KR20150086541A - Copper foil with carrier - Google Patents

Abstract

Thereby providing a carrier-bonded copper foil preferable for fine pitch formation. A carrier-coated copper foil having a carrier, a peeling layer, an ultra-thin copper layer and a maleic resin layer in this order, wherein the average value of Rz on the surface of the ultra-thin copper layer was measured by a contact- type roughness meter according to JIS B0601-1982, Mu m or less and a standard deviation of Rz is 0.1 mu m or less.

Description

{COPPER FOIL WITH CARRIER}

The present invention relates to a copper foil with a carrier. More particularly, the present invention relates to a copper foil with a carrier used as a material of a printed wiring board.

The printed wiring board is generally manufactured through a step of bonding an insulating substrate to a copper foil to form a copper clad laminate, and then forming a conductor pattern on the copper foil surface by etching. In recent years, along with an increase in the demand for miniaturization and high performance of electronic devices, mounting of high-density mounting parts and high frequency signals have been progressed, and conductor patterns (finer pitch) and high frequency response have been required for printed wiring boards.

In response to the fine pitching, a copper foil having a thickness of 9 占 퐉 or less and further having a thickness of 5 占 퐉 or less is required in recent years. However, such a copper foil with a very thin foil has low mechanical strength and is cracked, wrinkled A copper foil with a carrier in which a thin metal foil is used as a carrier and an extremely thin copper layer is electrodeposited with a release layer interposed therebetween has appeared. The surface of the ultra-thin copper layer is bonded to an insulating substrate, and after thermocompression bonding, the carrier is peeled off through the peeling layer. A microcircuit is formed by a modified method (MSAP: Modified-Semi-Additive-Process) in which a circuit pattern is formed on the exposed ultra-thin copper layer with a resist and then the ultra-thin copper layer is etched away with an etchant of sulfuric acid-hydrogen peroxide system.

Here, the surface of the ultra-thin copper layer of the copper foil with a carrier, which is the adhesion surface to the resin, is preferably such that the peel strength between the ultra-thin copper layer and the resin substrate is sufficient and the peel strength thereof is high temperature heating, It is required to be sufficiently retained even after treatment or the like. As a method of increasing the peeling strength between the ultra-thin copper layer and the resin substrate, a method of attaching a large amount of roughened particles on the ultra-thin copper layer having a generally increased profile (irregularity and roughness) of the surface is typical .

However, when a very thin copper layer having such a profile (irregularity and roughness) is used for a semiconductor package substrate which needs to form a particularly fine circuit pattern among printed wiring boards, unnecessary copper particles remain in circuit etching, And the like.

For this reason, in WO 2004/005888 (Patent Document 1), it has been attempted to use a copper foil with a carrier which is not roughened on the surface of the ultra-thin copper layer as a copper foil with a carrier for use in a fine circuit including a semiconductor package substrate . The adhesion (peel strength) between the ultra-thin copper layer and the resin not subjected to such roughening treatment tends to be lowered as compared with a general copper foil for a printed wiring board due to its low profile (unevenness, roughness and roughness). Therefore, further improvement is required for the copper foil with a carrier.

Therefore, Japanese Laid-Open Patent Publication No. 2007-007937 (Patent Document 2)

(Patent Document 3) discloses a method of forming an Ni layer and / or an Ni alloy layer on a surface to be contacted (adhered) to a polyimide resin substrate of an ultra-thin copper foil having a carrier, , A Cr layer and / or a Cr alloy layer is formed, a Ni layer and a chromate layer are formed, and a Ni layer and a Cr layer are formed. By forming these surface treatment layers, the adhesion strength between the polyimide resin substrate and the ultra-thin copper foil with the carrier adhered is reduced without (or finely) reducing the degree of coarsening treatment, thereby achieving a desired bonding strength. It is also described that surface treatment with a silane coupling agent or rust-preventive treatment is performed.

WO2004 / 005588 Japanese Patent Application Laid-Open No. 2007-007937 Japanese Laid-Open Patent Publication No. 2010-006071

In the development of the copper foil with a carrier, the prior art has focused on securing the peeling strength between the ultra-thin copper layer and the resin substrate. Therefore, the fine pitching has not yet been sufficiently examined, and there is still room for improvement. Therefore, it is an object of the present invention to provide a copper foil with a carrier suitable for fine pitch formation. Specifically, it is intended to provide a copper foil with a carrier capable of forming a fine wiring of L / S = 20 占 퐉 / 20 占 퐉, which is considered to be a limit that can be formed by conventional MSAP.

In order to achieve the above object, the inventors of the present invention have conducted intensive studies and, as a result, have found that the surface of the ultra-thin copper layer is made low in level, the fine roughening particles are uniformly formed in the surface, Can be formed. It has been found that the copper foil with a carrier is very effective for fine pitch formation.

The present invention is completed on the basis of the above finding and provides a carrier-attached copper foil having a carrier, a release layer, an ultra-thin copper layer, and a resin layer arbitrarily in this order on one side, The average value of Rz on the copper layer surface is a contact-type roughness meter, measured according to JIS B0601-1982, of not more than 1.5 占 퐉, and the standard deviation of Rz is not more than 0.1 占 퐉.

According to another aspect of the present invention, there is provided a carrier-coated copper foil having a carrier, a peeling layer, an ultra-thin copper layer, and a hydrophilic resin layer in this order, wherein the average value of Rt on the surface of the ultra- B0601-2001, and the standard deviation of Rt is 0.1 占 퐉 or less.

According to another aspect of the present invention, there is provided a carrier-coated copper foil having a carrier, a peeling layer, an ultra-thin copper layer, and a hydrophilic resin layer in this order, wherein the average value of Ra of the surface of the ultra- And a standard deviation of Ra of 0.03 占 퐉 or less as measured according to JIS B0601-1982.

In one embodiment of the copper foil with a carrier according to the present invention, the ultra-thin copper layer is roughened.

In another aspect, the present invention is a printed wiring board produced by using the copper foil with a carrier according to the present invention.

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

In another aspect, the present invention is a copper clad laminate produced by using the copper foil with a carrier according to the present invention.

The copper foil with a carrier according to the present invention is preferable for forming a fine pitch and can be formed by a fine line more than L / S = 20 占 퐉 / 20 占 퐉, for example, L / S = 15 占 퐉 / 15 占 퐉. Particularly, in the present invention, since the in-plane uniformity of the surface roughness in the ultra-thin copper layer is high, the in-plane uniformity is improved in the flash etching in the circuit formation by the MSAP method, and the yield is expected to be improved.

Fig. 1 is a schematic view showing a mooring method using a drum.
Fig. 2 is a schematic diagram showing a mooring method using the phrase bangbang.
Fig. 3 shows steps A to C for a concrete example of a method for producing a printed wiring board using the copper foil with a carrier according to the present invention.
Fig. 4 shows steps D to F for a specific example of a method for producing a printed wiring board using the copper foil with a carrier according to the present invention.
5 shows steps G to I of a concrete example of a method for producing a printed wiring board using the copper foil with a carrier according to the present invention.
6 shows steps J to K for concrete examples of the method for producing a printed wiring board using the copper foil with a carrier according to the present invention.

 <1. Carrier>

The carrier that can be used in the present invention is typically a metal foil or a resin film, and examples thereof include a copper foil, a copper alloy foil, a nickel foil, a nickel alloy foil, a foil, an iron alloy foil, a stainless steel foil, Is provided in the form of a resin film (for example, a polyimide film, a liquid crystal polymer (LCP) film, a polyethylene terephthalate (PET) film, a polyamide film, a polyester film, a fluororesin film or the like).

A copper foil is preferably used as a carrier usable in the present invention. The carrier is typically provided in the form of a rolled copper foil or an electrolytic copper foil. Generally, the electrolytic copper foil is produced by electrolytically depositing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is manufactured by repeating plastic working and heat treatment by a rolling roll. Examples of the material of the copper foil include high-purity copper such as tough pitch copper and oxygen-free copper, copper such as Sn-containing copper, Ag-containing copper, copper alloy containing Cr, Zr or Mg, Copper alloys such as copper alloys can also be used. In the present specification, when the term &quot; copper foil &quot; is used singly, copper alloy foil is also included.

The thickness of the carrier that can be used in the present invention is not particularly limited, but may be suitably adjusted to a thickness suitable for fulfilling the responsibility as a carrier. For example, it may be 12 占 퐉 or more. However, if the thickness is excessively large, the production cost is increased, and therefore, it is generally preferable to be 70 탆 or less. Thus, the thickness of the carrier is typically 12 to 70 占 퐉, and more typically 18 to 35 占 퐉.

<2. Peeling layer>

A peeling layer is formed on the carrier. Another layer may be formed between the copper foil carrier and the peeling layer. The release layer may be any release layer known to those skilled in the art in the case of the copper foil with a carrier. For example, the release layer may be formed of any one or more of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, Or a layer composed of any one or more of them. The release layer may be composed of a plurality of layers. Further, the release layer may have a diffusion preventing function. Here, the diffusion preventing function has a function of preventing diffusion of elements from the base material to the ultra-thin copper layer side.

In one embodiment of the present invention, the release layer comprises a single metal layer composed of any one element group selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Or an alloy layer containing at least one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, Or an oxide or an organic substance of at least one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn stacked thereon, A hydrate, or an oxide or an organic material.

The release layer may be a single metal layer composed of any one element group selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, An alloy layer containing at least one element selected from the group consisting of Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, Ni, Co, Fe, Mo, Ti, W, P, Cu, Fe, Mo, Ti, W, P, Cu, Al and Zn, Al, and Zn, or an alloy layer composed of at least one selected from the above elements. In addition, the total deposition amount of each element may be, for example, 1 to 6000 占 퐂 / dm2. A layer structure that can be used as a release layer may be used for the other layer.

The release layer is preferably composed of two layers of Ni and Cr. In this case, the Ni layer is laminated on the interface with the copper foil carrier and the Cr layer is brought into contact with the interface with the ultra-thin copper layer.

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

Further, for example, the release layer can be formed by stacking nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy and chromium in this order on a carrier. Since the adhesion strength between nickel and copper is higher than the adhesion between chromium and copper, it is peeled from the interface between the ultra-thin copper layer and chromium when the ultra-thin copper layer is peeled off. Further, a barrier effect for preventing the copper component from diffusing from the carrier into the ultra-thin copper layer is expected in the nickel of the release layer. The adhesion amount of nickel in the release layer is preferably 100 占 퐂 / dm 2 to 40000 占 퐂 / dm 2, more preferably 100 占 퐂 / dm 2 to 4000 占 퐂 / dm 2, more preferably 100 占 퐂 / d M2 or more and 2500 占 퐂 / dm2 or less, more preferably 100 占 퐂 / dm2 or more and less than 1,000 占 퐂 / dm2, and the adhesion amount of chromium in the release layer is preferably 5 占 퐂 / Do. When the release layer is formed only on one side, it is preferable to form a rust prevention layer such as a Ni plating layer on the opposite side of the carrier.

Further, the release layer may be formed on both sides of the carrier.

<3. Ultra-thin copper layer>

An extremely thin copper layer is formed on the release layer. Another layer may be formed between the peeling layer and the ultra-thin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamide or copper cyanide, and is used in a general electrolytic copper foil and can form a copper foil at a high current density. . The thickness of the ultra-thin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 占 퐉 or less. Typically from 0.5 to 12 microns, and more typically from 2 to 5 microns. The ultra-thin copper layer may be formed on both sides of the carrier. A layer structure that can be used as a release layer may be used for the other layer.

<4. Harmonization processing>

The roughened layer may be formed on the surface of the ultra-thin copper layer by, for example, roughening the roughened layer to improve adhesion to the insulating substrate. The roughening treatment can be carried out, for example, by forming coarse particles with copper or a copper alloy. The roughening treatment layer is preferably composed of fine particles from the viewpoint of fine pitch formation. When the current density is high, the copper concentration in the plating liquid is low, or the amount of Coulomb is increased with respect to the electroplating conditions at the time of forming the coarse particles, the particles tend to be fine.

The roughening treatment layer may be composed of any one selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc or an electrodeposited lip composed of an alloy containing at least one of them. have.

In order to increase the in-plane uniformity of the surface roughness on the surface-treated surface, it is effective to keep the distance between the anode and the cathode at the time of forming the roughened treatment layer constant. Although not limited, a method of securing a constant inter-pole distance by using a drum method using a drum or the like as a supporting medium is effective from the viewpoint of industrial production. Fig. 1 is a schematic diagram showing the mooring method. The coarse grain layer is formed on the surface of the ultra-thin copper layer by electroplating while the carrier copper foil transported by the transport roll is supported by the drum. The treated surface of the carrier copper foil supported by the drum doubles as the cathode and each electrolytic plating is performed in the plating liquid between the drum and the anode facing the drum. On the other hand, FIG. 2 shows a schematic diagram showing a mooring method using a conventional type of vernacular. In this method, there is a problem that it is difficult to make the distance between the anode and the cathode constant by the influence of the electrolytic solution and the ointment tension. In addition, in order to keep the distance between the anode and the cathode at the time of formation of the harmonic treatment layer by the mastication method using the bipolar method, it is effective to increase the tension for mounding and shorten the distance between the transport rolls.

As shown in Fig. 1, the drum-based mooring method can be used not only for roughening but also for formation of a peeling layer and formation of an ultra-thin copper layer. It is possible to improve the thickness precision of the peeling layer and the ultra-thin copper layer by adopting the drum-like method. Further, in order to keep the distance between the anode and the cathode at the time of forming the peeling layer or the ultra-thin copper layer by the cantilever method by the crocheting method, it is effective to increase the tension for mounding and shorten the distance between the transport rolls Do.

Although the inter-pole distance is not limited, the production cost is increased when the length is too long, while the in-plane variation is apt to increase when the length is too short, so 3 to 100 mm is generally preferable and 5 to 80 mm is more preferable.

After the roughening treatment, secondary particles, tertiary particles and / or rust preventive layers are formed by a single body of nickel, cobalt, copper, zinc or an alloy, and further chromate treatment, silane coupling treatment May be performed. That is, at least one layer selected from the group consisting of a rust preventive layer, a chromate treatment layer and a silane coupling treatment layer may be formed on the surface of the roughened treatment layer, and the roughening treatment may not be performed on the surface of the ultra- , A chromate treatment layer and a silane coupling treatment layer may be formed. These surface treatments have little influence on the surface roughness of the ultra-thin copper layer.

(Referred to as a "surface treated surface") of the ultra-thin copper layer after the surface treatment when various surface treatments such as roughening treatment are carried out are used as a contact type roughness meter in accordance with JIS B0601-1982 It is very advantageous from the viewpoint of fine pitch formation that the average value of Rz (10 point average roughness) is 1.5 mu m or less. The average value of Rz is preferably 1.4 占 퐉 or less, more preferably 1.3 占 퐉 or less, more preferably 1.2 占 퐉 or less, more preferably 1.0 占 퐉 or less, and even more preferably 0.8 占 퐉 or less. However, the average value of Rz is preferably 0.01 占 퐉 or more, more preferably 0.1 占 퐉 or more, still more preferably 0.3 占 퐉 or more, and most preferably 0.5 占 퐉 or more since the adhesion of the resin to the resin is lowered when the Rz becomes too small Do. In the present invention, the average value of Rz is adopted as the average value of Rz obtained when the standard deviation of Rz is obtained by the method described below.

In the present invention, the standard deviation of Rz on the surface of the ultra-thin copper layer can be 0.1 mu m or less, preferably 0.05 mu m or less, for example, 0.01 to 0.7 mu m. The standard deviation of Rz on the surface of the ultra-thin copper layer is obtained from the in-plane 100 point measurement data. Further, the measurement data of 100 points in the plane is obtained by dividing the sheet of 550 mm in length in the longitudinal direction and in the transverse direction into ten, and measuring each central portion of the 100 divided regions. Although this method is used to maintain in-plane uniformity, the verification method is not limited to this. For example, the same data can be obtained even when a sample having a size of 550 mm x 440 mm to 400 mm x 200 mm or the like, which is generally used, is divided into 100 parts in the plane (10 parts in width and height).

The surface of the ultra-thin copper layer is preferably a contact type roughness meter having an average value of Rt (maximum cross-sectional height) measured according to JIS B0601-2001 of 2.0 μm or less, preferably 1.8 μm or less, preferably 1.5 μm or less , It is preferable that the thickness is 1.3 μm or less, preferably 1.1 μm or less from the viewpoint of fine pitch formation. However, the average value of Rt is preferably not less than 0.5 占 퐉, more preferably not less than 0.6 占 퐉, still more preferably not less than 0.8 占 퐉, because the adhesion of the resin to the resin decreases as the average value of Rt becomes too small. In the present invention, the average value of Rt is adopted as the average value of each Rt obtained when the standard deviation of Rt is obtained by the method described below.

In the present invention, the standard deviation of Rt on the surface of the ultra-thin copper layer can be set to 0.1 mu m or less, preferably 0.05 mu m or less, for example, 0.01 to 0.6 mu m. The standard deviation of Rt on the surface of the ultra-thin copper layer is obtained from the measurement data of 100 points in the plane in the same manner as Rz.

The surface of the ultra-thin copper layer is preferably a contact-type roughness meter, in terms of fine pitch formation, with an average value of Ra (arithmetic mean roughness) measured according to JIS B0601-1982 of not more than 0.2 탆, More preferably 0.15 mu m or less. However, the average value of Ra is preferably 0.01 占 퐉 or more, more preferably 0.05 占 퐉 or more, still more preferably 0.12 占 퐉 or more, and most preferably, 0.13 mu m or more. In the present invention, the average value of Ra is adopted as the average value of each Ra obtained when the standard deviation of Ra is obtained by the method described below.

In the present invention, the standard deviation of Ra on the surface of the ultra-thin copper layer can be 0.03 mu m or less, preferably 0.02 mu m or less, for example, 0.001 to 0.03 mu m. The standard deviation of Ra on the surface of the ultra-thin copper layer is obtained from the measurement data of 100 points in the plane in the same manner as Rz.

When an insulating substrate such as a resin or a resin layer such as a resin is adhered to the surface of the ultra-thin copper layer, such as a copper foil with a carrier having a resin layer, a printed wiring board or a copper clad laminate, The surface roughness Ra, Rt, and Rz described above can be measured for the copper foil surface.

<5. Other Surface Treatment>

After the roughening treatment, a heat resistant layer or a rust preventive layer may be formed of a single body of nickel, cobalt, copper, zinc, or an alloy, or the surface may further be subjected to a treatment such as a chromate treatment or a silane coupling treatment. A heat resistant layer or a rust preventive layer may be formed of a single body of nickel, cobalt, copper, zinc or an alloy, and the surface thereof may be subjected to a treatment such as a chromate treatment or a silane coupling treatment. That is, at least one layer selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate treatment layer and a silane coupling treatment layer may be formed on the surface of the roughened treatment layer, , A chromate treatment layer and a silane coupling treatment layer may be formed. The heat-resistant layer, rust-preventive layer, chromate treatment layer and silane coupling treatment layer described above may be formed of a plurality of layers such as two or more layers or three or more layers, respectively.

As the heat-resistant layer and the rust-preventive layer, known heat-resistant layers and rust-preventive layers can be used. For example, the heat-resistant layer and / or the rust-preventive layer may be formed of a material selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, Or a layer containing at least one element selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, May be a metal layer or an alloy layer composed of at least one kind of element selected from the group consisting of The heat resistant layer and / or the rust preventive layer may be selected from the group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, Nitride, or silicide containing at least one element selected from the group consisting of oxides, nitrides, and silicides. The heat-resistant layer and / or rust-preventive layer may be a layer containing a nickel-zinc alloy. The heat-resistant layer and / or rust-preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% of nickel and 50 wt% to 1 wt% of zinc, other than 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, and preferably 20 to 100 mg / m 2. It is preferable that the ratio of the adhesion amount of nickel to the adhesion amount of nickel (= adhesion amount of nickel / adhesion amount of zinc) of the nickel-zinc alloy layer or the nickel-zinc alloy layer is 1.5 to 10. The adhesion amount of nickel in the nickel-zinc alloy layer or nickel-zinc alloy layer is preferably 0.5 mg / m 2 to 500 mg / m 2, more preferably 1 mg / m 2 to 50 mg / m 2 Do. When the heat-resistant layer and / or the rust-preventive layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate does not corrode well on the dispensing liquid when the inner wall portion of the through hole, And the resin substrate are improved.

For example, the heat resistant layer and / or the rust preventive layer may be formed of a nickel or nickel alloy layer having an adhesion amount of 1 mg / m2 to 100 mg / m2, preferably 5 mg / m2 to 50 mg / m2 and an adhesion amount of 1 mg / M 2 to 40 mg / m 2, and the nickel alloy layer may be formed of any one of nickel-molybdenum, nickel-zinc, and nickel-molybdenum-cobalt It may be composed of species. The total thickness of the heat-resistant layer and / or the rust-preventive layer is preferably 2 mg / m2 to 150 mg / m2, more preferably 10 mg / m2 to 70 mg / m2, of nickel or a nickel alloy and tin. It is preferable that the heat resistant layer and / or the rust preventive layer has a nickel adhesion amount of [nickel or nickel alloy] / [tin adhesion amount] = 0.25 to 10, more preferably 0.33 to 3. [ When the heat resistant layer and / or the rust preventive layer is used, the peel strength of the circuit after the copper foil with a carrier is processed on the printed wiring board, the deterioration resistance of the chemical strength of the peel strength, and the like are improved.

A known silane coupling agent may be used for the silane coupling agent used for the silane coupling treatment. For example, an amino silane coupling agent, an epoxy silane coupling agent, or a mercapto silane coupling agent may be used. Examples of the silane coupling agent include vinyltrimethoxysilane, vinylphenyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) Methoxysilane, imidazole silane, triazinilane, gamma-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. Two or more such silane coupling agents may be used in combination. Among them, it is preferable to use an amino-based silane coupling agent or an epoxy-based silane coupling agent.

Examples of the amino-based silane coupling agent include N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxy Silane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- Aminopropyl) trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane, 6- (aminohexylaminopropyl) , Aminophenyltrimethoxysilane, 3- (1-aminopropoxy) -3,3-dimethyl-1-propenyltrimethoxysilane, 3- (Methoxyethoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, omega -aminoundecyltrimethoxysilane, 3- (2-N- benzylaminoethylamino Propyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl- Aminopropyl) trimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) Methoxysilane, and methoxysilane.

The silane coupling treatment layer is preferably used in a range of 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 the above-mentioned range, the adhesion between the base resin and the surface-treated copper foil can be further improved.

Further, the surface of the ultra-thin copper layer, the roughened layer, the heat resistant layer, the rust-preventive layer, the silane coupling treatment layer or the chromate treatment layer may be coated with an inorganic filler such as those described in International Publication Nos. WO2008 / 053878, 2008-111169, International Publication No. WO2006 / 028207, Japanese Patent Publication No. 4828427, International Publication Nos. WO2006 / 134868, Japanese Patent Publication No. 5046927, International Publication Nos. WO2007 / 105635, Japanese Patent Publication No. 5180815, The surface treatment described in JP-A-19056 can be carried out.

[Resin layer on ultra-thin copper layer]

The resin layer may be provided on the ultra-thin copper layer of the copper foil with a carrier of the present invention (when the ultra-thin copper layer is subjected to the surface treatment, the surface treatment layer formed on the ultra-thin copper layer by the surface treatment). The resin layer may be an insulating resin layer.

The resin layer may be an adhesive resin, that is, an adhesive, or an insulating resin layer in a semi-cured state (B-stage state) for bonding. The semi-cured state (B-stage state) includes a state in which the insulating resin layer can be stacked and stored without being tacky even when the surface is touched with a finger, and a curing reaction occurs when subjected to heat treatment.

The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton or the like. In addition, the resin layer may be formed, for example, in International Publication Nos. WO2008 / 004399, WO2008 / 053878, WO2009 / 084533, JP- , Japanese Patent Publication No. 3184485, International Publication No. WO97 / 02728, Japanese Patent Publication No. 3676375, Japanese Patent Application Laid-Open No. 2000-43188, Japanese Patent Publication No. 3612594, Japanese Patent Application Laid-Open No. 2002-179772, JP-A-2002-359444, JP-A-2003-304068, JP-A-3992225, JP-A-2003-249739, JP-A-4136509, JP-A- 2004-82687, 4025177, 2004-349654, 4286060, 2005-262506, 4570070, 2005-53218, and 3949676, Japanese Patent Application Laid- , Japanese Patent Publication No. 4178415, International Publication Japanese Patent Application Laid-Open Nos. WO2004 / 005588, JP-A-2006-257153, JP-A-2007-326923, JP-A-2008-111169, JP-A-5024930, WO2006 / 028207, Japanese Patent Application Laid-Open No. 2009-71817, International Publication No. WO2007 / 105635, Japanese Patent Publication No. 5180815, International Patent Publication No. International Publication Nos. WO2008 / 114858, WO2009 / 008471, JP-A-2011-14727, WO009 / 001850, WO2009 / 145179, WO2011 / 068157, JP-A-2013-19056 (Resin, curing accelerator, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton, etc.) and / or a method of forming a resin layer and a forming apparatus .

The type of the resin layer is not particularly limited, and examples thereof include epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleic acid resin, (Also referred to as polyether sulfone, polyether sulfone), polyether sulfone (also referred to as polyether sulfone, polyether sulfone) resin, aromatic polyamide resin, aromatic polyamide resin But are not limited to, resin polymers, rubber resins, polyamines, aromatic polyamines, polyamideimide resins, rubber modified epoxy resins, phenoxy resins, carboxyl group modified acrylonitrile-butadiene resins, polyphenylene oxides, bismaleimide triazine resins, Phenylene oxide resin, cyanate ester resin, carboxylic acid (4-cyanatophenyl) propane, a phosphorus-containing phenol compound, a manganese naphthenate, a 2,2-bis (4-cyanatophenyl) propane, an anhydride, a polyhydric carboxylic acid anhydride, Modified polyamide-imide resin, cyanoester resin, phosphazene-based resin, rubber-modified polyamideimide resin, isoprene, hydrogenated poly (vinylidene fluoride) A resin containing at least one member selected from the group consisting of butadiene, polyvinyl butyral, phenoxy, polymer epoxy, aromatic polyamide, fluorine resin, bisphenol, block copolymerized polyimide resin and cyanoester resin is preferably used .

The above-mentioned epoxy resin can be used without particular problems, as long as it has two or more epoxy groups in the molecule and can be used for electric and electronic materials. The epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. In addition, epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD type epoxy resins, novolak type epoxy resins, cresol novolak type epoxy resins, alicyclic epoxy resins, Resin, phenol novolak type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolak type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanate A glycidyl amine compound such as N, N-diglycidyl aniline, a glycidyl ester compound such as tetrahydrophthalic acid diglycidyl ester, a phosphorus-containing epoxy resin, a biphenyl-type epoxy resin, One selected from the group of boric epoxy resins, trishydroxyphenylmethane epoxy resins, and tetraphenyl ethane epoxy resins It may may be used by mixing two or more kinds, or to use a halogenated material chena hydrogenation of the epoxy resin.

As the phosphorus-containing epoxy resin, a known phosphorus-containing epoxy resin can be used. The phosphorus-containing epoxy resin is, for example, 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 desirable.

The epoxy resin obtained as a derivative from this 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 (HCA-NQ) or (2) (HCA-HQ) by reacting naphthoquinone or hydroquinone in the presence of a phosphorus compound Epoxy resin.

[Chemical Formula 1]

(2)

The phosphorus-containing epoxy resin obtained as the E component obtained as the above-described compound as a raw material is preferably used by mixing one or two kinds of compounds having the structural formulas shown in any of the following formulas (3) to (5) This is because the stability of the resin quality in the semi-cured state is excellent, and at the same time, the flame retardant effect is high.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

As the brominated (canceled) epoxy resin, a known brominated (canceled) epoxy resin can be used. For example, the brominated (canceled) epoxy resin may be a brominated epoxy resin having a structural formula represented by the formula (6) obtained as a derivative from tetrabromobisphenol A having two or more epoxy groups in the molecule, It is preferable to use one or two of the brominated epoxy resins having the structural formula.

[Chemical Formula 6]

(7)

As the maleimide resin or aromatic maleimide resin or the maleimide compound or the polymaleimide compound, known maleimide resin or aromatic maleimide resin or maleimide compound or polymaleimide compound can be used. Examples of the maleimide resin or aromatic maleimide resin or the maleimide compound or the polymaleimide compound include 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 ) Benzene, and a polymer obtained by polymerizing the compound and the compound or other compounds. The maleimide-based resin may be an aromatic maleimide resin having two or more maleimide groups in the molecule, or may be a polymerized adduct obtained by polymerizing an aromatic maleimide resin having two or more maleimide groups in the molecule and a polyamine or aromatic polyamine do.

As the polyamines or aromatic polyamines, known polyamines or aromatic polyamines can be used. For example, as the polyamine or aromatic polyamine, there may be mentioned m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6- , 4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenyl ether, 4,4'-diamino- , 4,4'-diaminodiphenylsulfide, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, bis (4-aminophenyl) phenylamine, m- p-xylylenediamine, 1,3-bis [4-aminophenoxy] benzene, 3-methyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'- Diphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2 ', 5,5'-tetrachloro-4,4'-diaminodiphenylmethane, 2,2- Propane, 2,2-bis (3-methyl-4-aminophenyl) propane, (2,3-dimethyl-4-aminophenyl Bis (4- (4-aminophenoxy) phenyl) propane, and polymers obtained by polymerizing the above compounds and other compounds, or the like can be used. The known polyamines and / or aromatic polyamines or the above-mentioned polyamines or aromatic polyamines may be used alone or in combination.

As the phenoxy resin, a known phenoxy resin can be used. As the phenoxy resin, those synthesized by the reaction of a bisphenol and a divalent epoxy resin can be used. As the epoxy resin, a known epoxy resin and / or the above-mentioned epoxy resin can be used.

The bisphenol can be a known bisphenol and can be bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4'-dihydroxybiphenyl, HCA (9,10-Dihydro- Oxa-10-Phosphaphenanthrene-10-Oxide) and bisphenols obtained as adducts of quinones such as hydroquinone and naphthoquinone.

As the linear polymer having a crosslinkable functional group, a known linear polymer having a crosslinkable functional group can be used. For example, the linear polymer having a crosslinkable functional group preferably has a functional group contributing to a curing reaction of an epoxy resin such as a hydroxyl group or a carboxyl group. The linear polymer having a crosslinkable functional group is preferably soluble in an organic solvent having a boiling point of 50 ° C to 200 ° C. Specific examples of the linear polymer having a functional group as referred to herein include a polyvinyl acetal resin, a phenoxy resin, a polyether sulfone resin, and a polyamideimide resin.

The resin layer may contain a crosslinking agent. As the crosslinking agent, known crosslinking agents may be used. As the crosslinking agent, for example, a urethane resin can be used.

As the rubbery resin, a known rubbery resin may be used. For example, the rubbery resin is described as a concept including natural rubber and synthetic rubber. The latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, acrylonitrile- Acrylic rubber (acrylic acid ester copolymer), polybutadiene rubber, and isoprene rubber. In order to secure the heat resistance of the resin layer to be formed, it is also useful to selectively use heat-resistant synthetic rubbers such as nitrile rubber, chloroprene rubber, silicone rubber and urethane rubber. In order to produce a copolymer by reacting with the aromatic polyamide resin or polyamideimide resin, it is preferable that these rubbery resins are provided with various functional groups at both ends. In particular, it is useful to use CTBN (carboxyl-terminated butadiene nitrile). Among acrylonitrile butadiene rubbers, if it is a carboxyl modified product, it can take a crosslinked structure with an epoxy resin and improve the flexibility of the resin layer after curing. As the carboxyl-modified product, a carboxyl-terminated nitrile-butadiene rubber (CTBN), a carboxyl-terminated butadiene rubber (CTB) and a carboxy-modified nitrile-butadiene rubber (C-NBR) can be used.

As the polyamide-imide resin, a known polyimide-amide resin may be used. Examples of the polyimide amide resin include trimellitic anhydride, benzophenonetetracarboxylic acid anhydride and non-tolylene diisocyanate in the presence of N-methyl-2-pyrrolidone and / or N, N-dimethylacetamide Or the like, or a resin obtained by heating trimellitic anhydride, diphenylmethane diisocyanate and carboxyl-terminated acrylonitrile-butadiene rubber with N-methyl-2-pyrrolidone and / or N, N-dimethylacetamide In a solvent of water.

As the rubber-modified polyamide-imide resin, a known rubber-modified polyamide-imide resin can be used. The rubber-modified polyamide-imide resin is obtained by reacting a polyamide-imide resin with a rubber-based resin. The use of a polyamide-imide resin in reaction with a rubber-like resin is carried out for the purpose of improving the flexibility of the polyamide-imide resin itself. That is, a polyamide-imide resin is reacted with a rubber-like resin to replace part of the acid component (cyclohexanedicarboxylic acid, etc.) of the polyamide-imide resin with a rubber component. For the polyamide-imide resin, a known polyamide-imide resin can be used. As the rubbery resin, known rubbery resins or the aforementioned rubbery resins can be used. Examples of the solvent used for dissolving the polyamide-imide resin and the rubber-like resin in the polymerization of the rubber-modified polyamide-imide resin include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, Methane, nitroethane, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, acetonitrile, gamma -butyrolactone, and the like are preferably used in combination.

As the phosphazene resin, a known phosphazene resin can be used. The phosphazene-based resin is a resin containing phosphazene having a double bond containing phosphorus and nitrogen as constituent elements. The phosphazene resin can remarkably improve the flame retardant performance by the synergistic effect of nitrogen and phosphorus in the molecule. In addition, unlike the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, an effect of being stably present in the resin and preventing the occurrence of migration is obtained.

As the fluororesin, a known fluororesin can be used. As the fluororesin, for example, PTFE (polytetrafluoroethylene (tetrafluoro)), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene / hexafluoropropylene (Tetrafluoroethylene-ethylene copolymer), PVDF (polyvinylidene fluoride (difluoride)), PCTFE (polychlorotrifluoroethylene (trifluoromethyl)), polyallyl sulfone , An aromatic polysulfide, and an aromatic polyether, and a fluororesin comprising a fluororesin may be used.

The resin layer may contain a resin curing agent. As the resin curing agent, known resin curing agents may be used. Examples of the resin curing agent include 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, biphenyl-type phenol resins, phenol aralkyl type phenol resins, and the like. The resin layer may contain one or more of the above-mentioned resin curing agents. These curing agents are particularly effective for epoxy resins.

Specific examples of the biphenyl-type phenol resin are shown in Formula (8).

[Chemical Formula 8]

Specific examples of the phenol aralkyl type phenol resin are shown in the formula (9).

[Chemical Formula 9]

As the imidazoles, known ones can be used, for example, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, -Phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. These may be used alone or in combination.

Among them, it is preferable to use imidazoles having the following structural formula (10). By using the imidazoles of the structural formula (10), it is possible to remarkably improve the hygroscopicity of the resin layer in the semi-cured state, and the long-term storage stability is excellent. The imidazoles perform catalytic action upon curing of the epoxy resin and serve as a reaction initiator for causing a self-polymerization reaction of the epoxy resin in the initial stage of the curing reaction.

[Chemical formula 10]

As the resin curing agent for the amines, known amines can be used. As the resin curing agent for the amines, there can be used, for example, the above-mentioned polyamines or aromatic polyamines, and also aromatic polyamines and polyamides, and amine adducts obtained by polymerizing or condensing them with an epoxy resin or a polybasic carboxylic acid May be used alone or in combination of two or more. Examples of the resin curing agent for the amines include 4,4'-diaminodiphenylene sulfone, 3,3'-diaminodiphenylene sulfone, 4,4-diaminodiphenylene, 2,2-bis [ 4- (4-aminophenoxy) phenyl] propane or bis [4- (4-aminophenoxy) phenyl] sulfone.

The resin layer may contain a curing accelerator. As the curing accelerator, known curing accelerators may be used. As the curing accelerator, for example, tertiary amines, imidazoles, urea curing accelerators and the like can be used.

The resin layer may include a reaction catalyst. As the reaction catalyst, a known reaction catalyst may be used. For example, fine particles of silica, antimony trioxide or the like can be used as a reaction catalyst.

The anhydride of the polyvalent carboxylic acid is preferably a component contributing as a curing agent for the epoxy resin. The anhydride of the polyvalent carboxylic acid may be at least one selected from phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydroxyphthalic anhydride, hexahydroxyphthalic anhydride, methylhexahydroxyphthalic anhydride, Methylnadic acid is preferable.

The thermoplastic resin may be a thermoplastic resin having a functional group other than the alcoholic hydroxyl group polymerizable with the 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. In addition, the polyvinyl acetal resin may be obtained by introducing a carboxyl group, an amino group or an unsaturated double bond into the molecule.

Examples of the aromatic polyamide resin polymer include those obtained by reacting an aromatic polyamide resin with a rubbery resin. Here, the aromatic polyamide resin is synthesized by condensation polymerization of an aromatic diamine and a dicarboxylic acid. As the aromatic diamine at this time, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, m-xylene diamine, 3,3'-oxydianiline and the like are used. As the dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid and the like are used.

The rubbery resin to be reacted with the aromatic polyamide resin may be a known rubbery resin or the aforementioned rubbery resin.

This aromatic polyamide resin polymer is used for the purpose of not subjecting to damage by underetching by an etching liquid when the copper foil after being processed into a copper clad laminate is etched.

The resin layer is formed by successively stacking a cured resin layer (the term "cured resin layer" means a cured resin layer) and a semi-cured resin layer in this order from the copper foil side (ie, the ultra-thin copper layer side of the copper foil with a carrier) Or a resin layer formed thereon. The cured resin layer may be composed of a polyimide resin, a polyamide-imide resin, or a resin component of any of these composite resins having a thermal expansion coefficient of 0 ppm / ° C to 25 ppm / ° C.

A semi-cured resin layer having a thermal expansion coefficient of 0 ppm / ° C to 50 ppm / ° C after curing may be formed on the cured resin layer. The thermal expansion coefficient of the entire resin layer after curing of the cured resin layer and the semi-cured resin layer may be 40 ppm / 占 폚 or less. The cured resin layer may have a glass transition temperature of 300 캜 or higher. The semi-cured resin layer may be formed using a maleimide resin or an aromatic maleimide resin. The resin composition for forming the semi-cured resin layer preferably includes a maleimide resin, an epoxy resin, and a linear polymer having a crosslinkable functional group. The epoxy resin may be a known epoxy resin or the epoxy resin described in this specification. Examples of the maleimide-based resin, the aromatic maleimide resin, and the linear polymer having a cross-linkable functional group include known maleimide-based resins, aromatic maleimide resins, linear polymers having a cross-linkable functional group or the aforementioned maleimide- A mid resin, and a linear polymer having a crosslinkable functional group can be used.

In the case of providing a copper foil with a carrier having a resin layer, which is suitable for use in the production of a molded molded printed circuit board, it is preferable that the cured resin layer is a hardened polymeric polymer layer having flexibility. The polymeric polymer layer is preferably made of a resin having a glass transition temperature of 150 DEG C or more so as to withstand the solder packaging step. The polymer polymer layer is preferably composed of a mixed resin of at least one 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 . It is preferable that the thickness of the polymer polymer layer is 3 mu m to 10 mu m.

It is preferable that the polymer polymer layer contains at least one of epoxy resin, maleimide resin, phenol resin and urethane resin. The semi-cured resin layer is preferably composed of an epoxy resin composition having a thickness of 10 mu m to 50 mu m.

It is preferable that the epoxy resin composition contains the following components A to E, respectively.

Component A: an epoxy resin comprising at least one epoxy group 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.

Component B: High heat resistant epoxy resin.

Component C: phosphorus-containing flame retardant resin which is a resin obtained by mixing any one of phosphorus-containing epoxy resin and phosphazene resin or a mixture thereof.

Component D: a rubber-modified polyamide-imide resin modified with a liquid rubber component having a property of being soluble in a solvent having a boiling point in a range of from 50 캜 to 200 캜.

Component E: Resin curing agent.

The component B is a &quot; high heat resistant epoxy resin &quot; having a so-called glass transition point Tg. The "heat-resistant epoxy resin" referred to herein is preferably a polyfunctional epoxy resin such as novolak type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, and naphthalene type epoxy resin.

As the phosphorus-containing epoxy resin of component C, the above-mentioned phosphorus-containing epoxy resin can be used. As the C component phosphazene resin, the above-mentioned phosphazene resin can be used.

As the rubber-modified polyamide-imide resin of component D, the above-mentioned rubber-modified polyamide-imide resin can be used. As the resin curing agent for the component E, the aforementioned resin curing agent can be used.

A solvent is added to the resin composition as described above and used as a resin varnish to form a thermosetting resin layer as an adhesive layer of a printed wiring board. The resin varnish is prepared by adding a solvent to the above-mentioned resin composition to prepare a resin having a solid content of 30 wt% to 70 wt% and measuring the resin as measured according to MIL-P-13949G in MIL specification It is possible to form a semi-cured resin film having a flow in the range of 5% to 35%. For the solvent, a known solvent or the above-mentioned solvent may be used.

Wherein the resin layer is a resin layer having a first thermosetting resin layer in order from the copper foil side and a second thermosetting resin layer positioned on the surface of the first thermosetting resin layer, And the second thermosetting resin layer is formed of a resin component which is dissolved in a drug used in the desmear treatment in the process of producing a wiring board and is made of a resin that can be cleaned and removed Or the like. The first thermosetting resin layer may be formed using a resin component in which one or more of polyimide resin, polyethersulfone, and polyphenylene oxide are mixed. The second thermosetting resin layer may be formed using an epoxy resin component. The thickness t1 (占 퐉) of the first thermosetting resin layer is set such that t2 (占 퐉) is the thickness of the second thermosetting resin layer and Rz (占 퐉) It is preferable that the thickness satisfies the condition of &lt; t1 &lt; t2.

The resin layer may be a prepreg impregnated with a resin in a skeletal material. The resin impregnated in the skeleton is preferably a thermosetting resin. The prepreg may be a known prepreg or a prepreg used for manufacturing a printed wiring board.

The skeletal material may comprise aramid fibers or glass fibers or wholly aromatic polyester fibers. The skeleton material is preferably a nonwoven fabric or woven fabric of aramid fiber, glass fiber, or all aromatic polyester fiber. The total aromatic polyester fiber is preferably a wholly aromatic polyester fiber having a melting point of 300 캜 or higher. The above all-aromatic polyester fiber having a melting point of 300 ° C or higher is a fiber produced by using a resin called a liquid crystal polymer. The liquid crystal polymer is a polymer of 2-hydroxyl-6-naphthoic acid and p-hydroxybenzoic acid It is the main component. This whole aromatic polyester fiber has a low dielectric constant and a low dielectric loss tangent, and therefore has excellent performance as a constituent material of the electrically insulating layer and can be used in the same manner as glass fibers and aramid fibers.

The fibers constituting the nonwoven fabric and the woven fabric are preferably subjected to a silane coupling agent treatment in order to improve the wettability of the surface of the nonwoven fabric and the woven fabric with the resin. The silane coupling agent at this time may be a known silane coupling agent such as an amino-based or epoxy-based coupling agent or a silane coupling agent as described above.

The prepreg may be a nonwoven fabric using aramid fibers or glass fibers having a nominal thickness of 70 μm or less, or a prepreg impregnated with a thermosetting resin in a skeletal material composed of a glass cloth having a nominal thickness of 30 μm or less.

(When the resin layer includes a dielectric (dielectric filler)

The resin layer may include 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 forming a capacitor layer, thereby increasing the capacitance of the capacitor circuit. A dielectric powder of a composite oxide having a perovskite structure such as BaTiO 3, SrTiO 3, Pb (Zr-Ti) O 3 (commonly referred to as PZT), PbLaTiO 3 .PbLaZrO (commonly referred to as PLZT), or SrBi 2 Ta 2 O 9 Lt; / RTI &gt;

The dielectric (dielectric filler) may be in powder form. When the dielectric (dielectric filler) is in the form of powder, it is necessary that the particle size of the dielectric (dielectric filler) is firstly in the range of 0.01 탆 to 3.0 탆, preferably 0.02 탆 to 2.0 탆. Since the particle diameters referred to herein form a certain degree of secondary agglomeration among the granules, the precision is inferior in the indirect measurement in which the average particle diameter is estimated from the measurement values such as the laser diffraction scattering type particle size distribution measurement method and the BET method, And refers to an average particle size obtained by directly observing a dielectric (dielectric filler) with a scanning electron microscope (SEM) and analyzing the SEM image. In this specification, the particle size at this time is indicated by DIA. The image analysis of the powder of the dielectric (dielectric filler) observed using a scanning electron microscope (SEM) in the present specification was carried out using IP-1000PC manufactured by Asahi Engineering Co., Ltd., A value of 10 and an overlapping degree of 20, and the average particle diameter DIA was obtained.

According to the above-described embodiment, a carrier having a resin layer including a dielectric for improving the adhesion between the inner layer circuit surface of the inner layer core material and the resin layer including the dielectric and for forming the capacitor circuit layer having low dielectric tangent It is possible to provide an attached copper foil.

The resin and / or the resin composition and / or the compound contained in the resin layer described above may be dissolved in a solvent such as methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, , Ethanol, propylene glycol monomethyl ether, dimethyl formamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, (Resin varnish) by dissolving it in a solvent such as an amide or the like to form a resin solution (resin varnish) on the extremely thin copper layer or the heat resistant layer, the rust prevention layer, or the chromate treatment layer or the silane coupling agent layer, Coater method or the like, and then, if necessary, heated and dried to remove the solvent to obtain a B-stage state. For drying, for example, a hot-air drying furnace may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the resin layer is dissolved by using a solvent, and the resin solid content is 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably, 25 wt% to 40 wt% resin solution may be used. Further, it is most preferable to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone from the environmental viewpoint at the present stage. It is preferable to use a solvent having a boiling point in the range of 50 ° C to 200 ° C.

It is preferable that the resin layer is a semi-cured resin film having a resin flow in the range of 5% to 35% when measured according to MIL-P-13949G in the MIL standard.

In the present specification, the resin flow is a method of sampling 4 samples of 10 cm in length and 10 cm from a copper foil having a resin thickness of 55 탆 and having a resin thickness of 55 탆 according to MIL-P-13949G in the MIL standard, (Laminate) were laminated under the conditions of a press temperature of 171 占 폚, a pressing pressure of 14 kgf / cm2, and a pressing time of 10 minutes. From the results of measuring the resin outflow weight at that time, .

The resin-coated copper foil with the resin layer (resin-coated copper foil with a carrier) having the resin layer is superimposed on the base material and then thermally pressed to thermally cure the resin layer. Subsequently, the carrier is peeled, (Of course, the surface to be exposed is the surface of the intermediate layer side of the extremely thin copper layer), and is used as an embodiment of forming a predetermined wiring pattern there.

The use of the copper foil with a carrier to which the resin is adhered can reduce the number of prepreg materials used in manufacturing a multilayer printed wiring board. Furthermore, the thickness of the resin layer can be set to a sufficient thickness to ensure interlayer insulation, or a copper clad laminate can be manufactured without using any prepreg material. At this time, the surface of the substrate may be undercoated with an insulating resin to further improve the smoothness of the surface.

When the prepreg material is not used, the material cost of the prepreg material is reduced, and the lamination step is simplified. Therefore, the multilayer printed wiring board is economically advantageous and the thickness of the multilayer printed wiring board manufactured by the thickness of the prepreg material is It is possible to produce an ultra-thin multilayer printed circuit board having a thickness of 100 m or less in one layer.

The thickness of the resin layer is preferably 0.1 to 120 탆.

When the thickness of the resin layer is smaller than 0.1 占 퐉, the adhesive force is lowered, and when the copper foil with a carrier on which the resin is adhered is laminated on a base material provided with the inner layer material without interposing the prepreg material, It may be difficult to secure a certain amount of time. On the other hand, if the thickness of the resin layer is made larger than 120 占 퐉, it is difficult to form the resin layer having the desired thickness in one coating step, resulting in economical disadvantage because extra material cost and number of steps are involved.

When the copper foil with a carrier having a resin layer is used for producing an ultra-thin multilayered printed circuit board, the thickness of the resin layer is preferably 0.1 to 5 mu m, more preferably 0.5 to 5 mu m, It is preferable that the thickness is 1 占 퐉 to 5 占 퐉 in order to reduce the thickness of the multilayer printed wiring board.

When the resin layer contains a dielectric, the thickness of the resin layer is preferably 0.1 to 50 탆, more preferably 0.5 to 25 탆, and more preferably 1.0 to 15 탆.

The thickness of the total resin layer with respect to the cured resin layer and the semi-cured resin layer is preferably 0.1 μm to 120 μm, more preferably 5 μm to 120 μm, more preferably 10 μm to 120 μm, And more preferably in the range of about 60 占 퐉. The thickness of the cured resin layer is preferably 2 to 30 탆, more preferably 3 to 30 탆, and more preferably 5 to 20 탆. The thickness of the semi-cured resin layer is preferably in the range of 3 탆 to 55 탆, more preferably in the range of 7 탆 to 55 탆, and more preferably in the range of 15 탆 to 115 탆. If the thickness of the total resin layer exceeds 120 탆, it may be difficult to produce a multilayer printed wiring board having a thin thickness. If the total resin layer thickness is less than 5 탆, it is easy to form a multilayer printed wiring board having a thin thickness. However, The resin layer which is the insulating layer of the inner layer becomes too thin, and there is a tendency that the insulation between the circuits of the inner layer becomes unstable. If the thickness of the cured resin layer is less than 2 占 퐉, it may be necessary to consider the surface roughness of the copper foil roughened surface. On the other hand, if the thickness of the cured resin layer exceeds 20 占 퐉, the effect of the cured resin layer may not be particularly improved, and the total thickness of the insulating layer becomes thick.

When the thickness of the resin layer is from 0.1 to 5 占 퐉, it is preferable that the heat-resistant layer and / or the anticorrosion layer and / or the chromate treatment layer and / or the antireflection layer are formed on the ultra-thin copper layer in order to improve the adhesion between the resin layer and the copper- It is preferable to form a resin layer on the heat resistant layer or rustproof layer, the chromate treatment layer or the silane coupling treatment layer after the silane coupling treatment layer is formed.

The thickness of the resin layer mentioned above refers to an average value of the thickness measured at any 10 points by cross-sectional observation.

Further, as another product form of the copper foil with a carrier on which the resin is adhered, it is preferable that the resin layer is formed on the extremely thin copper layer or on the heat resistant layer, rustproofing layer or the chromate treatment layer, And after the carrier is semi-cured, the carrier may be peeled off to produce a resin-coated copper foil free from carriers.

<6. Printed circuit board>

Hereinafter, several examples of the manufacturing process of the printed wiring board using the surface-treated copper foil or the copper foil with a carrier according to the present invention are shown. In addition, by mounting electronic parts on the printed wiring board, the printed circuit board is completed.

Through the above-described process, a copper foil with a carrier having a copper foil carrier, a release layer and an ultra-thin copper layer in this order is produced. The method of using the copper foil with a carrier itself is well known to those skilled in the art. For example, the surface of the ultra-thin copper layer may be coated with paper phenol resin, paper base epoxy resin, synthetic fiber base epoxy resin, Bonded to an insulating substrate such as a glass fiber substrate epoxy resin, a polyester film, or a polyimide film by peeling the carrier after thermocompression to form a copper clad laminate, And finally, a printed wiring board can be manufactured.

The copper foil with a carrier according to the present invention is suitable for forming a printed wiring board with a fine pitch. For example, by using the copper foil with a carrier according to the present invention, it is possible to provide a semiconductor device having an insulating substrate and a copper circuit formed on the insulating substrate, wherein the circuit width of the copper circuit is less than 20 mu m, A printed wiring board having a thickness of less than 20 탆 can be produced. Further, it is also possible to produce a printed circuit board in which the circuit width of the copper circuit is 17 mu m or less and the space between adjacent copper circuits is 17 mu m or less. Further, it is also possible to produce a printed wiring board in which the circuit width of the copper circuit is 15 mu m or less and the space between adjacent copper circuits is 15 mu m or less. Furthermore, a printed circuit board having a circuit width of 5 to 10 mu m and a space width of 5 to 10 mu m between adjacent copper circuits can be manufactured.

In addition, by mounting electronic parts on a printed wiring board, a printed circuit board is completed. It is possible to use a copper foil with a carrier according to the present invention, for example, which has an insulating substrate and a copper circuit formed on the insulating substrate, wherein the circuit width of the copper circuit is less than 20 占 퐉, It is possible to manufacture a printed circuit board having a thickness of less than 20 mu m. Further, it is also possible to manufacture a printed circuit board in which the circuit width of the copper circuit is 17 mu m or less and the space between adjacent copper circuits is 17 mu m or less. Further, it is also possible to produce a printed circuit board in which the circuit width of the copper circuit is 17 mu m or less and the space between adjacent copper circuits is 17 mu m or less. Further, it is also possible to produce a printed circuit board in which the circuit width of the copper circuit is 15 mu m or less and the space between adjacent copper circuits is 15 mu m or less. Further, it is preferable that the circuit width of the copper circuit is 5 to 10 mu m, preferably 5 to 9 mu m, more preferably 5 to 8 mu m, and the width of the space between adjacent copper circuits is 5 to 10 mu m, 5 to 9 mu m, and more preferably 5 to 8 mu m. The pitch of the line and space is preferably less than 40 占 퐉, more preferably not more than 34 占 퐉, more preferably not more than 30 占 퐉, more preferably not more than 20 占 퐉, more preferably not more than 15 占 퐉. The lower limit of the line-and-space is not specifically defined, but is, for example, 6 mu m or more, 8 mu m or more, or 10 mu m or more.

The pitch of the line and space is a distance from the center of the width of the copper circuit to the center of the width of the adjacent copper circuit.

Hereinafter, several examples of the production steps of the printed wiring board using the copper foil with a carrier according to the present invention are shown.

In one embodiment of the method for manufacturing a printed wiring board according to the present invention, there is provided a method for manufacturing a printed wiring board, comprising the steps of: preparing a copper foil with a carrier and an insulating substrate according to the present invention; laminating the copper foil with a carrier and an insulating substrate; Is laminated so that the extremely thin copper side faces the insulating substrate and then the carrier of the copper foil with a carrier is peeled off to form a copper clad laminate. Thereafter, a semi-additive process, a modified semi-additive process, An additive method, and a subtractive method. It is also possible that the insulating substrate has an inner layer circuit inserted therein.

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

Therefore, in one embodiment of the method for producing the printed wiring board according to the present invention using the semi-additive method, the step of preparing the copper foil with a carrier and the insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of removing all of the extremely thin copper layer exposed by peeling off the carrier by a method such as etching or plasma using a corrosive solution such as an acid,

A step of forming a through hole and / or a blind via in the exposed resin layer and the insulating substrate by removing the extremely thin copper layer by etching,

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

A step of forming an electroless plating layer on a region including the resin and the through hole and / or the blind via,

A step of forming a plating resist on the electroless plating layer,

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

A step of forming an electroplating layer in a region where the circuit where the plating resist is removed is formed,

A step of removing the plating resist,

A step of removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like,

.

In another embodiment of the method for manufacturing a printed wiring board according to the present invention using the semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of removing all of the extremely thin copper layer exposed by peeling off the carrier by a method such as etching or plasma using a corrosive solution such as an acid,

A step of forming an electroless plating layer on the exposed surface of the resin layer by removing the extremely thin copper layer by etching,

A step of forming a plating resist on the electroless plating layer,

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

A step of forming an electroplating layer in a region where the circuit where the plating resist is removed is formed,

A step of removing the plating resist,

A step of removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like,

.

In the present invention, the modified semi-additive method is a method in which a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, a copper thickness is formed in the circuit forming portion by electroplating, And a metal foil other than the circuit forming portion is removed by (flash) etching to form a circuit on the insulating layer.

Therefore, 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 an insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of forming a through hole and / or a blind via in the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier,

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

A step of forming an electroless plating layer on a region including the through hole and / or the blind via,

A step of forming a plating resist on the surface of the ultra-thin copper layer exposed by peeling the carrier,

A step of forming a circuit by electroplating after the plating resist is formed,

A step of removing the plating resist,

A step of removing the exposed ultra-thin copper layer 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 a modified semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of forming a plating resist on the extremely thin copper layer exposed by peeling off the carrier,

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

A step of forming an electroplating layer in a region where the circuit where the plating resist is removed is formed,

A step of removing the plating resist,

A step of removing the ultra-thin copper layer in a region other than the region where the circuit is formed by flash etching or the like,

.

In the present invention, the palladium additive method is a method in which a catalyst core is provided on a substrate on which conductor layers are formed and, if necessary, punched holes for through-holes or via holes, etched to form conductor circuits, Refers to a method for producing a printed wiring board by forming a solder resist or a plating resist as necessary and then forming a thickness on the conductor circuit by through an electroless plating process on a through hole or a via hole or the like.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the palladium additive method, the step of preparing the copper foil with a carrier and the insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of forming a through hole and / or a blind via in the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier,

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

Providing a catalyst nucleus to a region including the through hole and / or the blind via,

A step of forming an etching resist on the surface of the ultra-thin copper layer exposed by peeling the carrier,

A step of exposing the etching resist to a circuit pattern,

Removing the ultra-thin copper layer and the catalyst core by a method such as etching or plasma using a corrosion solution such as an acid to form a circuit;

A step of removing the etching resist,

A step of forming a solder resist or a plating resist on the exposed surface of the insulating substrate by removing the extremely thin copper layer and the catalyst core by a method such as etching or plasma using a corrosive solution such as an acid,

A step of forming an electroless plating layer in a region where the solder resist or the plating resist is not formed,

.

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

Therefore, in one embodiment of the method for manufacturing a printed wiring board according to the present invention using the subtractive method, the step of preparing the copper foil with a carrier and the insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of forming a through hole and / or a blind via in the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier,

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

A step of forming an electroless plating layer on a region including the through hole and / or the blind via,

A step of forming an electroplating layer on the surface of the electroless plating layer,

A step of forming an etching resist on the surface of the electroplating layer and / or the ultra-thin copper layer,

A step of exposing the etching resist to a circuit pattern,

Removing the extremely thin copper layer, the electroless plating layer and the electroplating layer by a method such as etching or plasma using a corrosion solution such as an acid to form a circuit,

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 the subtractive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of forming a through hole and / or a blind via in the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier,

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

A step of forming an electroless plating layer on a region including the through hole and / or the blind via,

A step of forming a mask on the surface of the electroless plating layer,

A step of forming an electroplating layer on the surface of the electroless plating layer on which no mask is formed,

A step of forming an etching resist on the surface of the electroplating layer and / or the ultra-thin copper layer,

A step of exposing the etching resist to a circuit pattern,

Removing the extremely thin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit,

A step of removing the etching resist,

.

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

Here, specific examples of the method for producing a printed wiring board using the copper foil with a carrier according to the present invention will be described in detail with reference to the drawings. Although the copper foil with a carrier having an ultra-thin copper layer formed with a roughened treatment layer is described here as an example, the present invention is not limited to this, and a copper foil with a carrier having an ultra- A manufacturing method of a wiring board can be carried out.

First, as shown in Fig. 3-A, a copper foil with a carrier (first layer) having an ultra-thin copper layer having a roughened treatment layer formed on its surface is prepared.

Next, as shown in Fig. 3-B, a resist is coated on the roughened layer of the ultra-thin copper layer, exposure and development are performed, and the resist is etched into a predetermined shape.

Next, as shown in Fig. 3-C, a circuit plating for a circuit is formed and then the resist is removed to form circuit plating of a predetermined shape.

Next, as shown in Fig. 4-D, a resin layer is formed on the extremely thin copper layer so as to cover the circuit plating (so that the circuit plating is buried) to laminate the resin layer, Is bonded from the ultra-thin copper layer side.

Next, as shown in Fig. 4-E, the carrier is peeled from the second-layered copper foil with a carrier.

Next, as shown in FIG. 4-F, a laser hole is formed at a predetermined position of the resin layer, and the circuit plating is exposed to form a blind via.

Next, as shown in FIG. 5-G, copper is buried in the blind via to form a via fill.

Next, as shown in FIG. 5-H, circuit plating is formed on the via fill as shown in FIGS. 3-B and 3-C.

Next, as shown in Fig. 5-I, the carrier is peeled from the first-layer copper foil with a carrier.

Next, as shown in Fig. 6-J, the extremely thin copper layer on both surfaces is removed by flash etching to expose the surface of the circuit plating in the resin layer.

Next, as shown in Fig. 6-K, bumps are formed on the circuit plating in the resin layer, and a copper filler is formed on the solder. Thus, a printed wiring board using the copper foil with a carrier of the present invention is produced.

The copper foil with a carrier of the present invention may be used for the other copper foil with a carrier (second layer), or a conventional copper foil with a carrier may be used, or a conventional copper foil may be used. In addition, one or more layers may be further formed on the second layer circuit shown in Fig. 5-H, and the circuit formation may be performed by a semi-additive method, a subtractive method, a pattern additive method, And a semi-additive method.

The carrier-coated copper foil used for the first layer may have a substrate on the carrier-side surface of the carrier-coated copper foil. By having such a substrate or a resin layer, the copper foil with a carrier used in the first layer is supported, and wrinkles are hard to enter, so that productivity is improved. In addition, all the substrates can be used as long as they have the effect of supporting the copper foil with a carrier used for the first layer. For example, the substrate may be a carrier, a prepreg, a resin layer or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a foil of an inorganic compound, You can use pak.

The timing for forming the substrate on the carrier-side surface is not particularly limited, but it is necessary to form the carrier before peeling off. Particularly, it is preferable to form it before the step of forming the resin layer on the surface of the ultra-thin copper layer side of the carrier-coated copper foil, and it is more preferable to form it before the step of forming circuit on the surface of the ultra-

In the copper foil with a carrier according to the present invention, it is preferable that the color difference of the surface of the ultra-thin copper layer be controlled so as to satisfy the following (1). In the present invention, the term "color difference on the surface of the ultra-thin copper layer" refers to the color difference on the surface of the surface treatment layer when various surface treatments such as color difference on the surface of the ultra-thin copper layer or roughening treatment are carried out. That is, in the copper foil with a carrier according to the present invention, it is preferable that the color difference of the surface of the extremely thin copper layer, the roughened layer, the heat resistant layer, the rustproof layer, the chromate treated layer or the silane coupling layer is controlled to satisfy the following (1) .

(1) The color difference? E * ab based on JIS Z8730 on the surface of the ultra-thin copper layer, the roughened layer, the heat resistant layer, the rust-preventive layer, the chromate treated layer or the silane coupling treated layer is 45 or more.

Here, the color differences DELTA L, DELTA a and DELTA b are aggregate indices measured by the colorimeter and represented by using the L * a * b colorimetric system based on JIS Z8730 in consideration of black / white / red / green / ? L: black and white,? A: red color, and? B: white color. ? E * ab is expressed by the following equation using these color differences.

The above-described color difference can be adjusted by increasing the current density at the time of formation of the ultra-thin copper layer, lowering the copper concentration in the plating liquid, and increasing the line flow rate of the plating liquid.

The above-described color difference may be adjusted by forming a roughened treatment layer on the surface of the ultra-thin copper layer. In the case of forming the roughened layer, it is preferable to use an electric field solution containing copper and at least one element selected from the group consisting of nickel, cobalt, tungsten, and molybdenum to increase the current density (for example, 40 to 60 A / dm &lt; 2 &gt;) and the treatment time is shortened (for example, 0.1 to 1.3 seconds). When the roughening treatment layer is not formed on the surface of the ultra-thin copper layer, a plating bath in which the concentration of Ni is set to twice or more of the other elements is used to form an ultra-thin copper layer or heat resistant layer or rust- (For example, Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating) on the surface of the ring treatment layer at a lower current density (0.1 to 1.3 A / (20 seconds to 40 seconds) for a long period of time.

When the color difference ΔE * ab based on JIS Z8730 on the surface of the ultra-thin copper layer is 45 or more, for example, when a circuit is formed on the surface of the ultra-thin copper layer of the copper foil with a carrier, the contrast of the circuit with the ultra-thin copper layer becomes clear, As a result, visibility is improved, and alignment of the circuit can be performed with good precision. The color difference? E * ab based on JIS Z8730 on the surface of the ultra-thin copper layer is preferably 50 or more, more preferably 55 or more, still more preferably 60 or more.

When the color difference of the surface of the extremely thin copper layer, the roughened layer, the heat resistant layer, the rust prevention layer, the chromate treatment layer or the silane coupling layer is controlled as described above, the contrast with the circuit plating becomes clear and the visibility becomes good. Therefore, for example, in the case of the above-described printed wiring board, it is possible to form the circuit plating at a predetermined position with good precision in the manufacturing process as shown in Fig. 3-C. According to the above-described method of manufacturing a printed wiring board, since the circuit plating is embedded in the resin layer, when the ultra-thin copper layer is removed by flash etching as shown in, for example, , The circuit plating is protected by the resin layer and the shape thereof is maintained, thereby facilitating formation of a fine circuit. Further, since the circuit plating is protected by the resin layer, the migration resistance is improved and the conduction of the wiring of the circuit is well suppressed. Therefore, formation of a fine circuit is facilitated. As shown in Figs. 6-J and 6-K, when the ultra-thin copper layer is removed by flash etching, the exposed surface of the circuit plating becomes a depressed shape from the resin layer, The copper filler is easily formed thereon, and the production efficiency is improved.

Known resins and prepregs can be used for the buried resin (resin). For example, glass poison prepreg impregnated with BT (bismaleimide triazine) resin or BT resin, ABF film manufactured by Ajinomoto Fine Techno Co., Ltd. or ABF can be used. The resin layer and / or the resin and / or the prepreg described in this specification can be used for the above-mentioned embedding resin (resin).

Example

Hereinafter, the present invention will be described in more detail with reference to Examples of the present invention, but the present invention is not limited to these Examples at all.

1. Manufacture of copper foil with carrier

&Lt; Example 1 >

As the copper foil carrier, a long electrolytic copper foil having a thickness of 35 mu m (JTC manufactured by Nikko Nisseki Kinzoku JX) was prepared. The shiny side (Rz: 1.2 to 1.4 占 퐉) of the copper foil was electroplated with a roll-to-roll type continuous plating line (employing the phrase-aligning method shown in Fig. 2) Thereby forming an Ni layer having an adhered amount.

Ni layer

Nickel sulfate: 250 to 300 g / l

Nickel chloride: 35 to 45 g / l

Nickel acetate: 10 to 20 g / l

Sodium citrate: 15-30 g / l

Polishing agents: saccharin, butynediol, etc.

Sodium dodecyl sulfate: 30 to 100 ppm

pH: 4 to 6

Bath temperature: 50 ~ 70 ℃

Current density: 3 ~ 15 A / dm2

After washing with water and pickling, a Cr layer having an adhesion amount of 11 占 퐂 / dm2 was deposited on the Ni layer on a continuous roll-to-roll continuous plating line (employing the phrase binding method shown in Fig. 2) under the following conditions Chromate treatment.

· Electrolytic chromate treatment

Liquid composition: Potassium dichromate 1 to 10 g / l, zinc 0 to 5 g / l

pH: 3-4

Temperature: 50 to 60 ° C

Current density: 0.1 to 2.6 A / dm 2

Culm amount: 0.5 to 30 As / dm 2

Subsequently, an ultra-thin copper layer having a thickness of 3 占 퐉 was formed on the Cr layer by electroplating under the following conditions on a continuous plating line of roll-to-roll type (employing the drum method shown in Fig. 1) . In this embodiment, a copper foil with a carrier having a thickness of 1, 2, 5, or 10 mu m was also manufactured and evaluated in the same manner as in the example in which the thickness of the ultra-thin copper layer was 3 mu m. The results were the same regardless of thickness.

· Ultra-thin copper layer

Copper concentration: 30 ~ 120 g / ℓ

H ₂ SO ₄ concentration: 20 to 120 g / ℓ

Electrolyte temperature: 20 ~ 80 ℃

Current density: 10 to 100 A / dm 2

Subsequently, the following roughening treatment 1, roughening treatment 2, rust-proofing treatment, chromate treatment and silane coupling treatment were carried out in this order on the surface of the ultra-thin copper layer. For the harmony treatment 1 and the harmony treatment 2, a mast system using a drum shown in Fig. 1 (inter-pole distance of 50 mm) was employed, and the rustproofing treatment, the chromate treatment and the silane coupling treatment .

· Harmonization processing 1

(Liquid composition 1)

Cu: 10 to 30 g / l

H ₂ SO ₄ : 10 to 150 g / ℓ

W: 0 to 50 mg / l

Sodium dodecyl sulfate: 0 to 50 mg / l

As: 0 to 200 mg / l

(Electroplating condition 1)

Temperature: 30 ~ 70 ℃

Current density: 25 to 110 A / dm 2

Blend Coulomb amount: 50 ~ 500 As / d㎡

Plating time: 0.5 ~ 20 seconds

· Harmonization processing 2

(Liquid composition 2)

Cu: 20 to 80 g / l

H ₂ SO ₄ : 50-200 g / l

(Electroplating condition 2)

Temperature: 30 ~ 70 ℃

Current density: 5 to 50 A / dm 2

Blend Coulomb amount: 50 ~ 300 As / d㎡

Plating time: 1 ~ 60 seconds

· Antirust treatment

(Liquid composition)

NaOH: 40 to 200 g / l

NaCN: 70 to 250 g / l

CuCN: 50 to 200 g / l

Zn (CN) ₂ : 2 to 100 g / l

As ₂ O ₃ : 0.01 to 1 g / l

(Liquid temperature)

40 to 90 ° C

(Current condition)

Current density: 1 to 50 A / dm 2

Plating time: 1 ~ 20 seconds

· Chromate treatment

K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / ℓ

NaOH or KOH: 10 to 50 g / l

ZnOH or ZnSO ₄揃 7H ₂ O: 0.05 to 10 g / ℓ

pH: 7 to 13

Bath temperature: 20 ~ 80 ℃

Current density: 0.05 to 5 A / dm 2

Time: 5 ~ 30 seconds

· Silane coupling treatment

After spraying an aqueous solution of 3-glycidoxypropyltrimethoxysilane at 0.1 vol% to 0.3 vol%, it is dried and heated in air at 100 to 200 ° C for 0.1 to 10 seconds.

After the surface treatment, a resin layer of "A" described later was formed on the extremely thin copper layer side.

&Lt; Example 2 >

After the formation of a very thin copper layer on the copper foil carrier under the same conditions as in Example 1, the following Harmonizing Treatment 1, Hardening Treatment 2, rust-proofing treatment, chromate treatment and silane coupling treatment were carried out in this order. For the harmony treatment 1 and the harmony treatment 2, a mast system using a drum shown in Fig. 1 (inter-pole distance of 50 mm) was employed, and the rustproofing treatment, the chromate treatment and the silane coupling treatment . The thickness of the ultra thin copper foil was set to 3 탆.

· Harmonization processing 1

Liquid composition: copper 10 to 20 g / l, sulfuric acid 50 to 100 g / l

Solution temperature: 25 ~ 50 ℃

Current density: 1 to 58 A / dm 2

Culm volume: 4 ~ 81 As / d㎡

· Harmonization processing 2

Liquid composition: copper 10 to 20 g / l, nickel 5 to 15 g / l, cobalt 5 to 15 g / l

pH: 2-3

Temperature: 30 ~ 50 ℃

Current density: 24 ~ 50 A / dm2

Culm volume: 34 ~ 48 As / d㎡

· Antirust treatment

Liquid composition: nickel 5 to 20 g / l, cobalt 1 to 8 g / l

pH: 2-3

Solution temperature: 40 to 60 ° C

Current density: 5 to 20 A / dm 2

Culm volume: 10 ~ 20 As / d㎡

· Chromate treatment

Liquid composition: Potassium dichromate 1 to 10 g / l, zinc 0 to 5 g / l

pH: 3-4

Temperature: 50 to 60 ° C

Current density: 0 to 2 A / dm 2 (can also be performed in electroless for immersion chromate treatment)

Culm amount: 0 to 2 As / dm 2 (can also be performed in electroless for immersion chromate treatment)

· Silane coupling treatment

Application of an aqueous solution of diaminosilane (diaminosilane concentration: 0.1 to 0.5 wt%)

After the surface treatment, a resin layer of "B" described later was formed on the extremely thin copper layer side.

&Lt; Example 3 >

A long elongated electrolytic copper foil (HLP manufactured by Nikko Nisseki Kinzoku Co., Ltd.) having a thickness of 35 mu m was prepared as a copper foil carrier, and the shiny side (Rz: 0.1 to 0.3 mu m) To prepare a copper foil. However, the resin layer formed &quot; C &quot;

<Example 4>

A long elongated electrolytic copper foil (HLP manufactured by Nikko Nisseki Kikoko Co., Ltd.) having a thickness of 35 mu m was prepared as a copper foil carrier, and the shiny side (Rz: 0.1 to 0.3 mu m) To prepare a copper foil. However, the resin layer formed &quot; D &quot;

&Lt; Example 5 >

As the copper foil carrier, a long electrolytic copper foil having a thickness of 35 占 퐉 (HLP manufactured by JX Nikkisuke Kikoko Co., Ltd.) was prepared. The shiny side (Rz: 0.1 to 0.3 mu m) of this copper foil was electroplated with a roll-to-roll continuous plating line under the same conditions as in Example 1 to form an Ni layer having an adhesion amount of 4000 mu g / Subsequently, after the extremely thin copper layer was formed in the same procedure as in Example 1, the following anti-corrosive treatment (employing the passive anti-corrosive method) was carried out without the roughening treatment.

· Antirust treatment

Liquid composition: nickel 5 to 20 g / l, cobalt 1 to 8 g / l

pH: 2-3

Solution temperature: 40 to 60 ° C

Current density: 5 to 20 A / dm 2

Culm volume: 10 ~ 20 As / d㎡

After the surface treatment, a resin layer of "E" described later was formed on the extremely thin copper layer side.

&Lt; Comparative Example 1 &

After the ultra-thin copper layer was formed on the copper foil carrier under the same conditions as in Example 1, the following harmonic treatment 1, roughening treatment 2, anti-corrosive treatment, chromate treatment and silane coupling treatment were carried out in this order Respectively. For the harmony treatment 1 and the harmony treatment 2, a mast system using a drum shown in Fig. 1 (inter-pole distance of 50 mm) was employed, and the rustproofing treatment, the chromate treatment and the silane coupling treatment . The thickness of the ultra thin copper foil was set to 3 탆.

· Harmonization processing 1

(Liquid composition 1)

Cu: 31 to 45 g / l

H ₂ SO ₄ : 10 to 150 g / ℓ

As: 0.1 to 200 mg / l

(Electroplating condition 1)

Temperature: 30 ~ 70 ℃

Current density: 25 to 110 A / dm 2

Blend Coulomb amount: 50 ~ 500 As / d㎡

Plating time: 0.5 ~ 20 seconds

· Harmonization processing 2

(Liquid composition 2)

Cu: 20 to 80 g / l

H ₂ SO ₄ : 50-200 g / l

(Electroplating condition 2)

Temperature: 30 ~ 70 ℃

Current density: 5 to 50 A / dm 2

Blend Coulomb amount: 50 ~ 300 As / d㎡

Plating time: 1 ~ 60 seconds

· Antirust treatment

(Liquid composition)

NaOH: 40 to 200 g / l

NaCN: 70 to 250 g / l

CuCN: 50 to 200 g / l

Zn (CN) ₂ : 2 to 100 g / l

As ₂ O ₃ : 0.01 to 1 g / l

(Liquid temperature)

40 to 90 ° C

(Current condition)

Current density: 1 to 50 A / dm 2

Plating time: 1 ~ 20 seconds

· Chromate treatment

K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / ℓ

NaOH or KOH: 10 to 50 g / l

ZnOH or ZnSO ₄揃 7H ₂ O: 0.05 to 10 g / ℓ

pH: 7 to 13

Bath temperature: 20 ~ 80 ℃

Current density: 0.05 to 5 A / dm 2

Time: 5 ~ 30 seconds

· Silane coupling treatment

After spraying an aqueous solution of 3-glycidoxypropyltrimethoxysilane at 0.1 vol% to 0.3 vol%, it is dried and heated in air at 100 to 200 ° C for 0.1 to 10 seconds.

After the surface treatment, the resin layer was not formed.

&Lt; Comparative Example 2 &

Carrier-adhered copper foil was prepared in the same manner as in Example 1, except that the kneading process by the phrase binding process shown in Fig. 2 was employed for the roasting process 1 and the roasting process 2. [ However, no resin layer was formed.

&Lt; Comparative Example 3 &

Carrier-attached copper foil was prepared in the same manner as in Example 2, except that the kneading process by the phrase binding process shown in Fig. 2 was used for the kneading process 1 and the kneading process 2. [ However, no resin layer was formed.

&Lt; Comparative Example 4 &

A resin layer &quot; A &quot; to be described later was formed on the ultra-thin copper layer side of the copper foil with a carrier of Comparative Example 1. [

&Lt; Comparative Example 5 &

A resin layer &quot; B &quot; described later was formed on the side of the ultra-thin copper layer of the copper foil with a carrier of Comparative Example 2. [

&Lt; Comparative Example 6 >

A resin layer &quot; C &quot; to be described later was formed on the ultra-fine copper layer side of the copper foil with a carrier of Comparative Example 3. [

&Lt; Example 6 >

Carrier-adhered copper foil was prepared in the same manner as in Example 1 except that no resin layer was formed.

&Lt; Example 7 >

Carrier-attached copper foil was prepared in the same manner as in Example 2 except that no resin layer was formed.

&Lt; Example 8 >

Carrier-attached copper foil was prepared in the same manner as in Example 3 except that no resin layer was formed.

&Lt; Example 9 >

Carrier-adhered copper foil was produced in the same manner as in Example 4 except that no resin layer was formed.

&Lt; Example 10 >

Carrier-adhered copper foil was prepared in the same manner as in Example 5 except that no resin layer was formed.

&Lt; Formation of resin layer >

The formation of the resin layer was carried out as follows.

· "A"

(Resin synthesis example)

A three-liter three-necked flask equipped with a stirrer made of stainless steel, a nitrogen inlet tube and a trap equipped with a stopcock and equipped with a reflux condenser equipped with a cooling tube equipped with beads was charged with 3,4,3 ' (300 mmol) of 1,3-bis (3-aminophenoxy) benzene and 4.0 g (40 mmol) of? -Valerolactone were added to a solution of 117.68 g ), 300 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of toluene were added and the mixture was heated at 180 占 폚 for 1 hour and then cooled to room temperature Thereafter, 29.42 g (100 mmol) of 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride, 82.12 g (200 mmol) of 2,2-bis {4- (4-aminophenoxy) 200 g of NMP and 40 g of toluene were added and mixed at room temperature for 1 hour and then heated at 180 占 폚 for 3 hours to obtain a block copolymerized polyimide having a solid content of 38%. The block copolymer polyimide had the following general formula (1): general formula (2) = 3: 2, number average molecular weight: 70000, and weight average molecular weight:

(11)

The block copolymer polyimide solution obtained in Synthesis Example was further diluted with NMP to obtain a block copolymer polyimide solution having a solid content of 10%. (4-maleimidophenyl) methane (BMI-H, K-ion) was added to this block copolymer polyimide solution in a solid weight ratio of 35 and a block copolymer polyimide weight ratio of 65 (4-maleimidophenyl) methane solids weight: weight of solid content of block copolymer polyimide contained in the resin solution = 35: 65) was dissolved and mixed at 60 占 폚 for 20 minutes to prepare a resin solution. Thereafter, the resin solution was coated on the surface of the copper foil with a carrier on the surface of the copper foil before formation of the resin layer using a reverse roll coater and dried at 120 캜 for 3 minutes and at 160 캜 for 3 minutes in a nitrogen atmosphere, Finally, a heat treatment was performed at 300 캜 for 2 minutes to prepare a copper foil with a carrier. The thickness of the resin layer was set to 2 탆.

· "B"

B, resin compositions of 69 parts by weight of an epoxy resin, 11 parts by weight of a curing agent, 0.25 parts by weight of a curing accelerator, 15 parts by weight of a polymer component, 3 parts by weight of a crosslinking agent and 3 parts by weight of a rubbery resin were prepared. Specifically, it is shown below.

[Composition of resin composition]

Epoxy resin / bisphenol A type / YD-907 (manufactured by Toto Chemical) / 15 epoxy resin / bisphenol A type / YD-011 (produced by Toto Chemical Co., Ltd.) ) / 54 Hardener / aromatic amine / 4,41-diaminodiphenyl sulfone (manufactured by Wakayama Sansui) / 12

Curing accelerator / imidazole / 2E4MZ (manufactured by Shikoku Chemical) /0.4

Polymer component / polyvinyl acetal resin / 5000A (manufactured by Denki Kagaku Kogyo) / 15

Crosslinking agent / urethane resin / AP-Stable (manufactured by Nippon Polyurethane Industry Co., Ltd.) / 3

Rubber component / core shell type nitrile rubber / XER-91 (manufactured by JSR Corporation) / 3

Then, the above resin composition was adjusted to a resin solid content of 30% by weight using methyl ethyl ketone and dimethylacetamide to obtain a resin composition solution for forming a resin layer. The resin composition solution for forming the resin layer was applied to the surface of the copper foil with the carrier before the resin layer was formed on the surface of the ultra-thin copper layer using a gravure coater. Then, air drying for 5 minutes was performed, and then drying treatment was performed in a heating atmosphere of 140 占 폚 for 3 minutes to form a semi-cured resin layer (adhesive layer) having a thickness of 1.5 占 퐉 in a semi-cured state, . The resin flow of the semi-cured resin layer (adhesive layer) obtained at this time was measured by forming a semi-cured resin layer having a thickness of 40 占 퐉 on one side of a copper foil having a thickness of 18 占 퐉 with a resin composition solution for forming the resin layer, This was used as a sample for resin flow measurement. Then, four samples each having a length of 10 cm from the resin flow measurement sample were sampled, and the resin flow was measured according to the MIL-P-13949G described above. As a result, the resin flow was 1.5%.

· "C"

Thereby preparing a resin solution constituting the resin layer. In this resin solution, an epoxy resin (EPPN-502 manufactured by Nippon Yakusho Co., Ltd.) and a polyether sulfone resin (Sumika Excel PES-5003P manufactured by Sumitomo Chemical Co., Ltd.) were used as raw materials. Then, imidazole-based 2E4MZ (manufactured by Shikoku Chemical Industry Co., Ltd.) was added as a curing accelerator to the resin composition.

Resin composition: epoxy resin 50 parts by weight

Polyether sulfone resin 50 parts by weight

Curing accelerator 1 part by weight

This resin composition was further adjusted to a resin solid content of 30 wt% by using dimethylformamide to obtain a resin solution. The resin solution prepared as described above was applied to the surface of the copper foil with a carrier before the resin layer was formed on the surface of the ultra-thin copper layer using a gravure coater. Thereafter, the resultant was subjected to a drying treatment for 3 minutes in a heating atmosphere at 140 캜 to form a semi-cured resin layer having a thickness of 1.5 탆, thereby obtaining a copper foil with a carrier according to the present invention. On the other hand, for the measurement of the resin flow, a copper foil (copper foil having a thickness of 18 占 퐉) (hereinafter referred to as a "resin flow measurement sample") having a resin layer with a thickness of 40 占 퐉 was prepared. Then, four samples each having a length of 10 cm from the resin flow measurement sample were sampled, and the resin flow was measured according to the MIL-P-13949G described above. As a result, the resin flow was 1.4%.

· "D"

An example of a copper foil with a carrier using a maleimide resin for forming a polyimide resin layer as a cured resin layer and forming a semi-cured resin layer on the surface of the ultra-fine copper layer side of the copper foil with a carrier before forming the resin layer.

Preparation of polyamic acid varnish: Polyamic acid varnish for forming a cured resin layer by a casting method will be described. 1 mol of pyromellitic dianhydride and 1 mol of 4,4'-diaminodiphenyl ether were dissolved in N-methylpyrrolidone as a solvent and mixed. The reaction temperature at this time was 25 占 폚, and the reaction was carried out for 10 hours. Then, a polyamic acid varnish having a resin solid content of 20 mass% was obtained.

Formation of a cured resin layer: Next, using the obtained polyamic acid varnish, a cured resin layer was formed by a casting method. The polyamic acid varnish was applied to the surface of the copper foil with the carrier with the carrier before the resin layer was formed by a multi-coater (Mori-400 manufactured by Hiranotex Seed Co., Ltd.) under conditions of 110 占 폚 for 6 minutes in a hot-air dryer Lt; / RTI &gt; The resin thickness of the cured resin layer after drying was 35 占 퐉, and the residual solvent ratio at this stage was 32 wt% with respect to the total amount of the resin layer. The composite of the electrolytic copper foil coated with the polyamic acid varnish was placed in a hot air oven which was substituted with nitrogen, and the temperature was raised from room temperature to 400 캜 over a period of 15 minutes. Thereafter, the temperature was maintained at 400 캜 for 8 minutes and then cooled. As a result, the residual solvent is removed from the composite of the copper foil with the carrier coated with the polyamic acid, and the copper coating with the cured resin layer laminated on the surface of the ultra thin copper layer of the carrier- Thereby forming a polyimide resin base material. The solvent remaining ratio of the copper-clad polyimide resin base obtained by this final heat treatment was 0.5 wt% with respect to the total amount of the resin adhered to the copper foil with a carrier.

Next, the surface of the cured resin layer was subjected to corona treatment with a copper foil with a carrier (a copper-clad polyimide resin base) having a cured resin layer laminated thereon. The corona treatment was carried out under the conditions of electric power of 210 W, speed of 2 m / min, discharge amount of 300 W · min / m 2, and irradiation distance of 1.5 mm from the electrodes. Then, in order to measure the coefficient of thermal expansion of the cured resin layer, the copper foil with a carrier was removed from the copper foil with a carrier (a corona-treated copper-clad polyimide resin base) having the cured resin layer after the surface modification treatment laminated thereon, Respectively. As a result, the cured resin layer (polyimide film) obtained by removing the copper foil with a carrier had a resin thickness of 27 占 퐉 and a thermal expansion coefficient of 25 ppm / 占 폚.

Formation of a semi-cured resin layer: Here, a semi-cured resin layer is formed on a cured resin layer of a copper-coated polyimide resin base subjected to corona treatment. First, the resin composition shown below was dissolved by using N, N'-dimethylacetamide as a solvent to prepare a resin varnish having a resin solid content of 30 wt%.

[Resin composition for forming a semi-cured resin layer]

Maleimide resin: 4,4'-diphenylmethane bismaleimide (trade name: BMI-1000, manufactured by Daika Chemical Industry Co., Ltd.) / 30 parts by weight

Aromatic polyamine resin: 35 parts by weight of 1,3-bis [4-aminophenoxy] benzene (trade name: TPE-R, Wakayama Seiyaku Kogyo)

Epoxy resin: bisphenol A type epoxy resin (trade name: Epichron 850S, manufactured by Dainippon Ink and Chemicals, Inc.) / 20 parts by weight

Linear polymer having a crosslinkable functional group: polyvinyl acetal resin (trade name: DENKA BUTYRAL 5000A, manufactured by Denki Kagaku Kogyo) / 15 parts by weight

The resin varnish described above was applied to the polyimide resin surface of the copper-clad polyimide resin base subjected to the corona treatment, air-dried for 5 minutes at room temperature, and heated and dried under the condition of 160 占 폚 for 5 minutes, Respectively. The resin thickness of the semi-cured resin layer at this time was 20 占 퐉.

In order to measure the thermal expansion coefficient after curing of the semi-cured resin layer, the above-described resin varnish used for forming the semi-cured resin layer was applied to a fluorine heat-resistant film in the same manner as described above, Dried by heating under the conditions of 160 占 폚 for 5 minutes, and then further cured by heating at 200 占 폚 for 2 hours to form a 20 占 퐉 -thick curing resin layer for testing. That is, this test cured resin layer corresponds to the case where the semi-cured resin layer of the copper foil with a carrier according to the present invention is cured. The thermal expansion coefficient of the test cured resin layer was 45 ppm / 占 폚.

The total thickness of the resin layer of the copper foil with a carrier thus obtained was 47 占 퐉. Then, the copper foil was etched away from the copper foil to which the resin was adhered by using a method described later, and a resin layer composed of a cured resin layer and a semi-cured resin layer was used and cured by heating at 200 ° C for 2 hours, The thermal expansion coefficient of the entire resin layer after curing the semi-cured resin layer was measured. As a result, the thermal expansion coefficient was 35 ppm / 占 폚. The peel strength was 1.0 kgf / cm.

· "E"

First, a first resin composition constituting the resin layer was prepared. In the preparation of the first resin composition, a mixture of an o-cresol novolak type epoxy resin (YDCN-704 manufactured by Tohto Kasei Co., Ltd.), an aromatic polyamide resin polymer soluble in a solvent, and a cyclopentanone as a solvent BP3225-50P manufactured by Nippon Yakusho Co., Ltd. was used as a raw material. VH-4170 manufactured by Dainippon Ink and Co., Ltd. and 2E4MZ manufactured by Shikoku Chemical Co., Ltd. as a curing accelerator were added to the phenol resin as a curing agent to prepare a first resin composition having the mixing ratio shown below.

o-cresol novolak type epoxy resin 38 parts by weight

Aromatic polyamide resin polymer 50 parts by weight

Phenolic resin 18 parts by weight

Hardening accelerator 0.1 part by weight

This first resin composition was further adjusted to a resin solid content of 30% by weight by using methyl ethyl ketone to prepare a resin solution.

The surface of the copper foil with a carrier on which the resin layer was formed before the formation of the resin layer (when the surface treatment was applied to the ultra-thin copper layer, the surface treated with the copper foil) was subjected to gamma-glycidoxygenation so as to have a concentration of 5 g / Propyltrimethoxysilane was added to the solution. Then, in a furnace adjusted to an atmosphere of 180 占 폚 with an electric heater, water was blown over 4 seconds, and a condensation reaction of a silane coupling agent was carried out to form a silane coupling agent layer.

The resin solution prepared as described above was applied to the surface of the copper foil with carrier on which the silane coupling agent layer was formed by using a gravure coater. Then, air drying was carried out for 5 minutes, and then drying treatment was carried out in a heating atmosphere of 140 占 폚 for 3 minutes to form a semi-cured resin layer having a thickness of 1.5 占 퐉 to obtain a carrier- will be. Further, in the measurement of the resin flow, a copper foil (hereinafter referred to as a "resin flow measurement sample") with a resin having a primer resin layer of 40 μm thickness was produced.

Then, four samples each having a length of 10 cm from the resin flow measurement sample were sampled, and the resin flow was measured according to the MIL-P-13949G described above. As a result, the resin flow was 1.5%.

2. Characterization of copper foil with carrier

The copper foil with a carrier thus obtained was subjected to the characteristic evaluation in the following manner. The results are shown in Table 1. "3.91E-16" of "Ra" in the "standard deviation (μm) column" in Table 1 means 3.91 × 10 ^-16 (㎛), and "1.30E-02" means 1.30 × 10 ^-2 Mu m).

(Surface roughness)

From the copper foil with a carrier (square of 550 mm x 550 mm) before forming the resin layer, a straight line was drawn at a pitch of 55 mm in the longitudinal and lateral directions, and a square area of 55 mm x 55 mm was allocated to 100 points. (Ra and Rz) and JIS B0601-2001 (Rt) were measured for each area under the following measurement conditions using a contact type roughness tester (Surfcorder SE-3C manufactured by Kosaka Laboratory Co., Ltd.) The surface roughness (Ra, Rt, Rz) of the copper layer was measured, and the average value and the standard deviation thereof were measured.

<Measurement Conditions>

Cutoff: 0.25 mm

Reference length: 0.8 mm

Measuring environment Temperature: 23 ~ 25 ℃

(Migration)

Each of the copper foils with a carrier (square of 550 mm x 550 mm) before forming the resin layer was bonded to the bismuth resin, and then the carrier foil was peeled off. The thickness of the exposed ultra thin copper layer was set to 1.5 탆 by soft etching. Thereafter, after washing and drying, DF (trade name: RY-3625, manufactured by Hitachi Chemical Co., Ltd.) was laminated on the ultra-thin copper layer. (L / S) = 15 占 퐉 / 15 占 퐉 to form a resist pattern. The resist pattern was formed by using a developing solution (sodium carbonate) at 38 占 폚 for 1 minute by liquid jetting. Subsequently, after 15 탆 plating UP by using copper sulfate plating (CUBRITE21, manufactured by Ebara Corporation), DF was peeled off with a peeling liquid (sodium hydroxide). Thereafter, the extremely thin copper layer was etched away with a sulfuric acid-hydrogen peroxide-based etchant to form a wiring with L / S = 15 占 퐉 / 15 占 퐉. From the obtained wiring board, 100 wiring boards were cut out according to the area of 55 mm x 55 mm per one described above.

For each of the obtained wiring boards, the presence or absence of insulation deterioration between the wiring patterns was evaluated using a migration measuring instrument (MIG-9000 manufactured by IMV) under the following measurement conditions. The number of boards on which migration occurred on 100 wiring boards was evaluated.

Further, in Example 2, the pitch of the line-and-space is 20 占 퐉 (L / S = 8 占 퐉 / 12 占 퐉, L / S = 10 占 퐉 / 10 占 퐉 and L / S = 12 占 퐉 / 8 占 퐉) Wiring was formed to evaluate the migration described above. Further, in Example 3, the pitch of the line-and-space is 20 占 퐉 (L / S = 8 占 퐉 / 12 占 퐉, L / S = 10 占 퐉 / 10 占 퐉, L / S = 12 占 퐉 / 8 占 퐉) Wirings having a line-and-space pitch of 15 占 퐉 (L / S = 5 占 퐉 / 10 占 퐉 and L / S = 8 占 퐉 / 7 占 퐉) were formed to evaluate the migration described above. When the pitch of the line and space was 15 占 퐉, the thickness of the plating UP was 10 占 퐉. As a result, when wirings having L / S = 8 占 퐉 / 12 占 퐉, L / S = 10 占 퐉 / 10 占 퐉 and L / S = 12 占 퐉 / 8 占 퐉 were formed using the carrier-coated copper foil of Example 2, Migration incidence rates were 2/100, 2/100, and 3/100, respectively. L / S = 10 mu m / 10 mu m, L / S = 12 mu m / 8 mu m, L / S = 5 mu m / 10 mu m Μm and L / S = 8 μm / 7 μm, the in-plane migration rates were 1/100, 1/100, 2/100, 1/100, and 3/100, respectively.

<Measurement Conditions>

Threshold: 60% initial resistance down

Measuring time: 1000 h

Voltage: 60 V

Temperature: 85 ° C

Relative humidity: 85% RH

(Peel strength)

The peeling strength of the ultra-thin copper layer from the resin substrate was measured for the copper foil with a carrier on which the resin layer was formed (in the case where the resin layer was not formed, there was no resin layer). A BT substrate (bismaleimide triazine resin, GHPL-830MBT manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used as the resin substrate, and this was laminated on the resin layer side of the copper foil with a carrier, To obtain a copper clad laminate. Thereafter, after peeling off the carrier, a circuit with a width of 10 mm was produced by wet etching, and ten measurement samples were prepared for each of the examples / comparative examples. Thereafter, the ultra-thin copper layer forming the circuit was peeled off, and the 90 degree peel strength was measured for 10 samples, and the deviation, maximum value, minimum value, peel strength deviation ((maximum value-minimum value) / Average value 占 100 (%)). The BT substrate is a typical substrate for a semiconductor package substrate. The peel strength of the ultra-thin copper layer from the BT substrate when the BT substrate is laminated is preferably 0.70 kN / m or more, more preferably 0.85 kN / m or more.

Claims (33)

A carrier-coated copper foil having a carrier, a peeling layer, an ultra-thin copper layer and a maleic resin layer in this order, wherein the average value of Rz on the surface of the ultra-thin copper layer was measured by a contact- type roughness meter according to JIS B0601-1982, Mu m or less and the standard deviation of Rz is 0.1 mu m or less. The method according to claim 1,
The ultra-thin copper layer is harmonized. 3. The method according to claim 1 or 2,
The average value of Rt on the surface of the ultra-thin copper layer is 2.0 탆 or less as measured by a contact-type roughness meter in accordance with JIS B0601-2001, and the standard deviation of Rt is 0.1 탆 or less. 4. The method according to any one of claims 1 to 3,
The average value of Ra of the surface of the ultra-thin copper layer is 0.2 μm or less as measured by a contact-type roughness meter according to JIS B0601-1982, and the standard deviation of Ra is 0.03 μm or less. 5. The method according to any one of claims 1 to 4,
And the average value of Rz on the surface of the ultra-thin copper layer is 1.0 占 퐉 or less. 6. The method of claim 5,
Wherein the average value of Rz on the surface of the ultra thin copper layer is 0.5 占 퐉 or less. A carrier-bonded copper foil having a carrier, a peeling layer, an ultra-thin copper layer, and a vital resin layer in this order, wherein the average value of Rt on the surface of the ultra-thin copper layer was measured by a contact type roughness meter according to JIS B0601-2001 Mu m or less and the standard deviation of Rt is 0.1 mu m or less. 8. The method of claim 7,
The ultra-thin copper layer is harmonized. 9. The method according to claim 7 or 8,
The average value of Rz on the surface of the ultra-thin copper layer is 1.5 占 퐉 or less and the standard deviation of Rz is 0.1 占 퐉 or less as measured by a contact type illuminometer in accordance with JIS B0601-1982. 10. The method according to any one of claims 7 to 9,
The average value of Ra of the surface of the ultra-thin copper layer is 0.2 μm or less as measured by a contact-type roughness meter according to JIS B0601-1982, and the standard deviation of Ra is 0.03 μm or less. 11. The method according to any one of claims 7 to 10,
And the average value of Rt on the surface of the ultra thin copper layer is 1.0 占 퐉 or less. A carrier-coated copper foil having a carrier, a peeling layer, an ultra-thin copper layer, and a maleic resin layer in this order, wherein the average value of Ra on the surface of the ultra-violet copper layer was measured with a contact- type roughness meter according to JIS B0601-1982, Mu m or less and the standard deviation of Ra is 0.03 mu m or less. 13. The method of claim 12,
The ultra-thin copper layer is harmonized. The method according to claim 12 or 13,
The average value of Rz on the surface of the ultra-thin copper layer is 1.5 占 퐉 or less and the standard deviation of Rz is 0.1 占 퐉 or less as measured by a contact type illuminometer in accordance with JIS B0601-1982. 15. The method according to any one of claims 12 to 14,
The average value of Rt on the surface of the ultra-thin copper layer is 2.0 탆 or less as measured by a contact-type roughness meter in accordance with JIS B0601-2001, and the standard deviation of Rt is 0.1 탆 or less. 16. The method according to any one of claims 12 to 15,
Wherein the average value of Ra of the ultra-thin copper layer surface is 0.15 占 퐉 or less. A printed wiring board produced by using the copper foil with a carrier according to any one of claims 1 to 16. A printed circuit board manufactured using the copper foil with a carrier according to any one of claims 1 to 16. 18. The method of claim 17,
An insulating substrate,
And a copper circuit formed on the insulating substrate,
Wherein a circuit width of the copper circuit is less than 20 mu m and a width of a space between adjacent copper circuits is less than 20 mu m. 18. The method of claim 17,
An insulating substrate,
And a copper circuit formed on the insulating substrate,
Wherein the copper circuit has a circuit width of 17 mu m or less and a space between adjacent copper circuits has a width of 17 mu m or less. 19. The method of claim 18,
An insulating substrate,
And a copper circuit formed on the insulating substrate,
Wherein the circuit width of the copper circuit is less than 20 占 퐉 and the width of the space between adjacent copper circuits is less than 20 占 퐉. 19. The method of claim 18,
An insulating substrate,
And a copper circuit formed on the insulating substrate,
Wherein the copper circuit has a circuit width of 17 mu m or less and a space between adjacent copper circuits has a width of 17 mu m or less. 18. The method of claim 17,
Wherein the pitch of the line and space is less than 40 占 퐉. 18. The method of claim 17,
And the pitch of the line and space is 34 占 퐉 or less. 19. The method of claim 18,
Wherein the pitch of the line and space is less than 40 占 퐉. 19. The method of claim 18,
Wherein the pitch of the line and space is 34 占 퐉 or less. A copper clad laminate produced by using the copper foil with a carrier according to any one of claims 1 to 16. A method for manufacturing a semiconductor device, comprising the steps of: preparing the copper foil with a carrier according to any one of claims 1 to 16 and an insulating substrate;
A step of laminating the copper foil with a carrier and an insulating substrate,
After the step of laminating the carrier-bonded copper foil with the insulating substrate and the step of peeling the carrier of the carrier-coated copper foil, a copper clad laminate is formed,
And then forming a circuit by any one of a semi-additive method, a subtractive method, a padyly additive method, and a modified semi-additive method. Forming a circuit on the surface of the ultra thin copper layer side of the copper foil with a carrier according to any one of claims 1 to 16,
A step of forming a resin layer on the extremely thin copper layer side surface of the copper foil with a carrier so that the circuit is buried,
A step of forming a circuit on the resin layer,
A step of peeling the carrier after the circuit is formed on the resin layer, and
Exposing a circuit embedded in the resin layer formed on the extremely thin copper layer side surface by removing the extremely thin copper layer after peeling the carrier. 30. The method of claim 29,
Wherein the step of forming a circuit on the resin layer comprises a step of forming a circuit by using a copper foil with a carrier adhered to the resin layer by stacking another copper foil with a carrier on the resin layer from the ultra- (Method for manufacturing a wiring board). 31. The method of claim 30,
The method for producing a printed wiring board according to any one of claims 1 to 16, wherein the other copper-bonded copper bonded onto the resin layer is a copper-coated copper with a carrier. 32. The method according to any one of claims 29 to 31,
Wherein the step of forming a circuit on the resin layer is carried out by any one of a semi-additive method, a subtractive method, a pattern additive method, and a modified semi-additive method. 33. The method according to any one of claims 29 to 32,
Further comprising a step of forming a substrate on a carrier-side surface of the copper foil with a carrier before peeling off the carrier.

Images