TWI523756B - Attached copper foil - Google Patents

Description

Carrier copper foil

The present invention relates to a copper foil with a carrier. More specifically, the present invention relates to a carrier-attached copper foil used as a material of a printed wiring board for fine pattern use.

Printed wiring boards have grown tremendously in the past half century and are now used in almost all electronic machines. In recent years, as the demand for miniaturization and high performance of electronic equipment has increased, the high-density mounting of components and the high-frequency of signals have been gradually advanced, and the conductor pattern has been required to be miniaturized (fine pitch). In the case where an IC chip is mounted on a printed wiring board in particular, it is required to have a fine pitch of L/S = 20 μm / 20 μm or less.

The printed wiring board is first fabricated into a copper foil, with a glass epoxy substrate, BT resin (bismaleimide-triazine resin, bismaleimide-triazine resin A copper-clad laminate in which an insulating substrate such as a polyimide film is bonded. The bonding method is a method in which an insulating substrate is laminated on a copper foil and heated and pressurized (lamination method), or a varnish as a precursor of an insulating substrate material is applied onto a surface of a coating layer having a copper foil. A method of heating to harden it (casting method).

With the fine pitch, the thickness of the copper foil used in the copper clad laminate is also 9 μm, further 5 μm or less, that is, the foil thickness is gradually reduced. However, when the foil thickness is 9 μm or less, the workability in forming the copper clad laminate by the above lamination method or casting method is extremely deteriorated. Therefore, there has been a copper foil with a carrier on which a metal foil having a certain thickness is used as a carrier and an extremely thin copper layer is formed thereon via a peeling layer. The usual method of using the carrier copper foil is to bond the surface of the ultra-thin copper layer. After the thermocompression bonding is performed on the insulating substrate, the carrier is peeled off via the release layer.

As a technique for attaching a carrier copper foil, for example, Patent Document 1 discloses a method of sequentially forming a diffusion prevention layer, a release layer, and a copper plating layer on a surface of a carrier, and using a Cr or Cr hydrated oxide layer as a release layer. A simple substance or alloy of Ni, Co, Fe, Cr, Mo, Ta, Cu, Al, P is used as the diffusion preventing layer, thereby maintaining good peelability after heat pressing.

Further, it is known that the release layer is formed of Cr, Ni, Co, Fe, Mo, Ti, W, P or alloys thereof or such hydrates. Further, in Patent Documents 2 and 3, in order to stabilize the peeling property in a high-temperature use environment such as heat pressing, it is effective to provide Ni, Fe or an alloy layer on the base of the release layer.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-022406

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-006071

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-007937

For the copper foil with a carrier, it is necessary to prevent the ultra-thin copper layer from being peeled off from the carrier before the step of laminating the insulating substrate. On the other hand, it is necessary to peel the ultra-thin copper layer from the carrier after the step of laminating the insulating substrate. Further, in the case of the copper foil with a carrier, the presence of pinholes on the surface of the extremely thin copper layer side may result in poor performance of the printed wiring board, which is not preferable.

Regarding these aspects, the prior art has not been fully studied and there is still room for improvement. Accordingly, an object of the present invention is to provide a copper foil with a carrier which may be peeled off from the carrier before the step of laminating the insulating substrate, and which may be peeled off after the step of laminating the insulating substrate. A problem of the present invention is to provide a method for suppressing the side surface of an extremely thin copper layer. A carrier copper foil produced by pinholes.

In order to achieve the above object, the inventors have conducted intensive research and found that it is extremely effective to use copper foil as a carrier to form an intermediate layer between the ultra-thin copper layer and the carrier, and nickel in the order from the copper foil carrier side. Forming the intermediate layer with molybdenum or cobalt or molybdenum-cobalt alloy; controlling the adhesion amount of nickel, molybdenum and cobalt; and controlling nickel, molybdenum and cobalt of the surface portion of the intermediate layer when the intermediate layer/very thin copper layer is peeled off Atomic concentration. Further, it was found that the insulating film was thermocompression bonded to the ultra-thin copper layer to control the concentration of nickel, molybdenum, and cobalt atoms in the surface portion of the intermediate layer when the carrier was peeled off from the ultra-thin copper layer.

The present invention is based on the above findings, and a side is a copper foil with a carrier, which has a copper foil carrier, an intermediate layer, and an extremely thin copper layer, and the intermediate layer sequentially deposits nickel and molybdenum. Or cobalt or a molybdenum-cobalt alloy. In the above intermediate layer, the adhesion amount of nickel is 1000 to 40000 μg/dm ² , and in the case of containing molybdenum, the adhesion amount of molybdenum is 50 to 1000 μg/dm ² , in the case of containing cobalt. When the adhesion amount of cobalt is 50 to 1000 μg/dm ² , when peeling between the intermediate layer/very thin copper layer, the depth direction obtained by analyzing the depth direction from the surface using XPS (x: unit) The atomic concentration (%) of nickel in nm is set to g(x), the atomic concentration (%) of copper is h(x), and the total atomic concentration (%) of molybdenum is i(x), and cobalt is used. The atomic concentration (%) is set to j (x), the atomic concentration (%) of oxygen is k (x), the atomic concentration (%) of carbon is set to 1 (x), and other atomic concentrations (%) ) is set to m(x), the interval in the depth direction analysis from the surface of the above intermediate layer [0.0, 4.0], ∫i(x)dx/(∫g(x)dx+∫h(x)dx+∫i (x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) or ∫j(x )dx/(∫g(x)dx+∫h(x)dx+∫i(x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) is 20% ~80%, at [4.0,12.0],∫g(x)dx/(∫g(x)dx+∫h(x)dx+∫i(x)dx+∫j(x)dx+∫k(x)dx+∫ l(x)dx+∫m(x)dx) satisfies 40% or more.

Another aspect of the present invention is a method for producing a copper foil with a carrier, comprising: forming a molybdenum layer or a cobalt layer on the nickel layer by forming a nickel layer by dry plating or wet plating on a copper foil carrier or a step of forming an intermediate layer by a molybdenum-cobalt layer; and a step of forming an extremely thin copper layer on the intermediate layer by electroplating.

Another aspect of the present invention is a printed wiring board produced by using the copper foil with a carrier of the present invention.

Another aspect of the invention is a printed circuit board manufactured using the carrier-attached copper foil of the present invention.

Another aspect of the present invention is a copper clad laminate which is produced using the copper foil with a carrier of the present invention.

Another aspect of the present invention is a method of manufacturing a printed wiring board, comprising: preparing a copper foil with a carrier of the present invention and an insulating substrate; and stacking the copper foil with the insulating substrate; and attaching the above After the carrier copper foil is laminated with the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier of the carrier-attached copper foil, and thereafter, by semi-additive method, subtractive method, partial addition method or modified half-addition The method of forming a circuit by any of the Modified Semi Additives.

Another aspect of the present invention is a method of manufacturing a printed wiring board, comprising: forming a circuit on a side surface of the ultra-thin copper layer of the copper foil with a carrier of the present invention; and burying the above-mentioned circuit in the copper carrier a step of forming a resin layer on the side surface of the ultra-thin copper layer of the foil; a step of forming a circuit on the resin layer; a step of peeling off the carrier after forming a circuit on the resin layer; and removing the pole after peeling off the carrier The thin copper layer is formed by exposing a circuit buried in the resin layer on the side surface of the ultra-thin copper layer.

The copper foil with carrier of the present invention has a high adhesion force between the carrier and the ultra-thin copper layer before the lamination step to the insulating substrate, and on the other hand, the adhesion between the carrier and the ultra-thin copper layer after the lamination step to the insulating substrate is lowered. Further, peeling can be easily performed at the interface of the carrier/very thin copper layer, and the occurrence of pinholes on the side surface of the extremely thin copper layer can be satisfactorily suppressed.

Fig. 1 is a schematic view showing a cross section of a wiring board in a step of circuit plating and removal of a photoresist in a specific example of a method of manufacturing a printed wiring board with a copper foil with a carrier of the present invention.

Fig. 2 is a cross-sectional view of the wiring board in the step from the self-laminated resin and the second-layer carrier-attached copper foil to the laser opening in the specific example of the method for producing a printed wiring board with a copper foil with a carrier of the present invention; schematic diagram.

Fig. 3 is a schematic view showing a cross section of the wiring board in the step from the formation of the via filler to the peeling of the first carrier, in a specific example of the method for producing a printed wiring board with a copper foil with a carrier of the present invention.

Fig. 4 is a schematic view showing a cross section of a wiring board in a step from rapid etching to a step of forming a bump or a copper pillar in a specific example of a method of manufacturing a printed wiring board with a copper foil with a carrier of the present invention.

Fig. 5 is a view showing an XPS depth profile in the depth direction of the surface of the intermediate layer before bonding of the substrate of Example 5.

Fig. 6 is a schematic view for explaining an integration method of atomic concentration.

Fig. 7 is a schematic view showing a sample sheet of the XPS measurement region of the example.

<1. Carrier>

Copper foil is used as a carrier which can be used in the present invention. Typically, the support is provided in the form of a rolled copper foil or an electrolytic copper foil. Usually, the electrolytic copper foil is produced by electroplating copper from a copper sulfate plating bath on a titanium or stainless steel drum, and the rolled copper foil is repeatedly produced by plastic working and heat treatment using a calender roll. As the material of the copper foil, in addition to high-purity copper such as refined copper or oxygen-free copper, for example, Sn-doped copper, Ag-doped copper, a copper alloy to which Cr, Zr, or Mg is added, or Ni, Si, or the like may be used. A copper alloy such as a copper alloy. In addition, in the present specification, when the term "copper foil" is used alone, the meaning of the copper alloy foil is also included. The copper alloy foil may contain 0 mass% or more and 50 mass% or less, and may contain 0.0001 mass% or more and 40 mass% or less, and may contain 0.0005 mass% or more and 30 mass% or less, and may contain 0.001 mass% or more. And 20mass% or less.

The thickness of the carrier which can be used in the present invention is not particularly limited, and may be appropriately adjusted to a suitable thickness in addition to the action as a carrier, and may be, for example, 12 μm or more. However, if the thickness is too large, the production cost is increased. Therefore, it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically 12 to 70 μm, more typically 18 to 35 μm.

<2. Middle layer>

An intermediate layer is provided on the copper foil carrier. Other layers may also be provided between the copper foil carrier and the intermediate layer. Preferably, the intermediate layer is formed by sequentially depositing nickel, a molybdenum or cobalt or a molybdenum-cobalt alloy on a copper foil carrier. Generally, the adhesion between nickel and copper is higher than the adhesion between molybdenum or cobalt and copper, so that when the ultra-thin copper layer is peeled off, the interface between the ultra-thin copper layer and the molybdenum or cobalt or molybdenum-cobalt alloy is peeled off. Further, for the nickel of the intermediate layer, it is expected to prevent the barrier effect of the copper component from diffusing from the carrier to the extremely thin copper layer.

In the case of using an electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on a glossy surface from the viewpoint of reducing pinholes.

When the molybdenum or cobalt or molybdenum-cobalt alloy layer in the intermediate layer is present thinly at the interface of the ultra-thin copper layer, the ultra-thin copper layer may not be peeled off from the carrier before the lamination step to the insulating substrate, and on the other hand, After the step of laminating the insulating substrate, the ultra-thin copper layer can be peeled off from the carrier, so Better. When the nickel layer is not provided and the molybdenum or cobalt or molybdenum-cobalt alloy layer is present at the boundary between the carrier and the ultra-thin copper layer, the peeling property is hardly improved, and the layer is directly formed without the molybdenum or cobalt or molybdenum-cobalt alloy layer. In the case where the nickel layer and the ultra-thin copper layer are laminated, as the peeling strength of the nickel in the nickel layer is too strong or too weak, a suitable peel strength cannot be obtained.

Further, when a layer of molybdenum or cobalt or a molybdenum-cobalt alloy is present at the boundary between the support and the nickel layer, when the ultra-thin copper layer is peeled off, the intermediate layer is also peeled off, that is, peeling occurs between the carrier and the intermediate layer. Poor. This condition occurs not only when a molybdenum or cobalt or molybdenum-cobalt alloy layer is provided at the interface with the carrier, but also when a molybdenum or cobalt or molybdenum-cobalt alloy layer is provided at the interface with the ultra-thin copper layer. Too much will happen. This is considered to be because copper and nickel are easily dissolved in the solid state. Therefore, if these contacts are made, the adhesion force is increased by mutual diffusion, and the adhesion is less likely to occur. On the other hand, since molybdenum or cobalt and copper are not easily dissolved, it is difficult to form. Interdiffusion occurs, so that the interface between the molybdenum or cobalt or molybdenum-cobalt alloy layer and the copper is weak and easy to peel off. Further, when the amount of nickel in the intermediate layer is insufficient, only a trace amount of molybdenum or cobalt is present between the carrier and the ultra-thin copper layer, so that the two are in close contact with each other and become difficult to peel off.

The intermediate layer of nickel and cobalt or molybdenum-cobalt alloy can be formed by wet plating such as electroplating, electroless plating, and immersion plating, or dry plating such as sputtering, CVD, and PDV. Further, molybdenum can be formed only by dry plating such as CVD or PDV. From the viewpoint of cost, electroplating is preferred.

In the intermediate layer, the adhesion amount of nickel is 1000 to 40000 μg/dm ² , the adhesion amount of molybdenum is 50 to 1000 μg/dm ² , and the adhesion amount of cobalt is 50 to 1000 μg/dm ² . There is a tendency to increase the amount of pinholes with the amount of nickel, but if it is within this range, the number of pinholes is also suppressed. The nickel adhesion amount is preferably 5,000 to 20,000 μg/dm ² , and more preferably 7,500 to 15,000 μg/dm ^{2 from} the viewpoint of uniformly peeling off the ultra-thin copper layer and suppressing pinholes. The molybdenum adhesion amount is preferably 80 to 600 μg/dm ² , more preferably 100 to 400 μg/dm ² . The cobalt adhesion amount is preferably 80 to 600 μg/dm ² , more preferably 100 to 400 μg/dm ² .

<3. Impact plating>

An extremely thin copper layer is provided on the intermediate layer. Prior to this, in order to reduce the pinhole of the extremely thin copper layer, impact plating using a copper-phosphorus alloy was performed. Examples of the impact plating include a copper pyrophosphate plating solution.

<4. Very thin copper layer>

An extremely thin copper layer is provided on the intermediate layer. Other layers may be provided between the intermediate layer and the ultra-thin copper layer. Preferably, the ultra-thin copper layer can be formed by electroplating using an electrolytic bath of copper sulfate, copper pyrophosphate, copper sulfonate, copper cyanide or the like, and can be used at a high current density using a conventional electrolytic copper foil. In terms of forming a copper foil, a copper sulfate bath is preferred. The thickness of the ultra-thin copper layer is not particularly limited, and is usually thinner than the carrier, for example, 12 μm or less. Typically it is from 0.5 to 12 μm, more typically from 2 to 5 μm.

<5. Roughening treatment and other surface treatments>

The surface of the ultra-thin copper layer may be provided with a roughened layer by performing a roughening treatment, for example, in order to improve the adhesion to the insulating substrate. The roughening treatment can be carried out, for example, by forming roughened particles using copper or a copper alloy. The roughening process can be fine. The roughening treatment layer may be a simple substance selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc, or a layer composed of any one or more alloys. . Further, after the roughened particles are formed of copper or a copper alloy, a roughening treatment of providing secondary particles or tertiary particles by using a simple substance such as nickel, cobalt, copper or zinc or an alloy may be carried out. Thereafter, a heat-resistant layer or a rust-preventing layer may be formed using a single substance or an alloy of nickel, cobalt, copper or zinc, and the surface may be subjected to a treatment such as chromate treatment or decane coupling treatment. Alternatively, the heat-resistant layer or the rust-preventive layer may be formed of a simple substance such as nickel, cobalt, copper or zinc or an alloy without performing the roughening treatment, and the surface may be subjected to a treatment such as chromate treatment or decane coupling treatment. In other words, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer may be formed on the surface of the roughened layer, or may be formed in an extremely thin copper layer. One or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer are formed on the surface. Further, the heat-resistant layer, the rust-preventive layer, the chromate-treated layer, and the decane coupling treatment layer may each be formed of, for example, two or more layers and three or more layers.

As the heat-resistant layer and the rust-preventing layer, a known heat-resistant layer or rust-preventing layer can be used. For example, the heat resistant layer and/or the rustproof layer may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron. a layer of one or more elements in the group of bismuth, or may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum A metal layer or an alloy layer composed of one or more elements of a group of elements, iron, and lanthanum. Moreover, the heat-resistant layer and/or the rust-preventing layer may further comprise a component selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum. Oxides, nitrides, and tellurides of one or more elements in the group of iron and antimony. Further, the heat-resistant layer and/or the rust-preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and/or the rust-preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50% by weight to 99% by weight of nickel, and 50% by weight to 1% by weight of zinc, in addition to unavoidable impurities. The nickel-zinc alloy layer may have a total adhesion amount of zinc to nickel of 5 to 1000 mg/m ² , preferably 10 to 500 mg/m ² , preferably 20 to 100 mg/m ² . Further, the ratio of the adhesion amount of nickel to the nickel-zinc alloy layer or the nickel-zinc alloy layer to the adhesion amount of zinc (=the adhesion amount of nickel/the adhesion amount of zinc) is preferably 1.5 to 10. Further, the adhesion amount of the nickel-containing zinc alloy layer or the 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 . When the heat-resistant layer and/or the rust-preventing layer is a layer containing a nickel-zinc alloy, when the inner wall portion of the through hole or the guide hole or the like is brought into contact with the degreasing liquid, the interface between the copper foil and the resin substrate is not easily In addition to corrosion of the slag liquid, the adhesion between the copper foil and the resin substrate is improved.

For example, the heat-resistant layer and/or the rust-preventing layer may be a nickel or nickel alloy layer having a deposition amount of 1 mg/m ² to 100 mg/m ² , preferably 5 mg/m ² to 50 mg/m ² , and the adhesion amount is The tin alloy layer of 1 mg/m ² to 80 mg/m ² , preferably 5 mg/m ² to 40 mg/m ² , may be any of nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt. A composition. Further, the heat-resistant layer and/or the rust-preventive layer preferably have a total adhesion amount of nickel or a nickel alloy to tin of 2 mg/m ² to 150 mg/m ² , more preferably 10 mg/m ² to 70 mg/m ² . Further, the heat-resistant layer and/or the rust-preventive layer are preferably [the amount of nickel deposited in the nickel or nickel alloy] / [the amount of tin adhesion] = 0.25 to 10, more preferably 0.33 to 3. When the heat-resistant layer and/or the rust-preventing layer are used, the copper foil with a carrier is processed into a printed wiring board, and the peeling strength of the circuit, the chemical-resistant deterioration rate of the peeling strength, and the like are improved.

Further, as the decane coupling agent used for the decane coupling treatment, a known decane coupling agent may be used, and for example, an amine decane coupling agent, an epoxy decane coupling agent or a decyl decane coupling agent may be used. Further, as the decane coupling agent, vinyl trimethoxy decane, vinyl phenyl trimethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ-glycidoxy propyl trimethoxy group can also be used. Decane, 4-glycidylbutyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, N- 3-(4-(3-Aminopropyloxy)butoxy)propyl-3-aminopropyltrimethoxydecane, imidazolium, three Decane, γ-mercaptopropyltrimethoxydecane, and the like.

The decane coupling treatment layer can be formed using a decane coupling agent such as epoxy decane, amino decane, methacryloxy decane or decyl decane. Further, such a decane coupling agent may be used in combination of two or more kinds. Among them, it is preferred to use an amine decane coupling agent or an epoxy decane coupling agent.

The amino decane coupling agent herein may be selected from the group consisting of N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-(N-styrylmethyl-2-amine Ethylethylamino)propyltrimethoxydecane, 3-aminopropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, aminopropyl Trimethoxydecane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxydecane, N-(3-propenyloxy-2-hydroxypropyl)-3- Aminopropyltriethoxydecane, 4-aminobutyltriethoxydecane, (aminoethylaminomethyl)phenethyltrimethoxydecane, N-(2-aminoethyl- 3-aminopropyl)trimethoxynonane, N-(2-aminoethyl-3-aminopropyl)tris(2-ethylhexyloxy)decane, 6-(aminohexylaminopropyl) Trimethoxy decane, aminophenyl trimethoxy decane, 3-(1-aminopropoxy)-3,3-dimethyl-1-propenyltrimethoxydecane, 3-aminopropyl Tris(methoxyethoxyethoxy)decane, 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, ω-aminoundecyltrimethoxydecane 3-(2-N-benzylamine Ethyl aminopropyl) trimethoxy Silane, bis (2-hydroxyethyl) -3-aminopropyl triethoxysilane Silane, (N, N- diethyl-3-aminopropyl) Trimethoxydecane, (N,N-dimethyl-3-aminopropyl)trimethoxynonane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxy Decane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β-(aminoethyl) a group of -γ-aminopropyltrimethoxydecane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane The middle.

More preferably, the decane coupling treatment layer is set to 0.05 mg/m ² to 200 mg/m ² , preferably 0.15 mg/m ² to 20 mg/m ² , preferably 0.3 mg/m ² to 2.0 mg/in terms of ruthenium atom. The range of m ² . In the case of the above range, the adhesion between the base resin and the surface-treated copper foil can be further improved.

Moreover, the surface of the ultra-thin copper layer, the roughening treatment layer, the heat-resistant layer, the rust-proof layer, the decane coupling treatment layer or the chromate treatment layer may be subjected to International Publication No. WO2008/053878, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, International Publication No. WO2006/134868, Japanese Patent No. 5046927, International Publication No. WO2007/105635, Japanese Patent No. 5180815, Japanese Patent Special Open 2013 Surface treatment as described in No. -19056.

<6. With carrier copper foil>

Thus, as a preferred aspect, a copper foil with a carrier having a copper foil carrier, an intermediate layer formed on the copper foil carrier, and an extremely thin copper layer laminated on the intermediate layer is produced. The method of using the carrier copper foil itself is well known. For example, the surface of the ultra-thin copper layer can be bonded to the paper substrate phenol resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, glass cloth. - Paper composite substrate epoxy resin, glass cloth - glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, polyester film, polyimide film, fluororesin substrate, fluororesin film, etc. After the thermocompression bonding, the carrier is peeled off, and the ultra-thin copper layer next to the insulating substrate is etched into a target conductor pattern to finally produce a printed wiring board. In the case of the copper foil with carrier of the present invention, the peeling portion is mainly the interface between the intermediate layer and the extremely thin copper layer.

Further, the printed circuit board is completed by mounting electronic components on the printed wiring board. Further, when manufacturing a printed wiring board, a holder for reinforcing a carrier with a carrier copper foil may be attached to the surface of the carrier. Thereby, the operability can be further improved. Examples of the stent include an insulating substrate such as a prepreg or a resin. As the resin, the above resin layer can be used.

The copper foil with a carrier of the present invention is a nickel in the depth direction (x: unit nm) obtained by analyzing the depth direction from the surface by XPS when the intermediate layer/very thin copper layer is peeled off. The atomic concentration (%) is g(x), the atomic concentration (%) of copper is h(x), the total atomic concentration (%) of molybdenum is i(x), and the atomic concentration of cobalt (%) ), j (x), the atomic concentration (%) of oxygen is k (x), the atomic concentration (%) of carbon is 1 (x), and the other atomic concentration (%) is m ( x), the interval of the depth direction analysis from the surface of the above intermediate layer [0.0, 4.0], ∫i(x)dx/(∫g(x)dx+∫h(x)dx+∫i(x)dx+∫ j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) or ∫j(x)dx/(∫g(x)dx+∫h(x)dx+∫i(x) Dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) is 20%~80% at [4.0,12.0],∫g(x)dx/(∫g (x) dx+∫h(x)dx+∫i(x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) satisfy 40% or more.

Further, the interval [Y, Z] of the depth direction analysis from the surface of the intermediate layer means the calculation of the integral value of the concentration of each of the above elements (for example, ∫g(x)dx, ∫h(x)dx, ∫i( The integral interval of x)dx, ∫j(x)dx, ∫k(x)dx, ∫l(x)dx, ∫m(x)dx). That is, Y means the depth (nm) at which integration is started [SiO ₂ conversion], and Z means the depth (nm) of the end integration [in terms of SiO ₂ conversion].

That is, the case where the interval of the depth direction analysis from the surface of the intermediate layer is [Y, Z] means that the depth Y (nm) [SiO ₂ conversion] to the depth Z (nm) [SiO ₂ calculated from the surface of the intermediate layer is calculated. The integral value of the concentration of each element up to the conversion].

Here, the terms of SiO ₂ is meant to be only a depth of the SiO ₂ SiO ₂ in terms of the depth of sputtering of the substrate by sputtering under the sputtering time and conditions, the surface of the intermediate layer at the time of sputtering. At this time, the sputtering is performed using an ion gun attached to the apparatus. For example, so-called "in terms of SiO ₂ at a depth of 1nm" is meant to be 1nm sputtering on SiO ₂ substrate (SiO ₂ substrate of reduced thickness 1nm) plating time of sputtering and the sputtering depth under plating conditions, using an ion gun The depth at which the surface of the intermediate layer is sputtered.

Furthermore, the integral value of the concentration of each of the above elements is obtained by a trapezoidal formula.

Hereinafter, a method of integrating the concentration obtained by the trapezoidal formula will be described. Here, an example in which the atomic concentration of nickel is integrated in the section [0.0, 4.0] of the depth direction analysis from the surface of the intermediate layer will be described. Further, in order to simplify the description, a case where six points are measured in the section [0.0, 4.0] will be described as an example. Fig. 6 is a schematic view showing an integration method for explaining atomic concentration.

Fig. 6 is a graph in which the horizontal axis represents the depth x (nm) from the surface of the intermediate layer, and the vertical axis represents the nickel atom concentration (at%).

Points a, b, c, d, e, and f represent the measurement results of the nickel atom concentration at depths l, k, j, i, h, g (nm) from the surface of the intermediate layer, respectively.

As shown in Fig. 6, by XPS, the atomic concentration of nickel was measured at a specific depth (l~g) of several points from the interval [0.0, 4.0] in the depth direction analysis from the surface of the intermediate layer. Then, the area S1 of the trapezoid abk1, the area S2 of the trapezoidal bcjk, the area S3 of the trapezoidal cdij, the area S4 of the trapezoid dehi, and the area S5 of the trapezoid efgh are obtained. Further, the value of the total area of S1 to S5 is the integral value ∫g(x)dx of the atomic concentration of nickel in the section [0.0, 4.0] of the depth direction analysis from the surface of the intermediate layer. That is, ∫g(x)dx=S1+S2+S3+S4+S5 of the section [0.0, 4.0] of the depth direction analysis from the surface of the intermediate layer is calculated.

Here, for example, the area S1 of the trapezoid abk1 is represented by {(the atomic concentration of nickel of point a (at%)) + (the atomic concentration of nickel of point b (at%))}× (depth between points a and b) It is obtained by x1 (nm))/2. In the same manner, the area S2 of the trapezoidal bcjk, the area S3 of the trapezoidal cdij, the area S4 of the trapezoid dehi, and the area S5 of the trapezoid efgh are obtained.

Further, the point a is the measurement result of the nickel atom concentration closest to the depth l of the depth of 0.0 nm from the surface of the intermediate layer, and the point f is the nickel atom closest to the depth g of the depth of 4.0 nm from the surface of the intermediate layer. The measurement result of the concentration.

A preferred value of the measurement interval (x1, x2, x3, x4, x5 in Fig. 6) of each point is 0.10 to 0.30 nm (in terms of SiO ₂ ).

Therefore, in the case of the interval [0.0, 4.0], it means that the depth at which the integration starts is 0.0 nm (in terms of SiO ₂ ) (that is, the surface of the analysis object), and the depth of the integration integral is 4.0 nm (in terms of SiO ₂ ) ( Since the surface is at a depth of 4.0 nm). Similarly, in the case of the section [4.0, 12.0], the depth of the integration is 4.0 nm (in terms of SiO ₂ ) (depth from the surface of 4.0 nm), and the depth of the integrated integral is 12.0 nm (in terms of SiO ₂ conversion). ) (from the surface to a depth of 12.0 nm).

The copper foil with a carrier of the present invention is preferably a depth direction (x: unit nm) obtained by analyzing the depth direction from the surface by XPS when the intermediate layer/very thin copper layer is peeled off. The atomic concentration (%) of nickel is set to g(x), the atomic concentration (%) of copper is h(x), and the total atomic concentration (%) of molybdenum is i(x), and the atomic concentration of cobalt is determined. (%) is set to j (x), the atomic concentration (%) of oxygen is k (x), the atomic concentration (%) of carbon is set to 1 (x), and the other atomic concentration (%) is set to m(x) is the interval of the depth direction analysis from the surface of the above intermediate layer [0.0, 4.0], ∫i(x)dx/(∫g(x)dx+∫h(x)dx+∫i(x) Dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) or ∫j(x)dx/(∫g(x)dx+∫h(x)dx+∫i( x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) is 30%~60% at [4.0,12.0],∫g(x)dx/( ∫g(x)dx+∫h(x)dx+∫i(x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) satisfy 50% or more.

Here, regarding the copper foil with a carrier of the present invention, the determination of "the peeling between the intermediate layer and the ultra-thin copper layer" can be made that the atomic concentrations of nickel, molybdenum and cobalt on the side surface of the ultra-thin copper layer after peeling are respectively In the case of 50 at% or less, it is more preferable to set nickel, molybdenum and the surface of the side surface of the extremely thin copper layer after peeling. The atomic concentration of cobalt is 15 at% or less. When it is judged that the intermediate layer and the ultra-thin copper layer are peeled off when the atomic concentration is 15 at% or less, a more favorable peeling state can be observed.

Further, in the case where an extremely thin copper layer is attached to the intermediate layer side (for example, the interval in the depth direction analysis from the surface of the intermediate layer [0.0, 4.0], ∫h(x)dx/(∫g(x) ) dx + ∫ h (x) dx + ∫ i (x) dx + ∫ j (x) dx + ∫ k (x) dx + ∫ l (x) dx + ∫ m (x) dx) more than 15%; or in the atmosphere, Pressure: 20kgf/cm ² , 220 ° C × 2 hours, the insulating substrate is thermocompression bonded to the ultra-thin copper layer, when peeling between the intermediate layer/very thin copper layer, the depth from the surface of the intermediate layer Direction analysis interval [0.0,4.0], ∫h(x)dx/(∫g(x)dx+∫h(x)dx+∫i(x)dx+∫j(x)dx+∫k(x)dx+∫l (x) where dx+∫m(x)dx) exceeds 30%), the copper atom concentration is 10 at% or less, or the insulating substrate is placed in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours. When XPS analysis is performed after thermocompression bonding to an ultra-thin copper layer, the depth of the copper atom concentration of 15 at% or less is set to x=0.0 nm, and when it is peeled off between the intermediate layer/very thin copper layer, it is used. The atomic concentration (%) of nickel in the depth direction (x: unit nm) obtained from the depth direction analysis of XPS is set to g(x) ), the atomic concentration (%) of copper is h (x), the total atomic concentration (%) of molybdenum is i (x), and the atomic concentration (%) of cobalt is set to j (x), and oxygen is used. When the atomic concentration (%) is k(x), the atomic concentration (%) of carbon is 1 (x), and the other atomic concentration (%) is m (x), it can be calculated from the middle.区间i(x)dx/(∫g(x)dx+∫h(x)dx+∫i(x)dx+∫j(x)dx+∫k((), the interval of the depth direction analysis from the surface of the layer x)dx+∫l(x)dx+∫m(x)dx) or ∫j(x)dx/(∫g(x)dx+∫h(x)dx+∫i(x)dx+∫j(x)dx+∫ The value of k(x)dx+∫l(x)dx+∫m(x)dx), and [g(x)dx/(∫g(x)dx+∫h(x)dx+∫ of [4.0,12.0] The value of i(x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx).

Furthermore, in the case where it is assumed that an extremely thin copper layer is attached to the side of the intermediate layer, the self-intermediate layer Depth direction analysis of the surface The location of the shallowest (minimum depth) of the copper atom concentration of 10 at% or less is determined as the interval [0.0, 4.0] and [the depth direction analysis from the surface of the intermediate layer specified in the present invention. 4.0, 12.0] The starting point (0.0).

Further, in the case where the extremely thin copper layer is attached to the intermediate layer side, the insulating substrate is thermocompression bonded to the extremely thin copper layer in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours. In the case of performing XPS analysis, the location of the shallowest (minimum depth) of the copper atom concentration of 20 at% or less is measured in the depth direction from the surface of the intermediate layer, and the measurement from the surface of the intermediate layer as defined in the present invention is determined. The starting point (0.0) of the interval [0.0, 4.0] and [4.0, 12.0] in the depth direction analysis.

Further, the copper foil with a carrier of the present invention is preferably thermocompression bonded to an extremely thin copper layer in an atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours to allow the intermediate layer/pole. When peeling between thin copper layers, the interval in the depth direction analysis from the surface of the above intermediate layer [0.0, 4.0], ∫i(x)dx/(∫g(x)dx+∫h(x)dx+∫i( x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) or ∫j(x)dx/(∫g(x)dx+∫h(x)dx+∫ i(x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) becomes 20%~80% at [4.0,12.0],∫g(x)dx /(∫g(x)dx+∫h(x)dx+∫i(x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) becomes 40% or more.

Thus, the copper foil with carrier of the present invention is such that a certain amount or more of molybdenum or cobalt is present on the outermost surface of the intermediate layer when the intermediate layer/very thin copper layer is peeled off, and the innermost nickel concentration is higher on the outermost surface. Therefore, the occurrence of pinholes on the side surface of the ultra-thin copper layer can be satisfactorily suppressed. Moreover, the copper foil with the carrier after thermocompression bonding also has a certain amount of molybdenum or cobalt on the outermost surface of the intermediate layer when peeling between the intermediate layer/very thin copper layer, and the nickel is higher than the innermost concentration of the outermost layer. . Therefore, the occurrence of pinholes on the side surface of the ultra-thin copper layer can be satisfactorily suppressed.

The copper foil with carrier of the present invention is preferably used to peel off the intermediate layer/very thin copper layer. In the interval [0.0, 4.0] of the depth direction analysis from the surface of the above intermediate layer using XPS, ∫h(x)dx/(∫g(x)dx+∫h(x)dx+∫i(x)dx+ ∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) is 0.1 to 3%.

Further, the copper foil with a carrier of the present invention is preferably thermocompression bonded to an extremely thin copper layer in an atmosphere, at a pressure of 20 kgf/cm ² and at 220 ° C for 2 hours, so that the intermediate layer is extremely thin. When peeling between copper layers, the interval in the depth direction analysis from the surface of the above intermediate layer [0.0, 4.0], ∫h(x)dx/(∫g(x)dx+∫h(x)dx+∫i(x ) dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) becomes 0.5 to 5%.

Thus, the copper foil with a carrier of the present invention is such that a certain amount or more of copper is present inside the intermediate layer when the intermediate layer/very thin copper layer is peeled off. If the copper concentration in the intermediate layer is increased, the adhesion between the intermediate layer/very thin copper layer is increased. Therefore, the peel strength can be controlled by controlling the concentration of copper in the nickel. Further, the copper foil with the carrier after the thermocompression bonding also has a certain amount or more of copper in the intermediate layer when the copper foil carrier is peeled off from the ultra-thin copper layer. Therefore, there is an effect of preventing a decrease in the extreme peel strength after thermocompression bonding.

The current density of nickel is set higher, the electrodeposition speed per unit time is increased, and the transport speed of the carrier copper foil is accelerated, and the density of the nickel layer is lowered. If the density of the nickel layer is lowered, the copper of the carrier copper foil is easily diffused to the nickel layer, and the concentration of copper in the nickel can be controlled. Further, when the current density in the plating treatment of molybdenum and cobalt is lowered and the transport speed of the carrier copper foil is lowered, the density of the molybdenum and cobalt layers is increased. If the density of the molybdenum and cobalt layers is increased, the copper of the carrier copper foil and the nickel of the nickel layer are less likely to diffuse, and the concentrations of molybdenum and cobalt can be controlled.

Further, the copper foil with a carrier of the present invention preferably has a concentration of cobalt of the molybdenum-cobalt alloy in the intermediate layer of 20 to 80% by mass. According to this configuration, the effect of suppressing the diffusion of copper and nickel to the molybdenum-cobalt alloy layer is further enhanced, and the peel strength level after the pressure-bonding of the insulating substrate is low and stable.

Moreover, the copper foil with a carrier of the present invention may have a roughened layer on the ultra-thin copper layer, and may have a heat-resistant layer and/or a rust-proof layer on the roughened layer, and may be used in the heat-resistant layer and/or rust-proof layer. The layer has a chromate treatment layer, and a decane coupling treatment layer is provided on the chromate treatment layer.

Moreover, the copper foil with a carrier of the present invention may have a heat-resistant layer and/or a rust-proof layer on the ultra-thin copper layer, and may have a chromate-treated layer on the heat-resistant layer and/or the rust-proof layer, and may be used in the above-mentioned chromic acid. The salt treatment layer is provided with a decane coupling treatment layer.

Further, the copper foil with a carrier may be provided with a resin layer on the ultra-thin copper layer or on the roughened layer or on the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the decane coupling treatment layer. . The above resin layer may be an insulating resin layer.

Further, the order in which the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, and the decane coupling treatment layer are formed is not limited to each other, and the layers may be formed on the ultra-thin copper layer or the roughened layer in any order.

The resin layer may be a resin for subsequent use, that is, an adhesive, or an insulating resin layer which is followed by a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which the insulating resin layer can be stored in an overlapping manner even if the surface is touched with a finger, and the heat-treated reaction is caused by the heat treatment.

Further, the resin layer may contain a thermosetting resin or a thermoplastic resin. Further, 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 material, and the like. Further, as the resin layer, for example, a resin (resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, etc.) can be used. And/or a method of forming a resin layer, and forming a device: International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. Hei No. 11-5828, Japanese Patent Laid-Open Japanese Patent No. 11-140281, Japanese Patent No. 3184485, International Publication No. WO97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Special opening 2002-359444, Japanese patent special opening Japanese Patent No. 2003-304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, Japan Patent No. 4,286,060, Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent JP-A-2006-257153, JP-A-2007-326923, JP-A-2008-111169, JP-A No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, Japanese Patent Laid-Open No. 2009- No. 67029, International Publication No. WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/ 008471, Japanese Patent Laid-Open No. 2011-14727, International Publication No. WO2009/001850, International Publication No. WO2009/145179, International Publication No. WO2011/ 068157, Japanese Patent Laid-Open No. 2013-19056.

In addition, the type of the resin layer is not particularly limited, and examples thereof include a resin containing at least one selected from the group consisting of an epoxy resin, a polyimide resin, and a polyfunctional cyanide. Acid ester compound, maleic imine compound, polymaleimide compound, maleic imine resin, aromatic maleimide resin, polyvinyl acetal resin, urethane resin, poly Ether oxime (also known as polyethersulphone, polyethersulfone), polyether oxime (also known as polyethersulphone, polyethersulfone) resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubber resin, polyamine, aromatic poly Amine, polyamidoximine resin, rubber modified epoxy resin, phenoxy resin, carboxyl modified acrylonitrile-butadiene resin, polyphenylene ether, bismaleimide Resin, thermosetting polyphenylene ether resin, cyanate ester resin, acid anhydride, acid anhydride, linear polymer having crosslinkable functional group, polyphenylene ether resin, 2,2- Bis(4-cyanate phenyl)propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis(4-glycidylphenyl)propane, polyphenylene ether-cyanate resin, Alkane-modified polyamine amidoxime resin, cyanoester resin, phosphazene resin, rubber-denatured polyamidoximine resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, benzene An oxy group, a polymer epoxy resin, an aromatic polyamine, a fluororesin, a bisphenol, a block copolymer polyimine resin, and a cyanoester resin.

Further, the epoxy resin has two or more epoxy groups in its molecule, and can be used without any problem as long as it can be used for electrical or electronic materials. Further, the epoxy resin is preferably an epoxy resin obtained by epoxidizing a compound having two or more glycidyl groups in the molecule. Further, it can be used in combination: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolak type epoxy resin, cresol novolac Varnish type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenolic novolac epoxy resin, naphthalene epoxy resin, brominated bisphenol A epoxy resin, o-cresol Novolak type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, isocyanuric acid triglycidyl ester, N,N-diglycidyl aniline and other glycidylamine compounds, four a glycidyl ester compound such as hydrogen phthalic acid diglycidyl ester, a phosphorus-containing epoxy resin, a biphenyl type epoxy resin, a biphenol novolak type epoxy resin, a trishydroxyphenylmethane type epoxy resin, tetraphenylene One or two or more kinds of the group of the ethylenic epoxy resins may be used, or a hydrogenated or halogenated body of the above epoxy resin may be used.

A well-known phosphorus-containing epoxy resin can be used as the above phosphorus-containing epoxy resin. Further, the phosphorus-containing epoxy resin is preferably a derivative derived from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which has two or more epoxy groups in its molecule. The epoxy resin obtained in the form.

The epoxy resin obtained in the form of a derivative derived from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 9,10-dihydro-9-oxa- The 10-phosphaphenanthrene-10-oxide is reacted with naphthoquinone or hydroquinone to form a compound represented by the following 1 (HCA-NQ) or 2 (HCA-HQ), and then the OH group is made. The epoxy resin is reacted with an epoxy resin to form a phosphorus-containing epoxy resin.

[Chemical 1]

The phosphorus-containing epoxy resin which is the above-mentioned E component which is obtained as a raw material is preferably a compound having one or two kinds of structural formulas represented by any one of the following formulas 3 to 5. The reason for this is that the stability of the resin quality in the semi-hardened state is excellent, and the flame retardancy effect is high.

Further, as the brominated epoxy resin, a known brominated epoxy resin can be used. For example, it is preferable that the brominated epoxy resin is a mixture of one or two kinds of epoxy groups having two or more epoxy groups and having a form derived from a derivative derived from tetrabromobisphenol A. A brominated epoxy resin having a structural formula represented by the following formula and a brominated epoxy resin having a structural formula represented by Chemical Formula 7 shown below.

[Chemical 6]

As the maleic imine resin or the aromatic maleimide resin, the maleimide compound or the polymaleimide compound, a known maleic imine resin or aromatic mala can be used. A quinone imine resin or a maleic imine compound or a polymaleimide compound. For example, as a maleic imine resin or an aromatic maleic imine resin or a maleimide compound or a polymaleimide compound, 4,4'-diphenylmethane bismale can be used. Yttrium, polyphenylmethane maleimide, meta-phenyl bis-maleimide, 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 double Maleidin, 4,4'-diphenylindole, bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-double (4-horse An imine phenoxy)benzene, a polymer obtained by polymerizing the above compound with the above compound or other compound, and the like. Further, the maleic imine resin may be an aromatic maleimide resin having two or more maleimide groups in the molecule, or may have two or more maleimine in the molecule. A polymeric adduct formed by polymerizing an aromatic maleic imine resin with a polyamine or an aromatic polyamine.

As the polyamine or aromatic polyamine, a known polyamine or an aromatic polyamine can be used. For example, as the polyamine or aromatic polyamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2, can be used. 6-diaminopyridine, 4,4'-diaminodiphenylmethane, 2,2- Bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diamino-3-methyldiphenyl ether, 4,4'-diaminodiphenyl Thioether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylanthracene, bis(4-aminophenyl)phenylamine, m-xylylenediamine, p-benzene Dimethylamine, 1,3-bis[4-aminophenoxy]benzene, 3-methyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4 '-Diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2',5,5'-tetrachloro-4,4'-di Aminodiphenylmethane, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-ethyl-4-aminophenyl)propane, 2,2 - bis(2,3-dichloro-4-aminophenyl)propane, bis(2,3-dimethyl-4-aminophenyl)phenylethane, ethylenediamine and hexamethylenediamine, 2 , 2-bis(4-(4-aminophenoxy)phenyl)propane, and a polymer obtained by polymerizing the above compound with the above compound or other compound. Further, one or two or more kinds of known polyamines and/or aromatic polyamines or the above polyamines or aromatic polyamines may be used.

As the phenoxy resin, a known phenoxy resin can be used. Further, as the phenoxy resin, a compound which is synthesized by a reaction of a bisphenol and a divalent epoxy resin can be used. As the epoxy resin, a known epoxy resin and/or the above epoxy resin can be used.

As the bisphenol, a known bisphenol can be used, and bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4'-dihydroxybiphenyl, HCA (9, 10) can be used. - Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) Bisphenol obtained in the form of an adduct with an anthracene such as hydroquinone or naphthoquinone.

As the linear polymer having a crosslinkable functional group, a 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 such as a hydroxyl group or a carboxyl group which contributes to the hardening reaction of the epoxy resin. Further, the linear polymer having a crosslinkable functional group is preferably an organic solvent which is soluble in a boiling point of from 50 ° C to 200 ° C. Specific examples of the linear polymer having a functional group herein include a polyvinyl acetaldehyde resin, a phenoxy resin, a polyether oxime resin, and a polyamidoximine resin.

The above resin layer may contain a crosslinking agent. As the crosslinking agent, a known crosslinking agent can be used. For example, a urethane-based resin can be used as the crosslinking agent.

A well-known rubber resin can be used for the said rubber-type resin. For example, the above rubber resin system It is described as including natural rubber and synthetic rubber. The latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, acrylonitrile butadiene rubber, and acrylic resin. Rubber (acrylate copolymer), polybutadiene rubber, isoprene rubber, and the like. Further, when the heat resistance of the formed resin layer is ensured, it is also useful to use a heat-resistant synthetic rubber such as a nitrile rubber, a chloroprene rubber, a ruthenium rubber or a urethane rubber. In order to produce a copolymer by reacting with an aromatic polyamide resin or a polyamidoximine resin, it is preferable to provide various functional groups at both ends. In particular, it is useful for using CTBN (carboxy terminal butadiene nitrile). Further, when the acrylonitrile butadiene rubber is also a carboxyl group-modified body, an epoxy resin and a crosslinked structure can be obtained, and the flexibility of the resin layer after curing can be improved. As the carboxyl modified body, a carboxyl terminal nitrile rubber (CTBN), a carboxyl terminal butadiene rubber (CTB), or a carboxyl modified nitrile rubber (C-NBR) can be used.

As the above polyamidoximine resin, a known polyamidimide resin can be used. Further, as the polyamidoxime amide resin, for example, pyromellitic anhydride may be heated by a solvent such as N-methyl-2-pyrrolidone or/N,N-dimethylacetamide or the like. a resin obtained by using benzophenonetetracarboxylic anhydride and 3,3-dimethyl-4,4-biphenyldiisocyanate, or by N-methyl-2-pyrrolidone or/and N,N-di A solvent such as methyl acetamide is obtained by heating trimellitic anhydride, diphenylmethane diisocyanate, and carboxyl terminal acrylonitrile-butadiene rubber.

As the rubber-denatured polyamidoximine resin, a known rubber-denatured polyamidoximine resin can be used. The rubber-denatured polyamidoximine resin is obtained by reacting a polyamide amine imide resin with a rubber resin. The use of the polyamidoximine resin in a reaction with a rubber resin is carried out in order to improve the flexibility of the polyamide amidine resin itself. In other words, the polyamidoximine resin is reacted with a rubber resin, and one of the acid components (such as cyclohexanedicarboxylic acid) of the polyamidoximine resin is partially substituted with a rubber component. As the polyamidoximine resin, a known polyamidoximine resin can be used. Further, as the rubber resin, a known rubber resin or the above rubber resin can be used. For the polymerization of rubber-denatured polyamidoquinone imide resin, used to dissolve polyamidoximine resin and rubberity The solvent of the resin is preferably one or more kinds of dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylammonium, nitromethane, and nitrate. Ethylethane, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, acetonitrile, γ-butyrolactone, and the like.

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

As the fluororesin, a known fluororesin can be used. Further, as the fluororesin, for example, it is selected from, for example, PTFE (polytetrafluoroethylene (tetrafluoride)), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), and FEP (tetrafluoroethylene-hexafluoropropylene). Copolymer (tetrafluorohexafluoride), ETFE (tetrafluoroethylene-ethylene copolymer), PVDF (polyvinylidene fluoride (difluorinated)), PCTFE (polychlorotrifluoroethylene (trifluoride)), A fluororesin composed of at least one of a polyarylene, an aromatic polysulfide, and an aromatic polyether, and a fluororesin composed of a fluororesin.

Further, the resin layer may contain a resin curing agent. As the resin curing agent, a known resin curing agent can be used. For example, as the resin curing agent, an amine such as dicyanodiamine, an imidazole or an aromatic amine, a phenol such as bisphenol A or brominated bisphenol A, a phenol novolak resin, and a cresol novolak resin can be used. An anhydride such as a novolac type or a phthalic anhydride, a biphenyl type phenol type resin, or a phenol aralkyl type phenol type resin. Further, the resin layer may contain one or more kinds of the above-mentioned resin curing agents. These hardeners are especially effective for epoxy resins.

Specific examples of the above biphenyl type phenol-based resin are shown in Chemical Formula 8.

[化8]

Further, a specific example of the above phenol aralkyl type phenol resin is shown in Chemical Formula 9.

As the imidazole, a known one can be used, and examples thereof include 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, and 2-phenyl-4-methylimidazole. , 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-benzene Methyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. may be used singly or in combination.

Further, among them, an imidazole having a structural formula represented by the following formula 10 is preferably used. By using the imidazole of the structural formula represented by the chemical formula 10, the moisture absorption resistance of the resin layer in a semi-hardened state can be remarkably improved, and the long-term storage stability is excellent. The reason for this is that the imidazole is a catalyst which acts as a catalyst during curing of the epoxy resin, and functions as a reaction initiator for causing self-polymerization of the epoxy resin in the initial stage of the curing reaction.

[化10]

As the resin curing agent for the above amines, a known amine can be used. Further, as the resin curing agent for the amine, for example, the above polyamine or aromatic polyamine may be used, or an aromatic polyamine or a polyamine may be used, and the epoxy resin or the polycarboxylic acid may be used. One or two or more of the group of amine adducts obtained by acid polymerization or condensation. Further, as the resin hardener of the above amine, 4,4'-diaminodiphenylene fluorene, 3,3'-diaminodiphenylene fluorene, 4,4-diamino group is preferably used. Any one or more of biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane or bis[4-(4-aminophenoxy)phenyl]anthracene.

The above resin layer may contain a hardening accelerator. As the hardening accelerator, a known hardening accelerator can be used. For example, as the hardening accelerator, a tertiary amine, an imidazole, a urea-based hardening accelerator, or the like can be used.

The above resin layer may contain a reaction catalyst. As the reaction catalyst, a known reaction catalyst can be used. For example, as the reaction catalyst, finely pulverized ceria, antimony trioxide or the like can be used.

The acid anhydride of the above polyvalent carboxylic acid is preferably a component that functions as a curing agent for the epoxy resin. Further, the acid anhydride of the above polycarboxylic acid is preferably phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydroxyphthalic anhydride, hexahydroxyphthalic anhydride or methylhexahydroxybenzene. Dicarboxylic anhydride, ceric acid, methyl acid.

The above thermoplastic resin may be an alcoholic hydroxyl group which is polymerizable with an epoxy resin. A functional thermoplastic resin.

The above polyvinyl acetal resin may have a functional group other than a hydroxyl group and a hydroxyl group which can be polymerized with an epoxy resin or a maleimide compound. Further, the polyvinyl acetaldehyde resin may be one in which a carboxyl group, an amine group or an unsaturated double bond is introduced into the molecule.

The aromatic polyamine resin polymer is obtained by reacting an aromatic polyamide resin with a rubber resin. Here, the aromatic polyamine resin refers to a compound which is synthesized by condensation polymerization of an aromatic diamine and a dicarboxylic acid. At this time, the aromatic diamine is 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl hydrazine, m-xylylenediamine, 3,3'-diaminodi Phenyl ether and the like. Further, as the dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid or the like is used.

As the rubbery resin which can be reacted with the above aromatic polyamine resin, a known rubber resin or the above rubber resin can be used.

In order to etch the copper foil after processing the copper-clad laminate, the aromatic polyimide resin is not damaged by the undercut due to the etching solution.

Further, the resin layer may be formed with a hardened resin layer (the so-called "hardened resin layer" means a hardened resin layer) and a half from the side of the copper foil (that is, the side of the extremely thin copper layer of the carrier copper foil). A resin layer that hardens the resin layer. The hardened resin layer may be composed of any of a resin component having a thermal expansion coefficient of 0 ppm/° C. to 25 ppm/° C., a polyamidimide resin, and a composite resin.

Further, a semi-hardened resin layer having a thermal expansion coefficient after curing of from 0 ppm/° C. to 50 ppm/° C. may be provided on the cured resin layer. Further, the thermal expansion coefficient of the entire resin layer obtained by curing the cured resin layer and the semi-cured resin layer may be 40 ppm/° C. or less. The glass transition temperature of the above-mentioned cured resin layer may be 300 ° C or more. Further, the semi-cured resin layer may be formed by using a maleic imide resin or an aromatic maleic imine resin. The resin composition for forming the semi-cured resin layer is preferably a linear polymer comprising a maleic imide resin, an epoxy resin, and a functional group capable of crosslinking. Epoxy resin can use well-known epoxy resin or in this specification The epoxy resin is described. Further, as the linear polymer of the maleic imine resin, the aromatic maleic imine resin, and the functional group capable of crosslinking, a known maleic imine resin or aromatic mala can be used. An imide resin, a linear polymer having a crosslinkable functional group, or a maleic imine resin, an aromatic maleimide resin, or a linear polymer having a crosslinkable functional group.

Further, in the case of providing a copper foil with a carrier layer having a resin layer suitable for the production of a three-dimensionally formed printed wiring board, the cured resin layer is preferably a cured polymer layer having flexibility. The polymer polymer layer is preferably composed of a resin having a glass transition temperature of 150 ° C or higher in order to withstand the solder mounting step. The polymer layer is preferably composed of a polyamide resin, a polyether oxime resin, an aromatic polyamide resin, a phenoxy resin, a polyimide resin, a polyvinyl acetaldehyde resin, or a polyamidimide. Any one or two or more kinds of mixed resins of the resin. Further, the thickness of the polymer layer is preferably from 3 μm to 10 μm.

In addition, the polymer layer may be one or more selected from the group consisting of an epoxy resin, a maleimide resin, a phenol resin, and a urethane resin. Further, the semi-cured resin layer is preferably composed of an epoxy resin composition having a thickness of 10 μm to 50 μm.

Moreover, it is preferable that the epoxy resin composition contains each component of the following A component to E component.

Component A: one of a group of bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol AD type epoxy resins selected from the group consisting of liquid bisphenol A type epoxy resins selected from room temperature. Or two or more types of epoxy resins.

Component B: High heat resistant epoxy resin.

Component C: a phosphorus-containing flame retardant resin which is one of a phosphorus-containing epoxy resin and a phosphazene-based resin or a resin obtained by mixing the same.

Component D: A rubber-denatured polyamidoximine resin which is denatured by a liquid rubber component having a property of being soluble in a solvent having a boiling point of 50 ° C to 200 ° C.

Component E: Resin hardener.

The component B is a "high heat-resistant epoxy resin" in which the glass transition point Tg is high. The "high heat resistant epoxy resin" as used herein is preferably a polyfunctional epoxy such as a novolak type epoxy resin, a cresol novolac type epoxy resin, a phenol novolak type epoxy resin, or a naphthalene type epoxy resin. Resin.

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

As the rubber-denatured polyamidoximine resin of the component D, the above rubber-denatured polyamidoximine resin can be used. As the resin curing agent of the component E, the above-mentioned resin curing agent can be used.

A solvent is added to the resin composition shown above as a resin varnish, and a thermosetting resin layer is formed as an adhesive layer of a printed wiring board. The resin varnish is prepared by adding a solvent to the resin composition, and preparing the resin solid content in a range of 30% by weight to 70% by weight. When measured according to MIL-P-13949G in the MIL standard, the resin flow amount is 5 A semi-hardened resin film in the range of % to 35%. As the solvent, a known solvent or the above solvent can be used.

The resin layer is a resin layer having a first thermosetting resin layer and a second thermosetting resin layer on the surface of the first thermosetting resin layer, and a first thermosetting resin layer. The second thermosetting resin layer may be formed by using a resin component which is insoluble in the chemical treatment of the desmear process in the wiring board manufacturing process, and the second thermosetting resin layer may be a degumming residue which is soluble in the wiring board manufacturing process. The chemical formed by the treatment and the resin formed by washing and removing. The first thermosetting resin layer may be formed by using any one or two or more kinds of resin components in which a polyimine resin, a polyether oxime, or a polyphenylene ether is mixed. The second thermosetting resin layer may be formed by using an epoxy resin component. The thickness t1 (μm) of the first thermosetting resin layer is preferably such that the roughened surface roughness of the copper foil with a carrier is Rz (μm) and the thickness of the second thermosetting resin layer is t2 ( In the case of μm), t1 satisfies the thickness of the condition of Rz < t1 < t2.

The above resin layer may be a prepreg impregnated with a resin in a skeleton material. The resin impregnated in the above skeleton material is preferably a thermosetting resin. The above prepreg may also be a known prepreg A prepreg used in the manufacture of a body or printed wiring board.

The above skeleton material may contain an aromatic polyamide fiber or a glass fiber or a wholly aromatic polyester fiber. The above skeleton material is preferably a non-woven fabric or a woven fabric of an aromatic polyamide fiber or a glass fiber or a wholly aromatic polyester fiber. Further, the wholly aromatic polyester fiber is preferably a wholly aromatic polyester fiber having a melting point of 300 ° C or higher. The wholly aromatic polyester fiber having a melting point of 300 ° C or higher is a fiber produced by using a resin called a liquid crystal polymer, and the liquid crystal polymer is 2-hydroxy-6-naphthoic acid and p-hydroxy group. The benzoic acid polymer is the main component. Since the wholly aromatic polyester fiber has a low dielectric constant and a low dielectric loss tangent, it has excellent performance as a constituent material of the electrical insulating layer, and can be used in the same manner as glass fibers and aromatic polyamide fibers.

Further, in order to improve the wettability of the resin on the surface thereof, the fibers constituting the nonwoven fabric and the woven fabric are preferably subjected to a decane coupling agent treatment. In the decane coupling agent at this time, a known amide coupling agent such as an amine group or an epoxy group or the above decane coupling agent may be used depending on the purpose of use.

Further, the prepreg may be impregnated with a thermosetting resin in a skeleton material comprising a non-woven fabric of an aromatic polyamide fiber or a glass fiber having a nominal thickness of 70 μm or less or a glass cloth having a nominal thickness of 30 μm or less. a prepreg.

(In the case where the resin layer contains a dielectric (dielectric filler))

The above resin layer may contain a dielectric (dielectric filler).

In the case where a dielectric (dielectric filler) is contained in any of the above resin layers or resin compositions, it can be used for the purpose of forming a capacitor layer, and the capacitance of the capacitor circuit is increased. The dielectric (dielectric filler) is BaTiO ₃ , SrTiO ₃ , Pb(Zr-Ti)O ₃ (commonly known as PZT), PbLaTiO ₃ -PbLaZrO (commonly known as PLZT), and SrBi ₂ Ta ₂ O ₉ (commonly known as SBT). A dielectric powder having a composite oxide having a perovskite structure.

The dielectric (dielectric filler) can be in powder form. When the dielectric (dielectric filler) is in the form of a powder, the powder characteristics of the dielectric (dielectric filler) must first be the particle size. It is preferably in the range of 0.01 μm to 3.0 μm, preferably 0.02 μm to 2.0 μm. The term "particle size" as used herein refers to an indirect measurement in which the average particle diameter is estimated based on the measured values such as the laser diffraction scattering type particle size distribution measurement method or the BET method. The average particle diameter obtained by directly observing a dielectric (dielectric filler) by a scanning electron microscope (SEM) and analyzing the SEM image is impossible because it is inferior in accuracy. In this specification, the particle size at this time is expressed as DIA. In addition, the image analysis of the powder of the dielectric (dielectric filler) observed using a scanning electron microscope (SEM) in this specification is IP-1000PC manufactured by Asahi Engineering Co., Ltd., and is rounded. The average particle diameter DIA was determined by performing a circular particle analysis with a threshold value of 10 and an overlap degree of 20.

According to the embodiment described above, the following carrier copper foil can be provided, which can improve the adhesion between the inner layer circuit surface of the inner core material and the dielectric layer containing the dielectric, and has a lower content for inclusion. The dielectric loss is tangent to the resin layer of the dielectric of the capacitor circuit layer.

The resin and/or resin composition and/or compound contained in the above resin layer is dissolved in, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N -methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl stilbene, N-methyl-2- A resin liquid (resin varnish) is prepared by a solvent such as pyrrolidone, N,N-dimethylacetamide or N,N-dimethylformamide, and is coated by, for example, a roll coating method. On the ultra-thin copper layer or the heat-resistant layer, the rust-preventive layer, or the chromate-treated layer or the decane coupling agent layer, the solvent is removed by heating and drying as needed to form a B-stage state. The drying system may be, for example, a hot air drying oven, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The solvent is used to dissolve the composition of the above resin layer to obtain a resin solid content of 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. Further, from the viewpoint of the environment, it is most preferable to use a mixed solvent of methyl ethyl ketone and cyclopentanone for dissolution at this stage. Further, the solvent is preferably a solvent having a boiling point of from 50 ° C to 200 ° C.

Moreover, it is preferable that the resin layer is a semi-hardened resin film in the range of 5% to 35% of the resin flow amount measured according to MIL-P-13949G in the MIL standard.

In the present specification, the amount of resin flow refers to four pieces of 10 cm square samples taken from a resin-attached copper foil having a resin thickness of 55 μm according to MIL-P-13949G in the MIL standard. In the state of overlapping (layered body), the bonding was carried out under the conditions of a pressing temperature of 171 ° C, a pressing pressure of 14 kgf / cm ² , and a pressing time of 10 minutes, and the result based on the measurement of the resin outflow weight at this time was based on the number 1. Calculate the value.

The carrier-attached copper foil (resin-attached copper foil with resin) provided with the above-mentioned resin layer is used in such a manner that the resin layer is superposed on the substrate and then thermally bonded to the entire surface to thermally harden the resin layer, and then the resin layer is thermally cured. The carrier is peeled off to expose an extremely thin copper layer (of course, the surface on the intermediate layer side of the ultra-thin copper layer is exposed), and a specific wiring pattern is formed thereon.

When the copper foil with a carrier with a resin is used, the number of sheets of the prepreg used in the production of the multilayer printed wiring board can be reduced. Further, the thickness of the resin layer can be set to ensure the thickness of the interlayer insulation, or the copper-clad laminate can be produced without using the prepreg at all. Further, at this time, the insulating resin primer is applied to the surface of the substrate, and the smoothness of the surface can be further improved.

Moreover, when the prepreg material is not used, the material cost of the prepreg material can be saved, and the lamination step is also simplified, which is economically advantageous, and has the following advantages: only the prepreg material is manufactured. The thickness of the multilayer printed wiring board of the thickness is reduced, and it is possible to manufacture a very thin multilayer printed wiring board having a thickness of 100 μm or less.

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

When the thickness of the resin layer is less than 0.1 μm, the resin-attached carrier copper foil is laminated in the case where the prepreg is inserted without lowering the adhesion. When the inner layer material is on the substrate, it is difficult to ensure interlayer insulation between the circuit and the inner layer material. On the other hand, when the thickness of the resin layer is thicker than 120 μm, it is difficult to form a resin layer of a desired thickness in one coating step, and an unnecessary material cost and number of steps are required, which is economically disadvantageous. .

Further, when the copper foil with a carrier layer having a resin layer is used for producing an extremely thin multilayer printed wiring board, the thickness of the resin layer is set to be 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, or more. When the thickness is preferably from 1 μm to 5 μm, the thickness of the multilayer printed wiring board can be reduced, which is preferable.

Further, when the resin layer contains a dielectric material, the thickness of the resin layer is preferably from 0.1 to 50 μm, preferably from 0.5 μm to 25 μm, more preferably from 1.0 μm to 15 μm.

Further, the total thickness of the resin layer of the cured resin layer and the semi-hardened resin layer is preferably from 0.1 μm to 120 μm, preferably from 5 μm to 120 μm, preferably from 10 μm to 120 μm, more preferably from 10 μm to 60 μm. Further, the thickness of the cured resin layer is preferably from 2 μm to 30 μm, preferably from 3 μm to 30 μm, more preferably from 5 to 20 μm. Further, the thickness of the semi-hardened resin layer is preferably from 3 μm to 55 μm, preferably from 7 μm to 55 μm, more preferably from 15 to 115 μm. The reason for this is that when the total thickness of the resin layer exceeds 120 μm, it is difficult to produce an extremely thin multilayer printed wiring board. If it is less than 5 μm, it may be as follows: although an extremely thin multilayer printed wiring board is easily formed, it may be generated. The insulating layer between the circuits of the layer, that is, the resin layer, becomes too thin, and the insulation between the circuits of the inner layer tends to be unstable. Further, when the thickness of the cured resin layer is less than 2 μm, it is necessary to consider the surface roughness of the roughened surface of the copper foil. On the other hand, when the thickness of the cured resin layer exceeds 20 μm, the effect by the cured resin layer is not particularly improved, and the thickness of the total insulating layer becomes thick.

Further, when the thickness of the resin layer is 0.1 μm to 5 μm, in order to improve the adhesion between the resin layer and the copper foil with a carrier, it is preferable to provide a heat-resistant layer on the ultra-thin copper layer and/or After the rustproof layer and/or the chromate treatment layer and/or the decane coupling treatment layer, a resin layer is formed on the heat resistant layer or the rustproof layer or the chromate treated layer or the decane coupling treatment layer.

Furthermore, the thickness of the above resin layer means the thickness measured by an arbitrary 10-point viewing profile. The average value.

Further, as another form of the resin-attached copper foil with a resin, a resin layer may be coated on the ultra-thin copper layer, or the heat-resistant layer, the rust-proof layer, or the chromate-treated layer or the decane. After the semi-hardened state is formed on the coupling treatment layer, the carrier is subsequently peeled off and produced in the form of a resin-attached copper foil in the absence of the carrier.

Hereinafter, an example of a manufacturing procedure of a plurality of printed wiring boards using the copper foil with a carrier of the present invention will be described.

An embodiment of the method for producing a printed wiring board according to the present invention includes: a step of preparing a copper foil with a carrier of the present invention and an insulating substrate; a step of laminating the copper foil with the carrier and the insulating substrate; and After the copper layer side and the insulating substrate face each other, the copper foil with the carrier and the insulating substrate are laminated, and then the copper-clad laminate is formed by peeling off the carrier of the copper foil with the carrier, and then, by a semi-additive method And a step of forming a circuit by any one of a modified semi-additive method, a partial addition method, and a subtractive method. The insulating substrate can also be set as an inner layer circuit inlet.

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, and a pattern is formed, and a conductor pattern is formed by plating and etching.

Therefore, an embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate a step of peeling off the carrier with the carrier copper foil after laminating the copper foil with the carrier and the insulating substrate; and peeling off the carrier by etching or plasma using an etching solution such as acid or the like a step of completely removing the ultra-thin copper layer; providing a via hole or/and a via hole exposed by removing the ultra-thin copper layer by etching a step of blinding holes; a step of desmear treatment of the region including the through holes or/and the blind holes; and a step of providing an electroless plating layer in the resin and the region including the through holes or/and the blind holes; a step of providing a plating resist on the electroless plating layer; a step of exposing the plating resist, and thereafter removing a plating resist in a region where the circuit is formed; and removing the plating resist a step of forming an electrolytic plating layer in a region where the circuit is formed; a step of removing the plating resist; and a step of removing an electroless plating layer in a region other than the region in which the circuit is formed by rapid etching or the like.

Another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate a step of peeling off the carrier with the carrier copper foil after laminating the copper foil with the carrier, and peeling off the carrier by etching or plasma using an etching solution such as acid; a step of completely removing the thin copper layer; a step of providing an electroless plating layer on the surface of the resin exposed by removing the ultra-thin copper layer by etching; and providing a plating resist on the electroless plating layer a step of exposing the plating resist to the above, and thereafter removing the plating resist in the region where the circuit is formed; a step of disposing an electrolytic plating layer in a region where the above-mentioned circuit is formed by removing the plating resist; a step of removing the plating resist; and removing a region other than the region where the circuit is formed by rapid etching or the like The step of electrolytically plating a layer and an extremely thin copper layer.

In the present invention, the modified semi-additive method refers to laminating a metal foil on an insulating layer, protecting a non-circuit forming portion by a plating resist, and thickening the copper layer of the circuit forming portion by electrolytic plating to remove the light. The resist is a method of forming a circuit on the insulating layer by (fast) etching to remove the metal foil other than the above-described circuit forming portion.

Therefore, an embodiment of the method for producing a printed wiring board of the present invention using the modified semi-additive method includes the steps of: preparing the copper foil with a carrier of the present invention and an insulating substrate; and the copper foil and the insulating substrate with the carrier a step of laminating; after laminating the carrier-attached copper foil and the insulating substrate, peeling off the carrier of the carrier-attached copper foil; and providing a through-hole or/or an insulating layer on the extremely thin copper layer and the insulating substrate which are exposed by peeling off the carrier; a step of blinding holes; a step of desmear treatment of the region including the through holes or/and the blind holes; a step of providing an electroless plating layer in a region including the through holes or/and the blind holes; and peeling off the carrier a step of plating a resist on the surface of the exposed ultra-thin copper layer; a step of forming a circuit by electrolytic plating after the plating resist is disposed; a step of removing the plating resist; and removing the borrowing by rapid etching A step of removing an extremely thin copper layer by removing the above plating resist.

In another embodiment of the method of manufacturing a printed wiring board of the present invention using the modified semi-additive method, the method includes: a step of preparing a copper foil with a carrier of the present invention and an insulating substrate; a step of laminating the copper foil with the carrier and the insulating substrate; and laminating the carrier copper foil and the insulating substrate a step of providing a plating resist on the extremely thin copper layer exposed by peeling off the carrier; a step of exposing the plating resist, and thereafter removing the plating resist in the region where the circuit is formed; a step of removing the plating resist and forming an electrolytic plating layer in a region where the circuit is formed; a step of removing the plating resist; and removing electroless regions other than the region where the circuit is formed by rapid etching or the like The step of plating the layer and the ultra-thin copper layer.

In the present invention, the partial addition method refers to a method in which a catalyst core is provided on a substrate on which a conductor layer is provided, and a via hole or a hole for a via hole is formed as needed, and etching is performed. In the conductor circuit, if a solder resist or a plating resist is provided as needed, a via hole, an auxiliary hole, or the like is thickened on the conductor circuit by electroless plating to form a printed wiring board.

Therefore, in one embodiment of the method for producing a printed wiring board of the present invention using a partial addition method, the method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate a step of peeling off the carrier with the carrier copper foil after laminating the copper foil with the carrier and the insulating substrate; and providing a through hole or/and a blind hole on the extremely thin copper layer and the insulating substrate exposed by peeling the carrier Step of the hole; a step of desmear treatment of the region including the through hole or/and the blind hole; a step of imparting a catalyst core to the region including the through hole or/and the blind hole; and an extremely thin copper layer exposed by peeling off the carrier a step of providing an etch resist on the surface; a step of exposing the etch resist to form a circuit pattern; and removing the ultra-thin copper layer and the catalyst core by etching or plasma etching using an acid or the like a step of removing the etching resist; removing the surface of the insulating substrate by exposing the ultra-thin copper layer and the catalyst core by etching or plasma etching using an acid or the like, and providing a solder resist Or a step of plating a resist; and a step of providing an electroless plating layer in a region where the above-mentioned solder resist or plating resist is not provided.

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

Therefore, an embodiment of the method for producing a printed wiring board according to the present invention using the subtractive method includes the steps of: preparing the copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate a step of peeling off the carrier with the carrier copper foil after laminating the copper foil with the carrier, and providing a through hole or/and a blind hole in the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier a step of performing a desmear treatment on a region including the through hole or/and the blind hole; a step of providing an electroless plating layer in a region including the through hole or/and the blind hole; and the electroless plating described above a step of providing an electrolytic plating layer on the surface of the layer; a step of providing an etching resist on the surface of the electrolytic plating layer or/and the ultra-thin copper layer; a step of exposing the etching resist to form a circuit pattern; removing the ultra-thin copper layer, the electroless plating layer, and the electrolytic plating layer by etching or plasma using an etching solution such as acid a step of the circuit; and a step of removing the above etch resist.

In another embodiment of the method for producing a printed wiring board of the present invention using the subtractive method, the method includes the steps of: preparing the copper foil with a carrier of the present invention and an insulating substrate; and stacking the copper foil with the insulating substrate and the insulating substrate After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the through-hole or/and the blind via are provided on the extremely thin copper layer and the insulating substrate which are exposed by peeling off the carrier. a step of performing desmear treatment on a region including the through hole or/and the blind hole; a step of providing an electroless plating layer in a region including the through hole or/and the blind hole; and the electroless plating layer a step of forming a mask on the surface; an electrolytic plating layer on the surface of the electroless plating layer on which the mask is not formed; and an etching resist on the surface of the electrolytic plating layer or/and the ultra-thin copper layer a step of exposing the etching resist to form a circuit pattern; removing the ultra-thin copper layer and the electroless plating layer by etching or plasma using an etching solution such as acid to form electricity The steps of the road; and the step of removing the above etching resist.

The step of providing a through hole or/and a blind hole, and the subsequent desmear step may also be omitted.

Here, a specific example of a method of manufacturing a printed wiring board using the copper foil with a carrier of the present invention will be described in detail with reference to the drawings. Furthermore, here, there is a pole having a roughened layer formed thereon The copper foil with a carrier of the thin copper layer is described as an example. However, the present invention is not limited thereto, and the carrier copper foil having an ultra-thin copper layer in which the roughened layer is not formed may be used, and the following printed wiring board may be manufactured in the same manner. method.

First, as shown in Fig. 1-A, a carrier-attached copper foil (first layer) having a very thin copper layer on which a roughened layer is formed is prepared.

Next, as shown in FIG. 1-B, a photoresist is applied onto the roughened layer of the ultra-thin copper layer, exposed, developed, and the photoresist is etched into a specific shape.

Then, as shown in FIG. 1-C, after the plating for forming the circuit, the photoresist is removed, thereby forming a circuit plating of a specific shape.

Then, as shown in FIG. 2-D, a resin layer is embedded on the ultra-thin copper layer by coating the circuit layer (in the form of a buried circuit plating layer), and then the resin layer is laminated on the side of the ultra-thin copper layer. Carrier copper foil (layer 2).

Then, as shown in Fig. 2-E, the carrier was peeled off from the carrier copper foil of the second layer.

Then, as shown in FIG. 2-F, a laser opening is performed at a specific position of the resin layer to expose the circuit plating layer to form a blind hole.

Then, as shown in FIG. 3-G, a via fill of buried copper is formed in the blind via.

Then, as shown in FIG. 3-H, a circuit plating layer is formed on the via fill material in the manner of FIGS. 1-B and 1-C described above.

Then, as shown in Fig. 3-I, the carrier was peeled off from the carrier-attached copper foil of the first layer.

Then, as shown in FIG. 4-J, the extremely thin copper layer on both surfaces is removed by rapid etching to expose the surface of the circuit plating layer in the resin layer.

Then, as shown in FIG. 4-K, bumps are formed on the circuit plating layer in the resin layer, and copper pillars are formed on the solder. Thus, a printed wiring board using the copper foil with a carrier of the present invention was produced.

The above-mentioned other carrier copper foil (second layer) can be used with the copper foil with a carrier of the present invention, and a conventional copper foil with a carrier can be used, and a usual copper foil can also be used. Also, can be seen in Figure 3-H The circuit of the second layer is further formed into a one-layer or a plurality of layers, and the circuits can be formed by any one of a semi-additive method, a subtractive method, a partial addition method, or a modified semi-additive method.

The copper foil with a carrier of the present invention preferably controls the chromatic aberration of the surface of the ultra-thin copper layer in such a manner as to satisfy the following (1). In the present invention, the "chromatic aberration on the surface of the ultra-thin copper layer" means the chromatic aberration on the surface of the ultra-thin copper layer, or the chromatic aberration on the surface of the surface-treated layer when various surface treatments such as roughening treatment are performed. That is, the copper foil with a carrier of the present invention preferably controls the surface of the ultra-thin copper layer or the roughened layer or the heat-resistant layer or the rust-proof layer or the chromate-treated layer or the decane coupling layer in such a manner as to satisfy the following (1). Color difference.

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

Here, the color difference ΔL, Δa, and Δb are measured by a color difference meter, and black/white/red/green/yellow/blue is adopted, and a comprehensive index expressed by the L*a*b color system based on JISZ8730 is used. And expressed as ΔL: white black, Δa: red green, △ b: yellow blue. Further, ΔE* ab is expressed by the following formula using these chromatic aberrations.

The chromatic aberration can be adjusted by increasing the current density at the time of formation of the ultra-thin copper layer, lowering the concentration of copper in the plating solution, and increasing the linear flow rate of the plating solution.

Further, the chromatic aberration may be adjusted by performing a roughening treatment on the surface of the ultra-thin copper layer and providing a roughened layer. In the case where the roughening treatment layer is provided, it is possible to further increase the current density by using an electric field liquid containing one or more elements selected from the group consisting of copper and nickel, cobalt, tungsten, and molybdenum (for example, 40~) 60A/dm ² ), the processing time is shortened (for example, 0.1 to 1.3 seconds) and adjusted. In the case where a roughened layer is not provided on the surface of the ultra-thin copper layer, it can be used in a very thin copper layer or a heat-resistant layer or a rust-proof layer by using a plating bath in which the concentration of Ni is twice or more of other elements. The surface of the chromate treatment layer or the decane coupling treatment layer is set to a Ni alloy (for example, plating) in a manner lower than the conventional current density (0.1 to 1.3 A/dm ² ) and increasing the treatment time (20 seconds to 40 seconds). The Ni-W alloy, the Ni-Co-P alloy plating, and the Ni-Zn alloy plating are processed to achieve.

If the color difference ΔE* ab based on JIS Z8730 on the surface of the ultra-thin copper layer is 45 or more, the contrast between the ultra-thin copper layer and the circuit is clear when a circuit is formed on the surface of an extremely thin copper layer with a carrier copper foil, and the result is visually recognized. Good, the positional alignment of the circuit can be performed with high precision. The color difference ΔE* 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 chromatic aberration of the surface of the ultra-thin copper layer or the roughened layer or the heat-resistant layer or the rust-proof layer or the chromate-treated layer or the decane coupling layer is controlled as described above, the contrast with the circuit plating layer becomes clear, and the visibility is recognized. Good sex. Therefore, in the manufacturing steps shown in, for example, FIG. 1-C of the printed wiring board as described above, the circuit plating layer can be formed accurately at a specific position. Further, according to the method for manufacturing a printed wiring board as described above, since the circuit plating layer is embedded in the resin layer, for example, when the ultra-thin copper layer is removed by rapid etching as shown in FIG. 4-J, the resin layer is used. The protective circuit is plated and maintained in shape, whereby the fine circuit is easily formed. Moreover, in order to protect the circuit plating layer by the resin layer, the electron mobility resistance is improved, and the wiring of the circuit is favorably suppressed. Therefore, it is easy to form a fine circuit. Further, when the ultra-thin copper layer is removed by rapid etching as shown in FIG. 4-J and FIG. 4-K, the exposed surface of the circuit plating layer is formed into a shape recessed from the resin layer, so that it is easy to form a convex on the circuit plating layer, respectively. The block, which in turn forms a copper pillar, increases manufacturing efficiency.

Further, a well-known resin or prepreg can be used as the resin (Resin). For example, a BT resin or a glass cloth impregnated with a BT resin, that is, a prepreg, an ABF film manufactured by Ajinomoto Fine-Techno Co., Ltd. or ABF can be used. Further, as the above-mentioned embedded resin (Resin), the resin layer and/or the resin and/or the prepreg described in the present specification can be used.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples of the invention, but the invention should not be construed as limited.

1. Manufacture of carrier copper foil

As the copper foil carrier, a strip of electrolytic copper foil (JTC manufactured by JX Nippon Mining & Metals Co., Ltd.) having a thickness of 35 μm and a rolled copper foil (C1100 manufactured by JX Nippon Mining & Metals Co., Ltd.) having a thickness of 33 μm were prepared. The intermediate layer forming treatments shown in Tables 1 and 2 were carried out under the following conditions on the shiny surface of the copper foil by the reel type connecting wires on the carrier surface and the ultra-thin copper layer side under the following conditions. Water washing and pickling were carried out between the treatment steps of the surface side of the carrier and the side of the ultra-thin copper layer.

(plating conditions)

. Ni plating

Nickel sulfate: 250~500g/L

Nickel chloride: 35~45g/L

Nickel acetate: 10~20g/L

Trisodium citrate: 15~30g/L

Gloss agent: saccharin, butynediol, etc.

Sodium lauryl sulfate: 30~100ppm

pH: 4~6

Bath temperature: 50~70°C

Current density: 3~15A/dm ²

. Cobalt plating

Cobalt sulfate: 200~300g/L

Boric acid: 20~50g/L

pH: 2~5

Liquid temperature: 10~70°C

Current density: 0.5~20A/dm ²

. Molybdenum-cobalt alloy

Cobalt sulfate: 10~200g/L

Sodium molybdate: 5~200g/L

Sodium citrate: 2~240g/L

pH: 2~5

Liquid temperature: 10~70°C

Current density: 0.5~10 A/dm ²

(sputter condition)

Since the molybdenum layer cannot be formed by electroplating, it is produced by a roll-type sputtering apparatus. In this case, a coating layer can be formed by removing an oxide film having a thin copper foil surface by an ion gun (LIS). The thickness of the Ni layer and the Mo layer can be varied by adjusting the sputtering power.

. Device: Roller Sputtering Device (Shenzhen Seiki Co., Ltd.)

. The degree of vacuum reached: 1.0 × 10 ^-5 Pa

. Sputtering pressure: 0.25Pa

. Transport speed: 15m/min

. Ion gun power: 225W

. Sputtering power: 200~3000W

. target: Ni layer = Ni (purity 3N)

Mo layer = Mo (purity 3N)

. Film formation rate: Each target was formed into a film at a time of about 0.2 μm, and the thickness was measured by a three-dimensional measuring device to calculate the sputtering rate per unit time.

Then, on the reel-type connection plating line, an ultra-thin copper layer having a thickness of 2 to 5 μm was formed on the intermediate layer by electroplating under the following conditions to produce a copper foil with a carrier.

. Very thin copper layer

Copper concentration: 30~120g/L

H ₂ SO ₄ concentration: 20 ~ 120g / L

Electrolyte temperature: 20~80°C

Current density: 10~100A/dm ²

Further, Examples 1, 4, and 5 were subjected to the following roughening treatment, rust prevention treatment, chromate treatment, and decane coupling treatment on the surface of the ultra-thin copper layer.

. Coarsening

Cu: 10~20g/L

Co: 1~10g/L

Ni: 1~10g/L

pH: 1~4

Temperature: 40~50°C

Current density Dk: 20~30A/dm ²

Time: 1~5 seconds

Cu adhesion: 15~40mg/dm ²

Co adhesion: 100~3000μg/dm ²

Ni adhesion: 100~1000μg/dm ²

. Anti-rust treatment

Zn: 0~20g/L

Ni: 0~5g/L

pH: 3.5

Temperature: 40 ° C

Current density Dk: 0~1.7A/dm ²

Time: 1 second

Zn adhesion: 5~250μg/dm ²

Ni adhesion: 5~300μg/dm ²

. Chromate treatment

K ₂ Cr ₂ O ₇

(N ₂ Cr ₂ O ₇ or CrO ₃ ): 2~10g/L

NaOH or KOH: 10~50g/L

ZnO or ZnSO ₄ 7H ₂ O: 0.05~10g/L

pH: 7~13

Bath temperature: 20~80°C

Current density: 0.05~5A/dm ²

Time: 5~30 seconds

Cr adhesion: 10~150μg/dm ²

. Decane coupling treatment

Vinyl triethoxy decane aqueous solution

(Vinyl triethoxy decane concentration: 0.1~1.4wt%)

pH: 4~5

Time: 5~30 seconds

2. Various evaluations of copper foil with carrier

With respect to the copper foil with a carrier obtained as described above, various evaluations were carried out by the following methods. The results are shown in Tables 1 and 2.

<Measurement of adhesion amount>

The nickel adhesion amount was dissolved in a nitric acid having a concentration of 20% by mass, and was measured by ICP emission analysis using an ICP emission spectroscopic analyzer (model: SPS3100) manufactured by SII Corporation. The adhesion amount of molybdenum and cobalt was 7 mass%. The sample was dissolved in hydrochloric acid, and was determined by quantitative analysis using atomic absorption spectrometry using an atomic absorption spectrophotometer (Model: AA240FS) manufactured by VARIAN. In addition, the measurement conditions are the conditions recommended in each measurement apparatus.

<XPS Analysis>

The extremely thin copper layer side of the copper foil with a carrier was bonded to the insulating substrate, and after crimping under conditions of 20 kgf/cm ² and 220 ° C for 2 hours, the copper foil carrier was peeled off from the ultra-thin copper layer. Then, the exposed intermediate layer surface was subjected to XPS measurement to prepare a depth profile. The operating conditions of XPS are expressed as follows.

. Device: XPS measuring device (ULVAC-PHI, model 5600MC)

. Reaching vacuum: 3.8×10 ^-7 Pa

. X-ray: monochromatic AlKα or non-monochromatic MgKα, X-ray output 300W, detection area 800μm , the angle between the sample and the detector is 45°

. Ion line: ion species Ar ⁺ , accelerating voltage 3kV, scanning area 3mm × 3mm, sputtering rate 2.8nm / min (SiO ₂ conversion)

. Measurement interval of each element concentration in the depth direction: 0.28 nm (in terms of SiO ₂ ) (sputter time, measured every 0.1 minutes)

Further, in the copper foil with a carrier before the thermocompression bonding, the copper foil carrier was peeled off from the ultra-thin copper layer, and the surface of the exposed copper foil carrier was subjected to XPS measurement to prepare a depth profile.

In the longitudinal direction of each sample sheet, one portion in each of the regions from the both ends to within 50 mm, and one portion in the region of 50 mm × 50 mm in the center portion, that is, a total of three portions are measured by XPS. Get the depth map. The measurement sites of the three sites are shown in Fig. 7 . Then, based on the depth profile made in the region of the three parts, ∫i(x)dx/(∫g(x) of the interval [0.0, 4.0] of the depth direction analysis from the surface of the intermediate layer is obtained. Dx+∫h(x)dx+∫i(x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) and ∫j(x)dx/(∫g( x)dx+∫h(x)dx+∫i(x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) and ∫h(x)dx/(∫ g(x)dx+∫h(x)dx+∫i(x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx), and from the surface of the intermediate layer区间g(x)dx/(∫g(x)dx+∫h(x)dx+∫i(x)dx+∫j(x)dx+∫k(x) of the interval of the depth direction analysis of the initial calculation [4.0,12.0] The value of dx + ∫ l (x) dx + ∫ m (x) dx), and find the arithmetic mean of the above.

Further, in the case where the sample size is small, the region from the both ends to within 50 mm and the region of 50 mm × 50 mm at the center portion may overlap.

In the case where the intermediate layer and the ultra-thin copper layer are peeled off, the surface of the ultra-thin copper layer side can be measured by XPS in the same manner as the intermediate layer side to obtain a depth profile. Nickel, molybdenum, and cobalt, which are constituent elements of the intermediate layer side, were hardly detected on the extremely thin copper foil side. It is determined that when the XPS measurement is performed on the side surface of the ultra-thin copper layer, and the atomic concentrations of nickel, molybdenum, and cobalt on the surface of the ultra-thin copper layer are 15 at% or less, respectively, the intermediate layer and the ultra-thin copper layer are generated. Stripped.

Further, XPS means X-ray photoelectron spectroscopy. The above measurement was carried out using an XPS measuring device (Model 5600MC) of ULVAC-PHI Corporation. In the present invention, an XPS measuring device (model 5600MC or a measuring device equivalent to that manufactured and sold by ULVAC-PHI) of ULVAC-PHI Corporation is used as a premise, but in the case where such a measuring device cannot be obtained, the depth direction is The measurement interval of each element concentration is 0.10 to 0.30 nm (in terms of SiO ₂ ), and when the sputtering rate is 1.0 to 3.0 nm/min (in terms of SiO ₂ ), another XPS measuring device can be used.

Further, the larger the value of x, the darker (far) the surface of the intermediate layer exposed by the peeling of the ultra-thin copper layer.

<pinhole>

The number of pinholes was visually measured by using a backlight for photographic use for people's livelihood as a light source.

<peel strength>

The extremely thin copper layer side of the copper foil with a carrier is bonded to an insulating substrate, and is pressure-bonded in the air at 20 kgf/cm ² and 220 ° C for 2 hours, and the peel strength is obtained by using a load gauge to stretch the copper foil. The carrier side was measured in accordance with a 90° peeling method (JIS C 6471 8.1). Further, the peeling strength was also measured in the same manner as the copper foil with a carrier attached to the insulating substrate.

(Evaluation results)

Examples 1 to 7 were excellent in suppressing all pinholes, and further showed good peel strength.

In Comparative Examples 1 and 2, the intermediate layer was not formed, and the adhesion amount of nickel to molybdenum or cobalt or molybdenum cobalt alloy was small. Therefore, the carrier could not be peeled off from the ultra-thin copper layer even before thermocompression bonding.

In Comparative Example 3, since the molybdenum or cobalt or molybdenum-cobalt alloy layer was not formed in the intermediate layer, the carrier could not be peeled off from the ultra-thin copper layer even before thermocompression bonding.

In Comparative Example 4, the concentration of nickel was low, and no molybdenum or cobalt or molybdenum-cobalt alloy layer was formed in the intermediate layer. Therefore, the carrier could not be peeled off from the ultra-thin copper layer even before thermocompression bonding.

In Comparative Examples 5 and 7, the amount of cobalt adhered was large, so that the pinhole of the ultra-thin copper foil was excessive and the peel strength was low.

In Comparative Example 6, since the amount of adhesion of molybdenum was large, the pinhole of the ultra-thin copper foil was excessive, and the peel strength was low.

In Comparative Example 8, the concentration of molybdenum and cobalt was low, so that it could not be peeled off after pressing.

Fig. 5 is a view showing an XPS depth profile in the depth direction of the surface of the intermediate layer before bonding to the substrate in the fifth embodiment.

Further, in the examples and comparative examples in which the ultra-thin copper layer was peeled off from the carrier, any intermediate layer and the ultra-thin copper layer were peeled off.

Claims (24)

A copper foil with carrier, which has a copper foil carrier, an intermediate layer, and an ultra-thin copper layer, and the intermediate layer is sequentially laminated with nickel, molybdenum or cobalt or a molybdenum-cobalt alloy, in the middle The adhesion of nickel to the layer is 1000~40000μg/dm ² , the adhesion of molybdenum is 50~1000μg/dm ² in the case of molybdenum, and the adhesion of cobalt in the case of cobalt is 50~1000μg/dm ² . When the intermediate layer/very thin copper layer is peeled off, the atomic concentration (%) of nickel in the depth direction (x: unit nm) obtained according to the depth direction analysis from the surface by XPS is set to g ( x), the atomic concentration (%) of copper is h(x), the total atomic concentration (%) of molybdenum is i(x), and the atomic concentration (%) of cobalt is set to j(x). The atomic concentration (%) of oxygen is k (x), the atomic concentration (%) of carbon is 1 (x), and the other atomic concentration (%) is m (x). The interval from the surface depth analysis [0.0, 4.0], ∫i(x)dx/(∫g(x)dx+∫h(x)dx+∫i(x)dx+∫j(x)dx+∫k(x )dx+∫l(x)dx+∫m(x)dx) or ∫j(x)dx/(∫g(x)dx+∫h(x)dx+∫i(x)dx+∫j(x)dx+∫k (x)dx+∫l(x)dx+∫m (x)dx) is 20%~80%, at [4.0,12.0], ∫g(x)dx/(∫g(x)dx+∫h(x)dx+∫i(x)dx+∫j(x) Dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) satisfies 40% or more. The carrier-attached copper foil according to claim 1, wherein the interval between the depth direction analysis using the XPS from the surface of the intermediate layer is [0.0, 4.0] when the intermediate layer/very thin copper layer is peeled off. ,∫h(x)dx/(∫g(x)dx+∫h(x)dx+∫i(x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x) Dx) is 0.1 to 3%. The copper foil with carrier of the first aspect of the patent application, wherein the insulating substrate is thermocompression bonded to the ultra-thin copper layer in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours, and the above When the intermediate layer/very thin copper layer is peeled off, ∫i(x)dx/(∫g(x)dx+∫h(x) in the interval [0.0, 4.0] of the depth direction analysis from the surface of the intermediate layer )dx+∫i(x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) or ∫j(x)dx/(∫g(x)dx+∫h (x) dx+∫i(x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) becomes 20%~80%, in [4.0,12.0], ∫g(x)dx/(∫g(x)dx+∫h(x)dx+∫i(x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx ) became 40% or more. The copper foil with carrier of the first aspect of the patent application, wherein the insulating substrate is thermocompression bonded to the ultra-thin copper layer in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours, and the above When the intermediate layer/very thin copper layer is peeled off, ∫h(x)dx/(∫g(x)dx+∫h(x) in the interval [0.0, 4.0] of the depth direction analysis from the surface of the intermediate layer ) dx+∫i(x)dx+∫j(x)dx+∫k(x)dx+∫l(x)dx+∫m(x)dx) becomes 0.5 to 5%. The carrier-attached copper foil according to claim 1, wherein the cobalt-cobalt alloy of the intermediate layer has a cobalt concentration of 20 to 80% by mass. The carrier-attached copper foil according to claim 1, which has a roughened layer on the surface of the ultra-thin copper layer. The carrier-attached copper foil according to claim 6, wherein the roughening treatment layer is one selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc. A single layer or a layer composed of any one or more alloys. The carrier-attached copper foil according to claim 6, which has a surface selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer and a decane coupling treatment layer on the surface of the roughened layer. Above layer. The carrier-attached copper foil according to claim 1, wherein the surface of the ultra-thin copper layer has one selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane coupling treatment layer. Above layer. The carrier-attached copper foil according to claim 1, wherein the ultra-thin copper layer is provided with a resin layer. The carrier-attached copper foil according to claim 6 of the invention, comprising a resin layer on the roughened layer. The carrier-attached copper foil according to claim 8 which has a resin layer on one or more layers selected from the group consisting of the heat-resistant layer, the rust-preventive layer, the chromate-treated layer and the decane coupling treatment layer. . The carrier copper foil according to claim 10, wherein the resin layer contains a dielectric. A method for producing a copper foil with a carrier, which is a method for producing a copper foil with a carrier according to any one of claims 1 to 13, which comprises: by using dry plating or wet plating on a copper foil carrier Forming a nickel layer, forming a molybdenum layer or a cobalt layer or a molybdenum-cobalt layer on the nickel layer to form an intermediate layer; and forming a very thin copper layer by electroplating on the intermediate layer. The method for producing a copper foil with a carrier according to claim 14, which further comprises the step of forming a roughened layer on the ultra-thin copper layer. A printed wiring board manufactured by using the carrier-attached copper foil according to any one of claims 1 to 13. A printed circuit board manufactured by using the carrier copper foil of any one of claims 1 to 13. A copper-clad laminate produced by using the carrier-attached copper foil according to any one of claims 1 to 13. A manufacturing method of a printed wiring board, comprising: a step of preparing a carrier copper foil and an insulating substrate according to any one of claims 1 to 13; and a step of laminating the carrier copper foil and the insulating substrate; After laminating the carrier-attached copper foil and the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier of the carrier-attached copper foil, and then, by semi-additive method, subtractive method, partial addition method Or the step of forming a circuit by any of the modified semi-additive methods. A method of manufacturing a printed wiring board, comprising: forming a circuit on the side surface of the ultra-thin copper layer of the carrier copper foil according to any one of claims 1 to 13; a step of forming a resin layer on the side surface of the ultra-thin copper layer with a carrier copper foil; a step of forming a circuit on the resin layer; a step of peeling off the carrier after forming a circuit on the resin layer; and after peeling off the carrier The ultra-thin copper layer is removed, whereby the circuit buried in the resin layer on the side surface of the ultra-thin copper layer is exposed. The method for producing a printed wiring board according to claim 20, wherein the step of forming a circuit on the resin layer is to attach another copper foil with a carrier to the resin layer from the side of the ultra-thin copper layer, and to use the bonding. The step of forming the above circuit is carried out by attaching a carrier copper foil to the above resin layer. The method of manufacturing a printed wiring board according to claim 21, wherein the other carrier copper foil bonded to the resin layer is the carrier-attached copper foil according to any one of claims 1 to 13. The method of manufacturing a printed wiring board according to claim 20, wherein the step of forming a circuit on the resin layer is performed by a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. One method is carried out. The method of manufacturing a printed wiring board according to claim 20, wherein the copper foil with a carrier of the surface forming circuit has a substrate or a resin layer on a surface of the carrier of the copper foil with a carrier.