KR20170088602A - Electrolytic copper foil and method for producing the same, and copper clad laminate and printed circuit board having the same - Google Patents

Abstract

The present invention relates to an electrolytic copper foil and, more specifically, to an electrolytic copper foil with enhanced heat resistance, which has the greatest influence on defects, such as de-lamination, and a manufacturing method thereof. The present invention includes: a raw foil; a copper nodule layer provided with a plurality of nodule particles formed on the raw foil, wherein the nodule particle having a negative correction value among the plurality of nodule particles is in a range of 70% or more and 100% or less of the total number of nodule particles; and a barrier layer made of an inorganic-metal mixture on the copper nodule layer.

Description

TECHNICAL FIELD The present invention relates to an electrolytic copper foil, a copper clad laminate and a printed circuit board,

The present invention relates to an electrolytic copper foil, and more particularly, to a heat-resistant electrolytic copper foil having a great influence on defects such as de-lamination, a method of manufacturing the same, and a copper-clad laminate and a printed circuit board.

As the industry develops, the use of printed circuit boards in each industry area is increasing. Particularly, in recent years, there has been a rapid increase in demand for flexible printed circuit boards as well as rigid printed circuit boards.

Such a printed circuit board is generally manufactured by forming a plating layer on a copper clad laminate (CCL), and then patterning the circuit on the formed plating layer.

The copper foil used for the copper clad laminate may be an electrolytic copper foil.

Electrolytic copper foil, which is a basic material used in the production of such a printed circuit board, is manufactured by an electroplating process for producing a copper raw material by an electroplating method, a post-processing for performing a nodule treatment, a chemical resistant treatment, a heat resistant treatment, ≪ / RTI >

The copper foil produced by a conventional stamping process is peeled off from the negative electrode drum of the washer-dryer and is located on the other side of the glossy surface (S-side) and the glossy surface (S-side) And includes a matte side (M side).

The copper foil is subjected to a surface treatment to form a copper nodule and a barrier in a post-treatment process, thereby imparting physical and chemical properties suitable for a printed circuit board.

A copper layer is formed on the mat surface (M side) of the copper foil by a post-treatment process, and a barrier layer which is a plating layer such as nickel (Ni) and chromium (Cr) is formed on the copper layer, Oxidation and the like are imparted.

On the barrier layer, a silane coupling agent is additionally coated to improve adhesion to the resin film adhering to the copper foil.

The main physical and chemical properties of the electrolytic copper foil are determined by the structure of the surface treatment layer. When the post treatment is not properly carried out, the adhesion reliability between the copper foil and the resin film is poor and the etching property, peel strength, Deterioration may occur.

In particular, recently, the electrolytic copper foil is widely used as a material of a flexible printed circuit board (FCCL) for a flexible printed circuit board (FPC) applied to a bent portion of a portable electronic device, so that cracks, A copper foil with excellent heat resistance should be provided.

However, there is a limit in increasing the adhesive strength, heat resistance, acid resistance and the like by the conventional post-treatment process. In particular, in a high temperature heat treatment process in which a copper foil and a polymer resin are bonded, heat resistance is weak, And the etching property is poor.

Korean Patent Publication No. 10-2006-0006389 Korean Patent Publication No. 10-2014-0034698

It is an object of the present invention to provide an electrolytic copper foil whose heat resistance is enhanced according to a method of treating a surface treatment layer in a copper foil, a method for manufacturing the same, a copper-clad laminate, and a printed circuit board .

Another object of the present invention is to provide an electrolytic copper foil having improved formation structure of a copper layer, which is a surface treatment layer, a method for manufacturing the same, and a copper-clad laminate and a printed circuit board.

The objects of the present invention are not limited to the above-mentioned problems, and other technical subjects not mentioned can be clearly understood by the embodiments of the present invention.

An electrolytic copper foil according to one aspect of the present invention comprises: A nodule particle formed on the raw paper and having a plurality of nodule particles and having a correction value of negative nodule particle among the plurality of nodule particles is in a range of 70% or more and 100% or less of the total number of nodule particles; And a barrier layer made of an inorganic-metal mixture on the copper layer, wherein the correction elongation is defined as a ratio of a length of the nodule particle in a direction parallel to the surface of the raw- Can be calculated as (longitudinal-transverse) / longitudinal when the long axis of the nodule particle is expressed as a vertical length.

In addition, the electrolytic copper foil according to an aspect of the present invention further includes another copper layer having a plurality of nodule particles between the original foil and the copper layer.

Also, in the copper alloy layer of the electrolytic copper foil of one aspect of the present invention, the nodule particle having a negative correction value of the nodule particles is in a range of 80% to 100% of the total number of nodule particles.

(A + b) / L of the surface colorimeter of the electrolytic copper foil of one aspect of the present invention is in the range of 0.45 to 0.5, L is the reflectance of the color difference meter, a is the chromaticity diagram, and + a * -a * denotes the green direction, b denotes the chromaticity diagram, + b * denotes yellow, and -b * denotes blue direction.

Further, the barrier layer of the electrolytic copper foil of one aspect of the present invention includes a nickel barrier layer, a zinc barrier layer formed on the nickel barrier layer, and a chromium barrier layer formed on the zinc barrier layer, wherein the plating amount of nickel in the nickel barrier layer is 10 ~ 20mg / m is in the range of ^2, zinc coating weight of zinc (Zn) of the barrier layer 340 is in the range of 10 ~ 20mg / m ^{2, the} coating weight of the chromium in the chromium barrier layer is 1 ~ 4mg / m ² Lt; / RTI >

On the other hand, the copper-clad laminate of one aspect of the present invention comprises a raw foil and a copper layer of a nodule formed on the raw foil and having a plurality of nodule particles, wherein nodule particles having a negative correction value An electrolytic copper foil in a range of 70% or more and 100% or less of the number of nodular particles and including a barrier layer made of an inorganic-metal mixture on the copper nodule layer; And a polyimide film formed on the electrolytic copper foil.

In addition, the printed circuit board of one aspect of the present invention includes a raw foil and a copper module layer formed on the raw foil and having a plurality of nodule particles, wherein nodule particles having a negative correction value of the plurality of nodule particles An electrolytic copper foil in a range of 70% or more and 100% or less of the total number of nodule particles and including a barrier layer made of an inorganic-metal mixture on the copper nodule layer; And a copper foil laminate including a polyimide film formed on the electrolytic copper foil.

According to another aspect of the present invention, there is provided an electrolytic copper foil manufacturing method comprising: (A) a stripping step of performing a stripping process to produce a raw strip; (B) Copper is plated on the matte side (M side) of the raw material to form a nodule particle having a negative correction value among the nodule particles of 70% to 100% of the total number of nodule particles A nodule processing step; And (C) a surface treatment step of forming a barrier layer composed of an inorganic-metal mixture on the copper layer.

In addition, in the step (A) of the electrolytic copper foil manufacturing method of one aspect of the present invention, the basic composition of the electrolytic solution used in the stripping apparatus for preparing the raw foil in the stripping step is 50-200 g / l of H ₂ SO ₄ , Cu ^{+ 2} is 30 ~ 150 g / l, Cl - is a two to 200㎎ / l, and the temperature is room temperature to 80 ℃, the current density is 10 ~ 80ASD.

Further, in the electrolytic copper foil manufacturing method of one aspect of the present invention, the electrolytic solution of step (A) comprises copper sulfate as a main component and at least one of gelatin, HEC, SPS and thiourea as additives.

In addition, the electrolytic copper foil manufacturing method of one aspect of the present invention further includes the step of (D) forming another copper layered layer formed of a nodule structure having a plurality of copper nodule particles on the original foil before the step (B) .

In the step (B) of the electrolytic copper foil manufacturing method of one aspect of the present invention, the current density is 10 to 30 ASD, and the step (D) uses the current density of 5 to 20 ASD.

In addition, in the copper alloy layer of the step (B) of the electrolytic copper foil manufacturing method of one aspect of the present invention, nodule particles having a negative correction value of a plurality of nodule particles may be 100% to more than 80% Or less.

In the step (B) of the electrolytic copper foil manufacturing method of one aspect of the present invention, the basic composition of the electrolytic solution of the electrolytic plating bath is 60 to 150 g / l of H ₂ SO ₄ , 10 to 90 g / l of Cu, The electrolytic solution has a temperature of 35 to 55 ° C at room temperature and a current density of 10 to 30 ASD is used. In the step (D), the basic composition of the electrolytic solution of the other electrolytic plating bath is 60 to 150 g / l of H ₂ SO ₄ , Cu is 5 to 20 g / l, the temperature of the electrolytic solution is 25 to 40 ° C at room temperature, and the current density is 5 to 20 ASD.

In the step (B) of the electrolytic copper foil manufacturing method of one aspect of the present invention, the basic composition of the electrolytic solution of the electrolytic plating bath is 90 to 120 g / l of H ₂ SO ₄ , 30 to 55 g / l of Cu, The electrolytic solution has a temperature of 35 to 55 ° C at room temperature and a current density of 10 to 30 ASD is used. In the step (D), the basic composition of the electrolytic solution of the other electrolytic plating bath is 90 to 120 g / l of H ₂ SO ₄ , Cu is 5 to 20 g / l, the temperature of the electrolytic solution is 25 to 40 ° C at room temperature, and the current density is 5 to 20 ASD.

Generally, the defect rate differs depending on the heat resistance of the surface treatment of the copper foil in the product manufacturing process.

The product manufacturing process is a process of impregnating a copper foil and a polyimide substrate, and hot heating rolls of 350 degrees or more are used.

At this time, when the heat treatment of the surface treatment of the copper foil is weak, oxidation of the copper foil occurs.

In such a situation, the peeling strength of the copper foil and the substrate may be lowered in the area where the copper foil is oxidized, and if the chemical resistance of the polyimide and the copper foil interface is weakened when the flexible printed circuit board is formed, delamination of the circuit may occur.

The electrodeposited copper foil according to the present invention has no abnormality in the product even after a time of 50 seconds or more at 288 degrees in surface heat resistance.

In particular, the electrodeposited copper foil according to the present invention exhibits further improved heat resistance when the (a + b) / L by the colorimetric method is 0.45 to 0.5, and the discoloration time reaches 288 ° C for more than 50 seconds to 270 seconds.

Further, according to the present invention, it is easy to derive the uniform plating amount according to the nodule shape.

According to the present invention, the uniform barrier layer plating improves heat resistance and chemical resistance.

Further, according to the present invention, it is also possible to minimize the variation of the barrier plating amount of the product due to the plating uniformity.

1 is a flowchart of an electrolytic copper foil manufacturing method according to a preferred embodiment of the present invention.
Fig. 2 is a configuration diagram of the washer-washing device used in the balding process of Fig.
3 is a configuration diagram of an electrolytic plating apparatus used in the nodule treatment process and the surface treatment process of FIG.
4A is a cross-sectional view of an electrolytic copper foil according to an embodiment of the present invention, FIG. 4B is a plan view of the nodule layer of FIG. 4A, and FIGS. 4C and 4D are cross-sectional views taken along line A-A 'of FIG.
5 is a photographed image of a dipping machine for testing the heat resistance of a copper foil according to the present invention.
6 is a view showing a color difference meter used for detecting a color change for judging the heat resistance of the copper foil of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and specific embodiments will be described in detail below with reference to the accompanying drawings.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The terms first, second, etc. may be used to describe various components, but the components are not limited by the terms, and the terms are used only for the purpose of distinguishing one component from another Is used.

1 is a flowchart of an electrolytic copper foil manufacturing method according to a preferred embodiment of the present invention.

1, a method of manufacturing an electrolytic copper foil according to a preferred embodiment of the present invention includes: a lumbering step (S100) of producing a raw material foil by performing a lump processing; a matte surface (M A surface treatment step (S300) of forming a barrier layer made of an inorganic-metal mixture on the copper nodule structure to enhance physical and chemical properties, a nodule treatment step (S200) of forming a plurality of nodule structures by plating copper on the copper nodule surface, .

In this regard, FIG. 2 shows a schematic configuration of a stripping apparatus for an original foil for manufacturing an electrolytic copper foil according to a preferred embodiment of the present invention.

Referring to FIG. 2, an anti-skimming device according to a preferred embodiment of the present invention includes a container C in which an electrolyte 10 is continuously supplied, a cathode drum 20 rotatably installed in the container C, (30) spaced apart from the drum (20) within the drum (C).

The drum drum 20 rotates in the direction of the arrow and the electric power is supplied to the anode drum 20 and the anode 30 to be supplied to the drum 30 through the electrolyte 10 So that the plating process proceeds.

The main body blank 100 plated on the surface of the drum 20 is taken up by the guide roll 50.

Examples of the electrolytic solution for precipitating the electrolytic copper foil include a copper sulfate plating solution, a copper pyrophosphate plating solution, and a copper slurry plating solution. However, considering the cost, the copper sulfate plating solution is very suitable.

The basic composition of the electrolytic solution 10 is 50-200 g / l of H ₂ SO ₄ , 30-150 g / l of Cu ^{2 +} and 2-200 mg / l of Cl ^- 2. The temperature of the electrolytic solution is from room temperature to 80 ° C, and the current density is suitably from 10 to 80 ASD. It is preferable that TOC (total organic carbon) is 50 ppm or less.

In addition to gelatin, HEC, SPS and thio urea are further added to the electrolytic solution in order to lower the illuminance of the electrolytic copper foil and increase the tensile strength.

The amount of the gelatin to be added is preferably 0.1 to 100 g / l, more preferably 1 to 10 g / l, still more preferably 2 to 5 g / l. When gelatin is added at a concentration of 0.1 g / l or less, a fine initial structure can be obtained, but the electrolytic copper foil of the coarse tissue is obtained by promoting the growth of the electrolytic copper foil. The coarse tissue thus has a high peak height, Can not be obtained. When gelatin is added at 100 g / l or more, coarse growth can be suppressed to obtain a low-brightness copper foil. However, high temperature elongation (HTE) characteristics measured at 180 ° C It has a drawback of remarkably falling down.

The molecular weight of the gelatin is preferably 10,000 or more. If the molecular weight is 10,000 or more, the interaction between gelatin and other additive can be smoothly carried out, thereby making it possible to manufacture a low-light-weight copper foil.

The amount of the HEC added is preferably 0.05 to 50 g / l, more preferably 0.5 to 5 g / l, still more preferably 1 to 3 g / l. HEC has a role to work with SPS and gelatin to produce stable low-light copper foil. When HEC is added below 0.05 g / l, electrolytic copper foil is produced which is not uniform in performance due to alternating action. If added more than 50 g / l, it will cause copper foil to deposit on the electrolytic copper foil, which will cause the copper to remain in the manufacturing process of the printed circuit board.

The amount of SPS to be added is preferably 0.05 to 20 g / l, more preferably 0.1 to 10 g / l, still more preferably 0.5 to 3 g / l. SPS is a material used as a brightener in various plating processes and plays a role of lowering the illuminance of the plating structure through the interaction of HEC and gelatin. When SPS is added below 0.05 g / l, non-uniform electrolytic copper foil with high roughness is produced because of the alternating action ability. Addition of 20 g / l or more is not preferable because it increases the cost without any special role.

The addition amount of the thiourea is preferably 0.01 to 20 g / l, more preferably 0.1 to 5 g / l, still more preferably 0.6 to 1.0 g / l. The thiourea is a material used for improving the mechanical strength of the plating layer by forming a precipitated phase in the plating layer during plating. When the thiourea is added at a concentration of 0.01 g / l or less, it is difficult to produce an electrolytic copper foil which has an effect of reducing the formation of precipitates and improving the mechanical strength. If it is added in an amount of more than 20 g / l, the copper foil easily breaks due to a rapid decrease in the room temperature and high temperature elongation of the copper foil due to the excessive precipitation phase.

The basic composition of the electrolytic solution 10 is 130 g / l of H ₂ SO ₄ , 100 g / l of Cu ^{2 +} , 100 g / l of Cu ^{2 + -} is 20 mg / l. The temperature of the electrolytic solution was 48 ° C at room temperature, and the current density was 42 ASD. In this way, all the conditions were the same in the stamping process, but the process line speed was varied from 10 to 15 mpm. In addition, Comparative Examples 1 to 7 are also included in Table 1.

division

Stamping process fair
Speed

Electrolyte additive Temperature Current density H ₂ SO ₄ Cl Cu SPC HEC gelatin unit g / l g / l mg / l mg / l mg / l mg / l ℃ ASD mpm Example 1 130 20 100 6 2 3.5 48 42 10 Example 2 130 20 100 6 2 3.5 48 42 12 Example 3 130 20 100 6 2 3.5 48 42 12 Example 4 130 20 100 6 2 3.5 48 42 12 Comparative Example 1 130 20 100 6 2 3.5 48 42 11 Comparative Example 2 130 20 100 6 2 3.5 48 42 15 Comparative Example 2 130 20 100 6 2 3.5 48 42 12 Comparative Example 4 130 20 100 6 2 3.5 48 42 12 Comparative Example 5 130 20 100 6 2 3.5 48 42 10 Comparative Example 6 130 20 100 6 2 3.5 48 42 12 Comparative Example 7 130 20 100 6 2 3.5 48 42 15

Next, a nodule treatment process is performed on the raw paper, followed by a surface treatment process. 3 illustrates a first electrolytic plating tank 210 and a second electrolytic plating tank 220 for forming a nodular layer and includes a third electrolytic plating bath 230 to a fifth electrolytic plating bath 230 for forming a barrier layer, And an electrolytic copper foil manufacturing apparatus including a plating bath (250).

The nodule treatment process of the present invention, which is performed by the first electroplating tank 210 and the second electroplating tank 220, forms a nodule on the surface of the raw paper. Formation of a nodular layer on the raw paper is intended to enhance mechanical adhesion with the resin layer in the production of the copper-clad laminate.

Here, the method of forming the nodular layer on the raw paper may include a method of roughening treatment, etching treatment (chemical etching or electrolytic etching), and oxidation treatment (Brown oxide, Black oxide). Among them, it is preferable to use a harmonic treatment which is advantageous for forming a nodular layer.

Specifically, in the nodule treatment process, a raw material is charged into an electrolytic solution containing copper (Cu) in the first electroplating vessel 210, and then plating is performed at a constant current density or higher to generate metal nuclei on the surface of the raw material, And is then capped by using the electrolytic plating tank 220. At this time, the process of growing the metal nuclei is performed at a temperature higher than the temperature at which metal nuclei are generated, and the electrolyte is thicker than the concentration of the electrolytic solution that generates metal nuclei.

In the nodule formation, the basic composition of the electrolytic solution of the first electrolytic plating bath 210 is 60 to 150 g / l of H ₂ SO ₄ and 5 to 20 g / l of Cu ^{2 +} . Preferably, the basic composition of the electrolytic solution is 90 to 120 g / l of H ₂ SO ₄ . The temperature of the electrolytic solution is in the range of room temperature to 25 to 40 ° C, and the current density is preferably in the range of about 5 to 20 ASD.

In the nodule growth, the basic composition of the electrolytic solution of the second electroplating vessel 220 is 60 to 150 g / l of H ₂ SO ₄ and 10 to 90 g / l of Cu ^{2 +} . Preferably, the basic composition of the electrolytic solution is 90 to 120 g / l of H ₂ SO ₄ and 30 to 55 g / l of Cu ^{2 +} . The temperature of the electrolytic solution is 35 to 55 ° C at room temperature, and it is preferable to use a current density of about 10 to 30 ASD for the growth of the nodules.

In this process, a current density of 5 to 20 ASD is used for forming the first copper layer by using the first electroplating vessel 210, and the copper plating layer A current density of 10 to 30 ASD is used. In this case, when the long axis of the nodule particle in the direction parallel to the surface of the raw paper is referred to as transverse (xmax) and the long axis of the nodule particle in the direction perpendicular to the surface of the original is defined as longitudinal (ymax) (the aspect ratio can be referred to as " rectangle ", which is referred to as " correction rectangle "in the specification of the present invention) ymax-xmax) / ymax] of the first copper layer is in the range of 70% to 100% of the total number of nodules in the second copper layer, A nodular layer can be obtained. Preferably, in the second copper layer, a plurality of nodular particles having a negative correction value in a range of from 80% to 100% of the total number of nodule particles.

In this connection, in Table 2, the first to fourth embodiments show that the first copper layer is formed in a state where H ₂ SO ₄ is 150 g / l, Cu is 14 g / l, the temperature is 26 ° and the current density is 20 ASD or less And Comparative Examples 1 to 7 show process conditions for forming a first copper layer under the same conditions with a current density of 21 ASD or more.

In Examples 1 to 4 and Comparative Examples 1 to 7, the process conditions for forming the second copper layer were the same.

division Nodule formation process Primary copper layer Secondary copper layer Electrolyte Temperature
Current density Electrolyte Temperature
Current density
H ₂ SO ₄ Cu Current density H ₂ SO ₄ Cu unit g / l g / l Degree ASD g / l g / l  Degree ASD Example 1 150 14 26 17 90 85 55 16 Example 2 150 14 26 17 90 85 55 16 Example 3 150 14 26 13 90 85 55 16 Example 4 150 14 26 8 90 85 55 16 Comparative Example 1 150 14 26 22 90 85 55 16 Comparative Example 2 150 14 26 23 90 85 55 16 Comparative Example 3 150 14 26 23 90 85 55 16 Comparative Example 4 150 14 26 25 90 85 55 16 Comparative Examples 5 to 7 150 14 26 33 90 85 55 16

Next, the surface treatment process is composed of nickel plating, zinc plating and chromium plating.

To this end, the third electrolytic plating bath 230 contains a plating solution containing a nickel (Ni) alloy component excellent in heat resistance and excellent in acid resistance and corrosion resistance. In the plating solution, nickel (Ni) exists in the ion state, and is deposited on the copper nodule in the form of metal or alloy upon precipitation by electrolysis.

In order to further enhance the physical and chemical characteristics provided by the nickel component, the copper plating apparatus for a printed circuit includes a fourth electrolytic plating bath 240 containing a plating solution containing zinc (Zn) or zinc (Zn) , Chromium (Cr), or chromium (Cr) alloy components is contained in the fifth electrolytic plating bath 250.

The nickel content in the plating solution contained in the third electrolytic plating bath 230 can be designed to be 1 to 20 g / l. Here, the pH of the plating solution is preferably 12, and the temperature is preferably maintained at a room temperature to 80 ° C. It is preferable that the current density is maintained at 0.1 to 10 ASD. It is preferable that potassium pyrophosphate is maintained at 10 to 90 g / l. When nickel plating is performed in this state, since the surface area of the nodule layer is larger and uniform than in the prior art, a larger amount is plated even if the nickel layer has the same height. As a result, heat resistance is improved.

The zinc content in the plating solution contained in the fourth electroplating bath 240 may be designed to be 1 to 20 g / l. Here, the pH of the plating solution is preferably 12, and the temperature is preferably maintained at a room temperature to 80 ° C. The current density is preferably maintained at 0.1 to 10 ASD. It is preferable that potassium pyrophosphate is maintained at 10 to 90 g / l. When zinc plating is performed in this state, since the surface area of the nodule layer is larger and uniform than in the prior art, a larger amount of zinc is plated even though the same height is provided. As a result, heat resistance is improved.

The chromium content in the plating solution contained in the fifth electroplating bath 250 may be designed to be 1 to 20 g / l. Here, the pH of the plating solution is preferably 2 to 20, the temperature is preferably maintained at a room temperature to 80 ° C, and the current density is preferably maintained at 0.1 to 10 ASD. When chromium plating is performed under these conditions, since the surface area of the nodule layer is larger and uniform than in the prior art, a larger amount of the chromium plating is achieved even if the height is the same. As a result, heat resistance is improved.

The main body 100 manufactured by the stamping process is formed with a copper mold layer through the first electroplating tank 210 and the second electroplating tank 220 and the nickel plating tank 230 and the zinc plating tank 240 And the chromium plating bath 250 in this order, thereby forming a barrier layer by electroplating.

Here, the main body blank 100 is guided into the respective plating baths by a plurality of guide rolls 105 and finally wound on the winding rolls 106. The guide roll 105 disposed inside each plating tank is electrically connected to electrodes of a polarity corresponding to the polarity applied to the plating liquid for electroplating.

The surface-treated electrolytic copper foil may further be coated with a silane coupling agent to secure adhesion between the copper foil and the insulating material. The silane coupling agent may be a conventional silane coupling agent, for example, a silane coupling agent in which the functional group is epoxy, mercaptan, vinyl, Can be used alone or in combination. At this time, the silane coupling agent can chemically bond with the insulating material to improve the adhesion between the copper foil and the insulating material.

At this time, as examples of the surface treatment process and the conditions of the silane coupling agent treatment process, in all of Examples 1 to 4 and Comparative Examples 1 to 7, the nickel barrier layer had 3.5 g / l of Ni of the electrolytic solution and 45 g / l of pyrophosphoric acid , The temperature is 30 degrees Celsius, the current density is 1 ASD, the zinc barrier layer has the Zn of 2.4 g / l of the electrolytic solution, 45 g / l of pyrophosphoric acid, the temperature of 30 degrees, the current density of 1 ASD, The electrolyte had a Cr of 2 g / l, a PH of 12.6 g / l, a temperature of 26 °, a current density of 1 ASD, and a silane coupling agent of 1.7 g / l of Zn

4A is a plan view of the electrolytic copper foil fabricated by the electrolytic copper foil plating apparatus according to a preferred embodiment of the present invention, FIG. 4B is a plan view of the nodular layer of FIG. 4A, and FIGS. A-A 'of Fig.

4A, the copper foil for a printed circuit includes a main body 300, a first copper layer 310 formed on the M-plane of the main body 300, and a second copper layer 320 formed of a second copper layer And barrier layers 330 to 350 formed on the nodule layers 310 and 320 and including components such as nickel (Ni), zinc (Zn), and chrome (Cr).

The surface roughness Rz of the main body green 300 is preferably 0.2 탆 to 1 탆, more preferably 0.3 탆 to 0.8 탆 in consideration of the physical properties such as the adhesive strength required for the copper foil for a printed circuit. The thickness of the main body blank 300 is preferably 5 to 105 mu m.

The surface roughness Rz of the first copper layer 310 and the second copper layer 320 is preferably 0.2 to 4 탆. More preferably 0.3 mu m to 3 mu m.

When the current density is 5 to 20 ASD when the copper layer is formed using the first electroplating bath 210, the first copper layer 310 and the second copper layer 320 are formed as shown in FIG. 4B 4D, if the current density is 10 to 30 ASD when the first copper layer is formed and the second copper plating layer is formed using the second electroplating tank 220, (Ymax-xmax) / ymax] of the nodules having a negative value in the range of 70% or more to 100% or less of the total number of nodules in the second copper layer, Can be obtained.

Here, when a direction parallel to the surface of the raw paper of the second copper layer is defined as a width (x), as shown in FIG. 4C, a plurality of widths (x11 to x12, x21 to x24, x31 to x32, x41 to x43). Therefore, for each nodule particle, xmax is selected as the longest axis having the longest length among these multiple widths. For example, in FIG. 4C, the width of the long axis of the first nodule particle is x121, and the length of the long axis of the third nodule particle is x31, and the width of the long axis of the second nodule particle is x23, , And the width of the long axis of the fourth nodule particle is x43, which is expressed as xmax.

Similarly, when the direction perpendicular to the surface of the raw paper of the second copper layer is a length (y), as shown in FIG. 4 (d), a plurality of longitudinal lengths (y11 to y13, y21 to y24, y31 to y32, y41 to y44). Therefore, the length of the long axis having the longest length among the plurality of longitudinal lengths is selected as ymax for each nodule particle, and is used as a reference. For example, in FIG. 4D, the length of the long axis of the first nodule particle is y12, the length of the long axis of the third nodule particle is y32, and the length of the long axis of the second nodule particle is y23, , And the length of the long axis of the fourth nodule particle is y43, which is expressed as ymax.

The barrier layers 330 to 350 may include a nickel barrier layer 330 plated with a nickel component on the first and second copper layered layers 310 and 320 and a zinc barrier layer 340 formed on the nickel barrier layer 330, And a chromium barrier layer 350 formed on the zinc barrier layer.

The nickel barrier layer 330 formed on the first and second copper layer layers 310 and 320 may be formed by a method in which the nickel component is bonded to a resin film such as polyimide (PI), heat resistance, And so on.

In the barrier layers 330 to 350, it is effective for the nickel barrier layer 330 to have a plating amount of nickel (Ni) of 10 to 20 mg / m ² .

The zinc (Zn) and chromium (Cr) components enhance the heat resistance, chemical resistance, oxidation resistance, and the like of the barrier layers 330 to 350.

It is effective that the plating amount of zinc (Zn) in the zinc barrier layer 340 is 10 to 20 mg / m ² and that the chromium (Cr) plating amount of the chromium barrier layer 350 is 1 to 4 mg / m ² to be.

On the barrier layers 330 to 350, a silane coupling agent is additionally coated to improve adhesion to the resin film adhered to the copper foil. Here, as the silane, an epoxy type or an amine type is preferably adopted.

The copper foil for a printed circuit having the above configuration preferably has a tensile strength in the range of 25 kgf / mm ² to 35 kgf / mm ² and an elongation of 2.0% to 3.0%.

If the tensile strength is lower than the above range, there is a high possibility of occurrence of web defects such as tearing in the roll-to-roll process, and in the case of a flexible copper-clad laminate, the peel strength is lowered.

In addition, when the elongation is lower than the recommended conditions, the copper foil becomes less brittle and difficult to handle the web.

The surface roughness Rz of the barrier layers 330 to 350 is preferably 0.2 to 3 占 퐉. When the surface roughness exceeds 3 탆, a portion which is not impregnated when the polyimide is impregnated appears.

5 is a view for explaining a method for measuring heat resistance of an electrolytic copper foil according to an embodiment of the present invention.

As shown in Fig. 5, the electrolytic copper foil is poured on a dipper-type solder bath (model name: Quick Korea 100-15S) with the M side up, and the time when the color of the M side changes to black by oxidation is measured. At this time, available color difference meter is CM-5 of Minolta.

The colorimeter is a measuring device that measures the color difference in terms of a quantity based on a standard color sample and a comparative value with the standard color sample, and is also referred to as a spectroscopic colorimeter.

As shown in FIG. 6, the L * a * b * color indicator is a color space defined by the International Lighting Committee in the yellow-blue, green-red, The color space makes it easy to guess the range and direction of color when coloring, so it is widely used around the world.

The L * represents a brightness as a human's sensation in terms of reflectance and is expressed in units of decimal points in steps of 1 to 100.

And a * is a chromaticity diagram where + a * represents red and -a * represents green.

b * is a chromaticity diagram, where + b * denotes yellow and -b * denotes blue direction.

At this time, as shown in Tables 3 and 4, in Examples 1 to 4, when the time was from 50 seconds to 270 seconds, the Comparative Examples 1 to 7 showed good characteristics when compared with those which were changed within 32 seconds. The heat resistance was improved when (a + b) / L of the chromaticity system was 0.475 to 0.5.

Here, the method for measuring the size of the nodule particles of the second copper layer was performed by taking samples of one sample and the middle position (that is, all three) at intervals of 10 mm from the width of the roll of the copper foil, The size of the sample was 5 x 5 mm.

The method of measuring the size of the nodule particles of the second copper layer was performed by cutting the cross section of the analysis position using a focused ion beam (FIB) at 20,000 times using a scanning electron microscope (SEM) The size of nodule particles was confirmed.

As described above, when the correction length of the nodule particles of the nodule layer is negative as in the present invention, a copper layer of a large surface area is formed so that the subsequent barrier layers 330 to 350 are evenly distributed, It can be seen that more plating amount can be obtained and heat resistance is improved.

division
Nodular layer
(Number of floors) weight
(g / m 2) Original After surface treatment
Electrodeposition amount (mg / m 2)
Light intensity (Rz) Roughness (Ra, minimum value) Light intensity (Rz, average value) Roughness (Rmax, maximum value) Zn Ni Cr Example 1 2 288.3 0.7 0.31 1.8 2.4 12 10 One Example 2 2 291.25 0.7 0.33 1.9 2.4 10 15 3 Example 3 2 290.27 0.7 0.32 2.2 2.6 15 17 2 Example 4 2 289.12 0.7 0.36 2.3 2.8 19 13 3 Comparative Example 1 2 291.23 0.7 0.36 2.3 2.7 13 25 5 Comparative Example 2 2 292.04 0.7 0.33 2.1 2.5 6 14 6 Comparative Example 3 2 291.47 0.7 0.34 2.1 2.6 3 11 10 Comparative Example 4 2 288.87 0.7 0.43 2.3 2.7 15 24 One Comparative Example 5 2 290.91 0.7 0.51 2.9 3.5 9 12 One Comparative Example 6 2 292.2 0.7 0.48 2.7 3.4 22 24 4 Comparative Example 7 2 291.1 0.7 0.45 2.4 2.9 15 29 3

division
M-side discoloration time (288 degrees)
M side L a b (a + b) / L
(Ymax-xmax) / ymax of the second copper layer is negative relative to the total number of nodule particles Example 1 58 61.97 16.15 13.13 0.47 78% Example 2 51 60.03 16.75 13.54 0.50 73% Example 3 110 63.23 15.77 12.99 0.45 87% Example 4 270 64.18 15.72 13.02 0.45 92% Comparative Example 1 22 54.02 18.01 13.7 0.59 42% Comparative Example 2 21 54.86 16.9 13.05 0.55 45% Comparative Example 3 26 57.06 17.21 13.62 0.54 48% Comparative Example 4 16 55.94 17.01 13.08 0.54 32% Comparative Example 5 28 56.12 19.44 14.85 0.61 52% Comparative Example 6 32 56.32 19.44 15.04 0.61 58% Comparative Example 7 19 59.45 17.83 14.13 0.54 37%

According to another aspect of the present invention, there is provided a copper-clad laminate having a structure in which a polyimide resin is adhered to a surface treatment layer of an electrolytic copper foil. The polyimide resin is similar in thermal expansion coefficient to an electrolytic copper foil and has excellent heat resistance for stability such as IC chip bonding.

According to another aspect of the present invention, there is provided a printed circuit board having the copper-clad laminate and a predetermined circuit pattern formed on the copper-clad laminate by an etching process.

The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. In addition, the embodiments disclosed in the present invention are not intended to limit the scope of the present invention but to limit the scope of the technical idea of the present invention. Accordingly, the scope of protection of the present invention should be construed according to the claims, and all technical ideas within the scope of equivalents should be interpreted as being included in the scope of the present invention.

10: electrolyte solution 20: cathode drum
30: anode 50: guide roll
100: raw foil 310 to 350: electroplating bath

Claims (15)

Raw leaves;
A nodule particle formed on the raw paper and having a plurality of nodule particles and having a correction value of negative nodule particle among the plurality of nodule particles is in a range of 70% or more and 100% or less of the total number of nodule particles; And
And a barrier layer made of an inorganic-metal mixture on the copper node layer,
Wherein the correction elongation is calculated as (length-width) / length (length-width) when the long axis of the nodule particle in the direction parallel to the surface of the raw paper is transverse and the long axis of the nodule particle in the direction perpendicular to the surface of the raw- Wherein the electrolytic copper foil is a copper foil. The method according to claim 1,
Further comprising another copper module layer having a plurality of nodule particles between said raw foil and said copper module layer. The method according to claim 1,
The copper node layer
Wherein the nodule particle having a negative correction value of the plurality of nodule particles ranges from 80% to less than 100% of the total number of nodule particles. The method according to claim 1,
(A + b) / L of the surface colorimeter of the electrolytic copper foil is in the range of 0.45 to 0.5, L is the reflectance of the color difference meter, a is the chromaticity diagram, + a * , B is a chromaticity diagram, + b * represents yellow, and -b * represents blue direction. The method according to claim 1,
Wherein the barrier layer comprises a nickel barrier layer, a zinc barrier layer formed on the nickel barrier layer, and a chromium barrier layer formed on the zinc barrier layer,
The plating amount of nickel in the nickel barrier layer is in the range of 10 to 20 mg / m ² , the plating amount of zinc (Zn) in the zinc barrier layer 340 is in the range of 10 to 20 mg / m ² , Electrolytic copper foil having a plating amount ranging from 1 to 4 mg / m ² . Wherein a nodule particle having a negative correction value of a plurality of nodule particles is present in a range of 70% or more and 100% or less of the total number of nodule particles An electrolytic copper foil including a barrier layer made of an inorganic-metal mixture on the copper layer; And
And a polyimide film formed on the electrolytic copper foil,
Wherein the correction elongation is calculated as (length-width) / length (length-width) when the long axis of the nodule particle in the direction parallel to the surface of the raw paper is transverse and the long axis of the nodule particle in the direction perpendicular to the surface of the raw- Wherein the copper foil is laminated on the copper foil. Wherein a nodule particle having a negative correction value of a plurality of nodule particles is present in a range of 70% or more and 100% or less of the total number of nodule particles An electrolytic copper foil including a barrier layer made of an inorganic-metal mixture on the copper layer; And a polyimide film formed on the electrolytic copper foil,
Wherein the correction elongation is calculated as (length-width) / length (length-width) when the long axis of the nodule particle in the direction parallel to the surface of the raw paper is transverse and the long axis of the nodule particle in the direction perpendicular to the surface of the raw- Wherein the printed circuit board is a printed circuit board. (A) a stripping step of performing a stripping process to produce a raw strip;
(B) Copper is plated on the matte side (M side) of the raw material to form a nodule particle having a negative correction value among the nodule particles of 70% to 100% of the total number of nodule particles A nodule processing step; And
(C) a surface treatment step of forming a barrier layer made of an inorganic-metal mixture on the copper layer,
Wherein the correction elongation is calculated as (length-width) / length (length-width) when the long axis of the nodule particle in the direction parallel to the surface of the raw paper is transverse and the long axis of the nodule particle in the direction perpendicular to the surface of the raw- Wherein the electrolytic copper foil is manufactured by a method comprising the steps of: The method of claim 8,
The step (A)
The basic composition of the electrolytic solution used in the jebak apparatus for the production of original foil in the step jebak is the _{H 2 SO 4 50 ~ 200 g} / l, and ^{Cu 2 + 30 ~ 150 g /} l, Cl - 2 ~ 200㎎ / l, the temperature is from room temperature to 80 占 폚, and the current density is from 10 to 80 ASD. The method of claim 9,
Wherein the electrolytic solution of step (A) comprises copper sulfate as a main component and at least one of gelatin, HEC, SPS, and thiourea as an additive. The method of claim 8,
Before the step (B)
(D) forming another copper layer in a nodule structure having a plurality of copper nodule particles on the original foil. 12. The method of claim 11,
Wherein the step (B) uses a current density of 10 to 30 ASD, and the step (D) uses a current density of 5 to 20 ASD. The method of claim 8,
Wherein the copper nodule layer of step (B) has nodule particles having a negative correction value of a plurality of nodule particles ranging from 80% to 100% of the total number of nodule particles. 12. The method of claim 11,
In the step (B), the basic composition of the electrolytic solution of the electrolytic plating bath is 60 to 150 g / l of H ₂ SO ₄ , Is 10 to 90 g / l, the electrolyte temperature is 35 to 55 ° C at room temperature, a current density of 10 to 30 ASD is used,
In the step (D), the basic composition of the electrolytic solution of the other electroplating bath is H ₂ SO ₄ Wherein the electrolyte has a current density of 60 to 150 g / l, a Cu content of 5 to 20 g / l, an electrolyte temperature of 25 to 40 ° C, and a current density of 5 to 20 ASD. . 12. The method of claim 11,
In the step (B), the basic composition of the electrolytic solution of the electrolytic plating bath is 90 to 120 g / l of H ₂ SO ₄ , Is 30 to 55 g / l, the temperature of the electrolytic solution is 35 to 55 ° C at room temperature, the current density of 10 to 30 ASD is used,
In the step (D), the basic composition of the electrolytic solution of the other electroplating bath is H ₂ SO ₄ Wherein the electrolytic solution has a current density of 90 to 120 g / l, a Cu concentration of 5 to 20 g / l, an electrolyte temperature of 25 to 40 ° C, and a current density of 5 to 20 ASD .

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