KR101770687B1 - The surface treatment agent for communication-connector and mobile communication-connector and Surface treatment method of connector using the same - Google Patents

Abstract

The present invention relates to a connector surface treatment solution for communication, and a connector surface treatment method for communication using the same. More specifically, the present invention relates to a connector for communication, enabling a tin nickel surface treatment layer manufactured by a pyrophosphate salt bath-electrolytic plating method to be formed on a surface of a connector for communication by using surface treatment solution having a specific composition in order to secure excellent corrosion resistance, rigidity, and PIMD characteristics.

Description

TECHNICAL FIELD [0001] The present invention relates to a surface treatment agent for a wire / wireless communication connector and a surface treatment method for a connector for communication using the same.

The present invention relates to a method of treating a surface of a communication connector of a multimedia communication system capable of securing a stable communication product by improving the corrosion resistance of a communication connector with high efficiency and low cost and improving electrical characteristics such as passive intermodulation distortion (PIMD) To a surface treatment liquid of a wire / wireless communication connector.

An important factor for the development of mobile communication technology is increasing service capacity and improving call quality. In order to increase the service and improve the communication quality, inter-channel interference is an important issue at all times. Intermodulation distortion (IMD) is an important factor affecting the interference problem.

The IMD causes two or more signal frequencies to interfere with each other to generate an undesired parasitic signal, which is referred to as passive intermodulation distortion (PIMD) when such a phenomenon appears in a passive element. PIMD has been considered only in high power communication system such as satellite communication unlike active IMD which occurs in active device, and it has been almost ignored in commercial mobile communication. However, as the mobile communication service is expanded, the interference between neighboring base stations increases and the IMD problem increases accordingly, so that not only the active IMD but also the problem of PIMD are emerging.

A communication connector, one of the RF components used in repeaters and antennas, is used directly for cable and system connections between the main devices.

In RF parts including connectors, the cause of PIMD can be roughly classified into contact nonlinearity and material nonlinearity. The causes of contact nonlinearity include the junction capacitance due to the thin oxide film between the conductors, the tunnel effect due to the semiconductor action between the conductors in the metal contact, the gap between the metals and micro-discharge due to microcracks, And non-linearity related to corrosion of the plating film, discoloration, shrinkage resistance caused by metal bonding, etc. The causes of the material nonlinearity include plating of magnetic materials and magnetic materials such as hysteresis effects of nickel, iron and cobalt .

In addition, depending on the area where the RF connector is installed, that is, in an industrial area where the sea contains a lot of salinity in the air or various kinds of polluted gas are discharged, there is a problem that the surface is discolored or corroded and the soldering characteristic is lowered.

In addition, most of the communication connectors use metal materials such as brass, stainless steel, and aluminum. In many cases, corrosion of the air in a use environment is a problem. In this case, when RF signals of high frequency such as microwave are processed , A skin effect which causes a high frequency current to be maximized on the surface of the RF connection portion is generated and causes loss of signal processing. Corrosion causes a further increase in the loss, which requires excellent corrosion resistance.

In order to develop a connector having a technology for solving the PIMD which greatly affects the communication quality and the service capacity in the RF (radio frequency) and high frequency communication, the connector of the original material such as the copper and the copper alloy, This problem can be overcome by surface treatment of a plated metal or alloy.

Until now, the surface treatment of the connector used in the mobile communication system has been mainly conducted by electrolytic nickel plating or electroless nickel plating, which is a magnetic substance. In the case of electroless nickel plating, the soldering characteristic is poor. In the gas test and the salt spray test There is a disadvantage that discoloration and corrosion occur. In the case of electrolytic nickel plating, since uniform plating is not performed, the above-mentioned PIMD phenomenon may cause abnormal communication quality and cut off of communication.

In order to solve such a problem of nickel plating, a multilayer plating is coated with a single metal or an alloy of a nonmagnetic material, but the process is complicated and the plating cost is increased to 2 to 7 times or more, Silver plating, palladium alloy, etc., it is possible to obtain excellent PIMD characteristics, but the manufacturing cost is high, and in particular, the price fluctuation of the raw material is so severe that the supply of raw materials is not easy.

The tin-nickel alloy plating has conventionally been performed by an electrolytic plating method such as a chlorofluorocarbon bath or an acidic chloride bath, but the conventional electrolytic plating method has a problem of causing environmental pollution.

Therefore, there is a need for economical plating to replace precious metal plating such as gold plating and silver plating in consideration of a limited resource environment.

Korean Patent No. 10-1162584 (Published on July 4, 2012)

Accordingly, the present invention has been made to solve the above problems and to solve the above-mentioned problems, and it is an object of the present invention to provide a surface treating solution, such as plating of a wire / wireless communication connector, which is economically and corrosion- A method of surface-treating a connector for communication by an electrolytic plating method is proposed.

In order to solve the above problems, the surface treatment liquid for wire / wireless communication connector of the present invention comprises a precursor including a nickel precursor and a tin precursor, potassium pyrophosphate (K ₂ P ₂ O ₇ ), a compound represented by the following formula And a surface treatment liquid.

[Chemical Formula 1]

Wherein R ¹ is a hydrogen atom or a straight-chain alkyl group having ¹ to 5 carbon atoms, R ² and R ³ are independently a hydrogen atom, a hydroxyl group, a straight-chain alkyl group having 1 to 5 carbon atoms, An alkyl group or a phenyl group.

The present invention also relates to a method of surface-treating a communication connector, wherein a surface of a wired / wireless connector formed of a copper alloy and an aluminum alloy has a pretreatment step (step 1) of removing and cleaning foreign matter and organic contaminants; A cleaning step (step 2) of performing alkaline cleaning and alkaline electrolytic cleaning on the surface of the preprocessed wired / wireless connector; A surface activation treatment step (step 3) of neutralizing the remaining alkali cleaning component after cleaning and then activating the surface of the wired / wireless connector; Forming a ground plating layer on the surface of the surface-activated communication connector (step 4); Neutralizing the communication connector formed with the primary plating layer (step 5); And a step of forming a surface treatment layer on the upper surface of the underlying plating layer by plating the communication connector formed with the underlying plating layer by a pyrophosphoric acid salt-electrolytic plating method (step 6), thereby performing the surface treatment of the connector for communication have.

The surface treatment liquid for a communication connector according to the present invention is excellent in compatibility with a surface of a connector for communication and plating ability and can remarkably improve the corrosion resistance, hardness and current efficiency of a communication connector, and has excellent PIMD characteristics at low cost It is possible to prevent deterioration in the performance of the communication connector and to reduce the manufacturing cost. In addition, the galvanic corrosion caused by the potential difference between dissimilar metals is much improved compared with the conventional plating method.

Figs. 1 and 2 are photographs of a connector for a communication surface treated in Example 1. Fig.

Hereinafter, the method for processing a surface of a communication connector according to the present invention will be described in detail.

The surface treatment liquid for a connector of the present invention includes a surface treatment liquid containing a precursor including a nickel precursor and a tin precursor, potassium pyrophosphate (K ₂ P ₂ O ₇ ), a polyamine, a compound represented by the following general formula (1) do.

[Chemical Formula 1]

In the general formula (1), R ¹ is a hydrogen atom or a straight-chain alkyl group having ¹ to 5 carbon atoms, preferably a hydrogen atom or a straight-chain alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. R ² and R ³ are independently a hydrogen atom, a hydroxyl group, a straight-chain alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or a phenyl group. Preferably, R ² and R ³ are independently a hydrogen atom , A hydroxyl group or a straight-chain alkyl group having from 1 to 2 carbon atoms.

In the surface treatment solution composition of the present invention, the precursor preferably includes a nickel precursor and a tin precursor such that the nickel and tin contents satisfy the following formula (1). When the value of the formula (1) is less than 0.25, nickel tin ) Three phases of Ni, Ni ₃ Sn ₂ and NiSn in the plating layer, or a two-phase mixed structure of Ni and NiSn are formed in a large amount, and the corrosion resistance of the plating layer may be decreased. When the ratio exceeds 0.45, the content of tin in the plating layer is relatively large, There may be a problem that the electrical characteristics of the semiconductor device are reduced.

[Equation 1]

Sn content ratio = Sn mol ratio / (Sn mol ratio + Ni mol ratio)

The nickel precursor may be a conventional one used in the art, and preferably an organic nickel precursor or NiCl ₂ .2H ₂ O may be used.

The tin precursor may be a commonly used one, and preferably an organotin precursor or SnCl ₂ .6H ₂ O may be used.

The content of the potassium pyrophosphate (K ₂ P ₂ O ₇ ) in the surface treatment liquid component of the present invention is 30 to 80 parts by weight, preferably 40 to 70 parts by weight, more preferably 30 to 80 parts by weight, 45 to 65 parts by weight. If the content of potassium pyrophosphate is less than 30 parts by weight, electrolytic plating may not be performed well. If it exceeds 80 parts by weight, corrosion resistance of the nickel tin plating layer may be deteriorated.

In the surface treatment liquid component of the present invention, the compound represented by the above formula (1) reacts with nickel to form a complex salt upon nickel tin plating to assist in the reaction between tin and nickel, It is preferable to use 300 to 500 parts by weight, preferably 350 to 450 parts by weight, more preferably 350 to 400 parts by weight, based on 100 parts by weight of the resin. If the content of the compound is less than 300 parts by weight, the time for the pyrophosphate bath-electrolytic plating process is prolonged, and the probability of occurrence of three phases of Ni, Ni ₃ Sn ₂ and NiSn or two phases of Ni and NiSn in the plating layer If the amount of the metal salt is more than 500 parts by weight, unreacted compounds may be generated in a large amount and the surface of the nickel tin plating may be inferior in gloss.

The ammonium salt of the surface treatment solution component stabilizes the tin separated from the tin precursor upon nickel tin plating. The content of the ammonium salt is preferably from 350 to 600 parts by weight, more preferably, Is preferably 400 to 550 parts by weight, more preferably 420 to 500 parts by weight. If the content of the ammonium salt is less than 350 parts by weight, the probability of occurrence of the three phases of Ni, Ni ₃ Sn ₂ and NiSn or the two phases of Ni and NiSn in the plating layer may increase. If the ammonium salt content exceeds 600 parts by weight, The pyrophosphoric acid bath-electrolytic plating progress time is prolonged, and there may be a problem that the glossiness of the surface of the nickel tin plating is inferior. The ammonium salt is preferably an ammonium salt represented by the following formula (2) in terms of reactivity.

(2)

In the general formula (2), R ¹ to R ³ are independently a hydrogen atom or a C1 to C3 alkyl group, preferably a hydrogen atom or a methyl group. And X is a halogen atom, preferably a fluorine atom or a chlorine atom.

The surface treating solution of the present invention may further comprise a polyamine in addition to the precursor, potassium pyrophosphate (K ₂ P ₂ O ₇ ), polyamine, compound represented by the following formula (1) and ammonium salt. The content of the polyamine is preferably 2 to 10 parts by weight, preferably 2 to 8 parts by weight, more preferably 3 to 5 parts by weight based on 100 parts by weight of the precursor. If the content of the polyamine is less than 2 parts by weight, the effect of injecting the polyamine may not be obtained. If the content of the polyamine exceeds 10 parts by weight, the nickel and the compound represented by the formula (1) It is good to do.

The surface treatment liquid of the present invention may have a pH of 3.5 to 5.5, preferably 3.7 to 5.3, more preferably 3.8 to 5.2.

Hereinafter, a method of surface-treating a communication connector using the above-described surface treatment liquid will be described.

The present invention also relates to a method of surface-treating a communication connector, comprising a pre-treatment step (step 1) of removing and cleaning foreign matter and organic contaminants present on the surface of a wire / wireless connector made of a copper alloy and an aluminum alloy; A cleaning step (step 2) of performing alkaline cleaning and alkaline electrolytic cleaning on the surface of the preprocessed wired / wireless connector; A surface activation treatment step (step 3) of neutralizing the remaining alkali cleaning component after cleaning and then activating the surface of the wired / wireless connector; Forming a ground plating layer on the surface of the surface-activated communication connector (step 4); Neutralizing the communication connector formed with the primary plating layer (step 5); And a step of forming a surface treatment layer on the upper surface of the underlying plating layer by plating the communication connector formed with the underlying plating layer by a pyrophosphoric acid salt-electrolytic plating method (step 6), thereby performing the surface treatment of the connector for communication have.

In the present invention, the communication connector may be applied to various types of communication connectors in which plating is performed for securing corrosion resistance and improving PIMD. For example, it can be applied to various types of communication connectors such as N type, TNC type, BNC type, and SMA type in addition to the illustrated DIN type connector.

The first step is a pre-treatment step of removing foreign substances and organic contaminants on the surface of the connector for a plated material made of a copper alloy and an aluminum alloy, and can be cleaned by a general method used in the art have. More specifically, the cleaning method may include solvent degreasing or alkali immersion degreasing to remove foreign substances and organic matter, and the solution used for immersion degreasing may be 10-20 g / l of sodium phosphate, 30-50 g / lt; / RTI > solution for about 5 to 15 minutes. In this case, the temperature of the mixed solution of sodium phosphate and sodium silicate may be 40 to 70 ° C. Then, it can be sequentially washed in a multi-stage countercurrent water bath.

The second step is a step of performing alkaline cleaning and alkaline electrolytic cleaning in order to enhance the adhesion of the plating layer during electrolytic plating of the pre-treated communication connector. This is intended to have an effect of increasing degreasing cleaning by performing electrolysis. More specifically, the alkaline electrolytic washing is conducted by electrolytically degreasing the negative electrode by applying a communication connector to a negative electrode. The solution is treated for 1 to 3 minutes in an aqueous solution of sodium cyanide at a concentration of 120 g / l, ℃) to 60 ℃ can be used. Then, in the multi-stage countercurrent water bath, wash sequentially.

Step 3 is a step of treating the alkaline component remaining on the surface of the connector for communication, which is a material to be plated, after cleaning in the cleaning step to neutralize and remove the oxide film and the inorganic contaminants to activate the surface before plating. By doing so, the plating liquid can easily permeate into the plating layer, and the quality of the connector can be homogenized. As a specific preferable example, the oxide film can be removed by putting the communication connector in the acid activation tank for 1 to 2 minutes. At this time, it is preferable to use an aqueous solution of 8 to 15% sulfuric acid, preferably an aqueous solution of 8 to 12% sulfuric acid.

In the step 4, copper plating, silver plating and / or tin plating are performed by undercoating of the plating material in order to enhance adhesion of the plating layer. The copper plating is performed at 45 to 55 ° C for 1 to 3 minutes And silver plating is preferably performed at 20 to 30 ° C for 1 to 3 minutes.

In the case of the above copper plating, the copper plating solution containing 20 to 50 g / L of cyanogen chloride, 40 to 65 g / L of cyanide, 5 to 20 g / L of caustic soda, 10 to 20 g / L of sodium carbonate and 20 to 60 g / So that the underlying plating can be performed.

In the case of silver plating, the base plating may be performed using a silver plating solution containing 60 to 150 g / l of sodium cyanide and 1.4 to 4.0 g / l of potassium silicate.

In the case of the tin plating, the underlying plating may be performed using a tin plating solution containing 25 to 40 g / l of tin sulfate and 5 to 20 ml / l of sulfuric acid and a brightener.

And, the amount of the soymilk amount and the amount of the additive may be changed according to the quality requirement and the request of the consumer. Then, it can be washed sequentially in a multi-stage countercurrent water bath.

After the fourth step is performed, before the sixth step, neutralization of the communication connector in which the underlying plating layer is formed first may be further performed. In order to neutralize the neutralization, the neutralization may be carried out in an aqueous solution of 8 to 15% sulfuric acid, preferably in an aqueous solution of 8 to 12% It is immersed for 30 to 50 seconds, and the temperature is room temperature (15 to 30 ° C). Then, it can be washed sequentially in a multi-stage countercurrent water bath.

The above-mentioned step 6 is a step of forming a nickel tin plating layer. The above-described communication connector in which the base plating layer is formed by using the above-described surface treatment liquid for communication connector of the present invention is applied to a pyrophosphate bath - Electrolytic plating is performed to form a nickel tin plating layer. The surface treatment liquid is the same as described above. The conditions for performing the pyrophosphoric acid bath-electrolytic plating will be described below. Temperature 70 ℃ ~ 90 ℃, under a stirring speed of 200 to 800rpm, and a current density of 0.25 ~ 2.00A / dm ² conditions, and preferably at a temperature 75 ~ 88 ℃, stirring speed 300 ~ 600rpm and a current density of 0.50 ~ 1.50A / dm ² Conditions , A communication connector in which a base plating layer is formed can be inserted into the surface treatment liquid of the communication connector. In addition, it is preferable to use a nickel-plated titanium electrode as a positive electrode when performing the pyrophosphoric acid bath-electrolytic plating.

The surface treatment layer in the sixth step may contain 50 to 62% by weight of Sn and 38 to 50% by weight of Ni, preferably 53 to 60% by weight of Sn and 40 to 47% by weight of Ni. Of course, Other inevitable impurities and a small amount of Ni ₃ Sn ₂ and / or NiSn.

In addition, the surface treatment method of the present invention may further carry out a step (step 7) of carrying out the surface-treated communication connector for discoloration prevention and cleaning. As a specific preferable example, it is possible to prevent discoloration of the surface plated layer by treating the communication connector subjected to the final surface plating for 40 to 120 seconds with a sealing treatment agent having a concentration of 5 to 10%. At this time, it is preferable to set the process temperature at room temperature (15 to 30 ° C) to 50 ° C. Then, it can be sequentially washed in a multi-stage countercurrent water bath.

Further, the surface treatment method of the present invention may further include a step (step 8) of performing air dewatering and drying, and the method may be carried out using a general method used in the art.

The communication connector according to the present invention thus manufactured has a base metal plating layer having an average thickness of 1 to 3 占 퐉 formed on the surface of the connector for communication and a nickel tin surface treatment layer (plating layer) having an average thickness of 1 to 5 占 퐉 formed on the base plating layer, And a nickel tin surface treatment layer (plating layer) having an average thickness of 1.5 to 3.5 占 퐉 formed on the underlying plating layer and a base plating layer having a thickness of 1.5 to 2.5 占 퐉.

At this time, if the average thickness of the underlying plated layer is less than 1 탆, corrosion resistance and frequency characteristics may be deteriorated. If the average thickness of the nickel-tin surface treatment layer is less than 1 占 퐉, corrosion resistance may be deteriorated. If the average thickness exceeds 5 占 퐉, cracks may occur in the plating layer to deteriorate frequency characteristics and corrosion resistance. It is preferable that the thickness is formed to be within the thickness.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[Example]

Example 1: Preparation of connector surface treatment liquid

Based on the following formula (1), NiCl ₂ .2H ₂ O and SnCl ₂ .6H ₂ O were mixed to prepare a precursor so that the Sn content ratio satisfies 0.347.

[Equation 1]

Sn content ratio = Sn mol ratio / (Sn mol ratio + Ni mol ratio)

Subsequently, 55 parts by weight of potassium pyrophosphate (K ₂ P ₂ O ₇ ), 370 parts by weight of a compound represented by the following formula (1), 450 parts by weight of an ammonium salt represented by the following formula (2) Were mixed to prepare a surface treating solution having a pH of 4.9 to 5.0.

[Chemical Formula 1]

In Formula (1), R ¹ is a methyl group, and R ² and R ³ are all an ethyl group.

(2)

In the general formula (2), R ¹ to R ³ are methyl groups. And X is a chlorine atom.

Examples 2 to 3

A surface treatment liquid for a communication connector was prepared in the same manner as in Example 1 except that the precursor was prepared so that the Sn content ratio of the precursor was as shown in Table 1 and then the surface treatment liquid was prepared using the same, 3 respectively.

division Sn
Content ratio Precursor
(Parts by weight) Potassium pyrophosphate
(Parts by weight) Compound (1)
(Parts by weight) Ammonium salt
(Parts by weight) Polyamine
(Parts by weight) pH Example 1 0.347 100 55 370 450 3.7 4.9-5.0 Example 2 0.285 100 55 370 450 3.7 4.7 to 4.8 Example 3 0.431 100 55 370 450 3.7 5.0 to 5.1 Example 4 0.347 100 55 400 435 8.2 4.9-5.0 Example 5 0.347 100 65 445 500 3.7 5.3 to 5.4 Example 6 0.347 100 42 350 380 3.7 4.4 ~ 4.5 Comparative Example 1 0.225 100 55 370 450 3.7 4.9-5.0 Comparative Example 2 0.505 100 55 370 450 3.7 4.9-5.0 Comparative Example 3 0.347 100 25 370 450 3.7 4.9-5.0 Comparative Example 4 0.347 100 100 370 450 3.7 4.8 to 4.9 Comparative Example 5 0.347 100 55 270 450 3.7 4.7 to 4.8 Comparative Example 6 0.347 100 55 370 315 3.7 4.7 to 4.8 Comparative Example 7 0.347 100 55 370 650 3.7 5.4 to 5.5 Comparative Example 8 0.347 100 55 370 450 12 5.4 to 5.5

Manufacturing example  One : Surface-treated  Manufacture of communication connector

The communication connector was immersed in a mixed solution of 16 g / l of sodium phosphate and 42 g / l of sodium silicate for 10 minutes under the condition of 52 to 54 to remove foreign matters on the surface of the communication connector, and then taken out and washed in the countercurrent water bath to perform pretreatment.

Subsequently, the pre-treated communication connector was immersed in an aqueous solution of 35 to 36 sodium cyanide as a negative electrode, and then subjected to alkaline electrolytic washing for 2 minutes by energizing the communication connector, which was taken out and washed in a countercurrent water bath.

Next, the communication connector subjected to the alkali electrolytic cleansing was neutralized and then put in the acid activation tank containing the acid solution for 1 minute and 20 seconds to remove the oxide film, thereby performing the surface activation treatment. At this time, the acid solution is an aqueous sulfuric acid solution having a concentration of 10% by volume.

Then, the surface-activated communication connector was taken out and washed sequentially in the multi-stage countercurrent water bath.

Next, the surface-activated communication connector was subjected to plating treatment at 20 to 30 ° C for 2 minutes using a plating bath and then re-plating with a tin plating solution.

At this time, the silver plating solution contains 110 g / l of sodium cyanide and 2.7 g / l of potassium silicate, and the tin plating solution contains 32 g / l of tin sulfate, 8 ml / l of sulfuric acid and 11 ml /

Next, the grounding-plated communication connector was immersed in a sulfuric acid aqueous solution (27 to 28 DEG C) at a concentration of 10 vol% for 40 seconds to neutralize, and then washed in a multi-stage countercurrent water bath. At this time, the total thickness of the underlying plated layer was 2.2 탆.

Next, the communication connector in which the base plating layer was formed was subjected to the pyrophosphoric acid bath-electrolytic plating using the communication connector surface treatment solution prepared in Example 1. [ At this time, the pyrophosphoric acid bath-electrolytic plating was performed under the conditions of a temperature of 82 to 83 ° C, a stirring rate of 450 to 460 rpm and a current density of 1.0 A / dm ² , and a copper sheet was used as the cathode and a nickel electrode plated with nickel as the anode. The surface treatment layer formed was 55.5% by weight of Sn and 44.5% by weight of Ni, and the surface treatment layer thickness was 2.7 占 퐉.

Next, the communication connector subjected to the pyrophosphoric acid bath-electrolytic plating was treated with a sealing agent at a concentration of 7.8% at 40 to 42 DEG C for 90 seconds and then washed with a multi-stage countercurrent water bath.

Next, it was dewatered with air and dried to produce a connector for communication shown in Fig. 1 and Fig. 2 and the photograph.

Production Example 2 to Production Example 6 and Comparative Production Example 1 to Comparative Production Example 8

The surface of the connector for communication was surface-treated in the same manner as in Production Example 1 except that the surface treatment solutions of Examples 2 to 6 and Comparative Production Examples 1 to 8 were used in place of the surface treatment solution of Example 1, Production Examples 1 to 8 were respectively carried out in order to prepare a surface-treated communication connector.

Experimental Example 1: Measurement of corrosion resistance and gloss

The corrosion resistance and gloss of the surface-treated communication connector manufactured in the above Production Examples and Comparative Production Examples were measured. At this time, the corrosion resistance measurement was carried out through a neutral salt spray test according to KS D 9502, and the results are shown in Table 2 below.

Neutral spray brine time 240 hours 480 hours 720 hours Glossiness Production Example 1 Pass Pass Pass good Production Example 2 Pass Pass Pass good Production Example 3 Pass Pass Pass good Production Example 4 Pass Pass Pass good Production Example 5 Pass Pass Pass good Production Example 6 Pass Pass Pass good Comparative Preparation Example 1 Pass Fail Fail good Comparative Production Example 2 Pass Pass Pass Poor Comparative Production Example 3 Fail Fail Fail Poor Comparative Production Example 4 Pass Pass Fail good Comparative Preparation Example 5 Pass Pass Fail Poor Comparative Preparation Example 6 Pass Pass Fail good Comparative Preparation Example 7 Pass Pass Pass Poor Comparative Preparation Example 8 Pass Pass Fail Poor

As a result of the corrosion resistance measurement of Table 1, Production Examples 1 to 6 showed excellent corrosion resistance and glossiness as a whole. On the other hand, in Comparative Preparation Example 1 in which the Sn content ratio in the precursor was less than 0.25, a three-phase structure of Ni, Ni ₃ Sn ₂ and NiSn or a two-phase mixed structure of Ni and NiSn in the nickel tin plating layer was generated in many cases, Results.

In Comparative Production Example 3 where the amount of potassium pyrophosphate used was less than 30 parts by weight, the corrosion resistance was poor as a result of poor electrolytic plating. In Comparative Production Example 4 in which the amount of potassium pyrophosphate was more than 80 parts by weight, Showed the result of falling.

In Comparative Preparation Example 5 in which the amount of the compound represented by Chemical Formula 1 was less than 300 parts by weight and Comparative Preparation Example 6 in which the amount of ammonium salt was less than 350 parts by weight, the corrosion resistance was poor, It was judged that the mixed structure was formed as in Production Example 1 and the corrosion resistance of the plating layer was deteriorated.

In Comparative Preparation Example 8 in which the polyamine was used in an amount exceeding 10 parts by weight, nickel and the compound represented by the formula (1) were prevented from forming a complex due to excessive use of the polyamine, and the corrosion resistance was deteriorated.

Comparative Preparation Example 2 in which the Sn content ratio in the precursor was more than 0.45 and Comparative Preparation Example 7 in which the amount of the ammonium salt was more than 600 parts by weight showed excellent corrosion resistance but poor gloss.

Production Example 7 to Production Example 8 and Comparative Production Example 9 to Comparative Production Example 10

In the same manner as in Preparation Example 1, the undercoat layer was formed and the surface treatment solution of Example 1 was used to carry out the pyrophosphoric acid salt bath-electrolytic plating operation. In the pyrophosphoric acid bath-electrolytic plating, A speed of 480 to 490 rpm and a current density of 1.45 A / dm < ^{2 &} gt ;. The positive electrode was a copper sheet, and the positive electrode was a nickel plated titanium electrode. The surface treatment layer formed was 57.4% by weight of Sn and 42.6% by weight of Ni, and the surface treatment layer thickness was 3.3 占 퐉.

The surface treatment layer of the base plating layer and the surface treatment solution of Example 1 were subjected to the pyrophosphate salt-bath electroplating under the same conditions as in the following Table 3 to form the surface treatment layer in the same manner as in Preparation Example 1, 8 and Comparative Production Examples 9 to 10 were carried out.

division Pyrophosphate Bath - Current Density at Electroplating In the surface treatment layer
Sn and Ni wt% Surface treatment layer
thickness Production Example 1 1.0 A / dm ² Sn 55.5 wt%
Ni 44.5 wt% 2.7 탆 Production Example 7 1.75 A / dm ² Sn 57.4 wt%
Ni 42.6 wt% 3.3 탆 Production Example 8 0.45 A / dm ² Sn 53.2 wt%
Ni 46.8 wt% 1.8 탆 Comparative Preparation Example 9 0.20 A / dm ² Sn 47.3 wt%
Ni 52.7 wt% 0.8 탆 Comparative Preparation Example 10 2.10A / dm ² Sn 65.1 wt%
Ni 34.9 wt% 4.1 탆

Experimental Example  2: Corrosion resistance test 2

The corrosion resistance of the surface-treated communication connector manufactured in Production Example 1, Production Examples 7 to 8 and Comparative Production Examples 9 to 10 was measured. At this time, the corrosion resistance measurement was carried out by a neutral salt spray test according to KS D 9502, and the results are shown in Table 4 below.

Neutral spray brine time 240 hours 480 hours 720 hours Production Example 1 Pass Pass Pass Production Example 7 Pass Pass Pass Production Example 8 Pass Pass Pass Comparative Preparation Example 9 Fail Fail Fail Comparative Preparation Example 10 Pass Pass Pass

As a result of the corrosion resistance measurement, 0.25 A / dm ² , The surface treatment layer thickness was too thin, the tear content in the surface treatment layer was too low, and the corrosion resistance was also poor.

Experimental Example 3: Relative PIMD measurement experiment

The PIMD characteristic values (-dBc) of the surface-treated communication connectors prepared in Production Example 1, Production Examples 7 to 8 and Comparative Production Example 10 were measured, and Comparative Production Examples 7 to 8 and Comparative Production Examples The relative PIMD measurement results of Examples 9 to 10 are shown in Table 5 below.

PIMD characteristics -dBc Production Example 1 100% Production Example 7 105.2% Production Example 8 98.3% Comparative Preparation Example 10 103.6%

Electroplating at a current density of 2.0 A / dm ² In Comparative Production Example 10, the PIMD value was increased rather than that in Production Example 1, but the PIMD value was lowered in comparison with Production Example 7.

It is preferable to conduct the electrolytic plating at a current density of 0.25 to 2.00 A / dm ² , preferably at a current density of 0.50 to 1.50 A / dm ² , in the pyrophosphate bath-electrolytic plating through Experimental Example 2 and Experimental Example 3 It is possible to confirm that it is appropriate.

Claims (10)

delete delete A pretreatment step (step 1) of removing and cleaning foreign substances and organic contaminants present on the surface of the wire / wireless connector made of copper alloy and aluminum alloy;
A cleaning step (step 2) of performing alkaline cleaning and alkaline electrolytic cleaning on the surface of the preprocessed wired / wireless connector;
A surface activation treatment step (step 3) of neutralizing the remaining alkali cleaning component after cleaning and then activating the surface of the wired / wireless connector;
(Step 4) of forming a ground plating layer containing at least one selected from a copper plating layer, a silver plating layer and a tin plating layer on the surface of the surface-activated communication connector;
Neutralizing the communication connector formed with the primary plating layer (step 5); And
(6) forming a surface treatment layer on the upper surface of the underlying plating layer by plating the communication connector formed with the underlying plating layer with a pyrophosphoric acid salt-electrolytic plating method,
The above-described pyrophosphate bath-electrolytic plating method is carried out by electrolytic plating with a surface treatment solution containing a precursor including a nickel precursor and a tin precursor, potassium pyrophosphate (K ₂ P ₂ O ₇ ), a compound represented by the following formula 1 and an ammonium salt Thereby forming a surface treatment layer on the upper surface of the plating layer;
[Chemical Formula 1]

Wherein R ¹ is a hydrogen atom or a straight-chain alkyl group having ¹ to 5 carbon atoms, R ² and R ³ are independently a hydrogen atom, a hydroxyl group, a straight-chain alkyl group having 1 to 5 carbon atoms, An alkyl group or a phenyl group. The method according to claim 3, wherein the pyrophosphoric acid bath-electrolytic plating method is performed at a temperature of 70 to 90 ° C, a stirring speed of 200 to 800 rpm, and a current density of 0.25 to 2.00 A / dm ² . 4. The method according to claim 3, wherein the precursor of the surface treatment liquid has a Sn content ratio satisfying the following formula (1): " (1) "
[Equation 1]
Sn content ratio = Sn mol ratio / (Sn mol ratio + Ni mol ratio)
In the above formula (1), the Sn content ratio is 0.25 to 0.45. 4. The method according to claim 3, wherein the surface treatment layer in step 6 comprises 50 to 62% by weight of Sn and 38 to 50% by weight of Ni. A precursor including a nickel precursor and a tin precursor, potassium pyrophosphate (K ₂ P ₂ O ₇ ), a compound represented by the following formula (1), and an ammonium salt;
[Chemical Formula 1]

Wherein R ¹ is a hydrogen atom or a straight-chain alkyl group having ¹ to 5 carbon atoms, R ² and R ³ are independently a hydrogen atom, a hydroxyl group, a straight-chain alkyl group having 1 to 5 carbon atoms, An alkyl group or a phenyl group. 8. The connector connector surface treatment liquid according to claim 7, further comprising a polyamine. 8. The connector connector surface treating liquid according to claim 7, wherein the precursor includes a nickel precursor and a tin precursor so that the Sn content ratio satisfies the following formula:
[Equation 1]
Sn content ratio = Sn mol ratio / (Sn mol ratio + Ni mol ratio)
In the above formula (1), the Sn content ratio is 0.25 to 0.45. delete

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