TWI327605B - - Google Patents

Description

1327605. IX. DESCRIPTION OF THE INVENTION: 1. Field of the Invention The present invention relates to a water-based antioxidant for tin and tin alloys, and a surface treatment method using the same. Furthermore, the present invention relates to an electronic component treated with the water-based antioxidant, a solder ball, a solder powder, and a ball grid array using the solder ball, and a tin of the solder powder Solder paste, and the use of such mountings. [Prior Art] Soldering is a technique in which objects are joined to each other by using a material having a low melting point. In the modern industry, it is widely used in the joining and assembling of electronic machine crying. Generally, the solder used is a Sn_pb alloy, and the melting point of the eutectic composition (63% Sn-balance Pb) is as low as 183 〇 (:, pot tin soldering can be performed at urn: so for electronic components or substrates almost There is no thermal damage. In addition, the Sn_Pb alloy is rapidly solidified when it is soldered to the tin solder, and it has the advantage of being cracked or peeled off even if the solder is welded. In other words, the electronic device is made of a metal such as a frame conductor or a casing, and is treated as a tree and is almost completely buried in the vicinity of St;: where it is not burning, it tends to be acidic (acid rain), and is buried. In the soil == :!=,:: Groundwater becomes a problem. For this reason, in particular, the alternative development of the machine thief is 'immediately carrying out the wrong tin #, solder. ..., σ tin fresh, lead-free in the external lead of the electronic components #, and 'in order to improve its solder wet 318577 ^ ^ / 005, 】:: t 'mainly applied solder plating (9〇% Sn _ balance Pb), expected due, ", m material (four) candidates, can be roughly divided into pure. Point, to η: ΓΓ 2:: system, Sn-Bi system, each has its own advantages and disadvantages • 7 still It is impossible to replace the Sn-Pb alloy. j Sn plating, due to cost or plating workability, can be used as a lead-free mineral coating. However, pure % mineral coating will cause surface stress, except for crystals. In addition, there will be problems with the deterioration of tin's grain over time, and it is strongly expected to improve these problems. Kinki 7 'The system of gold' is due to the fusion point with the previous alloys. There is no need to change the current injury or step. In addition, the mechanical strength of the money coating is excellent, the cost is easy to oxidize due to & active metal, and the tin is very poor due to (five), the current stage of Xianxin The possibility of practical use is the lowest: tin ^ (10) der p perspective) in order to use the electronic zero group f board: used, in recent years its use has increased greatly. In terms of I;: It is based on soldering alloy powder, which is based on 舻 a 〇 蛘 蛘 蛘 ( ( ( ( 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有There is no research, although the research has been done, the alloy (10) is: Dibu 1 series alloy, but as mentioned above, the Sn_Zn alloy is close to the strong temperature after the disc force and the soldering temperature is close. However, as the first 扪 扪 alloy has been used as a solder Zn Γ, it is necessary to have an inert gas environment when the oxidation reaction of the active agent contained in the welding sword has the characteristics of solder wettability, preservation stability, and back to Tan (4) (10). Disadvantages. Defects 318577 6 1327605. ". According to the prior art, it has been confirmed that the tin and tin alloys are excellent in the wettability and lubricity by using the table of phosphoric acid vinegars. Patent Document 2 and Patent Document 3). Patent Document 1 discloses that a sulphate surfactant contains ethylene bromide and contains a phenyl group as a lipophilic group. In the form of the structure, although the lubricity is excellent - but due to the ring Ethane is hydrophilic and absorbs moisture, and when it is humidified, the anti-oxidation function is insufficient. In Patent Document 2, it is preferred to use a phosphate ester having a saturated or unsaturated base having a carbon number of 1 to 26. In Document 3, a phosphate ester containing a phenyl group or an alkyl group having 5 or less carbon atoms is disclosed. In this case, although the oxidation preventing function at the time of humidification is excellent, sufficient lubricating properties cannot be obtained. Furthermore, the three patent documents The phosphate ester compound disclosed in the above, the effect of discoloration or oxidation prevention during heating is low. ... In addition, according to the RoHS order, although the apricot plant has been undistorted since July, 6 There is a lot of problems and there are many problems in the state of 'two-two' JEITA started the error-free tin front to complete the emergency plan (four) (10) Qing like> lead-free completion of the emergency proposal report, 2, 5 years, the Association of Law Association , Installation Technology Standardization Committee). The issue of these questions is required for the day. Although it is known that it is improved as a tin-based plating solution or as a copper diffusion barrier layer (tin-based plating of baiTier丨aye〇: coating, etc., can reduce the internal stress of the film, and greatly change: two: connector In the case where the fitting part is applied, it is not possible to solve the problem.丨 stress (4) resistance to whisker, still patent document 1: 曰本专利特公平5-22322号 318577 7 • Lili Document 2: Japanese Patent Special Open Document 3: Japanese Patent No. 39 No. 2 Broken Bulletin. SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The object of the present invention is to provide an excellent anti-oxidation property through the treatment of tin people, and a good tin; two::::; two = purpose is provided when an external load is applied The crystal is a finely lubricated anti-oxidant. Means for Solving the Problem = The inventors' oxidation of the surface of tin and tin alloys, and the results of the anti-four research and development, found that there are two or more phosphonates contained in a bifurcated p X knives. A surface treatment agent having a total of (four) g/L or more in combination with a compound having no ester bond and/or a salt thereof, and imparting oxidation resistance, improving wettability, and suppressing generation of whiskers at the surface ( According to International Patent Publication No. 200 Lake 5498A1). However, in the case of containing the above-mentioned surface treatment agent having two or more phosphonic acid groups in one molecule and containing no vinegar bond in the molecule, although the oxidation resistance during soldering or humidification, tin soldering Although the wettability and the whisker resistance are excellent, the whisker resistance and the lubricating property of the external stress portion are insufficient, and sufficient characteristics cannot be obtained in the use of the fitting portion of the Fpc or the FFC and the connector. Here, as a result of further review, it was found that a compound having 2 or more phosphonic acid groups in one molecule and having no ester bond in the molecule and/or a salt thereof, and an alkyl group having 6 to 10 carbon atoms Phosphate ester water-based antioxidant 'surface treatment tin and tin alloy' anti-oxidation during heating or humidification 8 318577 1327605, .sex b, solder wettability, resistance to whiskers,) daily scraping white Excellent, at the same time, it is excellent in applying external stress whisker and full-slip performance, and is suitable for the bonding surface of tin or tin alloy used for Fpc or FI, the fitting portion of the connector. That is, the present invention is as follows. (1) 'A water-based antioxidant of a tin alloy, which is characterized by containing a compound having two or more linoleic acid groups in a molecule and having no vinegar bond in the molecule, and/or a salt thereof, and having a carbon number of 6 to ig The base of the yard is sour. (2) The water-based antioxidant of the tin and tin alloy according to (1) above, wherein the pH of the water-based antioxidant is 5 or less. (3) The water-based antioxidant of the tin and tin alloy according to (1) or (2) above, which further comprises a surfactant 〇.〇lg/L to i〇g/L. (4) The aqueous antioxidant of tin and tin alloy according to any one of the above (1) to (3), wherein the compound having two or more phosphonic acid groups in one molecule and having no ester bond in the molecule And/or a salt thereof, which is a compound represented by the following formula (〗 〖), (工工) or (ΙΠ), and/or an alkali metal salt thereof, an ammonium salt, or a salt with an amine compound, Ν 1 I 1 X丨C丨γ I ο=ρ丨ο i Η ο Η Η Η ο Η -Η I Η οHP丨ο ο=ρ丨ο 2 ·2ΓΪ - 3 X丨C丨γ X—C丨γ (in equation (1) 'X1 to X3 and Y1 to Y3 are the same or different, each represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms, 318577 9 1327605. r2>N-[CH2 -CH2-N]n-R4 (π> (In the formula (II), R!, R2 and R4 are the same or different, and represent the following group (A) 'R3 represents the following group (A), or a carbon number i to 5 Lower calcination, η represents an integer from 1 to 3, Η 0-Η 0 = Ρ 丨ο -1 xlc - γ (in the group (4), XI f is the same as defined in the above formula (1)) (III)

0X0 τ II I II HO-Pc-Ρ-〇Η III HO Y 〇Η 2 ), X represents a hydrogen atom or a lower alkyl (5) m having a carbon number of 1 to 5, and a low-grade carbon having a carbon number of 1 to 5. A surface treatment method of a base, a mercapto group or an amine group is characterized in that the tin and tin alloy m of the above item (1) is used for the surface of the anti-oxidation cut: neo tin or tin alloy. (6) - The type of electronic material 'characterized on the surface of the conductor of the electron, the anchor is thickened into the top of the crucible, and after the gold plating of any of the diseases t to (4), the above (] surface treatment is used. .. · Alloy water-based antioxidants, 3 (7) A solder (10) (4) ball or solder powder, characterized by the use of the above-mentioned test 318577 IDL IKJKJJ, .Π) to (4) Ning any one of the water-based antioxidants alloy. G agent built-in surface treated tin. (8) - a ball grid array, characterized by connecting components.吏Use the above (V solder ball as electric (9), an installation item, which is characterized in that the tin ball of the έ έ έ 〇 〇 乩 / / / / / 配置 配置 配置 配置 配置 配置 配置 配置 配置 配置 配置 配置 配置 配置On the circuit board, (10) A solder paste of the type (1) is prepared by the solder paste of the above (7). The effect of the invention is the use of the solder paste of the above. The present invention has been used by using a phosphate vinegar containing a compound having two or more phosphonic acid groups in a molecule and having no phosphonium group in the molecule and having no "曰 bond in the molecule, and an alkyl group" The number of disgusting 6 to 10 people is Hu shi ning anti-emulsification sword, surface treatment tin or tin 2 2 when wet, excellent anti-oxidation performance, showing excellent whisker characteristics and turbidity when external load is different Tin alloy. Moreover, too m: or FFC disk (4) =;: water-based antioxidant is suitable as an antioxidant. σ "^ tin or tin alloy ore portion" [Embodiment] The following detailed description of the present invention Antioxidant. The deposit of tin and tin alloy water (10) oxidant treated tin S gold, due to environmental sweat, look forward to R m

Sn ° r lead-free tin alloy is preferred. Exclude = one? : For example, a solder alloy containing Ζη, 〜, —, or one or more may be mentioned. The composition of the antioxidant of the present invention is an aqueous solution having a specific (IV) squarate, 318577, and a compound having two or more phosphonic acid groups in the molecule and having no vinegar bond in the molecule as a active ingredient. - a compound having two or more molecules in the molecule, and having no ester bond in the molecule, and a phosphoric acid having an alkyl group, and it is difficult to solve the problem of 'there', and it is necessary to select the vinegar portion of the latter, and = . It has been confirmed that the alkyl carbon number of the alkyl phosphate has! 】 The above % is low in the turnover of the aqueous solution. Further, although the base having a carbon number of 5 or less is dissolved, sufficient lubricating properties cannot be obtained. Therefore, from the balance between solubility and lubricity, it has been found that a disc acid vinegar having a carbon number of 6 to 10 is preferred. Further, it has been found that the combination of the specific disc acid ester and a compound having two or more phosphonic acid groups in one molecule and having no vinegar bond in the molecule is also effective for suppressing whiskers when external stress is applied. In the antioxidant, a compound having two or more phosphonic acid groups in one molecule and containing no (4) in the molecule and/or a salt thereof may be contained! It is also possible to contain two or more kinds, and it is preferable to contain 〇.01g/L or more. The effect is not small when it is not 0.01g/L. And = anti-ground, because the characteristic does not deteriorate even if the content is too large, there is no upper limit on the content, but from the cost problem, the content is preferably from (10) to 500 g/L, more preferably from 0.1 to 100 g/L. . Further, in the case of a compound having two or more phosphonic acid groups in one molecule, the compound having a private acid group in the knife is one compound, and the detailed mechanism is not clear, but it is confirmed that the oxidation resistance is excellent. The number of phosphonic acid groups in the molecule is preferably from 2 to 6 due to cost. In the knives, the yttrium compound having two or more phosphonic acid groups and having no ester bond in the molecule, and/or a salt thereof, may be exemplified by the following general formulas (1), (1), and (m), and/or Or a salt of an alkali metal salt, an ammonium salt thereof, and an ammonium compound. 318577 12 1327605.

ΟΗΠΡΙΟ-Ho H

«1 - 1 XICIY

Η Ho o -Η IH OHPIO OHPIO 2 - 2 3 - 3 XICIY XICIY r2 [CH2-CH2 - N] n - R4 (χΐ) (In formula (II), 'R1, R2 and R4 are the same or different , Table 8, the lower group (A), R3 represents the following group (eight), or carbon grade yard base, η represents an integer from 1 to 3, -

H 0 1 H o MM p I0 -1 XICIY

(A group (A), χΐ and f are the same as defined in the above formula (1)),

Η 0 -Η ohup I o IX丨c丨Y Io = p- o _ H o H \1/ (In the formula (III), X represents a hydrogen atom or a lower alkyl group having a carbon number of 1 to 5, and γ represents a deuterium atom. , a lower choline, a mercapto or an amine group having a carbon number of 1 to 5. The compound of the above formula (I), which is a compound of the formula (I), is particularly preferred because it is 318577 13 1327605. ''. Similarly, the compound of the above formula (II) is particularly preferably ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid or the like, and the above general formula (III). The compound is particularly preferred as hydroxyethane manganin diphosphonic acid or the like. The alkali metal salt of the above compound is preferably a sodium salt, a potassium salt or the like, and a salt of an amine compound, preferably a triethylamine salt or a triethanolamine salt. - A phosphate having an alkyl group having 6 to 10 carbon atoms, preferably a monoalkyl ester or a dialkyl ester, or a mixture of a monoalkyl ester and a dialkyl ester. When manufacturing a mixture of a single-base vinegar and a di-alkyl ester, it is necessary to separate the mixture, and the mixture can be used as it is. In the case of a mixture, it can also be a mixture of any ratio. The above phosphates are, for example, monohexyl phosphate, dihexyl phosphate, mono-2-ethylhexyl phosphate, di-2-ethylhexyl phosphate, monooctyl phosphate, dioctyl phosphate, monoisodecyl phosphate, Diisodecyl phosphate or the like is preferred. The content of the antioxidant is preferably 0.01 to 1 〇〇 g/L, more preferably 〇" to 10 g/L. When the content is less than 0.01 g/L, the film formation is insufficient. When Qin exceeds 100 g/L, the liquid stability is remarkably lowered. Further, among the antioxidants, the compound (A) having two or more phosphonic acid groups in one molecule and having no ester bond in the molecule, and the phosphate (B) having an alkyl group having 6 to 1 carbon atoms The ratio, in terms of weight ratio, is preferably a: b = 1:2 to 1.0.01 'more preferably 1:1 to 1: 〇1 ^ has two or more phosphonic acid groups in one molecule and is intramolecular When the ratio (A/B) of the compound (A) having no ester bond to the phosphate (B) having an alkyl group having 6 to 10 carbon atoms is less than 1/2, the moisture and oxidation resistance is lowered, and when it exceeds 100 hours , heat and oxidation resistance decreased. The antioxidant of the present invention may have two or more phosphines 318577 14 1327605 in one molecule. • Acid-based and compound having no ester bond in the molecule and/or its salt • H) The aqueous solvent is dissolved. The water coefficient is preferably water, but it is also water, but also a class of glycols, ketones, etc., in consideration of rotation and cost. Further, it has been found that the water-based antioxidant of the present invention has been improved to improve the oxidation resistance of the surface to be treated by adjustment. The antioxidant has a effect on the material, etc., and the pH is preferably from j to 5. Generally, the regulator can use an acid or a base which is easy to obtain. Further, by adding a surfactant 〇.〇10gjL to the aqueous antioxidant, the oxidation resistance of the surface to be treated can be further improved. Even if the addition amount of the surfactant is less than o.oig/L or more than 1 〇g/L, the oxidation resistance cannot be improved. The amount of the surfactant added is preferably 0 l〇g/L. The King 7 surfactant may be selected from commercially available anionic, cationic, nonionic, and amphoteric interfacial active species or two or more species. The anionic surfactant is preferably a sulfate salt type, a sulfonate type, a dish acid salt type, a 4-acid acid type, etc.; the daughter surfactant is preferably a quaternary ammonium salt type or an amine salt type. Etc.; the nonionic surfactant is preferably a higher alcohol oxyethylene sulphur adduct, a higher alcohol epoxidized adduct, a benzoin epoxiconate adduct, a polyoxyethylene ethoxylate Propyl propylene late stage polymer, ethylene ethoxylate extended ethyl polyoxypropyl propyl block polymer, higher aliphatic amine % oxyethylene adduct, aliphatic decyl amine ethylene oxide adduct The amphoteric surfactant is preferably an amino acid type, an internal salt type, etc.. When used in a pH range of 5 or less, it is preferred to use an appropriate choice of 318577 15 • Anionic, nonionic 1 Tian Yiqi / above. Among them, non-surfactant, especially polyethyl hydrazine non-ionic. Alcohol ethylene oxide adduct, higher alcohol hydrazine with 'Graphic, sub- and % hydrazine propane adducts , Rolling ethane adducts, polyoxygenated excipients, and phenolic phenols, etc., reducing the amount of non-oxygen propyl post-polymers, etc. Re-type is better. The anti-oxidant of γ is not used as a sulfate salt or a yttrium phosphate salt, and an additive in a range of the original properties is not provided for the purpose of imparting desired properties. The additive may be used as a preservative, a positive buffer, etc., and may be used. If it is conventionally known that the antioxidant of the present invention is surface-treated with tin or a tin alloy, it may be a method of forming a film on the surface, for example, tin or tin coating, or air knife coating, and scraper. ^ Coating method of knife coating, bar coating, knife coating, gravure coating, ^ coating, mold coating, and the like.

• The temperature of the antioxidant at the time of surface treatment is preferably 15 to (10). C is 30 to 70. Hey. / The shape of the tin or tin alloy surface-treated with the antioxidant of the present invention may be linear, plate, belt, spheroidal, granular, powdery, etc. The antioxidant of the present invention can handle electron zero Components, solder balls, solder powder, etc. When the tin or tin alloy (4) is applied to the surface of the conductor of the connection terminal portion of the electronic component by using the antioxidant of the present invention, the surface treatment can be excellent in t oxidation, solder wettability, whisker resistance, and lubrication. Sexual quality electronic components. Further, the electronic component of the present invention also includes a substrate. 318577 16 1327605 • Make the hybrid hair (four) less financial. Excellent chemical properties, good as an electrical connection member, oxygen-resistant. Placed in the electronic components, the zero group or the other, into the court according to the circuit board Installation. After the treatment with the antioxidant of the present invention, the flux can be used as a solder paste for the flux, the active agent, the thixotropic agent, and the surfactant agent. The solder paste is excellent in resistance to whisker and whisker. The above-mentioned adhesives, active agents, and solvents may be used in the following embodiments, but the present invention is not limited thereto. 1 to 8 and Comparative Examples 1 to 8 as shown in Table 1, a compound having 2 or more scaly acid groups in one molecule and having no ester bond in the molecule, and/or a salt thereof, and having a carbon number of 6 to 10 The alkyl phosphate was used as an active ingredient, and eight kinds of aqueous solutions were prepared (Examples 1 to 8). Further, the comparative examples were as shown in Table 2, and were adjusted in the same manner as in the examples (Comparative Example 1) 6). Comparative Example 7 was prepared without treatment with an antioxidant. Further, in Comparative Example 8, the hexyl phosphate of the solution of Example 2 was changed to a phosphatate, which was brownish brown. The active ingredient could not be completely dissolved. In addition, in Tables 1 and 2, hexyl hexanoate, 2-ethylhexyl silicate, isodecyl silicate, butyl phosphate, all monoalkyl phosphate and dioxane Mixture of vinegar. 318577 17 1327605 [Table 1] Examples of active ingredients __- PH 1 . Methylphosphonic acid: lg/L hexyl phosphate: 〇.5g/L ___ 2 2 Nitrogen trimethylene phosphonic acid: 1 g/L hexyl phosphate: 〇.5g/L Natural lauryl alcohol propylene oxide 12 mol Add 2 3 Diethylenetriamine pentadecylphosphonic acid: 1 g/L hexyl hexanoate: 0.5 g/L 2 4 Diethylenetriamine penta methylene phosphonic acid: lg/L hexanoic acid vinegar: 0.5 g /L Natural lauryl alcohol propylene oxide 12 molar addition: ig / L 2 5 Diethylene triamine penta methylene phosphonic acid: lg / L hexyl phosphate: 〇. 5g / L 壬 phenol oxirane 12 Moer addition product: lg/L 2 6 hydroxyethane-1,1-diphosphonic acid: lg/L 2-ethylhexyl phosphate: 〇.5g/L Natural lauryl alcohol propylene oxide 12 mol Adduct: 1 g/L 2 7 Nitrodiazepine phosphonic acid: lg/L Isodecyl phosphate: 〇.5g/L Natural lauryl alcohol propylene oxide 12 molar addition: lg/L 2 8 Nitrogen-diphenylphosphonium acid unsalted salt: 1 g/L hexyl phosphate: 0.5 g/L Natural lauryl alcohol propylene oxide 12 molar addition: lg/L 6 18 318577 1327605 • [Table 2] Active ingredients ΤηΊ 釓川二亚methylphosphonic acid: lg/L 2 Nitrogen dimethylidene phosphonic acid: lg/L ~--- alcohol propylene oxide 12 molar addition: lg/L 2 Nitrogen dimethylene Phosphine Acid: lg/L '----- 3 butyl phosphate: 0.5g/L 2 ~~~-~~~~_ Natural lauryl alcohol propylene oxide 12 molar addition: 1 g/L diethylene Amine penta methylene phosphonic acid: lg / L - 2 5 diethylenediamine pentadecylphosphonic acid: lg / L --- ---- ---- Natural lauryl alcohol propylene oxide 12 molar addition: Lg/L 2 6 Nitrogen trimethylidene phosphonate potassium salt: 丨g/L Natural lauryl alcohol propylene oxide 12 molar addition: lg/L 6 untreated ~-. In addition 'on copper (C1020P, l 〇mmx25mmx〇., —---J Perform the following pre-processing. Electrolytic degreasing (normal temperature, 15 A/dm2, about 30 seconds) 4 Washing acid soaking (10% sulfuric acid, normal temperature, 5 seconds) - Washing - Chemical grinding φ (CPB-40, normal temperature ' 1 minute impregnation _^Washing-acid leaching (1% sulfuric acid, normal temperature, 5 seconds) - tin plating of about 5 μm after the film is washed with water (plating bath: Tin coat K (manufactured by Nippon Mining Metals Co., Ltd.) , plating conditions: cathode current density 2A / dm2 'temperature 20 ° C, liquid flow and cathode vibration plating. The substrate to which tin plating was applied (hereinafter referred to as Sn substrate) was immersed in the above-mentioned antioxidant at a bath temperature of 60 ° C for 10 seconds, and then washed with water and dried as a test substrate. The test substrate was subjected to the following evaluation. The test results are shown in Table 3 and 318577 19 1327605 "Table 4. *. Heat resistance oxidation The test substrate was heat treated in an electric furnace maintained at 220 ° C in an atmospheric atmosphere. After 1 hour, the solder wettability (zero cross time) of the shipless solder was measured by the meniscograph according to the following measurement conditions. Device: Solder checker SAT-2000 (Rhesca) Manufacturing) Tin solder bath: Tin: Silver: Copper = 96.5: 3: 0.5 (bath temperature 245 ° C) Repair flux: NA-200 (Tamura Chemical Research) Dip depth: 2mm Immersion speed: 4mm / sec. Immersion time: 5 sec. The evaluation criteria are as follows: ◎: Zero-crossing time is less than 1 second 〇: Zero-crossing time is less than 1 second for less than 3 seconds φ △: Zero-crossing time is more than 3 seconds and less than 5 seconds X: Zero-crossing Moisture Oxidation Resistance of 5 Seconds or More After the PCT treatment (for 16 hours in a sealed pot at a temperature of 105 ° C and a humidity of 100%), the test substrate was subjected to the same method as the heat-resistant oxidizing property. Meniscograph) Determination of the solder wettability of zero-free soldering (zero cross time). The standard is as follows: ◎: Zero-crossing time is less than 1 second 20 318577 1327605 “ 〇: Zero-crossing time is less than 1 second. 3 seconds*. △: Zero-crossing time is less than 3 seconds and less than 5 seconds. .X·· The zero-crossing time is more than 5 seconds. The whisker resistance is placed in a constant temperature and humidity environment with a temperature of 85 ° C and a humidity of 85% for 24 hours. After that, the substrate is sufficiently dried and then scanned by an electron microscope. (SEM) The surface observation was carried out, and the generation of whiskers was not observed in the examples and the comparative examples. $ • Riding, the ball load test was also carried out (at room temperature, after the sample was carried out for 7 days, the crystal was observed by a microscope) The required production length is as follows. 〇: Not up to ιμιη △ : ΙΟμιη or more is less than 2〇μιη Χ: 20μιη or more ^Coefficient of friction ^ The lubricity of the surface of the test substrate is evaluated by the static friction coefficient.

, slowly 318577 21 1327605. Α·[Table 3]

- Examples 9 to 16 and Comparative Examples 9 to 15 For the filled copper strip steel (hoop) (18 mm X 100 mm), pretreatment with ruthenium was carried out. Alkaline electrolytic degreasing (normal temperature, 15A/dm2 'about 30 seconds of treatment water washing - acid impregnation (10% sulfuric acid, normal temperature, 5 seconds) - water washing - chemical grinding (CPB-40, normal temperature; 1 minute impregnation) - washing - Acid leaching (10% sulfuric acid, normal temperature, 5 seconds) - Washing the substrate with a film of about 5 μm Sn-9% Zn after plating (plating bath: 22 318577 1327605. . Coating conditions: cathode current density • 3 A/dm 2 , temperature 35 C, pH 4. 〇, liquid flow and cathodic vibration plating. For the solutions prepared in Examples 1 to 8 and Comparative Examples 1 to 6, the above Sn was applied. - Zn-plated substrate (hereinafter referred to as §η_ζη substrate), which was used as a test substrate (Examples 9 to 16, Comparative Example 9 Magic 4) at 4 (TC immersion 1 minute (four) 'washed and dried). The untreated substrate was used as the test substrate of Comparative Example 15. The evaluation of the substrates was carried out in the same manner as in Examples 丨 to 8 and Comparative Examples 1 to 7. The test results are shown in Tables 5 and 6 〇 [Table 5] Example solution heat oxidative resistance to moisture oxidation resistance to whisker (ball load static friction coefficient)

338577 23 1327605 [Table 6] Comparative Example Solution but Thermal Oxidation and Inch Wet Oxidation Resistance to Whisker (Ball Load Test) Static Friction Coefficient 9 Comparative Example 1 Δ Δ X 0.4 10 Comparative Example 2 〇〇Δ 0.4 11 Comparative Example 3 〇〇 Δ 0.4 12 Comparative Example 4 Δ Δ X 0.4 13 Comparative Example 5 〇〇Δ 0.4 14 Comparative Example 6 X Δ X 0.4 15 Untreated XXX 0.4 [Simple description of the drawing] Fig. 1 shows the measurement of the static friction coefficient in the example An overview of the method. 24 318577

Claims (1)

, 'A patent application for the first flight f 132844, ten, the scope of application for patents: ^ Talk - 曰) ..1.- A water-based antioxidant for tin and tin alloys, characterized by two plants in one molecule. The above-mentioned phosphonic acid group and a compound having no ester bond in the molecule 'and its salt' and an acid ester having a compound having a carbon number of 6 to 1 Å, which have two in the molecule. The compound having a scaly acid group and having no vinegar bond in the molecule and/or a salt thereof is represented by the following formula (1), (9) or (10). And/or its alkali metal salt, ammonium salt, or salt with an amine compound, a 〇 ο ι Η ο Η X丨C-γ Η Η ο ο -' Η I Η ο=ρ—ο ΟΗΡ丨ο 2 - 2 3 _ 3 XIC1Y XICIY (in the formula (1), X1 to X3 and γΐ to Υ3 are the same or different, representing a hydrogen atom, or carbon a lower alkyl group of 1 to 5), R1 R2 R3 ^>N- [CH2 -CHa - N] n- R4 (II) (in the formula (II), R1, ]^ and R4 are each the same or may be Different, the group below the group (A) 'R3 represents the following group (A), or the lower alkyl group of the carbon number 'η represents an integer of 1 to 3, X1 〇I II (Α) -CP-OH II Υ1 ΟΗ 318577 (Revised Edition) 25 1^27605 Patent No. 95132844 Shen Jing Hongnian April 13β$ 基圑(Α)中 'χΐ and γ1 are the same as defined in the above formula (1)), 〇X 〇II | II (III) HO-PcP-QH III HO Υ 〇Η (In the formula (ΙΠ), 'X represents a hydrogen atom, or a lower alkyl group having 1 to 5 carbon atoms, and a lower alkyl group, a mercapto group, or an amine having a hydrogen atom number of 1 to 5 Base) • The water-based antioxidant of tin and tin alloys as claimed in item 1 of the patent application) wherein the water-based antioxidant has a pH of 5 or less. ^ The patent claims that the water system of tin and tin alloys of item 1 or item 2/3=4, wherein 'recombination of surfactants (4)...[to i〇g/L,. The surface treatment method is characterized in that it is used in any of the water-based antioxidants of the surface tin or gold of any of the three items of the patent scope, the third to the third. The surface of the electronic conductor, the luxury from the 々 buckle person λ J bite set to move around the 4th to the 3rd ", /, after plating, using such as the patent patenting agent, tin and tin alloy The anti-oxidation of the water system is such that the film produced by the whisker is inhibited by the sulphur oxidant. 6. The type of bismuth tin (10) or the solder patent (4) to the third bond is used for the surface treatment of the tin alloy. 7 Water-based antioxidants, "Suppressing whisker-generating coatings. Wrong" "Water-based anti-oxidation brakes". A ball grid array characterized in that solder balls are used as electrical connection parts. Acknowledgment Patent Exercise No. 6 Training 577 (Revised Edition) 26 1327605. .8. An assembly, characterized in that the ball is disposed on the electronic component, and on. Patent Application No. 95132844 (April 13, 1999) Accepts (4) The solder of the sixth item of the U range is connected to the circuit board I tin solder paste, and its characteristics are used as the sixth item of the patent application scope. Solder powder 10·—Group bag solder paste. 'It is characterized by the use of welding as in the scope of claim 9 318577 (revision) 27