KR20130054447A - Copper foil for printed wiring board and method for producing same - Google Patents

Abstract

On at least one surface of copper foil, it has a roughening process layer which consists of needle-shaped fine roughening particle | grains of 0.1-2.0 micrometers in diameter, and the ratio of a vertical and a horizontal is 1.5 or more, The copper foil for printed wiring boards, and alkyl sulfate sulfate, Using an electrolytic bath composed of sulfuric acid and copper sulfate containing at least one or more of tungsten ions and arsenic ions, at least one surface of the copper foil has a diameter of 0.1 to 2.0 µm and a length-to-width ratio of 1.5 or more. The manufacturing method of the copper foil for printed wiring boards which forms the roughening process layer which consists of needle-shaped fine roughening particle | grains. It is to develop the copper foil for semiconductor package board | substrates which avoids the said circuit erosion phenomenon, without degrading other characteristics of copper foil. It is a subject to provide the copper foil for printed wiring boards which can improve the roughening process layer of copper foil especially, and to raise the adhesive strength of copper foil and resin, and its manufacturing method.

Description

Copper foil for printed wiring boards and its manufacturing method {COPPER FOIL FOR PRINTED WIRING BOARD AND METHOD FOR PRODUCING SAME}

This invention relates to the copper foil for printed wiring boards excellent in chemical-resistance and adhesiveness, and its manufacturing method. In particular, for a substrate for a package represented by a BT (bismaleimide triazine) resin-impregnated base material, a strong peeling strength can be obtained with respect to a chemical treatment during the formation of a fine pattern, and the copper foil which enables fine etching and The manufacturing method is provided. Moreover, in the method of forming a copper pattern by electroless plating after a whole surface etching of copper foil, the copper foil for printed wiring boards which can greatly improve peeling strength, and its manufacturing method are provided.

Although copper foil for semiconductor package substrates is generally called copper foil for printed wiring boards, Usually, it manufactures by the following processes. First, copper foil is laminated | stacked and bonded to base materials, such as synthetic resin, under high temperature and high pressure. Next, in order to form the target electroconductive circuit on a board | substrate, the circuit equivalent to a circuit is printed by materials, such as an etching resistant resin, on copper foil.

And the unnecessary part of the exposed copper foil is removed by an etching process. After etching, the printed portion made of a material such as resin is removed to form a conductive circuit on the substrate. Finally, predetermined elements are soldered to the formed conductive circuits to form various printed circuit boards for electronic devices. Finally, the resist or the build-up resin substrate is bonded. In general, the quality requirements for copper foil for printed wiring boards are different from the adhesive surface (so-called roughened surface) and the non-bonded surface (so-called glossy surface) to be bonded to the resin substrate, and it is necessary to satisfy both at the same time. Do.

For the gloss surface, (1) Good appearance and no oxidation discoloration during storage, (2) Solder wettability should be good, and (3) No oxidation discoloration at high temperature heating. And (4) good adhesion to the resist is required.

On the other hand, about the roughened surface, mainly (1) there should be no oxidative discoloration at the time of storage, (2) peeling strength with a base material should be enough even after high temperature heating, a wet process, soldering, chemical treatment, etc. (3 ) There is no so-called lamination blemish that occurs after lamination with the substrate and etching.

Moreover, with the refinement of the pattern in recent years, the low profile of copper foil is calculated | required. Increasingly, the peeling strength of the copper foil roughening surface was needed.

In addition, in electronic devices such as personal computers and mobile communication, high frequency of electric signals is progressing along with high speed and large capacity of communication, and a printed wiring board and a copper foil that can cope with this are demanded. When the frequency of the electric signal is 1 kHz or more, the effect of the skin effect that the current flows only on the surface of the conductor becomes remarkable, and the effect of changing the current transmission path due to unevenness of the surface and increasing the impedance cannot be ignored. Also from this point, it is desired that the surface roughness of the copper foil is small.

In order to answer these demands, many processing methods have been proposed for the copper foil for printed wiring boards.

Generally, the processing method of the copper foil for printed wiring boards uses a rolled copper foil or an electrolytic copper foil, and in order to raise the adhesive force (fill strength) of copper foil and resin first, generally, microparticles which consist of copper and copper oxide are given to the copper foil surface. Harmonizing processing is performed. Next, in order to have the characteristics of heat resistance and rust prevention, a heat resistant treatment layer (barrier layer) such as brass or zinc is formed.

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

Among these, the roughening process layer is playing the big role which raises the adhesive force (fill strength) of copper foil and resin especially. Conventionally, this roughening process has been considered that rounded (spherical) projections are good. This roundish protrusion is achieved by suppressing the development of dendrites. However, this rounded protrusion peeled off at the time of etching, and the phenomenon "falling off powder" generate | occur | produced. This phenomenon can be taken for granted. This is because the contact area between the spherical projections and the copper foil is very small compared with the diameter of the rounded (spherical) projections.

In order to avoid this "falling off" phenomenon, after the said roughening process, forming a thin copper plating layer on the projection and preventing peeling of a projection was performed (refer patent document 1). This has the effect of preventing "falling", but there is a problem that the process is increased and the "falling" prevention effect differs depending on the thin copper plating.

Moreover, the technique of forming the needle-shaped nodular coating layer which consists of an alloy of copper and nickel on copper foil is known (patent document 2). Since this nodular coating layer is needle-shaped, compared with the round (spherical) protrusion disclosed by the said patent document 1, adhesive strength with resin is considered to be increased, but a component is different from the copper foil which becomes a base material. As different copper-nickel alloys, at the time of etching forming a circuit of copper, they have different etching rates. Therefore, there is a problem that it is not suitable for stable circuit design.

When forming the copper foil for printed wiring boards, generally, forming a heat-resistant and antirust process layer is performed. Many copper foils which provided coating layers, such as Zn, Cu-Ni, Cu-Co, and Cu-Zn, as an example of the metal or alloy which form a heat-resistant processing layer are utilized (for example, refer patent document 3).

Among these, the copper foil in which the heat-resistant processing layer which consists of Cu-Zn (brass) was formed does not have the stain of a resin layer when it is laminated | stacked on the printed circuit board which consists of epoxy resins, etc., and there is little deterioration of the peeling strength after high temperature heating, etc. Since it has the outstanding characteristic of, it is used industrially widely.

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 in which the heat resistant layer which consists of such brass was formed is then etched in order to form a printed circuit. In recent years, a lot of hydrochloric acid type etching liquids are used for formation of a printed circuit.

By the way, the printed circuit board with copper foil to form a heat-resistant treatment layer formed of brass, an etchant of hydrochloric acid system to (for example, CuCl _2, FeCl _3, etc.), etching treatment with, and removing the unnecessary portions of copper foil other than the printed circuit section When a conductive circuit was formed, so-called erosion (circuit erosion) of circuit edges (edge portions) occurred on both sides of the circuit pattern, resulting in a problem that the peel strength with the resin substrate deteriorated.

This circuit erosion phenomenon is eroded by the said etching liquid from the etching side by which the adhesive boundary layer of the copper foil of the circuit formed by said etching process and the resin base material, ie, the heat-resistant and rust prevention process layer which consists of brass, was exposed, and Because of the lack of water washing, both sides which are usually yellow (because they are made of brass) are eroded to show red color, and the peel strength of the part is significantly degraded. And when this phenomenon arises in the whole circuit pattern surface, a circuit pattern will peel from a base material and will become a problem.

In this regard, after the roughening treatment, the rust prevention treatment of the zinc or zinc alloy, and the chromate treatment 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 hydrochloric acid resistance. A proposal to make is made (refer patent document 7).

[Prior Art Literature]

(Patent Document 1) Japanese Unexamined Patent Publication No. Hei 8-236930

(Patent Document 2) Japanese Patent No. 3459964

(Patent Document 3) Japanese Patent 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) Japanese Unexamined Patent Publication No. Hei 3-122298

The subject of this invention is to develop the copper foil for semiconductor package board | substrates which avoids the said circuit erosion phenomenon, without degrading the other characteristics of copper foil. It is a subject to provide the copper foil for printed wiring boards which can improve the roughening process layer of copper foil especially, and to raise the adhesive strength of copper foil and resin, and its manufacturing method.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, as a result of earnestly examining by this inventor, the following copper foil for printed wiring boards, and its manufacturing method are provided.

1) The copper foil for printed wiring boards which has a roughening process layer which consists of needle-like fine copper grains whose diameters are 0.1-2.0 micrometers, and a vertical-to-lateral ratio is 1.5 or more in the at least one surface of copper foil.

2) The copper foil for printed wiring boards which has a roughening process layer which consists of needle-like fine copper grains whose diameters are 0.1-2.0 micrometers, and a vertical-to-lateral ratio is 3.0 or more in the at least one surface of copper foil.

3) The number of needle-shaped roughening particles exists 5 or more in circuit width of 10 micrometers, Copper foil for printed wiring boards as described in said 1) or 2) characterized by the above-mentioned.

4) The number of needle-shaped roughened particles exists in 10 or more in circuit width of 10 micrometers, Copper foil for printed wiring boards as described in said 1) or 2) characterized by the above-mentioned.

5) A silane coupling on the chromate coating layer and the chromate coating layer on the heat treatment / rust prevention layer containing at least one or more elements selected from zinc, nickel, copper, and phosphorus on the roughening treatment layer; The copper foil for printed wiring boards in any one of 1) -4) characterized by including a ring agent layer.

6) Diameter is 0.1-2.0 micrometers in the at least one surface of copper foil using the electrolytic bath which consists of sulfuric acid and copper sulfate containing at least 1 sort (s) or more of the substance selected from the alkyl sulfate salt, tungsten ion, and arsenic ion, The manufacturing method of the copper foil for printed wiring boards which forms the roughening process layer which consists of the roughening particle | grains of needle-like fine copper whose ratio of length and width is 1.5 or more.

7) A heat and rust prevention layer containing at least one or more elements selected from zinc, nickel, copper and phosphorus is formed on the roughened layer, and a chromate coating layer is further formed on the heat and rust prevention layer. A silane coupling agent layer is formed on the said chromate coating layer, The manufacturing method of the copper foil for printed wiring boards as described in 6) characterized by the above-mentioned.

As shown above, the copper foil for printed wiring boards of this invention forms needle-shaped fine roughening particle | grains in at least one surface of copper foil, not the rounded (spherical) protrusion of the roughening process conventionally considered favorable. Thereby, the adhesive strength with the resin of copper foil itself can be raised, and peeling strength can also be enlarged also about the chemical treatment at the time of fine pattern formation with respect to the package board | substrate, and it can provide the copper foil which enabled fine etching, and its manufacturing method. Can have a great effect.

It is very effective as a board | substrate for semiconductor packages produced by adhering the copper foil for printed circuits (copper foil for semiconductor package board | substrates), the copper foil for semiconductor package board | substrates, and the resin for semiconductor packages in the recent progress of fine patterning and high frequency of a printed circuit.

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

Next, in order to make understanding of this invention easy, this invention is demonstrated concretely and in detail. The copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil.

As mentioned above, the copper foil for printed wiring boards of this invention is not the rounded (spherical) protrusion of the roughening process conventionally considered favorable, but forms roughly fine copper roughening particle | grains in at least one surface of copper foil. will be. The shape is a roughening process layer whose diameter is 0.1-2.0 micrometers and whose ratio of length (length) and width (diameter) is 1.5 or more.

Moreover, it is preferable that it is a roughened particle | grain of fine needle copper of the diameter of 0.1-2.0 micrometers, and the ratio of length and width is 3.0 or more, ie, a long thing.

The shape of this roughened particle | grain of copper has a shape of substantially topil (bamboo rice), and as shown to the micrograph mentioned later, in many cases, it has a convex part upward. The ratio between the minimum and maximum diameters is about 1: 1 to 1.2. Although this ratio becomes a factor which improves adhesive force further, if the needle shape of the said numerical value is sufficient, the objective of this invention can fully be achieved.

Moreover, in this needle-shaped fine copper roughening particle | grain, the diameter of 0.1-2.0 micrometers and the ratio of length (length) and width | variety (diameter) deviate from the numerical value of 1.5 or more, for example, the thing of short length and a heteromorphic particle of Although it is not uneventful, if the quantity is less than 5% of the whole, it will not affect the adhesive strength with resin of copper foil itself.

When the copper foil for printed wiring boards is etched and a circuit is formed, it is preferable that the number of the said needle-shaped roughening particles of copper exists 5 or more in circuit width of 10 micrometers. Thereby, the adhesive strength of copper foil and resin can be improved significantly. It is preferable that especially the number of needle-shaped roughening particles of copper exists in 10 micrometers of circuit widths.

The roughening process layer which consists of needle-shaped fine copper roughening particle | grains can be manufactured using the electrolytic bath which consists of sulfuric acid and copper sulfate containing at least 1 sort (s) or more of the substance selected from the alkyl sulfate salt, tungsten ion, and arsenic ion. .

It is preferable to coat the roughening process layer which consists of needle-like fine copper roughening particles with the electrolytic bath which consists of sulfuric acid and copper sulfate for powder fall prevention and peel strength improvement.

Specific processing conditions are as follows.

(Liquid composition 1)

CuSO ₄ · 5H ₂ O: 39.3-118 g / l

Cu: 10 to 30 g / l

H ₂ SO ₄ : 10 to 150 g / l

Na ₂ WO ₄ 2H ₂ O: 0-90 mg / l

W: 0-50 mg / l

Sodium dodecyl sulfate: 0-50 mg

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

As: 0-2000 mg / l

(Electroplating condition 1)

Temperature: 30-70 ℃

(Current condition 1)

Current density: 25 to 110 A / dm

Harmonic coulomb amount: 50 to 500 As / dm

Plating time: 0.5-20 seconds

(Liquid composition 2)

CuSO ₄ · 5H ₂ O: 78 to 314 g / l

Cu: 20 to 80 g / l

H ₂ SO ₄ : 50 to 200 g / l

(Electroplating condition 2)

Temperature: 30-70 ℃

(Current condition 2)

Current density: 5 to 50 A / dm 2

Harmonic coulomb amount: 50 to 300 As / dm

Plating time: 1 to 60 seconds

Furthermore, on the said roughening process layer, on the heat-resistant rust prevention layer containing at least 1 or more types of elements chosen from zinc, nickel, copper, and phosphorus, on the said heat-resistant rust prevention layer, on a chromate coating layer and the said chromate coating layer, A silane coupling agent layer can be formed and it can be set as the copper foil for printed wiring boards.

It does not restrict | limit especially as a heat resistant rust prevention layer, The conventional heat resistant rust prevention layer can be used. For example, the brass coating layer conventionally used can be used with respect to the copper foil for semiconductor package substrates.

In addition, a chromate coating layer and a silane coupling agent layer are formed in this heat and rust prevention layer, and let it be an adhesive surface with at least resin of copper foil. The copper foil which has a coating layer which consists of these chromate coating layers and a silane coupling agent layer was laminated | stacked and adhered to resin, and after forming a etch-resistant printed circuit on this copper foil, the unnecessary part of copper foil except a printed circuit part was used for etching. To form a conductive circuit.

As a heat resistant rust prevention layer, although the existing process can be used, the following can be used specifically ,, for example.

(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

As the chromate coating layer, an electrolytic chromate coating layer or an immersion chromate coating layer can be used. It is preferable that this chromate coating layer is 25-150 microgram / dm <2> in Cr amount.

If the amount of Cr is less than 25 µg / dm 2, there is no rust prevention layer effect. Moreover, when Cr amount exceeds 150 microgram / dm <2>, since an effect becomes saturated, it becomes unnecessary. Therefore, the amount of Cr is good to set it as 25-150 microgram / dm <2>.

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

(a) Immersion chromate treatment

K ₂ Cr ₂ O ₇ : 1-5 g / l, pH: 2.5-4.5, temperature: 40-60 ° C., time: 0.5-8 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 acid, pH: 1.0-3.5, temperature: 20-40 ° C., current density: 0.1-5 A / dm 2, time: 0.5- 8 sec

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

K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / l, NaOH or KOH: 10 to 50 g / l, ZnOH or ZnSO ₄ · 7H ₂ O: 0.05 to 10 g / L, pH: 7-13, Bath temperature: 20-80 degreeC, Current density: 0.05-5 A / dm <2>, Time: 5-30 second

(d) Electrolytic Chromate Treatment (Chrome-Zinc Treatment (Acid 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., current density 0.1 to 3.0 A / dm 2, time: 1 to 30 seconds

As a silane coupling agent layer used for the copper foil for semiconductor package substrates of this invention, the silane coupling agent normally used for copper foil can be used, It does not restrict | limit in particular. For example, the specific conditions of the silane treatment are as follows.

0.2% Epoxysilane / 0.4% TEOS, PH5

The thing containing 1 or more types of alkoxysilanes provided with the tetraalkoxysilane and the functional group which has the reactivity with resin can also be used. Although the selection of this silane coupling agent layer is arbitrary, it can be said that the selection which considered adhesiveness with resin is preferable.

Example

Next, an Example and a comparative example are demonstrated. In addition, a present Example shows a preferable example and this invention is not limited to these Examples. Accordingly, all modifications, other embodiments or aspects included in the technical idea of the present invention are included in the present invention.

In addition, the comparative example was published for the contrast with this invention.

(Example 1)

The roughening plating shown below was given to the rough surface (mat surface: M surface) of this copper foil using the electrolytic copper foil of thickness 12micrometer. The processing 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

As amount added: 1000 ppm: Use H ₃ AsO ₃ (60% aqueous solution)

(Electroplating temperature 1) 50 ℃

(Current condition 1)

Current density: 90 A / dm

Harmonic Coulomb Volume: 200 As / d㎡

After this roughening process, normal plating shown below was performed. The processing conditions are shown below.

(Liquid composition 2)

CuSO ₄ 5H ₂ O: 156 g / ℓ

Cu: 40 g / ℓ

H ₂ SO ₄ : 100 g / l

(Electroplating temperature 1) 40 ℃

(Current condition 1)

Current Density: 30 A / dm²

Harmonic Coulomb Volume: 150 As / d㎡

The SEM photograph of the roughening process layer of Example 1 is shown in FIG. The magnification of the SEM photograph on the left shown in FIG. 1 is (x3000), and the magnification of the SEM photograph on the right is (x30000). As shown in this FIG. 1, it turns out that it is formed in needle-like particle shape. The average particle diameter was 0.57 µm, the length of the particles was 1.56 µm, and the ratio between the length and the width was 2.7, which satisfied the conditions of the present invention.

Next, the heat-resistant antirust layer was formed on the roughening process surface of the said copper. This condition can be used a known heat-resistant and rust-preventing layer, but the present embodiment was carried out under the following conditions.

(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 ° C

(Current condition)

Current density: 6.7 A / dm

Current: 4.0 A

Plating time: 5 seconds

Next, the electrolytic chromate treatment was performed on the heat resistant rust prevention layer.

Electrolytic Chromate Treatment (Chrome, Zinc Treatment (Acid Bath))

Cr ₂ O ₃ : 0.73 g / ℓ

ZnSO ₄ 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 ℃

Current Density: 2.06 A / dm²

Time: 1-30 seconds

(PH adjustment is performed with sulfuric acid or potassium hydroxide)

Next, silane treatment (by coating) was performed on this chromate coating layer.

The conditions of a silane treatment are as follows.

0.2% Epoxysilane / 0.4% TEOS, PH5

The copper foil thus produced was laminated and bonded to a glass cross base material BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of Powder Falling

No powder fall was observed. The results are shown in Table 1.

(2) state peel strength

The state peel strength became 0.79 kg / cm, and had favorable peel strength. The results are shown in Table 1.

(3) hydrochloric acid resistance test

As for the hydrochloric acid resistance, the amount of loss after immersion for 90 minutes at 60 ° C. using 12 wt% hydrochloric acid in a 0.4 mm circuit is expressed as%. Hereinafter, the same applies. The amount of loss was 5%, and the amount of loss was small as compared with the comparative example mentioned later, and showed favorable property. The results are shown in Table 1.

(4) Test result of sulfuric acid peroxide resistance (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 degreeC)

It was carried out in a 0.4 mm circuit. In this case, the case where 2 micrometers etched was investigated. 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 small at 6.6%, and sulfuric acid permeability was good.

(Example 2)

The roughening plating (matte surface: M surface) of this copper foil was given the roughening plating shown below and the normal plating similar to Example 1 using the electrolytic copper foil of thickness 12micrometer. Below, roughening plating process conditions 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 addition amount: 3 ppm

(Electroplating temperature 1) 50 ℃

(Current condition 1)

Current Density: 40 A / dm²

Harmonic Coulomb Volume: 300 As / d㎡

The SEM photograph of the roughening process layer of Example 2 is shown in FIG. The magnification of the SEM photograph on the left shown in FIG. 2 is (× 3000), and the magnification of the SEM photograph on the right is (× 30000). 2, it turns out that it is formed in needle-like particle shape. The average particle diameter was 0.67 µm, the particle length was 1.78 µm, and the ratio between the length and the width was 2.7, which satisfied the conditions of the present invention.

Next, on the roughening process surface of the said copper, the same heat-resistant and rust prevention layer as Example 1 is provided, electrolytic chromate treatment is performed on this heat-resistant and rust prevention layer, and silane treatment (coating is further performed on this chromate coating layer. )).

The copper foil thus produced was laminated and bonded to a glass cross base material BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of Powder Falling

No powder fall was observed. The results are shown in Table 1.

(2) state peel strength

The state peel strength became 0.83 kg / cm, and had favorable peel strength. The results are shown in Table 1.

(3) hydrochloric acid resistance test

Regarding the hydrochloric acid resistance, the amount of loss after immersion at 60 ° C. for 90 minutes using 12 wt% hydrochloric acid in a 0.4 mm circuit is expressed as%. Hereinafter, the same applies. Loss amount was 2.3%, and compared with the comparative example mentioned later, the loss amount was few and showed favorable property. The results are shown in Table 1.

(4) Test result of sulfuric acid peroxide resistance (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 degreeC)

It was carried out in a 0.4 mm circuit. In this case, the case where 2 micrometers etched was investigated. 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 small at 4.4%, and sulfuric acid permeability was good.

(Example 3)

The roughening plating (matte surface: M surface) of this copper foil was given the roughening plating shown below and the normal plating similar to Example 1 using the electrolytic copper foil of thickness 12micrometer. Below, roughening plating process conditions 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

Amount of sodium dodecyl sulfate: 10 ppm

(Electroplating temperature 1) 50 ℃

(Current condition 1)

Current density: 100 A / dm 2

Harmonic Coulomb Volume: 200 As / d㎡

The SEM photograph of the roughening process layer of Example 3 is shown in FIG. The magnification of the SEM photograph on the left side shown in FIG. 3 is (x3000), and the magnification of the SEM photograph on the right side is (x30000). As shown in this FIG. 3, although it is a little close to spherical shape, it turns out that it maintains needle shape particle shape. The average particle diameter was 0.6 µm, the particle length was 1.5 µm, and the length-to-width ratio was 2.5, which satisfied the conditions of the present invention.

Next, on the roughening process surface of the said copper, the same heat-resistant and rust prevention layer as Example 1 is provided, electrolytic chromate treatment is performed on this heat-resistant and rust prevention layer, and silane treatment (coating is further performed on this chromate coating layer. )).

The copper foil thus produced was laminated and bonded to a glass cross base material BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of Powder Falling

No powder fall was observed. The results are shown in Table 1.

(2) state peel strength

The state peel strength became 0.75 kg / cm, and had favorable peel strength. The results are shown in Table 1.

(3) hydrochloric acid resistance test

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

(4) Test result of sulfuric acid peroxide resistance (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 degreeC)

It was carried out in a 0.4 mm circuit. In this case, the case where 2 micrometers etched was investigated. 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 small at 8.7%, and sulfuric acid permeability was good.

(Example 4)

The roughening plating (matte surface: M surface) of this copper foil was given the roughening plating shown below and the normal plating similar to Example 1 using the electrolytic copper foil of thickness 12micrometer. Below, roughening plating process conditions 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 ℃

(Current condition 1)

Current density: 90 A / dm

Harmonic Coulomb Volume: 200 As / d㎡

The SEM photograph of the roughening process layer of Example 4 is shown in FIG. The magnification of the SEM photograph on the left shown in FIG. 4 is (× 3000), and the magnification of the SEM photograph on the right is (× 30000). As shown in this FIG. 4, it turns out that it is formed in needle-like particle shape. The average particle diameter was 0.59 µm, the particle length was 1.9 µm, and the ratio of length to width was 3.2, which satisfied the conditions of the present invention.

Next, on the roughening process surface of the said copper, the same heat-resistant and rust prevention layer as Example 1 is provided, electrolytic chromate treatment is performed on this heat-resistant and rust prevention layer, and silane treatment (coating is further performed on this chromate coating layer. )).

The copper foil thus produced was laminated and bonded to a glass cross base material BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of Powder Falling

No powder fall was observed. The results are shown in Table 1.

(2) state peel strength

The state peel strength became 0.82 kg / cm, and had favorable peel strength. The results are shown in Table 1.

(3) hydrochloric acid resistance test

Regarding the hydrochloric acid resistance, the amount of loss after immersion at 60 ° C. for 90 minutes using 12 wt% hydrochloric acid in a 0.4 mm circuit is expressed as%. Hereinafter, the same applies. Loss amount was 4.3%, and compared with the comparative example mentioned later, the loss amount was few and showed favorable property. The results are shown in Table 1.

(4) Test result of sulfuric acid peroxide resistance (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 degreeC)

It was carried out in a 0.4 mm circuit. In this case, the case where 2 micrometers etched was investigated. 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 less than 6.8%, and sulfuric acid permeability was good.

(Example 5)

The roughening plating (matte surface: M surface) of this copper foil was given the roughening plating shown below and the normal plating similar to Example 1 using the electrolytic copper foil of thickness 12micrometer. Below, roughening plating process conditions 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 sodium dodecyl sulfate: 10 ppm

As amount added: 1000 ppm: Use H ₃ AsO ₃ (60% aqueous solution)

(Electroplating temperature) 50 ℃

(Current condition)

Current Density: 40 A / dm²

Harmonic Coulomb Volume: 240 As / d㎡

The SEM photograph of the roughening process layer of Example 5 is shown in FIG. The magnification of the SEM photograph on the left shown in FIG. 5 is (× 3000), and the magnification of the SEM photograph on the right is (× 30000). As shown in FIG. 5, it turns out that it is formed in the needle-like particle shape. The average particle diameter was 0.72 µm, the particle length was 1.93 µm, and the length-to-width ratio was 2.7, which satisfied the conditions of the present invention.

Next, on the roughening process surface of the said copper, the same heat-resistant and rust prevention layer as Example 1 is provided, electrolytic chromate treatment is performed on this heat-resistant and rust prevention layer, and silane treatment (coating is further performed on this chromate coating layer. )).

The copper foil thus produced was laminated and bonded to a glass cross base material BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of Powder Falling

No powder fall was observed. The results are shown in Table 1.

(2) state peel strength

The state peel strength became 0.83 kg / cm, and had favorable peel strength. The results are shown in Table 1.

(3) hydrochloric acid resistance test

Regarding the hydrochloric acid resistance, the amount of loss after immersion at 60 ° C. for 90 minutes using 12 wt% hydrochloric acid in a 0.4 mm circuit is expressed as%. Hereinafter, the same applies. Loss amount was 4.6%, and the loss amount was small compared with the comparative example mentioned later, and showed favorable property. The results are shown in Table 1.

(4) Test result of sulfuric acid peroxide resistance (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 degreeC)

It was carried out in a 0.4 mm circuit. In this case, the case where 2 micrometers etched was investigated. 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 less than 7.5%, and sulfuric acid permeability was good.

(Example 6)

The roughening plating (matte surface: M surface) of this copper foil was given the roughening plating shown below and the normal plating similar to Example 1 using the electrolytic copper foil of thickness 12micrometer. Below, roughening plating process conditions 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

Amount of sodium dodecyl sulfate: 10 ppm

(Electroplating temperature 1) 50 ℃

(Current condition 1)

Current density: 100 A / dm 2

Harmonic Coulomb Volume: 200 As / d㎡

The SEM photograph of the roughening process layer of Example 6 is shown in FIG. The magnification of the SEM photograph on the left shown in FIG. 6 is (× 3000), and the magnification of the SEM photograph on the right is (× 30000). As shown in FIG. 6, it turns out that it is formed in needle-like particle shape. The average particle diameter was 0.48 µm, the particle length was 1.6 µm, and the ratio of length to width was 3.3, which satisfied the conditions of the present invention.

Next, on the roughening process surface of the said copper, the same heat-resistant and rust prevention layer as Example 1 is provided, electrolytic chromate treatment is performed on this heat-resistant and rust prevention layer, and silane treatment (coating is further performed on this chromate coating layer. )).

The copper foil thus produced was laminated and bonded to a glass cross base material BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of Powder Falling

No powder fall was observed. The results are shown in Table 1.

(2) state peel strength

The state peel strength became 0.83 kg / cm, and had favorable peel strength. The results are shown in Table 1.

(3) hydrochloric acid resistance test

Regarding the hydrochloric acid resistance, the amount of loss after immersion at 60 ° C. for 90 minutes using 12 wt% hydrochloric acid in a 0.4 mm circuit is expressed as%. Hereinafter, the same applies. Loss amount was 3.9%, and compared with the comparative example mentioned later, the loss amount was few and showed favorable property. The results are shown in Table 1.

(4) Test result of sulfuric acid peroxide resistance (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 degreeC)

It was carried out in a 0.4 mm circuit. In this case, the case where 2 micrometers etched was investigated. Loss is expressed in%. Hereinafter, the same applies. The results are shown in Table 1.

As is clear from Table 1, the amount of loss was small at 5.2%, and sulfuric acid permeability was good.

(Example 7)

The roughening plating (matte surface: M surface) of this copper foil was given the roughening plating shown below and the normal plating similar to Example 1 using the electrolytic copper foil of thickness 12micrometer. Below, roughening plating process conditions 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

Amount of sodium dodecyl sulfate: 10 ppm

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

(Electroplating temperature 1) 50 ℃

(Current condition 1)

Current Density: 80 A / dm²

Harmonic Coulomb Volume: 280 As / d㎡

The SEM photograph of the roughening process layer of Example 7 is shown in FIG. The magnification of the SEM photograph on the left shown in FIG. 7 is (x3000), and the magnification of the SEM photograph on the right is (x30000). As shown in this FIG. 7, it turns out that it is formed in needle-like particle shape. The average particle diameter was 0.55 µm, the particle length was 1.7 µm, and the ratio of length to width was 3.1, which satisfied the conditions of the present invention.

Next, on the roughening process surface of the said copper, the same heat-resistant and rust prevention layer as Example 1 is provided, electrolytic chromate treatment is performed on this heat-resistant and rust prevention layer, and silane treatment (coating is further performed on this chromate coating layer. )).

The copper foil thus produced was laminated and bonded to a glass cross base material BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of Powder Falling

No powder fall was observed. The results are shown in Table 1.

(2) state peel strength

The state peel strength became 0.85 kg / cm, and had favorable peel strength. The results are shown in Table 1.

(3) hydrochloric acid resistance test

Regarding the hydrochloric acid resistance, the amount of loss after immersion at 60 ° C. for 90 minutes using 12 wt% hydrochloric acid in a 0.4 mm circuit is expressed as%. Hereinafter, the same applies. Loss amount was 1.6%, and the loss amount was small compared with the comparative example mentioned later, and showed favorable property. The results are shown in Table 1.

(4) Test result of sulfuric acid peroxide resistance (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 degreeC)

It was carried out in a 0.4 mm circuit. In this case, the case where 2 micrometers etched was investigated. Loss is expressed in%. Hereinafter, the same applies. The results are shown in Table 1.

As is clear from Table 1, the amount of loss was small at 4.5%, and sulfuric acid permeability was good.

(Comparative Example 1)

The roughening plating (matte surface: M surface) of this copper foil was given the roughening plating shown below and the normal plating similar to Example 1 using the electrolytic copper foil of thickness 12micrometer. Below, roughening plating process conditions are shown. In this case, the additive of this 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 ℃

(Current condition)

Current density: 90 A / dm

Harmonic Coulomb Volume: 200 As / d㎡

The SEM photograph of the roughening process layer of the comparative example 1 is shown in FIG. The magnification of the SEM photograph on the left shown in FIG. 8 is (x3000), and the magnification of the SEM photograph on the right is (x30000). As shown in FIG. 8, it turns out that it is formed in the shape of a dendrite particle | grain. The average particle diameter was 5 micrometers, the particle length was 25 micrometers, and the ratio of length and width was 5.0, and the conditions of this invention were satisfied.

Next, on the roughening process surface of the said copper, the same heat-resistant and rust prevention layer as Example 1 is provided, electrolytic chromate treatment is performed on this heat-resistant and rust prevention layer, and silane treatment (coating is further performed on this chromate coating layer. )).

The copper foil produced in this way was laminated | stacked and adhere | attached on the glass cross base material BT (bismaleimide triazine) resin board, and the following items were measured or analyzed.

* (1) Observation of Powder Falling

In this comparative example 1, powder fall was observed. The results are shown in Table 1.

(2) state peel strength

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

(3) hydrochloric acid resistance test

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

(4) Test result of sulfuric acid peroxide resistance (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 degreeC)

It was carried out in a 0.4 mm circuit. In this case, the case where 2 micrometers etched was investigated. Loss is expressed in%. The results are shown in Table 1.

As is clear from Table 1, the amount of loss was 31%, and the sulfuric acid permeability was poor.

(Comparative Example 2)

The roughening plating (matte surface: M surface) of this copper foil was given the roughening plating shown below and the normal plating similar to Example 1 using the electrolytic copper foil of thickness 12micrometer. Below, roughening plating process conditions are shown.

(Liquid composition)

CuSO ₄ 5H ₂ O: 58.9 g / ℓ

Cu: 15 g / l

H ₂ SO ₄ : 100 g / l

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

(Electroplating temperature) 50 ℃

(Current condition)

Current Density: 40 A / dm²

Harmonic Coulomb Volume: 240 As / d㎡

The SEM photograph of the roughening process layer of the comparative example 2 is shown in FIG. The magnification of the SEM photograph on the left shown in FIG. 8 is (x3000), and the magnification of the SEM photograph on the right is (x30000). As shown in FIG. 8, it turns out that it is formed in spherical particle shape. The average particle diameter was 1.3 mu m, the particle length was 1.8 mu m, and the ratio of length to width was 1.4, which did not satisfy the conditions of the present invention.

Next, on the roughening process surface of the said copper, the same heat-resistant and rust prevention layer as Example 1 is provided, electrolytic chromate treatment is performed on this heat-resistant and rust prevention layer, and silane treatment (coating is further performed on this chromate coating layer. )).

The copper foil thus produced was laminated and bonded to a glass cross base material BT (bismaleimide triazine) resin plate, and the following items were measured or analyzed.

(1) Observation of Powder Falling

No powder fall was observed. The results are shown in Table 1.

(2) state peel strength

The state peel strength became 0.82 kg / cm, and had favorable peel strength. The results are shown in Table 1.

(3) hydrochloric acid resistance test

Regarding the hydrochloric acid resistance, the amount of loss after immersion at 60 ° C. for 90 minutes using 12 wt% hydrochloric acid is expressed as%. Hereinafter, the same applies. Loss amount was 20%, and compared with the comparative example mentioned later, the loss amount was few and showed favorable property. The results are shown in Table 1.

(4) Test result of sulfuric acid peroxide resistance (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 degreeC)

It was carried out in a 0.4 mm circuit. In this case, the case where 2 micrometers etched was investigated. 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 large at 15%, and sulfuric acid permeability was poor.

As mentioned above, the copper foil for printed wiring boards of this invention is needle-shaped fine roughening on at least one surface of copper foil, not the round (spherical) protrusion of the roughening process or the dendrite shape of the roughening process conventionally considered favorable. By forming a particle | grain, the adhesive strength with resin of copper foil itself is raised, and peeling strength can also be enlarged also about the chemical | medical process at the time of fine pattern formation with respect to the board | substrate for packages, Copper foil which made fine etching and its manufacture It can be seen that it has a great effect that it can provide a method.

Industrial availability

As mentioned above, this invention improves adhesive strength with resin of copper foil itself by forming needle-like fine roughening particle | grains in at least one surface of copper foil, and the chemical | medical agent at the time of fine pattern formation with respect to the board | substrate for packages. Also about a process, peeling strength can be enlarged and it has the big effect that the copper foil which enabled fine etching, and its manufacturing method can be provided.

It is very effective as a board | substrate for semiconductor packages produced by adhering the copper foil for printed circuits (copper foil for semiconductor package board | substrates), the copper foil for semiconductor package board | substrates, and the resin for semiconductor packages in the recent progress of fine patterning and high frequency of a printed circuit.

Claims (1)

Copper foil for printed wiring boards as described in the detailed description of this invention.

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