KR20170029648A - Copper foil for printed wiring board and method for producing same - Google Patents

Abstract

Characterized in that at least one surface of the copper foil has a roughened treatment layer made of needle-shaped fine roughening particles having a diameter of 0.1 to 2.0 탆 and a ratio of length to width of at least 1.5, Wherein at least one surface of the copper foil has a diameter of 0.1 to 2.0 占 퐉 and a ratio of length to width of at least 1.5 Thereby forming a roughened treatment layer composed of needle-like fine roughening particles. The present invention is to develop a copper foil for a semiconductor package substrate that does not deteriorate other characteristics of the copper foil and avoids the circuit erosion phenomenon described above. In particular, it is an object of the present invention to provide a copper foil for a printed wiring board and a method of manufacturing the copper foil, which can improve the coarsened layer of the copper foil and increase the bonding strength between the copper foil and the resin.

Description

TECHNICAL FIELD [0001] The present invention relates to a copper foil for a printed wiring board,

The present invention relates to a copper foil for a printed wiring board excellent in chemical resistance and adhesiveness and a method for producing the copper foil. Particularly, for a package substrate typified by a BT (bismaleimide triazine) resin-impregnated substrate, a strong peeling strength can be obtained for a chemical treatment at the time of forming a fine pattern, and a copper foil and / And a manufacturing method thereof. Also disclosed is a copper foil for a printed wiring board and a method for producing the copper foil which can significantly improve the peel strength in a method of forming a copper pattern by electroless plating after etching the entire surface of the copper foil.

The copper foil for a semiconductor package substrate is also generally called a copper foil for a printed wiring board, and is usually manufactured by the following process. First, a copper foil is laminated and adhered to a base material such as a synthetic resin under high temperature and high pressure. Next, in order to form a desired conductive circuit on the substrate, a circuit equivalent circuit is printed on the copper foil by a material such as an etch-resistant resin.

Then, unnecessary portions of the exposed copper foil are removed by etching. After the etching, the printed portion made of a material such as resin is removed to form a conductive circuit on the substrate. Finally, a predetermined element is soldered to the formed conductive circuit to form various printed circuit boards for an electronic device. Finally, the resist or the build-up resin substrate is bonded. In general, the quality requirement for a copper foil for a printed wiring board is different from that of a bonding surface (so-called roughened surface) to be adhered to a resin substrate and a non-adhesive surface (so-called glossy surface) Do.

(2) good solder wettability; (3) there is no discoloration of oxidation at high temperature; and (4) , (4) good adhesiveness to a resist, and the like.

On the other hand, the roughened surface should be mainly (1) free from oxidative discoloration during storage, (2) peel strength from the substrate is sufficient after high temperature heating, wet processing, soldering, ) Lamination with the base material, and the absence of so-called stacking faults occurring after the etching.

In addition, along with the recent pattern refinement, a low profile of copper foil is required. It has become necessary to increase the peel strength of the copper foil screen.

[0004] In electronic devices such as PCs and mobile communications, the frequency of electric signals has been increasing with the increase in communication speed and capacity, and printed wiring boards and copper foils capable of coping with these demands have been demanded. When the frequency of the electric signal becomes 1 GHz or more, the influence of the skin effect that the current only flows on the surface of the conductor becomes remarkable, and the influence of the change of the current transmission path due to the surface irregularities and the increase of the impedance can not be ignored. Also in this respect, it is desired that the surface roughness of the copper foil is small.

To cope with such a demand, many processing methods have been proposed for a copper foil for a printed wiring board.

Generally, a method for treating a copper foil for a printed wiring board uses a rolled copper foil or an electrolytic copper foil and, in order to increase the adhesive force (peel strength) between the copper foil and the resin, generally, fine particles made of copper and copper oxide are applied Is performed. Next, a heat-resistant treatment layer (barrier layer) such as brass or zinc is formed in order to have characteristics of preventing heat and rust.

In order to prevent surface oxidation or the like during transportation or storage, the product is subjected to immersion or electrolytic chromate treatment or rust prevention treatment such as electrolytic chrome and zinc treatment.

Among these, the roughened treatment layer plays a large role in increasing the adhesive force (peel strength) between the copper foil and the resin. Conventionally, this harmonic treatment has been considered to be a rounded (spherical) projection. This rounded protrusion is achieved by suppressing the development of the dendrite. However, this rounded protrusion was peeled off at the time of etching, and a phenomenon called " drop of powder " occurred. This phenomenon can be taken for granted. This is because the contact area between the spherical protrusion and the copper foil is much smaller than the diameter of the rounded (spherical) protrusion.

In order to avoid this " flaking off " phenomenon, after the above-mentioned coarsening treatment, a thin copper plating layer is formed on the protrusions to prevent peeling of protrusions (see Patent Document 1). This has the effect of preventing " powder falling ", but there is a problem in that the process is increased, and the effect of preventing " powder falling " is different depending on the thin copper plating.

Further, there is known a technique of forming a needle-like nodular coating layer made of an alloy of copper and nickel on a copper foil (Patent Document 2). Since the nodular coating layer has a needle shape, it is considered that the bonding strength with the resin is increased as compared with the rounded (spherical) projections disclosed in Patent Document 1. However, the nodular coating layer has a component As different copper-nickel alloys, they have different etch rates during etching to form a circuit of copper. Therefore, there is a problem that it is not suitable for stable circuit design.

When a copper foil for a printed wiring board is formed, generally a heat-resistant / rust-proof treated layer is formed. A large number of copper foils in which a coating layer such as Zn, Cu-Ni, Cu-Co and Cu-Zn are formed as a metal or alloy forming the heat-resistant layer have been put to practical use (see, for example, Patent Document 3).

Among them, the copper foil having the heat-resistant layer made of Cu-Zn (brass) has no unevenness of the resin layer when laminated on a printed circuit board made of epoxy resin or the like, deterioration of peel strength after heating at high temperature is small And is widely used industrially.

The method of forming the heat-resistant layer made of this brass is described in detail in Patent Documents 4 and 5.

The copper foil having the heat-resistant layer made of such brass is then etched to form a printed circuit. In recent years, a hydrochloric acid etching solution has been widely used for forming a printed circuit.

However, a printed circuit board using a copper foil having a heat-resistant layer made of brass is etched with a hydrochloric acid-based etching solution (for example, CuCl ₂ or FeCl ₃ ) to remove unnecessary portions of the copper foil When a conductive circuit is formed, erosion (circuit erosion) of a circuit end portion (edge portion) occurs on both sides of the circuit pattern, and the peel strength with the resin base material is deteriorated.

This phenomenon of circuit erosion is a phenomenon in which the copper foil of the circuit formed by the above etching process is eroded by the etching liquid from the side of the etching where the adhesion boundary layer between the copper foil and the resin substrate, that is, the heat- Refers to a phenomenon in which the both sides representing yellow (because it is made of brass) are eroded due to lack of water so as to exhibit red color, and the peel strength of the portion is remarkably deteriorated. If this phenomenon occurs on the entire surface of the circuit pattern, the circuit pattern is peeled from the substrate, which is a problem.

In this respect, after the roughening treatment, the rust prevention treatment and the chromate treatment of the zinc or zinc alloy are performed on the surface of the copper foil, the silane coupling agent containing a small amount of chromium ions is adsorbed on the surface after the chromate treatment to improve the hydrochloric acid resistance (See Patent Document 7).

[Prior Art Literature]

(Patent Document 1) JP-A-8-236930

(Patent Document 2) Japanese Patent Publication No. 3459964

(Patent Document 3) Japanese Patent Laid-Open Publication No. 51-35711

(Patent Document 4) Japanese Patent Publication No. 54-6701

(Patent Document 5) Japanese Patent Publication No. 3306404

(Patent Document 6) Japanese Patent Application No. 2002-170827

(Patent Document 7) JP-A-3-122298

A problem to be solved by the present invention is to develop a copper foil for a semiconductor package substrate that avoids the above circuit erosion phenomenon without deteriorating other properties of the copper foil. In particular, it is an object of the present invention to provide a copper foil for a printed wiring board and a method of manufacturing the copper foil, which can improve the coarsened layer of the copper foil and increase the bonding strength between the copper foil and the resin.

Means for Solving the Problem In order to solve the above problems, the present inventors have intensively studied and, as a result, provided the following copper foil for a printed wiring board and a method for producing the same.

1) A copper foil for a printed wiring board, characterized in that at least one surface of the copper foil has a roughened treatment layer made of copper fine copper grains having a diameter of 0.1 to 2.0 탆 and a ratio of length to width of at least 1.5.

2) A copper foil for printed wiring boards, characterized in that at least one surface of the copper foil has a roughened treatment layer made of fine copper grains having a diameter of 0.1 to 2.0 탆 and a length to width ratio of 3.0 or more.

3) The copper foil for a printed wiring board according to 1) or 2) above, wherein the number of needle-like roughening particles is 5 or more in a circuit width of 10 탆.

4) The copper foil for a printed wiring board according to 1) or 2) above, wherein the number of needle-shaped roughening particles is 10 or more in a circuit width of 10 탆.

5) A heat-resistant and rust-preventive layer containing at least one kind of element selected from zinc, nickel, copper and phosphorus on the roughening treatment layer, a chromate coat layer and a silicate couple The copper foil for a printed wiring board according to any one of 1) to 4), further comprising a ring layer.

6) An electrolytic bath consisting of sulfuric acid / copper sulfate containing at least one of substances selected from an alkyl sulfate salt, tungsten ion and arsenic ion is used, and at least one surface of the copper foil has a diameter of 0.1 to 2.0 탆, Wherein the roughening treatment layer is formed of fine copper grains of acicular shape having a ratio of length to width of not less than 1.5.

7) A heat-resistant and rust-preventive layer containing at least one kind of element selected from zinc, nickel, copper, and phosphorus is formed on the roughening treatment layer, a chromate coat layer is formed on the heat- And a silane coupling agent layer is formed on the chromate coat layer. [5] The method for producing a copper foil for a printed wiring board according to [

INDUSTRIAL APPLICABILITY As described above, the copper foil for a printed wiring board of the present invention is not a rounded (spherical) protrusion of a coarsening process which has been considered to be a good convention, but fine acicular particles in the shape of needles are formed on at least one surface of the copper foil. As a result, it is possible to increase the bonding strength between the copper foil itself and the resin, thereby making it possible to increase the peel strength with respect to the chemical treatment at the time of forming the fine pattern on the package substrate, and to provide a copper foil capable of fine etching and a manufacturing method thereof Can have a great effect.

Recently, it is very effective as a substrate for a semiconductor package produced by adhering a copper foil for a printed circuit (a copper foil for a semiconductor package) and a resin for a semiconductor package to a copper foil for a semiconductor package substrate while the fine patterning and high frequency of the printed circuit are progressing.

1 is an SEM photograph of the coarsened layer of Example 1. Fig.
2 is an SEM photograph of the coarsened layer of Example 2. Fig.
3 is an SEM photograph of the coarsened layer of Example 3. Fig.
4 is a SEM photograph of Example 4. Fig.
5 is an SEM photograph of the coarsened layer of Example 5. Fig.
6 is a SEM photograph of Example 6. Fig.
7 is an SEM photograph of the coarsened layer of Example 7. Fig.
8 is an SEM photograph of the coarsened layer of Comparative Example 1. Fig.
9 is an SEM photograph of the coarsened layer of Comparative Example 2. Fig.

Next, in order to facilitate understanding of the present invention, the present invention will be described in detail. The copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil.

As described above, the copper foil for a printed wiring board of the present invention is not a rounded (spherical) protrusion of a coarsening process which has been considered to be a good convention, but a copper foil having fine copper particles of acicular shape formed on at least one surface of a copper foil will be. The shape is a roughened treatment layer having a diameter of 0.1 to 2.0 탆 and a ratio of length (length) to width (diameter) of 1.5 or more.

In addition, it is preferable that the fine particles are needle-shaped fine copper grains having a diameter of 0.1 to 2.0 탆 and a ratio of length to width of at least 3.0, that is, long.

The shape of the coarsely grained copper has a shape of approximately touchet (bamboo rice), and as shown in a photograph of a microscope to be described later, has a convex portion upward at most. The ratio of the minimum diameter to the maximum diameter is about 1: 1 to 1: 1.2. This ratio is a factor that further improves the adhesive force. However, the object of the present invention can be sufficiently achieved as long as it is a needle-shaped body having the above numerical value.

It is also preferable that the diameter of the fine copper grains of 0.1 to 2.0 mu m in diameter and the ratio of the length (length) to the width (diameter) are out of the range of 1.5 or more, for example, However, if the amount is within 5% of the total amount, the adhesive strength of the copper foil itself to the resin is not affected.

When a copper foil for a printed wiring board is etched to form a circuit, it is preferable that the number of the acicular coarse grains of the copper is 5 or more in a circuit width of 10 mu m. Thus, the bonding strength between the copper foil and the resin can be greatly improved. In particular, it is preferable that the number of needle-like roughening particles of copper is 10 or more in a circuit width of 10 mu m.

The roughened layer made of acicular fine copper roughening particles can be produced by using an electrolytic bath composed of a sulfuric acid-copper sulfate containing at least one kind of substance selected from alkyl sulfate salts, tungsten ions, and arsenic ions .

It is preferable that the roughened treatment layer composed of acicular fine copper roughened particles is covered with an electrolytic bath composed of sulfuric acid and copper sulfate to prevent falling off of the powder and to improve the strength of the fill.

Specific treatment conditions are as follows.

(Liquid composition 1)

CuSO ₄揃 5H ₂ O: 39.3 to 118 g / ℓ

Cu: 10 to 30 g / l

H ₂ SO ₄ : 10 to 150 g / ℓ

Na ₂ WO ₄ .2H ₂ O: 0 to 90 mg / l

W: 0 to 50 mg / l

Sodium dodecylsulfate: 0 to 50 mg

H ₃ AsO ₃ (60% aqueous solution): 0 to 6315 mg / l

As: 0 to 2000 mg / l

(Electroplating condition 1)

Temperature: 30 ~ 70 ℃

(Current condition 1)

Current density: 25 to 110 A / dm 2

Blend Coulomb amount: 50 ~ 500 As / d㎡

Plating time: 0.5 ~ 20 seconds

(Liquid composition 2)

CuSO ₄揃 5H ₂ O: 78 to 314 g / ℓ

Cu: 20 to 80 g / l

H ₂ SO ₄ : 50-200 g / l

(Electroplating condition 2)

Temperature: 30 ~ 70 ℃

(Current condition 2)

Current density: 5 to 50 A / dm 2

Blend Coulomb amount: 50 ~ 300 As / d㎡

Plating time: 1 ~ 60 seconds

Further, a heat-resistant and rust-preventive layer containing at least one kind of element selected from zinc, nickel, copper and phosphorus on the roughening treatment layer, a heat-resistant and rust-preventive layer on the heat- A silane coupling agent layer may be formed to provide a copper foil for a printed wiring board.

The heat-resistant / rust-preventive layer is not particularly limited, and a conventional heat-resistant / rust-preventive layer can be used. For example, conventionally used brass cladding layers can be used for copper foils for semiconductor package substrates.

Further, a chromate film layer and a silane coupling agent layer are formed on the heat-resistant / rust-preventive layer to form a bonding surface of the copper foil with at least the resin. A copper foil having a coating layer composed of these chromate coat layers and a silane coupling agent layer is laminated and adhered to a resin and an etch-resistant printed circuit is formed on the copper foil. Then, unnecessary portions of the copper foil excluding the printed circuit portion are etched Thereby forming a conductive circuit.

As the heat-resistant / rust-preventive layer, conventional treatments can be used. Specifically, for example, the following can be used.

(Liquid composition)

NaOH: 40 to 200 g / l

NaCN: 70 to 250 g / l

CuCN: 50 to 200 g / l

Zn (CN) ₂ : 2 to 100 g / l

As ₂ O ₃ : 0.01 to 1 g / l

(Liquid temperature)

40 to 90 ° C

(Current condition)

Current density: 1 to 50 A / dm 2

Plating time: 1 ~ 20 seconds

The chromate film layer may be an electrolytic chromate film layer or an immersion chromate film layer. The chromate film layer preferably has a Cr content of 25-150 占 퐂 / dm2.

When the amount of Cr is less than 25 占 퐂 / dm2, there is no effect of the antirust layer. In addition, when the Cr amount exceeds 150 占 퐂 / dm2, the effect becomes saturated and becomes unnecessary. Therefore, the amount of Cr is preferably 25-150 占 퐂 / dm2.

Examples of the conditions for forming the chromate film layer are described below. However, as described above, it is not necessary to be limited to this condition, and all the known chromate treatments can be used. This rust prevention treatment is one of the factors affecting the acid resistance, and the acid resistance is further improved by the chromate treatment.

(a) Immersion chromate treatment

K ₂ Cr ₂ O ₇ : 1 to 5 g / l, pH: 2.5 to 4.5, temperature: 40 to 60 ° C, time: 0.5 to 8 seconds

(b) Electrolytic chromate treatment (chrome-zinc treatment (alkaline bath))

_{K 2 Cr 2 O 7: 0.2} ~ 20 g / ℓ, acid: phosphoric acid, sulfuric acid, organic acids, pH: 1.0 ~ 3.5, temperature: 20 ~ 40 ℃, current density: 0.1 - 5 A / d㎡, time: 0.5 - 8 seconds

(c) Electrolytic chromium and zinc treatment (alkaline bath)

NaOH or KOH: 10 to 50 g / l, ZnOH or ZnSO ₄ .7H ₂ O: 0.05 to 10 g / l, K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ) , pH: 7 to 13, bath temperature: 20 to 80 캜, current density: 0.05 to 5 A / dm 2, time: 5 to 30 seconds

(d) electrolytic chromate treatment (chrome-zinc treatment (acidic bath))

K ₂ Cr ₂ O ₇ : 2 to 10 g / l, Zn: 0 to 0.5 g / l, Na ₂ SO ₄ : 5 to 20 g / l, pH: 3.5 to 5.0, bath temperature: 20 to 40 ° C, : 0.1 to 3.0 A / dm 2, Time: 1 to 30 seconds

As the silane coupling agent layer used in the copper foil for a semiconductor package substrate of the present invention, a silane coupling agent usually used for a copper foil can be used, and there is no particular limitation. For example, the specific conditions of the silane treatment are as follows.

0.2% epoxy silane / 0.4% TEOS, PH5

Tetraalkoxysilane and at least one alkoxysilane having a functional group having reactivity with a resin may be used. The silane coupling agent layer may be optionally selected, but it is preferable that the silane coupling agent layer is selected in consideration of adhesion with the resin.

Example

Next, examples and comparative examples will be described. It should be noted that the present embodiment shows a preferable example, and the present invention is not limited to these embodiments. Accordingly, all modifications, other embodiments or aspects included in the technical idea of the present invention are included in the present invention.

For comparison with the present invention, a comparative example is also shown.

(Example 1)

Using the electrolytic copper foil having a thickness of 12 占 퐉, the roughening plating shown below was performed on the roughened surface (matte side: M side) of the copper foil. The treatment conditions are shown below.

(Liquid composition 1)

_{CuSO 4 · 5H 2 O: 58.9} g / ℓ

Cu: 15 g / l

H ₂ SO ₄ : 100 g / l

Amount of As: 1000 ppm: H ₃ AsO ₃ (60% aqueous solution) is used

(Electroplating temperature 1) 50 캜

(Current condition 1)

Current density: 90 A / dm 2

Harmonious Coulomb Amount: 200 As / d㎡

After the present roughening treatment, the following normal plating was carried out. The treatment conditions are shown below.

(Liquid composition 2)

CuSO ₄揃 5H ₂ O: 156 g / ℓ

Cu: 40 g / l

H ₂ SO ₄ : 100 g / l

(Electroplating temperature 1) 40 DEG C

(Current condition 1)

Current density: 30 A / dm 2

Amount of Coulombs: 150 As / d㎡

An SEM photograph of the coarsened layer of Example 1 is shown in Fig. The magnification of the left SEM photograph shown in Fig. 1 is (x3000), and the magnification of the right SEM photograph is (x30000). As shown in Fig. 1, it can be seen that it is formed into a needle-like particle shape. The average particle diameter was 0.57 mu m, the particle length was 1.56 mu m, and the aspect ratio was 2.7, which satisfied the conditions of the present invention.

Next, a heat-resistant / rust-preventive layer was formed on the roughened surface of the copper. The heat-resistant / rust-preventive layer, which has been already known, can be used for this condition.

(Liquid composition)

NaOH: 72 g / l

NaCN: 112 g / l

CuCN: 91.6 g / l (Cu: 65 g / l)

Zn (CN) ₂ : 8.1 g / l (Zn: 4.5 g / l)

As ₂ O ₃ : 0.125 g / l (As: 95 ppm)

(Liquid temperature) 76.5 DEG C

(Current condition)

Current density: 6.7 A / dm < 2 >

Current: 4.0 A

Plating time: 5 seconds

Next, electrolytic chromate treatment was performed on the heat-resistant / rust-preventive layer.

Electrolytic chromate treatment (chrome-zinc treatment (acidic bath))

Cr ₂ O ₃ : 0.73 g / l

ZnSO ₄揃 7H ₂ O: 2.46 g / ℓ

Na ₂ SO ₄ : 18 g / l

H ₃ PO ₃ : 0.53 g / l

pH: 4.6, bath temperature: 37 DEG C

Current density: 2.06 A / dm < 2 >

Time: 1 to 30 seconds

(PH adjustment is carried out with sulfuric acid or potassium hydroxide)

Next, on this chromate film layer, a silane treatment (by coating) was carried out.

The conditions of the silane treatment are as follows.

0.2% epoxy silane / 0.4% TEOS, PH5

The copper foil thus produced was laminated and adhered to a glass cloth substrate BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of powder dropping

No flaking was observed. The results are shown in Table 1.

(2) Condition (normal condition) Peel strength

The state peel strength was 0.79 kg / cm and had a good peel strength. The results are shown in Table 1.

(3) Salt resistance test

With respect to hydrochloric acid resistance, the amount of loss after immersing in 12 wt% hydrochloric acid at 60 캜 for 90 minutes in a 0.4 mm circuit is shown in%. Hereinafter, the same applies. The amount of loss was 5%, and the amount of loss was smaller than that of the comparative example described later, showing good properties. The results are shown in Table 1.

(4) Test results of sulfuric acid hydrolysis (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ° C)

0.4 ㎜ circuit. In this case, the case of 2 占 퐉 etching was examined. The amount of loss is expressed in%. Hereinafter, the same applies. The results are shown in Table 1.

As can be seen from Table 1, the loss amount was as low as 6.6% and the sulfuric acid hydrolysis was good.

(Example 2)

Using the electrolytic copper foil having a thickness of 12 占 퐉, the rough surface plating (matte side: M side) of the copper foil was subjected to the following coarse plating and the same normal plating as in Example 1. Hereinafter, the conditions of the harmonious plating treatment are shown.

(Liquid composition 1)

_{CuSO 4 · 5H 2 O: 58.9} g / ℓ

Cu: 15 g / l

H ₂ SO ₄ : 100 g / l

Na ₂ WO ₄ .2H ₂ O: 5.4 mg / l

W Content: 3 ppm

(Electroplating temperature 1) 50 캜

(Current condition 1)

Current density: 40 A / dm 2

Harmonious Coulomb Amount: 300 As / d㎡

An SEM photograph of the coarsened layer of Example 2 is shown in Fig. The magnification of the left SEM photograph shown in Fig. 2 is (x3000) and the magnification of the right SEM photograph is (x30000). As shown in Fig. 2, it can be seen that it is formed into a needle-shaped particle shape. The average particle diameter was 0.67 mu m, the particle length was 1.78 mu m, and the aspect ratio was 2.7, which satisfied the condition of the present invention.

Next, the same heat-resistant / rust-preventive layer as in Example 1 was formed on the roughened surface of copper, electrolytic chromate treatment was performed on the heat-resistant / rust-preventive layer, and further, on this chromate film layer, ).

The copper foil thus produced was laminated and adhered to a glass cloth substrate BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of powder dropping

No flaking was observed. The results are shown in Table 1.

(2) State peel strength

The state fill strength was 0.83 kg / cm, and had a good fill strength. The results are shown in Table 1.

(3) Salt resistance test

The hydrochloric acid resistance is represented by the amount of loss in% after immersion for 90 minutes at 60 ° C using 12 wt% hydrochloric acid in a 0.4 mm circuit. Hereinafter, the same applies. The amount of loss was 2.3%, and the amount of loss was smaller than that of the comparative example described later, indicating good properties. The results are shown in Table 1.

(4) Test results of sulfuric acid hydrolysis (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ° C)

0.4 ㎜ circuit. In this case, the case of 2 占 퐉 etching was examined. The amount of loss is expressed in%. Hereinafter, the same applies. The results are shown in Table 1.

As apparent from Table 1, the amount of loss was as low as 4.4%, and the sulfuric acid hydrolysis was good.

(Example 3)

Using the electrolytic copper foil having a thickness of 12 占 퐉, the rough surface plating (matte side: M side) of the copper foil was subjected to the following coarse plating and the same normal plating as in Example 1. Hereinafter, the conditions of the harmonious plating treatment are shown.

(Liquid composition 1)

_{CuSO 4 · 5H 2 O: 58.9} g / ℓ

Cu: 15 g / l

H ₂ SO ₄ : 100 g / l

Sodium dodecyl sulfate added: 10 ppm

(Electroplating temperature 1) 50 캜

(Current condition 1)

Current density: 100 A / dm 2

Harmonious Coulomb Amount: 200 As / d㎡

An SEM photograph of the coarsened layer of Example 3 is shown in Fig. The magnification of the left SEM photograph shown in Fig. 3 is (x3000) and the magnification of the right SEM photograph is (x30000). As shown in Fig. 3, although it is close to a slightly spherical shape, it can be seen that the shape of the acicular shape is maintained. The average particle diameter was 0.6 mu m, the particle length was 1.5 mu m, and the aspect ratio was 2.5, which satisfied the conditions of the present invention.

Next, the same heat-resistant / rust-preventive layer as in Example 1 was formed on the roughened surface of copper, electrolytic chromate treatment was performed on the heat-resistant / rust-preventive layer, and further, on this chromate film layer, ).

The copper foil thus produced was laminated and adhered to a glass cloth substrate BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of powder dropping

No flaking was observed. The results are shown in Table 1.

(2) State peel strength

The state fill strength was 0.75 kg / cm, and had a good fill strength. The results are shown in Table 1.

(3) Salt resistance test

The hydrochloric acid resistance is represented by the amount of loss in% after immersion for 90 minutes at 60 ° C using 12 wt% hydrochloric acid in a 0.4 mm circuit. Hereinafter, the same applies. The amount of loss was 7.8%, and the amount of loss was smaller than that of the comparative example described later, showing good properties. The results are shown in Table 1.

(4) Test results of sulfuric acid hydrolysis (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ° C)

0.4 ㎜ circuit. In this case, the case of 2 占 퐉 etching was examined. The amount of loss is expressed in%. Hereinafter, the same applies. The results are shown in Table 1.

As apparent from Table 1, the amount of loss was as low as 8.7%, and the sulfuric acid hydrolysis was good.

(Example 4)

Using the electrolytic copper foil having a thickness of 12 占 퐉, the rough surface plating (matte side: M side) of the copper foil was subjected to the following coarse plating and the same normal plating as in Example 1. Hereinafter, the conditions of the harmonious plating treatment are shown.

(Liquid composition 1)

_{CuSO 4 · 5H 2 O: 58.9} g / ℓ

Cu: 15 g / l

H ₂ SO ₄ : 100 g / l

Na ₂ WO ₄ .2H ₂ O: 5.4 mg / l

W: 3 ppm

As: 150 ppm (using H ₃ AsO ₃ (60% aqueous solution))

(Electroplating temperature 1) 50 캜

(Current condition 1)

Current density: 90 A / dm 2

Harmonious Coulomb Amount: 200 As / d㎡

An SEM photograph of the coarsened layer of Example 4 is shown in Fig. The magnification of the left SEM photograph shown in Fig. 4 is (x3000), and the magnification of the right SEM photograph is (x30000). As shown in Fig. 4, it can be seen that it is formed into a needle-shaped particle shape. The average particle diameter was 0.59 mu m, the particle length was 1.9 mu m, and the aspect ratio was 3.2, which satisfied the condition of the present invention.

Next, the same heat-resistant / rust-preventive layer as in Example 1 was formed on the roughened surface of copper, electrolytic chromate treatment was performed on the heat-resistant / rust-preventive layer, and further, on this chromate film layer, ).

The copper foil thus produced was laminated and adhered to a glass cloth substrate BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of powder dropping

No flaking was observed. The results are shown in Table 1.

(2) State peel strength

The state fill strength was 0.82 kg / cm, and had a good fill strength. The results are shown in Table 1.

(3) Salt resistance test

The hydrochloric acid resistance is represented by the amount of loss in% after immersion for 90 minutes at 60 ° C using 12 wt% hydrochloric acid in a 0.4 mm circuit. Hereinafter, the same applies. The amount of loss was 4.3%, and the amount of loss was smaller than that of the comparative example described later, showing good properties. The results are shown in Table 1.

(4) Test results of sulfuric acid hydrolysis (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ° C)

0.4 ㎜ circuit. In this case, the case of 2 占 퐉 etching was examined. The amount of loss is expressed in%. Hereinafter, the same applies. The results are shown in Table 1.

As is apparent from Table 1, the amount of loss was as small as 6.8%, and the sulfuric acid hydrolysis was good.

(Example 5)

Using the electrolytic copper foil having a thickness of 12 占 퐉, the rough surface plating (matte side: M side) of the copper foil was subjected to the following coarse plating and the same normal plating as in Example 1. Hereinafter, the conditions of the harmonious plating treatment are shown.

(Liquid composition)

_{CuSO 4 · 5H 2 O: 58.9} g / ℓ

Cu: 15 g / l

H ₂ SO ₄ : 100 g / l

Sodium dodecyl sulfate added: 10 ppm

Amount of As: 1000 ppm: H ₃ AsO ₃ (60% aqueous solution) is used

(Electroplating temperature) 50 DEG C

(Current condition)

Current density: 40 A / dm 2

Amount of Coulombs: 240 As / d㎡

An SEM photograph of the coarsened layer of Example 5 is shown in Fig. The magnification of the left SEM photograph shown in Fig. 5 is (x3000), and the magnification of the right SEM photograph is (x30000). As shown in Fig. 5, it can be seen that it is formed in the shape of an acicular particle. The average particle diameter was 0.72 mu m, the particle length was 1.93 mu m, and the aspect ratio was 2.7, which satisfied the condition of the present invention.

Next, the same heat-resistant / rust-preventive layer as in Example 1 was formed on the roughened surface of copper, electrolytic chromate treatment was performed on the heat-resistant / rust-preventive layer, and further, on this chromate film layer, ).

The copper foil thus produced was laminated and adhered to a glass cloth substrate BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of powder dropping

No flaking was observed. The results are shown in Table 1.

(2) State peel strength

The state fill strength was 0.83 kg / cm, and had a good fill strength. The results are shown in Table 1.

(3) Salt resistance test

The hydrochloric acid resistance is represented by the amount of loss in% after immersion for 90 minutes at 60 ° C using 12 wt% hydrochloric acid in a 0.4 mm circuit. Hereinafter, the same applies. The amount of loss was 4.6%, and the amount of loss was smaller than that of the comparative example described later, showing good properties. The results are shown in Table 1.

(4) Test results of sulfuric acid hydrolysis (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ° C)

0.4 ㎜ circuit. In this case, the case of 2 占 퐉 etching was examined. The amount of loss is expressed in%. Hereinafter, the same applies. The results are shown in Table 1.

As apparent from Table 1, the amount of loss was as low as 7.5%, and the sulfuric acid hydrolysis was good.

(Example 6)

Using the electrolytic copper foil having a thickness of 12 占 퐉, the rough surface plating (matte side: M side) of the copper foil was subjected to the following coarse plating and the same normal plating as in Example 1. Hereinafter, the conditions of the harmonious plating treatment are shown.

(Liquid composition 1)

_{CuSO 4 · 5H 2 O: 58.9} g / ℓ

Cu: 15 g / l

H ₂ SO ₄ : 100 g / l

Na ₂ WO ₄ .2H ₂ O: 5.4 mg / l

W: 3 ppm

Sodium dodecyl sulfate added: 10 ppm

(Electroplating temperature 1) 50 캜

(Current condition 1)

Current density: 100 A / dm 2

Harmonious Coulomb Amount: 200 As / d㎡

An SEM photograph of the coarsened layer of Example 6 is shown in Fig. The magnification of the left SEM photograph shown in Fig. 6 is (x3000), and the magnification of the right SEM photograph is (x30000). As shown in Fig. 6, it can be seen that it is formed in the shape of an acicular particle. The average particle diameter was 0.48 mu m, the particle length was 1.6 mu m, and the aspect ratio was 3.3, which satisfied the conditions of the present invention.

Next, the same heat-resistant / rust-preventive layer as in Example 1 was formed on the roughened surface of copper, electrolytic chromate treatment was performed on the heat-resistant / rust-preventive layer, and further, on this chromate film layer, ).

The copper foil thus produced was laminated and adhered to a glass cloth substrate BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of powder dropping

No flaking was observed. The results are shown in Table 1.

(2) State peel strength

The state fill strength was 0.83 kg / cm, and had a good fill strength. The results are shown in Table 1.

(3) Salt resistance test

The hydrochloric acid resistance is represented by the amount of loss in% after immersion for 90 minutes at 60 ° C using 12 wt% hydrochloric acid in a 0.4 mm circuit. Hereinafter, the same applies. The amount of loss was 3.9%, and the amount of loss was smaller than that of the comparative example described later, showing good properties. The results are shown in Table 1.

(4) Test results of sulfuric acid hydrolysis (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ° C)

0.4 ㎜ circuit. In this case, the case of 2 占 퐉 etching was examined. The amount of loss is expressed in%. Hereinafter, the same applies. The results are shown in Table 1.

As apparent from Table 1, the amount of loss was as low as 5.2%, and the sulfuric acid hydrolysis was good.

(Example 7)

Using the electrolytic copper foil having a thickness of 12 占 퐉, the rough surface plating (matte side: M side) of this copper foil was subjected to the following coarse plating and the same normal plating as in Example 1. Hereinafter, the conditions of the harmonious plating treatment are shown.

(Liquid composition 1)

_{CuSO 4 · 5H 2 O: 58.9} g / ℓ

Cu: 15 g / l

H ₂ SO ₄ : 100 g / l

Na ₂ WO ₄ .2H ₂ O: 5.4 mg / l

W: 3 ppm

Sodium dodecyl sulfate added: 10 ppm

Amount of As: 150 ppm: H ₃ AsO ₃ (60% aqueous solution)

(Electroplating temperature 1) 50 캜

(Current condition 1)

Current density: 80 A / dm 2

Harmonious Coulomb Amount: 280 As / d㎡

An SEM photograph of the coarsened layer of Example 7 is shown in Fig. The magnification of the left SEM photograph shown in Fig. 7 is (x3000), and the magnification of the right SEM photograph is (x30000). As shown in Fig. 7, it can be seen that it is formed into a needle-shaped particle shape. The average particle diameter was 0.55 mu m, the particle length was 1.7 mu m, and the aspect ratio was 3.1, which satisfied the conditions of the present invention.

Next, the same heat-resistant / rust-preventive layer as in Example 1 was formed on the roughened surface of copper, electrolytic chromate treatment was performed on the heat-resistant / rust-preventive layer, and further, on this chromate film layer, ).

The copper foil thus produced was laminated and adhered to a glass cloth substrate BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of powder dropping

No flaking was observed. The results are shown in Table 1.

(2) State peel strength

The state fill strength was 0.85 kg / cm, and had a good fill strength. The results are shown in Table 1.

(3) Salt resistance test

The hydrochloric acid resistance is represented by the amount of loss in% after immersion for 90 minutes at 60 ° C using 12 wt% hydrochloric acid in a 0.4 mm circuit. Hereinafter, the same applies. The amount of loss was 1.6%, and the amount of loss was smaller than that of the comparative example described later, showing good properties. The results are shown in Table 1.

(4) Test results of sulfuric acid hydrolysis (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ° C)

0.4 ㎜ circuit. In this case, the case of 2 占 퐉 etching was examined. The amount of loss is expressed in%. Hereinafter, the same applies. The results are shown in Table 1.

As apparent from Table 1, the amount of loss was as low as 4.5%, and the sulfuric acid hydrolysis was good.

(Comparative Example 1)

Using the electrolytic copper foil having a thickness of 12 占 퐉, the rough surface plating (matte side: M side) of the copper foil was subjected to the following coarse plating and the same normal plating as in Example 1. Hereinafter, the conditions of the harmonious plating treatment are shown. In this case, the additive of the present invention was not used at all.

(Liquid composition)

_{CuSO 4 · 5H 2 O: 58.9} g / ℓ

Cu: 15 g / l

H ₂ SO ₄ : 100 g / l

(Electroplating temperature) 50 DEG C

(Current condition)

Current density: 90 A / dm 2

Harmonious Coulomb Amount: 200 As / d㎡

An SEM photograph of the coarsened layer of Comparative Example 1 is shown in Fig. The magnification of the left SEM photograph shown in Fig. 8 is (x3000), and the magnification of the right SEM photograph is (x30000). As shown in Fig. 8, it can be seen that it is formed into a dendrite-shaped particle shape. The average particle diameter was 5 mu m, the particle length was 25 mu m, and the aspect ratio was 5.0, which satisfied the conditions of the present invention.

Next, the same heat-resistant / rust-preventive layer as in Example 1 was formed on the roughened surface of copper, electrolytic chromate treatment was performed on the heat-resistant / rust-preventive layer, and further, on this chromate film layer, ).

The copper foil thus produced was laminated and adhered to a glass cloth substrate BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of powder dropping

In Comparative Example 1, dust was observed to be dropped. The results are shown in Table 1.

(2) State peel strength

The state peel strength was 0.58 kg / cm, and the peel strength was low. The results are shown in Table 1.

(3) Salt resistance test

The hydrochloric acid resistance is represented by the amount of loss in% after immersion for 90 minutes at 60 ° C using 12 wt% hydrochloric acid in a 0.4 mm circuit. Hereinafter, the same applies. The amount of loss was 32.4%, and the amount of loss was smaller than that of the comparative example described later, showing good properties. The results are shown in Table 1.

(4) Test results of sulfuric acid hydrolysis (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ° C)

0.4 ㎜ circuit. In this case, the case of 2 占 퐉 etching was examined. The amount of loss is expressed in%. The results are shown in Table 1.

As can be seen from Table 1, the amount of loss was as high as 31%, and the sulfuric acid hydrolysis was poor.

(Comparative Example 2)

Using the electrolytic copper foil having a thickness of 12 占 퐉, the rough surface plating (matte side: M side) of the copper foil was subjected to the following coarse plating and the same normal plating as in Example 1. Hereinafter, the conditions of the harmonious plating treatment are shown.

(Liquid composition)

_{CuSO 4 · 5H 2 O: 58.9} g / ℓ

Cu: 15 g / l

H ₂ SO ₄ : 100 g / l

Amount of As: 150 ppm: H ₃ AsO ₃ (60% aqueous solution)

(Electroplating temperature) 50 DEG C

(Current condition)

Current density: 40 A / dm 2

Amount of Coulombs: 240 As / d㎡

An SEM photograph of the roughened treatment layer of Comparative Example 2 is shown in Fig. The magnification of the left SEM photograph shown in Fig. 8 is (x3000), and the magnification of the right SEM photograph is (x30000). As shown in Fig. 8, it can be seen that it is formed into a spherical particle shape. The average particle diameter was 1.3 mu m, the particle length was 1.8 mu m, and the aspect ratio was 1.4, which did not satisfy the conditions of the present invention.

Next, the same heat-resistant / rust-preventive layer as in Example 1 was formed on the roughened surface of copper, electrolytic chromate treatment was performed on the heat-resistant / rust-preventive layer, and further, on this chromate film layer, ).

The copper foil thus produced was laminated and adhered to a glass cloth substrate BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of powder dropping

No flaking was observed. The results are shown in Table 1.

(2) State peel strength

The state fill strength was 0.82 kg / cm, and had a good fill strength. The results are shown in Table 1.

(3) Salt resistance test

The hydrochloric acid resistance is represented by the amount of loss in% after immersing in 12 wt% hydrochloric acid at 60 DEG C for 90 minutes. Hereinafter, the same applies. The amount of loss was 20%, and the amount of loss was smaller than that of the comparative example described later, showing good properties. The results are shown in Table 1.

(4) Test results of sulfuric acid hydrolysis (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ° C)

0.4 ㎜ circuit. In this case, the case of 2 占 퐉 etching was examined. The amount of loss is expressed in%. Hereinafter, the same applies. The results are shown in Table 1.

As apparent from Table 1, the amount of loss was as high as 15%, and the sulfuric acid hydrolysis was poor.

From the above, it can be seen that the copper foil for a printed wiring board of the present invention is not a rounded (spherical) projection or a dendritic crystal grain size of the harmony treatment which has been conventionally considered to be satisfactory, By forming the particles, it is possible to increase the bonding strength between the copper foil itself and the resin, thereby making it possible to increase the peel strength of the package substrate against the chemical treatment at the time of forming the fine pattern, It can be seen that it has a great effect that it can provide a method.

Industrial availability

INDUSTRIAL APPLICABILITY As described above, according to the present invention, by forming acicular fine roughening particles on at least one surface of a copper foil, the adhesion strength of the copper foil itself to the resin is increased, It is possible to provide a copper foil capable of increasing the peel strength and enabling fine etching, and a manufacturing method thereof.

Recently, it is very effective as a substrate for a semiconductor package produced by adhering a copper foil for a printed circuit (a copper foil for a semiconductor package) and a resin for a semiconductor package to a copper foil for a semiconductor package substrate while the fine patterning and high frequency of the printed circuit are progressing.

Claims (1)

A copper foil characterized by that described in the detailed description of the invention.

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