TWI301515B - Surface treating agent of metal - Google Patents

Description

1301515 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a surface treatment agent for metals, particularly Sn and alloys, and a surface treatment method using the surface treatment agent. Furthermore, the present invention relates to an electronic component, a substrate, a solder ball, a solder powder (sc> ider pGwder), and a ball grid array (10) using the solder ball by the surface treatment method: a ball grid Machi (4), the use of the solder powder, the tin 13b, and the use of the surface treatment agent. [Prior Art] The splicing system is a technique for joining objects between objects with low smudges, and is widely used in the art of joining and grouping of electronic machines in the modern industry. -: The solder used is (4) alloy, its eutectic composition (s/ to the melting point is as low as the boot, so the welding system is applied under 220 = C), so it will hardly cause heat for electronic parts or substrates. In addition, Sn-Pb is in + new mesh female># D σ金 has the characteristics of good weldability, • r=:tr is solidified, and even if vibration is applied to the tan joint, it is difficult to cause turtles. The advantages of cracking or peeling. A synthetic tree wax and a conductor such as a frame or a substrate are formed by the busy sea, and almost all of the waste disposal is buried underground. In recent years, the 卩 卩 人 允 允 允 允 允 允 、 、 、 、 、 、 、 、 、 When the rain drops to the ground, it shows the detection of acidity (S Wenyu), which will cause problems in the groundwater staining. Therefore, the special::: Tan Xi dissolves, so that the pollution in隹S deducts τ people J is in the electronic equipment industry, Zhengyuan; ^ instead of the wrong solder (no antimony tin) replacement trend. The external wire terminal m of the tweezers parts is soaring its solder infiltration 316814 5 1301515 sex and coffee, mainly The implementation of soldering iron ore (Sn 9〇%, the rest for this), and the goal can be achieved without error. No error soldering iron ore Although the candidate materials can be roughly classified into pure Sn, Sn-Ag (CU), and Sn_Zn, each has its advantages and disadvantages, and has not yet completely replaced the alloy. Pure Sn plating, cost or plating workability, etc. On the whole, it is best to use the error-free electric ore. However, the Sn electric ore layer is easy to produce metal (tin) due to surface oxidation or deer force, and the solder wettability is easy to deteriorate with time. It is strongly demanded to improve. Because of the melting point of the Sn-Zn alloy and the conventional Sn, the alloy is advantageous in that it does not need to change the current equipment or process. Also, the mechanical strength of the film is excellent. Zn is also active. However, Zn is active:: It is easy to oxidize. Because Sn-Zn alloy has poor weld wettability, it is considered to be the least likely to be put into practical use at present. Solder paste is Used to mount the surface of electronic parts on the substrate, its use has increased greatly in recent years. Solder pastes are generally based on solder alloy powders, plus additives, active agents, shakers, surfactants, refrigerants. Temple fluxer. Solder In the lead-free solder paste, the %/CIO-based alloy, the Sn-Zn-based alloy, and the Sn_Bi-based alloy were studied. However, the =-曰Zn-based alloy was as described above because of the eutectic near the conventional Sn_pi-based solder. The temperature is the best candidate for substitution. However, as described above, since Zn is easily oxidized, the Sn_Zn-based alloy is used as the solder paste of the solder powder and the active agent contained in the flux generates an oxidation reaction, and the solder wettability is obtained. The preservation of the virginity will be abrupt, so there will be a disadvantage of inert gas when reflowing." 316814 6 1301515 t · Corresponding to these problems, the special wish 2002-304554 has one or two of its salt. The inventors of the present invention have a surface treatment agent which is characterized in that it is characterized by an acid phosphate of a saturated or unsaturated alkyl group and a proposal 2 (Japanese Patent Laid-Open No. Hei 7-189942). It is composed of acid diphenyl vinegar. The phosphoric acid (tetra)(tetra)acid 3 in the a-base s and/or phosphorous is intended to pass the antioxidant effect of the higher temperature. Therefore, in the above technique, it is generally difficult to heat and dry the solder which is higher than the conventional one. Oxidation of a tin-corresponding material of a tin-based alloy material Patent Document 2: Patent Document 2: [Patent Document 2] Japanese Patent Application No. 2002-304554, Japanese Patent Application No. Hei No. 7-188942 In particular, % and such surface treatment agents which are resistant to oxidation and improve solder wettability. Further, the object of the present invention is to provide a surface treatment agent which suppresses % and the occurrence of whiskers. Mouth Mengjin, Jinben, and others, for the oxidation of metals, especially % and alloys, have been concentrating on the results and found that they contain more than two phosphonic acid groups in the molecule and do not contain vinegar bonds in the molecule. A surface treatment agent containing one or more of the compound and/or a salt thereof and having a total content of the compound and/or a salt thereof of 0.01 g/L or more is subjected to surface treatment to impart oxidation resistance to 316814 1301515. . Λ, it can be seen that the solder paste containing the surface treated _= tin powder is significantly improved in terms of preservation stability. The surface treatment of Sn and Sn alloys, the occurrence of metal whiskers is greatly affected: system. That is, the present invention is as follows. (!) A metal surface treatment agent which contains one or more of two or more phosphonic acid groups in a molecule and which does not contain a molecule in the molecule: The content of the compound and/or its salt is 0.01 g/L or more in total. (2) A metal surface treatment agent characterized by containing a compound having two or more phosphonic acid groups in the molecule and containing no g bond in the molecule: /曰 or its salt! 2 or more, and 3 of the compound and/or its salt, "heart δ ten is 〇. 01g / L or more; and the pH of the metal surface treatment agent solution is adjusted to 5 or less. (3) (2) The surface treatment agent of the metal according to any one of (1) to (3), wherein the surface treatment agent of the metal is further contained in the range of (1) to (3). A surface treatment agent which has two or more phosphonic acid groups in the above-mentioned molecule and which does not contain an ester bond in the molecule, and/or a salt thereof is represented by the following formula (j), (II) or a compound represented by (III), and/or an alkali metal salt thereof, an ammonium salt, or a salt with an amine compound: Ν 1 Γ X丨C丨γ ί ΟΠΝΡ丨ο ι Ηο Η Η)Ηο ο I Η I Η ο οπρ1ο X2—c—γ2χ3—C—γ3 8 316814 1301515 (in the formula (I), ^ to) ^ and 丫: to ^ may be the same or different, each represents a hydrogen atom, or a carbon number of 1 to 5 Lower alkyl); R1 R3 (Π) r2^>N-[CH2 ~CH2~N]ft~R4 (in formula (II), R, }, and R4 may be the same or different, each representing the following Based on (A), R3 represents the following group (A) or carbon 1-5 lower alkyl group; n is an integer of 1 to 3; the group (a) is:

X1 〇 I II (A)

A C—P—OH I I Y1 OH group (A) towel 'X】 and γ! is the same as defined in the general formula (1); 0X0

II I II (III)

卜 f—C—P—OH I I I

HO Y OH :—(1 ) towel X Table 7F hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms, a hydrogen atom, a lower alkyl group having a carbon number of 1 to 5, a trans group or an amine group). (5) Surface treatment of a metal according to any one of the above (1) to (N), wherein the metal is Sn or a Sn alloy. A surface treatment method which is carried out by the metal surface treatment agent of the above (1) to (5). The (:) electronic component or substrate is characterized in that it is surface-treated in an electronic dressing or substrate_terminal portion (four) ^ (1). ) 烊 烊 solder ball or solder powder, stand " Its buckle is used ··· Use 316814 9 1301515 (6) 表面 载 载 载 载 载 载 έ έ 去 去 去 去 去 去 去 去 去 去 去 去 去 去 去 去 去 去 去 去The 拇 曰 tin ^ 1 ball thumb array ‘ is characterized in that the bad solder ball of the above (8) is used as the electrical connection member. (10) - An 奘 . + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + Solder powder. 〒 月 ' ' 其 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The metal to be treated may be, for example, 6 Nl Co, Cr, Cu, Zn, Sn, Al, Mg, yttrium, Ag, Au, etc., which may be an alloy. The main official U is Sn and Sn alloy, and the Sn alloy is more suitable for environmental pollution. Examples of the alloy containing no lead include, for example, a solder alloy containing Zn, Bi, Cu, In, Ag, Sb or more in Sn. A ^ contains a compound having two or more phosphonic acid groups in one molecule and having no ester bond in the molecule, and/or a salt thereof, and the total content of the compound and/or its salt is 0.01 g/L or more. The surface treatment agent is subjected to surface treatment to impart oxidation resistance to the surface of the treated material and to improve solder wettability. When the amount of the compound having two or more phosphonic acid groups in one molecule and the ester bond is not contained in the molecule, and/or the salt thereof is less than 〇· Olg/L·, the effect is small. On the other hand, even if the amount added is too large, since the characteristics are not deteriorated, the amount of 316814 1301515 5 = upper limit is added, but the amount of addition is preferably ο. (η to 50〇g/L, more preferably 〇. Further, the surface treatment agent of the present invention is obtained by the treatment of the s key generated by the treatment of the ^=H❹ in the molecule without the vinegar bond, even if it is heat-treated by light weighting. It has a sufficient anti-oxidation effect. Therefore, the welding temperature is higher than that of the conventional high-error-free solder, such as Sn& ^, and it can also impart sufficient oxidation resistance. - There are two or more phosphonic acid groups in the molecule. : phosphine = one compound, excellent in oxidation resistance in terms of detailed mechanism = 2. It is preferably from 2 to 6 in one molecule. The number of sulfhydryl groups is more than two phosphines in one molecule. Examples of the compound and/or a salt thereof which are acid-based and intrinsic in the molecule include a compound represented by the following 3-indene or ((1)) and/or a base thereof: a salt of the compound: (11): 1 salt, or with amine φ N 1 13 X丨c丨γ ! οηπριο I Η ο Η Η Η ο ο 一Η I Η ΟΗΡ丨ο οηπρIο 2 - 2 3 - 3 xlc - γ xlc - γ (in the formula (I), the P or MP may be the same or a different atom, or a lower alkyl group having a carbon number of 1 to 5);

Ri f -[CH2 - CH2 - N]n-R4 316814 11 (II) 1301515 (In the formula (II), R1 and RlV may be the same or different and each represents the following group (A); R3 represents the following group (A) or a lower alkyl group having a carbon number of i to 5; η is an integer of 1 to 3; the base (phantom is Η? Ηο= ρ 1 ο X1 - c - γ1

In the base A (A), the 'χι and γι lines are the same as the formula (as defined in u) ο Η Ηοί Η ο = Ρ 丨 ο I X — CIY I Ομηρ

(I ο Η (In the formula (111), χ represents a hydrogen atom or a lower alkyl group having a carbon number of i to 5, and Y 仏 represents a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms, a hydroxyl group or an amine group). In the compound represented by the above formula (I), it is particularly preferable because the cyanotrisinosylphosphonic acid or the like can be obtained industrially. Similarly, the compound represented by the above formula (II) is particularly preferably Ethylene diamine tetradecylphosphonic acid, diethylenetriamine pentadecylphosphonic acid, etc. The compound represented by the above formula (111) is particularly preferably 1 - by Ethylene 1 > 1 ~ '- The alkali metal salt of the above compound is preferably a sodium salt or a potassium salt, and the salt of the amine compound is preferably a triethylamine salt or a triethanolamine salt. The surface treating agent of the present invention may have two molecules in one molecule. The above-mentioned phosphonic acid group, a compound having no ester bond in the molecule, and/or a salt thereof are dissolved in a solvent. The solvent to be used is not particularly limited as long as it is soluble. A polar solvent such as a diol, but it is preferably water if the solubility, cost, etc. are considered. 12 316814 1301515, when the surface treatment agent is found to be pH Modulated to 5 or less, is: oblique:: the emulsifying property is further improved. The pH of the surface treating agent is influenced by the effect of the second, preferably PH1 to 5. The pH adjusting agent can use the acid which can be obtained. Adding surfactant to the 001 to ^ surface treatment agent will be more important? =, to 5 or less, the surface to be treated is mixed. The amount of surfactant added is less than lg / liter, s P to add More than 1Gg/L' Φ can not be obtained, the amount of the oxidation-resistant surfactant is preferably from 0. 〗 〖 to 1 〇 g / L. Zhengguo" The surfactant can be appropriately selected using commercially available yin, sashimi, And the amphoteric surfactant-type or 2: anionic 糸 surfactant is preferably sulfuric acid (four) type, rhemic acid vine salt type, sulfo-type, etc., cationic interface ^ ^ : =: salt type, non-ionic The surfactant is preferably high-grade = ::==, burnt epoxy Ethylene burn adduct, polyoxyethylene polyoxypropylene core and "e-ethylenediamine polyoxyethylene polyoxypropylene insert, higher aliphatic amine The epoxy Ethylene burn adduct, the county of the aliphatic amine, B said that the addition of the compound temple 'sexual surfactants should be amino acid type, final inspection When using a pH of 5 or less, it is advisable to appropriately select a type of yin system or two types or more. Among them, the nonionic interface activity fee J is particularly a polyethylene glycol type, in particular, a higher alcohol can be used. Products: base _ oxyethylene sulphide adduct, polyoxyethylene bake polyoxypropylene embedded two; compound temple 'an ' anionic surfactants in the sulphate type, 316814 13 1301515 Further, the surface treating agent of the present invention may contain an additive in an amount that does not impair the original properties for the purpose of imparting desired properties. Examples of the added hydrazine include a preservative, a pH buffering agent, and the like. The method of treating a metal surface using the surface treatment agent of the present invention as long as it forms a film on the surface of the metal may be, for example, a method of damaging the surface treatment agent; Or a method of applying a surface treatment agent to a device such as a coating machine, a bar coater, a knife coater, a gravure coater, a reverse coater, or a casting machine. • The shape of the metal surface-treated with the surface treatment agent of the present invention may be any shape such as a line, a plate, a belt, a collar, a granule, a powder, or the like, and the surface treatment agent of the present invention can be processed. Electronic parts, substrates, tin balls, solder powder, etc. Use the surface treatment agent of the present invention to connect the electronic component or the substrate to the terminal portion (4), the surface of the body (4), and the surface of the conductor.

St:: Electronic parts or substrates with excellent surface shape and solder infiltration by surface treatment. I / 73 ^ The solder ball of the alloy treated by the surface treatment agent of the present invention can be suitably used as an excellent oxidation resistance, an electrical connection ball, and as an electronic component to be connected to a circuit board. The surface treatment agent of the present invention may also be used to treat, for example, an alloy powder, and then a flux containing a squeegee, an active agent, a shaker, a surfactant knife, a solvent, etc., 316814 14 1301515 may be added to form a solder paste, and the use stability may be used. There is a significant improvement in the effect. The above-mentioned dryness can be used in the past, and it can be used in the past. Hereinafter, the compounds of Examples 1 to 14 and Comparative Examples 1 to 5 of the present invention having two or more phosphonic acid groups in one molecule and having a fluorene bond in the molecule or a salt thereof are effectively described as examples. There are 15 types of aqueous solutions of the components (Finding Examples 1 to 14 and Comparative Example 1). The content is presented in Table 1. In addition, for copper (C1020P, l〇mmx 25 lx 0.2tmn〇, the following before treatment. Butadiene electrolytic degreasing (normal temperature, 15A / dm2 treatment for about 30 seconds) ~ water wash - acid impregnation (10% sulfuric acid, room temperature , 5 seconds) - water washing - chemical grinding (cpB - 4 〇 normal temperature, dipping for 1 minute) - water washing - acid leaching (1 〇% sulfuric acid, room temperature, seconds) - water washing the substrate, the film thickness is about 5μπι Sn electric key (electric mine bath,

Tincoat K (made by Metalplating Co., Ltd.), electric ore conditions: dangerous current density 2A/dm2, temperature 20 °C, liquid flow and cathode shaking electric ore) The substrate to be plated with Sn (the following Sn) a substrate) is a solution of a compound having two or more phosphonic acid groups in the above molecule and containing no vinegar bond in the molecule or a salt thereof, and after being immersed at a bath temperature of 60 ° C for 10 seconds, It was washed and dried without using it as a test substrate. For the test substrates of these, the following evaluations were performed. The test knots are shown in Table 1. 15 316814 1301515 And the thermal oxidizing properties of the test substrates were heat-treated in an electric furnace maintained at 220 ° C for 1 hour, and then subjected to the following conditions by the Meniscograph method. Solderability measured with lead-free solder (zero cross time) Device · Solder Checker SAT-2000 (manufactured by Rhesca) Solder bath; Tin: Silver: Copper = 96· 5 : 3 : 0· 5 (Bath Temperature 245 ° C) Flux: NA-200 (manufactured by Tamura Chemical Research) — Dipping depth: 2 mm • Immersion speed: 4 mm/sec • Immersion time: 5 seconds and a wet oxidizing test substrate for this. After the PCT treatment (for 16 hours in a sealed pot at a temperature of 105 ° C and a humidity of 100%), the weldability of the error-free solder φ was measured in the same manner as the heat oxidation resistance by the Menis scograph method. Zero cross time). Further, as a comparative example, the substrate of the Sn substrate was surface-treated with an isopropyl alcohol solution containing lg/L of dodecylphosphonic acid (however, there was no surface treatment after washing 5 Comparative Example 2), A substrate surface-treated with an aqueous solution containing diphenylphosphonate ig/L (Comparative Example 3), and the above-mentioned Sn substrate (Comparative Example 4) and the above-mentioned Sn substrate were used for the above-mentioned Sn substrate, and the above-mentioned Sn substrate was used. The surface treatment agent (aqueous solution containing diphenyl phosphonate 0.1 g/L) disclosed in the publication, and the substrate (Comparative Example 5) subjected to the treatment were also evaluated. The combined test results are presented in Table 1. 16 316814 1301515 (Table 1) Table 1 Surface treatment composition and evaluation results (Sn plating substrate) a Active ingredient and its content (g / L) Interface active biocide and its content (g / L) pH and only thermal oxygen ^ n Moisture-resistant oxidizing active ingredient content surfactant content Example 1 Cyanotris-decylphosphonic acid (formula (I)) 1 - 0 2 〇〇 2 Diethylenetriamine 5L hydrazinylphosphonic acid (formula (II) )) 1 0 2 〇〇 3 卜 总乙烧-1, 卜, grade (III)) 1 0 2 〇〇 4 cyanotrisole methylphosphonic acid K salt 1 0 6 〇 Δ 5 2 Triamine pentamethylphosphonic acid K salt 1 - 0 8 Δ Δ 6 1-hydroxyethylidene-1,1-diphosphonic acid K salt 1 - 0 7 Δ Δ 7 Cyanotris-decylphosphonic acid 1 Natural laurel Alcohol propylene oxide 12 molar addition 1 2 ◎ ◎ 8 Diethylene triamine pentadecylphosphonic acid 1 Nonyl phenol ethylene oxide 12 molar addition 1 2 ◎ ◎ 9 1-hydroxyethyl burning - 1,1-diphosphonic acid 1 natural lauryl alcohol Ethylene oxide 9 molar addition 1 2 ◎ ◎ 10 Cyanotrisylphosphonium K salt 1 Natural oleyl alcohol oxide 10 molar addition 1 6 〇〇11 diethylenetriamine pentamethylphosphonic acid K salt 1 polyoxyethylene polyoxypropylene Block polymer (fog point 75 ° C) 1 8 〇Δ 12 1-by keto _1,1-di bis- succinic acid K salt 1 fluorenyl hydrazine ethylene oxide 10 molar addition 1 7 〇 〇13 Cyanotrisole methylphosphonic acid 1 Natural lauryl alcohol propylene oxide 12 molar addition 20 2 〇Δ 14 Cyanotrisole methylphosphonic acid 1 Natural lauryl alcohol propylene oxide 12 molar addition 0.005 2 〇〇Comparative Example 1 Diethylenetriamine pentadecylphosphonic acid 0.005 A 0 4 XX 2 Dodecylphosphonic acid 1 0 0 Δ X 〇ύ niU -ιγ/λ 4J· "fr 1 — Foot :一丰制g · 丄一r\ U 4 X 4 No treatment one - - - XX 5 Special opening 7-188942 - One - 2 Δ Δ ◎ = Zero crossing time less than 1 second 〇 = Zero crossing time 1 Less than 3 seconds in seconds, zero crossing time, 3 seconds or more, less than 5 seconds, zero crossing time, 5 seconds or more, 17 316814

13.01515 A copper material (Cl 020P, 1 Ommx 25 mm x 0·2 mm) treated in the same manner as in Examples 1 to 14 and Comparative Examples 1 to 5 was subjected to a Sn-Zn electric bond having a film thickness of about 5 # m (electric clock bath: Manufactured by Meite Mineral Plating, • Electro-minening conditions: cathode current density 3A/dm2, temperature 35°C, pH 4. 0, liquid flow and cathode shaking plating). The substrate of the worker, the Sn-Zn electric clock (hereinafter, the following Sn-Zn substrate) was prepared by the modulation of φ as described in Examples 1 to 14, Comparative Examples 1 to 3, and Comparative Example 5. In the solution, after bathing at a bath temperature of 60 ° for 1 〇 second, the person who washed and dried with water and no treatment was used as a test substrate. The test substrates of the above were subjected to aging in the same manner as in the above Examples 1 to 14 and Comparative Examples ^ to 5, and then the weldability was measured. The test results are shown in Table 2. Using the further step as a comparative example, for the above-mentioned Sn_Zn substrate which is not treated, the surface treatment agent shown in 2002-304554 is exemplified (single two (octadecene win 1^1 citric acid brewed lwt% isopropyl alcohol) Solution) 'Processed substrate (Comparative Example ', a and ping. The test results are shown in Table 2. 316814 18 1301515 (Table 2) Table 2 Surface treatment composition and evaluation of crucible (Sn-Zn plating substrate) Active ingredient and its content (g/L) Surfactant and its content (g/L) pH Heat-resistant oxidation ί raw and wet oxidation 14 Active ingredient content Surfactant content Example 15 Cyanotrisole methylphosphonic acid 1 -0 2 〇〇16 diethylenetriamine penta-decylphosphonic acid 1 - 0 2 〇〇17 1-hydroxyethylidene-1,1-diphosphonic acid 1 - 0 2 〇〇18 Cyanotrisole methylphosphonic acid K Salt 1 - 0 6 Δ Δ 19 Diethylenetriamine pentadecylphosphonic acid K salt 1 - 0 8 Δ Δ 20 1-hydroxyethene-1,1-diphosphonic acid K salt 1 - 0 7 Δ Δ 21 Cyanide Base three exophosphonic acid 1 natural lauryl alcohol propylene oxide 12 molar addition 1 2 ◎ ◎ 22 diethylene triamine pentadecylphosphonic acid 1 壬 base test ethylene oxide 12 molar addition 1 2 ◎ ◎ 23 1-hydroxyethylidene-1,1-diphosphonic acid 1 Natural lauryl alcohol Ethylene oxide 9 molar addition 1 2 ◎ ◎ 24 Cyanotrisylphosphonic acid K salt 1 Natural oleyl alcohol ethylene oxide 10 molar addition 1 6 Δ 〇 25 diethylene triamine pentadecylphosphonic acid K salt 1 polyoxyethylene polyoxypropylene block polymer (fog point 75 ° C) 1 8 △ △ 26 1-hydroxy Burning-1,1-diphosphonic acid K salt 1 nonylphenol ethylene oxide 10 molar addition 1 7 Δ 〇27 cyanotrimethylmethylphosphonic acid 1 natural lauryl alcohol propylene oxide 12 molar addition 20 2 Δ △ 28 cyanotrisole methylphosphonic acid 1 natural lauryl alcohol propylene oxide 12 molar addition 0.005 2 〇〇Comparative Example 6 Diethylenetriamine pentadecylphosphonic acid 0.005 - 0 4 XX 7 Dodecylphosphonic acid 1 0 0 Δ X 〇 0 phosphonic acid diphenyl 1 丄 r r υ 4 9 No treatment one - one XX 10 Special opening 7-188942 - one one 2 Δ X 11 2002-304554 - 11 - X △ Zero crossing time less than 1 second 〇 = zero crossing time 1 second or more less than 3 seconds △ = zero crossing time 3 seconds or more less than 5 seconds zero crossing time 5 seconds or more 19 316814 1301515 ^ Climbing In Example 29 and Comparative Example 12, in Example 29, for the Sn electric ore, the generation of the whisker by the surface treatment agent showed that the knot which was significantly suppressed compared with the one without the surface treatment was passed through with the foregoing implementation. Example 7 was the same treatment of the Sn electrowinning substrate. The substrate which has not been surface-treated is placed in the environment of temperature step and humidity (4) for 24 hours. After that, the silk plate was fully used for scanning, and when the surface was observed by the sub-mirror (SEM), many of the metal whiskers were found without surface treatment (Comparative Example 12), but the surface treatment was completely absent. See metal whiskers (Example 29). (Industrial Applicability) II, a total of O-containing one or more compounds having two or more phosphonic acid groups in the molecule and containing one or more of the compounds in the molecule and/or their salts The surface treatment agent of Olg/L or more is subjected to metal surface treatment, which can reduce the risk of solder wettability. x, by adjusting the surface treatment agent to one or less, further by containing a surfactant 〇〇1 to 1〇g/L, to improve oxidation resistance. The use of the surface treating agent of the present invention and the solder paste containing the surface-treated Sn = gold solder powder can significantly improve the storage stability. The step-by-step hunting can greatly suppress the occurrence of whiskers by treating the surface treatment agent of the present invention with % and such as a plating alloy. (There is no picture in this case) 316814 20

Claims (1)

Patent Application No. 94106391 (June 6, 1997) 1301515 X. Patent Application Range: 1. A metal surface treatment agent, which is a metal surface treatment agent, characterized in that its active ingredient has 2 molecules in one molecule. One or more of the compounds having a phosphonic acid group and no ester bond in the molecule, and/or a salt thereof, and the content of the compound and/or its salt is 〇· Olg/L or more. And further comprising a surfactant 〇· 〇 lg / L to l 〇 g / L, wherein the metal to be treated is 811 or 311 alloy. 2 - a metal surface treatment agent, which is a metal surface treatment agent, its characteristics The active ingredient is one or more of a compound having two or more phosphonic acid groups in one molecule and having no ester bond in the molecule, and/or a salt thereof, and the compound and/or its salt The content is 〇· Olg/L or more in total, and further contains a surfactant 〇· to 10 g/L, and the metal surface treatment agent solution is adjusted to 5 or less, wherein the metal to be treated is Sn or a Sn alloy. If the patent application scope is from the second to the second The metal surface treatment agent of the present invention, wherein the compound having two or more phosphonic acid groups in the above molecule and containing no vinegar bond in the molecule and/or a salt thereof is represented by the following formula (1; Or a compound represented by (III) and/or an alkali metal salt thereof, an ammonium salt or a salt with an amine compound: N 1 7 1 xlc1Y I o=pIo ι H o H Η) Η ο ο ϊ -Η ι ο οπηρ丨ο ΟΗΡΙΟ 2 rr23 Γ3 xlc丨γ ^IcIY (Revised) 316814 .1301515 Patent Application No. 94106391 (May 6, 1997) (in the formula (I), X1 to P and ¥1 to Y3 may be the same or different and each represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms; (ID R1 R3 R2>N-[CH2-CH2-ilnn-R4 (in formula (II), R1, R2 and R4 may be the same or different and each represents the following group (A); R3 represents the following group (a) or a lower alkyl group having a carbon number of 1 to 5; n is an integer of 1 to 3; and the group (A) is: On ρ I 0 1 Γ XI c — γ § \—/ Η In the base (A), 'χ! and ... are the same as the formula (the definition in υ); 0X0 II I II Γ?^ΓΟΗ (ΙΠ) HO Y OH (in formula (III), X represents a hydrogen atom or carbon a lower alkyl alkoxide group of 1 to 5, wherein Y represents a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms, a hydroxyl group or an amine group.) 4. A surface treatment method as in the first to the following claims Any one of the metal surface treatment agents for surface treatment. An electronic component or substrate characterized in that after the surface of the conductor of the connection terminal portion of the electronic component or the substrate or the surface thereof is plated, the surface treatment is performed by applying a surface treatment method such as applying green (4). • Know the solder ball or solder powder, which is characterized by the use of a % alloy which is surface-treated by the surface treatment method of the fourth application of the patent application. (Revised) 316814 22 : ^01515 Patent Application No. 94106391 (May 6, 1997) 7· ‘It is characterized in that a solder ball as in the application of the scope β is used as an electrical connection member. • Seeding seismic products, which are characterized by the fact that the solder ball is placed on the electronics. ^ Please refer to item 6 of the patent scope. 9. Solder paste, which is characterized by the circuit board. The solder powder of the item. · "Applicable Patent Range No. 6 10·--Installation, which is characterized by the solder paste of the item. (Revised) 316814 23