TW201434623A - Copper foil with carrier, copper-clad laminate using copper foil with carrier, printed wiring board, printed circuit board, and printed wiring board production method - Google Patents

Abstract

Provided is a copper foil with a carrier in which there are no limits to the types of ultra-thin copper layers and carriers, nor to the thicknesses of the copper layers and carriers, and in which warping of the copper foil is satisfactorily suppressed. The copper foil with a carrier is provided with a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the intermediate layer. The residual stress of the outer surface of the copper foil carrier, and the residual stress of the outer surface of the ultra-thin copper layer are both contraction stresses or are both tensile stresses.

Description

Carrier copper foil, copper clad laminate using the same, printed wiring board, printed circuit board, and printed wiring board manufacturing method

The present invention relates to a method of manufacturing a carrier-attached copper foil, a copper-clad laminate using the same, a printed wiring board, a printed circuit board, and a printed wiring board.

Printed wiring boards have made great progress over this half century and have been used in almost all electronic machines. In recent years, with the increase in the demand for miniaturization and high performance of electronic devices, the high-density mounting of components and the development of high-frequency signals have been required, and the printed wiring boards have been required to be finer (fine pitch). )) or a high frequency or the like, in particular, when an IC wafer is placed on a printed wiring board, a fine pitch of L/S = 20 μm / 20 μm or less is required.

The printed wiring board is first produced by laminating a copper foil with a copper-clad laminate in which an insulating substrate mainly composed of a glass epoxy substrate, a BT resin, a polyimide film, or the like is bonded. The bonding method can be carried out by using a method in which an insulating substrate and a copper foil are combined and heated and pressurized (lamination method), or a varnish which is a precursor of an insulating substrate material is applied to a surface of a copper foil having a coating layer and carried out. Method of heating and hardening (casting method).

With the fine pitch, the thickness of the copper foil used for the copper-clad laminate is also 9 μm, further 5 μm or less, and the foil thickness is continuously reduced. However, when the thickness of the foil is 9 μm or less, the rationality of forming the copper clad laminate by the above lamination method or casting method is extremely deteriorated. Therefore, there has been a use of a metal foil having a thickness as a carrier to form a very thin copper layer via a peeling layer. The carrier copper foil attached to the layer. The usual method of using the carrier copper foil is to bond the surface of the ultra-thin copper layer to the insulating substrate and thermocompression bonding, and then peel the carrier through the release layer.

However, when the copper foil and the insulating substrate are bonded together, when the warpage of the copper foil is extremely large, there is a problem that the copper foil transfer device is in a state of failure, or the copper foil is pinched, and is bent or wrinkled. The problem is the situation of production technology problems. Further, there is a case where warpage of the copper clad laminate is completed due to warpage of the copper foil, and there is a possibility that a problem occurs in one step below the use of the copper clad laminate. A normal (unattached) copper foil having a thickness of 9 μm or more is a homogeneous material such as a mechanical property or a crystal structure in the thickness direction, and has a high rigidity because of its thickness, so that warpage becomes large. On the other hand, since the copper foil with a carrier is a composite body consisting of a carrier foil, a peeling layer, and an ultra-thin copper layer as described above, it is easy to warp due to the difference in mechanical properties or crystal structure of these constituent elements. The tendency to become bigger.

In order to solve such a problem, for example, Patent Document 1 discloses a method for correcting a curl of a composite foil which has a carrier copper layer of a carrier copper foil/organic release layer/very thin electrolytic copper foil. The extremely thin electrolytic copper foil of the foil, and the method for correcting the curl of the composite foil is characterized in that the composite foil is subjected to heat treatment at an ambient temperature of 120 ° C to 250 ° C for 1 hour to 10 hours. Further, according to such a configuration, it is possible to provide a method for correcting curl generated in a composite foil without causing damage such as adhesion or scratching of oil, and a composite foil having curl correction.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-68142

However, in the technique described in Patent Document 1, the warpage immediately after the copper foil with a carrier is directly produced by heat treatment is not caused by the occurrence of warpage in the production stage of the copper foil of the carrier. For the manufacturer of copper foil, the warpage generated when the carrier copper foil is produced is also correct. The operation in the manufacturing step causes obstacles, so it is more important to reduce the warpage of the carrier copper foil manufacturing stage. Further, it is also preferable to reduce the warpage at the manufacturing stage of the copper foil with a carrier without the need for an additional warpage correction step by heat treatment, that is, to reduce the manufacturing cost. Further, in the method described in Patent Document 1, the type of the ultra-thin copper layer and the carrier, and the thickness of the carrier are limited to suppress the warpage of the copper foil.

In view of the above, it is an object of the present invention to provide a copper foil with a carrier which can suppress the warpage of the copper foil without any limitation on the type of the ultra-thin copper layer and the carrier, and the copper-clad laminate using the same. , a printed wiring board, a printed circuit board, and a method of manufacturing a printed wiring board.

In order to achieve the above object, the present inventors conducted intensive studies and found that it is extremely effective to make the residual stress of the outer surface of the copper foil carrier and the residual stress of the outer surface of the ultra-thin copper layer in the same direction, that is, Both are shrinkage stresses or both are tensile stresses.

The present invention has been completed based on the above findings. In one aspect, the present invention is a copper foil with a carrier provided with a copper foil carrier, an intermediate layer laminated on a copper foil carrier, and an extremely thin layer laminated on the intermediate layer. The copper layer is formed, and 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 are both contraction stress or tensile stress.

In one embodiment of the copper foil with a carrier of the present invention, the residual stress on the outer surface of the copper foil carrier is 0.1 times or more and 5.0 times or less the residual stress of the outer surface of the ultra-thin copper layer.

In another embodiment of the copper foil with a carrier of the present invention, the residual stress on the outer surface of the copper foil carrier is 0.3 times or more and 3.0 times or less the residual stress of the outer surface of the ultra-thin copper layer.

In still another embodiment of the copper foil with a carrier of the present invention, the copper foil carrier is made of an electrolytic copper foil or a rolled copper foil.

In still another embodiment of the copper foil with carrier of the present invention, the intermediate layer is formed by a Ni layer contacting the interface with the copper foil carrier and a Cr layer contacting the interface with the ultra-thin copper layer, in the intermediate layer deposition amount of Ni of 1μg / dm ² or more and ² or less 40000μg / dm, deposition amount of Cr in the intermediate layer of of 1μg / dm ² or more and 100μg / dm ² or less, to the intermediate layer and further to 1μg / dm ² or more Further, Zn is present in an adhesion amount of 70 μg/dm ² or less.

In still another embodiment of the copper foil with a carrier of the present invention, the thickness of the ultra-thin copper layer is 1 μm or more and 10 μm or less.

In still another embodiment of the copper foil with a carrier of the present invention, the ultrafine copper layer has an average crystal grain size of less than 15 μm.

In still another embodiment, the copper foil with a carrier of the present invention has a roughened layer on the surface of the ultra-thin copper layer.

In still another embodiment, the copper foil with a carrier of the present invention has one or more selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer on the surface of the roughened layer. Layer.

In still another embodiment of the copper foil with a carrier of the present invention, at least one of the rustproof layer and the heat-resistant layer contains one or more elements selected from the group consisting of nickel, cobalt, copper, and zinc.

In still another embodiment of the copper foil with a carrier of the present invention, at least one of the rustproof layer and the heat-resistant layer is made of an element selected from the group consisting of nickel, cobalt, copper, and zinc.

In still another embodiment of the copper foil with a carrier of the present invention, the heat-resistant layer is provided on the roughened layer.

In still another embodiment of the copper foil with a carrier of the present invention, the rustproof layer is provided on the heat-resistant layer.

In still another embodiment of the copper foil with a carrier of the present invention, the rustproof layer is provided on the roughened layer.

In still another embodiment of the copper foil with a carrier of the present invention, the chromate treatment layer is provided on the rustproof layer.

In still another embodiment of the copper foil with a carrier of the present invention, the decane coupling treatment layer is provided on the chromate treatment layer.

In still another embodiment, the copper foil with a carrier of the present invention has one or more selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer on the surface of the ultra-thin copper layer. Layer.

In still another embodiment of the copper foil with a carrier of the present invention, when the copper foil with a carrier is cut into a sheet of 10 cm square and placed on a horizontal surface, the maximum height of the four corners of the sheet from the horizontal plane is 10 mm. the following.

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

In still another embodiment of the copper foil with a carrier of the present invention, a resin layer is provided on the roughened layer.

In still another embodiment, the copper foil with a carrier of the present invention comprises a resin layer on one or more layers selected from the group consisting of the heat-resistant layer, the rust-preventive layer, the chromate-treated layer, and the decane coupling treatment layer.

In still another embodiment of the copper foil with a carrier of the present invention, the resin layer contains a dielectric.

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

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

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

In another aspect, the present invention provides a method of manufacturing a printed wiring board, comprising the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; a step of laminating a foil and an insulating substrate; and after laminating the copper foil with the carrier and the insulating substrate, forming a copper clad laminate by peeling off the copper foil carrier with the carrier copper foil, and thereafter, by semi-additive method The step of forming a circuit by any one of a semi additive method, a subtractive method, a partial additive method, or a modified semi additive method.

In another aspect, the present invention provides a method of manufacturing a printed wiring board, comprising the steps of: forming a circuit on the side surface of the ultra-thin copper layer of the copper foil with carrier of the present invention; a step of forming a resin layer on the side surface of the ultra-thin copper layer of the copper foil with a carrier; a step of forming a circuit on the resin layer; a step of peeling off the carrier after forming a circuit on the resin layer; and The ultra-thin copper layer is removed, and a circuit buried in the resin layer on the side surface of the ultra-thin copper layer is exposed.

In a method of manufacturing a printed wiring board according to the present invention, in the step of forming a circuit on the resin layer, another copper foil with a carrier is bonded to the resin layer from the side of the ultra-thin copper layer, and is bonded to the resin layer. The copper foil with a carrier of the above resin layer forms the above-described circuit.

In another embodiment of the method for producing a printed wiring board according to the present invention, the other carrier copper foil bonded to the resin layer is the copper foil with a carrier of the present invention.

In still another embodiment of the method for producing a printed wiring board according to the present invention, the step of forming a circuit on the resin layer is performed by a semi-additive method, a subtractive method, a partial addition method or an improved semi-additive method. Either method is carried out.

In still another embodiment of the method for producing a printed wiring board according to the present invention, the method further comprises the step of forming a substrate on the side of the carrier side of the copper foil with a carrier before the peeling of the carrier.

The copper foil with a carrier of the present invention does not limit the kind of the ultra-thin copper layer and the carrier and the thickness of the carrier, and can suppress the warpage of the copper foil well.

1A to 1C are schematic views showing a cross section of a wiring board in a step of a plating circuit and a step of removing a resist, which are specific examples of a method for producing a printed wiring board with a copper foil with a carrier of the present invention.

2D to FIG. 2D are schematic views showing a cross section of the wiring board in the step of self-laminated resin and the second-layer carrier-attached copper foil to the laser opening in a specific example of the method for producing the printed wiring board with the carrier-attached copper foil of the present invention.

3G to 3 are schematic views showing a cross section of the wiring board in the step of forming a via-fill to peeling off the first layer carrier, which is a specific example of a method of manufacturing a printed wiring board with a copper foil with a carrier of the present invention.

4J to K are schematic views showing a cross section of a wiring board in a step of forming a bump and a copper pillar from a specific example of a method of manufacturing a printed wiring board with a copper foil with a carrier of the present invention.

<1. Carrier>

As the carrier usable in the present invention, a copper foil is used. The carrier is typically provided in the form of a rolled copper foil or an electrolytic copper foil. Usually, an electrolytic copper foil is produced by electrically analyzing copper from a copper sulfate plating bath on a titanium or stainless steel drum, and the rolled copper foil is repeatedly produced by plastic working and heat treatment by a calender roll. As a material of the copper foil, in addition to high-purity copper such as refined copper or oxygen-free copper, for example, copper such as Sn added, copper added with Ag, copper alloy added with Cr, Zr or Mg, or Ni may be added. And copper alloys such as Si and other Cason copper alloys. In addition, in the present specification, when the term "copper foil" is used alone, a copper alloy foil is also included.

The thickness of the carrier which can be used in the present invention is not particularly limited, and may be, for example, appropriately adjusted so as to function as a carrier and have a suitable rigidity. 12μm or more. However, if it is too thick, the production cost becomes high, and therefore it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically 12 μm or more and 70 μm or less, and more typically 18 μm or more and 35 μm or less.

<2. Middle layer>

An intermediate layer is provided on the copper foil carrier. Other layers may also be provided between the copper foil carrier and the intermediate layer. The intermediate layer can be formed by sequentially laminating a nickel layer and a chromate layer on a copper foil carrier. The adhesion between nickel and copper is higher than the adhesion between chromium and copper. Therefore, when the ultra-thin copper layer is peeled off, the interface between the ultra-thin copper layer and chromium is peeled off. Further, it is expected that the nickel of the intermediate layer has a barrier effect of preventing the copper component from diffusing from the carrier to the ultra-thin copper layer.

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

In order to obtain the following characteristics, it is preferred that the chromate layer in the intermediate layer is present thinly at the interface of the ultra-thin copper layer: the ultra-thin copper layer is not peeled off from the carrier before the lamination step to the insulating substrate, on the other hand, The characteristic that the ultra-thin copper layer can be peeled off from the carrier after the lamination step to the insulating substrate. When the nickel layer is not provided and the chromate layer is present at the boundary between the carrier and the ultra-thin copper layer, the peeling property is hardly improved. Further, when the nickel layer and the ultra-thin copper layer are directly laminated on the chromate-free layer, the peel strength is too strong or too weak depending on the amount of nickel in the nickel layer, so that appropriate peel strength cannot be obtained.

If the chromate layer is present at the boundary between the support and the nickel layer, the intermediate layer is also peeled off when the ultra-thin copper layer is peeled off, that is, peeling occurs between the carrier and the intermediate layer, which is not preferable. This is the case not only when a chromate layer is provided at the interface with the carrier, but also when a chromate layer is provided at the interface with the ultra-thin copper layer, if the amount of chromium is too large. The reason for this is that copper and nickel are easily dissolved in a solid state. Therefore, when these contacts are in contact with each other, the force is increased due to mutual diffusion, and it becomes difficult to peel off. On the other hand, chromium and copper are hardly dissolved, and mutual diffusion is less likely to occur. At the interface between chromium and copper, the adhesion is weak and easy to peel off. Moreover, when the amount of nickel in the intermediate layer is insufficient, only a trace amount of chromium exists between the carrier and the ultra-thin copper layer, so that the two are in close contact and are difficult to peel. from.

In the intermediate layer, the amount of nickel is attached to ² or less 1μg / dm ² or more and 40000μg / dm, the deposition amount of chromium 1μg / dm ² or more and 100μg / dm ² or less. As the amount of adhesion of nickel and chromium increases, the number of pinholes in the extremely thin copper layer tends to increase, but if it is within this range, the number of pinholes can be suppressed. Promise viewpoint of uniformity peeling of the thin copper layer, and suppressing the pinhole, the amount of nickel is preferably attached to the 1000μg / dm ² or more and ² or less 10000μg / dm, and the deposition amount of the chromium is set 10 μg/dm ² or more and 60 μg/dm ² or less, more preferably, the adhesion amount of nickel is 2000 μg/dm ² or more and 9000 μg/dm ² or less, and the adhesion amount of chromium is set to 15 μg/dm ² or more and 45 μg/ Dm ² or less. Further, in the present invention, it is preferred that the intermediate layer contains a trace amount of Zn. Thereby, the occurrence of pinholes can be intentionally reduced, and further, it is easy to obtain an appropriate peel strength, and thus contributes greatly to quality stability. The present invention is not intended to be limited by theory, but is considered to be due to the fact that an oxide film composed of Cr and Zn is formed by the presence of trace amounts of Zn in the intermediate layer, and the conductivity of the intermediate layer becomes more uniform and the conductivity is extremely high. Or the part with extremely low conductivity disappears. Thereby, the copper plating particles in the case where the ultra-thin copper layer is formed are uniformly adhered to the oxide film made of Cr and Zn, and the peel strength becomes an appropriate value (the peel strength is extremely high or the peel strength is extremely low).

Zn may be present in either or both of the Ni layer and the Cr layer in the intermediate layer. For example, when a Ni layer is formed, a zinc component is added to the plating solution to perform nickel-zinc alloy plating, thereby obtaining a Ni layer containing zinc. Further, a Cr layer containing zinc is obtained by adding a zinc component to the chromate treatment liquid. However, in either case, Zn diffuses in the intermediate layer, so Zn is usually detected in both the Ni layer and the Cr layer. Further, in the case where an oxide film composed of Cr and Zn is easily formed, Zn is preferably present in the Cr layer.

However, if the amount of adhesion of Zn in the intermediate layer is too small, the effect is limited. Therefore, it is preferably 1 μg/dm ² or more, and more preferably 5 μg/dm ² or more. On the other hand, when the amount of adhesion of Zn in the intermediate layer is too large, the peel strength is excessively large. Therefore, it is preferably 70 μg/dm ² or less, more preferably 30 μg/dm ² or less, and still more preferably It is set to 20 μg/dm ² or less.

The intermediate layer may also be composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn or alloys thereof, or such hydrates, or oxides thereof, or organic compounds A layer formed by any one or more of the layers. Also, the intermediate layer may be a plurality of layers.

For example, the intermediate layer from the side of the carrier may be composed of a single layer composed of any one of elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. a layer or an alloy layer composed of one or more elements selected from the group consisting of elements of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, and secondarily selected from the group consisting of Cr, Ni, A layer composed of a hydrate or an oxide or an organic substance of one or more elements of the element group of Co, Fe, Mo, Ti, W, P, Cu, Al, or Zn.

Further, for example, the intermediate layer from the side of the carrier may be composed of a single layer composed of any one of elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. a metal layer or an alloy layer composed of one or more elements selected from the group consisting of elements of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, and secondarily selected from the group consisting of Cr and Ni a single metal layer composed of any one of elemental groups of Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, An alloy layer composed of one or more elements of P, Cu, Al, and Zn.

<3. Priming plating>

An extremely thin copper layer is provided on the intermediate layer. In order to reduce pinholes of the ultra-thin copper layer, it is also possible to perform a base plating by a copper-phosphorus alloy on the intermediate layer. As the treatment liquid for the plating, a copper pyrophosphate plating solution or the like can be used. Thus, phosphorus is present on both the surface of the intermediate layer and the surface of the ultra-thin copper layer by the copper foil with a base plated by a copper-phosphorus alloy. Therefore, when peeling is performed between the intermediate layer/very thin copper layer, phosphorus can be detected from the surface of the intermediate layer and the ultra-thin copper layer. Further, since the plating layer formed by the primer plating is thinned, the thickness of the copper-phosphorus plating layer on the intermediate layer is 0.1 μm by cross-sectional observation using a FIB (focused ion beam) or a TEM (transmission electron microscope). When it is down, it can be judged to be the base plating.

<4. Very thin copper layer>

An extremely thin copper layer is provided on the intermediate layer. Other layers may be provided between the intermediate layer and the ultra-thin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfonate or copper cyanide, and can be used for a conventional electrolytic copper foil and can form copper at a high current density. In the case of a foil, a copper sulfate bath is preferred. The thickness of the ultra-thin copper layer is not particularly limited, and is usually thinner than the carrier, and is, for example, 12 μm or less, preferably 1 μm or more and 10 μm or less. It is typically 0.5 μm or more and 12 μm or less, and more typically 2 μm or more and 5 μm or less.

The ultra-thin copper layer of the copper foil with a carrier of the present invention is a heat treatment in which the recrystallization or excessive crystal grain growth is not performed in the ultra-thin copper layer, for example, a heat treatment at 180 ° C or more for 3 hours or longer. Thus, the average crystal grain size of the ultra-thin copper layer of the present invention in which the heat treatment for recrystallization or excessive crystal grain growth is not carried out is typically less than 15 μm. Further, the average crystal grain size is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less from the viewpoint of improving the strength of the ultra-thin copper layer. Further, in this case, the ultrafine copper layer of the present invention in which the heat treatment for recrystallization or excessive crystal grain growth is not performed in many cases is smaller than the thickness of the ultra-thin copper layer. Further, the ultra-thin copper layer of the copper foil with a carrier of the present invention may be applied as long as it is a heat treatment which does not cause the recrystallization or excessive crystal grain growth.

<5. Roughening treatment>

In order to make the adhesion to the insulating substrate excellent, for example, a roughening treatment layer may be provided on the surface of the ultra-thin copper layer by performing a roughening treatment. The roughening treatment can be carried out, for example, by forming roughened particles using copper or a copper alloy. The roughening treatment can also be fine. The roughening treatment layer may also be a layer composed of any one selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc, or a layer containing any one or more of the alloys. Wait. Further, after the roughened particles are formed by using copper or a copper alloy, the secondary particles or the tertiary particles may be subjected to roughening treatment using a monomer or an alloy of nickel, cobalt, copper or zinc. Thereafter, a single form or alloy of nickel, cobalt, copper or zinc may be used. The heat-resistant layer or the rust-preventing layer may be subjected to a treatment such as chromate treatment or decane coupling treatment. Alternatively, the heat-resistant layer or the rust-preventing layer may be formed by using a monomer, an alloy or the like of nickel, cobalt, copper or zinc without performing the roughening treatment, and the surface may be subjected to a treatment such as chromate treatment or decane coupling treatment. That is, a layer selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer may be formed on the surface of the roughened layer, or may be on the surface of the extremely thin copper layer. One or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer are formed. Further, the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, and the decane coupling treatment layer may each be formed into a plurality of layers (for example, two or more layers, three or more layers, or the like). Further, each layer may be a plurality of layers of two or three layers, and the order of the layers may be in any order, or the layers may be alternately laminated.

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

As the heat-resistant layer and the rust-preventing layer, a known heat-resistant layer or rust-preventing layer can be used. For example, the heat resistant layer and/or the rustproof layer may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron. a layer of one or more elements of the group of bismuth, or may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum A metal layer or an alloy layer composed of one or more elements of a group of elements, iron, and antimony. Moreover, the heat-resistant layer and/or the rust-preventing layer may further comprise a component selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum. Oxides, nitrides, and tellurides of one or more elements of the group of iron and antimony. Further, the heat-resistant layer and/or the rust-preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and/or the rust-preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50% by weight to 99% by weight of nickel and 50% by weight to 1% by weight of zinc, in addition to unavoidable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg/m ² , preferably 10 to 500 mg/m ² , and more preferably 20 to 100 mg/m ² . Further, the ratio of the nickel adhesion amount to the zinc adhesion amount of the nickel-zinc alloy-containing layer or the nickel-zinc alloy layer (=the adhesion amount of nickel/the adhesion amount of zinc) is preferably 1.5 to 10. Further, the nickel-zinc alloy-containing layer or the nickel-zinc alloy layer preferably has a nickel adhesion amount of 0.5 mg/m ² to 500 mg/m ² , more preferably 1 mg/m ² to 50 mg/m ² . When the heat-resistant layer and/or the rust-preventing layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate is difficult to be removed by the slag when the inner wall portion of the through hole or the guide hole or the like is in contact with the desmear liquid. The liquid is corroded, and the adhesion between the copper foil and the resin substrate is improved. The rustproof layer may also be a chromate treatment layer. A chromate treatment layer can be used with a known chromate treatment layer. For example, a chromate treatment layer means a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. The chromate treatment layer may also contain elements such as cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (may be metals, alloys, oxides, nitrides, sulfides). Any form). Specific examples of the chromate treatment layer include a pure chromate treatment layer, a zinc chromate treatment layer, and the like. In the present invention, a chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate is referred to as a pure chromate treatment layer. Further, in the present invention, a chromate-treated layer treated with a treatment liquid containing chromic anhydride or potassium dichromate 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 a nickel or nickel alloy layer having an adhesion amount of 1 mg/m ² to 100 mg/m ² , preferably 5 mg/m ² to 50 mg/m ² , and an adhesion amount of 1 mg/ The tin layer having m ² to 80 mg/m ² , preferably 5 mg/m ² to 40 mg/m ² is sequentially laminated, and the nickel alloy layer may also be composed of nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt. Any of the components. Further, the total adhesion amount of the nickel or nickel alloy of the heat-resistant layer and/or the rust-preventing layer to tin is preferably 2 mg/m ² to 150 mg/m ² , more preferably 10 mg/m ² to 70 mg/m ² . Further, the heat-resistant layer and/or the rust-preventive layer are preferably [the amount of nickel deposited in the nickel or nickel alloy] / [the amount of tin adhesion] = 0.25 to 10, more preferably 0.33 to 3. When the heat-resistant layer and/or the rust-preventing layer are used, the peeling strength of the circuit after processing the copper foil with a carrier to a printed wiring board, the chemical-resistant deterioration rate of the peeling strength, and the like are improved.

Further, as the heat-resistant layer and / or rust proof layer, may be formed in a deposition amount of 200 ~ 2000μg / dm ² of cobalt - deposition amount of 50 ~ 700μg / dm ² of cobalt and nickel - nickel alloy plated layer. This treatment can be regarded as a rust-proof treatment in a broad sense. The cobalt-nickel alloy plating layer must 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 μg/dm ² , the heat-resistant peel strength is lowered, and the oxidation resistance and chemical resistance are deteriorated. Further, another reason is that if the amount of cobalt is small, the treated surface becomes red and thus is not preferable.

As the decane coupling treatment layer, a known weather resistant layer can be used. Further, as the weather resistant layer, for example, a known decane coupling treatment layer can be used, and a decane coupling treatment layer formed using the following decane can be used.

As the decane coupling agent to be used in the decane coupling treatment, a known decane coupling agent can be used. For example, an amine decane coupling agent, an epoxy decane coupling agent, or a decyl decane coupling agent can be used. Further, as the decane coupling agent, vinyl trimethoxy decane, vinyl phenyl trimethoxy decane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyl propyl may also be used. Γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropyl Trimethoxydecane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane, imidazolium, three Decane, γ-mercaptopropyltrimethoxydecane, and the like.

The decane coupling treatment layer may be formed using a decane coupling agent such as epoxy decane, amino decane, methacryloxy decane or decyl decane. Further, such a decane coupling agent may be used in combination of two or more. Among them, those formed by using an amine-based decane coupling agent or an epoxy-based decane coupling agent are preferred.

The amino decane coupling agent referred to herein may also be selected from the group consisting of N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-(N- Styrylmethyl-2-aminoethylamino)propyltrimethoxydecane, 3-aminopropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltri Ethoxy decane, aminopropyl trimethoxy decane, N-methylaminopropyl trimethoxy decane, N-phenylaminopropyl trimethoxy decane, N-(3-propenyloxy-2 -hydroxypropyl)-3-aminopropyltriethoxydecane, 4-aminobutyltriethoxydecane, (aminoethylaminomethyl)phenethyltrimethoxydecane, N- (2-Aminoethyl-3-aminopropyl)trimethoxydecane, N-(2-aminoethyl-3-aminopropyl)tris(2-ethylhexyloxy)decane, 6 -(Aminohexylaminopropyl)trimethoxyanthracene Alkyl, aminophenyltrimethoxydecane, 3-(1-aminopropoxy)-3,3-dimethyl-1-propenyltrimethoxynonane, 3-aminopropyltri(methoxy) Ethyl ethoxy ethoxy) decane, 3-aminopropyl triethoxy decane, 3-aminopropyl trimethoxy decane, ω-aminoundecyltrimethoxy decane, 3-(2 -N-benzylaminoethylaminopropyl)trimethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, (N,N-diethyl-3 -aminopropyl)trimethoxydecane, (N,N-dimethyl-3-aminopropyl)trimethoxydecane, N-methylaminopropyltrimethoxydecane, N-phenylamine Propyltrimethoxydecane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β (Aminoethyl) γ-aminopropyltrimethoxydecane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane .

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

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

[very thin copper layer, heat-resistant layer, rust-proof layer, chromate treatment layer or resin layer on decane coupling treatment layer]

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

Moreover, the copper foil with carrier of the present invention may also have a heat-resistant layer and/or a rust-proof layer on the ultra-thin copper layer. A chromate treatment layer may be provided on the heat-resistant layer and/or the rust-preventing layer, or a decane coupling treatment layer may be provided on the chromate-treated layer.

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

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

The resin layer may be an adhesive or an insulating resin layer which is used in a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which even if the surface is touched with a finger, there is no adhesive feeling, and the insulating resin layer can be stored in a superposed state, and if it is further subjected to heat treatment, a hardening reaction is caused.

The resin layer may be an adhesive which is followed by a resin, or an insulating resin layer which is used in a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which there is no adhesive feeling even when a finger is brought into contact with the surface thereof, and the insulating resin layer can be stored in a superposed manner, and if it is further subjected to heat treatment, a curing reaction is caused.

Further, the resin layer may contain a thermosetting resin or a thermoplastic resin. Further, the resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. Further, as the resin layer, for example, those described in the following patents (resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material) may be used. And / or a method of forming a resin layer, and forming a device: International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. 11-5828, Japanese Patent Laid-Open No. 11 -140281, Japanese Patent No. 3184485, International Publication No. WO97/02728, Japanese Patent No. 3676375 No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003- 249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070 Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent Laid-Open No. 2006-257153, Japanese Patent Laid-Open No. 2007-326923, Japanese Patent Laid-Open No. 2008-111169 No., Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, Japanese Patent Laid-Open No. 2009-67029, International Publication No. WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471, Japanese Patent Laid-Open No. 2011-14727, International Publication No. WO2009/00 1850, International Publication No. WO2009/145179, International Publication No. WO2011/068157, and Japanese Laid-Open Patent Publication No. 2013-19056.

Further, the type of the resin layer is not particularly limited, and examples thereof include a resin containing at least one selected from the group consisting of epoxy resins, polyimine resins, and polyfunctional cyanates. Compound, maleimide compound, polym-butyleneimine compound, maleimide resin, aromatic maleimide resin, polyvinyl acetal resin, amine Ethyl formate resin, polyethersulfone (also known as polyethersulphone, polyethersulfone), polyether oxime (also known as polyethersulphone, polyether sulfone) Resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamidimide resin, rubber modified epoxy resin, phenoxy resin, Carboxyl modified acrylonitrile-butadiene resin, polyphenylene ether, di-n-butylene diimide Resin, thermosetting polyphenylene ether resin, cyanate resin, carboxylic anhydride, polycarboxylic acid anhydride, linear polymer having crosslinkable functional groups, polyphenylene ether resin, 2,2-bis(4- Cyanate-based phenyl)propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis(4-glycidylphenyl)propane, polyphenylene ether-cyanate resin, oxime modification Polyamidoximine resin, cyanoester resin, phosphazene resin, rubber modified polyamidoximine resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, Phenoxy group, polymer epoxy, aromatic polyamine, fluororesin, bisphenol, block copolymerized polyimide resin and cyanoester resin.

Further, the epoxy resin is one having two or more epoxy groups in the molecule, and can be used without any problem as long as it can be used for electrical or electronic materials. Further, the epoxy resin is preferably an epoxy resin obtained by epoxidizing a compound having two or more glycidyl groups in the molecule. Further, one or a mixture of two or more selected from the group consisting of hydrides or halides of the following epoxy resins may be used: bisphenol A type epoxy resin, bisphenol F type epoxy resin , bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolak type epoxy resin, cresol novolac type epoxy resin, cycloaliphatic epoxy resin, brominated epoxy resin, A Phenolic novolak type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, o-cresol novolak type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidyl amine type a glycidylamine compound such as an epoxy resin, triglycidyl isocyanurate or N,N-diglycidylamine, or a glycidyl ester compound such as tetrahydrophthalic acid diglycidyl ester, or phosphorus Epoxy resin, biphenyl type epoxy resin, biphenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin.

As the phosphorus-containing epoxy resin, a known epoxy resin containing phosphorus can be used. Further, the phosphorus-containing epoxy resin preferably has, for example, two or more epoxy groups in the molecule derived from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9). An epoxy resin obtained from a derivative of 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide).

The epoxy resin obtained as a derivative derived from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 9,10-dihydro-9-oxa-10-phosphine Phenanthrene-10-oxide and naphthoquinone or p-phenylene The phenol is reacted to obtain a compound represented by the following 1 (HCA-NQ) or 2 (HCA-HQ), and then the OH group portion is reacted with an epoxy resin to prepare a phosphorus-containing epoxy resin.

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

Further, as the brominated epoxy resin, a known bromination can be used. (brominated) epoxy resin. For example, the brominated epoxy resin is preferably a brominated epoxy resin having a structural formula represented by Chemical Formula 6, and a brominated epoxy resin having the structural formula shown by Chemical Formula 7 shown below. One type or two types are used in combination; and the structural formula represented by the formula 6 is derived from a derivative derived from tetrabromobisphenol A having two or more epoxy groups in the molecule.

As the maleimide-based resin or the aromatic maleimide resin or the maleimide compound or the poly-n-butylene imide compound, a known butylene can be used. A quinone imine resin or an aromatic maleimide resin or a maleimide compound or a poly-n-butylene imine compound. For example, as a maleimide-based resin or an aromatic maleimide resin or a maleimide compound or a poly-n-butylene imine compound, 4, 4'- can be used. Diphenylmethane bis-m-butylene iminoimide, polyphenylmethane maleimide, inter-phenyl bis-bis-succinimide, bisphenol A diphenyl ether bis-butene Yttrium imine, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bis-n-butylene diimide, 4-methyl-1,3-extension Phenylbis-n-butyleneimine, 4,4'-diphenyl ether bis-n-butylene imide, 4,4'-diphenylfluorene bis-n-butylene diimide, 1,3 - bis(3-maleoximine phenoxy)benzene, 1,3-bis(4-maleoximine phenoxy)benzene, and the above compound, the above compound or other compound Polymers, etc. Further, the maleimide-based resin may be an aromatic maleimide resin having two or more maleimide groups in the molecule, or may have two molecules in the molecule. A polymerized adduct obtained by polymerizing more than one maleicimide-based aromatic maleimide resin with a polyamine or an aromatic polyamine.

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

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

As the bisphenol, a known bisphenol can be used, and bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4'-dihydroxybiphenyl, or HCA (9, 10) can be used. -Dihydro-9-Oxa-10-Phosphaphenanthrene-10-Oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and terpenoids such as hydroquinone and naphthoquinone The bisphenol obtained from the adduct, and the like.

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

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

A well-known rubber resin can be used for the said rubber-type resin. For example, the above rubbery resin is described as containing the concept of natural rubber and synthetic rubber, and the latter synthetic rubber is styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, acrylonitrile butadiene. Rubber, acrylic rubber (acrylate copolymer), polybutadiene rubber, isoprene rubber, and the like. Further, in order to secure the heat resistance of the formed resin layer, it is also useful to use a heat-resistant synthetic rubber such as a nitrile rubber, a chloroprene rubber, a ruthenium rubber or an urethane rubber. In order to produce a copolymer by reacting with an aromatic polyamide resin or a polyamidoximine resin, it is preferable to provide various functional groups at both ends. It is especially useful to use CTBN (carboxy terminal butadiene nitrile). Further, in the acrylonitrile butadiene rubber, when it is a carboxyl group-modified material, an epoxy resin and a crosslinked structure can be obtained, and the flexibility of the resin layer after curing can be improved. As the carboxyl group-modified material, a carboxyl terminal nitrile butadiene rubber (CTBN), a carboxyl terminal butadiene rubber (CTB), or a carboxyl-modified nitrile butadiene rubber (C-NBR) can be used. As the above polyamidoximine resin, a known polyamidimide resin can be used. Further, as the polyimine amide resin, for example, trimellitic anhydride, benzophenonetetracarboxylic anhydride, and 3,3-dimethyl-4,4-biphenyldiisocyanate can be used in N- The resin obtained by heating in a solvent such as methyl-2-pyrrolidone or/and N,N-dimethylacetamide or by using trimellitic anhydride, diphenylmethane diisocyanate and carboxyl terminal acrylonitrile- The butadiene rubber is heated in a solvent such as N-methyl-2-pyrrolidone or / and N,N-dimethylacetamide.

As the rubber-modified polyamidoximine resin, a known rubber-modified polyamidoximine resin can be used. The rubber-modified polyamidoximine resin is obtained by reacting a polyamidoximine resin with a rubber resin. The use of the polyamidoximine resin to react with the rubber resin is carried out in order to enhance the flexibility of the polyamidoximine resin itself. In other words, the polyamidoximine resin is reacted with a rubber resin, and one of the acid components (such as cyclohexanedicarboxylic acid) of the polyamidoximine resin is partially substituted with a rubber component. As the polyamidoximine resin, a known polyamidoximine resin can be used. Further, as the rubber resin, a known rubber resin or the above rubber resin can be used. To make rubber change When the polyamidoquinone imine resin is polymerized, the solvent used for dissolving the polyamidoximine resin and the rubber resin is preferably one or two or more kinds of dimethylformamide or dimethylacetamidine. Amine, N-methyl-2-pyrrolidone, dimethyl hydrazine, nitromethane, nitroethane, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, acetonitrile, γ-butyrolactone and the like are used in combination.

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

As the fluororesin, a known fluororesin can be used. Further, as the fluororesin, for example, a fluororesin composed of at least one thermoplastic resin selected from the group consisting of fluororesin or the like: PTFE (polytetrafluoroethylene (tetrafluoride)), PFA (tetrafluoroethylene-all) may be used. Fluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene-hexafluoropropylene copolymer (tetra, hexafluoride)), ETFE (tetrafluoroethylene-ethylene copolymer), PVDF (polyvinylidene fluoride) Fluorinated)), PCTFE (polychlorotrifluoroethylene (trifluoride)), polyallyl fluorene, aromatic polysulfide and aromatic polyether.

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

A specific example of the above biphenyl type phenol resin is shown in Chemical Formula 8.

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

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

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

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

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

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

The polycarboxylic acid anhydride is preferably a component that functions as a curing agent for an epoxy resin. Further, the polycarboxylic acid anhydride is preferably phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic dianhydride, tetrahydroxyphthalic anhydride, hexahydroxyphthalic anhydride, or Hexahydroxyphthalic anhydride, vanadic acid, methylvanadic acid.

The thermoplastic resin may be a thermoplastic resin having a functional group other than an alcoholic hydroxyl group polymerizable with an epoxy resin.

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

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

As the rubber resin to be reacted with the above aromatic polyamide resin, a known rubber resin or the above rubber resin can be used.

The aromatic polyamide resin polymer is used for the purpose of etching the copper foil after the copper clad laminate is processed, and is not affected by the etching due to the etching liquid.

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

Further, a semi-hardened resin layer having a thermal expansion coefficient after curing of from 0 ppm/° C. to 50 ppm/° C. may be provided on the cured resin layer. Further, the entire resin layer after the hardened resin layer and the semi-hardened resin layer are cured may have a thermal expansion coefficient of 40 ppm/° C. or less. The glass transition temperature of the above-mentioned cured resin layer may be 300 ° C or more. Further, the semi-cured resin layer may be formed by using a maleimide-based resin or an aromatic maleimide resin. The resin composition for forming the semi-hardened resin layer preferably contains a maleimide-based resin or an epoxy resin. A linear, linear polymer having a crosslinkable functional group. As the epoxy resin, a known epoxy resin or an epoxy resin described in the present specification can be used. Further, as the maleimide-based resin, the aromatic maleimide resin, and the linear polymer having a crosslinkable functional group, a known maleimide-based resin can be used. , an aromatic maleimide resin, a linear polymer having a crosslinkable functional group or the above maleimide resin, an aromatic maleimide resin, and having a crosslinkable A linear polymer of a functional group.

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

Further, the polymer layer preferably contains any one or two or more of an epoxy resin, a maleimide-based resin, a phenol resin, and an urethane resin. Further, the semi-cured resin layer is preferably composed of an epoxy resin composition having a thickness of 10 μm to 50 μm.

Further, the epoxy resin composition preferably contains the following components of the components A to E.

Component A: one of a group of bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol AD type epoxy resins selected from the group consisting of epoxy equivalents of 200 or less and liquid at room temperature or Two or more epoxy resins.

Component B: High heat resistant epoxy resin.

Component C: a phosphorus-containing epoxy resin or a phosphazene-based resin, or a phosphorus-containing flame retardant resin.

Component D: using a solvent having a solubility in a solvent having a boiling point in the range of 50 ° C to 200 ° C A rubber-modified polyamidoximine resin modified by a liquid rubber component.

Component E: Resin hardener.

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

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

As the rubber component of the D-component, that is, a rubber-modified polyamidoximine resin, the above-mentioned rubber-modified polyamidoximine resin can be used. As the resin curing agent of the E component, the above resin curing agent can be used.

A resin varnish is added to the resin composition shown above to prepare a resin varnish, and the adhesive layer of the printed wiring board is formed to form a thermosetting resin layer. A solvent is added to the resin composition to prepare a resin solid content in the range of 30% by weight to 70% by weight, and the resin varnish can be formed into a 5% by weight when measured according to MIL-P-13949G in the MIL specification. A semi-hardened resin film in the range of 35%. As the solvent, a known solvent or the above solvent can be used.

The resin layer is a resin layer having a first thermosetting resin layer and a second thermosetting resin layer on the surface of the first thermosetting resin layer, and a first thermosetting resin. The layer may be formed of a resin component of a drug which is insoluble in the desmear process in the wiring board manufacturing process, and the second thermosetting resin layer may be a drug used in the desmear process which is dissolved in the wiring board manufacturing process. And the resin former can be washed away. The first thermosetting resin layer may be formed by using a resin component obtained by mixing one or a mixture of two or more of a polyimide resin, a polyether oxime, and a polyphenylene oxide. The second thermosetting resin layer may be formed using an epoxy resin component. The thickness t1 (μm) of the first thermosetting resin layer is such that the roughened surface roughness of the copper foil with a carrier is Rz (μm) and the thickness of the second thermosetting resin layer is t2 ( In the case of μm), t1 is preferably a thickness satisfying the condition of Rz < t1 < t2.

The resin layer may be a prepreg obtained by impregnating a resin bone into a frame material. The resin impregnated in the above skeleton material is preferably a thermosetting resin. The prepreg may be a prepreg used in the manufacture of a known prepreg or printed wiring board.

The above framework material may also contain aromatic polyamide fibers or glass fibers or wholly aromatic polyester fibers. The above skeleton material is preferably a non-woven fabric or a woven fabric of an aromatic polyamide fiber or a glass fiber or a wholly aromatic polyester fiber. Further, the wholly aromatic polyester fiber is preferably a wholly aromatic polyester fiber having a melting point of 300 ° C or higher. The above-mentioned wholly aromatic polyester fiber having a melting point of 300 ° C or more refers to a fiber produced by using a resin called a so-called liquid crystal polymer which is 2-hydroxy-6-naphthoic acid and p-hydroxybenzene. The polymer of formic acid is the main component. The wholly aromatic polyester fiber has a low dielectric constant and a low dielectric dissipation factor, and thus has excellent properties as a constituent of an electrical insulating layer, and can be combined with glass fibers and aromatic polyamides. The fibers are used in the same way.

Further, in order to improve the wettability of the surface of the fiber constituting the nonwoven fabric and the woven fabric, it is preferred to carry out the treatment with a decane coupling agent. In the decane coupling agent at this time, a known decane coupling agent such as an amine group or an epoxy group or the above decane coupling agent can be used depending on the purpose of use.

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

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

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

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

The dielectric (dielectric filler) can be in powder form. When the dielectric (dielectric filler) is in the form of a powder, the powder characteristics of the dielectric (dielectric filler) must first be from 0.01 μm to 3.0 μm, preferably from 0.02 μm to 2.0. The range of μm. Regarding the particle diameter referred to herein, since the particles form a fixed secondary secondary aggregation state and are inferior in accuracy, the laser diffraction scattering particle size distribution measurement method or BET (Brunauer-Emmett-Teller, The measured value of the Buert method or the like is estimated to be unusable in the measurement of the average particle diameter, and the dielectric (dielectric filler) is directly observed by a scanning electron microscope (SEM), and the SEM image is subjected to image analysis. The average particle diameter referred to herein is obtained. The particle size at this time is expressed as DIA in this specification. In addition, the image analysis of the powder of the dielectric body (dielectric filler) observed using a scanning electron microscope (SEM) in this specification is performed using the IP-1000 PC manufactured by Asahi Engineering Co., Ltd. for roundness threshold. 10. Round particle analysis with a degree of coincidence of 20, and the average particle diameter DIA is obtained.

According to the above embodiment, it is possible to provide a carrier-attached copper foil having a resin layer containing a dielectric body which improves the adhesion between the inner layer circuit surface of the inner core material and the resin layer containing the dielectric material, and the dielectric The system is used to form a capacitor circuit layer with a lower dielectric loss factor.

The resin and/or resin composition and/or compound contained in the above resin layer is dissolved in, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N- Methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl stilbene, N-methyl-2-pyrrolidine A resin liquid (resin varnish) is prepared in a solvent such as ketone, N,N-dimethylacetamide or N,N-dimethylformamide, and is applied to the resin liquid (resin varnish) by, for example, a roll coating method. The ultra-thin copper layer or the heat-resistant layer, the rust-preventive layer, or the chromate-treated layer or the decane coupling agent layer is then heated and dried as necessary to remove the solvent to be in a B-stage state. For drying, for example, a hot air drying oven may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the resin layer may be dissolved in a solvent to form a resin solid content of 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt%. ~40 wt%, more preferably 25 wt% to 40 wt% of the resin liquid. Furthermore, in terms of environmental aspects, it is best to use a mixed solvent of methyl ethyl ketone and cyclopentanone to dissolve at this stage. Further, the solvent is preferably a solvent having a boiling point of from 50 ° C to 200 ° C.

Moreover, it is preferable that the resin layer is a semi-hardened resin film in which the resin flow rate is 5% to 35% in accordance with MIL-P-13949G in the MIL standard.

In the present specification, the term "resin overflow" refers to a value calculated based on the result of the following method based on the number 1, which is based on MIL-P-13949G in the MIL specification, and a resin-attached copper having a resin thickness of 55 μm. Four 10 cm square samples were taken from the foil, and the four samples were placed in a state of being stacked (layered body) under a pressure of 171 ° C, a pressurization pressure of 14 kgf / cm ² , and a pressurization time of 10 minutes. The adhesive was measured and the resin outflow weight at this time was measured.

The copper foil with a carrier (the resin-attached copper foil with a resin) which has the above-mentioned resin layer can be used in the following aspect, after superposing this resin layer and a base material, the whole resin layer is thermo-compressed, and the resin layer is heat-hardened, and the carrier is peeled. An extremely thin copper layer is exposed (of course, the surface of the intermediate layer side of the ultra-thin copper layer is exposed), and a specific wiring pattern is formed thereon.

When the carrier-attached copper foil with the resin is used, the number of sheets of the prepreg material used in the production of the multilayer printed wiring board can be reduced. Further, the copper clad laminate can be produced without ensuring that the thickness of the resin layer is such that the thickness of the interlayer insulation can be ensured or not all of the prepreg material is used. Further, at this time, the surface of the substrate may be primed with an insulating resin to further improve the smoothness of the surface.

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

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

If the thickness of the resin layer becomes thinner than 0.1 μm, there is a case where the force is lowered, and the copper foil with the resin attached to the resin is laminated on the substrate having the inner layer material without interposing the prepreg material. It is difficult to ensure interlayer insulation between the circuits of the inner layer material. On the other hand, when the thickness of the resin layer is made thicker than 120 μm, there is a case where it is difficult to form a resin layer of a desired thickness by a single coating step, and an extra material cost and a number of steps are required, which is economically disadvantageous.

Further, when the copper foil with a carrier having a resin layer is used for producing an extremely thin multilayer printed wiring board, the thickness of the resin layer is set to be 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, still more preferably 1 μm. The case of ~5 μm is preferable because the thickness of the multilayer printed wiring board is reduced.

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

Further, the total resin layer thickness of the cured resin layer and the semi-hardened resin layer is preferably from 0.1 μm to 120 μm, preferably from 5 μm to 120 μm, preferably from 10 μm to 120 μm, more preferably from 10 μm to 60 μm. Further, the thickness of the cured resin layer is preferably from 2 μm to 30 μm, preferably from 3 μm to 30 μm, more preferably from 5 to 20 μm. Further, the thickness of the semi-hardened resin layer is preferably from 3 μm to 55 μm, preferably from 7 μm to 55 μm, more preferably from 15 to 115 μm. The reason is that when the total resin layer thickness exceeds 120 μm, it is difficult to manufacture a multilayer printed wiring board having a small thickness. If it is less than 5 μm, a multilayer printed wiring board having a thin thickness is easily formed, but a circuit as an inner layer is generated. The resin layer of the insulating layer in the middle tends to be too thin, and the insulation between the circuits of the inner layer tends to be unstable. Further, when the thickness of the cured resin layer is less than 2 μm, there is a need to consider the surface roughness of the roughened surface of the copper foil. On the other hand, if the thickness of the cured resin layer exceeds 20 μm, the effect of the cured resin layer is not particularly enhanced, and the total thickness of the insulating layer becomes thick.

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

Further, the thickness of the above resin layer means the average value of the thickness measured by the cross-sectional observation at any ten points.

Further, as another product form of the copper foil with a carrier to which the resin is attached, the ultra-thin copper layer or the heat-resistant layer, the rust-proof layer, or the chromate-treated layer or the decane coupling treatment layer may be used. The upper layer is coated with a resin layer to form a semi-hardened state, and then the carrier is peeled off, and the carrier is produced in the form of a copper foil with a resin in which no carrier is present.

<6. With carrier copper foil>

In this manner, a copper foil with a carrier having a copper foil carrier, an intermediate layer formed on the copper foil carrier, and an extremely thin copper layer laminated on the intermediate layer was produced. The method of using the carrier copper foil itself is well known, for example, bonding the surface of the ultra-thin copper layer to the paper substrate phenol resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, glass cloth-paper composite The substrate epoxy resin, the glass cloth-glass non-woven composite substrate epoxy resin, the glass cloth substrate epoxy resin, the polyester film, the polyimide film, and the like are coated on the insulating substrate, and the carrier is peeled off after thermocompression bonding. Then, the conductor pattern for the ultra-thin copper layer on the insulating substrate is etched to finally produce a printed wiring board. In the case of the copper foil with carrier of the present invention, the peeling portion is mainly the interface between the intermediate layer and the extremely thin copper layer. Further, the printed circuit board is completed by mounting electronic components on the printed wiring board. Hereinafter, examples of the manufacturing steps of several printed wiring boards using the copper foil with a carrier of the present invention will be exemplified.

An embodiment of the method for producing a printed wiring board according to the present invention includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and stacking the copper foil with the insulating substrate; and the copper carrier The foil and the insulating substrate are laminated so that the ultra-thin copper layer side faces the insulating substrate, and then the copper-clad laminate is formed by peeling off the carrier with the carrier copper foil, and then the semi-additive method and the modified half are formed. Addition method, partial addition method and subtractive method Either method of forming a circuit. The insulating substrate can also be made with an inner layer circuit.

In the present invention, the semi-additive method refers to a method of forming a conductor pattern by plating and etching after performing thin electroless plating on an insulating substrate or a copper foil seed layer.

Therefore, an embodiment of a method for producing a printed wiring board of the present invention using a semi-additive method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate a step of peeling off the carrier with the carrier copper foil after laminating the copper foil with the carrier and the insulating substrate; removing all the thin copper exposed by peeling off the carrier by etching or plasma etching using an acid or the like a step of forming a via hole or/and a blind via on the resin exposed by removing the ultra-thin copper layer by etching; and performing desmear treatment on the region containing the via hole or/and the blind via hole a step of providing an electroless plating layer in a region containing the resin and the through hole or/and the blind hole; a step of providing a plating resist on the electroless plating layer; exposing the plating layer, and then removing the region forming the circuit a step of preventing plating; a step of removing an electrolytic plating layer in a region where the plating resist is formed by the circuit; and a step of removing the plating resist; Step electroless plating layer of the area other than the area of the circuit and the like formed is removed is located.

Another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate ; a step of laminating the carrier-attached copper foil and the insulating substrate to peel off the carrier of the carrier-attached copper foil; and removing the extremely thin copper layer exposed by peeling off the carrier by etching or plasma etching using an etching solution such as acid a step of providing an electroless plating layer on a surface of the resin exposed by etching to remove the ultra-thin copper layer; a step of providing a plating resist on the electroless plating layer; exposing the plating layer, and then removing the circuit a step of preventing plating of the region; a step of providing an electrolytic plating layer in a region formed by removing the above-mentioned circuit of the plating resist; a step of removing the plating resist; and removing no region outside the region where the circuit is formed by flash etching or the like The step of electroplating and an extremely thin copper layer.

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

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

Another embodiment of the method for producing a printed wiring board of the present invention using the modified semi-additive method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate a step of laminating the carrier-attached copper foil and the insulating substrate to peel the carrier of the carrier-attached copper foil; and providing a plating resist layer on the ultra-thin copper layer exposed by peeling off the carrier; and exposing the plating resist layer, a step of removing an anti-plating layer in a region where the circuit is formed; a step of providing an electroplated layer in a region where the circuit for removing the anti-plating layer is formed; a step of removing the anti-plating layer; and removing the electrode forming the circuit by flash etching or the like The step of a very thin copper layer in an area outside the area.

In the present invention, the partial addition method refers to a method in which a substrate having a conductor layer is provided, and a catalyst core is provided on a substrate which is formed through a hole for a via hole or a via hole, and is etched. After the conductor circuit is formed, if necessary, a solder resist layer or a plating resist layer is provided, and a thickness is applied to the via hole or the via hole by electroless plating treatment on the conductor circuit, thereby manufacturing a printed wiring board.

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

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

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

Another embodiment of the method for producing a printed wiring board of the present invention using the subtractive method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and stacking the copper foil with the carrier and the insulating substrate; a step of laminating the carrier-attached copper foil and the insulating substrate, and then peeling off the carrier of the carrier-attached copper foil; and providing a through-hole or/and a blind via on the extremely thin copper layer and the insulating substrate exposed by peeling off the carrier; a step of removing the slag treatment in the region containing the through hole or/and the blind hole; a step of providing an electroless plating layer on the region including the through hole or/and the blind hole; forming a mask on the surface of the electroless plating layer a step of providing an electrolytic plating layer on the surface of the electroless plating layer on which the mask is not formed; a step of providing an etching resist layer on the surface of the electrolytic plating layer or/and the ultra-thin copper layer; and the etching resist layer a step of forming a circuit pattern by exposure; a step of forming an electric circuit by removing the ultra-thin copper layer and the electroless plating layer by etching or plasma etching using an acid or the like; In addition to the above steps of etching the resist layer.

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

Here, a specific example of a method of manufacturing a printed wiring board using the copper foil with a carrier of the present invention will be described in detail with reference to the drawings. Furthermore, here, there is a roughening treatment layer The copper foil with a carrier of the ultra-thin copper layer is described as an example. However, the present invention is not limited thereto. Even if a copper foil with a carrier having an extremely thin copper layer having no roughened layer is used, the following printed wiring board can be similarly produced. Manufacturing method.

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

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

Next, after the plating for the circuit is formed as shown in Fig. 1-C, the resist is removed, thereby forming a circuit plating of a specific shape.

Next, as shown in FIG. 2-D, a method of covering the circuit plating (in the form of a buried circuit plating) is provided on the ultra-thin copper layer with a resin embedded and a resin layer, followed by the ultra-thin copper layer side Carrier copper foil (layer 2).

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

Next, as shown in Fig. 2-F, the laser opening is performed at a specific position of the resin layer to form a blind hole in such a manner that the circuit plating is exposed.

Next, as shown in Fig. 3-G, the blind holes are embedded with copper to form a hole.

Next, as shown in Fig. 3-H, circuit plating is formed on the filling holes in the manner of Fig. 1-B and Fig. 1-C described above.

Next, the carrier was peeled off from the carrier copper foil of the first layer as shown in Fig. 3-1.

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

Next, as shown in Fig. 4-K, a bump is formed on the circuit plating in the resin layer, and a copper pillar is formed on the solder. A printed wiring board using the copper foil with a carrier of the present invention was produced in this manner.

The above-mentioned other carrier copper foil (second layer) may be a copper foil with a carrier of the present invention, or a conventional copper foil with a carrier may be used, and a usual copper foil may be used. Also, in Figure 3-H The circuit of the second layer shown further forms a layer or a plurality of layers of circuitry, which are formed by any of a semi-additive process, a subtractive process, a partial addition process or a modified semi-additive process.

Further, the copper foil with a carrier used for the first layer may have a substrate on the side of the carrier side of the copper foil with the carrier. By having the substrate or the resin layer, the carrier-attached copper foil used for the first layer is supported, and wrinkles are less likely to occur, so that productivity is improved. Further, the substrate may be any substrate as long as it has an effect of supporting the copper foil with a carrier used for the first layer. For example, as the substrate, a carrier, a prepreg, a resin layer, or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, an inorganic compound plate, an inorganic compound foil, or an organic compound described in the specification of the present application can be used. Plate, organic compound foil.

The timing for forming the substrate on the side surface of the carrier is not particularly limited, and it is necessary to form the substrate before peeling off the carrier. In particular, it is preferable to form a substrate before the step of forming a resin layer on the side surface of the ultra-thin copper layer of the copper foil with a carrier, and more preferably to form a circuit on the side surface of the ultra-thin copper layer of the copper foil with a carrier. The substrate was formed before.

The copper foil of the carrier-attached copper foil of the present invention is preferably controlled to have the chromatic aberration of the surface of the extremely thin copper layer to satisfy the following (1). In the present invention, the "chromatic aberration on the surface of the ultra-thin copper layer" means the chromatic aberration on the surface of the ultra-thin copper layer or the chromatic aberration on the surface of the surface-treated layer when various surface treatments such as roughening treatment are performed. That is, the copper foil of the carrier of the present invention is preferably an ultra-thin copper layer or a roughened layer or a heat-resistant layer or a rust-preventive layer or a chromate-treated layer or a surface of a decane coupling layer is controlled to satisfy the following (1) .

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

Here, the color difference ΔL, Δa, and Δb are measured by a color difference meter, and black/white/red/green/yellow/blue is added, which is a comprehensive index shown by the L*a*b color system based on JISZ8730. ΔL represents white black, Δa represents red-green, and Δb represents yellow-blue. Further, ΔE*ab is expressed by the following formula using these chromatic aberrations.

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

Further, the chromatic aberration may be adjusted by providing a roughening treatment layer by roughening the surface of the ultra-thin copper layer. In the case where the roughening treatment layer is provided, it can be adjusted by using an electrolyte containing copper and one or more elements selected from the group consisting of nickel, cobalt, tungsten, and molybdenum to increase the current density earlier. (e.g., 40 ~ 60A / dm ^2), to reduce processing time (e.g., 0.1 to 1.3 seconds). In the case where the roughened layer is not provided on the surface of the ultra-thin copper layer, it can be achieved by using a plating bath having a concentration of Ni more than twice that of other elements, and a current lower than before. The processing time (20 seconds to 40 seconds) is set for a long time under a density (0.1 to 1.3 A/dm ² ) for the surface of an extremely thin copper layer or a heat-resistant layer or a rust-proof layer or a chromate treatment layer or a decane coupling treatment layer. Ni alloy plating (for example, Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating) treatment.

If the color difference ΔE*ab of the surface of the ultra-thin copper layer is 45 or more based on JISZ8730, for example, when a circuit is formed on the surface of the ultra-thin copper layer of the copper foil with a carrier, the contrast between the ultra-thin copper layer and the circuit becomes clear, and the result is clear. The visibility is good, and the positioning of the circuit can be performed with high precision. The color difference ΔE*ab based on JISZ8730 on the surface of the ultra-thin copper layer is preferably 50 or more, more preferably 55 or more, still more preferably 60 or more.

When the chromatic aberration on the surface of the ultra-thin copper layer, the roughened layer, the heat-resistant layer, the rust-proof layer, the chromate-treated layer or the decane coupling layer is controlled in the above manner, the contrast with the circuit plating becomes clear, and the visibility changes. good. Therefore, in the manufacturing steps shown in, for example, FIG. 1-C of the printed wiring board as described above, the circuit plating can be accurately formed at a specific position. Further, according to the method for manufacturing a printed wiring board as described above, the circuit plating is formed in the resin layer. Therefore, for example, when the ultra-thin copper layer is removed by flash etching as shown in FIG. 4-J, the circuit is plated with a resin. The layer protection is maintained in shape, whereby the formation of the fine circuit becomes easy. Also, since the circuit is plated with a resin layer The protection is improved, and the migration resistance is improved, and the wiring of the circuit can be well suppressed. Therefore, the formation of a fine circuit becomes easy. Moreover, when the ultra-thin copper layer is removed by flash etching as shown in FIG. 4-J and FIG. 4-K, the exposed surface of the circuit plating is formed into a shape recessed from the resin layer, so that it is easy to plate the circuit. The bumps are formed, and copper pillars are easily formed thereon, thereby improving manufacturing efficiency.

Further, a well-known resin or prepreg can be used for the embedded resin (resin). For example, impregnated BT (bis-s-butylene diimine III) can be used. A prepreg of a glass cloth of a resin or a BT resin, an ABF film (Ajinomoto Build-up Film, Ajinomoto accumulation film) manufactured by Ajinomoto Fine-Techno Co., Ltd., or ABF. Further, the resin layer and/or the resin and/or the prepreg described in the present specification can be used as the above-mentioned embedded resin (resin).

The surface of the copper foil carrier with the carrier copper foil of the present invention and the surface of the ultra-thin copper layer opposite to the intermediate layer, that is, the residual stress of the outer surface are both contraction stress or tensile stress. Thus, 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 are residual stresses in the same direction, and thus the types of the carrier copper foil and the ultra-thin copper layer, and the thickness thereof are not limited. And the warpage of the copper foil can be satisfactorily suppressed. Further, in order to suppress the warpage of the copper foil more satisfactorily, the residual stress on the outer surface of the copper foil carrier is preferably 0.1 times or more and 5.0 times or less, and more preferably 0.3 times or more, of the residual stress on the outer surface of the ultra-thin copper layer. 3.0 times or less.

[Examples]

Hereinafter, the present invention will be described in further detail by way of examples of the invention, but the invention is not limited by the examples.

(Examples 1 to 6)

1. Manufacture of carrier copper foil

As a copper foil carrier, a long strip of electrolytic copper foil (manufactured by JX Nippon Mining & Metal Co., Ltd., JTC (product name), thickness: 18 μm) and rolled copper foil (manufactured by JX Nippon Mining & Metals Co., Ltd.) were prepared. , C1100 (product name), thickness 18μm).

The residual stress of each copper foil which becomes the outer side when the copper foil with a carrier is formed is adjusted to -30 MPa. Above and within the range of 30 MPa or less. Here, when the residual stress is a positive value, the contraction stress is expressed, and when the residual stress is a negative value, the tensile stress is expressed. In the case where an electrolytic copper foil is used as the copper foil carrier, the residual stress of the surface layer can be adjusted to an arbitrary range by optimizing the composition of the electrolytic bath and the electrolysis conditions, and the residual stress of the outer surface of the ultra-thin copper layer described later. . An electrolytic copper foil was formed on an electrolytic drum made of stainless steel using the following electrolytic bath composition and electrolytic conditions. Further, when the flow rate of the electrolytic solution is increased, the residual stress of the copper foil tends to act in the shrinkage direction (the shrinkage stress easily acts), and if the flow rate of the electrolytic solution is lowered, the residual stress of the copper foil is stretched. It tends to act in the direction (the tensile stress is easy to function). In addition, when the current density is increased, the residual stress of the copper foil tends to act in the shrinkage direction (the shrinkage stress easily acts), and when the current density is lowered, the residual stress of the copper foil acts in the stretching direction ( The tendency of tensile stress to act easily. Further, the residual stress can also be adjusted by adding an additive of an electrolytic solution (for example, Cl, animal glue, or the like).

(electrolytic bath composition)

Cu: 80~120g/L

H ₂ SO ₄ : 80~120g/L

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

Animal glue: 0.1~6.0mg/L (Examples 1, 2, 5, 6, Comparative Example 1)

(electrolysis conditions)

Liquid temperature: 55~65°C

Current density: 100A/dm ²

Electrolyte flow rate: 1.5m / sec

When a rolled copper foil is used as the copper foil carrier, the residual stress of the surface layer can be adjusted to an arbitrary range by optimizing the rolling conditions and heat treatment conditions in the rolled copper foil manufacturing step, which is easy for the manufacturer and Is known. It suffices to adjust the range of the residual stress on the outer surface of the ultra-thin copper layer described below. In this embodiment, the calendering in the final cold rolling The degree of processing was set to 95%, the degree of calendering of the final pass in the final cold rolling was set to 5%, and the diameter of the calender roll used in the final pass in the final cold rolling was set to 80 mm. Further, the residual stress of the surface layer of the rolled copper foil can be adjusted by changing the roll diameter of the calender roll used in the final cold rolling, or can be adjusted by controlling the degree of calendering of the final cold rolling. For example, when the roll diameter is large, the residual stress of the surface layer tends to act in the stretching direction (the tensile stress easily acts), and when the roll diameter is small, the residual stress of the surface layer acts in the shrinkage direction (shrinkage stress) In the case where the degree of calendering at the final cold rolling is high, the residual stress in the surface layer tends to act in the shrinkage direction (the shrinkage stress easily acts), and the calendering degree in the final cold rolling is low. At the time, it tends to act in the stretching direction (the tensile stress easily acts). In addition, when the degree of rolling processing in the final pass of the final cold rolling is small, the residual stress of the surface layer tends to act in the shrinkage direction (the shrinkage stress easily acts), and the final rolling process in the final cold rolling is large. At the time, the residual stress of the surface layer tends to act in the stretching direction (the tensile stress easily acts).

Regarding the surface of the carrier and the side of the ultra-thin copper layer, the intermediate layer formation treatment described in Table 1 was carried out on the smooth side of the copper foil under the following conditions using a roll-to-roll continuous production line under the following conditions. . Water washing and pickling were carried out between the treatment steps of the surface side of the carrier and the side of the ultra-thin copper layer.

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

Nickel sulfate: 250~300g/L

Nickel chloride: 35~45g/L

Nickel acetate: 10~20g/L

Trisodium citrate: 15~30g/L

Gloss agent: saccharin, butynediol, etc.

Sodium lauryl sulfate: 30~100ppm

ZnSO ₄ : 0.05~5g/L

pH: 4~6

Bath temperature: 50~70°C

Current density: 3~15A/dm ²

. Ni plating (Example 5, Comparative Example 2)

Nickel sulfate: 250~300g/L

Nickel chloride: 35~45g/L

Nickel acetate: 10~20g/L

Trisodium citrate: 15~30g/L

Gloss agent: saccharin, butynediol, etc.

Sodium lauryl sulfate: 30~100ppm

pH: 4~6

Bath temperature: 50~70°C

Current density: 3~15A/dm ²

. Electrolytic chromate treatment

Liquid composition: potassium dichromate 1~10g/L, zinc 0~5g/L

pH: 3~4

Liquid temperature: 50~60°C

Current density: 0.1~2.6A/dm ²

Coulomb amount: 0.5~30As/dm ²

. Impregnated chromate treatment

Liquid composition: potassium dichromate 1~10g/L, zinc 0~5g/L

pH: 3~4

Liquid temperature: 50~60°C

Immersion time: 1~20 seconds

Then, on the roll-to-roll continuous plating line, an ultra-thin copper layer having a thickness of 3 to 5 μm was formed on the intermediate layer by electroplating under the following conditions to prepare a copper foil with a carrier. Furthermore, the residual stress of the extremely thin copper layer can also be adjusted in the same manner as the electrolytic copper foil carrier. In the present case, the examples and comparative examples were adjusted by controlling the chloride ion concentration and current density.

. Very thin copper layer

Copper concentration: 30~120g/L

H ₂ SO ₄ concentration: 20~120g/L

Chloride ion concentration: 20~80mg/L

Electrolyte temperature: 20~80°C

Current density: 10~100A/dm ²

Further, in Examples 1, 2, and 5, the surface of the ultra-thin copper layer was subjected to the following roughening treatment, rust prevention treatment, chromate treatment, and decane coupling treatment.

. Coarsening

Cu: 10~20g/L

Co: 1~10g/L

Ni: 1~10g/L

pH: 1~4

Temperature: 40~50°C

Current density Dk: 20~30A/dm ²

Time: 1~5 seconds

Cu adhesion: 15~40mg/dm ²

Co adhesion: 100~3000μg/dm ²

Ni adhesion: 100~1000μg/dm ²

. Anti-rust treatment

Zn: 0~20g/L

Ni: 0~5g/L

pH: 3.5

Temperature: 40 ° C

Current density Dk: 0~1.7A/dm ²

Time: 1 second

Zn adhesion: 5~250μg/dm ²

Ni adhesion: 5~300μg/dm ²

. Chromate treatment

K ₂ Cr ₂ O ₇

(Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2~10g/L

NaOH or KOH: 10~50g/L

ZnO or ZnSO ₄ 7H ₂ O: 0.05~10g/L

pH: 7~13

Bath temperature: 20~80°C

Current density 0.05~5A/dm ²

Time: 5~30 seconds

Cr adhesion: 10~150μg/dm ²

. Decane coupling treatment

Vinyl triethoxy decane aqueous solution

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

pH: 4~5

Time: 5~30 seconds

(Comparative examples 1 to 3)

In Comparative Example 1, a copper foil with a carrier was produced under the same conditions as in Example 2 except that the foil current density of the copper foil carrier was 60 A/dm ² and an ultrathin copper layer was formed without forming an intermediate layer. In Comparative Examples 2 and 3, copper foil with a carrier was produced under the same conditions as in Example 3 except that the following conditions were as follows: The calendering degree in the final cold rolling in the production of the rolled copper foil as a carrier was set to 85%, respectively. 70%, the calendering degree of the final pass in the final cold rolling is set to 10%, 20%, respectively, and the diameter of the calender roll used in the final pass of the final cold rolling is set to 100 mm, 120 mm, respectively. In Comparative Example 2, Ni plating was performed as an intermediate layer, and in Comparative Example 3, Ni-Zn plating and electrolytic chromate treatment were performed as an intermediate layer.

2. Various evaluations of copper foil with carrier

Regarding the copper foil with a carrier obtained in the above manner, various evaluations were carried out by the following methods. The results are shown in Table 1.

<Measurement of average crystal grain size of extremely thin copper layer>

The cross section of the ultra-thin copper layer was observed using FIB-SIM, and the diameter of the smallest circle surrounding the crystal grains was taken as the crystal grain size, and all the crystal grains existing in the observation field of view were measured. (Specifically, photographs are taken and measured based on the photographs.) Further, cross-sectional observation using an extremely thin copper layer of FIB-SIM can be performed by exposing a cross section by using a focused ion beam (FIB). This profile was observed by a scanning ion microscope (SIM). Further, the average value of 20 or more crystal grain diameters is defined as an average crystal grain size. When there are no more than 20 crystal grains in the observation field, the observation field is increased until the number of crystal grains measured by the crystal grain size is 20 or more and measured. Further, the magnification when the cross section of the ultra-thin copper layer is observed by FIB-SIM is not particularly limited as long as the magnification of the crystal grains can be observed. For example, the crystal grain size can be measured at a magnification of 2,500 to 40,000 times.

<Measurement of adhesion amount>

Nickel (Ni) adhesion amount was measured by dissolving a sample with a concentration of 20% by mass of nitric acid and measuring by ICP (Inductively Coupled Plasma) luminescence analysis, chromium (Cr) adhesion amount, and zinc (Zn) adhesion amount. This was measured by dissolving a sample with hydrochloric acid having a concentration of 7 mass% and performing quantitative analysis by atomic absorption.

<Measurement of residual stress>

The residual stress on the outer surface of the copper foil carrier and the outer surface of the ultra-thin copper layer was measured by an X-ray diffraction method. In this method, the measured value of the lattice plane interval of the majority of crystals constituting the copper layer to be measured, the lattice plane spacing of copper measured under the known stress-free state, and the elastic constant of copper and the Poisson's ratio (Poisson's Ratio) Determine the residual stress on the surface of the copper layer.

In the present case, the measurement of the residual stress was carried out using an X-ray diffraction device RINT 2100 manufactured by Rigaku Co., Ltd. The correction of the diffraction angle is carried out using standard Si crystals. Further, the calculation of the residual stress was performed using the calculation software attached to the X-ray diffraction device RINT2100 manufactured by Rigaku Co., Ltd., and using the measured value of the diffraction peak.

Since the depth of penetration of X-rays is usually about several micrometers to 10 micrometers, the average lattice plane spacing and residual stress which are affected by the X-ray attenuation in the depth range from the surface of the measurement surface can be obtained. In the copper foil with a carrier, the thickness of the copper foil carrier and the ultra-thin copper layer is substantially the same as or higher than the X-ray intrusion depth. Therefore, it is considered that the residual stress measured indicates the residual stress of the surface layer of the copper foil carrier and the ultra-thin copper layer. . Further, when the outer surface of the ultra-thin copper layer is subjected to surface treatment such as roughening treatment, heat treatment, rust prevention treatment, chromate treatment, or decane coupling treatment, the surface treatment is performed (from the surface treatment layer). Determination of residual stress. Further, in the case of surface treatment such as roughening treatment, heat treatment, rust prevention treatment, chromate treatment, or decane coupling treatment on the outer surface of the copper foil carrier, it is preferred to carry out the surface treatment (from the surface treatment layer). The measurement of residual stress was carried out.

<Measurement of warpage amount>

The warpage amount was obtained by cutting the copper foil with a carrier into a sheet of 10 cm square, and allowing the ultra-thin copper layer side to stand on the horizontal surface for 24 hours or more, and then measuring the maximum value of the lift height from the horizontal plane of the four corners of the sheet. When the four corner portions of the sheet are not floated and bent in the downward direction, the ultra-thin copper layer side is placed downward to measure the maximum value of the floating height of the four corner portions of the sheet.

(Evaluation results)

The residual stress on the outer surface of the copper foil carrier of each of Examples 1 to 6 and the residual stress on the outer surface of the ultra-thin copper layer were both contraction stress or tensile stress. Therefore, the warpage of the copper foil can be favorably suppressed.

The residual stress on the outer side surface of the copper foil carrier of each of the comparative examples 1 to 3 was a tensile stress, and the residual stress on the outer side surface of the ultra-thin copper layer was a contraction stress, which was a stress in a different direction. Therefore, the maximum amount of warpage of the copper foil exceeds 10 mm, so that the warpage of the copper foil cannot be suppressed.

Further, the copper foil carrier was evaluated to have a thickness of 12 μm, an extremely thin copper layer of 2 μm and 5 μm, a thickness of the copper foil carrier of 70 μm, and an extremely thin copper layer of 2 μm and 5 μm. As a result, when 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 are both contraction stress or tensile stress, the maximum amount of warpage of the copper foil is 10 mm or less. The warpage of the copper foil can be satisfactorily suppressed.

Further, the copper foil with a carrier of Example 3 was heated at 195 ° C for 6 hours, and then the residual stress was measured. As a result, 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 were both 0 MPa. Further, the average crystal grain size of the heated ultra-thin copper layer was 16.1 μm.

Claims (35)

A carrier-attached copper foil comprising a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and an extremely thin copper layer laminated on the intermediate layer, and residual stress of the outer side surface of the copper foil carrier and the pole The residual stress on the outer side surface of the thin copper layer is either a shrinkage stress or a tensile stress. The carrier-attached copper foil according to claim 1, wherein the residual stress on the outer surface of the copper foil carrier is 0.1 times or more and 5.0 times or less the residual stress of the outer surface of the ultra-thin copper layer. The carrier-attached copper foil according to claim 2, wherein the residual stress on the outer surface of the copper foil carrier is 0.3 times or more and 3.0 times or less the residual stress of the outer surface of the ultra-thin copper layer. The carrier copper foil according to claim 1, wherein the copper foil carrier is composed of an electrolytic copper foil or a rolled copper foil. The carrier copper foil according to claim 1, wherein the intermediate layer is composed of a Ni layer contacting the interface with the copper foil carrier and a Cr layer contacting the interface with the ultra-thin copper layer, wherein the intermediate layer is Ni deposition amount of 1μg / dm ² or more and 40000μg / ² or less dm, deposition amount of Cr in the intermediate layer of of 1μg / dm ² or more and 100μg / ² or less dm, the intermediate layer and further to 1μg / dm ² or more and 70μg / Zn is present in the adhesion amount below dm ² . The carrier-attached copper foil according to claim 1, wherein the ultra-thin copper layer has a thickness of 1 μm or more and 10 μm or less. The carrier-attached copper foil according to claim 1, wherein the ultra-thin copper layer has an average crystal grain size of less than 15 μm. The carrier-attached copper foil according to claim 1, wherein the surface of the ultra-thin copper layer has a roughened layer. The carrier copper foil according to item 8 of the patent application, wherein the surface of the roughening layer is One or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer. The carrier-attached copper foil according to claim 9, wherein at least one of the rustproof layer and the heat-resistant layer contains one or more elements selected from the group consisting of nickel, cobalt, copper, and zinc. The carrier-attached copper foil according to claim 9, wherein at least one of the rustproof layer and the heat-resistant layer is composed of one or more elements selected from the group consisting of nickel, cobalt, copper, and zinc. The carrier-attached copper foil according to claim 8, wherein the heat-resistant layer is provided on the roughened layer. The carrier-attached copper foil according to claim 12, wherein the rust-preventing layer is provided on the heat-resistant layer. The carrier-attached copper foil according to claim 8, wherein the rust-preventing layer is provided on the roughened layer. The carrier copper foil according to claim 9, wherein the chromate treatment layer is provided on the rustproof layer. The carrier-attached copper foil according to claim 9, wherein the decane coupling treatment layer is provided on the chromate treatment layer. The carrier-attached copper foil according to claim 1, wherein the surface of the ultra-thin copper layer has one or more selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer. Layer. The copper foil with carrier of the first aspect of the patent application, wherein the copper foil with the carrier is cut into a sheet of 10 cm square and placed on a horizontal surface, the maximum height of the four corners of the sheet from the horizontal plane is 10 mm. the following. The carrier-attached copper foil according to claim 1, wherein the ultra-thin copper layer is provided with a resin layer. The carrier copper foil according to item 8 of the patent application, wherein the roughening layer is provided Resin layer. The carrier-attached copper foil according to claim 9, wherein the resin layer is provided on one or more layers selected from the group consisting of the heat-resistant layer, the rust-preventive layer, the chromate-treated layer, and the decane coupling treatment layer. The carrier-attached copper foil according to claim 17, wherein the resin layer is provided on one or more layers selected from the group consisting of the heat-resistant layer, the rust-preventive layer, the chromate-treated layer, and the decane coupling treatment layer. The carrier copper foil according to claim 19, wherein the resin layer contains a dielectric. The carrier copper foil according to claim 20, wherein the resin layer contains a dielectric. The carrier copper foil according to claim 21, wherein the resin layer contains a dielectric. The carrier copper foil according to claim 22, wherein the resin layer contains a dielectric. A copper clad laminate is produced by using the carrier copper foil of any one of claims 1 to 26. A printed wiring board produced by using the carrier copper foil of any one of claims 1 to 26. A printed circuit board produced by using the carrier copper foil of any one of claims 1 to 26. A manufacturing method of a printed wiring board, comprising the steps of: preparing a copper foil with a carrier and an insulating substrate according to any one of claims 1 to 26; and stacking the copper foil with the carrier and the insulating substrate; After laminating the copper foil with the carrier and the insulating substrate, the copper-clad laminate is formed by peeling off the copper foil carrier with the carrier copper foil, and then, by semi-additive method, subtractive method, partial addition The method of forming a circuit by either of the methods or the modified semi-additive method. A method of manufacturing a printed wiring board, comprising the steps of: forming a circuit on the side surface of the ultra-thin copper layer of the carrier copper foil according to any one of claims 1 to 26; and burying the circuit a step of forming a resin layer on the side surface of the ultra-thin copper layer of the copper foil with a carrier; a step of forming a circuit on the resin layer; a step of peeling off the carrier after forming a circuit on the resin layer; and After the carrier is removed, the ultra-thin copper layer is removed, and a circuit formed on the side surface of the ultra-thin copper layer and buried in the resin layer is exposed. The method of manufacturing a printed wiring board according to claim 31, wherein the step of forming a circuit on the resin layer is to attach another copper foil with a carrier to the resin layer from the side of the ultra-thin copper layer, and to use the bonding. The step of forming the above circuit is performed on the copper foil with a carrier of the above resin layer. The method of manufacturing a printed wiring board according to claim 32, wherein the other carrier copper foil bonded to the resin layer is the carrier copper foil of any one of claims 1 to 26. The method of manufacturing a printed wiring board according to claim 31, wherein the step of forming a circuit on the resin layer is performed by a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Either method is carried out. The method for producing a printed wiring board according to claim 31, further comprising the step of forming a substrate on a carrier side surface of the carrier copper foil before peeling off the carrier.