrier provided with an ultrathin copper layer in this order, and a resin base material;
Laminating the copper foil with carrier on the resin substrate from the ultrathin copper layer side,
After laminating the copper foil with carrier and the resin base material, the step of peeling the carrier of the copper foil with carrier,
The process of obtaining the resin base material as described in any one of Claims 1-3 by removing the ultra-thin copper layer on the resin base material after peeling the said carrier,
A method for producing a printed wiring board, comprising a step of forming a circuit on the surface of a resin substrate from which the ultrathin copper layer has been removed. A surface-treated copper foil is laminated on the resin substrate according to claim 1 or 2 from the surface-treated layer side to form a copper-clad laminate, and then a semi-additive method , a subtractive method, a partially additive method, or a modified semi A printed wiring board manufacturing method including a step of forming a circuit by any one of the additive methods. Laminating a carrier, an intermediate layer, a copper foil with a carrier provided with an ultrathin copper layer in this order from the ultrathin copper layer side to the resin substrate according to claim 1 or 2 ,
After laminating the copper foil with carrier and the resin base material, 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 partial additive method or a modified semi-additive method. A printed wiring board manufacturing method including a step of forming a circuit by any one of the methods. Preparing a metal foil having a circuit formed on the surface;
Forming a resin base material on the surface of the metal foil so that the circuit is buried;
Laminating a surface-treated copper foil on the resin substrate from the surface-treated layer side,
The process of removing the surface treatment copper foil on the said resin base material, and obtaining the resin base material as described in any one of Claims 1-3 ,
Forming a circuit on the surface of the resin base material from which the surface-treated copper foil has been removed; and
A method for producing a printed wiring board, comprising: removing the metal foil to expose a circuit formed on the surface of the metal foil and buried in the resin base material. Carrier, an intermediate layer, forming a circuit on the ultrathin copper layer side surface of the first copper foil with carrier having ultrathin copper layer in this order,
Forming a resin base material on the ultrathin copper layer side surface of the first carrier-attached copper foil so that the circuit is buried;
Preparing a second copper foil with a carrier provided with a carrier, an intermediate layer, and an ultrathin copper layer in this order, and laminating the resin base material from the ultrathin copper layer side of the second copper foil with a carrier;
A step of peeling the carrier of the second carrier-attached copper foil after laminating the second carrier-attached copper foil on the resin substrate;
The process of obtaining the resin base material as described in any one of Claims 1-3 by removing the ultra-thin copper layer on the resin base material after peeling the carrier of the copper foil with said 2nd carrier,
Forming a circuit on the surface of the resin substrate from which the ultrathin copper layer has been removed,
After forming the circuit on the resin base material, the step of peeling the carrier of the first copper foil with carrier, and
After peeling the carrier of the first copper foil with carrier, the ultra thin copper layer side surface of the first copper foil with carrier is removed by removing the ultra thin copper layer of the first copper foil with carrier. A method for producing a printed wiring board, comprising the step of exposing a circuit embedded in the resin base material, which is formed on the substrate. Preparing a metal foil having a circuit formed on the surface;
Forming the resin base material according to claim 1 or 2 on the surface of the metal foil so that the circuit is buried;
A surface-treated copper foil is laminated on the resin substrate from the surface-treated layer side, and a circuit is formed on the resin substrate by any of the semi-additive method , subtractive method, partly additive method, or modified semi-additive method. And the process of
A method for producing a printed wiring board, comprising: removing the metal foil to expose a circuit formed on the surface of the metal foil and buried in the resin base material. Carrier, an intermediate layer, forming a circuit on the ultrathin copper layer side surface of the first copper foil with carrier having ultrathin copper layer in this order,
Forming the resin base material according to claim 1 or 2 on the ultrathin copper layer side surface of the first carrier-attached copper foil so that the circuit is buried;
Prepare a second carrier-attached copper foil provided with a carrier, an intermediate layer, and an ultrathin copper layer in this order, and laminate the resin base material from the ultrathin copper layer side of the second carrier-attached copper foil. Removing the carrier of the second carrier-attached copper foil, and forming a circuit on the resin substrate by any one of a semi-additive method , a subtractive method, a partial additive method, or a modified semi-additive method,
After forming the circuit on the resin base material, the step of peeling the carrier of the first copper foil with carrier, and
After peeling the carrier of the first copper foil with carrier, the ultra thin copper layer side surface of the first copper foil with carrier is removed by removing the ultra thin copper layer of the first copper foil with carrier. A method for producing a printed wiring board, comprising the step of exposing a circuit embedded in the resin base material, which is formed on the substrate. Preparing a metal foil having a circuit formed on the surface;
Forming a resin base material on the surface of the metal foil so that the circuit is buried;
Laminating a carrier, an intermediate layer, a copper foil with a carrier provided with an ultrathin copper layer in this order from the ultrathin copper layer side surface to the resin base material,
The process of obtaining the resin base material as described in any one of Claims 1-3 after removing the ultra-thin copper layer on the said resin base material, after peeling the carrier of the said copper foil with a carrier,
Forming a circuit on the surface of the resin substrate from which the ultrathin copper layer has been removed, and
The step of exposing the circuit buried in the resin base material formed on the surface of the metal foil by removing the metal foil
A method of manufacturing a printed wiring board including: Forming a circuit on the ultrathin copper layer side surface of the carrier-added copper foil provided with the carrier, the intermediate layer, and the ultrathin copper layer in this order;
Forming a resin base material on the ultrathin copper layer side surface of the copper foil with carrier so that the circuit is buried;
Laminating a surface-treated copper foil on the resin substrate from the surface-treated layer side,
The process of removing the surface treatment copper foil on the said resin base material, and obtaining the resin base material as described in any one of Claims 1-3,
Forming a circuit on the surface of the resin base material from which the surface-treated copper foil has been removed,
After forming the circuit on the resin substrate, the step of peeling the carrier of the copper foil with carrier, and
After peeling the carrier of the copper foil with carrier, by removing the ultra thin copper layer of the copper foil with carrier, the resin base material formed on the ultra thin copper layer side surface of the copper foil with carrier The process of exposing the buried circuit
A method of manufacturing a printed wiring board including: Preparing a metal foil having a circuit formed on the surface;
Forming the resin base material according to claim 1 or 2 on the surface of the metal foil so that the circuit is buried;
After preparing the carrier, the intermediate layer, the copper foil with a carrier provided with the ultra-thin copper layer in this order, and laminating the copper foil with the carrier from the ultra-thin copper layer side of the copper foil with the carrier, Peeling the carrier, and then forming a circuit on the resin substrate; and
The step of exposing the circuit buried in the resin base material formed on the surface of the metal foil by removing the metal foil
A method of manufacturing a printed wiring board including: Forming a circuit on the ultrathin copper layer side surface of the carrier-added copper foil provided with the carrier, the intermediate layer, and the ultrathin copper layer in this order;
The step of forming the resin substrate according to claim 1 or 2 on the ultrathin copper layer side surface of the copper foil with carrier so that the circuit is buried,
Laminating a surface-treated copper foil on the resin substrate from the surface treatment layer side, and then forming a circuit on the resin substrate;
After forming the circuit on the resin substrate, the step of peeling the carrier of the copper foil with carrier, and
After peeling the carrier of the copper foil with carrier, by removing the ultra thin copper layer of the copper foil with carrier, the resin base material formed on the ultra thin copper layer side surface of the copper foil with carrier The process of exposing the buried circuit
A method of manufacturing a printed wiring board including: