KR20060026963A - Copper electrolytic solution containing polymer having dialkylamino group of specified structure and organic sulfur compound as additive and electrolytic copper foil produced therewith - Google Patents

Abstract

An electrolytic copper foil of low profile whose surface roughness on the rough surface side (side opposite to shiny surface) in the electrolytic copper foil production using a cathode drum is low, which electrolytic copper foil can especially realize fine pattern formation and excels in extensibility and tensile strength at ordinary and high temperatures. In particular, there are provided a copper electrolytic solution comprising as additives a polymer having dialkylamino group, this polymer obtained by carrying out homopolymerization of an acrylic compound having dialkylamino group or copolymerization thereof with another compound having unsaturated bond, and an organic sulfur compound; and an electrolytic copper foil produced with the electrolytic solution.

Description

Copper electrolyte containing a dialkylamino group containing polymer and an organic sulfur compound which have specific frame | skeleton as an additive, and the electrolytic copper foil manufactured by this FOIL PRODUCED THEREWITH}

This invention relates to the copper electrolyte used for manufacture of an electrolytic copper foil, especially the copper electrolyte used for manufacture of the electrolytic copper foil which can be fine-patterned and is excellent in elongation and tension at normal temperature and high temperature.

Generally, in order to manufacture an electrolytic copper foil, it uses the rotating metal negative electrode drum which polished the surface, and the insoluble metal anode (anode) which surrounds the circumference | surroundings of the said negative electrode drum arrange | positioned at the position of the substantially lower half part of the said negative electrode drum, At the same time as the copper electrolyte flows between the cathode drum and the anode, a potential difference is applied to the electrode to deposit copper on the cathode drum, and the copper electrodeposited from the cathode drum is peeled off continuously at a predetermined thickness. Prepare the gourd.

Although copper foil obtained in this way is generally known as raw foil, it is used for the printed wiring board etc. after giving some surface treatment after that.

The outline | summary of the conventional copper foil manufacturing apparatus is shown in FIG. This electrolytic copper foil apparatus is provided with the negative electrode drum 1 in the electrolytic tank which accommodates electrolyte solution. The cathode drum 1 is rotated while being partially immersed in the electrolyte (nearly the lower half).

An insoluble anode (anode) 2 is provided to surround the lower half of the outer periphery of the cathode drum 1. There is a constant gap (gap) 3 between the cathode drum 1 and the anode 2, and the electrolyte flows therebetween. Two anode plates are arranged in the apparatus of FIG.

In the apparatus of FIG. 1, an electrolyte is supplied from the bottom, and this electrolyte flows from the upper edge of the anode 2 through the gaps 3 of the cathode drum 1 and the anode 2, and further the electrolyte solution It is configured to circulate. A predetermined voltage can be maintained between the cathode drum 1 and the anode 2 through a rectifier.

As the negative electrode drum 1 rotates, the copper electrodeposited from the electrolytic solution increases in thickness, and when the thickness becomes more than a certain thickness, the raw foil 4 is peeled off and continuously wound. The raw foil produced in this way can be adjusted in thickness by the distance between the negative electrode drum 1 and the anode 2, the flow rate of the supplied electrolyte solution, or the amount of electricity to be supplied.

In the copper foil manufactured by such an electrolytic copper foil manufacturing apparatus, the surface in contact with the negative electrode drum becomes a mirror surface, but the surface on the opposite side is a rough surface with irregularities. In normal electrolysis, the roughness of this rough surface is severe, and undercutting is liable to occur at the time of etching, and it has a problem that fine patterning is difficult.

On the other hand, in recent years, with increasing density of a printed wiring board, copper foil which can be fine-patterned with narrowing of a circuit width and multilayering has been calculated | required. For this fine patterning, copper foil having an etching rate and uniform solubility, that is, copper foil having excellent etching characteristics is required.

On the other hand, the performance required for the copper foil for printed wiring boards is required not only for elongation at room temperature, but also for high temperature elongation characteristics for preventing cracking due to thermal stress, and also for high dimensional stability of printed wiring boards. By the way, copper foil with severe roughness as mentioned above has a problem that it is not suitable at all for fine patterning as mentioned above. From this, low profile of the rough surface is examined.

In general, it is known that this low profile can be achieved by adding a large amount of glue or thiourea to the electrolyte.

However, such an additive has a problem that the elongation at normal temperature and high temperature is drastically lowered and the performance as a copper foil for a printed wiring board is greatly reduced.

Disclosure of the Invention

The present invention provides a low profile electrolytic copper foil having a small surface roughness on the rough surface side (the opposite side of the gloss surface) in the production of an electrolytic copper foil using a negative electrode drum, in particular, fine patterning is possible, and at room temperature and high temperature. The task is to obtain an electrolytic copper foil excellent in elongation and tensile strength.

MEANS TO SOLVE THE PROBLEM The present inventors acquired the knowledge that the electrolytic copper foil which can be fine-patterned and is excellent in elongation and tension at normal temperature and high temperature can be obtained by adding the optimal additive which can be low-profiled to electrolyte solution.

Based on this knowledge, the present inventors electrolytic copper foil which flows a copper electrolyte solution between a negative electrode drum and an anode, electrodeposits copper on a negative electrode drum, and peels electrodeposited copper foil from the said negative electrode drum, and continuously manufactures a copper foil. In the production method, a fine patterning is possible by electrolyzing using a copper electrolyte containing a dialkylamino group-containing polymer having a specific skeleton and an organic sulfur compound, and an electrolytic copper foil having excellent elongation and tensile strength at room temperature and high temperature. It was found that can be obtained to reach the present invention.

That is, this invention consists of the following structures.

[1] A copper electrolyte containing a dialkylamino group-containing polymer obtained by copolymerizing an acrylic compound having a dialkylamino group with a compound having a homopolymerization or other unsaturated bond and an organic sulfur compound as an additive.

[2] The copper electrolyte solution as described in [1], wherein the acryl-based compound having the dialkylamino group is represented by the following General Formula (1), (2) or (3).

(In General Formulas (1) to (3), R ₁ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, R ₂ and R ₃ each represent an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 5 .)

[3] The copper electrolyte according to [1], wherein the organic sulfur compound is a compound represented by the following General Formula (4) or (5).

XR ^1- (S) _n -R ² -Y- (4)

R ⁴ -SR ³ -SO ₃ Z (5)

(In General Formula (4) and (5), R <^1> , R <^2> and R <^3> is a C1-C8 alkylene group, R <^4> is hydrogen,

X is selected from the group consisting of hydrogen, sulfonic acid group, phosphonic acid group, sulfonic acid or alkali metal base or ammonium base group of phosphonic acid, Y is sulfonic acid group, phosphonic acid group, sulfonic acid or It is selected from the group 1 consisting of alkali metal base groups of phosphonic acid, Z is hydrogen or an alkali metal, n is 2 or 3.)

[4] An electrolytic copper foil produced using the copper electrolyte solution according to any one of [1] to [3].

[5] A copper clad laminate comprising the electrolytic copper foil according to the above [4].

To practice the invention  Best form for

In the present invention, it is important to include a dialkylamino group-containing polymer obtained by copolymerizing an acryl-based compound having a dialkylamino group with a compound having a homopolymerization or other unsaturated bond and an organic sulfur compound in the electrolyte solution. With only one addition, the object of the present invention cannot be achieved.

As an acryl-type compound which has a dialkylamino group in this invention, the acryl compound which has a dialkylamino group, the methacryl compound which has a dialkylamino group, etc. are mentioned, The thing which the alkyl group couple | bonded with the carbon inside the vinyl group in a compound is mentioned. Include. As an acryl-type compound which has a dialkylamino group, the compound represented by following General formula (1)-(3) is preferable.

(In General Formula (1)-(3), R <_1> represents hydrogen or a C1-C5 alkyl group, R <_2> and R <_3> represent a C1-C5 alkyl group, n represents the integer of 1-5. )

As R <_1> , hydrogen or a methyl group is preferable, and as a C1-C5 alkyl group of R <_2> , R <_3> , a methyl group or an ethyl group is preferable.

As a compound represented by said General Formula (1)-(3), For example, dimethyl amino ethyl acrylate, diethyl amino ethyl methacrylate, dimethyl amino ethyl methacrylate, N, N-diethyl acrylamide, N, N-dimethyl acrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylamide, etc. can be used.

The dialkylamino group containing polymer which has a specific skeleton can be obtained by homopolymerizing the acryl-type compound containing these dialkylamino groups, or copolymerizing with the compound which has another unsaturated bond.

In order to homopolymerize, it is preferable to use water as a solvent and to use radical generators, such as potassium peroxodisulfate and ammonium peroxodisulfate, as a polymerization initiator.

Moreover, as a compound which has another unsaturated bond in the case of copolymerizing with the compound which has another unsaturated bond, although it is a copolymerizable unsaturated compound, as a preferable compound, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2- Hydroxyethyl methacrylate, and the like.

As a weight average molecular weight of the alkylamino group containing polymer obtained by homopolymerization or copolymerization, 1000-500,000 are preferable.

Although reaction is not fully completed and a monomer may remain, there is no problem in a characteristic even if it uses a mixture with a monomer as long as a residual monomer is 40% or less in molar ratio.

Moreover, it is preferable that an organosulfur compound is a compound which has a structural formula of the said General formula (4) or (5).

As an organosulfur compound represented by the said General formula (4), the following are used preferably, for example.

H ₂ O ₃ P- (CH ₂ ) ₃ -SS- (CH ₂ ) ₃ -PO ₃ H ₂

HO ₃ S- (CH ₂ ) ₄ -SS- (CH ₂ ) ₄ -SO ₃ H

NaO ₃ S- (CH ₂ ) ₃ -SS- (CH ₂ ) ₃ -SO ₂ Na

HO ₃ S- (CH ₂ ) ₂ -SS- (CH ₂ ) ₂ -SO ₃ H

CH ₃ -SS-CH ₂ -SO ₃ H

NaO ₃ S- (CH ₂ ) ₃ -SSS- (CH ₂ ) ₃ -SO ₃ Na

(CH ₃ ) ₂ -CH-SS- (CH ₂ ) ₂ -SO ₃ H

Moreover, as an organic sulfur compound represented by the said General formula (5), the following are mentioned, for example, It is used preferably.

The ratio of the dialkylamino group-containing polymer and the organic sulfur compound in the copper electrolyte is preferably 1: 5 to 5: 1 by weight, more preferably 1: 2 to 2: 1. The concentration in the copper electrolyte of the dialkylamino group-containing polymer is preferably 1 to 200 ppm.

In addition to the dialkylamino group-containing polymer and the organic sulfur compound, a known additive such as polyether compounds such as polyethylene glycol and polypropylene glycol, polyethylene-imine, phenadine dye, glue, and cellulose may be added to the copper electrolyte.

Moreover, the copper clad laminated board obtained by laminating | stacking the electrolytic copper foil of this invention can be fine-patterned, and becomes a copper clad laminated board excellent in elongation and tensile strength at normal temperature and high temperature.

1 illustrates the outline of a conventional copper foil production apparatus.

This electrolytic copper foil apparatus is provided with the negative electrode drum 1 in the electrolytic tank which accommodates electrolyte solution. The cathode drum 1 is rotated while being partially immersed in the electrolyte (nearly the lower half).

An insoluble anode (anode) 2 is provided to surround the lower half of the outer periphery of the cathode drum 1. There is a constant gap (gap) 3 between the cathode drum 1 and the anode 2, and the electrolyte flows therebetween. Two anode plates are arranged in the apparatus of FIG.

An Example is shown to the following and this invention is demonstrated in detail.

Dialkylamino group  Of containing polymers Synthesis Example  One

50 g of N and N-dimethylaminopropyl acrylamide were dissolved in 50 g of ion-exchanged water, 0.5 g of potassium peroxodisulfate was added thereto, and polymerization reaction was carried out at 60 ° C. for 3 hours under a nitrogen atmosphere. The obtained compound was a mixture of dialkylamino group-containing polymer (I) (weight average molecular weight 8500) represented by the following formula and its monomer, and the monomer content was 20 to 30%.

Dialkylamino group  Of containing polymers Synthesis Example  2

The polymerization was carried out in the same manner as in Synthesis Example 1 except that N, N-dimethylaminopropylacrylamide of Synthesis Example 1 was changed to dimethyl aminoethyl methacrylate. The obtained compound was a mixture of dialkylamino group-containing polymer (II) (weight average molecular weight 4500) represented by the following formula and its monomer, and the monomer content was about 6%.

Dialkylamino group  Of containing polymers Synthesis Example  3

The polymerization was carried out in the same manner as in Synthesis Example 1 except that N, N-dimethylaminopropylacrylamide in Synthesis Example 1 was changed to N, N-dimethylacrylamide. The obtained compound was a mixture of dialkylamino group-containing polymer (III) (weight average molecular weight 9200) represented by the following formula and its monomer, and the monomer content was about 10%.

Example  1 to 6 and Comparative example  1 to 5

Using the electrolytic copper foil manufacturing apparatus as shown in FIG. 1, the electrolytic copper foil with a thickness of 35 micrometers was manufactured. The electrolyte composition is as follows.

Cu: 90g / L

H ₂ SO ₄ : 80g / L

Cl: 60ppm

Polyethylene Glycol (PEG): 20mg / L or 0mg / L

Liquid temperature: 55 ~ 57 ℃

Additive A: Bis (3-sulfopropyl) disulfide disodium

          (SPS made in RASCHIG company)

Additive B1: having a specific structure obtained in Synthesis Example 1

            Dialkylamino group-containing polymer mixture

Additive B2: Having a specific structure obtained in Synthesis Example 2

            Dialkylamino group-containing polymer mixture

Additive B3: Having a specific structure obtained in Synthesis Example 3

            Dialkylamino group-containing polymer mixture

According to JIS B 0601, the surface roughness Rz (µm) of the obtained electrolytic copper foil was IPC for room temperature elongation (%), room temperature elongation (kgf / mm ² ), high temperature elongation (%), and high temperature elongation (kgf / mm ² ). It measured according to -TM650. The results are shown in Tables 1-3.

TABLE 1

PEG (mg / L) Additive A (mg / L) Additive B1 (mg / L) Rz (μm) Room temperature elongation (%) Room temperature tension (kgf / mm ² ) High temperature elongation (%) High Temperature Tensile Force (kgf / mm ² ) Example 1 20 50 100 0.98 11.0 34.8 15.0 20.9 Example 2  O 50 100 0.75 9.7 37.0 16.2 20.8 Comparative Example 1 20 O O 5.5 9.85 35.2 12.3 19.8 Comparative Example 2 20 O 100 5.8 0.8 13.2 1.5 14.3 Comparative Example 3 20 50 O 5.1 0.2 10.6 2.9 12.6

TABLE 2

PEG (mg / L) Additive A (mg / L) Additive B2 (mg / L)   Rz (μm) Room temperature elongation (%) Room temperature tension (kgf / mm ² ) High temperature elongation (%) High Temperature Tensile Force (kgf / mm ² ) Example 3 20 50 100 0.88 10.5 36.2 15.8 20.5 Example 4 O 50 100 0.91 9.5 35.5 15.7 20.7 Comparative Example 4 20 O 100 5.4 0.5 9.9 3.2 13.2

TABLE 3

PEG (mg / L) Additive A (mg / L) Additive B3 (mg / L)   Rz (μm) Room temperature elongation (%) Room temperature tension (kgf / mm ² ) High temperature elongation (%) High Temperature Tensile Force (kgf / mm ² ) Example 5 20 50 100 0.82 10.0 35.2 16.0 20.8 Example 6 O 50 100 0.82 10.8 35.4 15.8 20.6 Comparative Example 5 20 O 100 5.3 0.6 11.4 2.6 12.8

As shown in Tables 1 to 3, for Examples 1 to 6 to which the additive (dialkylamino group-containing polymer and organic sulfur compound having a specific structure) of the present invention was added, the surface roughness Rz was 0.75 to 0.98 µm, and room temperature. The elongation was 9.5-11.0%, the room temperature tension was 34.8-37.0 kgf / mm ² , the high temperature elongation was 15.0-16.2%, and the high temperature tension was 20.5-20.9 kgf / mm ² . Although the remarkable low profiling can be achieved in this way, the room temperature elongation, room temperature elongation, high temperature elongation and high temperature elongation show the outstanding characteristic equivalent to the comparative example 1 in which none added the additive. On the other hand, low profiling cannot be achieved in Comparative Examples 1 and 5 in which only one of Additive-free Comparative Example 1 and an additive is added. In addition, when only one side of the additive was added, the room temperature elongation and room temperature elongation, the high temperature elongation, and the high temperature elongation were rather bad.

As mentioned above, the copper electrolyte which added the dialkylamino group containing polymer and organosulfur compound which have the specific structure of this invention is very effective for the low profile of the rough surface of the obtained electrolytic copper foil, and also it is elongation at normal temperature. In addition, it was confirmed that the excellent characteristics that the high temperature extension characteristics can be effectively maintained and high tensile strength can be obtained in the same manner. In addition, said coaddition is important, and the said characteristic can be obtained by this.

Moreover, using the electrolytic copper foil of this invention, the copper clad laminated board suitable for fine patterning can be obtained by a conventional method.

Claims (5)

A copper electrolytic solution containing a dialkylamino group-containing polymer obtained by copolymerizing an acrylic compound having a dialkylamino group with a compound having a homopolymerization or other unsaturated bond and an organic sulfur compound as an additive. The copper electrolyte solution according to claim 1, wherein the acryl-based compound having the dialkylamino group is represented by the following general formulas (1), (2) or (3).

(In General Formulas (1) to (3), R ₁ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, R ₂ and R ₃ each represent an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 5 .) The copper electrolyte solution according to claim 1, wherein the organosulfur compound is a compound represented by the following general formula (4) or (5). XR ^1- (S) _n -R ² -Y (4) R ⁴ -SR ³ -SO ₃ Z (5) (In General Formulas (4) and (5), R ¹ , R ^2, and R ³ are alkylene groups having 1 to 8 carbon atoms, and R ⁴ is hydrogen,

X is selected from the group consisting of hydrogen, sulfonic acid group, phosphonic acid group, sulfonic acid or alkali metal base or ammonium base group of phosphonic acid, Y is sulfonic acid group, phosphonic acid group, sulfonic acid or It is selected from the group 1 consisting of alkali metal base groups of phosphonic acid, Z is hydrogen or an alkali metal, n is 2 or 3.) The electrolytic copper foil manufactured using the copper electrolyte solution of any one of Claims 1-3. The copper clad laminated board which uses the electrolytic copper foil of Claim 4.

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