High granulated agent replenishing solution for plating solution, and method for producing tin-based plated product

Abstract

To provide a fine granulated agent replenishing liquid for a plating liquid, with the replenishing liquid being excellent in the initial stability and safety, and the replenished plating liquid being excellent in the aging stability, without damaging the appearance of a plating film when replenished for a long period of time nor dissolving an organic resist film present on a material to be plated.SOLUTION: A fine granulated agent replenishing liquid for a plating liquid, replenishing a fine granulated agent to a tin-based plating solution including one or two or more kinds of compounds selected from the group consisting of benzaldehyde, 1-naphthaldehyde, 1-naphthoic acid, 1-acetonaphthone, DL-1-(1-naphthyl)ethylamine, and benzylidene acetone, includes a phenyl glycol-based surfactant, the fine granulated agent and water, with a content of the fine granulated agent therein being in a range of 0.1 g / L or more and 10.0 g / L or less, a content of the phenyl glycol-based surfactant therein being in a range of 5 g / L more and 50 g / L or less, and a content of alcohol being less than 1 mass%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a plating solution atomizing agent replenisher used when replenishing a tin-based plating solution containing an atomizing agent with the atomizing agent, and a method for producing a tin-based plated product using the plating solution atomizing agent replenisher. [Background technology]

[0002] In tin-based plating solutions (e.g., tin plating solutions, tin-copper alloy plating solutions, tin-silver plating solutions, tin-bismuth plating solutions, etc.) used to form tin-based plating films on the surface of substrates, various additives are essential to obtain good plating films by electroplating. Components of these additives include atomizing agents. Here, as disclosed in Patent Document 1, for example, substances that are relatively poorly soluble in water, such as benzaldehyde, naphthaldehyde, and benzylidene acetone, are used as atomizing agents.

[0003] The atomizing agent in the tin-based plating solution tends to decrease when the tin-based plating solution is continuously used in electroplating to form a plating film. When the tin-based plating solution is used for a long period of time, in order to maintain a constant quality of the plating film, it is necessary to replenish the amount of atomizing agent that has decreased or to replace the entire tin-based plating solution in the electroplating equipment. Here, replenishing the atomizing agent has the advantage of reducing costs and environmental loads compared to replacing the entire plating solution.

[0004] When replenishing the atomizing agent to take advantage of this advantage, since the atomizing agent is water-insoluble, it is difficult to dissolve even if it is added directly to the aqueous solution. On the other hand, since the atomizing agent is soluble in organic solvents such as alcohol, it can be replenished to the plating solution without any problems if it is dissolved in water-soluble alcohol.

[0005] Here, organic solvents such as alcohol have a low flash point and are treated as dangerous materials under the Fire Service Act, so depending on the working environment of electroplating, it may be difficult to replenish the atomizing agent dissolved in alcohol or the like. In addition, under the Fire Service Act's exceptions to hazardous materials, saturated primary alcohols with 1 to 3 carbon atoms per molecule are excluded from Class 4 hazardous materials if the alcohol content is less than 60% by mass and the flash point is above 60°C. Therefore, if ion-exchanged water is added to such alcohol to make an aqueous solution and then the atomizing agent is dissolved in it, it is possible to reduce, even if only slightly, the barriers in the work environment for supplying the atomizing agent.

[0006] However, if the content of the organic solvent in the replenisher is reduced by this aqueous solution, the precipitation or deposition of the atomizing agent is likely to occur, which may reduce the stability of the replenisher. Therefore, if a surfactant that helps to solubilize the atomizing agent is used in combination with alcohol, this concern can be resolved and the stability of the replenisher can be improved.

[0007] When selecting this surfactant, even if a common surfactant such as polyethylene glycol (PEG) is used, the solubilizing power of the atomizing agent is insufficient and little effect can be expected. Furthermore, when a tin-based plating solution is used for a long period of time, the surfactant components do not decrease, and the surfactant concentration in the solution increases relatively, which may adversely affect plating properties. Therefore, there was a need for a surfactant with high solubilizing power that can dissolve the atomizing agent even when used in small proportions.

[0008] Here, Patent Document 2 proposes a replenisher liquid that contains a saturated primary alcohol having 1 to 3 carbon atoms as an organic solvent, polyoxyethylene naphthyl ether as a surfactant, and an additive (brightener), in which the saturated primary alcohol is contained in a proportion of less than 60% by mass relative to 100% by mass of the replenisher liquid. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-044001 [Patent Document 2] Japanese Patent Publication No. 2020-076120 Summary of the Invention [Problem to be solved by the invention]

[0010] However, the replenishment solution described in Patent Document 2 contains a relatively large amount of saturated primary alcohol, and as the solution is replenished, the alcohol accumulates in the plating solution, increasing the alcohol concentration, which has the property of dissolving the organic resist film on the object to be plated (hereinafter referred to as resist attack property), and there is a risk that plating cannot be carried out stably. Furthermore, if decomposition products of the atomizing agent accumulate in the plating bath, the decomposition products may precipitate in the plating bath due to the evaporation of alcohol, and may adhere to the object to be plated, resulting in plating defects. Furthermore, the amount of impurities in the plating film may increase, which may result in deterioration of the properties of the plating film.

[0011] The present invention has been made in view of the above-mentioned circumstances, and has as its object to provide a plating solution atomizing agent replenisher which has excellent initial stability and safety as a replenisher, excellent stability over time of the replenished plating solution, does not impair the appearance of the plating film even when replenished over a long period of time, and does not dissolve the organic resist film on the object to be plated, and a method for manufacturing a tin-based plated material using this plating solution atomizing agent replenisher. [Means for solving the problem]

[0012] In order to solve the above-mentioned problems, the plating solution atomizing agent replenisher liquid of Aspect 1 of the present invention is a plating solution atomizing agent replenisher liquid for replenishing a tin-based plating solution containing, as an atomizing agent, one or more compounds selected from the group consisting of benzaldehyde, 1-naphthaldehyde, 1-naphthoic acid, 1-acetonaphthone, DL-1-(1-naphthyl)ethylamine and benzylideneacetone, said atomizing agent, and characterized in that it contains a phenyl glycol-based surfactant, said atomizing agent and water, the content of said atomizing agent being in the range of 0.1 g / L or more and 10.0 g / L or less, the content of said phenyl glycol-based surfactant being in the range of 5 g / L or more and 50 g / L or less, and the content of alcohol being less than 1 mass %.

[0013] According to the first aspect of the present invention, the plating solution atomizing agent replenisher contains a phenyl glycol surfactant, the atomizing agent, and water. The atomizing agent content is in the range of 0.1 g / L to 10.0 g / L, the phenyl glycol surfactant content is in the range of 5 g / L to 50 g / L, and the alcohol content is less than 1 mass %. Therefore, the atomizing agent is sufficiently dissolved by the phenyl glycol surfactant, and the plating solution atomizing agent replenisher replenisher has excellent initial stability and safety, and the replenished plating solution has excellent stability over time. Furthermore, the precipitation of decomposition products of the atomizing agent in the plating bath (tin-based plating solution) is suppressed, allowing for stable plating work. Furthermore, the incorporation of impurities into the formed plating film is suppressed, allowing for the formation of a high-quality plating film with excellent characteristics. Furthermore, plating can be performed stably without dissolving the organic resist film on the plated object.

[0014] The plating solution atomizing agent replenisher of aspect 2 of the present invention is characterized in that, in the plating solution atomizing agent replenisher of aspect 1, the phenyl glycol surfactant is polyoxyethylene phenyl ether represented by the following general formula (1), where n is 2 or more. [ka]

[0015] According to the plating solution atomizing agent replenisher solution of aspect 2 of the present invention, the phenyl glycol surfactant is polyoxyethylene phenyl ether represented by formula (1) (where n is 2 or more), and therefore the atomizing agent (one or more compounds selected from the group consisting of benzaldehyde, 1-naphthaldehyde, 1-naphthoic acid, 1-acetonaphthone, DL-1-(1-naphthyl)ethylamine, and benzylideneacetone) can be dissolved more satisfactorily. Therefore, the initial stability and safety of the replenisher solution are excellent, and the stability of the replenished plating solution over time is particularly excellent.

[0016] A method for producing a tin-based plated product according to a third aspect of the present invention is a method for producing a tin-based plated product in which a tin-based plating film is formed on the surface of a substrate using a tin-based plating solution, wherein the tin-based plating solution contains, as a grain refiner, one or more compounds selected from the group consisting of benzaldehyde, 1-naphthaldehyde, 1-naphthoic acid, 1-acetonaphthone, DL-1-(1-naphthyl)ethylamine, and benzylideneacetone, and when the grain refiner in the tin-based plating solution reaches a predetermined concentration or less, the plating solution grain refiner replenisher according to the first or second aspect is replenished to the tin-based plating solution.

[0017] According to the method for producing a tin-based plated product of the third aspect of the present invention, when the concentration of the atomizing agent in the tin-based plating solution reaches a predetermined concentration or less, the plating solution atomizing agent replenisher of the first or second aspect is replenished to the tin-based plating solution. Therefore, the concentration of the atomizing agent in the tin-based plating solution is adjusted to be within a predetermined range, and it becomes possible to stably form a high-quality plating film with excellent characteristics. [Effects of the Invention]

[0018] According to the present invention, it is possible to provide a plating solution atomizing agent replenisher that is excellent in initial stability and safety, and that provides excellent stability over time of the replenished plating solution, does not impair the appearance of the plating film even when replenished over a long period of time, and does not dissolve the organic resist film on the object to be plated, and a method for manufacturing a tin-based plated material using this plating solution atomizing agent replenisher. [Brief explanation of the drawings]

[0019] [Figure 1] FIG. 2 is a cross-sectional view showing the thickness of a polyimide (PI) film before a plating film is formed using a plating solution and the thickness of a dry film resist (DFR) formed thereon in an example. [Figure 2] FIG. 2 is a plan view of a wafer having a resist layer prepared for evaluation in the examples. DETAILED DESCRIPTION OF THE INVENTION

[0020] Hereinafter, a plating solution atomizing agent replenisher solution and a method for producing a tin-based plated product according to an embodiment of the present invention will be described.

[0021] [Replenishing solution for atomizing agent for plating solution] The plating solution atomizing agent replenisher of this embodiment is used when replenishing the above-mentioned atomizing agent to a tin-based plating solution containing, as an atomizing agent, one or more compounds selected from the group consisting of benzaldehyde, 1-naphthaldehyde, 1-naphthoic acid, 1-acetonaphthone, DL-1-(1-naphthyl)ethylamine, and benzylideneacetone. The tin-based plating solution may be a pure tin plating solution or a tin alloy plating solution, such as a tin-copper alloy plating solution, a tin-silver plating solution, or a tin-bismuth plating solution.

[0022] The plating solution atomizing agent replenisher of this embodiment contains a phenyl glycol surfactant, the above-mentioned atomizing agent, and water. The content of the atomizing agent is set to be within the range of 0.1 g / L or more and 10.0 g / L or less, the content of the phenyl glycol surfactant is set to be within the range of 5 g / L or more and 50 g / L or less, and the content of alcohol is set to be less than 1 mass % relative to 100 mass % of the plating solution atomizing agent replenishment solution.

[0023] Here, in the plating solution atomizing agent replenishment liquid of this embodiment, if the content of the atomizing agent is less than 0.1 g / L, the frequency of replenishment work using this plating solution atomizing agent replenishment liquid increases, and the plating solution is diluted by the replenishment, which may cause changes in the concentrations of other components. On the other hand, if the content of the atomizing agent exceeds 10.0 g / L, the stability of the plating solution over time may decrease. For this reason, in this embodiment, the content of the atomizing agent in the plating solution atomizing agent replenishment liquid is set within the range of 0.1 g / L or more and 10.0 g / L or less. The lower limit of the content of the atomizing agent is preferably 0.1 g / L or more, more preferably 0.5 g / L or more, and the upper limit of the content of the atomizing agent is preferably 10.0 g / L or less, more preferably 5.0 g / L or less.

[0024] In the plating solution atomization agent replenisher of this embodiment, if the content of the phenyl glycol-based surfactant is less than 5 g / L, the solubilizing power of the atomization agent becomes insufficient, and the atomization agent may not be sufficiently dissolved. On the other hand, if the content of the phenyl glycol-based surfactant exceeds 50 g / L, a large amount of the phenyl glycol-based surfactant will be present in the tin-based plating solution after replenishment, and there is a risk that a high-quality plating film with excellent characteristics may not be stably formed. For this reason, in this embodiment, the content of the phenyl glycol surfactant in the plating solution atomizing agent replenisher is set within the range of 5 g / L or more and 50 g / L or less. The lower limit of the content of the phenyl glycol surfactant is preferably 5.0 g / L or more, more preferably 10.0 g / L or more in order to fully dissolve the atomizing agent, and the upper limit of the content of the phenyl glycol surfactant is preferably 50.0 g / L or less, more preferably 40.0 g / L or less in order to prevent the surfactant from accumulating in the plating solution.

[0025] In the plating solution atomizing agent replenisher of this embodiment, if the alcohol content is 1 mass % or more, the alcohol concentration in the plating bath (tin-based plating solution) increases due to the replenishment, which may dissolve the organic resist film. In addition, the evaporation of alcohol may reduce the long-term stability of the plating solution atomizing agent replenisher and the replenished plating bath (tin-based plating solution). For this reason, in this embodiment, the content of alcohol in the plating solution atomizing agent replenisher is set to less than 1 mass %. The upper limit of the alcohol content is preferably 1.0% by mass or less, and more preferably 0.8% by mass or less. There is no particular lower limit to the alcohol content, and it may be 0% by mass.

[0026] Here, in the plating solution atomizing agent replenisher liquid of this embodiment, the phenyl glycol surfactant is preferably polyoxyethylene phenyl ether represented by the above formula (1). By using polyoxyethylene phenyl ether as the phenyl glycol surfactant, it becomes possible to reliably dissolve the atomizing agent.

[0027] [Method for preparing a replenisher solution for atomizing agent for plating solution] The plating solution atomizing agent replenisher of this embodiment is prepared, for example, by adding and dissolving the above-mentioned atomizing agent in water as a solvent, and then dissolving a phenyl glycol-based surfactant in this solution. In preparation, the amount of each component added is determined so as to be the content ratio in the plating solution atomizing agent replenisher.

[0028] [Method for producing tin-based plated products] The method for producing a tin-based plated product of this embodiment involves forming a tin-based plating film on the surface of a substrate using a tin-based plating solution containing, as a grain refiner, one or more compounds selected from the group consisting of benzaldehyde, 1-naphthaldehyde, 1-naphthoic acid, 1-acetonaphthone, DL-1-(1-naphthyl)ethylamine, and benzylideneacetone.

[0029] When plating is carried out using the above-mentioned tin-based plating solution, the grain refiner is consumed, and the concentration of the grain refiner in the plating bath (tin-based plating solution) decreases. Therefore, in the method for producing a tin-based plated product of this embodiment, when the concentration of the atomizing agent in the tin-based plating solution reaches a predetermined concentration or less, the above-mentioned plating solution atomizing agent replenisher of this embodiment is replenished to the tin-based plating solution, thereby adjusting the concentration of the atomizing agent in the plating bath (tin-based plating solution) to a certain range.

[0030] In addition, a measurement sample may be taken from a plating bath (tin-based plating solution) in operation, and the concentration of the atomizing agent may be calculated by analyzing the plating solution components, and the atomizing agent replenisher for plating solution of this embodiment may be replenished when this concentration falls below a predetermined standard. Methods for calculating the concentration of the atomizing agent include analysis using UV and electrochemical measurement such as measurement of a polarization curve. By analyzing, the amount of decrease in the atomizing agent can be accurately calculated. Furthermore, without carrying out the analysis as described above, the filling ability of the tin-based plating solution decreases with the decrease in the concentration of the atomizing agent, and therefore, the plating solution atomizing agent replenisher may be replenished at the time when a decrease in the performance of the tin-based plating solution is observed.

[0031] The atomizing agent replenisher for plating solution of this embodiment configured as described above contains a phenyl glycol surfactant, an atomizing agent, and water, with the atomizing agent content being in the range of 0.1 g / L to 10.0 g / L, the phenyl glycol surfactant content being in the range of 5 g / L to 50 g / L, and the alcohol content being less than 1 mass %. Therefore, the atomizing agent is sufficiently dissolved by the phenyl glycol surfactant, and the replenisher solution has excellent initial stability and safety, and the replenished plating solution has excellent stability over time. In addition, the decomposition products of the atomizing agent are prevented from precipitating in the plating bath (tin-based plating solution), allowing for stable plating operations, and the incorporation of impurities into the formed plating film is prevented, allowing for the formation of a high-quality plating film with excellent characteristics. Furthermore, since the alcohol content is extremely low, it is not classified as a hazardous material under the Fire Service Act, and does not dissolve organic resist films on the object to be plated, allowing for stable plating.

[0032] In the plating solution atomizing agent replenisher of this embodiment, when the phenyl glycol surfactant is polyoxyethylene phenyl ether represented by the above formula (1), the above atomizing agent can be dissolved more satisfactorily, and therefore the initial stability and safety of the replenisher are excellent, and the stability of the replenished plating solution over time is particularly excellent.

[0033] Furthermore, according to the method for producing a tin-based plated product of this embodiment, when the concentration of the atomizing agent in the tin-based plating solution reaches a predetermined concentration or less, the plating solution atomizing agent replenisher of this embodiment is replenished to the tin-based plating solution. Therefore, the concentration of the atomizing agent in the plating bath (tin-based plating solution) is adjusted to be within a predetermined range, and it becomes possible to stably form a high-quality plating film with excellent characteristics.

[0034] Although the embodiment of the present invention has been described above, the present invention is not limited to this and can be modified as appropriate within the scope of the technical idea of ​​the invention. [Example]

[0035] The results of confirmation experiments conducted to confirm the effectiveness of the present invention will be described below.

[0036] (tin plating solution) One liter (L) of Sn plating solution having the following composition was prepared. Sn methanesulfonate (Sn 2+ as): 60g / L Methanesulfonic acid (as free acid): 120g / L Polyoxyethylene laurylamine (as surfactant): 15g / L 1-Naphthaldehyde: 0.05g / L Catechol: 0.9g / L Isopropanol: 5g / L Ion-exchanged water: balance

[0037] (Replenishing agent for plating solution) The atomizing agent replenishment liquid for plating solution of the present invention and the comparative example was prepared by mixing the atomizing agent, surfactant, alcohol, and water (ion-exchanged water) in the prescribed ratio so as to have the composition shown in Table 1.

[0038] The obtained plating solution atomizing agent replenisher solutions of the present invention and comparative examples were evaluated as follows.

[0039] (Initial and aging stability of the replenisher for plating solution) To evaluate the initial stability and stability over time of the plating solution atomizing agent replenisher, the target solution samples were sealed in transparent glass bottles immediately after preparation and one month after preparation. The bottle was stored at a low temperature (5°C), a room temperature (25°C), and a high temperature (35°C), and the appearance of the liquid was visually inspected. In visual inspection, if the sample was transparent compared to ion-exchanged water at all temperatures of 5°C, 25°C, and 35°C, it was judged as "good," and if cloudiness or precipitation was present at any temperature, it was judged as "poor." Furthermore, even if the sample appeared transparent to the naked eye, if scattered light was observed when light was irradiated at any temperature, it was judged as "slightly poor."

[0040] (Dangers of replenishment solution for atomizing agents for plating solutions) The obtained plating solution atomization agent replenisher was evaluated in accordance with the Ministry of Internal Affairs and Communications Fire and Disaster Management Agency's Class 4 Hazardous Material Verification Test, and was judged as "good" if it fell under the category of "non-hazardous material" or "designated flammable material," and was judged as "poor" if it fell under the category of "Class 4 Hazardous Material." The flash point, combustion point, and kinematic viscosity were measured as follows. Flash point measurement: Tag closed type, Seta closed type, and Creepland open type are all performed in accordance with JIS K 2265. Combustion point measurement: Creep land open type, performed in accordance with JIS K 2265. Dynamic viscosity measurement: Performed in accordance with JIS K 2283.

[0041] (Bump appearance) While continuing electroplating using the Sn plating solution having the above-mentioned composition, when a decrease in the filling property of the bumps was observed and a decrease in the amount of the refiner was confirmed by electrochemical measurement, the refiner replenisher for plating solution of the present invention example and the comparative example was replenished. While preparing the solution as described above, plating was carried out continuously for 15 hours at a current density of 3ASD. Using the plating solution after the continuous plating process, plating was carried out on a wafer with a recessed area consisting of a dry film resist (DFR) film thickness (T1) of 56 μm and a polyimide (PI) film thickness (T2) of 10 μm, as shown in Figure 1. When visually inspecting the appearance, if there were no abnormal deposits such as lumps or burns, and when visually inspecting the bottom of the recessed area, if the plating was smooth and the hole was filled, it was judged to be "good." If there was a recess in the center of the bump or if abnormal deposits were observed on the edge of the bump, it was judged to be "poor."

[0042] (presence or absence of voids in the bump) An electrically conductive seed layer of 0.1 μm titanium and 0.3 μm copper was formed on the surface of an 8-inch wafer by sputtering, and a dry film resist (50 μm thick) was laminated on top of the seed layer. The dry film resist was then partially exposed to light through an exposure mask and then developed. In this way, as shown in Figure 2, a resist layer 3 was formed on the surface of the wafer 1, with a pattern of openings 2 with a diameter of 75 μm formed at different pitch intervals: a: 150 μm, b: 225 μm, and c: 375 μm.

[0043] The wafer 1 on which the resist layer 3 was formed was immersed in a plating device (dip-type paddle stirring device), and the openings 2 in the resist layer 3 were plated under the conditions of a plating solution temperature of 27°C and a current density of 3ASD. The plating solution was prepared using the plating solution refiner replenisher solutions of the present invention and the comparative example, and the plating treatment was carried out continuously for 15 hours at a current density of 3 ASD, and the plating solution after the continuous plating treatment was used.

[0044] Next, the wafer 1 was removed from the plating equipment, washed, and dried, and then the resist layer 3 was stripped off using an organic solvent. In this way, a bumped wafer was produced in which bumps with a diameter of 75 μm were formed in one die in a pattern arranged at different pitch intervals of 150 μm, 225 μm, and 375 μm. The target plating film thickness (bump height) was 25 μm. The bumped wafer was placed in a reflow equipment and heated to 250°C to melt the bumps. After cooling, the bumps (1000 in total) arranged at pitch intervals of 150μm, 225μm, and 375μm were subjected to transmission X-ray images at a magnification of 50x. The images were visually inspected, and if one or more voids with a size of 1% or more of the bump size were observed, it was judged as "voids present," and if no voids were observed, it was judged as "voids absent."

[0045] (Resist attack resistance) As shown in the embodiment, the wafer on which the resist layer was formed was immersed in a plating device (dip-type paddle stirrer), and the openings in the resist layer were plated under the conditions of a plating solution temperature of 27°C and a current density of 3ASD. The plating solution was prepared using the plating solution refiner replenisher solutions of the present invention and the comparative example, and the plating treatment was carried out continuously for 15 hours at a current density of 3 ASD, and the plating solution after the continuous plating treatment was used. The plating solution used in the above plating process was analyzed by high performance liquid chromatography (HPLC), and when component peaks of the resist layer were detected, it was judged as "poor", and when no component peaks were observed, it was judged as "good".

[0046] [Table 1]

[0047] [Table 2]

[0048] In Comparative Example 1, the alcohol content was as high as 5.0% by mass, and the product was evaluated as being unsafe and could not be handled easily. Also, the resist attack resistance was poor. In Comparative Example 2, since no surfactant was contained, the atomizing agent could not be sufficiently dissolved, resulting in poor initial stability and long-term stability. In addition, the atomizing agent could not be sufficiently replenished to the plating solution, resulting in poor bump appearance.

[0049] In Comparative Example 3, the content of the atomizing agent was as low as 0.05 g / L, and the atomizing agent could not be sufficiently replenished to the plating solution, resulting in poor bump appearance. In Comparative Example 4, the content of the atomizing agent was as high as 15.0 g / L, and a large amount of undissolved atomizing agent was present, resulting in poor initial stability and stability over time.

[0050] In Comparative Example 5, the surfactant content was as low as 2.0 g / L, and the atomizing agent could not be sufficiently dissolved, resulting in poor initial stability and stability over time. In addition, the atomizing agent could not be sufficiently replenished to the plating solution, resulting in poor bump appearance. In Comparative Example 6, the surfactant content was as high as 60.0 g / L, and a large amount of surfactant was present in the plating solution after replenishment, resulting in poor bump appearance.

[0051] In Comparative Example 7, since alcohol is used as a solvent instead of water, the atomizing agent can be dissolved without using a surfactant, but since it contains a large amount of alcohol, the evaluation of danger is poor, and it is not easy to handle. Also, the resist attack property is poor.

[0052] In Comparative Examples 8 and 9, since a phenyl glycol surfactant was not used as the surfactant, the atomizing agent could not be sufficiently dissolved, resulting in poor initial stability and long-term stability. In addition, the atomizing agent could not be sufficiently replenished to the plating solution, resulting in poor bump appearance. In Comparative Example 10, although no phenyl glycol surfactant was used as the surfactant, the content was high, so the initial stability and stability over time were good. However, because the surfactant accumulated and plating properties changed, the bump appearance became poor and voids were also observed.

[0053] In contrast, in Examples 1 to 7 of the present invention, the content of the atomizing agent was in the range of 0.1 g / L to 10.0 g / L, the content of the phenyl glycol surfactant was in the range of 5 g / L to 50 g / L, and the content of alcohol was less than 1 mass%, so that the initial stability and stability over time were excellent, the risk assessment was good, and the handling was easy. In addition, the bump appearance, voids, and resist attack resistance were also good, and high-quality plating films could be stably formed.

[0054] From the results of the above confirmatory experiments, it was confirmed that the present invention can provide a plating solution atomizing agent replenisher that is excellent in initial stability and safety of the empty replenisher, and excellent in stability over time of the replenished plating solution, does not impair the appearance of the plating film when replenished over a long period of time, and does not dissolve the organic resist film on the object to be plated, as well as a method for manufacturing a tin-based plated material using this plating solution atomizing agent replenisher.

Claims

1. A plating solution atomization agent replenisher for tin-based plating solutions, which contains one or more compounds selected from the group consisting of benzaldehyde, 1-naphthaldehyde, 1-naphthoic acid, 1-acetonaphthone, DL-1-(1-naphthyl)ethylamine, and benzylideneacetone as atomization agents, and which replenishes the atomization agent to the tin-based plating solution, A phenyl glycol surfactant, the atomizing agent, and water are included, a content of the atomizing agent in the range of 0.1 g / L or more and 10.0 g / L or less, a content of the phenyl glycol-based surfactant in the range of 5 g / L or more and 50 g / L or less, and an alcohol content of less than 1 mass %.

2. 2. The plating solution atomizing agent replenisher according to claim 1, wherein the phenyl glycol surfactant is polyoxyethylene phenyl ether represented by the following general formula (1): In formula (1), n ​​is 2 or more. 【Chemical 1】

3. A method for producing a tin-based plated product in which a tin-based plating film is formed on a surface of a substrate using a tin-based plating solution, comprising: The tin-based plating solution contains, as a particle-refining agent, one or more compounds selected from the group consisting of benzaldehyde, 1-naphthaldehyde, 1-naphthoic acid, 1-acetonaphthone, DL-1-(1-naphthyl)ethylamine, and benzylideneacetone; 3. A method for producing a tin-based plated product, comprising: replenishing the plating solution atomization agent replenisher according to claim 1 or 2 to the tin-based plating solution when the concentration of the atomization agent in the tin-based plating solution reaches a predetermined concentration or less.

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