KR20190117596A - Metal materials for electronic components and manufacturing methods thereof, connector terminals, connectors and electronic components using the same - Google Patents

Abstract

Provided is a metal material for electronic parts having low adhesion wear. The metal material for an electronic component is formed on the base material, the lower layer comprised from the 1 type (s) or 2 or more types chosen from the group of military A constituent elements which consist of Ni, Cr, Mn, Fe, Co, and Cu formed on the base material, and the lower layer In the intermediate layer, one or two selected from the group of soldier B constituent elements composed of Sn and In formed on the intermediate layer, and in the group of soldier C constituent elements composed of Ag, Au, Pt, Pd, Ru, Rh, Os and Ir The upper layer which consists of a selected 1 type, or 2 or more types of alloys, and the processing layer formed on the upper layer with C content of 60 at% or more and O content of 30 at% or less are provided. The intermediate layer is composed of one or two or more selected from the A constituent group and one or two selected from the B constituent group, and the oxide particles adhered to the surface of the treated layer after heating at 250 ° C. for 30 seconds. The area ratio is 0.1% or less.

Description

Metal materials for electronic components and manufacturing methods thereof, connector terminals, connectors and electronic components using the same

TECHNICAL FIELD This invention relates to the metal material for electronic components, its manufacturing method, the connector terminal using this, a connector, and an electronic component.

As a connector which is a connection part for civilian and vehicle-mounted electronic devices, the material which carried out the plating of Ni or Cu on the surface of brass or phosphor bronze, and further performed Sn or Sn alloy plating on it is used. In general, Sn or Sn alloy plating is required to have characteristics such as low contact resistance and high solder wettability, and in recent years, reduction in insertion force at the time of fitting male and female terminals formed by press forming a plating material has been required. .

In contrast, Patent Literature 1 discloses a coating material having a base material having conductivity and a coating layer formed on the base material, wherein the coating layer includes at least a surface side of Sn and an intermetallic compound of a noble metal. Is disclosed. According to this, it is described that contact resistance is low and it has a low friction coefficient and is effective in reducing an insertion force.

Japanese Patent Laid-Open No. 2005-126763

In the technique described in Patent Literature 1, the coating layer contains Sn and an intermetallic compound of a noble metal, and the thickness of the Ag-Sn alloy layer containing Sn and an intermetallic compound (Ag ₃ Sn) of a noble metal is preferably 1 It is set to more than 3 micrometers. However, in the evaluation of the present inventors, the insertion force could not be sufficiently lowered at this thickness. In addition, this alloy layer is in a state where Sn is exposed because the intermetallic compound particles are dispersed in the Sn matrix. However, under corrosive environments, this surface is likely to corrode. This leads to an increase in electrical resistance.

Thus, the problem that the insertion force cannot fully be lowered still remains in the metal material for electronic components which has the conventional Sn-Ag alloy / Ni base plating structure.

This invention is made | formed in order to solve the said subject, and makes it a subject to provide the metal material for electronic components which has a low adhesion wear property, the connector terminal, the connector, and the electronic component using the same. In addition, adhesion wear means the wear phenomenon which arises because the adhesion part which comprises the actual contact area between solids is sheared by frictional motion. As the adhesion wear increases, the insertion force when the male terminal and the female terminal are fitted together increases.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, by providing a lower metal, an intermediate | middle layer, an upper layer, and a processing layer with the predetermined metal on a base material, and controlling the adhesion amount of the oxide particle of the surface after heating of the said processing layer, it has low adhesive abrasion property. It discovered that the metal material for electronic components can be manufactured.

The present invention completed based on the above findings, in one aspect, includes one or two or more selected from a base material and a group of military A constituent elements consisting of Ni, Cr, Mn, Fe, Co, and Cu formed on the base material. At least one selected from the group consisting of a lower layer consisting of a lower layer, an intermediate layer formed on the lower layer, and a group B constituent element group consisting of Sn and In formed on the intermediate layer, Ag, Au, Pt, Pd, Ru, Rh, An upper layer composed of one or two or more alloys selected from the group of constituent C constituents composed of Os and Ir, and a treatment layer having a content of C formed on the upper layer of 60 at% or more and an O content of 30 at% or less; And the intermediate layer is composed of one or two or more selected from the group A constituents, and one or two selected from the group B constituents, wherein the intermediate layer is heated at 250 ° C. for 30 seconds. Oxidation attached to the surface The area ratio of particles with a metal material for electronic parts than 0.1%.

In one embodiment, the metal material for electronic components of this invention WHEREIN: The said processing layer contains 1 or more types chosen from the group which consists of S, P, and N further.

According to another aspect of the present invention, there is provided a substrate, a lower layer composed of one or two or more selected from the group of constituent A constituents consisting of Ni, Cr, Mn, Fe, Co, and Cu formed on the substrate, One or two selected from the group B constituent element group consisting of an intermediate layer formed on the lower layer, and a group of Sn and In formed on the intermediate layer, and a soldier formed of Ag, Au, Pt, Pd, Ru, Rh, Os and Ir. An upper layer composed of one or two or more kinds of alloys selected from the C constituent element groups, wherein the intermediate layer is one or two or more selected from the A constituent element groups, and one or more selected from the B constituent element groups, or The content of C is 60 at% or more and the content of O on the surface of the said metal material by providing the metal material consisting of two types in the process liquid containing 2.5-5.0 g / L of phosphate ester process liquids, and ultrasonically stirring. 30 at% or less Comprising a step of forming a process layer, a method of manufacturing the metallic material for an electronic component.

In one Embodiment, the manufacturing method of the metal material for electronic components of this invention is the said phosphate ester process liquid, At least 1 sort (s) of the phosphate ester represented by following General formula [1] and [2], and the following general formula It is a phosphate ester liquid containing at least 1 sort (s) chosen from the cyclic organic compound group shown by [3] and [4].

[Formula 1]

[Formula 2]

(In formula [1] and [2], R <_1> and R <_2> represents substituted alkyl, and M represents hydrogen or an alkali metal.)

[Formula 3]

[Formula 4]

, R ₁ of the (formula [3], [4] is a hydrogen, alkyl or substituted alkyl, R ₂ represents an alkali metal, hydrogen, alkyl or substituted alkyl, R ₃ represents an alkali metal or hydrogen, R ₄ Represents -SH, an amino group substituted with an alkyl or aryl group, or an alkyl substituted imidazolylalkyl, and R ₅ and R ₆ represent -NH ₂ , -SH or -SM (M represents an alkali metal)

In yet another aspect, the present invention is a connector terminal provided with a contact portion of the metal material for electronic component of the present invention.

In yet another aspect, the present invention is a connector provided with the connector terminal of the present invention.

In yet another aspect, the present invention is an FFC terminal provided with a metal material for an electronic component of the present invention in a contact portion.

In yet another aspect, the present invention is an FPC terminal provided with a contact portion of the metal material for electronic component of the present invention.

In yet another aspect, the present invention is an FFC having an FFC terminal of the present invention.

In yet another aspect, the present invention is an FPC provided with an FPC terminal of the present invention.

In yet another aspect, the present invention is an electronic component provided with an electrode for external connection with the metal material for electronic component of the present invention.

According to another aspect of the present invention, a female terminal connecting portion is provided on one side of a mounting portion provided in a housing, and a board connecting portion is provided on the other side, and the substrate connecting portion is pressed into a through hole formed in the substrate and installed on the substrate. It is an electronic component provided with the metal material for electronic components of this invention in a press-fit terminal.

According to the present invention, it is possible to provide a metal material for an electronic component having low adhesion wear.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the structure of the metal material for electronic components which concerns on embodiment of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, the metal material for electronic components which concerns on embodiment of this invention is demonstrated. As shown in FIG. 1, in the metal material for electronic component 10 according to the embodiment, a lower layer 12 is formed on a base material 11, an intermediate layer 13 is formed on a lower layer 12, The upper layer 14 is formed on the intermediate layer 13.

<Configuration of Metal Material for Electronic Components>

(materials)

Although it does not specifically limit as the base material 11, For example, metal base materials, such as copper and a copper alloy, Fe type material, stainless steel, titanium and a titanium alloy, aluminum and an aluminum alloy, can be used. Moreover, what combined the resin layer with the metal base material may be sufficient. The composite of the resin layer on the metal substrate includes, for example, an electrode portion on the FPC or FFC substrate.

(Upper floor)

The upper layer 14 is one or two selected from the group of soldier B constituent elements composed of Sn and In, and one selected from the group of soldier C constituent elements composed of Ag, Au, Pt, Pd, Ru, Rh, Os, and Ir. It consists of a species or two or more types of alloys.

Sn and In, although oxidizing metals, have the feature of being relatively flexible among metals. Therefore, even if the oxide films are formed on the Sn and In surfaces, the oxide films are easily cut and the contacts become metals, for example, when the male terminal and the female terminal are fitted with the metal material for electronic components as the contact material. Contact resistance is obtained.

Sn and In are excellent in gas corrosion resistance to gases such as chlorine gas, sulfurous acid gas, and hydrogen sulfide gas, for example, Ag having poor gas corrosion resistance in the upper layer 14, and gas corrosion resistance in the lower layer 12. When copper which is inferior to gas corrosion resistance and copper alloy are used for falling Ni and the base material 11, it has the effect | action which improves the gas corrosion resistance of the metal material for electronic components. In Sn and In, Sn is preferable because In is strictly regulated based on the technical guidelines for the prevention of health disorders of the Ministry of Health, Labor and Welfare.

Ag, Au, Pt, Pd, Ru, Rh, Os, Ir are characterized by having relatively heat resistance among metals. Therefore, the composition of the base material 11 and the lower layer 12 is suppressed from spreading to the upper layer 14 side, and heat resistance is improved. In addition, these metals form a compound with Sn or In of the upper layer 14 to suppress the oxide film formation of Sn and In, thereby improving solder wettability. Further, among Ag, Au, Pt, Pd, Ru, Rh, Os, and Ir, Ag is more preferable from the viewpoint of conductivity. Ag has high conductivity. For example, when Ag is used for high frequency signal use, the impedance resistance is lowered due to the skin effect.

It is preferable that the ζ (zeta) phase which is SnAg alloy containing 11.8-22.9 at% Sn exists in the upper layer 14. By the presence of the ζ (zeta) phase, the gas corrosion resistance is improved, and even when the gas corrosion test is performed, the appearance is less likely to be discolored.

It is preferable that the ζ (zeta) phase and the epsilon (epsilon) phase which is Ag ₃ Sn exist in the upper layer 14. Due to the presence of the epsilon (epsilon) phase, the film is harder than in the case where only the zeta (zeta) phase is present in the upper layer 14, and the adhesion wear decreases. In addition, since the Sn ratio of the upper layer 14 increases, the gas corrosion resistance is improved.

In the upper layer 14, it is preferable that only the epsilon (epsilon) phase which is Ag ₃ Sn exists. Since the ε (epsilon) phase alone exists in the upper layer 14, the film becomes harder as compared with the case where the ζ (zeta) phase and the ε (epsilon) phase, which is Ag ₃ Sn, exist in the upper layer 14, resulting in reduced adhesive wear. In addition, as the Sn ratio of the upper layer 14 increases, the gas corrosion resistance also improves.

The upper layer 14, it is preferable that the phase of ε (epsilon) Ag ₃ Sn and, Sn single phase in the presence βSn. By the presence of the ε (epsilon) phase, which is Ag ₃ Sn, and βSn, which is the Sn single phase, the Sn ratio of the upper layer is higher than that in the case where only the ε (epsilon) phase is present in the upper layer 14, thereby improving gas corrosion resistance. do.

In the upper layer 14, a ζ (zeta) phase, which is a SnAg alloy containing 11.8-22.9 at% Sn, an ε (epsilon) phase, which is Ag ₃ Sn, and βSn, which is a single Sn phase, are preferably present. By the presence of the ζ (zeta) phase, the ε (epsilon) phase of Ag ₃ Sn, and βSn, which is a Sn single phase, the gas corrosion resistance is improved, and the appearance is hardly discolored even after performing a gas corrosion test, and adhesion wear is reduced. . This configuration is not an equilibrium structure that occurred during diffusion.

The upper layer 14 should not exist by βSn alone. When βSn alone is present, adhesion wear is large, whiskers are also generated, and heat resistance and fretting wear resistance are inferior.

It is preferable that the upper layer 14 contains 10-50 at% of metals of the B structural element group. If the metal of the group B constitutes less than 10 at%, the gas corrosion resistance is poor, and the appearance may be discolored when the gas corrosion test is performed. On the other hand, when the metal of the B component element group exceeds 50 at%, the metal ratio of the B component element group in the upper layer 14 becomes large, adhesion wear increases, and whiskers also tend to occur. In addition, fretting wear may be poor.

(Treatment layer)

On the upper layer 14, the processing layer whose content of C is 60at% or more and content of O is 30at% or less is provided. The treatment layer is formed by a surface treatment such as a sealing treatment performed after the upper layer 14 is formed, and C included in the treatment layer is a component that is a surface treatment group such as the sealing treatment. The treatment layer may further include one or more selected from the group consisting of S, P, and N. Lubricity improves that C content of a process layer is 60 at% or more and O content is 30 at% or less.

After heating at 250 degreeC for 30 second with respect to a process layer, it is controlled so that the area ratio of the oxide particle adhering to the surface of the said process layer may be 0.1% or less. Since the oxide particles adhering to the surface of the treated layer after the heating adversely affect the adhesion wear property of the metal material for electronic parts, the metal parts for electronic parts having low adhesion wear properties are controlled by controlling the area ratio of the oxide particles to 0.1% or less. Material is obtained.

(Middle floor)

The intermediate layer 13 is at least one selected from the group A constituent elements composed of Ni, Cr, Mn, Fe, Co, and Cu, and at least one selected from the group B constituent elements composed of Sn and In. It is composed of species. According to such a structure, it has the effect of improving heat resistance and solder wettability. In this case, the thickness of the intermediate layer 13 is preferably 0.01 µm or more and less than 0.40 µm. Sn and In are excellent in gas corrosion resistance to gases such as chlorine gas, sulfurous acid gas, hydrogen sulfide gas, and the like, for example, Ni which is poor in gas corrosion resistance in the lower layer 12, and copper which is poor in gas corrosion resistance to the base material 11. And when a copper alloy is used, it has the effect | action which improves the gas corrosion resistance of the metal material for electronic components. Ni, Cr, Mn, Fe, Co, and Cu have a harder film than Sn or In, so that adhesion wear is less likely to occur, preventing the constituent metal of the base material 11 from diffusing to the upper layer 14, and the heat resistance test. And durability such as suppressing solder wettability deterioration.

When the thickness of the intermediate | middle layer 13 is less than 0.01 micrometer, there exists a possibility that a coating may become hard and adhesive wear may reduce. On the other hand, when the thickness of the intermediate | middle layer 13 is 0.40 micrometer or more, bending workability will fall, mechanical durability will fall, and plating cutting may generate | occur | produce.

Among Sn and In, Sn is preferable because In is strictly regulated based on technical guidelines on the prevention of health disorders of the Ministry of Health, Labor and Welfare. Moreover, Ni is preferable among Ni, Cr, Mn, Fe, Co, and Cu. This is because Ni is hard and adhesion wear hardly occurs, and sufficient bending formability is obtained.

In the intermediate layer 13, it is preferable that the metal of B constituent group is 35 at% or more. When Sn becomes 35at% or more, a film may become hard and adhesive wear may reduce.

The intermediate layer 13 may be composed of Ni ₃ Sn and Ni ₃ Sn ₂ , or may be composed of Ni ₃ Sn ₂ or Ni ₃ Sn ₄ alone. The presence of Ni ₃ Sn, Ni ₃ Sn ₂ , and Ni ₃ Sn ₄ may improve the heat resistance and the solder wettability.

It is preferable that Ni ₃ Sn ₄ and βSn which is a single phase Sn exist in the intermediate layer 13. When these exist, heat resistance and solder wettability may improve heat resistance and solder wettability compared with the case where Ni ₃ Sn ₄ and Ni ₃ Sn ₂ are present.

In this case, the thickness of the upper layer 14 is preferably 0.02 µm or more and less than 1.00 µm. If the thickness of the upper layer 14 is less than 0.02 micrometer, gas corrosion resistance will worsen, and an external appearance will discolor when a gas corrosion test is performed. On the other hand, when the thickness of the upper layer 14 is 1.00 micrometers or more, the thin film lubrication effect by the hard base material 11 or the lower layer 12 will fall, and adhesive wear will increase. Moreover, mechanical durability falls and plating cutting becomes easy to generate | occur | produce. It is preferable that the thickness of the upper layer 14 is less than 0.50 micrometer.

(substratum)

The lower layer 12 is comprised from 1 type (s) or 2 or more types chosen from the group of the group A structural elements which consist of Ni, Cr, Mn, Fe, Co, and Cu. By this structure, the metal element of the base material 11 can be suppressed from spreading to the intermediate | middle layer 13 and the upper layer 14. FIG.

It is preferable that the thickness of the lower layer 12 is 0.05 micrometer or more. When the thickness of the lower layer 12 is less than 0.05 µm, the thin film lubrication effect due to the hard lower layer is lowered, and there is a fear that the adhesion wear increases. The constituent metal of the base material 11 tends to diffuse to the upper layer 14, and there exists a possibility that heat resistance and solder wettability may fall. On the other hand, it is preferable that the thickness of the lower layer 12 is less than 5.00 micrometers. When thickness is 5.00 micrometers or more, there exists a possibility that bending workability may be bad.

(Other composition of the lower layer)

The lower layer 12 may have a composition in which the total amount of metals in the A constituent element group is 50 mass% or more, and the total amount of one or two or more metals selected from the group consisting of B, P, Sn, and Zn is less than 50 mass%. By the alloy composition of the lower layer 12 being such a structure, the lower layer 12 is more hardened, the thin film lubrication effect is further improved, and adhesion wear is further lowered, and the alloying of the lower layer 12 is made of the constituent metal of the base 11. Diffusion to this upper layer may be further prevented to improve durability such as heat resistance and solder wettability.

(Other composition of the upper layer)

In the upper layer 14, the total amount of metals in the B component group and the C component group is 50 mass% or more, and As, Bi, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, W And Zn may have a composition in which the total amount of one or two or more metals selected from the group consisting of Zn is less than 50 mass%. Such a structure may further reduce adhesion wear, suppress the occurrence of whiskers, and further improve durability, such as heat resistance and solder wettability.

(Other compositions of the middle layer)

In the intermediate layer 13, the total amount of metals of the C constituent element group is 50 mass% or more, and Bi, Cd, Co, Cu, Fe, In, Mn, Mo, Ni, Pb, Sb, Se, Sn, W, Tl and The group consisting of Zn may have a composition in which the total amount of one or two or more metals selected is less than 50 mass%. Such a structure may further reduce adhesion wear, suppress the occurrence of whiskers, and further improve durability, such as heat resistance and solder wettability.

(Method for producing metal material for electronic parts)

First, the method for producing a metal material for an electronic component of the present invention includes one or two or more selected from a base material and a group of military A constituent elements consisting of Ni, Cr, Mn, Fe, Co and Cu formed on the base material. At least one selected from the group consisting of a lower layer consisting of a lower layer, an intermediate layer formed on the lower layer, and a group B constituent element group consisting of Sn and In formed on the intermediate layer, Ag, Au, Pt, Pd, Ru, Rh, An upper layer composed of one or two or more kinds of alloys selected from the group of constituent C constituents composed of Os and Ir, and the intermediate layer is one or two or more selected from the group A constituents, and the B component A metal material composed of one or two selected from the group is prepared. The metal material can be formed by wet (electrophoresis, electroless) plating, dry (sputtering, ion plating, etc.) plating, or the like.

The upper layer 14, the intermediate layer 13, and the lower layer 12 form one or two or more kinds selected from the A constituent element groups on the substrate 11, and thereafter, one or more selected from the B constituent element groups. Two types of films may be formed, and then, one or two or more types selected from the C constituent element groups may be formed, and the respective elements of the B constituent element group and the C constituent element group may be formed, respectively. For example, when the metal of the B component group is Ag and the metal of the C component element group is Sn, the diffusion of Ag into Sn is rapid, and a Sn-Ag alloy layer is formed by natural diffusion. By forming an alloy layer, Sn adhesion force can be further reduced, and low whisker property and durability can be further improved.

After forming the upper layer 14, heat treatment may be performed for the purpose of further suppressing adhesion wear and further improving low whisker property and durability. The heat treatment diffuses the metal of the B component group and the metal of the C component group in the upper layer to form an alloy layer more easily, further reducing the adhesion of Sn and further improving the low whisker property and durability. have. In addition, the heat treatment may be performed in a reducing atmosphere or a non-oxidizing atmosphere.

In addition, about this heat processing, processing conditions (temperature x time) can be selected suitably. In addition, this heat treatment is not particularly necessary. Further, the heat treatment is performed at the metal melting point or higher of the B constituent group, and at least one alloy layer selected from the B constituent group and one or two alloy layers selected from the A constituent group, and 1 selected from the B constituent group. Formation of one or two or more kinds of alloy layers selected from species or two kinds and C constituent element groups facilitates formation of the alloy layer more favorably. In addition, when the heat treatment is performed at the melting point or more of the metals of the B component element group, and one or two or more kinds of alloy layers selected from the C component element group and one or two kinds of alloy layers selected from the B component element group are formed, the alloy layer It becomes easy to form more satisfactorily.

Next, after heat treatment is performed on the upper layer 14 or on the upper layer 14, post-treatment is performed for the purpose of further lowering the adhesive wear property and also improving the low whisker property and durability. To form. As the post-treatment, the treatment solution containing 2.5 to 5.0 g / L of the phosphate ester-based treatment liquid is prepared, and the content of C is 60 at% or more on the surface of the metal material by ultrasonic stirring, and the content of O is 30 at%. The treatment layer which is below is formed.

In the manufacturing method of the metal material for electronic components of this invention, in the formation of the process layer provided in the surface (surface of an upper layer) of a metal material in this way, it contains a phosphate ester process liquid at high concentration of 2.5-5.0 g / L. By using the treating solution to finely disperse the sealing component in the treatment liquid by ultrasonic stirring, a firm sealing film is formed and the oxidation rate by heat treatment or the like is prevented, thereby reducing the area ratio of the oxide particles adhered to the surface after heating of the treatment layer. 0.1% or less can be controlled. If the concentration of the phosphate ester-based treatment liquid is less than 2.5 g / L, the concentration is low and there is a problem in corrosion resistance and heat resistance. If it exceeds 5.0 g / L, adhesion wear is increased. As for the density | concentration of a phosphate ester process liquid, it is more preferable that it is 3.0-4.0 g / L. In addition, it is preferable that the electrolysis potential at the time of forming a process layer is 2.0-3.5V. If the electrolytic potential is less than 2.0 V, a firm sealing film may not be formed, which may cause problems in corrosion resistance and heat resistance, and when it exceeds 3.5 V, there may be a problem of discoloration. Moreover, it is more preferable that the said electrolysis potential is 3.0-3.5V.

In addition, by post-treatment, in addition to the decrease in adhesion wear resistance, the lubricity can be improved, and the durability such as heat resistance and solder wettability can be improved. Specific post-treatments include phosphate treatment using an inhibitor, lubrication treatment, silane coupling treatment, and the like. In addition, about this heat processing, processing conditions (temperature x time) can be selected suitably.

Before the post-treatment, it is preferable to perform oxide removal on the surface oxidized by heat treatment. The removal of the oxide may be performed by pickling or reverse electrolysis with the same liquid as the post-treatment liquid. Thereby, the fresh alloy surface which is not oxidized is exposed. Here, the aftertreatment component is adsorbed. It is expected that the lubricity and durability will be further improved because more organic matters having a specific structure are attached to the surface where the alloy is exposed than the surface where the oxide is exposed. Of course, when the heat treatment is performed in a reducing atmosphere, the oxide removal treatment may not be performed.

As a post-treatment, it is preferable to perform the surface of the upper layer 14 using 1 type, or 2 or more types of phosphate ester, and the aqueous solution containing 1 type, or 2 or more types of cyclic organic compounds (called phosphate ester type | system | group liquid). . The phosphate ester added to the phosphate ester-based liquid functions as an antioxidant and a lubricant for plating. Phosphoric acid ester used for this invention is represented by General formula [1] and [2]. Among the compounds represented by the general formula [1], preferred are lauric acid phosphate monoesters. A lauric acid diphosphate ester etc. are mentioned among the compounds represented by General formula [2].

[Formula 5]

[Formula 6]

(In formula [1] and [2], R <_1> and R <_2> represents substituted alkyl, and M represents hydrogen or an alkali metal.)

The cyclic organic compound added to a phosphate ester liquid functions as an antioxidant of plating. The group of cyclic organic compounds used for this invention is shown by General formula [3] and [4]. Examples of the cyclic organic compound group represented by the general formulas [3] and [4] include, for example, mercaptobenzothiazole, Na salt of mercaptobenzothiazole, K salt of mercaptobenzothiazole, and benzotriazole. , 1-methyltriazole, tolyltriazole, triazine compounds and the like.

[Formula 7]

[Formula 8]

, R ₁ of the (formula [3], [4] is a hydrogen, alkyl or substituted alkyl, R ₂ represents an alkali metal, hydrogen, alkyl or substituted alkyl, R ₃ represents an alkali metal or hydrogen, R ₄ Represents -SH, an amino group substituted with an alkyl group or an aryl group or an alkyl substituted imidazolylalkyl, and R ₅ and R ₆ represent -NH ₂ , -SH or -SM (M represents an alkali metal)

It is more preferable to perform the treatment so that both P and N are present on the upper layer 14 surface after the post treatment. If P does not exist in the plating surface, solderability will fall easily and also the lubricity of a plating material will worsen. On the other hand, when N does not exist in Sn or Sn alloy plating surface, the contact resistance of a plating material may rise easily in a high temperature environment.

<Characteristics of Metallic Materials for Electronic Components>

It is preferable that the maximum height Rz of the surface of the upper layer 14 is 3 micrometers or less. If the maximum height Rz of the surface of the upper layer 14 is 3 micrometers or less, since the convex part which is easy to corrode becomes small and becomes smooth, gas corrosion resistance will improve.

<Use of Metallic Materials for Electronic Components>

Although the use of the metal material for electronic components of this invention is not specifically limited, For example, the connector terminal provided with the metal material for electronic components in a contact part, the FFC terminal or FPC terminal provided with the metal material for electronic components in a contact part, The electronic component etc. which provided the metal material for electronic components with the electrode for external connection are mentioned. In addition, about a terminal, it does not depend on the joining method with a wiring side, such as a crimp terminal, a soldering terminal, and a press-fit terminal. Examples of the external connection electrode include a connection component having a surface treatment on a tab, a material having a surface treatment on an under bump metal of a semiconductor, and the like.

In addition, a connector may be manufactured using the connector terminal formed in this way, and FFC or FPC may be produced using an FFC terminal or an FPC terminal.

In the metal material for electronic components of the present invention, a female terminal connecting portion is provided on one side of the mounting portion provided in the housing, and a board connecting portion is provided on the other side, and the substrate connecting portion is pressed into the through hole formed in the substrate, You may use for the press-fit terminal provided.

As for a connector, the metal material for electronic components of this invention may be sufficient as both a male terminal and a female terminal, and only one of a male terminal and a female terminal may be sufficient as it. In addition, by using both the male terminal and the female terminal as the metal material for electronic components of the present invention, low insertion efficiency is further improved.

Example

Hereinafter, although the Example and comparative example of this invention are shown together, these are provided in order to understand this invention better, and it does not intend that this invention is limited.

As Examples 1-7 and Comparative Examples 1-6, after performing electrolytic degreasing, pickling, and 1st plating, 2nd plating, 3rd plating, and heat processing, the metal oxide layer ( The tin oxide layer) was removed and anode electrolysis was performed. In addition, when the heat treatment is performed in a reducing atmosphere, such a metal oxide layer is not formed. In that case, the oxide removal step does not need to be performed.

(Material)

(1) Plate: 0.30 mm thick, 30 mm wide, component Cu-30Zn

(2) Male terminal: Thickness 0.64 mm, Width 2.3 mm, Component Cu-30Zn

(3) Press-fit terminal: manufactured by Tokiwa Shoko, Press-fit terminal PCB connector, R800

(1st plating condition)

(Condition 1) Semi-gloss Ni Plating

Surface treatment method: electroplating

Plating Solution: Sulfamnic Acid Ni Plating Solution + Saccharin

Plating temperature: 55 ℃

Current Density: 0.5 to 4 A / dm ²

(Condition 2) Polished Ni Plating

Surface treatment method: electroplating

Plating solution: sulfamic acid Ni plating solution + saccharin + additive

Plating temperature: 55 ℃

Current Density: 0.5 to 4 A / dm ²

(Condition 3) Ni-Co Plating

Surface treatment method: electroplating

Plating solution: sulfamic acid bath + cobalt sulfate

Plating temperature: 55 ℃

Current Density: 0.5 to 4 A / dm ²

(Condition 4) Matte Ni Plating

Surface treatment method: electroplating

Plating solution: sulfamic acid Ni plating solution

Plating temperature: 55 ℃

Current Density: 0.5 to 4 A / dm ²

(Condition 5) Ni-P Plating

Surface treatment method: electroplating

Plating solution: sulfamic acid Ni plating solution + phosphite

Plating temperature: 55 ℃

Current Density: 0.5 to 4 A / dm ²

(2nd plating condition)

Ag plating

Surface treatment method: electroplating

Plating Solution: Cyanide Ag Plating Solution

Plating temperature: 40 ℃

Current density: 0.2-4 A / dm ²

(Third plating condition)

Sn plating

Surface treatment method: electroplating

Plating Solution: Methanesulfonic Acid Sn Plating Solution

Plating temperature: 40 ℃

Current Density: 0.5 to 4 A / dm ²

(Heat treatment)

The heat treatment was performed by placing a sample on a hot plate and confirming that the surface of the hot plate became a predetermined temperature.

(Intermediate processing)

The sample after heat treatment was immersed in dilute sulfuric acid (10 g / 1 L) for 5 seconds. Then, it was immersed in pure water for 5 seconds.

(After treatment)

In addition, using the A-12: phosphate ester treatment liquid of the concentration shown in Table 2 as the surface treatment liquid, anodic electrolysis (electrolysis potential shown in Table 2, constant voltage electrolysis) was performed for 2 seconds, and surface treatment was performed to the plating surface. . About Examples 1-7 and Comparative Examples 2, 4-6, ultrasonic stirring was performed at the time of treatment liquid drying, and the said electrolysis was performed from it. Ultrasonic stirring conditions of the processing liquid were made into stirring by an ultrasonic disperser (ultrasound frequency: 20 Hz, ultrasonic output: 500 W for 10 minutes). After these treatments, the samples were immersed for 2 seconds and then dried by warm air.

(Measurement of thickness of upper layer, middle layer and lower layer, determination of composition and structure of upper layer)

The thickness measurement of the upper layer and the intermediate | middle layer of the obtained sample, and the composition determination of the upper layer were performed by the line analysis by STEM (scanning electron microscope) analysis. The analyzed elements are the composition of the upper layer, the middle layer, and the lower layer, and C, S, and O. Make these elements the designated element. Moreover, the sum total of the designated element was made into 100%, and the density | concentration (at%) of each element was analyzed. The thickness corresponds to the distance obtained from the line analysis (or surface analysis). Nippon Denshi Corporation JEM-2100F was used for the STEM apparatus. The acceleration voltage of this device is 200 kW.

The determination of the structure of the upper layer was determined by comparing the composition determined by STEM with the state diagram.

In addition, the thickness of the lower layer was measured by the fluorescent X-ray film thickness measuring instrument (Seiko Instruments SEA5100, a collimator 0.1 mmΦ).

The thickness measurement of the upper layer, the intermediate | middle layer, and the lower layer, the composition of the upper layer, and the determination of the structure were evaluated and averaged about arbitrary ten points.

(evaluation)

The following evaluation was performed about each sample.

C concentration of treated layer

The C concentration of the treated layer was measured by the following method.

The XPS analyzer (model: PHI5000 Versa Probe II) manufactured by Albac Pie Co., Ltd. was used to measure XPS under the following conditions. Thereby, C density | concentration in the outermost surface was measured.

(Measuring conditions)

Reach vacuum degree: 2.2 × 10 ^-7 ㎩

Here: Monochrome AlK

Output: 25W

Detecting Area: 100㎛φ

Incident angle: 90 degrees

Blowout angle: 45 degrees

Chinese Guns: None

(Sputter condition)

Ionic species: Ar ⁺

Acceleration voltage: 2 kW

Sweep area: 3 mm x 3 mm

Rate: 0.4 nm / min (SiO ₂ equivalent)

Area ratio of oxide particles adhered to the surface after heating of the treatment layer

The area ratio of the oxide particle adhering to the surface of the process layer after 30 second heating at 250 degreeC was measured with the following method.

EDS surface analysis was performed using a scanning electron microscope (model: SU-70) manufactured by Hitachi High Technologies, Inc. to confirm that the oxide was oxide. The thing which has 82% or more of brightness | luminance is recognized as oxide particle, and the area ratio was computed.

In addition, the heating put the sample on the hot plate, and heated for 30 second after the surface of the hot plate became 250 degreeC.

Adhesion wear

Adhesion wear property was evaluated by the male terminal which plated using the commercially available Sn reflow-plated female terminal (090 type Sumitomo TS / Yazaki 090II series female terminal non-water-resistant / F090-SMTS), and the insertion test.

The measuring device used for the test was 1311NR manufactured by Aiko Engineering, and was evaluated at a sliding distance of 5 mm for the male pin. The number of samples was five, and adhesive wear was evaluated using the insertion force. The insertion force employ | adopted the value which averaged the maximum value of each sample. As a blank material of adhesive wear, the sample of the comparative example 1 was employ | adopted, and the adhesive wear property with respect to the sample of the said comparative example 1 was evaluated.

The test conditions and test results are shown in Tables 1-2.

(Evaluation results)

Examples 1-7 were the metal materials for electronic components which have the outstanding low adhesion wear property.

Since Comparative Examples 1 and 3 did not ultrasonically stir the electrolyte solution when forming the treatment layer, the area ratio of the oxide particles was large, and adhesion adhesion was high.

In Comparative Example 2, since the concentration of A-12 was low and the electrolytic potential at the time of forming the treatment layer was low, the C concentration of the treatment layer was low, that is, a sufficient sealing film was not obtained, resulting in increased oxide particles. For this reason, adhesion wear property was high.

In Comparative Example 4, the concentration of A-12 was high, but the electrolytic potential at the time of forming the treatment layer was low. Therefore, the C concentration of the treatment layer was low, that is, a sufficient sealing film was not obtained, resulting in a large amount of oxide particles. For this reason, adhesion wear property was high.

Since the density | concentration of A-12 was low, the comparative example 5 had low C density | concentration of a process layer, ie, sufficient sealing film was not obtained and many oxide particles increased. For this reason, adhesion wear property was high.

In the comparative example 6, the density | concentration of A-12 was low, C density | concentration of the process layer became low, ie, sufficient sealing film was not obtained, and oxide particle increased. For this reason, adhesion wear property was high.

10: metal material for electronic components
11: description
12: lower layer
13: middle layer
14: upper floor

Claims (12)

With the base material,
A lower layer composed of one or two or more selected from the group of constituent A constituents consisting of Ni, Cr, Mn, Fe, Co, and Cu formed on the substrate;
An intermediate layer formed on the lower layer,
1 or 2 selected from the group B constituent elements composed of Sn and In formed on the intermediate layer, and 1 selected from the group C constituent elements composed of Ag, Au, Pt, Pd, Ru, Rh, Os, and Ir. An upper layer composed of one or two or more alloys,
The treated layer formed on the upper layer, the content of C is 60 at% or more, and the content of O is 30 at% or less
Equipped,
The intermediate layer is composed of one kind or two or more kinds selected from the A constituent element group, and one kind or two kinds selected from the B constituent element group,
The metal material for electronic components whose area ratio of the oxide particle adhering to the surface of the said processing layer after 30 second heating at 250 degreeC is 0.1% or less. The method of claim 1,
The metal material for electronic components which the said processing layer contains further 1 or more types chosen from the group which consists of S, P, and N further. With the base material,
A lower layer composed of one or two or more selected from the group of constituent A constituents consisting of Ni, Cr, Mn, Fe, Co, and Cu formed on the substrate;
An intermediate layer formed on the lower layer,
1 or 2 selected from the group B constituent elements composed of Sn and In formed on the intermediate layer, and 1 selected from the group C constituent elements composed of Ag, Au, Pt, Pd, Ru, Rh, Os, and Ir. The upper layer composed of two or more alloys
Equipped, and
The intermediate layer contains 2.5 to 5.0 g / L of a phosphate ester-based treatment liquid of a metal material composed of one or two or more selected from the A component group and one or two selected from the B component group. It manufactures in the to-be-processed liquid, and manufactures the metal material for electronic components which includes the process of forming the processing layer whose content of C is 60at% or more and the content of O is 30at% or less on the surface of the said metal material by ultrasonic stirring. Way. The method of claim 3,
At least one of the phosphate ester treatment liquid selected from at least one of phosphate esters represented by the following general formulas [1] and [2] and a cyclic organic compound group represented by the following general formulas [3] and [4] The manufacturing method of the metal material for electronic components which is a phosphate ester liquid containing 1 type.
[Formula 1]

[Formula 2]

(In formula [1] and [2], R <_1> and R <_2> respectively represent substituted alkyl and M represents hydrogen or an alkali metal.)
[Formula 3]

[Formula 4]

, R ₁ of the (formula [3], [4] is a hydrogen, alkyl or substituted alkyl, R ₂ represents an alkali metal, hydrogen, alkyl or substituted alkyl, R ₃ represents an alkali metal or hydrogen, R ₄ Represents -SH, an amino group or an alkyl substituted imidazolylalkyl substituted with an alkyl group or an aryl group, R ₅ and R ₆ represent -NH ₂ , -SH or -SM (M represents an alkali metal) The connector terminal provided with the contact part with the metal material for electronic components of Claim 1 or 2. The connector provided with the connector terminal of Claim 5. The FFC terminal provided with the contact material with the metal material for electronic components of Claim 1 or 2. The FPC terminal provided with the contact part with the metal material for electronic components of Claim 1 or 2. An FFC provided with the FFC terminal according to claim 7. The FPC provided with the FPC terminal of Claim 8. The electronic component provided with the electrode for external connection with the metal material for electronic components of Claim 1 or 2. The female terminal connection part is provided in one side of the mounting part installed in a housing, and the board connection part is provided in the other side, respectively, The press-type terminal which press-fits the said board connection part to the through-hole formed in the board | substrate, and installs in the said board | substrate, Claim 1 or The electronic component provided with the metal material for electronic components of Claim 2.

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