KR101751622B1 - Surface-treated copper foil and laminated sheet, printed wiring board, and electronic device using same, as well as method for producing printed wiring board - Google Patents

Abstract

A surface-treated copper foil excellent in resin transparency after being adhered well to a resin and having removed the copper foil by etching, and a laminated board using the same. At least is formed with conditioning particles by a roughening treatment to the copper foil surface of one, is formed in a long diameter of not more than 50 / ㎛ ² area the roughening particles less than 100 ㎚ unit with respect to the conditioning particles of the roughened surface, the roughened surface MD Of 60 degree gloss of 76 to 350%.

Description

TECHNICAL FIELD [0001] The present invention relates to a surface-treated copper foil, a laminated board using the same, a printed wiring board, an electronic device, and a method for manufacturing a printed wiring board,

The present invention relates to a surface-treated copper foil, a laminated board using the same, a printed wiring board, an electronic apparatus, and a method for producing a printed wiring board, A printed wiring board, an electronic apparatus, and a method for manufacturing a printed wiring board.

Flexible printed wiring boards (hereinafter referred to as " FPC ") are used in small electronic devices such as smart phones and tablet PCs in terms of ease of wiring and light weight. In recent years, the speeding up of the signal transmission speed has been progressed by increasing the function of these electronic devices, and impedance matching is also an important factor in the FPC. As a measure for impedance matching with an increase in the signal capacity, a post-layering (thickening) of a resin insulating layer (for example, polyimide) as a base of the FPC is progressing. On the other hand, the FPC is subjected to processing such as bonding to a liquid crystal substrate or mounting of an IC chip. In this case, alignment is performed by passing the resin insulating layer remaining after etching the copper foil in the laminate of the copper foil and the resin insulating layer, The visibility of the resin insulating layer becomes important.

The copper clad laminate which is a laminate of a copper foil and a resin insulating layer can also be produced by using a rolled copper foil whose surface is roughened. This rolled copper foil is usually produced by using tough pitch copper (oxygen content 100 to 500 ppm by weight) or oxygen free copper (oxygen content 10 ppm by weight or less) as a raw material, hot rolling these ingots, And annealing are repeated.

As such a technique, for example, in Patent Document 1, a polyimide film and a low-illuminance copper foil are laminated, and the light transmittance at a wavelength of 600 nm of the film after copper foil etching is 40% or more and the haze value (HAZE) 30% or less, and an adhesive strength of 500 N / m or more.

Patent Document 2 discloses a chip-on-flexible (COF) substrate having an insulating layer in which conductor layers are laminated by an electrolytic copper foil and having a light transmittance of an insulating layer of 50% or more in an etching region when a circuit is formed by etching the conductor layer. ), Wherein the electrolytic copper foil is provided with a rust-preventive treatment layer of a nickel-zinc alloy on a bonding surface to be bonded to an insulating layer, the surface roughness (Rz) of the bonding surface is 0.05 to 1.5 탆 And a mirror polish degree at an incidence angle of 60 DEG is 250 or more. The present invention relates to a COF flexible printed wiring board.

Patent Document 3 discloses a method of treating a copper foil for a printed circuit, which comprises the steps of forming a cobalt-nickel alloy plating layer on the surface of a copper foil after roughening treatment by copper-cobalt-nickel alloy plating and forming a zinc- And a copper foil for a printed circuit board.

Japanese Patent Application Laid-Open No. 2004-98659 WO2003 / 096776 Japanese Patent No. 2849059

In the case of Patent Document 1, in the case of a low-illuminated copper foil obtained by improving the adhesiveness by an organic treating agent after a blackening treatment or a plating treatment, the copper clad laminate may be broken due to fatigue in an application requiring flexibility, .

Also, in Patent Document 2, the roughening treatment is not performed and the adhesion strength between the copper foil and the resin is low in applications other than the COF flexible printed wiring board, which is insufficient.

Further, in the treatment method described in Patent Document 3, although fine processing with Cu-Co-Ni for the copper foil was possible, excellent transparency could not be realized for the resin after the copper foil was bonded to the resin and removed by etching.

The present invention provides a surface-treated copper foil excellent in resin transparency after being well adhered to a resin and also having a copper foil removed by etching, and a laminated board using the same.

As a result of intensive researches, the inventors of the present invention have found that, in a copper foil having roughened particles formed on its surface by roughening treatment, the number density and the degree of gloss of the roughening particles having a predetermined long diameter on the roughened surface are controlled by resin transparency In the study.

In one aspect of the present invention, completed on the basis of the above findings, at least one surface of a copper foil has roughened particles formed by roughening treatment, and the roughening particles having a long diameter of 100 nm or less, per 50 / ㎛ ² and later are formed, and the surface-treated copper foil 60 of the MD of roughening the surface gloss degree of 76 ~ 350%.

In one embodiment of the surface-treated copper foil according to the present invention, harmonic grains having a long diameter of 200 nm or less are formed at a ratio of 90 pieces / mu m ² or more per unit area to the above roughening grains on the roughened surface.

In another embodiment of the surface-treated copper foil according to the present invention, the long diameter with respect to the roughening particles are formed of more than 50 100 ㎚ also coating the blend unit particles less than 150 ㎚ / ㎛ ² or less of the surface roughening treatment.

In another embodiment of the surface-treated copper foil according to the present invention, the 60 degree glossiness of the MD is 90 to 250%.

In another embodiment of the surface-treated copper foil according to the present invention, the ratio C (C = (60 degree gloss of MD) / (60 of TD) / 60 Degree of gloss)) is from 0.80 to 1.40.

In another embodiment of the surface-treated copper foil according to the present invention, the ratio C (C = (60 degree gloss of MD) / (60 of TD) / 60 Degree of gloss)) is 0.90 to 1.35.

In another embodiment of the surface-treated copper foil according to the present invention, the ratio A / B of the surface area A of the above-mentioned coarse particles to the area B obtained when the above-mentioned coarse particles are viewed from the surface side of the copper foil is 1.90 to 2.40.

In another embodiment of the surface-treated copper foil according to the present invention, the A / B ratio is 2.00 to 2.20.

In another embodiment of the surface-treated copper foil according to the present invention, when the copper foil is bonded to both surfaces of a resin substrate having a thickness of 50 mu m from the roughened surface side and then the copper foils on both surfaces are removed by etching , And the resin substrate has a haze value of 20 to 70%.

The present invention is, in another aspect, a laminated board comprising a surface-treated copper foil of the present invention and a resin substrate laminated.

In another aspect, the present invention is a printed wiring board using the surface-treated copper foil of the present invention.

According to another aspect of the present invention, there is provided an electronic apparatus using the printed wiring board of the present invention.

According to another aspect of the present invention, there is provided a method for manufacturing a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards of the present invention.

In another aspect of the present invention, there is provided a printed wiring board comprising at least one printed wiring board of the present invention and a step of connecting a printed wiring board other than the one of the present invention or the printed wiring board of the present invention to the printed wiring board Or more of the printed wiring boards.

According to another aspect of the present invention, there is provided an electronic device using at least one printed wiring board to which at least one printed wiring board of the present invention is connected.

According to another aspect of the present invention, there is provided a method of manufacturing a printed wiring board including at least a step of connecting a printed wiring board and a component of the present invention.

According to still another aspect of the present invention, there is provided a method for manufacturing a printed wiring board, comprising the steps of connecting at least one printed wiring board of the present invention, a printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention, Or a step of connecting a printed wiring board to which at least two printed wiring boards of the present invention are connected and a component are connected to each other.

According to the present invention, it is possible to provide a surface-treated copper foil excellent in resin transparency after good adhesion with a resin and removing the copper foil by etching, and a laminated board using the same.

1 is a SEM photograph of the copper foil surface of Example 4. Fig.
2 is a SEM photograph of the surface of the copper foil of Comparative Example 1. Fig.
3 is a SEM photograph of the copper foil surface of Comparative Example 7. Fig.

[Form of surface-treated copper foil and manufacturing method]

The copper foil used in the present invention is useful for a copper foil to be used by bonding a resin substrate to produce a laminate and removing the copper foil by etching.

The copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil. A roughening treatment is generally performed on the surface of the copper foil to be adhered to the resin substrate, that is, roughening, in order to improve the peel strength of the copper foil after the laminating, to perform electrodeposition of a rugged shape on the surface of the copper foil after degreasing. The electrolytic copper foil has irregularities at the time of manufacture, but the convex portions of the electrolytic copper foil are strengthened by roughening treatment to further increase the irregularities. In the present invention, this roughening treatment can be performed by copper-cobalt-nickel alloy plating or copper-nickel-phosphorus alloy plating. Conventional copper plating or the like may be applied as a pretreatment before conditioning, and conventional copper plating or the like may be applied to prevent electrodeposition from coming off as a finish treatment after conditioning. Rolled copper foil and electrolytic copper foil may have slightly different treatments. In the present invention, known treatments related to the copper foil harmonization, including the pretreatment and finishing treatments, will be collectively referred to as harmonization treatment as necessary.

The rolled copper foil according to the present invention also includes a copper alloy foil containing at least one element selected from Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb and V . When the concentration of the element is high (for example, 10 mass% or more in total), the conductivity may be lowered. The electrical conductivity of the rolled copper foil is preferably 50% IACS or more, more preferably 60% IACS or more, and still more preferably 80% IACS or more.

The copper-cobalt-nickel alloy plating as the roughening treatment is preferably a copper-cobalt-nickel alloy plating having a copper content of 15 to 40 mg / dm 2 and a nickel content of 100 to 3000 μg / To form an alloy layer. When the Co deposition amount is less than 100 占 퐂 / dm2, the heat resistance is deteriorated and the etching property is sometimes deteriorated. When the Co deposition amount exceeds 3,000 占 퐂 / dm2, it is not preferable when the effect of magnetism is to be considered, etching unevenness occurs, and acid resistance and chemical resistance deteriorate in some cases. When the Ni adhesion amount is less than 100 占 퐂 / dm2, the heat resistance may be deteriorated. On the other hand, if the amount of Ni adhered exceeds 1500 / / dm 2, etching residues may increase. The preferred Co deposition amount is 1000 to 2500 占 퐂 / dm2, and the preferable nickel deposition amount is 500 to 1200 占 퐂 / dm2. Here, the term "etching unevenness" means that Co remains unmelted when etching with copper chloride, and the term "etching residue" means that Ni remains unmelted when subjected to alkali etching with ammonium chloride.

An example of a general bath and plating condition for forming such a ternary copper-cobalt-nickel alloy plating is as follows:

Plating bath composition: 10 to 20 g / l of Cu, 1 to 10 g / l of Co, 1 to 10 g / l of Ni

pH: 1-4

Temperature: 30 ~ 50 ℃

Current density D _k : 20 to 30 A / dm 2

Plating time: 1 to 5 seconds

After the roughening treatment, a cobalt-nickel alloy plating layer of nickel having an adhesion amount of 200 to 3000 占 퐂 / dm2 and a cobalt-100 to 700 占 퐂 / dm2 can be formed on the roughened surface. This treatment can be regarded as a kind of rust treatment in a broad sense. This cobalt-nickel alloy plating layer needs to be carried out to such an extent that the bonding strength between the copper foil and the substrate is not substantially lowered. When the cobalt adherence amount is less than 200 占 퐂 / dm2, the heat-resisting peel strength may be lowered and the oxidation resistance and chemical resistance may be deteriorated. In addition, as another reason, if the amount of cobalt is small, the treated surface becomes reddish, which is not preferable. If the amount of cobalt adhered exceeds 3000 占 퐂 / dm2, it is not preferable when the effect of magnetism must be taken into consideration, etching unevenness may occur, and acid resistance and chemical resistance may be deteriorated. The preferable cobalt deposition amount is 500 to 2500 占 퐂 / dm2. On the other hand, when the nickel adhesion amount is less than 100 占 퐂 / dm2, the heat peel strength may be lowered and the oxidation resistance and the chemical resistance may be deteriorated. If the nickel exceeds 1300 占 퐂 / dm2, the alkali etching property is deteriorated. The preferred amount of nickel adhered is 200 to 1200 占 퐂 / dm2.

An example of the conditions of the cobalt-nickel alloy plating is as follows:

Plating bath composition: Co 1 to 20 g / l, Ni 1 to 20 g / l

pH: 1.5 to 3.5

Temperature: 30 ~ 80 ℃

Current density D _k : 1.0 to 20.0 A / dm 2

Plating time: 0.5 to 4 seconds

According to the present invention, a zinc plating layer having an adhesion amount of 30 to 250 占 퐂 / dm2 is further formed on the cobalt-nickel alloy plating. When the zinc adhesion amount is less than 30 占 퐂 / dm2, the effect of improving the heat deterioration rate may be lost. On the other hand, if the zinc adhesion amount exceeds 250 占 퐂 / dm2, the hydrochloric acid deterioration rate may be extremely deteriorated. Preferably, the zinc adhesion amount is 30 to 240 占 퐂 / dm2, more preferably 80 to 220 占 퐂 / dm2.

An example of the conditions of the zinc plating is as follows:

Plating bath composition: Zn 100 ~ 300 g / ℓ

pH: 3-4

Temperature: 50 ~ 60 ℃

Current density D _k : 0.1 to 0.5 A / dm 2

Plating time: 1 to 3 seconds

Further, a zinc alloy plating layer such as a zinc-nickel alloy plating layer may be formed in place of the zinc plating layer, or a rust-preventive layer may be formed on the outermost surface by chromate treatment, application of a silane coupling agent or the like.

[Number density of harmonic particles]

Surface treatment of the present invention, copper foil is formed at least are formed roughening particles by a roughening treatment to the copper foil surface of one, the 50 area is a long diameter with respect to the roughening particles units roughening particles less than 100 ㎚ of roughening the surface / ㎛ ² or more . With such a constitution, the peel strength is increased, the resin is well adhered to the resin, and the degree of fogging (haze value) of the resin after the copper foil is removed by etching is reduced and the transparency is enhanced. As a result, it becomes easy to align the IC chip when mounting the IC chip through a positioning pattern which is visible through the resin. If the coarse particles having a long diameter of 100 nm or less are less than 50 / μm ² per unit area, the roughening treatment of the surface of the copper foil is insufficient and can not be sufficiently bonded to the resin. When the particle diameter is more than 100 nm and the number of particles per unit volume is small, the adhesiveness to the resin is secured, but the degree of fogging (haze value) of the resin after the removal of the copper foil by etching becomes large and transparency becomes low. The coarse particles having a long diameter of 100 nm or less are preferably formed at a ratio of 60 / μm ² or more per unit area, more preferably 150 / μm ² or more. The upper limit is not particularly set, but the upper limit of the number of particles of the coarse particles having a long diameter of 100 nm or less is, for example, 2,500 particles / 탆 ² or less.

Surface-treated copper foil of the present invention It is preferable that with respect to the conditioning particles of roughening the surface, the major axis is formed more than 90 / ㎛ ² per area is not more than 200 particles conditioner ㎚ unit. With such a constitution, the peel strength is increased, the resin is well adhered to the resin, and the degree of fogging (haze value) of the resin after the copper foil is removed by etching is reduced and the transparency is enhanced. As a result, there is an effect that it becomes easy to position the IC chip when mounting the IC chip through a positioning pattern which is visible through the resin. If the coarse grains having a long diameter of 200 nm or less are less than 90 / μm ² per unit area, there is a possibility that the roughening treatment of the surface of the copper foil is insufficient and the resin can not be sufficiently bonded to the resin. Further, when the particle diameter is more than 200 nm and the number of particles per unit volume is small, adhesion with the resin is ensured, but there is a problem that the degree of fogging (haze value) of the resin after removal of the copper foil by etching becomes large, . Blend particle long diameter of not less than 200 ㎚ is preferably is formed in units of 100 or more / ² ㎛ area is formed more preferably not less than 150 / ㎛ ^2. There is no particular upper limit set, but the upper limit of the number of particles of coarse particles having a long diameter of 200 nm or less is, for example, 2500 / 탆 ² or less.

Surface-treated copper foil of the present invention It is preferable that with respect to the conditioning particles of roughening the surface, the major axis is formed with more than 50 100 ㎚ also coating the blend unit particles less than 150 ㎚ / ㎛ ² below. With such a configuration, there is obtained an effect that the fogging degree (haze value) of the resin after removing the copper foil by etching, while securing the adhesion with the resin, is increased and good transparency is obtained. If the number of the coarse grains having a long diameter of more than 100 nm and not more than 150 nm is 50 / μm ² or more per unit area, the haze value of the resin after removal of the copper foil by etching becomes large, which may cause a problem of low transparency. A long diameter of not more than 100 ㎚ also not more than 150 ㎚ conditioning particles preferably are formed per unit area of 30 / ㎛ ² or less, the formation is preferably 10 / ㎛ ² below. There is no particular limitation on the lower limit, but the lower limit of the number of particles having a long diameter of more than 100 nm and not more than 150 nm is 0 / μm ² or more.

[Polishing degree]

The degree of glossiness at an incident angle of 60 degrees in the rolling direction (MD) of the roughened surface of the surface-treated copper foil largely affects the haze value of the above-mentioned resin. That is, the haze value of the above-mentioned resin becomes smaller as the copper foil having a larger degree of gloss of the roughened surface. For this reason, the surface-treated copper foil of the present invention preferably has a coarseness of 76 to 350%, preferably 80 to 350%, more preferably 90 to 300%, more preferably 90 to 250% More preferably 100 to 250%.

Here, in order to further improve the visibility effect of the present invention, it is also important to control the illuminance (Rz) and gloss of the TD on the surface of the treated side of the copper foil before the surface treatment. Specifically, the surface roughness (Rz) of the TD of the copper foil before the surface treatment is 0.30 to 0.80 mu m, preferably 0.30 to 0.50 mu m, the glossiness at the incidence angle of 60 degrees in the rolling direction (MD) is 350 to 800% And the current density is higher than that of the conventional roughening treatment to shorten the roughening treatment time, the gloss of the surface-treated copper foil after the surface treatment at the incident angle of 60 degrees in the rolling direction (MD) 76 to 350%. Such a copper foil can be produced by rolling (high gloss rolling) by adjusting the oil film equivalent of the rolling oil, or by chemical polishing such as chemical etching or electrolytic polishing in a phosphoric acid solution. By setting the surface roughness (Rz) and gloss of the TD of the copper foil before the treatment to the above-described range, it is possible to easily control the number density and gloss of the roughening particles having a predetermined length of the copper foil after treatment.

In the case where the glossiness at an incident angle of 60 degrees in the rolling direction (MD) after the surface treatment is intended to be higher (for example, glossiness at an incidence angle of 60 degrees in the rolling direction (MD) = 350%), The surface roughness (Rz) of the TD on the surface of the copper foil before treatment is 0.18 to 0.80 mu m, preferably 0.25 to 0.50 mu m and the glossiness at the incidence angle of 60 degrees in the rolling direction (MD) is 350 to 800% 500 to 800%, and the current density is higher than that of the conventional harmonic treatment, thereby shortening the harmonization processing time.

The high-gloss rolling can be carried out by setting the oil film equivalent defined by the following formula to 13000 or more to 24000 or less. Further, in the case where the glossiness at 60 degrees of incidence in the rolling direction (MD) after the surface treatment is desired to be higher (for example, glossiness at an incidence angle of 60 degrees in the rolling direction (MD) = 350%), The film equivalent weight defined by the following formula is set to 12000 or more and 24000 or less.

(Yielding stress [kg / mm < 2 >]) of the material = {(rolling oil viscosity [cSt]) x (passing speed [mpm] + roll main speed [mpm])} }

The viscosity of the rolling oil [cSt] is the kinematic viscosity at 40 ° C.

In order to make the film equivalent of 12,000 or more to 24,000 or less, it is possible to use a known method such as using low-viscosity rolling oil or slowing the passing speed.

The chemical polishing is carried out for a long period of time by lowering the concentration by an etching solution such as a sulfuric acid-hydrogen peroxide-water system or an ammonia-hydrogen peroxide-water system.

It is preferable that the ratio C (C = (60 degree glossiness of MD) / (60 degree glossiness of TD)) of 60 degree glossiness of MD and 60 degree glossiness of TD of harmony treated surface is 0.80 to 1.40. If the ratio C of the 60 degree glossiness of the MD and the 60 degree glossiness of the TD of the roughened surface is less than 0.80, the haze value may be higher than that of 0.80 or more. If the ratio C exceeds 1.40, the haze value may be higher than when the ratio C is 1.40 or less. The ratio C is more preferably 0.90 to 1.35, and even more preferably 1.00 to 1.30.

[Haze value]

As described above, the surface-treated copper foil of the present invention has an average roughness Rz and gloss of the roughened surface controlled, so that the haze value of the resin substrate at the portion where the copper foil is removed after being bonded to the resin substrate is reduced. Here, the haze value (%) is a value calculated by (diffusion transmittance) / (total light transmittance) x 100. Specifically, the surface-treated copper foil of the present invention is a copper foil having a haze value of 20 to 70% when the copper foil is removed by etching after being applied to both surfaces of a resin substrate having a thickness of 50 탆 from the roughened surface side , More preferably from 30 to 55%.

[Particle surface area]

The ratio A / B of the three-dimensional surface area A of the roughened surface and the two-dimensional area B obtained when the roughened surface is viewed from the roughened surface side greatly affects the haze value of the above-described resin. That is, when the surface roughness Rz is the same, the haze value of the above-mentioned resin becomes smaller as the copper foil with smaller A / B is. Therefore, the surface-treated copper foil of the present invention has a ratio A / B of 1.90 to 2.40, preferably 2.00 to 2.20.

By controlling the current density and the plating time at the time of particle formation, the shape and the formation density of the particles are determined, and the surface roughness Rz, the gloss and the area ratio A / B of the particles can be controlled.

[Etching Factor]

When the value of the etching factor at the time of forming the circuit using the copper foil is large, the sagging of the circuit bottom portion generated at the time of etching becomes small, so that the space between the circuits can be narrowed. Therefore, the larger the value of the etching factor is, the better for the circuit formation by the fine pattern. In the surface-treated copper foil of the present invention, for example, the value of the etching factor is preferably 1.8 or more, more preferably 2.0 or more, preferably 2.2 or more, more preferably 2.3 or more, and more preferably 2.4 or more.

In the printed wiring board or the copper clad laminate, the aforementioned area ratio (A / B) of the particles to the surface of the copper circuit or the copper foil, the degree of gloss, and the density of the number of coarse grains can be measured by dissolving and removing the resin.

[Transmission Loss]

When the transmission loss is small, the attenuation of the signal at the time of performing the signal transmission at the high frequency is suppressed, so that it is possible to perform the stable signal transmission in the circuit that performs the signal transmission at the high frequency. Therefore, a smaller value of the transmission loss is preferable because it is suitable for use in a circuit application that carries out signal transmission at a high frequency. The surface-treated copper foil was laminated with a commercially available liquid crystal polymer resin (Vecstar CTZ-50 mu m, manufactured by Kuraray Co., Ltd.), and microstrip lines were formed by etching so as to have a characteristic impedance of 50 OMEGA. Using a network analyzer HP8720C , The transmission loss at a frequency of 20 GHz is preferably less than 5.0 dB / 10 cm and less than 4.1 dB / 10 cm when the transmission loss is measured at a frequency of 20 GHz and a frequency of 40 GHz, And more preferably less than 3.7 dB / 10 cm.

The surface treated copper foil of the present invention can be bonded to the resin substrate from the roughened surface side to produce a laminate. The resin substrate is not particularly limited as long as it has properties applicable to a printed wiring board and the like. For example, for a rigid PWB, a paper base phenol resin, a paper base epoxy resin, a synthetic fiber base epoxy resin, , A glass cloth / glass nonwoven fabric composite base epoxy resin, a glass cloth base epoxy resin, and the like, and for the FPC, a polyester film, a polyimide film, a liquid crystal polymer (LCP) film and a fluororesin film can be used. When a liquid crystal polymer (LCP) film or a fluororesin film is used, the peel strength of the film and the surface-treated copper foil tends to be smaller than that in the case of using a polyimide film. Therefore, when a liquid crystal polymer (LCP) film or a fluororesin film is used, the film is not peeled off from the copper circuit by covering the copper circuit with the cover film after forming the copper circuit, The peeling of the film and the copper circuit can be prevented.

Since the liquid crystal polymer (LCP) film or the fluororesin film has a small dielectric loss tangent, the copper clad laminate, the printed wiring board and the printed circuit board using the liquid crystal polymer (LCP) film or the fluororesin film and the surface- Circuit (a circuit that carries out signal transmission at a high frequency). The surface-treated copper foil according to the present invention has a surface roughness Rz of a small value and a high gloss, so that the surface is smooth and suitable for use in a high-frequency circuit.

In the case of the rigid PWB, the prepreg is prepared by impregnating a base material such as glass cloth with resin and hardening the resin to a semi-hardened state. The copper foil may be superimposed on the prepreg from the opposite side of the coating layer and heated and pressed. In the case of an FPC, a laminated board can be manufactured by laminating and bonding to a base material such as a polyimide film with an adhesive or without using an adhesive under high temperature and high pressure, or by applying a polyimide precursor, drying and curing have.

The laminate of the present invention can be applied to various printed wiring boards (PWB), and is not particularly limited. For example, it can be applied to single-sided PWB, double-sided PWB, multilayer PWB (three or more layers) And the rigid PWB, the flexible PWB (FPC), and the rigid flex PWB in view of the kind of the insulating substrate material.

[Laminating Plate and Positioning Method of Printed Circuit Board Using It]

A method of positioning the laminated board of the surface-treated copper foil and the resin substrate of the present invention will be described. First, a laminated board of a surface-treated copper foil and a resin substrate is prepared. As a specific example of the laminate of the surface-treated copper foil and the resin substrate of the present invention, copper wiring is formed on at least one surface of a main substrate and an accessory circuit board and a resin substrate such as polyimide used for electrically connecting them In an electronic apparatus constituted by a flexible printed circuit board, a flexible printed circuit board is precisely positioned and pressed onto a wiring end of the main circuit board and the accessory circuit board. That is, in this case, the laminated board is a laminate in which the end portions of the flexible printed circuit board and the main board are bonded by pressing, or a laminated board in which the wiring end portions of the flexible printed board and the circuit board are bonded by compression bonding. The laminated board has a mark formed of a part of the copper wiring or a separate material. The position of the mark is not particularly limited as long as it can be photographed by a photographing means such as a CCD camera over the resin constituting the laminated plate. Here, "mark" refers to a mark used for detecting a position of a laminated plate, a printed wiring board, etc., positioning, or alignment.

In the thus prepared laminated plate, when the above-described mark is photographed by the photographing means over resin, the position of the mark can be detected satisfactorily. Thus, the position of the mark can be detected, and the position of the laminate of the surface-treated copper foil and the resin substrate can be satisfactorily positioned based on the detected position of the mark. Also in the case where a printed wiring board is used as the laminated board, the position of the mark is well detected by the photographing means by such a positioning method, and positioning of the printed wiring board can be performed more accurately.

Therefore, it is considered that when one printed wiring board is connected to another printed wiring board, defective connection is reduced and the yield is improved. As a method of connecting one printed wiring board to another printed wiring board, a connection via anisotropic conductive film (ACF), a connection via anisotropic conductive paste (ACP), or a connection through an anisotropic conductive film A known connection method such as a connection through an adhesive having conductivity can be used. In the present invention, the " printed wiring board " includes a printed wiring board on which components are mounted, a printed circuit board, and a printed board. It is also possible to manufacture a printed wiring board to which two or more printed wiring boards are connected by connecting two or more printed wiring boards according to the present invention. Further, at least one printed wiring board of the present invention, Alternatively, a printed wiring board not corresponding to the printed wiring board of the present invention can be connected, and an electronic apparatus can be manufactured using such a printed wiring board. In the present invention, the "copper circuit" is also assumed to include a copper wiring. Further, the printed wiring board of the present invention may be connected to parts to produce a printed wiring board. It is also possible to connect at least one printed wiring board of the present invention to another printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention, And the printed wiring board may be connected to each other to manufacture a printed wiring board in which two or more printed wiring boards are connected. Examples of the " parts " include electronic parts such as a connector, a liquid crystal display (LCD), and a glass substrate used for an LCD, an integrated circuit (IC), a large scale integrated circuit (LSI) (E.g., an IC chip, an LSI chip, a VLSI chip, and an ULSI chip) including a semiconductor integrated circuit such as a ULSI (Ultra-Large Scale Integration), a component for shielding an electronic circuit, And the parts necessary for fixing them.

Further, the positioning method according to the embodiment of the present invention may include a step of moving the laminate (including a laminate of a copper foil and a resin substrate or a printed wiring board). In the moving process, for example, it may be moved by a conveyor such as a belt conveyor or a chain conveyor, or may be moved by a moving device having an arm mechanism, or may be moved by a moving device or a moving device Or a moving device or a moving device (including a roller or a bearing) for moving a laminated plate by rotating an article such as a substantially cylindrical shape, a moving device or a moving device using a hydraulic pressure as a power source, a moving device using air pressure as a power source Or moving means having a stage such as a moving device or a moving means using a motor as a power source, a gantry moving linear guide stage, a gantry moving air guide stage, a stacked linear guide stage, a linear motor driving stage, . Also, a moving process by a known moving means may be carried out. In the step of moving the laminated plate, the laminated plate can be moved and aligned. It is believed that the connection is reduced when connecting one printed wiring board to another printed wiring board or parts, thereby improving the yield.

The positioning method according to the embodiment of the present invention may be used in a surface mount machine or a chip mounter.

The laminate of the surface-treated copper foil and the resin substrate positioned in the present invention may be a resin board and a printed wiring board having a circuit formed on the resin board. In this case, the mark may be the circuit.

In the present invention, " positioning " includes " detecting the position of a mark or an object ". In the present invention, " alignment " includes " moving a mark or an object to a predetermined position based on the detected position after detecting the position of the mark or object ".

Example

Various copper foils were prepared as Examples 1 to 23 and Comparative Examples 1 to 13, and plating treatment was carried out on one surface of the substrate under the conditions shown in Tables 1 to 8 as a roughening treatment.

After the above-described coarse plating treatment, plating treatment for forming the following heat-resistant layer and rust-preventive layer was performed on Examples 1 to 12, 14 to 19, 21 to 23, and Comparative Examples 2, 4 and 7 to 10 .

The formation conditions of the heat resistant layer 1 are shown below.

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

pH: 2-3

Solution temperature: 40 to 60 ° C

Current density: 5 to 20 A / dm 2

Culm volume: 10 ~ 20 As / d㎡

Resistant layer 2 was formed on the copper foil on which the heat-resistant layer 1 was formed. In Comparative Examples 3, 5 and 6, the heat-resistant layer 2 was directly formed on the prepared copper foil without performing the roughening treatment. The formation conditions of the heat resistant layer 2 are shown below.

Liquid composition: 2 to 30 g / l of nickel, 2 to 30 g / l of zinc

pH: 3-4

Temperature: 30 ~ 50 ℃

Current density: 1 to 2 A / dm 2

Culm volume: 1 ~ 2 As / d㎡

A rust preventive layer was further formed on the copper foil on which the heat resistant layers 1 and 2 were formed. The formation conditions of the anticorrosive layer are shown below.

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

pH: 3-4

Temperature: 50 to 60 ° C

Current density: 0 to 2 A / dm 2 (for immersion chromate treatment)

Culm amount: 0 to 2 As / dm 2 (for immersion chromate treatment)

Resistant layer was further formed on the copper foil on which the heat-resistant layers 1 and 2 and the anticorrosive layer were formed. The formation conditions are shown below.

N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (Example 16), N-2- (aminoethyl) -3-aminopropyltriethoxysilane Aminopropyl trimethoxysilane (Example 17), 3-aminopropyltrimethoxysilane (Example 18), 3 (aminopropyl) trimethoxysilane -Aminopropyltriethoxysilane (Example 19), 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (Example 21) Methoxy silane (Example 22) and dried to form a weather resistant layer. These silane coupling agents may be used in combination of two or more.

The rolled copper foil was prepared as follows. A copper ingot having the composition shown in Table 9 was prepared and subjected to hot rolling. Annealing and cold rolling of the continuous annealing line at 300 to 800 캜 were repeated to obtain a rolled plate having a thickness of 1 to 2 mm. This rolled sheet was annealed in a continuous annealing line at 300 to 800 캜 to be recrystallized and finally cold rolled to the thickness of Table 9 to obtain a copper foil. "Tough pitch copper" in the "Type" column of Table 9 indicates tough pitch copper specified in JIS H3100 C1100, and "oxygen free copper" indicates oxygen free copper specified in JIS H3100 C1020. "Tough pitch copper + Ag: 100 ppm" means that Ag is added to tough pitch copper at 100 mass ppm.

The electrolytic copper foil was an electrolytic copper foil HLP foil manufactured by JX Nikko Nisseki KINZOKUSA. When the electrolytic polishing or the chemical polishing is carried out, the plate thickness after electrolytic polishing or chemical polishing is described.

Table 9 shows the points of the copper foil manufacturing process before the surface treatment. "High gloss rolling" means that the final cold rolling (cold rolling after the final recrystallization annealing) is carried out at the value of the oil film equivalent described above. The term " ordinary rolling " means that the final cold rolling (cold rolling after final recrystallization annealing) is carried out at the value of the oil film equivalent described above. &Quot; chemical polishing " and " electrolytic polishing " mean that they are carried out under the following conditions.

The "chemical polishing" used was an etching solution of 1 to 3 mass% of H ₂ SO ₄ and 0.05 to 0.15 mass% of H ₂ O ₂ , and the polishing time was 1 hour.

Electrolytic polishing was carried out under the conditions of 67% phosphoric acid + 10% sulfuric acid + 23% water at a voltage of 10 V / cm 2 and the time shown in Table 9 (electrolytic polishing for 10 seconds yields a polishing amount of 1 to 2 占 퐉) Respectively.

Various evaluations of the samples prepared in the above-described Examples and Comparative Examples were carried out as follows.

(1) area ratio of particles (A / B);

The surface area of the coarse particles was measured by a laser microscope. Dimensional surface area A in an area B equivalent to 100 × 100 μm (9982.52 μm ^{2 in} actual data) at a magnification of 2,000 times of the roughened surface by using a laser microscope VK8500 manufactured by Keith Co., Ltd., and the three- And surface area B = area ratio (A / B).

(2) glossiness;

(MD, in the case of an electrolytic copper foil, in the case of an electrolytic copper foil) and in a direction perpendicular to the rolling direction (TD, in the case of an electrolytic copper foil, by using a gloss gauge Handy Gloss meter PG-1 manufactured by Nippon Seisin Kogyo K.K. (Direction perpendicular to the main scanning direction).

The gloss of the copper foil before the surface treatment was also determined in the same manner.

(3) haze value;

The copper foil was laminated on both sides of a polyimide film (thickness: 50 mu m, thickness: 80 mu m, with a thermosetting adhesive for lamination) and the copper foil was removed by etching (ferric chloride aqueous solution) to prepare a sample film. The haze value of the sample film was measured using a haze meter HM-150 manufactured by Murakami Color Research Laboratory based on JIS K7136 (2000).

(4) visibility (resin transparency);

The copper foil was laminated on both sides of a polyimide film (thickness: 50 mu m, thickness: 80 mu m, with a thermosetting adhesive for lamination) and the copper foil was removed by etching (ferric chloride aqueous solution) to prepare a sample film. A print (black circle having a diameter of 6 cm) was attached to one surface of the obtained resin layer, and the visibility of the print was judged from the opposite surface to the resin layer. The outline of the black circle of the printed matter is not less than 90% of the circumference, and the outline of the black circle is not less than 80% and not more than 90% of the circumference, Of the circumference of the circumference was less than 0 to 80% of the circumference, and that the contour was broken was evaluated as " x " (rejection).

(5) Peel strength (adhesive strength);

According to PC-TM-650, state (normal) fill strength was measured with a tensile tester Autograph 100, and the state fill strength was 0.7 N / mm or more so that it could be used for laminated board applications.

(6) Condensation particle number density;

The coarsened particles of the surface-treated copper foil were observed at a magnification of 80,000 times (area: 1.58 mu m x 1.19 mu m = 1.88 mu m < ² >) using a scanning electron microscope photograph S4700 manufactured by Hitachi High- Respectively. Further, when a straight line is drawn on a particle of a scanning electron microscopic photograph, the length of the longest straight line across the particle is taken as the longest diameter of the particle. The number of observed particles is shown in the table as the number of particles per unit area using an area of 1.88 占 퐉 ² .

(7) Circuit shape by etching (fine pattern characteristics)

The copper foil was bonded to both surfaces of a polyimide film (thickness: 50 mu m, Uffeyrex manufactured by Ube Industries, Ltd.) with a thermosetting adhesive for lamination. In order to form a fine pattern circuit, it is necessary to make the thickness of the copper foil the same, and here, the thickness of the copper foil of 12 탆 is used as a reference. That is, when the thickness is thicker than 12 탆, the thickness is reduced to 12 탆 by electrolytic polishing. On the other hand, when the thickness is thinner than 12 탆, the thickness is increased to 12 탆 by copper plating treatment. A fine pattern circuit was printed on the copper foil glossy side of the obtained double-sided laminated board on the side of the laminated copper foil by applying a photosensitive resist and an exposure step and an unnecessary portion of the copper foil was etched under the following conditions to obtain L / A fine pattern circuit having a thickness of 20 mu m was formed. Here, the circuit width was such that the bottom width of the circuit section was 20 μm.

(Etching condition)

Apparatus: Spray type small etching equipment

Spray pressure: 0.2 MPa

Etching solution: Ferric chloride aqueous solution (specific gravity 40 bar)

Liquid temperature: 50 ℃

After forming a fine patterned circuit, the photosensitive resist film was peeled by immersing in an aqueous NaOH solution at 45 캜 for one minute.

(8) Calculation of etching factor (Ef)

The fine pattern circuit sample obtained above was observed from the top of the circuit at a magnification of 2000 times using a scanning electron microscope photograph S4700 manufactured by Hitachi High Technologies Corporation and the top width Wa at the top of the circuit and the bottom width (Wb) was measured. The thickness (T) of the copper foil was set to 12 탆. The etch factor Ef was calculated by the following equation.

Etching factor Ef = (2 x T) / (Wb - Wa)

(9) Solder heat resistance evaluation;

The copper foil was bonded to both surfaces of a polyimide film (thickness: 50 mu m, Uffeyrex manufactured by Ube Industries, Ltd.) with a thermosetting adhesive for lamination. Test coupons conforming to JIS C6471 were prepared for the obtained double-sided laminates. The prepared test coupon was exposed for 48 hours under high temperature and high humidity conditions of 85 캜 and 85% RH, and then heated in a solder bath at 300 캜 to evaluate solder heat resistance characteristics. After the soldering heat resistance test, it was found that the interface was discolored by swelling at an area of 5% or more of the copper foil area in the test coupon at the interface between the copper foil roughening treatment surface and the polyimide resin adhesion surface, and the area was less than 5% Was evaluated as & cir & & cir & at all when no swelling discoloration occurred.

(10) Measurement of transmission loss

(Vecstar CTZ-50 占 퐉, manufactured by Kuraray Co., Ltd.) for each sample having a thickness of 18 占 퐉, a microstrip line was formed so as to have a characteristic impedance of 50? By etching, The transmission coefficient was measured using a network analyzer HP8720C manufactured by Hitachi, Ltd., and the transmission loss was measured at a frequency of 20 GHz and a frequency of 40 GHz. The evaluation of the transmission loss at a frequency of 20 ㎓ was ◎ for less than 3.7 dB / 10 cm, ◯ for more than 3.7 dB / 10 cm and less than 4.1 dB / 10 cm, and less than 5.0 dB / 10 cm △, and 5.0 dB / 10 ㎝ or more, respectively.

The conditions and evaluation of each of the above tests are shown in Tables 1 to 11.

[Evaluation results]

In Examples 1 to 23, haze value, visibility and peel strength were all good.

In Comparative Examples 1 to 2, 4, 7 to 11 and 13, the haze value was remarkably high and the visibility was poor.

In Comparative Examples 3, 5, 6 and 12, the visibility was excellent, but the peel strength was insufficient and the substrate adhesion was poor.

In Example 4, the 60 degree glossiness and the surface area ratio A / B of the MD of Example 14 were almost the same value, but the ratio of the 60 degree glossiness of MD to the 60 degree glossiness of TD of the roughened surface of Example 4 Since the value of C was within the range of 0.84 and 0.80 to 1.40, the haze value was smaller than that of Example 14 in which the value of C was outside the range of 0.75 and 0.80 to 1.40.

For the same reason, the haze value of Example 15 was smaller than that of Example 16.

Fig. 1 shows the SEM observation of the copper foil surface in Example 4, Fig. 2 shows the Comparative Example 1, and Fig. 3 shows the Comparative Example 7.

Claims (25)

At least the roughening particles are formed by a roughening treatment to the copper foil surface of one, and the major axis is formed more than 50 / ㎛ ² per area is not more than 100 particles conditioner ㎚ unit with respect to the conditioning particles of the surface roughening treatment,
When the straight line is drawn on the coarse grain of a scanning electron microscope photograph obtained by observing the coarsened particles of the surface-treated copper foil with a scanning electron microscope, the length of the longest straight line crossing the coarsened particles is the length In addition,
A surface treated copper foil having a 60 degree gloss of MD of 76 to 350% on the roughened surface. The method according to claim 1,
Conditioning a long diameter of not less than 200 ㎚ with respect to the conditioning particles of the treated surface roughening particles per unit area of 90 / ㎛ ² or more are surface-treated copper foil that is formed. The method according to claim 1,
Roughening exceed the long diameter with respect to the blend of the particles 100 ㎚ surface 150 also ㎚ or less roughening particles per unit area of 50 / ㎛ ² surface-treated copper foil is formed as follows. 3. The method of claim 2,
Roughening exceed the long diameter with respect to the blend of the particles 100 ㎚ surface 150 also ㎚ or less roughening particles per unit area of 50 / ㎛ ² surface-treated copper foil is formed as follows. The method according to claim 1,
Wherein the MD has a 60 degree gloss of 90 to 250%. 5. The method according to any one of claims 2 to 4,
Wherein the MD has a 60 degree gloss of 90 to 250%. The method according to claim 1,
(C = (60 degree gloss of MD) / (60 degree glossiness of TD)) of 60 degree gloss of MD and 60 degree gloss of TD on the roughened surface is 0.80 to 1.40. 6. The method according to any one of claims 2 to 5,
(C = (60 degree gloss of MD) / (60 degree glossiness of TD)) of 60 degree gloss of MD and 60 degree gloss of TD on the roughened surface is 0.80 to 1.40. 8. The method of claim 7,
(C = (60 degree gloss of MD) / (60 degree glossiness of TD)) of 60 degree gloss of MD and 60 degree gloss of TD on the roughened surface is 0.90 to 1.35. The method according to claim 1,
A surface-treated copper foil having a three-dimensional surface area A of the roughened surface and a ratio A / B of a two-dimensional area B obtained when the roughened surface is viewed from the side of the roughened surface is 1.90 to 2.40. 9. The method of claim 8,
A surface-treated copper foil having a three-dimensional surface area A of the roughened surface and a ratio A / B of a two-dimensional area B obtained when the roughened surface is viewed from the side of the roughened surface is 1.90 to 2.40. 10. The method according to any one of claims 2 to 5, 7, and 9,
A surface-treated copper foil having a three-dimensional surface area A of the roughened surface and a ratio A / B of a two-dimensional area B obtained when the roughened surface is viewed from the side of the roughened surface is 1.90 to 2.40. 11. The method of claim 10,
Wherein said A / B is from 2.00 to 2.20. The method according to claim 1,
Wherein the haze value of the resin substrate is 20 to 70% when the copper foil on both sides is removed by etching after the roughened surface side of the copper foil is bonded to both sides of the resin substrate having a thickness of 50 占 퐉. 9. The method of claim 8,
Wherein the haze value of the resin substrate is 20 to 70% when the copper foil on both sides is removed by etching after the roughened surface side of the copper foil is bonded to both sides of the resin substrate having a thickness of 50 占 퐉. 13. The method of claim 12,
Wherein the haze value of the resin substrate is 20 to 70% when the copper foil on both sides is removed by etching after the roughened surface side of the copper foil is bonded to both sides of the resin substrate having a thickness of 50 占 퐉. 14. A method according to any one of claims 2 to 5, 7, 9, 10, and 13,
Wherein the haze value of the resin substrate is 20 to 70% when the copper foil on both sides is removed by etching after the roughened surface side of the copper foil is bonded to both sides of the resin substrate having a thickness of 50 占 퐉. A laminated board comprising the surface-treated copper foil according to any one of claims 1 to 5, 7, 9, 10, 13 and 14 and a resin substrate laminated. A printed wiring board using the surface-treated copper foil according to any one of claims 1 to 5, 7, 9, 10, 13 and 14. An electronic device using the printed wiring board according to claim 19. A method for producing a printed wiring board in which two or more printed wiring boards according to claim 19 are connected and two or more printed wiring boards are connected. At least one printed wiring board according to claim 19 and a printed wiring board according to any one of claims 19 to 19 or a printed wiring board not corresponding to the printed wiring board according to claim 19, By weight based on the total weight of the printed wiring board. A printed wiring board manufactured by a method for manufacturing a printed wiring board in which two or more printed wiring boards according to claim 19 are connected and at least two printed wiring boards are connected,
At least one printed wiring board according to claim 19 and a printed wiring board according to any one of claims 19 to 19 or a printed wiring board not corresponding to the printed wiring board according to claim 19, Wherein at least one printed wiring board manufactured by the method for manufacturing a printed wiring board is connected to at least one printed wiring board. A method of manufacturing a printed wiring board including at least a step of connecting a printed wiring board according to claim 19 and a component. A step of connecting at least one of the printed wiring boards according to claim 19 and another printed wiring board according to claim 19 or a printed wiring board not corresponding to the printed wiring board according to claim 19;
At least one printed wiring board according to claim 19 or a printed wiring board according to claim 19 and a printed wiring board according to another 19th aspect or a printed wiring board not corresponding to the printed wiring board according to claim 19 A printed wiring board having at least two printed wiring boards connected by a method of manufacturing a printed wiring board to which at least two printed wiring boards are connected, How to.

Images