TW200848552A - Electrolytic gold plating solution and gold film produced by using the same - Google Patents

Abstract

Disclosed is an electrolytic gold plating solution which can ensure to provide an excellent solder joint strength of a lead-free solder ball even when the solder ball is used for connection. Specifically disclosed is an electrolytic gold plating solution comprising at least gold cyanide, a dicarboxylic acid or a dicarboxylic acid salt represented by the formula (1) and a dicarboxylic acid or a dicarboxylic acid salt represented by the formula (2). [In the formula (1), -CnH2n- represents an alkylene group which may be linear or have a side chain; X<1> and X<2> independently represent H, Na, K or NH4; and n represents a positive integer of 0 or greater.] [In the formula (2), X<3> and X<4> independently represent H, Na, K or NH4; and Y represents a hydrogen atom, an alkyl group or a hydroxyalkyl group.]

Description

200848552 IX. Description of the Invention: [Technical Field] The present invention relates to an electrolytic gold plating solution, a gold film obtained therefrom, a method for producing a gold film on a nickel-plated film using the same, and a plating method using the same Gold film on the nickel film. [Prior Art] Gold plating on a nickel film (hereinafter referred to as "nickel/gold plating" for the reasons of excellent corrosion resistance, heat resistance, mechanical properties, electrical properties, etc. of gold) It is widely used in the application of protecting the surface of the terminal connection portion of an electronic component, and the substrate material to be applied is also various, and there are plastic, ceramic, metal, film, and the like. A solder ball can be mounted on a connection terminal portion covered with a nickel/gold plating film, and the solder ball is connected to the other electronic component by soldering the solder, and the solder ball is usually used. 63% by mass of tin and 37 shells! The "tin/wrong eutectic solder ball" composed of the fault of 〇. However, in recent years, the concept of environmental protection has been limited, and the use of / silver/copper has been described as a "small tin ball" to the tin eutectic solder ball. The use of "tin / ::: indicates: compared with the conventional tin / wrong eutectic solder ball: = 吏: the temperature required for tin refining is set higher;: ^ fully 'and spread to the gold-plated film The underlying metal ability knows the temperature rise of the solder ball, because: the melting 97105852 uses tin/wrong eutectic solder balls compared to the surface, the surface is more =:,: 5 200848552 = tin connection strength is reduced. _If the connection strength is lowered, there is a problem that the solder ball is detached, the electronic components that are connected to each other are disconnected, and the electronic function is functioning. ..., no other aspects, as the electrolytic mineral gold patent document 1 and patent for the purpose of improving the solder joint strength. In Document 2, it is revealed that there is an increase in the shovel property or an impurity metal ion which is not easily mixed by a jig or the like. However, when the connection is made with an error-free tin ball, the connection strength is insufficient. Patent Document 1 曰 专利 专利 4 _0 _0 _0 _0 _0 _0 _0 _0 _0 _0 _0 _0 _0 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The purpose of Providing an electrolytic gold plating solution with solder joint strength even when connected with an error-free solder ball. What is the cause of the problem? In order to solve the above problem, the researcher has repeatedly studied it and found that The use of an electrolytic gold liquid containing at least a gold cyanide salt and a two-acid or dibasic acid salt having a specific chemical structure as a constituent component to the H film', even in the case of bonding with an error-free solder ball, The present invention can also be obtained by the excellent solder joint strength. That is, the present invention provides an electrolytic gold plating solution characterized by containing at least a gold cyanide salt and a dicarboxylic acid or a dicarboxylic acid salt represented by the following formula (1). And a dibasic acid or a diacid salt represented by the following formula (2): 97105852 200848552 [Chemical Formula 1] X^OC-C^n-COOX2 (1) [In the formula (1), '-Cl- indicates An alkyl group having a straight chain or a side chain; χ1 and X2 may be the same or different from each other, and represent H, Na, and K^t ΝΗ4; η represents a natural number of 0 or more.] [Chemical 2] (2) x3ooch2c -n-ch2coox4

Y

In the formula (7), X3 may be the same or different from each other, and it means that H, Na, K or 丽4'·Y represents a hydrogen atom, a hospital group or a (tetra)alkyl group. Further, the present invention provides a gold film obtained by electrolytic gold plating using the above electrolytic gold plating solution. Further, the present invention provides a method for producing a gold film, characterized in that electrolytic gold is deposited on a mineral film using the above electrolytic gold plating solution. The present invention provides a gold film on a recording film, which is characterized in that: by using the above-mentioned electrolytic gold liquid, electrolytic gold plating is performed on the ore (invention effect), the following gold plating film is obtained in the following: The gold film of the mine is connected to the ball off even with a lead-free solder ball that is used in consideration of the problem of the near-electronics. In addition, the excellent tan-join strength can be obtained, and the solder electrolysis = probability is small. In addition, the present invention is described in the following by means of a gold interview on the joint film of the present invention. The present invention is not limited to the following specific examples. The embodiment can be implemented arbitrarily within the scope of the technical idea. The present invention is an electrolytic gold plating solution characterized by containing at least a gold cyanide salt, a dicarboxylic acid or a dicarboxylic acid salt represented by the following formula (1), and a dicarboxylic acid represented by the following formula (2) or Two tartrate salts. X1OOC - CnH2ri-COOX2 (1) [In the formula (1), -CnH2n- represents an alkyl group which may have a straight chain or a side chain; χ1 and X2 may be the same or different from each other, indicating Η, Na, Κ or ΝΗ 4 ; η represents the natural number above 〇. ] [Chemical 4] X3OOCH2C—Ν—CH2C〇〇X4 (2)

Y

[In the formula (2), X3 and χ4 may be the same or different from each other, and represent η, Na, Κ or NHU; Υ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group. The electrolytic gold plating solution of the present invention must contain a gold cyanide salt. The gold cyanide salt is used as a gold source for the electrolytic gold plating solution of the present invention. Here, the terms "cyanide gold" - "cyanide gold salt" and "tetracyano acid salt" have the same meaning. The gold cyanide salt is not limited to one type, and two or more types may be used in combination. As the bismuth cyanide gold salt, a gold cyanide metal or a gold ammonium cyanide is preferred. In addition, as the valence (oxidation number) of the gold of the cyanide gold salt, either one of the valence or the valence can be used, and from the viewpoint of the precipitation efficiency of gold, it is preferably one valence. That is, a gold cyanide salt is preferred. 97105852 8 200848552 Specific examples of the gold cyanide salt include cyanide cyanide, cyanide gold removal, cyanide gold, cyanide gold, atmospheric gold, and ammonium chloride. Among them, from the viewpoints of electroplating performance, cost, and ease of selection such as the precipitation efficiency of gold, it is preferable that the cyanide chlorinated sodium, the condensed argon hydride or the argon ammonium arsenic Particularly preferred is potassium cyanide. The content of the electrolytic gold plating in the electrolytic gold plating of the present invention is particularly limited, and the optimum content of the following flash electrolytic electrolytic gold plating and thick electrolytic gold plating is not the same, but generally, regardless of which one, relative to the electrolytic gold plating liquid As a whole, the metal gold is 0.05 g/L to 50 g/L, preferably 〇"g/L~%-, and particularly preferably 〇5 g/L to 20 g/L. If the content of the metal gold in the electrolytic gold plating solution is too small, it may be difficult to realize the golden gold ore, and it may be difficult to use it as a flash electrolytic gold plating solution. On the other hand, in the case where the amount of metal gold in the electrolytic forging gold liquid is too large, there is no particular problem as the performance of the electrolytic gold plating solution. However, metal gold is a very expensive metal, and may be contained in the electrolyte. It is not economical to save it in the state. The above description of the gold cyanide salt stipulates that the gold cyanide salt is present in the electrolysis gold liquid of the present invention, and the electrolytic gold plating liquid of the present invention uses the above-mentioned cyanide gold salt as a dissolved raw material. Preferably. In the electrolytic gold plating solution of the present invention, it is necessary to contain the above-mentioned two-line acid salt represented by the above formula (1) (hereinafter, 'sometimes "two (four) or two _ = di-decanoic acid (salt)"), and the above formula (7) The two shown _ (salt). The special two functions as at least a conductive salt in the electrolytic gold liquid. If both the dicarboxylic acid (salt) and the dicarboxylic acid (4) represented by the formula (2) are used in the case of using a solder-free solder ball, a gold-plated crucible having excellent solder bonding strength of 97105852 9 200848552 can be obtained. Strength improvement. The gold film on the nickel film achieves excellent soldering and is connected to the stretching group of the above formula (1), that is, it can be used as a slow acid (salt) m-indicating that it can have a side chain, and X1 and 〃, straight The chain structure may also be an alkyl group of a side chain structure. K or νη4Γη, ν mesh may be the same or different from each other 'representing H, Na, or the formula (2) * or Cong 4 may be present with the above-mentioned cyanide gold salt or the following in electrolytic plating, m) The number of cation exchanges, etc., Zhuo 31!) 7 ^ diterpenic acid (salt) in the 'n table * 0 or more of the number of defects, preferably 〇 ~ 8 workers < 曰 ..., the nature The number, the number of the natural numbers in the second circle is particularly good, and the range of 0 to 6 is that the natural number 4 η in the range of water is too large to be obtained. 'The degree of solution is not sufficient to form a specific concentration, or it is difficult to be equal, and it is good, such as electric ore performance, solubility in water, and easy availability. _r: Dicarboxylic acid (salt) represented by the above formula (1) Preferably, the formula (1), η, 2n- has an alkylene group having a linear structure. The use of ίί (ΐ) is not limited to the use of the type of salt, but also can be used in two or more. Specific examples of the dicarboxylic acid (salt) represented by the formula (:), preferably, for example, s-ethyl, sodium oxalate, potassium oxalate, ammonium oxalate, and propylene dibutide Sodium, potassium malonate, ammonium malonate, succinic acid, sodium succinate, - ^ unloading, succinic acid, glutaric acid, potassium glutarate, sodium glutarate, pentyl pentoxide p — deficiency acid, sodium pimelate diphosphate, potassium adipate, ammonium adipate, heptane, potassium heptanoate, ammonium pimelate, suberic acid, sodium dioctate, 97105852 200848552 G-sodium octanoic acid ammonium, sebacic acid, sodium sebacate, potassium sebacate, ammonium sebacate, sebacic acid, sodium sebacate, azelaic acid, ammonium sebacate, &quot;酉 酉 κ κ 甲基 甲基 甲基 、 、 、 κ κ 1 1 “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基Sodium, 1·decyl-u-malonate, potassium methyl, 3_propyl dimethyl hydrazine, 1 small dimethyl decyl 3-propane dicarboxylic acid, u dimethyl hydrazine -methyl-1,3-propanedicarboxylate, ammonium dimethylmalonate, 2-methyl],3,didecanoic acid, 2-mercapto-1,3-propane Sodium, potassium 2_ Yue-1,3-dimethyl propyl group or 2_ Yue, "^ Yue and ammonium malonate. In the far-end, good soldering performance, ease of water dissolution, excellent solder joint strength, easy accessibility, and low cost of lead-free solder balls. Sodium, potassium oxalate, ammonium oxalate, sodium malonate, potassium malonate, ammonium malonate, sodium succinate, potassium succinate, ammonium butyrate, sodium glutarate, glutaric acid Potassium, ammonium glutarate, sodium adipate, potassium adipate, ammonium adipate, etc. The content of the dicarboxylic acid represented by the above formula (1) in the electrolytic gold plating solution of the invention is not particularly limited, and The overall thickness of the electrolytic gold plating solution is preferably g/L to 500 g/L 'more preferably 10 g/L to 3 〇〇g/L, and particularly preferably 5 〇 machine to g/L. Further, when using two or more types In the case of the acid (salt) represented by the above formula (1), the above number indicates that the total content of the content of 4 is excessive, and there is a solder strength of the following method in which the error-free ball is obtained, or a channel ratio of the conductive salt is formed. The lower 咚S is ancient and the sorrow is sorrowful, and the precipitation of gold is reduced. On the other hand, if the content is too much, there is a di-mineral salt represented by the formula (1) which is difficult to dissolve in water, and Since the above-described effects of the present invention are further increased by the absence of ί 97105852 200848552, it is uneconomical. The above description of the "dicarboxylic acid (salt) represented by the formula (1)" stipulates that "(1) is not a dicarboxylic acid. The acid (salt) is present in the electrolytic gold plating solution of the present invention. However, in the preparation of the electrolytic gold plating solution of the present invention, it is preferred to use the above-mentioned "di-acid (salt) of the formula (1) as a solvent for dissolving. .电解 The electrolytic gold plating solution of the present invention contains, in addition to the dicarboxylic acid represented by the above formula (1), a dicarboxylic acid (salt) represented by the above formula (2) as an essential component, and two different structures are used in combination. The carboxylic acid (salt), even in the case of using lead-free solder balls, the gold-plated film on the nickel film can obtain excellent solder joint strength in the dicarboxylic acid (salt) represented by the above formula (2), and 3 and χ4 They may be the same or different from each other and represent Η, Na, K or NH4. The ruthenium, Na, K or Nh4 I is present in the electrolytic gold plating solution in a state of being subjected to cation exchange with the above-mentioned gold cyanide salt or "dicarboxylic acid (salt) represented by the formula (1)". The dicarboxylic acid (salt) represented by the above formula (2) is not limited to the use of one type.

Use two or more. In the above formula (2), Y represents a hydrogen atom, a hospital base or a base group, and has excellent plating performance, ease of dissolution in water, excellent solder joint strength of lead-free solder balls, easy availability, low cost, and the like. In view of the above, a good atom, a carbon number of five, or a carbon number of five, is particularly preferably a hydrogen atom, an alkyl group having a carbon number of 丨~3 or a carbon number of 丨~ 3 hydroxyalkyl groups. Specifically, γ is particularly preferably a hydrogen atom, a methyl group, an ethyl group, a propylhydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group or the like. Further, the dicarboxylic acid (salt) represented by the above formula (2) is preferably an imidodicarboxylic acid derivative or a salt thereof of 97105852 12 200848552. Specific examples of the dicarboxylic acid (salt) represented by the above formula (2) are excellent in plating performance, ease of dissolution in water, excellent solder joint strength in lead-free solder balls, availability, and low cost. Preferably, for example, an imido-acetic acid, an imidodiacetic acid di-nano, an imidodiacetic acid, a unloading, an imidodiacetic acid, a mercaptoimine group Acetic acid, methylimido-monoacetic acid-nano, decyl imido-monoacetic acid diammonium, mercaptoimido diacetic acid diammonium, ethylimidodiacetic acid, ethyl iminodiacetic acid disodium Ethylimido-acetic acid·monoclinic, ethyliminodiacetic acid diacetate, propylimino-acetic acid, propylimido-monoacetic acid, monopropanyl, propyliminodiacetic acid Dipotassium, propyliminodiacetic acid diammonium, butyliminodiacetic acid, disodium butylimidodiacetic acid, dipotassium butylimidodiacetic acid, diammonium butylenimine diacetate , amyl iminodiacetic acid, disodium pentylimidodiacetic acid, dipotassium pentyliminodiacetic acid, diammonium pentylimidate diacetate, hydroxyl group Iminodiacetic acid, disodium hydroxymercaptodiacetate, hydroxymethyl (dipotassium iminodiacetic acid, diammonium hydroxymercaptodiamine diacetate, hydroxyethyliminodiacetic acid, hydroxyl Disodium ethylimidodiacetic acid, dipotassium hydroxyethyliminodiacetic acid, diammonium hydroxyethyliminodiacetic acid, hydroxypropyliminodiacetic acid, hydroxypropyliminodiacetic acid Sodium, hydroxypropyl. Iminodiacetic diacetate, hydroxypropyliminodiacetic acid diammonium, hydroxybutylimidodiacetic acid, hydroxybutylimidodiacetic acid disodium, hydroxybutylimine Dipotassium diacetate, diammonium hydroxybutylimidodiacetic acid, hydroxypentyliminodiacetic acid, disodium hydroxypentylimidate diacetate, dipotassium hydroxypentylimidate diacetate, hydroxypenta In the electrolytic gold plating solution of the present invention, the dicarboxylic acid (salt) represented by the above formula (2) is not particularly limited, and the above is the same as the entire electrolytic gold plating solution. The formula (maximum carboxylic acid (salt) is preferably from 0. 1 g/L to 200 g/L, more preferably · 5 g / L 〇 g / L, 'excellently 1 g / L ~ 50 g / L. In addition, when using two kinds of dicarboxylic acid (salt) shown by the above formula (2), The above number indicates the δg g 1 of the same. If the content in the electrolytic gold liquid is too small, the following conditions may occur: the excellent solder joint strength of the lead-free solder ball cannot be obtained, or the state of y into the 'electric salt component is insufficient. On the other hand, if the content is too large, it may be uneconomical because the effect of the present invention cannot be further increased. The above-mentioned "dicarboxylic acid (salt) represented by the formula (2)" The description stipulates that the dicarboxylic acid (salt represented by the formula) is present in the electrolytic gold plating solution of the present invention, but when the electrolytic gold plating solution of the present invention is prepared, the above-mentioned two types of tickic acid represented by the formula are used. (Salt) is also preferred as a raw material for dissolution. The content ratio of the dicarboxylic acid (salt) represented by the above formula (1) to the dicarboxylic acid (salt) represented by the above formula (2) in the electric (iv) gold liquid of the present invention is not particularly limited, and it is not wrong. It is preferable that the content of the dicarboxylic acid (salt) represented by the above formula (1) is the mass of the content of the diacid (salt) represented by the above formula from the viewpoint of the excellent solder joint strength of the solder ball. More preferably, it is 15 to 5 〇 quality times 'te good for 2 to 20 times the mass. The electrolytic gold plating solution of the present invention is characterized in that the electrolytic gold plating solution contains both the second tickic acid (salt) represented by the above formula (1) and the second retarded salt (salt) represented by the above formula (7). Thereby, even in the case of using a solderless ball, a gold plating film having excellent solder joint strength can be obtained particularly on a recording film. Into 97105852 200848552, the effect is more significant at each of the above contents and/or content ratios. In the electrolytic gold plating solution of the present invention, in addition to the above-mentioned essential components, the following agents may be appropriately used as needed: a buffer for maintaining the pH of the plating solution at a fixed value, and a gold crystal diameter for adjusting the gold plating film. The crystal modulating back is a surfactant for sufficiently removing the pinhole of the gold plating film or sufficiently defoaming the electroplating liquid, a brightening agent for smoothing the gold plating film, and the like. The buffering agent to be contained in the electrolytic gold plating solution of the present invention is not particularly limited as long as it is a well-known buffering agent, and examples thereof include inorganic acids such as boric acid and phosphoric acid, and hydroxycarboxylic acids such as citric acid, tartaric acid, and malic acid. Wait. These may be used alone or in combination of two or more. Further, the content of the buffering agent in the electrolytic gold plating solution of the present invention is not particularly limited, and is usually 1 g/L to 500 g/L, preferably 1 〇g/L to 1 〇〇. g/L. If the content of the buffer in the electro-mineral liquid is too small, it is difficult to exert a buffering effect. On the other hand, if the content is too large, there is a case where the buffering effect does not increase due to the increase in the damping effect. = is a crystal modulating agent, and is not particularly limited as long as it is a well-known crystal modifier. Examples thereof include a metal such as n or a metal such as ruthenium; or a compound containing the metal. These can be ^ two or more. 4. Use-type or mixed use The content of the crystal modulo in the electrolytic gold plating solution of the present invention is not particularly limited, and is usually 1 ppm to 5 Gppm, preferably 2 Å to 2 Å PPm. If the crystallizing agent in the plating solution exerts the effect of crystallization adjustment, the second: two inclusions: if it is difficult to be too much in the right 3, then 97105852 200848552 is uneconomical due to the fact that the crystallization adjustment effect does not rise. The surfactant is not particularly limited as long as it is a well-known surfactant. A nonionic surfactant, an anionic surfactant, an amphoteric surfactant or a cationic surfactant can be used. These may be used alone or in combination of two or more. Examples of the nonionic surfactant include a thiol condensate, a naphthalene polyoxylate, a butyl phthalene polysiloxane, and a styrenated phenol polyalkoxy group. An ether type nonionic surfactant such as an amide group, an amine type non-ionic surfactant such as an octylamine polysiloxane, an hexamethylene amine polysiloxane, or a linoleylamine polyalkoxylate. Examples of the anionic surfactant include (IV) sulfates such as sodium dodecyl sulfate; polyoxyethylene sulphates such as polyoxyethylene sulphate; polyoxyethylene alkyl phenyl ether sulfate; and alkyl benzene sulfonate. Acid salt, etc. Examples of the amphoteric surfactant include 1-undecyl-indole-methylmethyl-1-hydroxyethylimidazolium betaine, hydrazine-octadecylphosphonium, and dimethylidene-dicarboxyl Betaine, dodecyldimethylamine oxide, and the like. As the cationic surfactant, there may be mentioned lauryl trimethylammonium eleven alkyl monomethyl beet test, twelve alkyl σ ratio biting salt, oleyl imidazolium salt or octadecylamine. Acetate and the like. These may be used alone or in combination of two or more, preferably a nonionic surfactant or an amphoteric surfactant. The content of the surfactant in the electrolytic gold liquid of the present invention is preferably 〇 〇 1 g / L 〜 20 g / L, as long as the desired performance is exerted, and is not particularly limited. 97105852 16 200848552 The light-reducing agent is not particularly limited as long as it is a brightening agent known in the art, and an amine compound having a pyridine skeleton or the like can be given. These may be used alone or in combination of two or more. Examples of the amine compound having a pyridine skeleton include 2-aminopyridine, tris-aminopyridine, and 4-aminopyridine. The content of the brightener in the electrolytic gold plating solution of the present invention is preferably from 0. 01 g/L to 20 g/L. The content is not particularly limited as long as the desired performance is exhibited. f When electrolytic gold plating is performed using the electrolytic gold plating solution of the present invention, it is preferred to form 2 nickel films in advance as the underlayer plating treatment. The nickel plating solution at this time is not particularly limited, and is preferably a commonly used Watt bath, an amine sulfonic acid bath, a nickel bromide bath, or the like. Further, the nickel plating liquid to be used may optionally contain an anti-cavity agent, a primary brightener or a secondary brightener. The method of using the nickel plating bath is not particularly limited and can be used according to the # gauge method. In addition, there is no particular limitation on the film thickness of the nickel-plated film, and it is preferably 〇·5 #m~2〇# m, especially good for the work #爪~“m ° [, the plating of the electrolytic gold plating solution of the present invention described above The conditions are not particularly limited, and the temperature is preferably from 20 ° C to 80 ° C, particularly preferably from 25 ° C to 60 ° C. Further, the pH of the plating solution is preferably from pH 2 pH to pH 9 〇, particularly preferably Further, the cathode current density is preferably 0.1 A/dm 2 to 1 〇A/dm ', particularly preferably 〇3 A/dm 2 〜5 A/dm 2 . The electrolytic gold plating solution of the present invention can be preferably used. Electrolytic gold plating solution for flash-melting electrolytic gold plating (also referred to as "thin-plating gold plating" or "Gold Strike Plating") for the purpose of making the gold-plated film and the underlying metal adhere well (hereinafter, This is simply referred to as "flash-melting electrolytic gold plating solution"). In addition, 97105852 17 200848552 can be preferably used as an electrolytic gold liquid until the desired gold film thickness is advanced on the flash gold plating film (the following 'has The time is simply referred to as "thick layer electrolytic gold plating solution"). Further, it can be preferably used as an electrolytic gold liquid which is subjected to thick electrolytic bond gold treatment directly on the underlying metal without performing flash electrolytic gold plating. • When performing electrolytic gold plating using the electrolytic gold plating solution of the present invention, whether it is used as a flash electrolytic electrolytic gold plating liquid or as a thick layer electrolytic gold plating liquid, a lead-free solder ball (it is known that the joint strength is good white, and the error-free solder is further improved) From the viewpoint of ball joint strength, it is preferred that both of them use the electrolytic gold plating solution of the present invention. In the case where the electrolytic gold plating solution of the present invention is used for flash electrolytic electrolytic gold plating (thin layer gold plating, gold impact plating), gold The thickness of the film is not particularly limited, but is preferably 0.001 //m~(U &quot;m, particularly preferably 〇01茁茁5〇〇5#m. Further, a thick layer electrolytic gold plating treatment is further performed thereon until reaching The film thickness of the gold film required for the thickness of the gold film required or the thick layer electrolytic gold plating treatment directly on the underlying metal is not particularly limited, and is preferably [〇·01 #m~20 // m, The present invention is more preferably 0.05 // m to 5 // m. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited to the examples as long as the gist of the invention is not exceeded. In addition, as for the composition of the electrolytic plating solution The number of concentrations is 结晶, in the case where the component contains crystal water, the number is determined based on the mass which does not include the mass of the crystal water. In addition, the following is performed on the flash-melting electrolytic gold plating treatment. Further performing the thick-layer electrolytic gold plating treatment until the desired gold film thickness of 97105852 18 200848552 is reached, and any of the "flash-melting electrolytic gold plating liquid" and the "thick-layer electrolytic gold plating liquid" use the electrolytic gold plating liquid of the present invention.丨~3 and Examples 6 to 8 are only the singapore electroless gold liquid. The fourth embodiment of the electrolytic gold plating solution of the present invention, and only the "thick-layer electrolytic gold plating liquid" are used in the fifth embodiment of the electrolytic gold plating solution of the present invention. Note that even if only one of the electroless gold plating liquids of the present invention is used, the effects of the present invention can be sufficiently exerted. [Example 1] (In the evaluation of the solder joint strength, the solder ball test substrate shown in Fig. 1 was used. In the solder ball test substrate, the photoresist has a thickness of 2 〇 # m, the thickness of the copper material is 12 /zm, and the substrate size is 1 mm (thickness) x 4 〇 mm x 4 () mm. For the solder ball test substrate, pAC2 〇〇 ( Murata (MU RATA) Co., Ltd., manufactured by Nippon Co., Ltd., was subjected to degreasing treatment for 5 minutes at rc, and then washed with water. Then, MEOX (manufactured by Murata Co., Ltd.) was used, and 3 (TC was subjected to i minute etching treatment, followed by Water washing is carried out, and then 10% by volume of dilute sulfuric acid is used, and 25 minutes is carried out at 25 π, pickling, followed by washing with water. Next, using a nickel sulfonic acid electroplating solution which is bathed at the following concentration, that is, The % acid nickel plating solution SNConc (manufactured by Murata Co., Ltd.) is 500 mL/L, the commercially available vaporized nickel is 1 〇g/L, and the commercially available boric acid is • 3〇g/L anti-concave 彳# 82 (named by Ebara_Udylite Co., Ltd.) is 2 mL/L, and the cathode current density is set to 2 W: at 5 (TC is nickel-plated for 12 minutes to form a nickel film of (5), It is then washed with water. Next, dilute sulfuric acid of 帛1〇% by volume was acid-washed at °C for 1 minute, and then washed with water. 97105852 19 200848552 A flash fusion electrolytic gold plating solution of the following composition of 1 L· was placed in a beaker, in which a cathode current density of 2 A/dm 2 was set, and a flash fusion electrolytic gold plating treatment was performed at 25 ° C for 30 seconds, followed by Washed with water. [Composition of the flash-melting electrolytic gold plating solution of Example 1] Potassium cyanide, sodium malonate, imine diacetic acid, pH of citric acid, 6.0 1 g/L (calculated as metal gold)

60 g/L (η=ι in the above formula (1)) 30 g/L (Y=H in the above formula (2)) 80 g/L (pH is adjusted by using 10% by volume of sulfuric acid and 1 N potassium hydroxide, Let it reach 6.0.) Next, a thick layer of electrolytic gold plating solution of the following composition of 1 L· was placed in a beaker, in which a cathode current density of 0.2 A/dm 2 was set, and gold plating was performed at 65 ° C for 2 minutes and 10 seconds. Then, it is washed with water. [Composition of thick layer electrolytic gold plating solution of Example 1] Potassium cyanide sodium malonate Iminodiacetic acid potassium citrate 8 g/L (calculated as metal gold)

60 g / L (n = 1 in the above formula (1)) 30 g / L (Y = H in the above formula (2)) 80 g / L sulfuric acid Ming 15 ppm (in terms of metal) pH is 6 · 0 ( The pH was adjusted to 6.0 by using 1% sulphuric acid and 1 Ν nitrous oxide clock.) After the electro-mine treatment, it was washed with water and dried, and evaluated by the following measurement method: 97105852 20 200848552. The results are shown in Table 1. [Method for measuring the thickness of gold film] X ί Γ 铜 焊 solder ball test substrate copper pad part 'Using fluorescent system, singer\SFT9255 (Seik〇Instruments Co., Ltd. clothing k), according to The thickness of the film and the nickel film. [Method for Measuring the Bond Strength of Solder Balls] Coating on the copper enamel portion of the solder ball test substrate with a gold film

After the flux, the coreless solder ball with a diameter of 〇.76 mm was 95 5 mass% 'Ag was 4 mass%, Cu was 0.5 mass%), and in the manner shown in Fig. 2, at room temperature, the crucible was 25 generations. The tensile strength of the solder ball that is reflowed under the peak temperature condition is referred to as "solder ball joint strength (gf)". Dage #4〇〇〇 (manufactured by Dage Co., Ltd.) was used for the measurement, and the stretching speed was set to 5 〇〇〇 # m/s. [Method for Determining Significant Difference in Bond Strength of Solder Balls] Stretching by Measurement Method for Bond Strength of Solder Balls

In the case of the intensity data, the statistical analysis software JMP (manufactured by S AS Institute JAPAN Co., Ltd.) was used, and the student's t test was used to determine that the significance level was less than 5%, and there was a significant difference. The so-called significance level is less than 5%, which means that the error probability is less than 5%, and the system calculates that there is a significant difference between the comparison samples. [Example 2] An electric ore treatment was carried out in the same manner as in Example 1 except that the flash-melting electrolytic gold plating solution and the thick-layer electrolytic gold liquid in Example 1 were replaced with the following composition. Thereafter, evaluation was carried out by the same measurement method as in Example 1 at 97105852 21 200848552. The results are shown together in Table 1. [Composition of the flash-melting electrolytic gold plating solution of Example 2] Potassium cyanide 1 g/L (calculated as metal gold) Sodium malonate 60 g/L (n = 1 in the above formula (1)) Hydroxyethyl Iminodiacetic acid 30 g/L (Y = C2H4OH in the above formula (2))

Potassium citrate 80 g/L pH was 6.0 (using 10% by volume of sulfuric acid and barium hydroxide to adjust ρΗ to 6.0). [Composition of thick layer electrolytic gold plating solution of Example 2] Cyanide Potassium sulphate, sodium sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate g/L (80 g/L 15 ppm (in terms of metal ruthenium) in the above formula (2) (using 10% by volume of sulfuric acid and 1N potassium hydroxide to modulate ?11 to 6.0.) °°[ [Example 3] The electroplating treatment was carried out in the same manner as in Example 除 except that the flash-melting electrolytic gold plating solution and the thick-layer electrolytic gold plating in Example 1 were replaced with the following composition. The same measurement method and the evaluation formula of the formula 97105852 22 200848552 are shown in Table 1. The results are shown together in Table 1. [Composition of the flash-melting electrolytic gold plating solution of Example 3]

Potassium cyanide sodium oxalate iminodiacetic acid citrate pH 6.0 (using 10% by volume of sulfuric acid and 1 to achieve 6.0.) 1 g/L (calculated as metal gold)

60 g/L (^=0 in the above formula (1)) 30 g/L (γ=Η in the above formula (2)) 80 g/LN potassium hydroxide adjusts the pH, [thick layer electrolysis of Example 3] Composition of gold plating solution] Cyanide sulphate sodium sulphate imide diacetic acid citrate potassium sulphate pH 6.0

8 g/L (calculated in metal gold)

6〇g/L (in the above formula) 〇3〇g/L (γ=Η in the above formula (2)) 80 g/L 15 ppm (calculated as metal ruthenium) (Using 1〇% by volume of sulfuric acid A1N Potassium hydroxide was adjusted to pH to 6.0.) £ [Example 4] In the same manner as in Example 1, except that the thick layer electrolytic gold liquid in Example 1 was replaced with the following composition Conduct electric ore processing. Thereafter, the evaluation was carried out by the same measurement method as in Example 1. The result is the same [Composition of thick layer electrolytic gold plating solution of Example 4] 97105852 23 200848552

8 g/L (calculated as metal gold) 100 g/L 15 ppm (calculated as metal ruthenium) (pH adjusted with 10% 1% sulfuric acid and 1 N potassium hydroxide to achieve 6.0.) [Examples] 5]

Potassium cyanide potassium citrate Barium sulphate pH was 6.0. The plating treatment was carried out in the same manner as in Example 1 except that the flash-melting electrolytic gold plating solution of Example 1 was replaced with the following composition. Thereafter, the evaluation was carried out by the same measurement method as in Example 1. The results are shown together in Table 1. [Composition of the flash-melting electrolytic gold plating solution of Example 5] Potassium cyanide 1 g/L (calculated as metal gold)

The citric acid was discharged at 100 g/L and the pH was 6.0 (pH was adjusted with 10% by volume of sulfuric acid and 1 N of potassium oxyhydroxide to achieve 6.0.) [Example 6] In addition to the flash-melting electrolytic gold plating in Example 1. The liquid and the thick layer electrolytic gold liquid were replaced with the same composition as in Example 1, and the plating treatment was carried out in the same manner as in Example 1. Thereafter, the evaluation was carried out by the same measurement method as in Example 1. The results are shown together in Table 1. [Composition of the flash-melting electrolytic gold plating solution of Example 6] Potassium cyanide 1 g/L (calculated as metal gold) 97105852 24 200848552 Sodium succinate Iminodiacetic acid Potassium citrate pH 6.0

60 g / L (n = 2 in the above formula (1)) 3 〇 g / L (γ = Η in the above formula (2)) 80 g / L (using 10% by volume of sulfuric acid and 1 N potassium hydroxide versus pH Adjust to make it reach 6.0.) [Example 6 thick layer electrolytic gold plating liquid cyanide gold removal succinate potassium iminodiacetic acid potassium citrate sulphate pH 6.8 composition] 8 g / L (in terms of metal gold) 60 g/L (n==2 in the above formula (1)) 30 g/L (γ = Η in the above formula (2)) 80 g/L 15 ppm (in terms of metal ruthenium) ( The pH was adjusted to 6.0 by using 10% by volume of sulfuric acid and 1 N of potassium hydroxide.)

[Example 7] A plating treatment was carried out in the same manner as in Example 1 except that the flash-melting electrolytic gold plating solution and the thick-layer electrolytic gold-plated liquid of Example 1 were replaced with the following composition. Thereafter, the evaluation was carried out by the same measurement method as in Example 1. The results are shown together in Table 1. [Composition of the flash-melting electrolytic gold plating solution of Example 7] Gold cyanide potassium glutaric acid n-iminodiacetic acid 1 g/L (calculated as metal gold) 60 g/L (30 g/L in the above formula (1) (only in the above formula (2)) 97105852 25 200848552

Potassium citrate 80 g / L pH 6.0 (using 10% by volume of sulfuric acid and IN potassium hydroxide to pH, 敕, to reach 6.00.) &quot; 正 [Example 7 thick layer electrolytic gold plating solution Composition] Potassium cyanide potassium glutarate iminodiacetic acid diacetic acid citrate barium sulfate pH is 6.8 g / L (calculated as metal gold) 6 〇 g / L (n = n in the above formula (1) 3)

30 g / L (γ == 拗 80 g / L 15 ppm (in terms of metal ruthenium in the above formula (2)) (using 10% by volume of sulfuric acid and 1 N potassium hydroxide to pH around 敕 to 6.0 .) [Embodiment 8]

The electric ore treatment was carried out in the same manner as in Example 1 except that the flash-melting electrolytic gold plating solution and the thick-layer electrolytic gold in the first embodiment were replaced with the following components. Thereafter, the evaluation was carried out by the same measurement, and the evaluation as in Example 1. The results are shown together in Table 1. [Composition of the flash-melting electrolytic gold plating solution of Example 8] Gasification gold removal sodium adipate iminodiacetic acid potassium citrate

1 g/L (calculated as metal gold) 60 g/L (3 〇g/L in the above formula (1) (80 g/L in the above formula (2) pH is 6.9 97105852 26 200848552 (using 10% by volume of sulfuric acid) And 1 N potassium hydroxide adjusted the pH to 6.0.) [Composition of thick layer electrolytic gold plating solution of Example 8] Potassium cyanide potassium adipate imino diacetic acid potassium citrate 8 g/L (calculated in metal gold)

60 g/L (n===4 in the above formula (1)) 30 g/L (γ: η in the above formula (2)) 80 g/L 15 ppm (calculated as metal ruthenium) pH is 6.0 (using 10 The % of sulfuric acid and 1 N of potassium oxide were adjusted to pH to 6.0. [Comparative Example 1] The flash-melting electrolytic gold plating solution and the thick-layer electrolytic gold liquid in Example 1 were replaced with the following The plating treatment was carried out in the same manner as in Example 1 except for the composition. Thereafter, the same measurement method as in Example 1 was carried out (the evaluation was carried out. The results are shown together in Table 1. [Comparison of the flash-melting electrolytic gold plating solution of Comparative Example 1] Potassium cyanide 1 g/L (with metal) Gold meter)

Iminodiacetic acid 30 g/L

Potassium citrate 100 g/L (no compound of the above formula (1)) pH 6.0 (pH adjusted with 10% by volume of sulfuric acid and i N potassium hydroxide to achieve 6.0.) i 97105852 27 200848552 [ The composition of the thick layer electrolytic gold plating solution of Comparative Example 1] potassium cyanide iminodiacetic acid potassium citrate sulfate I

8 g/L (calculated as metal gold) 30 g/L 100 g/L 15 ppm (based on metal I) (no compound of formula (1) above) pH 6.0 (using 10% by volume of sulfuric acid and 1 Ν The pH of the potassium hydroxide was adjusted to 6.0. [Comparative Example 2] Except that the flash-melting electrolytic gold plating solution and the thick-layer electrolytic gold plating liquid in Example 1 were replaced with the following components, The plating treatment was carried out in the same manner as in Example 1. Thereafter, the evaluation was carried out by the same measurement method as in Example 1. The results are shown together in Table 1. [Composition of the flash-melting electrolytic gold plating solution of Comparative Example 2] Potassium cyanide 1 g/L (calculated as metal gold)

Potassium citrate 100 g/L (the compound of the above formula (1) and the above formula (2)) has a pH of 6.0 (the pH is adjusted by using 10% by volume of sulfuric acid and 1N of potassium aroxide to bring it to 6.0.) Composition of thick layer electrolytic gold plating solution of Comparative Example 2] Potassium cyanide 8 g/L (calculated as metal gold)

Potassium citrate 100 g/L 97105852 28 200848552 Barium sulphate 15 ppm (calculated as metal ruthenium) (The compound of the above formula (1) and the above formula (2)) PH is 6.0 (using 10% by volume of sulfuric acid and 1 N hydrogen) Potassium oxide was adjusted to pH to 6.0. [Comparative Example 3] Except that the flash-melting electrolytic gold plating solution and the thick-layer electrolytic gold plating liquid in Example 1 were replaced with the following components, The electric ore treatment is carried out in the same manner. Thereafter, the evaluation was carried out by the same measurement method as in Example 1. The results are shown together in Table 1. [Composition of the flash-melting electrolytic gold plating solution of Comparative Example 3] Gold cyanide unloading oxalic acid nitrilotriacetic acid 1 g/L (calculated as metal gold) 60 g/L (η 〇 in the above formula (1)) 30 g/L (the compound represented by the above formula (2) is not a dicarboxylic acid but a tricarboxylic acid) (the element of the above formula (2) is not satisfied)

Potassium citrate 100 g/L pH was 6.0 (using 10% by volume of sulfuric acid and 1 Torr of potassium hydroxide to sputum to 6.0.) i ' [Comparative Example 3 thick layer electrolytic gold plating solution Composition] Potassium cyanide potassium oxalate nitrilotriacetic acid 8 g / L (calculated as metal gold) 6 〇 g / L (n ==... 3 〇 g / L in the above formula (1) (the above formula (2) 97105852 29 200848552 The compound is not a dicarboxylic acid but a tricarboxylic acid) (the element of γ in the above formula (2) is not satisfied)

Potassium citrate 80 g/L barium sulphate 15 PPm (calculated as metal ruthenium) pH 6.0 (pH was adjusted with 10% by volume of sulfuric acid and i N potassium hydroxide to achieve 6.0.) i [Comparative Example 4] The electric key treatment was carried out in the same manner as in Example 1 except that the flash-melting electrolytic gold plating solution and the thick-layer electrolytic gold liquid in Example 1 were replaced with the following composition. Thereafter, the evaluation was carried out by the same measurement as in Example 1. The results are shown together in Table 1. [Composition of the flash-melting electrolytic gold plating solution of Comparative Example 4] Potassium cyanide 1 g/L (calculated as metal gold) Sodium acetate 60 g/L (The compound represented by the above formula (1) is not a dicarboxylic acid. Monocarboxylic acid) iminodiacetic acid 30g/L (γ = Η in the above formula (2)

Potassium citrate 80 g/L pH 6.0 (pH was carried out using 10% by volume of sulfuric acid and 1 N of potassium oxide, and the ratio was 6.0.) i ' [Comparative Example 4 Thick Layer Electrolytic Gold Plating Composition] Cyanide Potassium gold 1 g / L (calculated as metal gold) sodium acetate 6 § / L (97105852 30 200848552 compound represented by the above formula (1) is not a dicarboxylic acid but a monocarboxylic acid) iminodiacetic acid 30 g/L (γ = Η in the above formula (2))

Potassium citrate 80 g/L Sulfuric acid 15 ppm (according to metal) pH 6.0 (pH adjusted with 10% by volume of sulfuric acid and 1 N potassium hydroxide to achieve 6.0.) f [Comparative Example 5 The electroplating treatment was carried out in the same manner as in Example 1 except that the flash-melting electrolytic gold plating solution and the thick-layer electrolytic gold liquid in Example 1 were replaced with the following composition. Thereafter, the same measurement method as in Example 1 was used for evaluation. The results are shown together in Table 1.

[Composition of the flash-melting electrolytic gold plating solution of Comparative Example 5] Potassium cyanide 1 g/L (calculated as metal gold) Sodium citrate 60 g/L (The compound represented by the above formula (1) is not a dicarboxylic acid. Is a tricarboxylic acid) imine diacetic acid 30g / L (in the above formula (2)

Potassium citrate 80 g/L pH 6.0 (pH Η was adjusted with 10% by volume of sulfuric acid and 1 Torr of potassium hydroxide to achieve 6.0.) ι ' [Comparative Example 5 Thick Electrolytic Gold Plating Composition] Cyanide Potassium citrate 1 g / L (calculated as metal gold) 6 〇 g / L (97105852 31 200848552 compound represented by the above formula (1) is not a dicarboxylic acid but a tricarboxylic acid) Potassium citrate acetate

30 g / L (γ = Η in the above formula (2)) 80 g / L barium sulfate pH is 6 · 0 15 ppm (based on metal ruthenium) (Adjust pH with 10% by volume of sulfuric acid and 1N potassium hydroxide (Comparative Example 6) Electroplating treatment was carried out in the same manner as in Example 除 except that the flash-melting electrolytic gold plating solution and the thick-layer electrolytic gold plating liquid in Example 1 were replaced with the following components. . Thereafter, the same measurement method as in Example = was used for evaluation. The results are shown together in Table 1. [Composition of the flash-melting electrolytic gold plating solution of Comparative Example 6] Potassium cyanide potassium succinate glycine 1 g/L (calculated as metal gold) 6 〇 g / L (n> in the above formula (1) 2) M g/L (the compound represented by the above formula (2) is not a dicarboxylic acid but a monocarboxylic acid)

Potassium citrate 80 g/L pH was 6.0 (using pH 10% by weight of sulfuric acid and 1 Torr of potassium hydroxide to bring the pH to 6 · 0.). $ [Compound composition of thick layer electrolytic gold plating solution of Comparative Example 6] Potassium cyanide 1 g/L (calculated as metal gold) Sodium succinate 60 g/L (97105852 32 in the above formula (1) 200848552 Glycine 30 g /L (the compound represented by the above formula (2) is not a dicarboxylic acid but a monocarboxylic acid)

Potassium citrate 80 g/L Barium sulphate 15 ppm (based on metal ruthenium) pH 6.0 (pH adjusted with 10% by volume of sulfuric acid and 1 N argon oxynitride to achieve 6 · 0.) [Table 1]

No. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 0.30 0.30 0.31 0.30 0.31 0.30 0.30 0.30 Film thickness of gold film β m β m β m β m β m β m β m β m solder ball determination number 70 70 70 70 70 70 70 70 solder balls joint strength average 2090 g 2044 g 2077 g 2038 g 2031 g 2093 g 2055 g 2054 g No. Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 0.29 0.30 0.30 0.31 0.30 0.30 Film thickness of gold film μ m β m β m β m β m β m Number of solder balls 70 The average value of 70 70 70 70 70 70 solder balls 1906 g 1924 g 1874 g 1875 g 1863 g 1814 g degree will be determined according to the above "Method for Judging the Significant Difference of Solder Ball Bond Strength" The results are shown in Figure 3. In Fig. 3, "each pair of Student's t-test 0.05" is a measure of the relationship between the pairs, the difference between the average turns, and the difference between the pairs. In Fig. 3, the examples and comparative examples were clearly distinguished by solder ball bonding strength 2000 (gf). It shows that the bonding strength of the solder balls of the embodiment and the comparative example is significantly inferior. The solder ball bonding strength of the embodiment is significantly higher than that of the solder ball of the comparative example, and does not concentrate on the uneven bonding strength of the solder balls in the embodiment. . 97105852 33 200848552 According to the measurement results, it is understood that either the flash electrolytic gold plating solution or the thick layer electrolytic gold liquid is used in any of Examples 1 to 3 and Examples 6 to 8 of the electrolytic gold liquid of the present invention, even if The lead-free solder balls were fused, and the solder joint strength was also significantly better than Comparative Examples 1 to 6 of the prior art. Further, it is understood that when either the flash-melting electrolytic gold plating solution or the thick-layer electrolytic gold plating liquid uses the electrolytic gold plating solution of the present invention, the electrolytic solution of the present invention is also used for both the flash-melting electrolytic gold plating liquid and the thick-layer electrolytic gold plating liquid. In the case of the gold plating solution, the same was true for the error-free solder joint strength (Example 4 and Example 5). Further, in the electrolytic gold plating composition of Comparative Example to Comparative Example 6, neither the flash-melting electrolytic gold plating solution nor the thick-layer electrolytic gold plating liquid used the electrolytic gold plating liquid of the present invention, so that the lead-free solder joint strength was inferior. (Industrial Applicability) Even when the electrolytic gold plating solution of the present invention is used for either a flash electrolytic electrolytic gold plating liquid or a thick electrolytic gold plating liquid towel, the solder joint strength of the Xiang Wu solder ball can be made. Knowing the technology, the f-plating solution of the present invention is widely used in the field of electrolytic nickel plating/gold plating of electronic parts which are used for environmental considerations. The present application is based on Japanese Patent Application No. 2GG7_G43748 filed on Feb. 23, 2007, the entire contents of which are hereby incorporated by reference in its entirety in BRIEF DESCRIPTION OF THE DRAWINGS [Measurement of Solder Ball Bonding Strength] FIG. 1 is a view showing a solder ball test substrate used in Examples and Comparative Examples. 97105852 34 200848552 FIG. 2 is a view showing solder when measuring solder ball joint strength. Fig. 3 is a view showing the results of statistical calculation of the solder ball joint strength measured in the examples and the comparative examples using the statistical analysis software.

97105852 35

Claims (1)

200848552 X. Patent application scope: i An electrolytic gold plating solution characterized in that: (1) a heart acid or a 4 acid salt, and a carboxylic acid or a dicarboxylic acid salt represented by the following formula (7), [Chemical Formula 1] X1OOC~CnH2n~COOX2 (1) [In the formula 2 (1), _CnH2n_ represents a stretching group which may have a straight chain or a side chain; χ1 and X may be the same or different from each other, and represent H, NmNH4; η represents a natural number above 0] [Chemical 2] (2) X3OOCH2C - Ν-CH2COOX4 Y [In the formula (2), 'X3 and X4 may be the same or different from each other, and represent h, Na ' K or NH 4 ; Y represents a hydrogen atom, a burnt group or a thiol group] . 2. The electrolytic gold plating solution according to the scope of the patent application, wherein the gold cyanide salt is a gold cyanide metal or a gold ammonium cyanide. 3. The electrolytic gold plating solution according to item 2 of the patent application, wherein the cyanide disk salt is sodium cyanide sodium, potassium cyanide, ammonium gold cyanide, gold sodium cyanide, gold oxide or cyanide Gold I. 4. The electrolytic gold plating solution according to claim 1, wherein the dicarboxylic acid or dicarboxylic acid salt represented by the above formula (1) is oxalic acid, sodium oxalate, potassium oxalate or oxalic acid. Ammonium, malonic acid, sodium malonate, potassium malonate, ammonium malonate, succinic acid, sodium succinate, potassium succinate, ammonium succinate, glutaric acid, potassium glutarate, pentane Sodium diacid, ammonium glutarate, adipic acid, sodium adipate, adipic acid 97105852 36 200848552 Potassium, ammonium adipate, pimelic acid, sodium pimelate, potassium pimelate, ammonium pimelate, Suberic acid, sodium dioctylate, potassium suberate, ammonium suberate, azelaic acid, sodium sebacate, potassium sebacate, sebacic acid, azelaic acid, sodium azelaic acid, sebacic acid Potassium or ammonium sebacate. • 5. The electrolytic gold plating solution according to item 1 of the patent application, wherein the dicarboxylic acid or dicarboxylic acid salt represented by the above formula (2) is iminodiacetic acid, disodium iminodiacetic acid, or sub Dipotassium aminodiacetic acid, diammonium iminodiacetic acid, decyl imidodiacetic acid, disodium decyl imidodiacetic acid, fluorenyl imidodiacetic acid f-unloaded, fluorenyl imido Diacetic acid diacetate, ethylimidodiacetic acid, disodium ethylimidodiacetic acid, dipotassium ethyliminodiacetic acid, diammonium ethylimidodiacetic acid, propyliminodiacetic acid , disodium propyliminodiacetic acid, dipotassium propyliminodiacetic acid, diammonium propyliminodiacetic acid, butyliminodiacetic acid, disodium butyliminodiacetic acid, butyl Dipotassium iminodiacetate, diammonium butylimidodiacetic acid, pentyliminodiacetic acid, disodium pentylimidodiacetic acid, dipotassium pentylimidate diacetate, amyl Idiammonium diamine diamine, hydroxymercapto iminodiacetic acid, disodium hydroxymethyliminodiacetic acid, dipotassium hydroxymethyliminodiacetic acid, hydroxymethylimine Diammonium diacetate, hydroxyethyliminodiacetic acid, disodium hydroxyethyliminodiacetic acid, dipotassium hydroxyethyliminodiacetic acid, diammonium hydroxyethyliminodiacetic acid, hydroxypropyl Iminodiacetic acid, disodium hydroxypropylimidodiacetic acid, dipotassium hydroxypropyliminodiacetic acid, diammonium hydroxypropyliminodiacetic acid, hydroxybutylimidodiacetic acid, hydroxyl Disodium butyl iminodiacetic acid, dipotassium hydroxybutyl iminodiacetic acid, diammonium hydroxybutyl iminodiacetic acid, hydroxypentylimido diacetic acid, transylpentyl imine 97105852 37 200848552 Disodium bisacetate, dipotassium pentyl iminodiacetate or diammonium hydroxypentylimidate diacetate. A gold film obtained by electrolytic gold plating using an electrolytic gold plating solution according to any one of claims 1 to 5 is obtained. 7. A method of producing a gold film, characterized in that the electroless gold is deposited on a nickel plating film using an electrolytic gold plating solution according to any one of claims 1 to 5. 'It is characterized in that it is applied to the nickel-plated film by using the electrolytic gold plating solution of any one of the applications. 8. The gold enamel on the nickel film is obtained by electrolytic gold plating in the first to fifth patent ranges. 97105852 38