KR101357230B1 - Copper foil with resin and process for producing copper foil with resin - Google Patents

Abstract

An object of the present invention is to provide a resin-clad copper foil capable of improving the dimensional stability of a build-up printed wiring board and forming a fine pitch circuit. In order to achieve this objective, the resin-clad copper foil which formed the cured resin layer and the semi-hardened resin layer sequentially on the surface of copper foil, The surface roughness (Rzjis) of the copper foil of the side which contact | connects the said cured resin layer is 0.5 micrometer-2.5 micrometers. And a cured resin layer composed of a polyimide resin having a thermal expansion coefficient of 0 ppm / ° C to 25 ppm / ° C, a polyamideimide resin, and a resin component of any one of these composite resins, and the cured resin layer. The resin-clad copper foil provided with the semi-hardened resin layer whose subsequent thermal expansion coefficient is 0 ppm / degrees C-50 ppm / degrees C, and its manufacturing method are employ | adopted.

Description

Copper foil with resin and manufacturing method of copper foil with resin {COPPER FOIL WITH RESIN AND PROCESS FOR PRODUCING COPPER FOIL WITH RESIN}

The present invention relates to a method for producing a resin-clad copper foil and a resin-clad copper foil used as a printed wiring board material.

The resin-clad copper foil is obtained by laminating a resin layer as an insulating layer on a copper foil as a conductor, and in various fields such as the manufacturing field of a multilayer printed wiring board (hereinafter, simply referred to as a "build-up printed wiring board") manufactured by a build-up method. It has been used for the purpose. For example, in manufacture of a buildup printed wiring board, the insulating layer formed from the resin layer of the copper foil with resin bonded to the inner core material was resonated by laser processing, and a via hole was formed, and this via hole was carried out. After the interlayer conduction plating is performed on the inner circumferential wall surface of the hole, the surface of the outer layer copper foil is pattern etched to form an outer layer circuit. And the copper foil with resin is further laminated | stacked on the surface of the outer layer circuit after pattern etching process, the same outer layer circuit formation is repeated, and a buildup printed wiring board is manufactured.

In recent years, miniaturization of circuits and high-density mounting of electronic components have progressed in printed wiring circuits, and the printed wiring boards are required to have circuit position accuracy for improving the etching factor and mounting density of circuits in consideration of high frequency characteristics. In particular, in a buildup printed wiring board on which repeated lamination is performed, the problem of the positional accuracy of the conductor circuit between layers arises as the circuit formed by etching copper foil becomes finer. For example, when the position shift between layers is caused by the thermal history during the processing of the printed wiring board, the stack position of the stacking via hole is shifted, and a good interlayer conduction state cannot be obtained. As a result, even in the case of using a resin-clad copper foil as a build-up printed wiring board material, in order to secure good etching performance, it has been required to provide a resin layer having a thin copper foil layer and having excellent dimensional stability.

In order to meet this demand, for example, Patent Document 1 discloses a product in which an inorganic filler such as silica is added to a resin layer to lower the coefficient of thermal expansion to improve dimensional stability of a printed wiring board product. In addition, in this patent document 1, in order to reduce a thermal expansion coefficient, resin with high glass transition temperature, such as bismaleimide resin and cyano ester resin, is used a lot. By the way, when the inorganic filler is dispersed and mixed in the resin as in the resin material used for forming the resin layer of the resin-clad copper foil disclosed in Patent Document 1, the thermal expansion coefficient as the resin layer can be reduced, and the circuit between the layers of the build-up printed wiring board can be reduced. Although the relationship of a position becomes favorable, there exists a tendency for the resin layer after hardening to be fragile, and the adhesive stability of the circuit formed from copper foil and a resin layer falls. For this reason, in order to improve the adhesiveness of copper foil and a resin layer in resin foil copper foil, fine metal particle adheres to the copper foil surface of the side to bond with a resin layer, or forms a roughening surface by the etching method, etc. The anchor effect was exhibited at the time of joining using the copper foil which performed the roughening process of the.

Patent Document 1: Japanese Patent Application Laid-Open No. 2005-322682 Patent Document 2: Japanese Patent Application Laid-Open No. 11-10794

However, when the insulating layer is bonded to the surface of the roughened copper foil used in Patent Document 1 and the copper foil layer is etched, it is necessary to secure the over etching time for etching removal of the roughened shape. There is a problem that formation of a fine pitch circuit becomes difficult.

On the other hand, focusing only on the etching factor of a circuit and focusing on formation of a fine pitch circuit, for example, as disclosed in Patent Literature 2, the peeling strength comparable to that in the case of using a roughened copper foil and the copper particles after the etching treatment are resins. There exists a copper foil for copper clad laminated boards which provides 2 or more layers of adhesive layers in an unharmonized copper foil for the purpose of providing the copper foil for copper clad laminated boards excellent in the circuit formation which does not remain inside. By the way, in the uncoated copper foil which provided the adhesive layer of two or more layers which can be grasped | ascertained from the content disclosed by patent document 2, the adhesive stability of an uncoated copper foil and a resin layer is lacking, and various characteristics, such as solder heat resistance and a thermal shock resistance, have been made of the recent circuit. Since it was not a level compatible with fine pitching, the thermal expansion performance equivalent to that of the resin-clad copper foil disclosed in Patent Document 1 was not obtained, and it was not possible to improve the dimensional stability of the build-up printed wiring board.

From the above, the resin-clad copper foil which can improve the dimensional stability of a buildup printed wiring board and can form a fine pitch circuit has been calculated | required.

Then, as a result of repeating research, this inventor employ | adopted the manufacturing method of the following copper foil with resin and copper foil with resin. The resin-clad copper foil which concerns on this invention is equipped with the resin layer with a low thermal expansion coefficient, and is excellent in the dimensional stability at the time of processing by the printed wiring board. In addition, the resin-clad copper foil according to the present invention described below is excellent in adhesion stability with the resin layer even when a low roughness uncoated copper foil is used, and is suitable as a high-density printed wiring board material. Hereinafter, the outline | summary of this invention is demonstrated.

Resin-clad copper foil: The resin-clad copper foil according to the present invention is a resin-clad copper foil in which a cured resin layer and a semi-cured resin layer are sequentially formed on the surface of the copper foil, and the surface roughness (Rzjis) of the copper foil on the side in contact with the cured resin layer. Is 0.5 µm to 2.5 µm, and the cured resin layer is composed of a polyimide resin having a thermal expansion coefficient of 0 ppm / ° C. to 25 ppm / ° C., a polyamideimide resin, and a resin component which is any one of these composite resins. On the resin layer, it is characterized by including a semi-cured resin layer having a thermal expansion coefficient of 0 ppm / 占 폚 to 50 ppm / 占 폚 after curing.

As for the resin foil with resin which concerns on this invention, More preferably, the thermal expansion coefficient of the whole resin layer after hardening of the cured resin layer and semi-hardened resin layer which were formed on the surface of the said copper foil is 40 ppm / degrees C or less.

As for the copper foil with a resin which concerns on this invention, More preferably, the said cured resin layer has a glass transition temperature of 300 degreeC or more.

As for the resin foil with resin which concerns on this invention, More preferably, the said semi-hardened resin layer is formed using maleimide resin.

More preferably, the above-mentioned maleimide resin is an aromatic maleimide resin having two or more maleimide groups in a molecule.

More preferably, the maleimide resin is a polymerization adduct obtained by polymerizing an aromatic maleimide resin and an aromatic polyamine having two or more maleimide groups in a molecule.

More preferably, the said semi-cured resin layer contains 20 weight part-70 weight part of maleimide resins when the said semi-hardened resin layer makes 100 weight part of said semi-hardened resin layers concerning this resin.

As for the copper foil with a resin which concerns on this invention, More preferably, the said cured resin layer is 3 micrometers-30 micrometers in thickness.

As for the resin foil with resin which concerns on this invention, More preferably, the said semi-hardened resin layer is 7 micrometers-55 micrometers in thickness.

As for the copper foil with a resin which concerns on this invention, More preferably, the total thickness of the said cured resin layer and the said semi-hardened resin layer is 10 micrometers-60 micrometers.

In the copper foil with a resin which concerns on this invention, it is more preferable that the said copper foil uses an un Harmonized copper foil.

Manufacturing method of copper foil with resin: As a manufacturing method of the above-mentioned resin copper foil, it passes through the following process A and process B, It is characterized by the above-mentioned.

Process A: The resin component which is any one of polyimide resin, polyamideimide resin, and the composite resin whose thermal expansion coefficient is 0 ppm / degreeC-25 ppm / degreeC on the surface of copper foil whose surface roughness (Rzjis) is 0.5 micrometer-2.5 micrometers. The cured resin layer is formed using.

Process B: The resin foil copper foil is obtained by providing the semi-hardened resin layer whose thermal expansion coefficient after hardening is 0 ppm / degreeC-50 ppm / degreeC on the said cured resin layer.

In the method for producing a resin-clad copper foil according to the present invention, more preferably, in the step A, a polyimide having a thermal expansion coefficient of 0 ppm / ° C to 25 ppm / ° C on the surface of the copper foil having a surface roughness (Rzjis) of 0.5 µm to 2.5 µm. When forming the cured resin layer using a mid resin, the casting method or the laminating method is used.

In the manufacturing method of the resin foil with resin which concerns on this invention, More preferably, when the amount of the resin composition containing the maleimide resin used in order to form the said semi-hardened resin layer in the said process B is 100 weight part, It uses the resin composition containing 20 weight part-70 weight part of mid type resin.

In the manufacturing method of the resin foil with resin which concerns on this invention, More preferably, between the said process A and the process B, the surface modification process of plasma-processing or corona-processing the surface of a cured resin layer is provided.

Since the copper foil with resin which concerns on this invention is equipped with the resin layer which was excellent in the adhesiveness between metal foil and a resin layer, it is excellent in the adhesive stability of the copper foil (circuit) and hardened resin layer after processing with the printed wiring board. In addition, since the thermal expansion coefficient of the resin layer after hardening of the said copper foil with resin is small, the buildup printed wiring board using the resin foil with resin which concerns on this invention maintains favorable dimensional stability with respect to the thermal history at the time of processing to a printed wiring board. Can be. And the resin-clad copper foil which concerns on this invention can obtain favorable adhesiveness between copper foil and a resin layer, without giving a roughening process to the surface of the resin layer side of copper foil, and even after processing with a printed wiring board, Good adhesion stability is shown between the constituent copper foil and the cured resin layer.

Moreover, since the resin foil consists of a cured resin layer and a semi-hardened resin layer, since the resin foil consists of hard cured resin layers, even if it is a thing with the thickness which cannot be handled by copper foil alone, since the copper foil at the time of handling It is excellent in handling since it can effectively prevent damage such as wrinkles and folding. Moreover, since the copper foil with a resin which concerns on this invention can also use an unharmonized copper foil, it is suitable for formation of a fine pitch circuit. In addition, since the resin-clad copper foil according to the present invention has a low coefficient of thermal expansion after the resin layer is cured, the positional accuracy between the interlayer circuits of the build-up printed wiring board can be improved, and the circuit can be easily densified.

And the manufacturing method of the resin foil copper foil which concerns on this invention does not require special special equipment, when laminating | stacking copper foil, a cured resin layer, and a semi-hardened resin layer, and manufactures the outstanding resin foil copper foil without investing new equipment. Is possible.

EMBODIMENT OF THE INVENTION Hereinafter, the best embodiment is demonstrated in order about the manufacturing method of the resin foil with resin and copper foil with resin concerning this invention.

Resin-clad copper foil: The resin-clad copper foil which concerns on this invention is a resin foil copper foil formed in the state which laminated | stacked the cured resin layer and the semi-hardened resin layer sequentially on the surface of copper foil.

The copper foil with a resin which concerns on this invention is one of the characteristics which use as a copper foil the surface roughness (Rzjis) of the side which contact | connects a cured resin layer at 0.5 micrometer-2.5 micrometers and use very low roughness copper foil or an uncoated copper foil. Moreover, the copper foil with a resin which concerns on this invention can also use the copper foil whose surface roughness of the side which contact | connects a cured resin layer is 0.5 micrometer-2.0 micrometers, and responds to the low profile of copper foil currently requested | required recently. It is possible to do that. Conventionally, the roughening process was given to the surface of copper foil in order to improve the adhesiveness of a resin layer and copper foil. By the way, the resin foil with resin which concerns on this invention is equipped with favorable adhesiveness of copper foil and a resin layer, without giving a roughening process to copper foil. That is, in the copper foil with a resin which concerns on this invention, although the cured resin layer is laminated | stacked and arrange | positioned on the copper foil surface, even if the surface of the copper foil of the side which arrange | positions this cured resin layer is low roughness, it is excellent in adhesiveness with a cured resin layer. In particular, when an uncoated copper foil is used as the copper foil constituting the resin-clad copper foil according to the present invention, not only the manufacturing cost as the copper foil can be reduced, but also the low profile as the copper foil can be achieved. And since etching at the time of conductor circuit formation is performed uniformly and it is not necessary to provide long over etching time, formation of the fine pitch circuit with a favorable etching factor becomes easy. On the other hand, although the thickness of copper foil is not specifically limited, When using an electrolytic copper foil, thickness 7 micrometers-18 micrometers are preferable. In addition, when using the copper foil of 5 micrometers or less, it is preferable to use the copper foil with a carrier.

In this specification, a "cured resin layer" is a layer comprised by resin of the grade which does not reflow by heating. In other words, it refers to a resin layer formed of a resin that is at least harder than the semi-cured resin (resin of the B stage) and cured to a degree that is not substantially refluided even when heated to the extent of refluidization.

And it is preferable that this cured resin layer is comprised from resin whose thermal expansion coefficient after hardening is 0 ppm / degreeC-25 ppm / degreeC. When the coefficient of thermal expansion of the cured resin layer exceeds 25 ppm / ° C, when processed into resin-clad copper foil and used for build-up molding, remarkable thermal expansion occurs in the cured resin layer, and at the interface with the copper foil having a smaller thermal expansion than the cured resin layer. Adhesion falls, it becomes impossible to prevent the circuit peeling by the expansion / contraction behavior by the thermal history or thermal shock of a printed wiring board manufacturing process, and the dimensional accuracy of the resulting buildup printed wiring board becomes difficult to obtain. On the other hand, the lower the thermal expansion coefficient of the cured resin layer, the better the dimensional accuracy of the build-up printed wiring board using the resin-clad copper foil, so the lower limit of the thermal expansion coefficient is 0 ppm / 占 폚. On the other hand, the coefficient of thermal expansion of the cured resin layer is 0 ppm / ° C. to 25 ppm / ° C. by the selection or combination of the acid component, the amine component, and the isocyanate component which are the raw materials of the polyimide resin or the polyamideimide resin, and the molecular weight adjustment during the addition reaction. Can be adjusted. On the other hand, the thermal expansion coefficient is more preferably 20 ppm / ° C or less.

And if a resin component is equipped with such a thermal expansion coefficient and exhibits sufficient insulation in an electric and electronic material use, it can be used for the resin foil with a resin of this invention. However, it is preferable to use the resin component which is any one of polyimide resin, polyamideimide resin, and these composite resin among resin which has such a thermal expansion coefficient. These resins have very good electrical insulation performance, mechanical strength, and flexible performance, and are suitable for use in electronic materials. Therefore, even if the copper foil layer used in order for this cured resin layer to function as a support layer of copper foil is thin and lacks handling property, favorable handling performance can be obtained when it is set as resin foil copper foil. Here, in the cured resin layer, the coefficient of thermal expansion is included in the above range, and when appropriate fluidity adjustment is required, a required amount of maleimide resin, epoxy resin, polyethersulfone resin, cyanoester resin, or the like may be added. .

Here, a polyimide resin performs addition reaction of two carboxylic dianhydrides in a molecule | numerator, such as pyromellitic acid, and a polyamine compound which has two amino groups in a molecule | numerator, such as 4,4'- diamino diphenylmethane. Then, it is obtained by causing dehydration and ring closure by heating. The polyamideimide resin is obtained by reacting a compound having both a carboxyl group and a carboxylic anhydride in a molecule such as trimellitic anhydride and an isocyanate compound such as methylene diisocyanate. The composite resin of the polyimide resin and the polyamideimide resin is a polyimide-modified polyamideimide resin obtained by substituting a part of the acid component of the polyamideimide resin with a substance having two carboxylic acid dianhydrides in a molecule thereof. Say

Moreover, it is preferable to use the thing of glass transition temperature 300 degreeC or more for the said cured resin layer from a viewpoint of improving the heat resistance characteristic calculated | required by various printed wiring boards, such as solder heat resistance, heat shock resistance, and high temperature durability. When the glass transition temperature of this cured resin layer is less than 300 degreeC, at the temperature, such as the thermal shock by the solder reflow loaded in the manufacturing process of resin foil copper foil, the manufacturing process of a buildup printed wiring board, and the high temperature heating by press work, etc. It is unpreferable because peeling phenomenon in the interface of copper foil or a circuit "and a" curable resin layer "arises, and the risk of delamination and circuit peeling increases.

The suitable thickness of the cured resin layer described above is 3 micrometers-30 micrometers. When the thickness of a cured resin layer is less than 3 micrometers, since the effect which improves the dimensional stability of the multilayer printed wiring board manufactured by the buildup method is not acquired enough, it is unpreferable. On the other hand, when the thickness of a cured resin layer exceeds 30 micrometers, in the process of forming a cured resin layer on copper foil, the deformation called a curl arises strongly by the heating at the time of apply | coating and drying a resin composition, Since it will be in the state which rolled up to the cured resin layer side, handling property as a copper foil with a resin falls, and since automatic layup using an automatic filing device becomes impossible, it is unpreferable. And as for the thickness of a cured resin layer, it is more preferable to set it as 5 micrometers-30 micrometers. In this specification, "thickness" refers to the calculated thickness of the resin film obtained by apply | coating a fixed amount of resin here on the assumption that the surface of copper foil is a perfect flat surface.

The cured resin layer using the polyimide resin and polyamideimide resin which were described above has the adhesiveness outstanding also with an uncoated copper foil, and is compared with the resin composition of the epoxy resin type generally used for the resin layer of copper foil with a resin. This shows a significantly lower coefficient of thermal expansion. However, since such a cured resin layer has high heat resistance and is not reflowed, even if the resin is to be filled in the inter-circuit gap of the inner layer circuit on the surface of the inner layer core material by press molding of the build-up method, the resin of the gap between circuits It is in the hardened state which is difficult to bury. Then, in this invention, the semi-hardened resin layer is further laminated | stacked and arrange | positioned on this cured resin layer, and resin filling of the inter-circuit gap of an inner layer circuit is attained.

This semi-hardened resin layer is a resin layer provided on the cured resin layer, is reflowed by heating, and is formed of a thermosetting resin which causes a curing reaction. The semi-cured resin layer preferably has a thermal expansion coefficient of 0 ppm / 占 폚 to 50 ppm / 占 폚 after curing. By making the thermal expansion coefficient after hardening into such a range, the difference with the thermal expansion coefficient of a cured resin layer can be suppressed, and the interlayer peeling etc. by the deviation of the shrinkage behavior with respect to the heat which the whole resin layer after hardening receives can be prevented. On the other hand, the more preferable range of the thermal expansion coefficient after hardening of a semi-hardened resin layer is 0 ppm / degrees C-30 ppm / degrees C.

And it is preferable that the thermal expansion coefficient after the whole resin layer which consists of a cured resin layer and a semi-hardened resin layer is hardened shall be 40 ppm / degrees C or less. The dimensional stability of a printed wiring board product can be improved by restraining the thermal expansion coefficient of the whole resin layer after hardening low to 40 ppm / degrees C or less.

It is preferable to form such a semi-hardened resin layer using maleimide resin. Maleimide-based resins exhibit high fluidity before curing, but have excellent heat resistance and low coefficient of thermal expansion after curing. In addition, the coefficient of thermal expansion of the maleimide resin is lower than that of the epoxy resin. However, since this maleimide-based resin exhibits a hard and brittle property once cured, the adhesion to metal foils such as copper foil is lowered, and practical adhesion strength is not obtained even when used in combination with an uncoated copper foil. Therefore, the semi-cured resin layer formed of maleimide-based resin can be used for formation of the resin layer of the copper foil with resin only after being combined with the cured resin layer described above.

As for the maleimide resin here, use of the aromatic maleimide resin which has a 2 or more maleimide group in a molecule | numerator is preferable. In addition, although the said aromatic maleimide resin may be used as it is, maleimide resin may be used as a polymerization adduct which superposed | polymerized the aromatic maleimide resin and aromatic polyamine which have two or more maleimide groups in a molecule | numerator. At this time, since an aromatic polyamine also acts as a hardening | curing agent of an epoxy resin, when using a maleimide resin and an epoxy resin together, addition of an aromatic polyamine is useful as a means to bridge | crosslink both. These are described in detail in the following manufacturing methods.

And when the said semi-cured resin layer makes 100 weight part of formed semi-cured resin layers, it is preferable to contain 20 weight part-70 weight part of maleimide resin. By mix | blending maleimide resin in content of this range, it becomes possible to make compatible the function of reducing the thermal expansion coefficient, and the function of suppressing the fragility of resin. Here, when content of maleimide resin is less than 20 weight part, since the effect of reducing the thermal expansion coefficient of the semi-hardened resin layer after hardening cannot be acquired, it is not preferable. On the other hand, when the content of the maleimide resin exceeds 70 parts by weight, when the semi-cured resin layer is cured, it becomes a fragile resin layer, and cracks tend to occur in the resin layer, which is not preferable because the reliability of the insulating layer of the printed wiring board is lowered. not.

And the suitable thickness of the semi-hardened resin layer here is 7 micrometers-55 micrometers. When the thickness of the said semi-hardened resin layer is less than 7 micrometers, even if it is going to fill resin in the inter-circuit gap of the inner-layer circuit on the surface of an inner-layer core material, resin embedding of the inter-circuit gap will become difficult. On the other hand, when the thickness of semi-hardened resin exceeds 55 micrometers, the dispersion | variation in the resin layer thickness of the resin adhesive copper foil hardened | cured at the time of the press work by a buildup method will become large, and will promote the thickness variation in the surface of a printed wiring board. Because it is not desirable. On the other hand, as for the thickness of a semi-hardened resin layer, it is more preferable to set it as 15 micrometers-55 micrometers.

Moreover, in the copper foil with a resin which concerns on this invention, it is preferable that the sum total of the thickness of a cured resin layer and a semi-hardened resin layer is 10 micrometers-60 micrometers. When the total thickness of the resin layer of this resin foil with resin is less than 10 micrometers, the thickness of the cured resin layer mentioned above becomes thick and the thickness of a semi-hardened resin layer becomes thinner than a suitable range. As a result, embedding of an inner layer circuit becomes difficult and it becomes the copper foil with resin which is not suitable for practical use. On the other hand, in recent years, via holes have been formed having a diameter of about 50 µm by laser processing. In consideration of this, when the total of the thickness of the cured resin layer and the semi-cured resin layer of the resin-clad copper foil according to the present invention exceeds 60 µm, the hole shape by laser processing is in a good state, and the inner circumferential wall surface of the via hole hole is It becomes difficult to bring it into a smooth surface state. As a result, since it becomes a problem in the interlayer conduction plating process after via hole formation, it is unpreferable. On the other hand, the total thickness of the cured resin layer and the semi-cured resin layer is more preferably 20 µm to 60 µm.

The resin-clad copper foil which concerns on this invention is equipped with the semi-hardened resin layer which enables joining to an inner core material, and also has a cured resin layer, and suppresses thermal expansibility and is suitable for a buildup method. Thus, when the resin layer of the copper foil with a resin is comprised from the said cured resin layer and the said semi-hardened resin layer, mutual resin composition is common at the interface of this cured resin layer and a semi-hardened resin layer from a resin composition viewpoint. A phased layer exists, and the adhesiveness in the interface of both resin layers is ensured, and the dimensional change by the thermal history and thermal shock received by the processing process after lamination can be suppressed.

The copper foil with resin which concerns on this invention is not limited to a printed wiring board use, It can be used also as a capacitor circuit formation material which uses a cured resin layer as a dielectric layer. For example, by laminating and hot pressing the resin-clad copper foil according to the present invention in a copper circuit pattern, the resin-clad copper foil is pushed so that the semi-cured resin layer is located between the copper circuit patterns, and the cured resin layer is made to hit the copper circuit pattern. By making it hard, a cured resin layer can be used as a dielectric layer.

Manufacturing method of resin foil with resin: The resin foil with resin which concerns on this invention described above is manufactured through the following process A and process B. FIG. The process will be described below.

Process A: The resin component which is any one of polyimide resin, polyamideimide resin, and the composite resin whose thermal expansion coefficient is 0 ppm / degreeC-25 ppm / degreeC on the surface of copper foil whose surface roughness (Rzjis) is 0.5 micrometer-2.5 micrometers. The cured resin layer is formed using. First, copper foil is described. The copper foil here is described by the concept including all the copper foils manufactured by the rolling method and the electrolytic method. However, in consideration of product cost, use of an electrolytic copper foil is preferable.

And it is preferable to form an antirust process layer on the said electrolytic copper foil. An antirust process layer is formed in order to prevent oxidative corrosion of the surface of an electrolytic copper foil so that it may not cause trouble in the manufacturing process of a copper clad laminated board and a printed wiring board. The method used for the rust prevention treatment may be any of organic rust prevention using benzotriazole, imidazole and the like, or inorganic rust prevention using zinc, chromate, zinc alloy and the like. It becomes possible to employ | adopt techniques, such as showering coating of an electrolytic copper foil, an electrodeposition method. In the case of inorganic rust prevention, it is possible to use the method of depositing a rust prevention element on the surface of an electrolytic copper foil by electrolysis, and also what is called a substitutional precipitation method. For example, when trying to perform a zinc rust prevention process, it is possible to use a zinc pyrophosphate plating bath, a zinc cyanide plating bath, a zinc sulfate plating bath, etc. For example, in the zinc pyrophosphate plating bath, the concentration is 5 g / l to 30 g / l of zinc, 50 g / l to 500 g / l of potassium pyrophosphate, 20 ° C. to 50 ° C., pH 9 to 12, and current density of 0.3 A /. What is set as conditions of d <2> m ~ 10A / dm <2> is mentioned.

On the other hand, the kind of rust prevention treatment is not limited as described above, but in order to use the electrolytic copper foil used in the present invention without performing a roughening treatment, in order to improve the wettability of the resin film and the surface of the copper foil as much as possible to increase the adhesion It is preferable to use the following rust prevention treatment. That is, it is preferable to use a nickel-zinc alloy as an antirust process layer. In particular, the nickel-zinc alloy constituting the antirust treatment layer is preferably one having a composition containing 50 wt% to 99 wt% of nickel and 50 wt% to 1 wt% of zinc except for unavoidable impurities. It is because the tendency which improves adhesiveness with respect to the structural resin of a base material becomes remarkable by presence of nickel in an antirust process layer. If the nickel content is less than 50 wt%, the antirust treatment layer formed of the nickel-zinc alloy cannot expect an effect of improving adhesion with various resin films. In addition, when the nickel content exceeds 99 wt%, the tendency to remain after the etching becomes stronger, which is not preferable. According to the research of the present inventors, in the resin-clad copper foil according to the present invention, when forming a rust-preventing layer of nickel and zinc, the total adhesion amount of nickel and zinc is preferably in the range of 20 mg / m 2 to 100 mg / m 2. . In particular, when the anti-rust treatment layer made of the nickel-zinc alloy is formed, the electrolytic copper foil is not easily peeled off from the bonding interface when adhered to a special substrate on which adhesion strength is hard to be secured, It is excellent in solder heat resistance. If the said total adhesion amount is less than 20 mg / m <2>, the rustproof process layer of uniform thickness will not be obtained and the variation of adhesive strength will become large. On the other hand, when the total amount of adhesion exceeds 100 mg / m 2, the etching residue of the nickel component tends to be generated during the etching of the conductor circuit formation, which is not preferable.

In addition, it is confirmed that the higher the nickel amount, the more the adhesive strength, the chemical resistance property, the moisture resistance, and the solder heat resistance tend to be improved, and when the amount of zinc is increased, the chemical resistance and the solder heat resistance tend to be lowered. When forming the antirust process layer by a nickel-zinc alloy, when the total adhesion amount of nickel and zinc is 20 mg / m <2> -100 mg / m <2>, the ratio of nickel and zinc is nickel: zinc = 6: 4-8: It turned out that it is suitable practically to make into the range of 2. If the nickel ratio exceeds 80%, there is a tendency to generate etching residues when the circuit is formed. On the other hand, when the zinc ratio exceeds 40%, the chemical resistance characteristics and the solder heat resistance characteristics tend to be lowered.

Moreover, it is also preferable to comprise an antirust process layer with a nickel- zinc alloy layer and a chromate layer. By the presence of the chromate layer, there is a tendency that the corrosion resistance is improved and the adhesion with the resin layer is also improved at the same time. In the formation of the chromate layer at this time, any of the substitution method and the electrolytic method may be employed in accordance with a conventional method.

And after a nickel-zinc alloy plating process and chromate treatment, a silane coupling agent process is performed. A silane coupling agent process is a process for chemically improving adhesiveness with an insulation layer constitution material after a roughening process, an antirust process, etc. are complete | finished. The silane coupling agent used for the silane coupling agent treatment mentioned here does not require limitation in particular, and the epoxy silane coupling agent and the amino silane are considered in consideration of the properties of the insulating layer constituent material to be used and the plating solution used in the manufacturing process of the printed wiring board. It is possible to use arbitrarily selected from a coupling agent, a mercapto system silane coupling agent, and the like.

More specifically, vinyltrimethoxysilane, vinylphenyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, mainly on coupling agents such as those used for glass cloth of prepregs for printed wiring boards. , γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- 3- (4- (3-aminopropoxy) methoxy) propyl-3-aminopropyltrimethoxysilane, imidazole silane, triazine silane, gamma -mercaptopropyl trimethoxysilane, etc. can be used.

Next, the method to form a cured resin layer on the surface of copper foil is demonstrated. In order to provide the cured resin layer on the surface of the copper foil, a method of depositing copper by electroless method on the cured resin layer, growing by electrolytic method to obtain a laminated state, a method of laminating a resin film on the surface of the copper foil, pressing and bonding, All the well-known techniques, such as the coating method which apply | coats a resin varnish to the surface of copper foil, heats it, and hardens, is applicable. However, when forming a polyimide resin layer or a polyamideimide resin layer, it is preferable to use the casting method or the laminating method.

When forming a polyimide resin layer using the casting method, the polyimide precursor varnish is apply | coated to the surface of metal foil, an imidation reaction is caused by heating, and it hardens | cures and repeats the process of making a polyimide resin several times. In addition, when forming a polyamide-imide resin layer using the casting method, resin which melt | dissolved the reaction product of the acid component of trimellitic anhydride and isocyanate, such as methylene diisocyanate, in organic solvents, such as N-methylpyrrolidone. It is formed by applying a varnish to the copper foil surface and removing a solvent by heating. At this time, unlike the case where the above-mentioned polyimide resin layer is formed, since the production of the imide group is completed, dehydration and ring closure reaction are not accompanied. This casting method has the advantage that it is easy to form a polyimide resin layer or a polyamideimide resin layer of a desired thickness.

When using the lamination method, after apply | coating a bonding agent, you may make it the form which laminated | stacked the polyimide film, the polyamideimide film, etc. by the lamination method. On the other hand, the present applicant employs a copper foil with a binder layer already proposed in Japanese Patent No. 3949676, and a commercially available polyimide film or the like is laminated on the adhesive layer (ultra thin primer resin layer) of the copper foil with a binder layer by a laminating method. You may.

Step B: In this step, a resin-clad copper foil is obtained by providing a semi-cured resin layer having a thermal expansion coefficient of 0 ppm / ° C to 50 ppm / ° C after curing on the cured resin layer. A semi-hardened resin layer is formed using the resin composition containing 20 weight part-70 weight part of maleimide resin, when the amount of the resin composition containing maleimide resin is 100 weight part. Content of maleimide-type resin in this resin composition is prescribed | regulated in the range which shows the characteristic preferable as a semi-hardened resin layer of the copper foil with resin. Hereinafter, the resin composition for forming a semi-hardened resin layer is described. The resin composition used here makes a linear polymer which has maleimide resin, an epoxy resin, and a crosslinkable functional group an essential component. And as a maleimide resin, the polymerization addition product which superposed | polymerized the aromatic maleimide resin and aromatic polyamine can also be used. Moreover, you may add the cyano ester resin and epoxy resin which have reactivity with maleimide resin as needed to a semi-hardened resin layer.

As maleimide-type resin here, 4,4'- diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'- dimethyl- 5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 4,4'-diphenyletherbismaleimide, 4,4 ' Diphenyl sulfone bis maleimide, 1, 3-bis (3- maleimide phenoxy) benzene, 1, 3-bis (4- maleimide phenoxy) benzene, etc. can be used. When content of maleimide resin is less than 20 weight part, since the effect of reducing the thermal expansion coefficient of the semi-hardened resin layer after hardening cannot be acquired, it is not preferable. On the other hand, when the content of the maleimide resin exceeds 70 parts by weight, when the semi-cured resin layer is cured, it becomes a fragile resin layer, and cracks tend to occur in the resin layer, which is not preferable because the reliability of the insulating layer of the printed wiring board is lowered. not.

The epoxy resin used here is a so-called bisphenol epoxy resin. And it is preferable to mix and use 1 type (s) or 2 or more types chosen from the group of bisphenol-A epoxy resin, bisphenol F-type epoxy resin, and bisphenol AD-type epoxy resin. Here, the bisphenol epoxy resin is selected and used because it is a liquid epoxy resin at 25 degreeC, and when the resin foil copper foil with a semi-cured resin layer is manufactured, the suppression effect of a curl phenomenon will be acquired remarkably. to be. Moreover, it is because it is possible to obtain the suitable resin flow according to the favorable adhesiveness of the resin film after hardening and copper foil, and the shape of the uneven | corrugated surface. On the other hand, in the case where the liquid epoxy is of high purity, the crystallization state is maintained even when the liquid epoxy is subjected to overcooling and returned to room temperature, and may appear to be solid in appearance. In this case, since it is possible to return to a liquid state and use it, it is contained in the liquid epoxy resin here. In addition, the temperature of 25 degreeC is described here in order to clarify the meaning in the vicinity of room temperature.

And when epoxy equivalent exceeds 200, since it becomes semi-solid or solid at 25 degreeC, preparation of a resin composition is difficult, too, and since it becomes unable to contribute to the suppression of the curl phenomenon at the time of manufacturing copper foil with resin, it is unpreferable. In addition, the epoxy equivalent here is the number of grams (g / eq) of resin containing a 1-gram equivalent epoxy group. Moreover, as long as it is a bisphenol-type epoxy resin mentioned above, you may use individually by 1 type, or may mix and use 2 or more types. In addition, when mixing and using 2 or more types, there is no special limitation also regarding the mixing ratio.

When this bisphenol-type epoxy resin makes a resin composition 100 weight part, it is used by the compounding ratio of 3 weight part-20 weight part. When the said epoxy resin is less than 3 weight part, the hardened resin layer becomes easy to crack, and a crack becomes easy to produce. On the other hand, when it exceeds 20 weight part, since adhesiveness arises on the resin surface at 25 degreeC, handling property is inadequate.

It is preferable that the linear polymer which has a crosslinkable functional group is provided with the functional group which contributes to hardening reaction of epoxy resins, such as a hydroxyl group and a carboxy group. And it is preferable that the linear polymer which has this crosslinkable functional group is soluble in the organic solvent whose boiling point is 50 degreeC-200 degreeC. Specific examples of the linear polymer having a functional group include polyvinyl acetal resin, phenoxy resin, polyether sulfone resin, polyamideimide resin and the like. When the linear polymer which has this crosslinkable functional group makes a resin composition 100 weight part, it is used by the compounding ratio of 3 weight part-30 weight part. When the linear polymer which has the said crosslinkable functional group is less than 3 weight part, resin flow will become large. As a result, generation | occurrence | production of resin powder is observed a lot from the edge part of the manufactured copper clad laminated board, and the hygroscopic resistance of the resin layer in a semi-hardened state cannot also be improved. On the other hand, even if it exceeds 30 weight part, resin flow is small and it becomes easy to produce defects, such as a void, in the insulating layer of the manufactured copper clad laminated board.

And when forming the polymerization adduct which superposed | polymerized the aromatic maleimide resin and aromatic polyamine which have two or more maleimide groups in a molecule | numerator, as an aromatic polyamine, for example, m-phenylenediamine, p-phenylenediamine, 4 , 4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, 4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) Propane, 4,4'-diaminodiphenylether, 4,4'-diamino-3-methyldiphenylether, 4,4'-diaminodiphenylsulfide, 4,4'-diaminobenzophenone, 4 , 4′-diaminodiphenylsulfon-bis (4-aminophenyl) phenylamine, m-xylenediamine, p-xylenediamine, 1,3-bis [4-aminophenoxy] benzene, 3-methyl-4, 4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2 ' , 5,5'-tetrachloro-4,4'-diaminodi Nelmethane, 2,2-bis (3-methyl-4-aminophenyl) propane, 2,2-bis (3-ethyl-4-aminophenyl) propane, 2,2-bis (2,3-dichloro-4 -Aminophenyl) propane, bis (2,3-dimethyl-4-aminophenyl) phenylethane, ethylenediamine, hexamethylenediamine and the like are preferably used.

And when an epoxy resin hardener is needed, amines, such as dicyandiamide, imidazole, aromatic amine, phenols, such as bisphenol A and brominated bisphenol A, novolaks, such as a phenol novolak resin and a cresol novolak resin, And acid anhydrides such as phthalic anhydride and the like. Since the addition amount of the epoxy resin hardening | curing agent with respect to the epoxy resin at this time is derived by itself from each equivalent, special limitation of addition amount is not performed.

It is preferable to set it as the resin varnish for the resin composition comprised by the above-mentioned resin component using the organic solvent whose boiling point is 50 degreeC-200 degreeC. When boiling point is less than 50 degreeC, the base acid of a solvent by heating becomes remarkable, and when it is set as semi-hardened resin from a resin varnish state, it becomes difficult to obtain a favorable semi-hardened state. On the other hand, when a boiling point exceeds 200 degreeC, a solvent will remain easily in a semi-hardened state. That is, it does not satisfy the volatilization rate normally required and does not satisfy industrial productivity. Specific examples of the organic solvent mentioned herein include one selected from the group consisting of methanol, ethanol, methyl ethyl ketone, toluene, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, and ethyl cellosolve. It is a single solvent or two or more types of mixed solvents.

Using the resin composition described above as a resin varnish, the said resin varnish is apply | coated on the cured resin layer of copper foil, and a semi-hardened resin layer is formed by drying. There is no special limitation regarding the coating method and the drying method at this time.

Moreover, it is more preferable to provide the surface modification process of a cured resin layer between a process A and the process B by a plasma process or a corona treatment as an addition process. It is because the surface of a cured resin layer is modified by providing this surface modification process, and adhesiveness with a semi-hardened resin improves. That is, since the cured resin layer and the semi-cured resin layer are formed of different resin compositions and one resin layer has already been cured, the adhesiveness between the two resin layers may be deteriorated. By performing plasma treatment or corona treatment on the surface, the adhesion between the cured resin layer and the semi-cured resin layer is improved.

The plasma treatment herein refers to a treatment performed by bringing the plasma airflow generated by applying a high voltage generally used into contact with the surface of the hard resin layer. In addition, corona treatment performs surface modification of a hard resin layer by arrange | positioning the copper foil provided with the cured resin layer between electrodes, and performing corona discharge by applying a high frequency and a high voltage. On the other hand, all known methods can be applied to the plasma treatment or the corona treatment.

Hereinafter, an Example is shown and this invention is demonstrated concretely. In addition, this invention is not limited to a following example.

Example 1

As Example 1, a polyimide resin layer is formed as a cured resin layer on the surface of an electrolytic copper foil, and the example of the copper foil with resin which used maleimide resin for formation of a semi-hardened resin layer is shown.

Electrolytic Copper Foil: An electrolytic copper foil having a thickness of 12 µm having a glossy surface of Rzjis = 0.70 µm was used as the surface roughness. This electrolytic copper foil was immersed for 30 seconds at 30 degreeC of liquid temperature using the dilute sulfuric acid solution of concentration 100g / l, and wash | cleaned. Subsequently, as a rust prevention process of a gloss surface, it processed in order of nickel- zinc alloy plating process, chromate treatment, and silane coupling agent process. Nickel-zinc alloy plating was carried out under the conditions of a pyrophosphate bath (nickel 2.5 g / l, zinc 0.5 g / l, liquid temperature 40 ° C., current density of 0.6 A / dm 2, 8 seconds). In addition, electrolytic chromate treatment was made into chromic acid with a concentration of 1.0 g / l, pH 12, liquid temperature of 30 degreeC, current density of 1.8 A / dm 2, and electrolysis time of 8 seconds.

In addition, the silane coupling agent treatment uses a solution obtained by adding γ-aminopropyltrimethoxysilane to a concentration of 5.0 g / l using ion-exchanged water as a solvent. It adsorbed by spraying on the surface and the silane coupling agent layer was formed on the antirust process layer.

After the silane coupling agent treatment is finished, the furnace is heated for 4 seconds to dry the atmosphere temperature after adjusting the atmospheric temperature so that the foil temperature is 140 ° C by the heater, and the condensation reaction of the silane coupling agent is promoted. And the completed electrolytic copper foil was obtained. The surface roughness of the gloss surface after this surface treatment was Rzjis = 0.72 µm.

Preparation of polyamic acid varnish: Next, the polyamic acid varnish for forming a cured resin layer by the casting method is demonstrated. 1 mol of pyromellitic dianhydride and 1 mol of 4,4'-diaminodiphenyl ether were dissolved in N-methylpyrrolidone as a solvent and mixed. The reaction temperature at this time was 25 degreeC, and was made to react for 10 hours. And the polyamic-acid varnish whose resin solid content is 20 mass% was obtained.

Formation of cured resin layer: Then, the cured resin layer was formed by the casting method using the obtained polyamic acid varnish. The polyamic acid varnish was apply | coated to the glossiness surface of the electrolytic copper foil mentioned above by the multicoater (M-400 by HIRANO TECSEED company), and it dried in the hot air dryer on 110 degreeCx 6 minutes conditions. The resin thickness of the resin layer after drying was 35 micrometers, and the solvent residual ratio in this step was 32 wt% with respect to the total amount of the resin layer. The composite of the electrolytic copper foil to which this polyamic acid varnish was apply | coated was put into the hot air oven substituted with nitrogen, and it heated up over 15 minutes from room temperature to 400 degreeC, and after cooling at 400 degreeC for 8 minutes, it cooled. Thereby, the copper clad polyimide resin of the state in which the hardening resin layer was laminated | stacked on the copper foil surface by the imide reaction which remove | eliminates a residual solvent from the composite of the electrolytic copper foil to which polyamic acid was apply | coated, and dehydrated-closes a polyamic acid. It was made into a base material. The solvent residual ratio of the copper clad polyimide resin base material obtained by this final heat processing was 0.5 wt% with respect to the total amount of resin adhering to the electrolytic copper foil.

Next, the copper foil (copper polyimide resin base material) in which the cured resin layer was laminated was subjected to corona treatment to perform surface modification of the cured resin layer. Corona treatment was performed under conditions of an electric power of 210 W, a speed of 2 m / min, a discharge amount of 300 W · min / m 2, and an irradiation distance of 1.5 mm from the electrode.

And in order to measure the thermal expansion coefficient of a cured resin layer, the electrolytic copper foil was removed by the etching from the copper foil (corona treated copper-coated polyimide resin base material) in which the cured resin layer after surface modification treatment was laminated | stacked. As a result, the resin thickness of the cured resin layer (polyimide film) obtained by removing an electrolytic copper foil was 27 micrometers, and the thermal expansion coefficient was 25 ppm / degreeC.

Formation of semi-cured resin layer: Here, a semi-cured resin layer is formed on the cured resin layer of the corona-treated copper-clad polyimide resin substrate. First, the resin composition shown below was melt | dissolved using N, N'-dimethylacetamide as a solvent, and it was prepared so that resin solid content might be 30 wt% resin varnish.

[Resin composition to form semi-cured resin layer of Example 1]

Maleimide resin: 4,4'- diphenylmethane bismaleimide (brand name: BMI-1000, Daiwa Kasei Co., Ltd.) / 30 weight part

Aromatic polyamine resin: 1,3-bis [4-aminophenoxy] benzene (trade name: TPE-R, manufactured by Wakayama Seika Co., Ltd.) / 35 parts by weight

Epoxy resin: Bisphenol A type epoxy resin (brand name: epicron 850S, product of Nippon Ink Chemical Co., Ltd.) / 20 weight part

Linear polymer having a crosslinkable functional group: polyvinyl acetal resin (trade name: Denka Butyral 5000A, product of Denki Kagaku Co., Ltd.) / 15 parts by weight

The above-mentioned resin varnish is applied to the polyimide resin surface of the corona-treated copper-clad polyimide resin base material, air-dried for 5 minutes at room temperature, heat-dried under the conditions of 160 degreeC * 5 minutes, and the semi-hardened resin layer Lamination was formed. The resin thickness of the semi-hardened resin layer at this time was 20 micrometers.

And in order to measure the thermal expansion coefficient after hardening of a semi-hardened resin layer, the above-mentioned resin varnish used for formation of a semi-hardened resin layer is apply | coated to the fluorine-type heat resistant film by the method mentioned above, and air-dried for 5 minutes at room temperature. Was carried out, heat-dried under the conditions of 160 ° C for 5 minutes, and curing heating at 200 ° C for 2 hours to obtain a cured resin layer for testing having a thickness of 20 µm. That is, this test cured resin layer corresponds to the case where the semi-cured resin layer of the resin foil with resin according to the present invention is cured. The thermal expansion coefficient of this test cured resin layer was 45 ppm / degreeC.

The thickness of the whole resin layer of the resin foil with resin obtained as mentioned above is 47 micrometers. And the number after copper foil is etched-removed from this resin foil with resin, hardening heating for 200 degreeC * 2 hours using this resin layer which consists of a cured resin layer and a semi-hardened resin layer, and hardened the said semi-hardened resin layer. The thermal expansion coefficient of the whole strata was measured. As a result, the coefficient of thermal expansion was 35 ppm / 占 폚. In addition, the peeling strength was 1.0 kgf / cm.

Example 2

Example 2 differs in thickness from the cured resin layer of Example 1. That is, in forming the cured resin layer of Example 1, the resin thickness after drying of 110 degreeC x 6 minutes was made into 35 micrometers in Example 2, while the resin thickness after drying of 110 degreeC x 6 minutes was made into 8 micrometers. . Others produced the copper foil with a resin by the method similar to Example 1. In the cured resin layer of this Example 2, the resin thickness after drying at 400 degreeC x 8 minutes was 5 micrometers, and the solvent residual ratio was 0.1 wt%. And the thermal expansion coefficient of the whole resin layer after fully hardening semi-hardened resin was 38 ppm / degreeC, and peeling strength of copper foil was 0.95 kgf / cm.

Example 3

Example 3 differs in the structure of a cured resin layer compared with Example 1. That is, in the formation of the cured resin layer, the resin used is vylomax HR16NN (manufactured by Toyo Spun Co., Ltd., brand name), the thickness of the cured resin layer after drying at 110 ° C. for 6 minutes is 28 μm, and the maximum temperature of subsequent drying conditions is set. Was 380 ° C. Others produced the copper foil with a resin by the method similar to Example 1. At this time, the thickness of the cured resin layer after drying at 380 ° C for 8 minutes was 24 µm, the solvent residual ratio was 0.8 wt%, and the thermal expansion coefficient of the cured resin layer was 23 ppm / ° C. Moreover, the thermal expansion coefficient of the whole resin layer of the resin foil copper foil after fully hardening a semi-hardened resin was 34 ppm / degreeC, and peeling strength of the copper foil was 0.80 kgf / cm.

Example 4

In Example 4, in the formation of the semi-hardened resin layer, a resin-clad copper foil was produced in the same manner as in Example 1 except that the resin to be used was made into the following composition.

[Resin composition to form semi-cured resin layer of Example 4]

Maleimide resin: Bisphenol A diphenyl ether bis maleimide (brand name: BMI-4000 Daiwa Kasei Co., Ltd.) / 25 weight part

Epoxy resin: Cresol novolak-type epoxy resin (brand name: Efototo YDCN-703, product of Totokasei Co., Ltd.) / 25 weight part

Linear polymer having a crosslinkable functional group: Polyvinyl acetal resin (trade name: Denka Butyral 5000A, product of Denki Kagaku Co., Ltd.) / 10 parts by weight

Epoxy resin curing agent: Cyanate ester resin (brand name: Primaset PT-30, Lonza Ltd, product) / 40 parts by weight

The said resin composition was dissolved using dimethylacetamide as a solvent, and it prepared so that resin solid content might be 40wt%. Thereafter, an imidazole compound (trade name: curezol 2P4MHZ, manufactured by Shikoku Chemical Co., Ltd.) / 0.5 parts by weight, and acetylacetone zinc (0.01 parts by weight of a reagent) were further added as a curing catalyst to obtain a resin varnish. This resin varnish was apply | coated, dried, and hardened | cured by the method similar to Example 1, and the semi-hardened resin layer was laminated | stacked and formed. The resin thickness of the semi-hardened resin layer at this time was 20 micrometers.

And the thermal expansion coefficient after hardening of the semi-hardened resin layer was measured by the method similar to Example 1. As a result, the coefficient of thermal expansion was 48 ppm / 占 폚. In addition, when the thermal expansion coefficient after hardening the whole resin layer of the resin foil with resin obtained in Example 4 was measured using the method similar to Example 1, a thermal expansion coefficient is 38 ppm / degreeC and the peeling strength of copper foil is 1.0 kgf. / Cm.

Comparative Example

Comparative Example 1

In the comparative example 1, the example of the resin foil copper foil with which only the semi-hardened resin layer similar to Example 1 was formed in the same electrolytic copper foil used in Example 1 is shown.

The resin composition varnish for semi-cured resin layers prepared on the same gloss side of the same electrolytic copper foil as used in Example 1 was applied under the same conditions as in Example 1, air-dried at room temperature for 5 minutes, and 160 ° C for 5 minutes. It dried under conditions and formed the semi-hardened resin layer. The thickness of the semi-hardened resin layer at this time was 20 micrometers.

In addition, the thermal expansion coefficient after hardening of the semi-hardened resin layer was measured similarly to Example 1. The thickness after hardening of the semi-hardened resin layer at this time was 20 micrometers, and the thermal expansion coefficient was 45 ppm / degreeC. And the peeling strength after hardening a semi-hardened resin layer by the method similar to Example 1 was measured. As a result, the peeling strength was 0.3 kgf / cm. These values are collectively shown in Table 1 to enable contrast with the examples.

[Comparative Example 2]

Comparative Example 2 shows an example in which the copper foil and the cured resin layer were manufactured under the same conditions as in Example 1 except that the composition of the semi-hardened resin layer was different from that of Example 1. In order to avoid the overlapping base material, description of the structure of a copper foil and a cured resin layer is abbreviate | omitted.

The semi-hardened resin layer formed in the comparative example 2 dissolves the following resin compositions using N, N'-dimethylacetamide as a solvent, and was prepared so that resin solid content might be 30 wt% resin varnish.

[Resin Composition to Form Semi-Cured Resin Layer]

Heat-resistant epoxy resin: Naphthalene type heat-resistant epoxy resin (brand name: HP-4700, product made by Nippon Ink Chemical Co., Ltd.) / 40 weight part

Aromatic polyamine: 1,3-bis [4-aminophenoxy] benzene (trade name: TPE-R, manufactured by Wakayama Seika Co., Ltd.) / 25 parts by weight

Epoxy resin: Bisphenol A type epoxy resin (brand name: epicron 850S, product of Nippon Ink Chemical Co., Ltd.) / 20 weight part

Linear polymer having a crosslinkable functional group: polyvinyl acetal resin (trade name: Denka Butyral 5000A, product of Denki Kagaku Co., Ltd.) / 15 parts by weight

In addition, the said resin varnish was apply | coated to the surface of the polyimide resin layer of the corona treated copper clad polyimide resin base material manufactured on the same conditions as Example 1, air-dried for 5 minutes at room temperature, and 160 degreeC * 5 minutes. It heat-dried on condition of the semi-hardened resin layer. The resin thickness of the semi-hardened resin layer at this time was 20 micrometers.

In addition, the thermal expansion coefficient after hardening of the semi-hardened resin layer was measured similarly to Example 1. The thickness after hardening of the semi-hardened resin layer at this time was 20 micrometers, and the thermal expansion coefficient was 70 ppm / degreeC. In addition, the thickness of the whole resin layer of the resin foil with resin obtained by the comparative example 2 was 47 micrometers. And the thermal expansion coefficient and peeling strength of the whole resin layer which consists of a cured resin layer and a semi-hardened resin layer after hardening a semi-hardened resin layer by the method similar to Example 1 were measured. As a result, the coefficient of thermal expansion was 62 ppm / 占 폚 and the peel strength was 1.0 kgf / cm. These values are collectively shown in Table 1 to enable contrast with the examples.

Thermal expansion coefficient: ppm / ℃ Solder Heat Resistance (260 ℃)
second Peel strength
kgf / cm Cured resin layer Semi-hardened resin layer Whole resin layer Example 1 25 45 35 > 600 1.00 Example 2 25 45 38 > 600 0.95 Example 3 23 45 34 > 600 0.80 Example 4 25 48 38 > 600 1.00 Comparative Example 1 - 45 45 378 0.30 Comparative Example 2 25 70 62 > 600 1.00

[Contrast of Examples and Comparative Examples]

The measurement results of solder heat resistance, peel strength, and coefficient of thermal expansion of the resin-clad copper foil obtained in Examples and Comparative Examples are shown in Table 1, and the Examples and Comparative Examples are compared with reference to Table 1. First, in the case of Examples 1-4, the result which shows the outstanding value of all the characteristic is outstanding. In contrast, Comparative Example 1 is an example in which only the semi-cured resin layer of Example 1 was formed, and the thermal expansion coefficient, peel strength, and solder heat resistance did not all exhibit values sufficient for actual use. From this, it can be said that the resin foil with resin which is not practical is obtained by forming only a semi-hardened resin layer on the surface of copper foil.

Next, in comparison with Examples 1 to 4 and Comparative Example 2, the solder heat resistance and peel strength are equivalent, but the Examples 1 to 4 show obviously lower values for the coefficient of thermal expansion than Comparative Example 2. . From this, it can be understood that reduction of the thermal expansion coefficient of the resin layer after hardening can be aimed at by using maleimide resin for formation of the semi-hardened resin layer formed after forming hardened resin layer on the copper foil surface.

Hereinafter, the solder heat resistance, the evaluation method of peeling strength, and the measuring method of a thermal expansion coefficient are shown. The printed wiring board was produced for evaluation of solder heat resistance and peeling strength. The resin-clad copper foil obtained by the Example or the comparative example was carried out using the vacuum press apparatus on both surfaces of the copper clad laminated board of the thickness of 0.5 mm of FR-4 grade on which the 12-micrometer inner layer circuit which blackening process was performed on the surface was carried out. It pressed and laminated on the conditions of the pressure of 20 kgf / cm <2>, and temperature of 170 degreeC x 60 minutes. The multilayer printed wiring board provided with the obtained four-layer copper layer was manufactured.

And this multilayer printed wiring board was cut out, the solder heat test piece of 2.5 cm x 2.5 cm size was taken, it floated in the solder bath at 260 degreeC, and time until blister generate | occur | produced was measured.

In addition, the peeling strength measured the peeling strength by etching the outer layer copper foil of the said multilayer printed wiring board, forming the linear circuit for 10 mm width peeling strength measurement, and peeling this linear circuit with respect to a board | substrate at 90 degreeC direction.

In addition, the thermal expansion coefficient prepared each two pieces of copper foil with resin obtained by each Example or the comparative example, laminated | stacked so that the resin surfaces of the said resin coated copper foil might contact, and hardened | cured by the hot press. Curing conditions at this time were 170 degreeC x 60 minutes at the pressure of 20 kgf / cm <2>. After hardening, copper foil was removed by the etching method, the said copper foil with resin was laminated | stacked again, and copper foil was etched away. By repeating this, a resin plate having a thickness of about 0.2 mm was produced. And the thermal expansion coefficient of this resin plate was measured based on JISC6481.

The resin-clad copper foil which concerns on this invention consists of two layers of a cured resin layer and a semi-hardened resin layer, and is good adhesiveness between a resin layer and copper foil, even if the copper foil surface which prepares a resin layer is a low profile low profile copper foil. It becomes possible to obtain. Moreover, since the resin foil with resin which concerns on this invention is equipped with the resin layer with a low coefficient of thermal expansion compared with the conventional copper foil with resin, when used as a raw material of manufacture of a multilayer printed wiring board in a buildup method, it is the manufacture of the said printed wiring board. Excellent dimensional stability against high temperature thermal history and thermal shock loaded in the process enables the provision of high quality multilayer printed wiring boards. As a result, it is possible to easily cope with the fine pitch and the high density of the circuit of the build-up printed wiring board, and the stable production of the fine wiring printed wiring board can be realized. Moreover, the copper foil with a resin which concerns on this invention can be used as a capacitor circuit formation material which uses a cured resin layer as a dielectric layer.

Claims (15)

As a copper foil with resin which formed the cured resin layer and the semi-hardened resin layer sequentially on the surface of copper foil,
The surface roughness (Rzjis) of the copper foil of the side which contact | connects the said cured resin layer is 0.5 micrometer-2.5 micrometers,
The cured resin layer is composed of a polyamideimide resin having a thermal expansion coefficient of 0 ppm / ° C. to 25 ppm / ° C.,
On the cured resin layer, a semi-cured resin layer having a thermal expansion coefficient of 0 ppm / ° C to 50 ppm / ° C after curing is provided.
The copper foil with a resin provided on the surface of the said copper foil, The antirust process layer formed from the nickel- zinc alloy containing 50 wt%-99 wt% nickel and 50 wt%-1 wt% zinc. The method of claim 1,
The copper foil with a resin whose thermal expansion coefficient of the whole resin layer after hardening the cured resin layer and the semi-hardened resin layer formed on the surface of the said copper foil is 40 ppm / degrees C or less. The method of claim 1,
The said cured resin layer is a copper foil with resin whose glass transition temperature is 300 degreeC or more. The method of claim 1,
The said semi-hardened resin layer is a copper foil with resin formed using maleimide resin. 5. The method of claim 4,
The said maleimide resin is copper foil with resin which is aromatic maleimide resin which has two or more maleimide groups in a molecule | numerator. 5. The method of claim 4,
The said maleimide resin is a copper foil with resin which is a polymerization addition product which superposed | polymerized the aromatic maleimide resin and aromatic polyamine which have two or more maleimide groups in a molecule | numerator. The method of claim 1,
The said semi-hardened resin layer is a copper foil with resin which contains 20 weight part-70 weight part of maleimide resin, when the said semi-hardened resin layer is 100 weight part. The method of claim 1,
The said cured resin layer is a copper foil with a resin whose thickness is 3 micrometers-30 micrometers. The method of claim 1,
The semi-cured resin layer is a copper foil with a resin having a thickness of 7 μm to 55 μm. The method of claim 1,
Copper foil with a resin whose total thickness of the said cured resin layer and the said semi-hardened resin layer is 10 micrometers-60 micrometers. The method of claim 1,
The said copper foil is a resin foil with resin using an unharmonized copper foil. As a manufacturing method of the resin foil with resin of Claim 1, it passes through the following process A and the process B, The manufacturing method of the copper foil with resin characterized by the above-mentioned:
(Step A) Rust prevention treatment formed with nickel-zinc alloy containing surface roughness Rzjis of 0.5 µm to 2.5 µm and containing 50 wt% to 99 wt% nickel and 50 wt% to 1 wt% zinc on the surface. Forming a cured resin layer on the surface of the copper foil on which the layer is formed, using a polyamideimide resin having a thermal expansion coefficient of 0 ppm / ° C to 25 ppm / ° C; And
(Step B) The step of obtaining a copper foil with a resin by providing a semi-cured resin layer having a thermal expansion coefficient of 0 ppm / ° C to 50 ppm / ° C after curing on the cured resin layer. The method of claim 12,
In the said process A, when forming the cured resin layer using the polyamideimide resin whose thermal expansion coefficient is 0 ppm / degrees C-25 ppm / degreeC on the surface of copper foil whose surface roughness Rzjis is 0.5 micrometer-2.5 micrometers, The manufacturing method of the copper foil with resin which uses a lamination method. The method of claim 12,
In the said process B, when the amount of the resin composition containing the maleimide resin used in order to form the said semi-hardened resin layer is 100 weight part, the resin composition containing 20 weight part-70 weight part of maleimide resin is used. The manufacturing method of the copper foil with resin to use. The method of claim 12,
The manufacturing method of the copper foil with resin containing the surface modification process of plasma-processing or corona-processing the surface of a cured resin layer between the said process A and the process B.