KR101569253B1 - Copper foil with carrier, and copper clad laminate, printed wiring board and printed circuit board using the same, and method for maunfacturing printed wiring board - Google Patents

Abstract

assignment
There is provided a copper foil to which a carrier whose warpage of the copper foil is preferably suppressed without being restricted by the kind of the ultra thin copper foil and the carrier and the thickness thereof.
Solution
A copper foil having a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and a carrier having an ultra thin copper foil laminated on the intermediate layer, wherein the copper foil has a thickness of one half of the total thickness T of the copper foil with the carrier, (T / 2) x D] of the product of the difference between the residual stress on the surface and the residual stress on the outer surface of the ultra-thin layer is not less than 0 (mu m -MPa) and not more than 155 (mu m- Copper foil.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper foil with a carrier, a copper clad laminate using the same, a printed circuit board, a printed circuit board, and a method for producing a printed circuit board PRINTED WIRING BOARD}

The present invention relates to a copper foil with a carrier, a copper clad laminate using the same, a printed wiring board, a printed circuit board, and a method for producing a printed wiring board.

Printed circuit boards have made great strides over the past half century, and today they have been used in almost all electronic devices. In recent years, along with an increase in the demand for miniaturization and high performance of electronic devices, mounting of high-density mounting parts and high frequency signals have been advanced, and a printed circuit board has been required to have finer conductor patterns (fine pitch) Particularly, when an IC chip is placed on a printed wiring board, a fine pitch of L / S = 20 占 퐉 / 20 占 퐉 or less is required.

The printed wiring board is first produced as a copper-clad laminate in which a copper foil and an insulating substrate mainly made of a glass epoxy substrate, a BT resin, a polyimide film, etc. are bonded. The bonding is performed by a method (lamination method) in which an insulating substrate and a copper foil are laminated and heated and pressed, or a method in which a varnish, which is a precursor of an insulating substrate material, is applied to a surface having a coating layer of a copper foil and heated and cured do.

The thickness of the copper foil used in the copper clad laminate is also reduced to 9 占 퐉 and further to 5 占 퐉 or less as the pitch is made smaller. However, when the thickness is 9 占 퐉 or less, the handling property when the copper clad laminate is formed by the above-described lamination method or casting method is extremely deteriorated. Therefore, a copper foil with a carrier having a thin copper foil with a thin copper foil interposed therebetween is used as a carrier. The surface of the ultra thin copper layer is bonded to an insulating substrate and thermocompression bonded. Thereafter, the carrier is peeled off through the peeling layer.

However, when the copper foil and the insulating substrate are bonded to each other, when the warpage of the copper foil is extremely large, there is a problem in handling such as a problem that the carrying device of the copper foil stops and the copper foil hangs, May occur. In addition, warpage may remain in the completed copper clad laminate due to the warping of the copper clad, which may cause a problem in the next step using the copper clad laminate. A general (carrier-free) copper foil having a thickness of 9 탆 or more is a material having homogeneous mechanical properties, crystal structure and the like in the thickness direction, and since it is highly rigid due to its thickness, the warpage is less likely to increase. On the other hand, since the copper foil with the carrier is a composite comprising the carrier foil, the peel layer and the ultra thin copper foil as described above, the warp tends to become large due to the difference in the mechanical characteristics or crystal structure of each of these constituent elements.

For example, Patent Document 1 discloses an ultra-thin electrolytic copper foil having a carrier copper foil having a three-layered structure of a carrier foil / organic release layer / ultra-thin electrolytic copper foil, And a heat treatment is performed at 250 占 폚 for 1 hour to 10 hours. According to such a configuration, it is described that the curl generated in the composite foil can be calibrated without damaging the oil adhesion, scratch, or the like, and a composite foil in which the curl is calibrated.

Japanese Laid-Open Patent Publication No. 2011-68142

However, in the technique described in Patent Document 1, the warp just after the manufacture of the copper foil with the carrier is merely corrected by heat treatment, and the occurrence of warpage itself at the copper foil manufacturing step with the carrier is not prevented. The warp generated at the time of manufacturing the copper foil with the carrier may cause the handling of the copper foil in the manufacturing process to be hindered, so it is more important to reduce the warping at the copper foil manufacturing step with the carrier. The reduction of warpage in the copper foil manufacturing step with the carrier is also preferable from the viewpoint of the manufacturing cost reduction that does not require an additional bending correction step by the heat treatment. Further, in the method described in Patent Document 1, there is a risk that the possible suppression of the warp of the copper foil may be limited with respect to the kind of the ultra thin copper layer and the carrier, and the thickness thereof.

Therefore, the present invention is not limited to the types of ultra thin copper layers and carriers, and their thicknesses, but is preferably a copper foil with a carrier whose warpage of the copper foil is suppressed, a copper clad laminate using the same, a printed circuit board, And a method for manufacturing a printed wiring board.

To achieve the above object, the inventors of the present invention have conducted intensive studies, and as a result, have found that the difference between the total thickness T of the copper foil and the residual stress of the outer surface of the copper foil carrier and the residual stress of the outer surface of the ultra- It has been found that it is very effective that the absolute value of the product [(T / 2) x D] is equal to or smaller than a predetermined value.

The present invention is completed on the basis of the above finding and provides a copper foil having a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and a carrier having an ultra thin copper foil laminated on the intermediate layer, The absolute value [(T / 2) x D] of the product of one-half of the total thickness T of the attached copper foil and the residual stress of the outer surface of the outer surface of the copper foil carrier and the residual stress of the outer surface of the ultra- (Mu m · MPa) or more and 155 (mu m · MPa) or less.

In one embodiment, the copper foil with a carrier according to the present invention has a ratio of one-half of the total thickness T of the copper foil on which the carrier is adhered to the residual stress on the outer surface of the copper foil carrier and the residual stress on the outer surface of the ultra- The absolute value [(T / 2) x D] of the product of the difference D is greater than 0 (占 퐉 占 ㎫) and equal to or less than 155 (占 퐉 占 ㎫).

The copper foil with a carrier according to another embodiment of the present invention is characterized in that the difference D of the residual stress at the outer surface of the copper foil carrier and the residual stress at the outer surface of the ultra- The absolute value of the product [(T / 2) x D] is not less than 10 (占 퐉 MPa) and not more than 135 (占 퐉 MPa).

In the copper foil with a carrier according to another embodiment of the present invention, the difference between the total thickness T of the copper foil and the residual stress on the outer surface of the copper foil carrier and the residual stress on the outer surface of the ultra- (T / 2) x D] of 15 (占 퐉 占 ㎫) or more and 130 (占 퐉 占 ㎫) or less.

In another embodiment of the copper foil with a carrier according to the present invention, the copper foil carrier comprises an electrolytic copper foil or a rolled copper foil.

In a further embodiment of the copper foil with a carrier according to the present invention, the intermediate layer is composed of a Cr layer in contact with an interface between the Ni layer and the ultra thin copper layer in contact with the interface with the copper foil carrier, Dm < 2 > or more and less than 100 mu g / dm < 2 > in the intermediate layer, and an addition amount of 1 mu g / lt; 2 > or more and 70 mu g / dm < 2 > or less.

In another embodiment of the copper foil with a carrier according to the present invention, the thickness of the ultra thin copper layer is 1 占 퐉 or more and 10 占 퐉 or less.

In another embodiment of the copper foil with a carrier according to the present invention, the average grain diameter of the ultra-thin copper layer is less than 15 mu m.

The copper foil with a carrier of the present invention according to another embodiment has a roughened treatment layer on the ultra thin copper layer surface.

In the copper foil with a carrier according to another embodiment of the present invention, at least one layer selected from the group consisting of a heat resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer is provided on the surface of the roughened treatment layer .

In another embodiment of the copper foil with a carrier according to the present invention, at least one of the rust preventive layer and the heat resistant layer contains at least one element selected from nickel, cobalt, copper and zinc.

In another embodiment of the copper foil with a carrier according to the present invention, at least one of the rust preventive layer and the heat resistant layer is made of one or more elements selected from nickel, cobalt, copper and zinc.

The copper foil with a carrier of the present invention according to another embodiment has the heat resistant layer on the roughened treatment layer.

In another embodiment of the copper foil with a carrier according to the present invention, the copper foil has the rust prevention layer on the roughening treatment layer.

In a further embodiment of the copper foil with a carrier according to the present invention, the chromate treatment layer is provided on the rust preventive layer.

In another embodiment of the copper foil with a carrier according to the present invention, the copper foil has the silane coupling treatment layer on the chromate treatment layer.

In another embodiment of the copper foil with a carrier according to the present invention, at least one layer selected from the group consisting of a heat resistant layer, a rustproof layer, a chromate treatment layer and a silane coupling treatment layer is provided on the surface of the ultra thin copper layer .

In the copper foil with a carrier according to the present invention, the copper foil with the carrier attached thereto is cut out into a sheet of 10 cm in length and 10 cm from the horizontal plane of the four corners of the sheet when the carrier is placed on a horizontal plane The maximum value of the height of the lifting portion of the main body 10 is 10 mm or less.

In another embodiment of the copper foil with a carrier according to the present invention, a resin layer is provided on the ultra thin copper layer.

In a copper foil with a carrier according to another embodiment of the present invention, a resin layer is provided on the roughening treatment layer.

In another embodiment of the copper foil with a carrier according to the present invention, a resin layer is provided on at least one layer selected from the group consisting of the heat resistant layer, the rust prevention layer, the chromate treatment layer and the silane coupling treatment layer.

In another embodiment of the copper foil with a carrier according to the present invention, the resin layer includes a dielectric.

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

According to another aspect of the present invention, there is provided a printed wiring board manufactured using the copper foil having the carrier of the present invention.

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

According to another aspect of the present invention, there is provided a method for manufacturing a copper foil, comprising the steps of: forming a circuit on the surface of the ultra thin copper layer of the copper foil having the carrier of the present invention; A step of forming a layer on the resin layer, a step of forming a circuit on the resin layer, a step of peeling the carrier after forming a circuit on the resin layer, and a step of removing the ultra thin copper layer , And a step of exposing a circuit formed on the surface of the ultra thin copper layer and buried in the resin layer.

According to another aspect of the present invention, in the step of forming a circuit on the resin layer of the present invention, a step of stacking a copper foil having another carrier on the resin layer from the ultra-thin copper layer side, Is a step of forming the circuit using a copper foil with a carrier.

According to another aspect of the present invention, there is provided a copper foil to which a carrier according to any one of claims 1 to 21 is adhered, the copper foil having another carrier adhered on the resin layer of the present invention.

According to another aspect of the present invention, there is provided a method for forming a circuit on a resin layer according to any one of the semi-additive method, the subtractive method, the protein additive method, and the modified semi- Lt; / RTI >

In another aspect, the present invention further includes a step of forming a substrate on the carrier-side surface of the copper foil on which the carrier is attached before peeling the carrier of the present invention.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising the steps of: preparing a copper foil and an insulating substrate with the carrier of the present invention; laminating the copper foil with the carrier and the insulating substrate; And then peeling the copper foil carrier of the copper foil on which the carrier is adhered to form a copper clad laminate. Thereafter, a semi-additive process, a subtractive process, a patty additive process, or a modified semi-additive process A method of manufacturing a printed wiring board including a step of forming a circuit by any method.

The copper foil with the carrier according to the present invention can suppress the warping of the copper foil favorably without being limited by the kind of the ultra thin copper foil and the carrier and the thickness thereof.

1 (A) to (C) are schematic diagrams of a section of a wiring board in a process up to circuit plating and resist removal, relating to a specific example of a method for producing a printed wiring board using the copper foil with a carrier according to the present invention.
Fig. 2D to Fig. 2D are cross-sectional views of a wiring board cross-section in a process from the lamination of the resin and the second-layer carrier to the laser drilling, which is related to the concrete example of the method for producing a printed wiring board using the copper- It is a schematic diagram.
3G to 3I are schematic views of a wiring board section in a process from the via fill formation to the first layer carrier peeling, which relates to a concrete example of a production method of a printed wiring board using the copper foil with a carrier according to the present invention.
4A to 4K are schematic views of a wiring board section in a process from flash etching to bump-copper filler formation, according to a specific example of a method for producing a printed wiring board using the copper foil with a carrier according to the present invention.

<1. Carrier>

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

The thickness of the carrier which can be used in the present invention is not particularly limited. However, it may be suitably adjusted to a thickness having a suitable rigidity in the role of a carrier, for example, 12 mu m or more. However, if it is excessively thick, the production cost becomes high, and therefore, it is generally preferable to be 35 mu m or less. Therefore, the thickness of the carrier is typically 12 占 퐉 or more and 70 占 퐉 or less, and more typically 18 占 퐉 or more and 35 占 퐉 or less.

<2. Middle layer>

An intermediate layer is formed on the copper foil carrier. Another layer may be formed between the copper foil carrier and the intermediate layer. The intermediate layer can be constituted by stacking a nickel layer and a chromate layer in this order on a copper carrier. Since the adhesive force between nickel and copper is higher than the adhesive force between chrome and copper, it is peeled off at the interface between the ultra-thin copper layer and chromium when the ultra-thin copper layer is peeled off. In addition, a barrier effect for preventing the copper component from diffusing from the carrier into the ultra-thin copper layer is expected for nickel in the intermediate layer.

When an electrolytic copper foil is used as the carrier, it is preferable to form the intermediate layer on the shiny side from the viewpoint of reducing pinholes.

The reason why the chromate layer in the intermediate layer is thinly present at the interface of the ultra thin copper layer is that the ultra thin copper layer is not peeled off from the carrier before the laminating step to the insulating substrate and the ultra thin copper layer is peelable from the carrier after the laminating step to the insulating substrate Is preferable. When the chromate layer is present at the boundary of the carrier and the ultra-thin copper layer without forming the nickel layer, the peelability is hardly improved. When a nickel layer and an ultra thin copper layer are directly laminated without a chromate layer, the peel strength becomes excessively strong or too weak depending on the amount of nickel in the nickel layer, so that adequate peel strength can not be obtained.

If the chromate layer is present at the boundary between the carrier and the nickel layer, the intermediate layer is also adhered to peel off when peeling off the ultra thin copper layer, that is, peeling occurs between the carrier and the intermediate layer. Such a situation may occur not only when the chromate layer is formed at the interface with the carrier but also when the amount of chromium is excessively large even if the chromate layer is formed at the interface with the ultra thin copper layer. This is because the copper and nickel are likely to be solved, and if they are in contact, the adhesive force is increased due to mutual diffusion, so that it is difficult to peel off. On the other hand, since chromium and copper are not dissolved well, It is considered that the cause of the peeling is that the adhesive force is weak and it is easily peeled off. When the amount of nickel in the intermediate layer is insufficient, since there is only a trace amount of chrome between the carrier and the ultra-thin copper layer, they are closely adhered to each other and can not be easily peeled off.

The adhesion amount of nickel in the intermediate layer is 1 占 퐂 / dm2 or more and 40000 占 퐂 / dm2 or less, and the adhesion amount of chromium is 1 占 퐂 / dm2 or more and 100 占 퐂 / dm2 or less. As the amount of nickel and chromium deposited increases, the number of pinholes in the ultra-thin copper layer tends to increase. However, in this range, the number of pinholes is also suppressed. From the viewpoint of uniformly peeling off the ultra thin copper layer and from the viewpoint of suppressing pinholes, the adhesion amount of nickel is preferably 1000 占 퐂 / dm 2 to 10000 占 퐂 / dm 2 or less and the deposition amount of chromium of 10 占 퐂 / More preferably not less than 2000 μg / dm 2 or more and not more than 9000 μg / dm 2, and the deposition amount of chromium is not less than 15 μg / dm 2 and not more than 45 μg / dm 2. Further, in the present invention, it is preferable that the intermediate layer contains a small amount of Zn. As a result, the occurrence of pinholes can be significantly reduced, and further, it is easy to obtain an appropriate peel strength, which contributes greatly to the quality stability. Although there is no intention that the present invention be limited by theory, the presence of a small amount of Zn in the intermediate layer forms an oxide film composed of Cr and Zn so that the electric conductivity of the intermediate layer becomes more uniform, Part of the extremely low conductivity is lost. Thereby, the electrodeposited particles of copper at the time of forming the ultra-thin copper layer are uniformly adhered to the oxide film composed of Cr and Zn, and the peel strength becomes an appropriate value (the peeling strength becomes extremely high or the peeling strength is extremely low (Or not) to be able to do so.

Zn may be present in either one or both of the Ni layer and the Cr layer in the intermediate layer. For example, at the time of forming the Ni layer, a zinc component is added to the plating solution and nickel zinc alloy plating is performed, whereby a Ni layer containing zinc is obtained. Further, by adding a zinc component to the chromate treatment liquid, a Cr layer containing zinc can be obtained. However, in either case, since Zn is diffused in the intermediate layer, it is generally detected in both the Ni layer and the Cr layer. Further, Zn is preferably present in the Cr layer because an oxide film composed of Cr and Zn is easily formed.

However, if the amount of Zn adhered to the intermediate layer is too small, the effect is limited. Therefore, it is preferably 1 占 퐂 / dm2 or more, more preferably 5 占 퐂 / dm2 or more. On the other hand, the adhesion amount of Zn in the intermediate layer is preferably 70 占 퐂 / dm2 or less, more preferably 30 占 퐂 / dm2 or less, and more preferably 20 占 퐂 / dm2 Or less.

The intermediate layer may be a layer containing at least one of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn or an alloy thereof or a hydrate thereof, May be formed. The intermediate layer may be a plurality of layers.

For example, the intermediate layer may be formed of a single metal layer made of any one of the elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Ni, Co, Fe, Mo, Ti, W, P, Cu, and at least one element selected from the group consisting of Fe, Mo, Ti, W, P, Cu, Al, , Al, and Zn, or an oxide or an organic material of an organic material.

For example, the intermediate layer may be formed of a single metal layer composed of any one of the elements of the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Ni, Co, Fe, Mo, Ti, W, P, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, A single metal layer composed of any one element group of Cu, Al and Zn or one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, As shown in Fig.

<3. Strike plating>

And an extremely thin copper layer is formed on the intermediate layer. The strike plating by the copper-phosphorus alloy may be performed on the intermediate layer before the pinhole of the ultra thin copper layer is reduced. A copper pyrophosphate plating solution or the like can be used as the treatment liquid for the strike plating. As described above, in the copper foil carrying the carrier subjected to the strike plating by the copper-phosphorus alloy, phosphorus exists on both the surface of the intermediate layer and the surface of the ultra-thin copper layer. For this reason, when peeling is performed between the intermediate layer and the ultra thin copper layer, phosphorus is detected from the surface of the intermediate layer and the ultra thin copper layer. Since the plating layer formed by strike plating becomes thinner, it can be judged that plating is strike when the thickness of the plating layer of copper on the intermediate layer is 0.1 mu m or less by observing a cross section by FIB, TEM or the like.

<4. Ultra-thin layer>

And an extremely thin copper layer is formed on the intermediate layer. Another layer may be formed between the intermediate layer and the ultra thin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamide or copper cyanide, and is used in a general electrolytic copper foil and in that a copper sulfate bath can be formed at a high current density, desirable. Thickness of the ultra thin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 占 퐉 or less, preferably 1 占 퐉 or more and 10 占 퐉 or less. Typically, it is not less than 0.5 μm and not more than 12 μm, more typically not less than 2 μm and not more than 5 μm.

The ultra thin copper layer of the copper foil to which the carrier of the present invention is adhered is not subjected to a heat treatment such as recrystallization or excessive grain growth in an extremely thin copper layer, for example, a heat treatment at 180 占 폚 or more for 3 hours or more. The average grain diameter of the ultra-thin copper layer in the present invention, which is not subjected to the heat treatment for causing recrystallization or excessive crystal grain growth, is typically less than 15 μm. From the viewpoint of improving the strength of the ultra-thin copper layer, the average grain diameter is preferably 10 占 퐉 or less, more preferably 5 占 퐉 or less, and even more preferably 3 占 퐉 or less. The average grain diameter of the ultra-fine copper layer in the present invention, which is not subjected to the heat treatment for causing recrystallization or excessive grain growth, is often smaller than the thickness of the ultra-fine copper layer. The ultra-thin copper layer of the copper foil to which the carrier of the present invention is adhered may be carried out as long as the above recrystallization or heat treatment does not cause excessive crystal growth.

<5. Harmonization processing>

The roughened treatment layer may be formed on the surface of the ultra-thin copper layer by, for example, performing a roughening treatment in order to improve adhesion to the insulating substrate. The roughening treatment can be carried out, for example, by forming coarse particles with copper or a copper alloy. The harmonic treatment may be fine. The roughening treatment layer may be a layer made of an alloy containing any one or more selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc. It is also possible to carry out a harmonizing treatment for forming secondary particles or tertiary particles with nickel, cobalt, copper, zinc alone, or an alloy of nickel, cobalt, zinc, or the like after the roughening particles are formed of copper or a copper alloy. Thereafter, a heat resistant layer or rust preventive layer may be formed of a single body of nickel, cobalt, copper, zinc, or an alloy, or the surface may further be subjected to a treatment such as a chromate treatment or a silane coupling treatment. A heat resistant layer or a rust preventive layer may be formed of a single body of nickel, cobalt, copper, zinc or an alloy, and the surface thereof may be subjected to a treatment such as a chromate treatment or a silane coupling treatment. That is, at least one layer selected from the group consisting of a heat resistant layer, a rust preventive layer, a chromate treatment layer and a silane coupling treatment layer may be formed on the surface of the roughened treatment layer, and a heat resistant layer, A treatment layer and a silane coupling treatment layer may be formed. The heat resistant layer, rust preventive layer, chromate treatment layer and silane coupling treatment layer described above may be formed of a plurality of layers (for example, two or more layers, three or more layers, etc.). Each layer may be a plurality of layers such as two or three layers, and the order of laminating the layers may be any order, and the layers may be alternately laminated.

Here, a well-known heat-resistant layer can be used as the heat-resistant layer. In addition, for example, the following surface treatment can be used.

As the heat-resistant layer and the rust-preventive layer, known heat-resistant layers and rust-preventive layers can be used. For example, the heat-resistant layer and / or the rust-preventive layer may be formed of a material selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, Or a layer containing at least one element selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, May be a metal layer or an alloy layer composed of at least one kind of element selected from the group consisting of The heat resistant layer and / or the rust preventive layer may be selected from the group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, Nitride, or silicide containing at least one element selected from the group consisting of oxides, nitrides, and silicides. The heat-resistant layer and / or rust-preventive layer may be a layer containing a nickel-zinc alloy. The heat-resistant layer and / or rust-preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% of nickel and 50 wt% to 1 wt% of zinc, other than inevitable impurities. The total adhesion amount of zinc and nickel of the nickel-zinc alloy layer may be 5 to 1000 mg / m 2, preferably 10 to 500 mg / m 2, more preferably 20 to 100 mg / m 2. It is preferable that the ratio of the adhesion amount of nickel to the adhesion amount of nickel (= adhesion amount of nickel / adhesion amount of zinc) of the nickel-zinc alloy layer or the nickel-zinc alloy layer is 1.5 to 10. The adhesion amount of nickel in the nickel-zinc alloy layer or nickel-zinc alloy layer is preferably 0.5 mg / m 2 to 500 mg / m 2, more preferably 1 mg / m 2 to 50 mg / m 2 Do. When the heat-resistant layer and / or the rust-preventive layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate does not corrode well on the dispensing liquid when the inner wall portion of the through hole, And the resin substrate are improved. The rust-preventive layer may be a chromate treatment layer. A known chromate treatment layer may be used for the chromate treatment layer. For example, the chromate treatment layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromic acid or anchromate. The chromate treatment layer contains an element (metal, alloy, oxide, nitride, sulfide or the like) such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium You can. Specific examples of the chromate treatment layer include a pure chromate treatment layer and a zinc chromate treatment layer. In the present invention, the chromate treatment layer treated with an aqueous solution of chromic acid anhydride or potassium dichromate is referred to as a pure chromate treatment layer. In the present invention, a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium chromate and zinc is referred to as a zinc chromate treatment layer.

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

Further, as the heat-resistant layer and / or the anti-corrosive layer, the coating weight is 200 ~ 2000 ㎍ / dm ² of cobalt - 50 ~ 700 ㎍ / dm ² of nickel in the cobalt-nickel alloy plating layer can be formed. This treatment can be seen as a kind of rust treatment in a broad sense. This cobalt-nickel alloy plating layer needs to be carried out to such an extent that the bonding strength between the copper foil and the substrate is not substantially lowered. When the cobalt adhesion amount is less than 200 / / dm ² , the heat peel strength may be lowered and the oxidation resistance and chemical resistance may be deteriorated. Another reason is that if the amount of cobalt is small, the surface to be treated becomes red, which is not preferable.

As the silane coupling treatment layer, a known weather-resistant layer can be used. As the weather resistant layer, for example, a well-known silane coupling treatment layer can be used, and a silane coupling treatment layer formed using the following silane can be used.

A known silane coupling agent may be used for the silane coupling agent used in the silane coupling treatment. For example, an amino silane coupling agent, an epoxy silane coupling agent, or a mercapto silane coupling agent may be used. Examples of the silane coupling agent include vinyltrimethoxysilane, vinylphenyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxy Aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) butoxy) propyl-3-aminopropyl Trimethoxysilane, imidazole silane, triazinilane, gamma-mercaptopropyltrimethoxysilane, or the like may be used.

The silane coupling treatment layer may be formed using a silane coupling agent such as an epoxy silane, an amino silane, a methacryloxy silane, or a mercapto silane. Two or more such silane coupling agents may be used in combination. Among them, it is preferable to use an amino-based silane coupling agent or an epoxy-based silane coupling agent.

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

The silane coupling treatment layer is formed in a range of 0.05 mg / m 2 to 200 mg / m 2, preferably 0.15 mg / m 2 to 20 mg / m 2, preferably 0.3 mg / m 2 to 2.0 mg / . In the above-mentioned range, the adhesion between the base resin and the surface-treated copper foil can be further improved.

[Ultrafine copper layer, heat resistant layer, anticorrosive layer, chromate treatment layer or resin layer on the silane coupling treatment layer]

The copper foil with a carrier of the present invention may be provided with a roughened treatment layer on the ultra thin copper layer and may include a heat resistant layer and / or rust preventive layer on the roughened treatment layer, and the heat resistant layer and / A chromate treatment layer may be provided on the chromate treatment layer, and a silane coupling treatment layer may be provided on the chromate treatment layer.

The copper foil with the carrier of the present invention may be provided with a heat resistant layer and / or rust preventive layer on the ultra thin copper layer, a chromate treatment layer may be provided on the heat resistant layer and / or rust preventive layer, A silane coupling treatment layer may be provided.

The copper foil with the carrier may be provided with a resin layer on the ultrafine copper layer, the roughening treatment layer, or the heat resistant layer, the anticorrosive layer, the chromate treatment layer, or the silane coupling treatment layer. The resin layer may be an insulating resin layer.

The order of forming the heat-resistant layer, rust-preventive layer, chromate treatment layer and silane coupling treatment layer is not limited to each other, and the layers may be formed in any order on the ultra-fine copper foil or the roughened treatment layer.

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

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

The resin layer may include a thermosetting resin or a thermoplastic resin. The resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton or the like. In addition, the resin layer may be formed, for example, in International Publication Nos. WO2008 / 004399, WO2008 / 053878, WO2009 / 084533, JP- , Japanese Patent No. 3184485, International Publication No. WO97 / 02728, Japanese Patent No. 3676375, Japanese Patent Application Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Application Laid-Open No. 2002-179772, Japanese Patent Application Laid- JP-A No. 359444, JP-A No. 2003-304068, JP-A No. 3992225, JP-A No. 2003-249739, JP-A No. 4136509, JP-A No. 2004-82687, No. 4025177, Patent Publication Nos. 2004-349654, 4286060, 2005-262506, 4570070, 2005-53218, 3949676, 4178415, International Patent Publication Nos. Publication numbers WO2004 / 005588, JP-A-2006-2 Japanese Patent Laid-open Publication No. 57153, Japanese Patent Laid-Open Publication No. 2007-326923, Japanese Laid-Open Patent Publication No. 2008-111169, Japanese Patent No. 5024930, International Publication Nos. WO2006 / 028207, Japanese Patent No. 4828427, Japanese Laid-Open Patent Publication No. WO2006 / 134868, Japanese Patent No. 5046927, Japanese Laid-Open Patent Publication No. 2009-173017, International Publication No. WO2007 / 105635, Japanese Patent No. 5180815, International Publication No. WO2008 / 114858, International Publication No. WO2009 / 008471, (Resins, resin curing agents, compounds, curing agents) disclosed in Patent Publication No. 2011-14727, International Publication No. WO2009 / 001850, International Publication No. WO2009 / 145179, International Publication Nos. WO2011 / 068157 and 2013-19056 A catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, etc.) and / or a method of forming a resin layer and a forming apparatus.

The kind of the resin layer is not particularly limited, and examples thereof include epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleimide (Also referred to as polyether sulfone, polyether sulfone) resin, an aromatic polyamide resin, an aromatic polyamide resin, an aromatic polyamide resin, a polyimide resin, Polyamide resin, polyamide resin, polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamideimide resin, rubber modified epoxy resin, phenoxy resin, carboxyl group denatured acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine resin, Polyphenylene oxide resin, cyanate ester resin, A linear polymer having a crosslinkable functional group, a polyphenylene ether resin, 2,2-bis (4-cyanatophenyl) propane, a phosphorus-containing phenol compound, (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, siloxane-modified polyamideimide resin, cyanoester resin, phosphazene resin, rubber modified polyamide At least one member selected from the group consisting of a polyisocyanate compound, a polyisocyanate compound, a polyisocyanate compound, a polyisocyanate compound, a polyisocyanate compound, a polyisobutylene compound, a polyisocyanate compound, Can be mentioned as preferred.

The above-mentioned epoxy resin can be used without particular problems, as long as it has two or more epoxy groups in the molecule and can be used for electric and electronic materials. The epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. In addition, epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD type epoxy resins, novolak type epoxy resins, cresol novolak type epoxy resins, alicyclic epoxy resins, Resin, phenol novolak type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolak type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanate A glycidyl amine compound such as N, N-diglycidyl aniline, a glycidyl ester compound such as tetrahydrophthalic acid diglycidyl ester, a phosphorus-containing epoxy resin, a biphenyl-type epoxy resin, A cyclohexane type epoxy resin, a cyclohexane type epoxy resin, a cyclohexane type epoxy resin, a cyclohexane type epoxy resin, a cyclohexane type epoxy resin, Two or more of them may be used in combination, or a hydrogenated product or a halogenated product of the above epoxy resin may be used.

An epoxy resin containing phosphorus known as phosphorus-containing epoxy resin may be used. The phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule desirable.

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

The resin layer may include a dielectric (dielectric filler).

When a dielectric (dielectric filler) is included in any resin layer or resin composition, it can be used for forming a capacitor layer to increase the capacitance of the capacitor circuit. The dielectric material (dielectric filler) includes perovellum such as BaTiO ₃ , SrTiO ₃ , Pb (Zr-Ti) O ₃ (commonly referred to as PZT), PbLaTiO ₃ PbLaZrO (commonly referred to as PLZT), and SrBi ₂ Ta ₂ O ₉ A dielectric powder of a complex oxide having a skite structure is used.

The dielectric (dielectric filler) may be in powder form. When the dielectric (dielectric filler) is in the form of powder, it is preferable that the dielectric property (dielectric filler) has a particle diameter in the range of 0.01 탆 to 3.0 탆, preferably 0.02 탆 to 2.0 탆. In addition, when a dielectric is photographed with a scanning electron microscope (SEM) and a straight line is drawn on the dielectric particles in the photograph, the length of the dielectric particles in the longest straight line across the dielectric particles is calculated Diameter of the dielectric particles. The average value of the diameters of the dielectric particles in the measurement visual field is defined as the particle diameter of the dielectric.

The resin and / or the resin composition and / or the compound contained in the resin layer described above may be dissolved in a solvent such as methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, , Ethanol, propylene glycol monomethyl ether, dimethyl formamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, (Resin varnish), which is then coated on the roughened surface of the surface-treated copper foil by, for example, a roll coater method or the like, followed by heating and drying if necessary to remove the solvent to obtain B Stage state. For drying, for example, a hot-air drying furnace may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the resin layer is dissolved by using a solvent 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 may be used. Further, it is most preferable to dissolve by using a mixed solvent of methyl ethyl ketone and cyclopentanone from the environmental viewpoint at the present stage. It is preferable to use a solvent having a boiling point in the range of 50 to 200 占 폚.

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

In the present specification, the resin flow refers to a method in which four samples of 10 cm in length and 10 cm length are sampled from a surface-treated copper foil having a resin thickness of 55 탆 and a resin thickness in accordance with MIL-P-13949G in the MIL standard, The results are shown in Table 1. From the result of measuring the resin outflow weight at the time of attaching the four samples in a superimposed state (laminate) under conditions of a press temperature of 171 DEG C, a press pressure of 14 kgf / cm2, and a press time of 10 minutes, .

The surface-treated copper foil having the resin layer (resin-adhered surface-treated copper foil) is formed by superimposing the resin layer on a substrate and thermally bonding the entire body to thermally cure the resin layer, In the case of a thin copper foil having a very thin copper foil, the carrier is peeled to expose an extremely thin foil layer (of course, the exposed surface is the surface of the intermediate foil layer of the ultra thin copper foil) To form a pattern.

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

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

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

When the thickness of the resin layer is thinner than 0.1 占 퐉, the adhesive force is lowered. When the surface-treated copper foil having the resin adhered thereto is laminated on a substrate having an inner layer material without interposing the prepreg material therebetween, It may be difficult to ensure insulation. On the other hand, if the thickness of the resin layer is made thicker than 120 탆, it is difficult to form a resin layer having a desired thickness in one coating step, resulting in an economical disadvantage because extra material cost and number of steps are required have.

When the surface-treated copper foil having a resin layer is used for producing a very thin multilayered printed circuit board, the thickness of the resin layer is preferably 0.1 to 5 mu m, more preferably 0.5 to 5 mu m, It is preferable to set the thickness to 1 占 퐉 to 5 占 퐉 in order to reduce the thickness of the multilayered printed circuit board.

<6. Copper with carrier>

In this manner, a copper foil having a copper foil carrier, an intermediate layer formed on the copper foil carrier, and a carrier having an ultra thin copper foil laminated on the intermediate layer is produced. The method of using the copper foil with the carrier itself is well known to those skilled in the art. For example, the surface of the ultra thin copper layer may be coated with paper phenol resin, paper base epoxy resin, synthetic fiber cloth epoxy resin, , A glass / glass / non-woven composite substrate epoxy resin, and a glass-clad base epoxy resin, a polyester film, and a polyimide film, peeling the carrier after thermocompression bonding, It is possible to finally produce a printed wiring board by etching with a conductor pattern. In the case of the copper foil with the carrier according to the present invention, the peeling point is mainly an interface between the intermediate layer and the ultra-thin copper layer. In addition, by mounting electronic parts on the printed wiring board, a printed circuit board is completed. Hereinafter, several examples of the manufacturing process of the printed wiring board using the copper foil with the carrier according to the present invention are shown.

In one embodiment of the method for producing a printed wiring board according to the present invention, there is provided a method for manufacturing a printed wiring board, comprising the steps of: preparing a copper foil and an insulating substrate with a carrier according to the present invention; laminating the copper foil with the carrier and the insulating substrate; A step of peeling the carrier of the copper foil on which the carrier is adhered to form a copper clad laminate after the laminated copper foil and the insulating substrate are laminated so that the ultra thin copper layer side faces the insulating substrate and then the semi- And a step of forming a circuit by any one of a freeze semi-additive method, a palladium additive method, and a subtractive method. The insulating substrate may contain an inner layer circuit.

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

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

A step of laminating the copper foil on which the carrier is adhered and the insulating substrate,

A step of peeling the carrier of the copper foil on which the carrier is adhered after laminating the copper foil with the carrier and the insulating substrate,

A step of peeling off the carrier to completely remove the exposed ultra thin copper layer by a method such as etching or plasma using a corrosive solution such as an acid,

Forming a through hole and / or a blind via in the exposed resin by removing the ultra thin copper layer by etching;

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

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

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

Exposing the plating resist to light, removing the plating resist in a region where the circuit is formed,

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

A step of removing the plating resist,

And removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like.

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

A step of laminating the copper foil on which the carrier is adhered and the insulating substrate,

A step of peeling the carrier of the copper foil on which the carrier is adhered after the copper foil on which the carrier is adhered and the insulating substrate are laminated,

A step of peeling off the carrier to completely remove the exposed ultra thin copper layer by a method such as etching or plasma using a corrosive solution such as an acid,

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

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

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

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

A step of removing the plating resist,

And removing the electroless plating layer and the ultra thin copper layer in regions other than the region where the circuit is formed by flash etching or the like.

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

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

A step of laminating the copper foil on which the carrier is adhered and the insulating substrate,

A step of peeling the carrier of the copper foil on which the carrier is adhered after the copper foil on which the carrier is adhered and the insulating substrate are laminated,

A step of peeling the carrier to form a through hole and / or a blind via in an exposed ultra thin copper layer and an insulating substrate,

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

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

Peeling the carrier to form a plating resist on the exposed ultra thin copper layer surface,

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

A step of removing the plating resist,

And a step of removing the exposed ultra thin copper layer by flash etching by removing the plating resist.

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

A step of laminating the copper foil on which the carrier is adhered and the insulating substrate,

A step of peeling the carrier of the copper foil on which the carrier is adhered after the copper foil on which the carrier is adhered and the insulating substrate are laminated,

A step of peeling the carrier to form a plating resist on the exposed ultra thin copper layer,

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

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

A step of removing the plating resist,

And removing the electroless plating layer and the ultra thin copper layer in regions other than the region where the circuit is formed by flash etching or the like.

In the present invention, the palladium additive method is a method in which catalyst layers are formed on a substrate on which a conductor layer is formed and, if necessary, a catalyst core is formed on a substrate formed by punching holes for through holes or via holes, , A solder resist or a plating resist is formed and then a thickness is given to the conductor circuit through a through hole or a via hole by electroless plating to thereby produce a printed wiring board.

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

A step of laminating the copper foil on which the carrier is adhered and the insulating substrate,

A step of peeling the carrier of the copper foil on which the carrier is adhered after the copper foil on which the carrier is adhered and the insulating substrate are laminated,

A step of peeling the carrier to form a through hole and / or a blind via in an exposed ultra thin copper layer and an insulating substrate,

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

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

Peeling the carrier to form an etching resist on the exposed ultra thin copper layer surface,

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

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

A step of removing the etching resist,

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

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

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

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

A step of laminating the copper foil on which the carrier is adhered and the insulating substrate,

A step of peeling the carrier of the copper foil on which the carrier is adhered after the copper foil on which the carrier is adhered and the insulating substrate are laminated,

A step of peeling the carrier to form a through hole and / or a blind via in an exposed ultra thin copper layer and an insulating substrate,

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

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

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

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

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

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

And removing the etching resist.

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

A step of laminating the copper foil on which the carrier is adhered and the insulating substrate,

A step of peeling the carrier of the copper foil on which the carrier is adhered after the copper foil on which the carrier is adhered and the insulating substrate are laminated,

A step of peeling the carrier to form a through hole and / or a blind via in an exposed ultra thin copper layer and an insulating substrate,

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

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

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

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

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

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

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

And removing the etching resist.

The step of forming the through hole and / or the blind via, and the subsequent desmearing step may not be performed.

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

First, as shown in Fig. 1-A, a copper foil (first layer) to which a carrier having an ultra-thin copper layer having a roughened treatment layer formed on its surface is prepared.

Next, as shown in Fig. 1-B, a resist is applied on the roughened layer of an ultra-thin copper layer, exposure and development are performed, and the resist is etched in a predetermined shape.

Next, as shown in Fig. 1-C, circuit plating is formed and then the resist is removed to form circuit plating of a predetermined shape.

Next, as shown in Fig. 2-D, a resin layer is formed on the ultra-thin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then the resin layer is laminated. ) From the ultra thin copper layer side.

Next, as shown in Fig. 2-E, the carrier is peeled from the copper foil on which the second layer carrier is adhered.

Next, as shown in FIG. 2-F, a laser hole is formed at a predetermined position of the resin layer, and the circuit plating is exposed to form a blind via.

Next, as shown in FIG. 3-G, copper is buried in the blind via to form a via fill.

Next, as shown in FIG. 3-H, circuit plating is formed on the via fill as shown in FIG. 1-B and FIG. 1-C.

Next, as shown in Fig. 3-I, the carrier is peeled from the copper foil with the first-layer carrier.

Next, as shown in Fig. 4-J, the ultra thin copper foil on both surfaces is removed by flash etching to expose the surface of the circuit plating in the resin layer.

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

The copper foil with the carrier of the present invention may be used as the copper foil with the other carrier (second layer), or a conventional copper foil with a carrier may be used, or a conventional copper foil may be used. In addition, on the second-layer circuit shown in FIG. 3-H, one circuit or a plurality of layers may be additionally formed, and their circuit formation may be formed by a semi-additive method, a subtractive method, a patty additive method, And the additive method.

The copper foil with the carrier used in the first layer may have a substrate on the carrier-side surface of the copper foil on which the carrier is adhered. By having the substrate or the resin layer, the copper foil with the carrier used for the first layer is supported, and wrinkles are not easily generated, which is advantageous in that the productivity is improved. Further, all the substrates can be used as long as they are effective for supporting the copper foil with the carrier used for the first layer. For example, the substrate may be a carrier, a prepreg, a resin layer or a known carrier, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a plate of an inorganic compound, Can be used.

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

In the copper foil with the carrier according to the present invention, it is preferable that the color difference of the ultra thin copper layer surface is controlled so as to satisfy the following (1). In the present invention, the term &quot; color difference of the ultra-fine copper layer surface &quot; indicates the color difference of the surface treatment layer surface when various surface treatments such as color difference of the surface of ultra-fine copper layer or harmony treatment are performed. That is, in the copper foil with the carrier according to the present invention, it is preferable that the color difference of the surface of the ultra thin copper film or the roughening treatment layer, the heat resistance layer, the anticorrosion layer, the chromate treatment layer or the silane coupling layer is controlled to satisfy the following (1) Do.

(1) The color difference (? E * ab) based on JIS Z 8730 on the surface of the ultra-thin copper or coarsened layer, heat resistant layer, rustproofing layer, chromate treatment layer or silane coupling treatment layer is 45 or more.

Here, the color differences DELTA L, DELTA a, and DELTA b are measured in the respective colorimeters, and are represented by using the L * a * b color system based on JIS Z 8730, adding black / white / red / green / Is represented by? L: black and white,? A: red color, and? B: white color. In addition,? E * ab is expressed by the following equation using these color differences.

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

The above-described color difference may be adjusted by forming a roughened treatment layer by applying roughening treatment to the surface of an extremely thin copper layer. In the case of forming the roughened layer, the electrolytic solution containing copper and at least one element selected from the group consisting of nickel, cobalt, tungsten, and molybdenum is used to increase the current density (for example, 40 to 60 A / dm &lt; ² &gt;) and the treatment time is shortened (for example, 0.1 to 1.3 seconds). In the case where the roughened layer is not formed on the surface of the ultra thin copper layer, a plating bath in which the concentration of Ni is at least two times as large as the other elements is used to form an ultra thin copper or heat resistant layer or a rust prevention layer or a chromate treatment layer, (Ni-W alloy plating, Ni-Co-P alloy plating and Ni-Zn alloy plating) on the surface of the treated layer at a low current density (0.1 to 1.3 A / dm ² ) (20 seconds to 40 seconds).

When the color difference (DELTA E * ab) based on JIS Z 8730 of the ultra thin copper layer surface is 45 or more, for example, when a circuit is formed on the ultra thin copper layer surface of the copper foil with the carrier, the contrast of the circuit with the ultra thin copper layer becomes clear, As a result, the visibility is improved, and alignment of the circuit can be performed with good precision. The color difference (? E * ab) based on JIS Z 8730 of the ultra-thin copper layer surface is preferably 50 or more, more preferably 55 or more, and even more preferably 60 or more.

When the color difference between the surface of the ultra thin copper layer or the roughening treatment layer or the heat resistance layer or the anticorrosive layer or the surface of the chromate treatment layer or the silane coupling layer is controlled as described above, the contrast with the circuit plating becomes clear and the visibility becomes good. Therefore, in the example of the printed wiring board described above, it is possible to form the circuit plating at a predetermined position with good precision in the manufacturing process shown in Fig. 1-C. According to the above-described method for producing a printed wiring board, since the circuit plating is embedded in the resin layer, when the ultra thin copper layer is removed by flash etching shown in, for example, The plating is protected by the resin layer and the shape thereof is maintained, thereby facilitating formation of a fine circuit. Further, since the circuit plating is protected by the resin layer, migration resistance is improved, and conduction of the circuit wiring is satisfactorily suppressed. Therefore, formation of a fine circuit is facilitated. As shown in Figs. 4-J and 4-K, when the ultra-thin copper layer is removed by flash etching, the exposed surface of the circuit plating becomes a depressed form from the resin layer, so that bumps are formed on the circuit plating, The copper filler is easily formed thereon, and the production efficiency is improved.

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

The copper foil with the carrier of the present invention has a total thickness of one-half of the total thickness T of the copper foil and the residual stress on the surface opposite to the intermediate layer in the copper foil carrier, i.e., the outer surface, The absolute value [(T / 2) x D] of the product of the difference D from the residual stress on the surface on the opposite side, that is, the outer surface is controlled to be not less than 0 (占 퐉 占 ㎫) and not more than 140 占 퐉 占 ㎫. This (T / 2) x D represents the center line moment of the copper foil. That is, the (T / 2) x D represents the difference between the distance from the center line of the copper foil (one-half of the total thickness T) and the residual stress, And the driving force for generating warpage on the ultra-thin copper layer surface becomes small. Therefore, the kind of the copper foil and the ultra thin copper layer to which the carrier is adhered, and further, the thickness thereof are not limited, and the warpage of the copper foil is satisfactorily suppressed. In order to further suppress the warping of the copper foil, the absolute value of the product of the one-half of the total thickness T of the copper foil and the difference between the residual stress on the outer surface of the copper foil carrier and the residual stress on the outer surface of the ultra- (Mu m · MPa) or more and less than or equal to 135 (mu m · MPa) and more preferably 15 (mu m · MPa) or less, (MPa) or more and 130 (占 퐉 · MPa) or less.

Example

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

(Examples 1 to 8)

1. Manufacture of copper foil with carrier

(JX (product name), thickness 12, 18, and 70 占 퐉) and rolled copper foil (JX manufactured by Nikko Nisseki Metal Co., Ltd., thickness: C1100 (product name), thickness 18 占 퐉).

Each of the copper foils was adjusted to have a residual stress of -30 MPa or more and 30 MPa or less on the outer side of the copper foil with the carrier. Here, when the residual stress is a positive value, it indicates a shrinkage stress, and when it is a negative value, it indicates a tensile stress. When the electrolytic copper foil is used as the copper foil carrier, the residual stress in the surface layer can be adjusted to an arbitrary range in accordance with the residual stress range of the outer surface of the ultra-thin copper layer to be described later by optimizing the electrolytic bath composition and electrolysis conditions. Electrolytic copper foil was foiled on an electrolytic drum made of stainless steel using the following electrolytic bath composition and electrolytic conditions. When the flow rate of the electrolytic solution is increased, the residual stress of the copper foil tends to act in the shrinking direction (shrinkage stress tends to act). When the flow rate of the electrolytic solution is lowered, the residual stress of the copper foil acts in the tensile direction It tends to be easy to operate. When the current density is increased, the residual stress of the copper foil tends to act in the shrinking direction (shrinkage stress tends to act). When the current density is lowered, the residual stress of the copper foil acts in the tensile direction Easy). The residual stress can also be adjusted by adding an additive for the electrolytic solution (for example, Cl or glue).

(Electrolytic bath composition)

Cu: 80 to 120 g / l

H ₂ SO ₄ : 80 to 120 g / ℓ

Cl: 20 to 80 mg / l (Example 5, Comparative Example 1)

Glue: 0.1 to 6.0 mg / l (Examples 1, 2, 5, 6, 7, 8, Comparative Example 1)

(Electrolysis condition)

Solution temperature: 55 ~ 65 ℃

Current density: 100 A / dm 2

Electrolyte flow rate: 1.5 m / sec

When the rolled copper foil is used as the copper foil carrier, the residual stress in the surface layer can be adjusted to an arbitrary range by optimizing the rolling conditions and the heat treatment conditions in the rolled copper foil production process, and the method is easily known to those skilled in the art and is already known. It may be adjusted according to the range of the residual stress on the outer surface of the extreme thin-film layer to be described later. In the present embodiment, the rolling process degree in the final cold rolling is 95%, the final pass rolling degree in the final cold rolling is 5%, and the diameter of the rolling roll used in the final pass of the final cold rolling is 80 mm. The residual stress in the surface layer of the rolled copper foil can also be adjusted by changing the roll diameter of the rolling roll used in the final cold rolling and can also be adjusted by controlling the rolling process degree of the final cold rolling. For example, when the roll diameter is large, the residual stress in the surface layer tends to act in the tensile direction (tensile stress tends to act). When the roll diameter is small, the residual stress in the surface layer acts as the shrinkage direction The stress tends to act). When the final cold rolling has a high rolling degree, the residual stress in the surface layer tends to act in the shrinkage direction (shrinkage stress tends to act). When the rolling degree of the final cold rolling is low, (Tensile stress is likely to act). When the rolling process of the final pass of the final cold rolling is small, the residual stress in the surface layer tends to act in the shrinkage direction (shrinkage stress is likely to act), and the rolling process of the final pass of the final cold rolling is large , The residual stress in the surface layer tends to act in the tensile direction (tensile stress tends to act).

With respect to the shiny side of the copper foil, the intermediate layer forming treatment described in Table 1 was carried out successively on the carrier surface and the ultra-thin copper layer side in a roll-to-roll continuous line under the following conditions under the following conditions. Between the treatment on the carrier surface side and the treatment on the ultrafine copper layer side, washing and pickling were carried out. The line tension was set as shown in Table 1.

- Ni-Zn plating (Examples 1 to 4, 8, Comparative Example 3)

Nickel sulfate: 250 to 300 g / l

Nickel chloride: 35 to 45 g / l

Nickel acetate: 10 to 20 g / l

Sodium citrate: 15-30 g / l

Polishing agents: saccharin, butynediol, etc.

Sodium dodecyl sulfate: 30 to 100 ppm

ZnSO ₄ : 0.05 to 5 g / l

pH: 4 to 6

Bath temperature: 50 ~ 70 ℃

Current density: 3 ~ 15 A / dm2

- Ni plating (Examples 5 and 7, Comparative Example 2)

Nickel sulfate: 250 to 300 g / l

Nickel chloride: 35 to 45 g / l

Nickel acetate: 10 to 20 g / l

Sodium citrate: 15-30 g / l

Polishing agents: saccharin, butynediol, etc.

Sodium dodecyl sulfate: 30 to 100 ppm

pH: 4 to 6

Bath temperature: 50 ~ 70 ℃

Current density: 3 ~ 15 A / dm2

ㆍ electrolytic chromate treatment

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

pH: 3-4

Temperature: 50 to 60 ° C

Current density: 0.1 to 2.6 A / dm 2

Coulomb amount: 0.5 ~ 30 As / d㎡

ㆍ Immersion chromate treatment

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

pH: 3-4

Temperature: 50 to 60 ° C

Immersion time: 1 to 20 seconds

Subsequently, an ultra thin copper layer having a thickness of 3 to 5 占 퐉 was formed on the intermediate layer on a roll-to-roll continuous plating line by electroplating under the following conditions to prepare a copper foil with a carrier. The residual stress in the ultra-thin copper layer can also be prepared in the same manner as the electrolytic copper foil carrier. In this example, all of the examples and comparative examples were adjusted by controlling the chloride ion concentration and the current density.

ㆍ Ultra-thin layer

Copper concentration: 30 ~ 120 g / ℓ

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

Chloride ion concentration: 20 to 80 mg / l

Electrolyte temperature: 20 ~ 80 ℃

Current density: 10 to 100 A / dm 2

For Examples 1, 2 and 5, the following roughening treatment, rust-proofing treatment, chromate treatment and silane coupling treatment were carried out in this order on the surface of an extremely thin copper layer.

ㆍ Harmonization

Cu: 10 to 20 g / l

Co: 1-10 g / l

Ni: 1 to 10 g / l

pH: 1-4

Temperature: 40 ~ 50 ℃

Current density Dk: 20 to 30 A / dm 2

Time: 1 to 5 seconds

Cu adhesion amount: 15 to 40 mg / dm 2

Co Coverage: 100 ~ 3000 ㎍ / d㎡

Ni deposition amount: 100 ~ 1000 / / d㎡

ㆍ Anti-rust treatment

Zn: 0 to 20 g / l

Ni: 0 to 5 g / l

pH: 3.5

Temperature: 40 ° C

Current density Dk: 0 ~ 1.7 A / dm2

Time: 1 second

Zn deposition amount: 5 ~ 250 / / dm 2

Ni deposition amount: 5 ~ 300 / / dm 2

ㆍ Chromate treatment

K ₂ Cr ₂ O ₇

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

NaOH or KOH: 10 to 50 g / l

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

pH: 7 to 13

Bath temperature: 20 ~ 80 ℃

Current density: 0.05 to 5 A / dm 2

Time: 5 ~ 30 seconds

Cr deposition amount: 10-150 / / dm 2

ㆍ Silane coupling treatment

Aqueous solution of vinyltriethoxysilane

 (Vinyltriethoxysilane concentration: 0.1 to 1.4 wt%)

pH: 4 to 5

Time: 5 ~ 30 seconds

(Comparative Examples 1 to 3)

In Comparative Example 1, a copper foil with a carrier adhered was prepared under the same conditions as in Example 2 except that the copper foil carrier had an amorphous current density of 60 A / dm 2 and an ultra-thin copper layer was formed without forming an intermediate layer. In Comparative Examples 2 and 3, the rolling process degree in the final cold rolling at the time of manufacturing the rolled copper foil as the carrier was 85% and 70%, respectively, and the rolling process degree of the final pass in the final cold rolling was 10% and 20% Except that the rolls used for the last pass of the final cold rolling were respectively 100 mm and 120 mm in diameter and Ni plating in Comparative Example 2 and Ni-Zn plating and electrolytic chromate treatment in Comparative Example 3 as intermediate layers , And a carrier-adhered copper foil was prepared under the same conditions as in Example 3.

2. Various evaluation of copper foil with carrier

Various evaluations were conducted on the copper foil with the carrier thus obtained, by the following method. The results are shown in Table 1.

&Lt; Measurement of Average Grain Size of Ultra-thin Layer &gt;

The cross section of the extremely thin copper layer was observed by using FIB-SIM, and the diameter of the minimum circle surrounding the crystal grains was taken as the crystal grain size, and measurement was carried out for all crystal grains existing in the observation field (specifically, photographing was carried out And measured based on the photographs). Cross sectional observation of the ultra-thin copper layer using FIB-SIM is performed by processing the cross section exposed with a converged ion beam (FIB) and observing this cross section with a scanning ion microscope (SIM). The mean value of the grains of 20 or more grains was determined as the average grain size. When 20 or more crystal grains do not exist in the observation field, measurement was performed by widening the observation field until the number of crystal grains subjected to the crystal grain diameter measurement was 20 or more. The magnification at the time of observing the cross section of the ultra-thin copper layer using FIB-SIM is not particularly limited, but may be a magnification at which crystal grains can be observed. For example, the crystal grain size can be measured at a magnification of 2500 to 40,000 times.

&Lt; Measurement of adhesion amount &

The nickel (Ni) adhesion amount was determined by dissolving the sample with nitric acid at a concentration of 20 mass% and measuring by ICP emission analysis. The chromium (Cr) adhesion amount and the zinc (Zn) adhesion amount were determined by dissolving the sample in hydrochloric acid at a concentration of 7 mass% , And quantitative analysis was carried out by the atomic absorption method.

<Measurement of Residual Stress>

Residual stresses on the outer surface of the copper foil carrier and the outer surface of the extreme thin foil were measured by X-ray diffractometry. In this method, the lattice spacing measurement values of a plurality of crystals constituting the copper layer to be measured and the lattice spacing of the copper measured in the previously known stress-free state, the elastic constants of the copper and the Poisson's ratio, Is obtained.

In this embodiment, the measurement of the residual stress was carried out using RINT2100 manufactured by Rigaku Corporation. Calibration of the diffraction angle was performed using standard Si crystals. The calculation of the residual stress was carried out by using the measurement value of the diffraction peak top using the calculation software attached to the RINT2100 manufactured by RIGAKU CORPORATION.

Since the depth of penetration of the X-rays is usually several micrometers to 10 micrometers, the average lattice spacing and the residual stress are obtained from the surface of the measurement surface to which the influence of the X-ray attenuation in the penetration depth range is added. Since the thickness of the copper foil carrier and the ultra thin copper layer in the copper foil with the carrier is almost equal to or greater than the X-ray penetration depth, the measured residual stress is considered to represent the residual stress in the surface layer of the copper foil carrier and the ultra- Does not matter. When surface treatment such as roughening treatment, heat treatment, rust-proofing treatment, chromate treatment or silane coupling treatment is performed on the ultra-thin copper layer outer surface, after the surface treatment (from above the surface treatment layer) Respectively. When surface treatment such as roughening treatment, heat treatment, rust-proofing treatment, chromate treatment or silane coupling treatment is performed on the outer surface of the copper foil carrier, after the surface treatment (from above the surface-treated layer) .

When the copper foil having the carrier has a resin layer, the residual stress described above can be measured after removing the resin layer with a solvent or the like.

&Lt; Measurement of bending amount &

The amount of warpage was measured by cutting out the copper foil with the carrier on a sheet of 10 cm long and standing on the horizontal plane for 24 hours or more with the ultra thin copper layer side up and then measuring the maximum value of the height of the lift portion from the horizontal plane of the four corners of the sheet Respectively. When the four corners of the sheet were curled downwardly, the height of the extreme portion of the four corners of the sheet was measured with the extreme thin layer side down.

(Evaluation results)

In Examples 1 to 8, the absolute value of the product of the half of the total thickness T of the copper foil with the carrier attached thereto and the difference between the residual stress on the outer surface of the copper foil carrier and the residual stress on the outer surface of the ultra- T / 2) x D] was both 0 (占 퐉 占 ㎫) and 155 (占 퐉 占 ㎫) or less. Therefore, the warpage of the copper foil was favorably suppressed.

In Comparative Examples 1 to 3, the absolute value of the product of the half of the total thickness T of the copper foil with the carrier attached thereto and the difference between the residual stress on the outer surface of the copper foil carrier and the residual stress on the outer surface of the ultra- T / 2) x D] exceeded 155 (占 퐉 占 ㎫). Therefore, it is understood that the maximum value of the amount of deflection of the copper foil exceeds 10 mm, and the warpage of the copper foil is not suppressed.

The carrier foil of Example 3 was heated at 195 占 폚 for 6 hours and then the residual stress was measured. As a result, both the residual stress on the outer surface of the copper foil carrier and the residual stress on the outer surface of the ultra-thin copper layer became 0 MPa. As a result, the absolute value [(T / 2) x D] of the product of the difference between the residual stress on the outer surface of the copper foil carrier and the residual stress on the outer surface of the ultra-thin layer was 0 (占 퐉 占 ㎫). The average grain diameter of the ultra-fine copper layer after the heating was 16.1 占 퐉.

Claims (36)

1. A copper foil having a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and a carrier having an ultra thin copper foil laminated on the intermediate layer,
(T / 2) x D, which is a product of a half of the total thickness T of the copper foil on which the carrier is attached and the difference between residual stress on the outer surface of the copper foil carrier and residual stress on the outer surface of the ultra thin layer ] Is not less than 0 (占 퐉 占 ㎫) and not more than 155 (占 퐉), and the average grain diameter of the ultra-thin copper layer is less than 15 占 퐉. 1. A copper foil having a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and a carrier having an ultra thin copper foil laminated on the intermediate layer,
(T / 2) x D, which is a product of a half of the total thickness T of the copper foil on which the carrier is attached and the difference between residual stress on the outer surface of the copper foil carrier and residual stress on the outer surface of the ultra thin layer ] Is greater than 0 (탆 · MPa) and equal to or less than 155 (탆 · MPa). 3. The method of claim 2,
The absolute value [(T / 2) x D] of the product of one-half of the total thickness T of the copper foil and the residual stress of the outer surface of the copper foil carrier and the residual stress of the outer surface of the ultra- (Mu m · MPa) or more and 135 (mu m · MPa) or less. The method of claim 3,
The absolute value [(T / 2) x D] of the product of one-half of the total thickness T of the copper foil and the residual stress of the outer surface of the outer surface of the copper foil carrier and the residual stress of the outer surface of the ultra- (탆 占 ㎫) and not more than 130 (占 퐉 占 ㎫). The method according to claim 1,
Wherein the copper foil carrier comprises an electrolytic copper foil or a rolled copper foil. The method according to claim 1,
Wherein the intermediate layer is composed of a Cr layer in contact with an interface between the Ni layer and the ultra thin copper layer in contact with the copper foil carrier and the adhesion amount of Ni in the intermediate layer is 1 to 40000 占 퐂 / Wherein the amount of Cr deposited on the intermediate layer is not less than 1 占 퐂 / dm2 and not more than 100 占 퐂 / dm2, and the intermediate layer further contains Zn in an adhesion amount of not less than 1 占 퐂 / dm2 and not more than 70 占 퐂 / Copper with carrier attached. The method according to claim 1,
Wherein the ultra thin copper layer has a thickness of 1 占 퐉 or more and 10 占 퐉 or less. delete The method according to claim 1,
And a roughened treatment layer on the ultra thin copper layer surface. 10. The method of claim 9,
Wherein the surface of the roughening treatment layer has at least one layer selected from the group consisting of a heat resistant layer, a rust preventive layer, a chromate treatment layer and a silane coupling treatment layer. 11. The method of claim 10,
Wherein at least one of the rust preventive layer and the heat resistant layer contains at least one element selected from nickel, cobalt, copper and zinc. 11. The method of claim 10,
Wherein at least one of the rust preventive layer and the heat resistant layer is composed of at least one element selected from the group consisting of nickel, cobalt, copper and zinc. 11. The method of claim 10,
And the heat-resistant layer on the roughening treatment layer. 11. The method of claim 10,
And the rust-preventive layer on the roughening treatment layer. 14. The method of claim 13,
And the rust-preventive layer on the heat resistant layer. 11. The method of claim 10,
And a chromate treatment layer on the rust preventive layer. 16. The method of claim 15,
And a chromate treatment layer on the rust preventive layer. 11. The method of claim 10,
And the silicate coupling treatment layer on the chromate treatment layer. 18. The method of claim 17,
And the silicate coupling treatment layer on the chromate treatment layer. The method according to claim 1,
A carrier-adhered copper foil having at least one layer selected from the group consisting of a heat resistant layer, a rust preventive layer, a chromate treatment layer and a silane coupling treatment layer on the surface of the ultra thin copper layer. The method according to claim 1,
Wherein the copper foil with the carrier is cut into a sheet of 10 cm in length and 10 cm in length and the maximum value of the height of the lift portion from the horizontal plane of the four corners of the sheet when the carrier is held on a horizontal plane is 10 mm or less, . The method according to claim 1,
And a resin layer on the ultra thin copper layer. 10. The method of claim 9,
And a resin layer on the roughening treatment layer. 11. The method of claim 10,
And a resin layer on at least one layer selected from the group consisting of the heat resistant layer, the rust prevention layer, the chromate treatment layer and the silane coupling treatment layer. 23. The method of claim 22,
Wherein the resin layer comprises a dielectric. 24. The method of claim 23,
Wherein the resin layer comprises a dielectric. 25. The method of claim 24,
Wherein the resin layer comprises a dielectric. A copper clad laminate produced by using the copper foil having the carrier according to any one of claims 1 to 7 or 9 to 27. [ A printed wiring board produced by using the copper foil with a carrier according to any one of claims 1 to 7 or 9 to 27. A printed circuit board manufactured by using the copper foil with the carrier according to any one of claims 1 to 7 or 9 to 27. A method for manufacturing a semiconductor device, comprising the steps of preparing a copper foil and an insulating substrate with the carrier according to any one of claims 1 to 7 or 9 to 27,
A step of laminating the copper foil on which the carrier is adhered and the insulating substrate,
The copper clad laminate is formed by laminating the copper foil with the carrier and the insulating substrate and then peeling off the copper foil carrier of the copper foil on which the carrier is adhered to form a copper clad laminate. Thereafter, a semi-additive method, A step of forming a circuit by any one of a positive additive method, a differential additive method, and a modified semi additive method. A method for manufacturing a copper foil, comprising the steps of: forming a circuit on the surface of the copper foil having the carrier according to any one of claims 1 to 7 or 27 to 27 on the ultra-
Forming a resin layer on the ultra thin copper layer side surface of the copper foil on which the carrier is adhered so that the circuit is buried,
A step of forming a circuit on the resin layer,
A step of forming a circuit on the resin layer and thereafter peeling the carrier,
And exposing a circuit buried in the resin layer formed on the surface of the ultra thin copper layer by removing the ultra thin copper layer after peeling the carrier. 33. The method of claim 32,
Wherein the step of forming a circuit on the resin layer comprises a step of bonding a copper foil having another carrier on the resin layer from the side of the ultra thin copper layer and bonding the copper foil with the carrier bonded to the resin layer, And forming a circuit on the printed circuit board. A step of forming a circuit on the surface of the ultra thin copper layer of the copper foil having the carrier,
Forming a resin layer on the ultra thin copper layer side surface of the copper foil on which the carrier is adhered so that the circuit is buried,
A step of forming a circuit on the resin layer, wherein a copper foil having another carrier adhered on the resin layer is bonded from the side of the ultra-thin copper layer, and the copper foil with the carrier adhered to the resin layer is used, A step of forming a circuit on the resin layer, which is a step of forming a circuit,
A step of forming a circuit on the resin layer and thereafter peeling the carrier,
And exposing a circuit embedded in the resin layer formed on the surface of the ultra thin copper layer by removing the ultra thin copper layer after peeling the carrier,
Wherein the copper foil with the carrier and the other carrier to which the carrier is adhered on the resin layer is a copper foil having the carrier according to any one of claims 1 to 7 or 9 to 27, (Method for manufacturing a wiring board). 33. The method of claim 32,
Wherein the step of forming a circuit on the resin layer is carried out by any one of a semi-additive method, a subtractive method, a pattern additive method, and a modified semi-additive method. 33. The method of claim 32,
Further comprising a step of forming a substrate on the carrier-side surface of the copper foil on which the carrier is adhered before peeling off the carrier.

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