WO2007029589A1 - Aqueous antioxidant for tin or tin alloy - Google Patents

Aqueous antioxidant for tin or tin alloy Download PDF

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Publication number
WO2007029589A1
WO2007029589A1 PCT/JP2006/317199 JP2006317199W WO2007029589A1 WO 2007029589 A1 WO2007029589 A1 WO 2007029589A1 JP 2006317199 W JP2006317199 W JP 2006317199W WO 2007029589 A1 WO2007029589 A1 WO 2007029589A1
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WO
WIPO (PCT)
Prior art keywords
tin
antioxidant
solder
molecule
alkyl group
Prior art date
Application number
PCT/JP2006/317199
Other languages
French (fr)
Japanese (ja)
Inventor
Takashi Ouchi
Katsuyuki Tsuchida
Original Assignee
Nippon Mining & Metals Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Mining & Metals Co., Ltd. filed Critical Nippon Mining & Metals Co., Ltd.
Priority to JP2007534363A priority Critical patent/JP4601670B2/en
Priority to CN2006800328749A priority patent/CN101258268B/en
Publication of WO2007029589A1 publication Critical patent/WO2007029589A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/066—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors phosphorus-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/167—Phosphorus-containing compounds
    • C23F11/1673—Esters of phosphoric or thiophosphoric acids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/167—Phosphorus-containing compounds
    • C23F11/1676—Phosphonic acids
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/061—Metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/063—Ammonium or amine salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/08—Groups 4 or 14
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
    • H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/12—Using specific substances
    • H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax, thiol

Definitions

  • the present invention relates to an aqueous antioxidant for tin and a tin alloy, and a surface treatment method using the same. Furthermore, the present invention relates to an electronic component, a solder ball, a solder powder, a ball grid array using the solder ball, a solder paste using the solder powder, the electronic component processed with the aqueous anti-oxidation agent, It relates to a mounted product using them.
  • soldering is a technique for joining objects using a material having a relatively low melting point, and is widely used in joining and assembling electronic devices in the modern industry.
  • solder is Sn-Pb alloy, and its eutectic composition (63% Sn-remainder Pb) has a low melting point of 183 ° C, so soldering is 220-230 °. Since it is performed in C, it causes little thermal damage to electronic components and boards.
  • the Sn-Pb alloy also has good solderability and solidifies immediately during soldering, and does not easily crack or peel even when vibration is applied to the soldered part. Have it.
  • Pure Sn plating is the best lead-free plating in terms of cost and workability. It is considered promising. However, pure Sn plating has a problem that it is easy to generate a whisker due to the internal stress of the surface acid, and the solder wettability deteriorates over time. Is strongly demanded.
  • Sn—Zn alloys have melting points close to those of conventional Sn—Pb alloys, Sn—Zn alloys are advantageous in that it is not necessary to change current facilities and processes.
  • the plating film is excellent in mechanical strength and cost.
  • Zn is an active metal species, the solder wettability of Sn-Zn alloys, which are easily oxidized, is very poor. .
  • solder paste is used for surface mounting an electronic component on a substrate, and its usage is increasing in recent years.
  • the solder paste is generally composed of a solder alloy powder as a main component and added with a flux containing an adhesive, an activator, a thixotropic agent, a surfactant, a solvent, and the like.
  • Sn-Ag (Cu), Sn-Zn, and Sn-Bi alloys are being investigated as lead-free solder pastes. Because it is close to the eutectic temperature of a solder, it is considered as a promising alternative candidate.
  • solder paste using Sn-Zn alloy as solder powder causes an acid-oxidation reaction with the activator contained in the flux, resulting in solder wettability and storage stability.
  • an inert gas atmosphere is required during reflow.
  • Patent Document 1 exemplifies a phosphate ester type surfactant containing ethylene oxide and having an alkylphenol group having 8 to 30 carbon atoms as a lipophilic group.
  • Patent Document 2 describes that a phosphate ester containing a saturated or unsaturated alkyl group having 10 to 26 carbon atoms is preferable.
  • Patent Document 3 describes a phosphate ester containing a phenyl group or an alkyl group having 5 or less carbon atoms. In this case, the anti-oxidation function during humidification is excellent, but sufficient lubrication performance cannot be obtained. These are described in three patent documents. The phosphoric acid ester compounds listed are less effective in preventing discoloration and acidification during heating.
  • Patent Document 1 Japanese Patent Publication No. 5-22322
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2004-137574
  • Patent Document 3 Japanese Patent No. 3155139
  • An object of the present invention is to provide an antioxidant exhibiting excellent solder wettability by treating tin or a tin alloy, which is excellent in antioxidant performance during heating or humidification. It is another object of the present invention to provide an anti-oxidation agent having excellent whisker characteristics and lubricity when an external load is applied.
  • the surface treatment agent in the case of a surface treatment agent containing a ⁇ compound having two or more phosphonic acid groups in one molecule and no ester bond in the molecule, the surface treatment agent is heated or calorieated. Excellent anti-humidity performance, wettability and whisker resistance in wet conditions, but insufficient whisker resistance and lubrication in areas where external stress is applied. However, sufficient characteristics were not obtained.
  • the present invention is as follows.
  • a compound having two or more phosphonic acid groups in one molecule and no ester bond in the molecule, and Z or a salt thereof, and a phosphate ester having an alkyl group having 6 to 10 carbon atoms An aqueous anti-oxidation agent for tin and tin alloys.
  • a compound having two or more phosphonic acid groups in one molecule and no ester bond in the molecule, and Z or a salt thereof are represented by the following formula (1), ( ⁇ ) or (III) Or a salt of Z or an alkali metal salt thereof, an ammonium salt, or an aminic compound thereof, and the compound according to any one of (1) to (3) above, Water-based antioxidant for tin and tin alloys.
  • x 3 and ⁇ O ⁇ oPH I 3 may be the same or different hydrogen atoms, or
  • Table 1 represents a lower alkyl group having 1 to 5 carbon atoms.
  • R 2 and R 4 each represent the following group (A), which may be the same or different, R 3 represents the following group (A), or a lower alkyl group having 1 to 5 carbon atoms, n is Represents an integer from 1 to 3.
  • X represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms
  • Y represents a hydrogen atom
  • a surface treatment method characterized by treating the surface of tin or a tin alloy with the aqueous acid / soaking agent according to any one of (1) to (4).
  • a solder ball or solder powder characterized by using a tin alloy which has been subjected to a surface treatment using the aqueous acid-rich inhibitor according to any one of (1) to (4).
  • a compound having two or more phosphonic acid groups in one molecule and no ester bond in the molecule, and Z or a salt thereof, and a phosphate ester having an alkyl group having 6 to 10 carbon atoms By surface-treating tin or a tin alloy with the water-based antioxidant of the present invention containing bismuth, it has excellent anti-oxidation performance during heating and humidification, exhibits good solder wettability, and has excellent whisker characteristics and lubrication when an external load is applied. It becomes tin or a tin alloy which is excellent in properties. Therefore, the water-based antioxidant of the present invention is suitable as an antioxidant for the tin- or tin-alloy-attached portion of the fitting portion between the FPC or FFC and the connector.
  • tin alloys are more preferred because they do not contain lead in terms of environmental pollution and other problems.
  • Sn alloy that does not contain lead Sn alloy such as solder alloy containing one or more of Zn, Bi, Cu, In, Ag and Sb.
  • the composition of the antioxidant of the present invention comprises a phosphoric acid ester having a specific alkyl group and a compound having two or more phosphonic acid groups in one molecule and no ester bond in the molecule.
  • This is an aqueous solution. It is difficult to dissolve a compound having two or more phosphonic acid groups in one molecule and not containing an ester bond in the molecule and a phosphate ester having an alkyl group. It is necessary to select the number of carbon atoms in the alkyl group. It was confirmed that the solubility in aqueous solution was low when the alkyl group of the phosphate ester having an alkyl group had 11 or more carbon atoms.
  • a compound having two or more phosphonic acid groups in one molecule and no ester bond in the molecule, and Z or a salt thereof may be contained singly or in combination.
  • the total content is preferably 0. OlgZL or more. 0. Less than OlgZL, the effect is small.
  • there is no upper limit of the content because the properties do not deteriorate even if the content is too high, but the content is more preferably 0.01 to 500 g / L due to cost problems. More preferably, 0.1 to: LOOgZL.
  • the force of a compound having two or more phosphonic acid groups in one molecule is more detailed than that of a compound having one phosphonic acid group in one molecule. It turned out to be excellent.
  • the number of phosphonic acid groups in one molecule is preferably 2 to 6 because of cost issues.
  • ⁇ 3 and ⁇ 3 each represent the same or different and Yogu hydrogen atom, or a lower alkyl group of 1 to 5 carbon atoms.
  • R 2 and R 4 each represent the following group (A), which may be the same or different, R 3 represents the following group (A), or a lower alkyl group having 1 to 5 carbon atoms, n is Represents an integer from 1 to 3.
  • X represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms
  • Y represents a hydrogen atom
  • Child a lower alkyl group having 1 to 5 carbon atoms, Yc xll alkyl group, hydroxyl group, or amino group.
  • ethylenediaminetetrakismethylenephosphonic acid, diethylenetriamine pentakismethylenephosphonic acid, etc. are particularly preferred as the compound represented by the above general formula (III).
  • 1-hydroxyethane 1,1-diphosphonic acid is particularly preferred.
  • the alkali metal salt of the above compound is preferably a sodium salt, potassium salt or the like.
  • the salt with an amine compound is preferably a triethylamine salt or a triethanolamine salt!
  • the phosphate ester having an alkyl group having 6 to 10 carbon atoms may be a mixture of a monoalkyl ester and a dialkyl ester, preferably a monoalkyl ester or a dialkyl ester! /. When it is obtained as a mixture of monoalkyl ester and dialkyl ester in production, it can be used as it is without separation, and in the case of a mixture, it may be a mixture in any proportion.
  • the phosphate ester examples include monohexyl phosphate ester, dihexyl phosphate ester, mono 2-ethylhexyl phosphate ester, di-2-ethylhexyl phosphate ester, monooctyl phosphate ester, dioctyl phosphate ester, monoiso Decyl phosphate ester, diisodecyl phosphate ester and the like are preferable.
  • the content of the antioxidant is preferably from 0.01 to LOOgZL, more preferably from 0.1 to LOg / L. When the content is less than 0. Olg / L, the film formation is insufficient, and when it exceeds lOOgZL, the stability of the liquid is remarkably lowered.
  • the anti-oxidation agent of the present invention comprises a compound having two or more phosphonic acid groups in one molecule and containing no ester bond in the molecule, Z or a salt thereof, and 6 to 10 carbon atoms.
  • a phosphate ester having an alkyl group can be used by dissolving in an aqueous solvent.
  • aqueous solvent water is preferable in consideration of solubility and cost, but alcohols, glycols, ketones and the like may be contained in addition to water.
  • the aqueous antioxidant of the present invention further improves the acid resistance of the surface to be treated by adjusting the pH to 5 or less.
  • the pH of the anti-oxidation agent is more preferably ⁇ 1 to 5 in view of the influence on the material and the like.
  • As the pH adjuster generally available acids and alkalis can be used.
  • the acid resistance of the surface to be treated is further improved. Even if the addition amount of the surfactant is less than 0. OlgZL or exceeds 1OgZL, the effect of improving acid resistance cannot be obtained.
  • the addition amount of the surfactant is preferably 0.1 to LOg / L.
  • surfactant one or more of commercially available ion-based, cationic, non-ionic, and amphoteric surfactants can be appropriately selected and used.
  • cationic surfactant sulfate ester type, sulfonate salt type, phosphate ester salt type, sulfosuccinate type, etc.
  • quaternary ammonium salt type Amine salt type isotropic non-ionic surfactants include: products with higher alcohol ethylene oxide, products with higher alcohol propylene oxide, alkylphenol ethylene oxide adducts, polyoxyethylene polyoxypropylene Block polymers 1, ethyleneoxyamine polyoxyethylene polyoxypropylene block polymers, higher aliphatic amine amine oxide adducts, aliphatic amide ethylene oxide carbonates, etc., are amphoteric surfactants such as amino acid type and betaine type. Etc. are preferred.
  • one or more of one-on or two-on Is preferably selected and used.
  • nonionic surfactants the higher glycol ethylene oxide adducts, higher alcohol propylene oxide adducts, alkyl phenol ethylene oxide adducts, polyoxyethylene polyoxypropylene block polymers are particularly preferred for the polyethylene glycol type. Etc. can be particularly preferably used.
  • a sulfate ester salt type and a phosphate ester salt type are particularly preferable.
  • the antioxidant of the present invention may contain an additive in an amount within a range that does not impair the original properties for the purpose of imparting desired performance.
  • additives include preservatives and pH buffering agents, and conventionally known additives can be used.
  • any method that forms a film on the surface of tin or tin alloy may be used.
  • tin or tin alloy may be used. Examples include a method of simply immersing in an antioxidant, a method of applying an antioxidant using a shower or a device such as an air coater, blade coater, rod coater, knife coater, gravure coater, reverse coater, cast coater, etc. .
  • the temperature of the antioxidant during the surface treatment is preferably 15 to 80 ° C, more preferably 30 to 70 ° C.
  • the surface of the conductor of the connection terminal portion of the electronic component is tinned or tin-plated and then surface-treated to provide excellent oxidation resistance, solder wettability, and whisker resistance.
  • An electronic component with good lubricity can be obtained.
  • the electronic component in the present invention includes a substrate.
  • a solder ball using a tin alloy treated with the anti-oxidation agent of the present invention has excellent oxidation resistance and is disposed as a ball grid array as an electrical connection member or in an electronic component. It can be used favorably as a mounted product connected to.
  • a tin alloy powder is treated with the antioxidant of the present invention, and a flux containing an adhesive, an activator, a thixotropic agent, a surfactant, a solvent, and the like is added to the solder paste. It can also be used. This solder paste is excellent in oxidation resistance and whisker resistance. Conventionally known pressure-sensitive adhesives, activators, thixotropic agents, surfactants and solvents can be used.
  • Comparative Example 2 As a comparative example, as shown in Table 2, six types of aqueous solutions were prepared in the same manner as in the examples (Comparative Examples 1 to 6). Since Comparative Example 7 was not treated with antioxidant, no antioxidant was prepared. Further, as Comparative Example 8, the power obtained by changing the hexyl phosphate of the solution of Example 2 to oleyl phosphate was suspended in brown, and the active ingredient was completely dissolved.
  • hexyl phosphate ester, 2-ethylhexyl phosphate ester, isodecyl phosphate ester and butyl phosphate ester are all mixtures of monoalkyl phosphate ester and dialkyl phosphate ester.
  • Nitrilotrismethylenephosphonic acid 1 / L 2 Hexyl phosphate: 0.5g / L
  • Nonylphenol ethylene oxide 12 mol adduct 1 g / L
  • Nitrilotrismethylenephosphonic acid K salt 1 g / s 6 Hexyl phosphate: 0.5 g / L
  • Nitrilotrismethylenephosphonic acid 1 g / L 2
  • Nitryltrismethylenephosphonic acid K salt 1 g / L 6
  • This substrate was tinned with a thickness of about 5 m (plating bath: Tincoat K (manufactured by Nikko Metal Plating Co., Ltd.)), plating conditions: cathode current density 2AZdm 2 , temperature 20 ° C , Liquid flow and force sword rocking).
  • This tinned base material (hereinafter referred to as "Sn base material”) was immersed in the above antioxidant for 10 seconds at a bath temperature of 60 ° C, then washed with water and dried to obtain a test substrate. It was.
  • test boards were heat-treated in an electric furnace maintained at 220 ° C for 1 hour in the air atmosphere, and then solder wettability (zero cross time) with lead-free solder was measured by the meniscograph method based on the following measurement conditions .
  • the evaluation criteria are as follows.
  • ⁇ Zero crossing time 1 second or more and less than 3 seconds
  • ⁇ Zero crossing time 3 seconds or more and less than 5 seconds
  • test boards were PCT-treated (temperature standing at 105 ° C, humidity 100% for 16 hours), and solder wettability (zero cross time) with lead-free solder was measured by meniscograph method. The measurement was performed in the same manner as the term of heat resistance and acidity.
  • the evaluation criteria are as follows.
  • ⁇ Zero crossing time 1 second or more and less than 3 seconds
  • ⁇ Zero crossing time 3 seconds or more and less than 5 seconds
  • the substrate was left for 24 hours in a constant temperature and humidity atmosphere at a temperature of 85 ° C and a humidity of 85%. Thereafter, after the substrate was sufficiently dried, the surface was observed with a scanning electron microscope (SEM). As a result, no whisker was generated in any of the examples and comparative examples.
  • SEM scanning electron microscope
  • the evaluation criteria are as follows.
  • the lubricity of the surface of the test substrate was evaluated by the coefficient of static friction.
  • Sn-Zn substrate Sn-Zn plated substrate

Abstract

Disclosed is an antioxidant which, when used for the treatment of tin or an tin alloy, shows an excellent antioxidant property during heating or humidication of the tin or tin alloy, and also shows a good solder-wettability. Also disclosed is an antioxidant which shows excellent in whisker property and lubricating property during external loading. An aqueous antioxidant for tin or a tin alloy, which comprises a compound having two or more phosphoante groups and no ester bond in the molecule and/or a salt thereof and a phosphoric acid ester having a C6-10 alkyl group. The antioxidant preferably has a pH value of up to 5, and more preferably contains a surfactant in an amount of 0.01 to 10 g/L.

Description

明 細 書  Specification
錫および錫合金の水系酸化防止剤  Aqueous antioxidants of tin and tin alloys
技術分野  Technical field
[0001] 本発明は、錫及び錫合金に対する水系酸化防止剤、及びそれを用いた表面処理 方法に関する。更に、本発明は、その水系酸ィ匕防止剤を用いて処理を行った電子部 品、はんだボール、はんだ粉末、及び該はんだボールを用いたボールグリッドアレイ 、該はんだ粉末を用いたはんだペースト、それらを用いた実装品に関する。  The present invention relates to an aqueous antioxidant for tin and a tin alloy, and a surface treatment method using the same. Furthermore, the present invention relates to an electronic component, a solder ball, a solder powder, a ball grid array using the solder ball, a solder paste using the solder powder, the electronic component processed with the aqueous anti-oxidation agent, It relates to a mounted product using them.
背景技術  Background art
[0002] はんだ付けは、融点が比較的低い物質を用いて物体同士を接合する技術であり、 現代産業において、電子機器の接合、組み立て等に幅広く用いられている。一般的 に用いられているはんだは Sn— Pb合金であり、その共晶組成（63%Sn—残部 Pb) の融点が 183°Cと低いものであることから、そのはんだ付けは 220〜230°Cで行われ るため、電子部品や基板に対しほとんど熱損傷を与えない。し力も、 Sn—Pb合金は 、はんだ付け性が良好であるとともに、はんだ付け時にすぐに凝固して、はんだ付け 部に振動が加わっても割れや剥離を起こし難 ヽと ヽぅ優れた特徴も有して ヽる。  [0002] Soldering is a technique for joining objects using a material having a relatively low melting point, and is widely used in joining and assembling electronic devices in the modern industry. Generally used solder is Sn-Pb alloy, and its eutectic composition (63% Sn-remainder Pb) has a low melting point of 183 ° C, so soldering is 220-230 °. Since it is performed in C, it causes little thermal damage to electronic components and boards. The Sn-Pb alloy also has good solderability and solidifies immediately during soldering, and does not easily crack or peel even when vibration is applied to the soldered part. Have it.
[0003] 一般に電子機器は、外枠や基板等の合成樹脂と導体部やフレーム等の金属により 形成されており、廃棄処分された場合は、焼却処分されず、ほとんどが地中に埋め立 てられる。近年、地上に降る雨は酸性を示す傾向にあり（酸性雨）、地中に埋められ た電子機器のはんだを溶出させて、地下水を汚染することが問題ィ匕している。このた め、特に電子機器業界において、鉛を含まないはんだ (鉛フリーはんだ)への代替の 動きが急速に進んでいる。  [0003] Generally, electronic devices are formed of synthetic resin such as an outer frame and a substrate, and metal such as a conductor and a frame, and when disposed, they are not incinerated and mostly buried in the ground. It is done. In recent years, rain on the ground has a tendency to show acidity (acid rain), and it has been a problem to contaminate groundwater by eluting the solder of electronic equipment buried in the ground. For this reason, there is a rapid movement to replace lead-free solder (lead-free solder), especially in the electronics industry.
[0004] 電子部品の外部リード端子には、そのはんだ濡れ性と耐食性を向上させるため、主 にはんだめつき（90%Sn—残部 Pb)が施されており、その鉛フリー化への対応が望 まれている。鉛フリーはんだめつきの候補としては、純 Sn、 Sn— Ag (Cu)系、 Sn— Z n系、 Sn—Bi系に大別される力 それぞれ一長一短があり Sn—Pb合金を完全に代 替するには未だ至って!/、な!/、。  [0004] External lead terminals of electronic components are mainly soldered (90% Sn—remaining Pb) to improve solder wettability and corrosion resistance. Is desired. Candidates for lead-free soldering can be classified into pure Sn, Sn—Ag (Cu), Sn—Zn, and Sn—Bi. I still have to come! /
[0005] 純 Snめっきは、コストやめつきの作業性等、総合的にみて鉛フリーめつきとしては最 有力と考えられる。しかし、純 Snめっきは表面の酸ィ匕ゃ内部応力に起因して、ゥイス カーが発生し易 、ことに加え、経時的にはんだ濡れ性が劣化し易 ヽと 、う課題があり 、その改善が強く要望されている。 [0005] Pure Sn plating is the best lead-free plating in terms of cost and workability. It is considered promising. However, pure Sn plating has a problem that it is easy to generate a whisker due to the internal stress of the surface acid, and the solder wettability deteriorates over time. Is strongly demanded.
[0006] Sn— Zn系合金は、従来の Sn—Pb系合金と融点が近いことから、 Sn— Zn系めつ きは、現在の設備や工程を変える必要がないという点で有利である。また、めっき被 膜の機械的強度に優れ、コスト的にも優れている。しかし、 Znは活性な金属種である ことから酸ィ匕し易ぐ Sn—Zn系合金のはんだ濡れ性が非常に悪いため、現時点では 、実用化される可能性は最も低いと考えられている。  [0006] Since Sn—Zn alloys have melting points close to those of conventional Sn—Pb alloys, Sn—Zn alloys are advantageous in that it is not necessary to change current facilities and processes. In addition, the plating film is excellent in mechanical strength and cost. However, because Zn is an active metal species, the solder wettability of Sn-Zn alloys, which are easily oxidized, is very poor. .
[0007] はんだペーストは、電子部品を基板に表面実装するために用いられ、近年その使 用量が増大している。はんだペーストは、一般には、はんだ合金粉末を主体とし、粘 着剤、活性剤、チクソトロピック剤、界面活性剤、溶剤等を含むフラックスを加えたもの である。はんだペーストの鉛フリー化として、 Sn— Ag (Cu)系合金、 Sn— Zn系合金、 Sn— Bi系合金が検討されている力 Sn—Zn系合金は前述した通り、従来の Sn— P b系はんだの共晶温度に近いことから、代替の有力な候補として考えられている。し かし、前述の通り Znの酸化されやすさから、 Sn—Zn系合金をはんだ粉末として用い たはんだペーストはフラックスに含まれる活性剤と酸ィ匕反応を起こし、はんだ濡れ性、 保存安定性が著しく悪ぐまたリフロー時に不活性ガス雰囲気が必要という欠点があ る。  [0007] Solder paste is used for surface mounting an electronic component on a substrate, and its usage is increasing in recent years. The solder paste is generally composed of a solder alloy powder as a main component and added with a flux containing an adhesive, an activator, a thixotropic agent, a surfactant, a solvent, and the like. Sn-Ag (Cu), Sn-Zn, and Sn-Bi alloys are being investigated as lead-free solder pastes. Because it is close to the eutectic temperature of a solder, it is considered as a promising alternative candidate. However, as described above, because of the ease of oxidation of Zn, solder paste using Sn-Zn alloy as solder powder causes an acid-oxidation reaction with the activator contained in the flux, resulting in solder wettability and storage stability. However, there is a disadvantage that an inert gas atmosphere is required during reflow.
[0008] 従来の技術より、リン酸エステル化合物を用いて表面処理することにより、錫および 錫合金の耐湿性および潤滑性が優れることが確認されている (特許文献 1、特許文 献 2、特許文献 3参照)。特許文献 1では、エチレンオキサイドを含有し、親油基として 炭素数 8〜30のアルキルフエ-ル基を含有するリン酸エステル型界面活性剤が例示 されている。このような構造の場合、潤滑性には優れるものの、エチレンオキサイドが 親水性のため吸湿し、加湿時の酸ィ匕防止機能が十分でない。特許文献 2では、炭素 数 10〜26の飽和または不飽和アルキル基を含有するリン酸エステルが好ましいこと が記載されている。特許文献 3では、フエニル基または炭素数 5以下のアルキル基を 含有するリン酸エステルが記載されている。この場合、加湿時における酸ィ匕防止機能 は優れるものの、潤滑性能が十分に得られない。また、これらに 3件の特許文献に記 載されているリン酸エステル系化合物は、加熱時の変色や酸ィ匕防止には効果が低い [0008] From the prior art, it has been confirmed that surface treatment with a phosphoric ester compound improves the moisture resistance and lubricity of tin and tin alloys (Patent Document 1, Patent Document 2, Patent) Reference 3). Patent Document 1 exemplifies a phosphate ester type surfactant containing ethylene oxide and having an alkylphenol group having 8 to 30 carbon atoms as a lipophilic group. In the case of such a structure, although lubricity is excellent, ethylene oxide absorbs moisture because of hydrophilicity, and the function of preventing oxidation during humidification is not sufficient. Patent Document 2 describes that a phosphate ester containing a saturated or unsaturated alkyl group having 10 to 26 carbon atoms is preferable. Patent Document 3 describes a phosphate ester containing a phenyl group or an alkyl group having 5 or less carbon atoms. In this case, the anti-oxidation function during humidification is excellent, but sufficient lubrication performance cannot be obtained. These are described in three patent documents. The phosphoric acid ester compounds listed are less effective in preventing discoloration and acidification during heating.
[0009] また、 RoHS指令により 2006年 7月力 鉛フリー化が実施されることとなっているが 、鉛フリー化に伴う 、くつかの問題が未だ解決されて 、な 、状況であり、 JEITAでは 鉛フリーはんだ完遂緊急プロジェクトが発足した CFEITA鉛フリー化完遂緊急提言報 告書、 2005年 3月、社団法人電子情報技術産業協会、実装技術標準化委員会より ) oそれらの問題の 1つがウイスカーである。錫系めつき液の改良や銅の拡散ノ リヤー 層として錫系めつき前に Niめっきを行う等により、被膜の内部応力を低減し、耐ゥイス カー性が大幅に改善されることがわ力つてきている力 FPC (フレキシブル印刷回路) または FFC (フレキシブルフラットケーブル）とコネクターの嵌合部のように外部応力 力 Sかかるところでの耐ゥイスカー性が未だ解決できて 、な 、状況にある。 [0009] In addition, the RoHS directive will lead to lead-free implementation in July 2006, but some of the problems associated with lead-free implementation have not yet been solved. (From the CFEITA Lead-Free Immediate Proposal Report, March 2005, Japan Electronics and Information Technology Industries Association, Mounting Technology Standardization Committee) is there. By improving the tin-based plating solution and performing Ni plating before tin-based plating as a copper diffusion layer, it is possible to reduce the internal stress of the coating and greatly improve the whisker resistance. Current force Whisker resistance in places where external stress force S is applied, such as FPC (flexible printed circuit) or FFC (flexible flat cable) and connector fittings, is still in a situation.
特許文献 1：特公平 5 - 22322号公報  Patent Document 1: Japanese Patent Publication No. 5-22322
特許文献 2：特開 2004 - 137574号公報  Patent Document 2: Japanese Patent Application Laid-Open No. 2004-137574
特許文献 3：特許第 3155139号公報  Patent Document 3: Japanese Patent No. 3155139
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0010] 本発明は、錫や錫合金を処理することにより、加熱や加湿時の酸化防止性能に優 れ、良好なはんだ濡れ性を示す酸化防止剤を提供することを目的とする。更に、外 部荷重をカゝけた際のウイスカー特性および潤滑性にも優れる酸ィ匕防止剤を提供する ことを目的とする。 [0010] An object of the present invention is to provide an antioxidant exhibiting excellent solder wettability by treating tin or a tin alloy, which is excellent in antioxidant performance during heating or humidification. It is another object of the present invention to provide an anti-oxidation agent having excellent whisker characteristics and lubricity when an external load is applied.
課題を解決するための手段  Means for solving the problem
[0011] 本発明者らは、錫及び錫合金表面の酸ィ匕抑制に対し、鋭意研究を重ねた結果、既 に、一分子内に 2個以上のホスホン酸基を持ち、分子内にエステル結合を含まない 化合物、及び Z又はその塩の 1種もしくは 2種以上を合計で 0. OlgZL以上含む表 面処理剤で表面処理することにより、耐酸化性を付与し、はんだ濡れ性を改善し、ゥ イスカーの発生を抑制することができることを見出した（国際公開第 2005Z085498 A1号パンフレット参照)。しかし、前記一分子内に 2個以上のホスホン酸基を持ち、 分子内にエステル結合を含まな ヽ化合物を含有する表面処理剤では、加熱時やカロ 湿時の酸化防止性能、はんだ濡れ性、耐ゥイスカー性に優れるものの、外部応力が 力かる部分の耐ゥイスカー性、潤滑性能が不十分であり、 FPCまたは FFCとコネクタ 一の嵌合部分の使用には十分な特性が得られかった。 [0011] As a result of intensive studies on the suppression of acid and soot on the surface of tin and tin alloys, the present inventors have already had two or more phosphonic acid groups in one molecule and ester in the molecule. Surface treatment with a surface treatment agent containing a total of 0. OlgZL or more of a compound that does not contain a bond, and one or more of Z or a salt thereof provides oxidation resistance and improves solder wettability. They found that the occurrence of whisker can be suppressed (see pamphlet of International Publication No. 2005Z085498 A1). However, in the case of a surface treatment agent containing a ヽ compound having two or more phosphonic acid groups in one molecule and no ester bond in the molecule, the surface treatment agent is heated or calorieated. Excellent anti-humidity performance, wettability and whisker resistance in wet conditions, but insufficient whisker resistance and lubrication in areas where external stress is applied. However, sufficient characteristics were not obtained.
[0012] そこで、更に検討した結果、一分子内に 2個以上のホスホン酸基を持ち、分子内に エステル結合を含まない化合物、及び Z又はその塩と、炭素数 6〜 10のアルキル基 を有するリン酸エステルとを含む水系酸化防止剤で錫および錫合金を表面処理する ことにより、加熱時や加湿時の酸ィ匕防止性能、はんだ濡れ性、耐ゥイスカー性にも優 れるとともに、外部応力がかかる部分の耐ゥイスカー性、潤滑性能にも優れ、 FPCま たは FFCとコネクターとの嵌合部の錫または錫合金めつき表面に使用しても好適で あることを見出した。  [0012] Therefore, as a result of further investigation, a compound having two or more phosphonic acid groups in one molecule and no ester bond in the molecule, and Z or a salt thereof, and an alkyl group having 6 to 10 carbon atoms By surface-treating tin and tin alloys with an aqueous antioxidant containing a phosphate ester, it has excellent anti-oxidation performance, solder wettability and whisker resistance during heating and humidification, as well as external stress. It has been found that this part has excellent whisker resistance and lubrication performance, and is suitable for use on a tin or tin alloy plating surface at the joint between FPC or FFC and connector.
[0013] 即ち本発明は、以下のとおりである。  [0013] That is, the present invention is as follows.
(1)一分子内に 2個以上のホスホン酸基を持ち、分子内にエステル結合を含まない 化合物、及び Z又はその塩と、炭素数 6〜 10のアルキル基を有するリン酸エステルと を含むことを特徴とする錫および錫合金の水系酸ィ匕防止剤。  (1) A compound having two or more phosphonic acid groups in one molecule and no ester bond in the molecule, and Z or a salt thereof, and a phosphate ester having an alkyl group having 6 to 10 carbon atoms An aqueous anti-oxidation agent for tin and tin alloys.
(2)前記水系酸ィ匕防止剤の pHが 5以下であることを特徴とする前記（1)記載の錫お よび錫合金の水系酸化防止剤。  (2) The aqueous antioxidant for tin and tin alloy according to the above (1), wherein the pH of the aqueous antioxidant is 5 or less.
(3)更に界面活性剤を 0. 01g/L〜10g/L含有することを特徴とする前記（1)また は（2)に記載の錫および錫合金の水系酸化防止剤。  (3) The tin- and tin-alloy aqueous antioxidant according to (1) or (2) above, further containing a surfactant in an amount of 0.01 g / L to 10 g / L.
[0014] (4)前記一分子内に 2個以上のホスホン酸基を持ち、分子内にエステル結合を含ま ない化合物、及び Z又はその塩が下記式 (1)、 （Π)又は (III)で表される化合物、及び Z又はそのアルカリ金属塩、アンモニゥム塩、又はアミンィ匕合物との塩であることを特 徴とする前記（1)〜（3)の 、ずれか一項に記載の錫および錫合金の水系酸化防止 剤。  [0014] (4) A compound having two or more phosphonic acid groups in one molecule and no ester bond in the molecule, and Z or a salt thereof are represented by the following formula (1), (Π) or (III) Or a salt of Z or an alkali metal salt thereof, an ammonium salt, or an aminic compound thereof, and the compound according to any one of (1) to (3) above, Water-based antioxidant for tin and tin alloys.
[化 1]
Figure imgf000006_0001
[Chemical 1]
Figure imgf000006_0001
(式 (I)中、 x3及び 〜 O丫 oPH I 3は各々同一もしくは異なってもよぐ水素原子、又は (In the formula (I), x 3 and ~ O 丫 oPH I 3 may be the same or different hydrogen atoms, or
XI  XI
炭素数 1〜5の低級アルキル基を表 〇 =す。 ) Table 1 represents a lower alkyl group having 1 to 5 carbon atoms. )
[化 2] ] n - R1 (Π) [Chemical 2]] n -R 1 (Π)
(式 (II)中、
Figure imgf000006_0002
R2及び R4は、各々同一もしくは異なってもよぐ以下の基 (A)を表し 、 R3は、以下の基 (A)、又は炭素数 1〜5の低級アルキル基を表し、 nは 1〜3の整数 を表す。 (In the formula (II),
Figure imgf000006_0002
R 2 and R 4 each represent the following group (A), which may be the same or different, R 3 represents the following group (A), or a lower alkyl group having 1 to 5 carbon atoms, n is Represents an integer from 1 to 3.
[化 3] [Chemical 3]
Figure imgf000006_0003
基 (A)中、 X1、及び Y1は、一般式 (I)における定義と同じである。 )
Figure imgf000006_0003
In the group (A), X 1 and Y 1 are the same as defined in the general formula (I). )
[化 4] [Chemical 4]
Figure imgf000006_0004
Figure imgf000006_0004
(式 (III)中、 Xは水素原子、又は炭素数 1〜5の低級アルキル基を表し、 Yは水素原 子、炭素数 1〜5の低級アルキル基、水酸基、又はアミノ基を表す。 ) (In the formula (III), X represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms; Y represents a hydrogen atom; And a lower alkyl group having 1 to 5 carbon atoms, a hydroxyl group, or an amino group. )
[0017] (5)前記（1)〜 (4)のいずれか一項に記載の水系酸ィ匕防止剤を用いて錫または錫 合金の表面を処理することを特徴とする表面処理方法。 [0017] (5) A surface treatment method characterized by treating the surface of tin or a tin alloy with the aqueous acid / soaking agent according to any one of (1) to (4).
(6)電子部品の接続端子部の導体表面に、錫または錫合金めつきを施した後に、前 記（1)〜 (4)の 、ずれか一項に記載の水系酸ィ匕防止剤を用いて表面処理を行った ことを特徴とする電子部品。  (6) After applying tin or tin alloy plating to the conductor surface of the connection terminal portion of the electronic component, the water-based anti-oxidation agent according to any one of (1) to (4) above is applied. An electronic component characterized by using a surface treatment.
(7)前記（1)〜 (4)の 、ずれか一項に記載の水系酸ィヒ防止剤を用いて表面処理を 行った錫合金を用いたことを特徴とするはんだボールもしくははんだ粉末。  (7) A solder ball or solder powder characterized by using a tin alloy which has been subjected to a surface treatment using the aqueous acid-rich inhibitor according to any one of (1) to (4).
(8)前記（7)に記載のはんだボールを電気的接続部材として用いたことを特徴とする ボールグリッドアレイ。  (8) A ball grid array using the solder balls described in (7) as an electrical connection member.
(9)前記（7)に記載のはんだボールを電子部品に配置し、これを回路基板に接続し たことを特徴とする実装品。  (9) A mounted product in which the solder ball according to (7) is arranged on an electronic component and connected to a circuit board.
(10)前記（7)に記載のはんだ粉末を用 V、たことを特徴とするはんだペースト。  (10) A solder paste, wherein the solder powder according to (7) is used V.
( 11 )前記（ 10)に記載のはんだペーストを用 、たことを特徴とする実装品。  (11) A mounted product using the solder paste according to (10) above.
発明の効果  The invention's effect
[0018] 一分子内に 2個以上のホスホン酸基を持ち、分子内にエステル結合を含まない化 合物、及び Z又はその塩と、炭素数 6〜 10のアルキル基を有するリン酸エステルとを 含む本発明の水系酸化防止剤で錫または錫合金を表面処理することにより、加熱や 加湿時の酸化防止性能に優れ、良好なはんだ濡れ性示し、外部荷重をかけた際の ゥイスカー特性および潤滑性にも優れる錫または錫合金となる。したがって、本発明 の水系酸化防止剤は、 FPCまたは FFCとコネクターとの嵌合部の錫または錫合金め つき部分の酸化防止剤として好適である。  [0018] A compound having two or more phosphonic acid groups in one molecule and no ester bond in the molecule, and Z or a salt thereof, and a phosphate ester having an alkyl group having 6 to 10 carbon atoms By surface-treating tin or a tin alloy with the water-based antioxidant of the present invention containing bismuth, it has excellent anti-oxidation performance during heating and humidification, exhibits good solder wettability, and has excellent whisker characteristics and lubrication when an external load is applied. It becomes tin or a tin alloy which is excellent in properties. Therefore, the water-based antioxidant of the present invention is suitable as an antioxidant for the tin- or tin-alloy-attached portion of the fitting portion between the FPC or FFC and the connector.
図面の簡単な説明  Brief Description of Drawings
[0019] [図 1]実施例における静摩擦係数の測定方法を示す概略図である。  FIG. 1 is a schematic view showing a method for measuring a static friction coefficient in an example.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0020] 以下に本発明の酸化防止剤について詳述する。 [0020] The antioxidant of the present invention is described in detail below.
本発明の錫および錫合金の水系酸化防止剤で処理される錫合金としては、環境汚 染等の問題力も鉛を含まな 、錫合金がより好まし 、。鉛を含まな 、Sn合金としては、 Sn〖こ Zn、 Bi、 Cu、 In、 Ag、 Sbのいずれか一つもしくは二つ以上を含むはんだ合金 等が挙げられる。 As the tin alloy to be treated with the tin and tin alloy aqueous antioxidant of the present invention, tin alloys are more preferred because they do not contain lead in terms of environmental pollution and other problems. As an Sn alloy that does not contain lead, Sn alloy such as solder alloy containing one or more of Zn, Bi, Cu, In, Ag and Sb.
[0021] 本発明の酸化防止剤の組成は、特定のアルキル基を有するリン酸エステルと、一 分子内に 2個以上のホスホン酸基を持ち分子内にエステル結合を含まない化合物と を有効成分とした水系溶液である。一分子内に 2個以上のホスホン酸基を持ち分子 内にエステル結合を含まな ヽ化合物と、アルキル基を有するリン酸エステルとを溶解 するのは困難であり、そのため後者のリン酸エステルのエステル部分のアルキル基の 炭素数を選択することが必要となる。アルキル基を有するリン酸エステルのアルキル 基の炭素数が 11以上であると水溶液としての溶解性が低いことが確認された。また、 炭素数が 5以下のアルキル基では溶解するものの、潤滑性能が十分に得られな!/、。 したがって溶解性および潤滑性のバランスとして、炭素数 6〜： L0のアルキル基を有 するリン酸エステルが良いことを見出した。また、この特定のリン酸エステルと、一分 子内に 2個以上のホスホン酸基を持ち分子内にエステル結合を含まない化合物との 組み合わせは、外部応力がかけられた際のウイスカー抑制にも効果的であることが見 出された。  The composition of the antioxidant of the present invention comprises a phosphoric acid ester having a specific alkyl group and a compound having two or more phosphonic acid groups in one molecule and no ester bond in the molecule. This is an aqueous solution. It is difficult to dissolve a compound having two or more phosphonic acid groups in one molecule and not containing an ester bond in the molecule and a phosphate ester having an alkyl group. It is necessary to select the number of carbon atoms in the alkyl group. It was confirmed that the solubility in aqueous solution was low when the alkyl group of the phosphate ester having an alkyl group had 11 or more carbon atoms. Also, although alkyl groups with 5 or less carbons can be dissolved, sufficient lubrication performance cannot be obtained! /. Therefore, it has been found that a phosphate ester having an alkyl group having 6 to C0 carbon atoms is good as a balance between solubility and lubricity. In addition, the combination of this specific phosphate ester with a compound having two or more phosphonic acid groups in the molecule and no ester bond in the molecule also suppresses whisker when external stress is applied. It was found to be effective.
[0022] 酸化防止剤中、一分子内に 2個以上のホスホン酸基を持ち、分子内にエステル結 合を含まない化合物、及び Z又はその塩は、 1種もしくは 2種以上含有してもよぐ合 計で 0. OlgZL以上含有することが好ましい。 0. OlgZL未満であるとその効果が 小さい。また、逆に含有量が多過ぎても特性が劣化することはないため、含有量の上 限はないが、コスト的な問題から、含有量は 0. 01〜500g/Lがより好ましぐさらに 好ましくは 0. 1〜： LOOgZLである。  [0022] In the antioxidant, a compound having two or more phosphonic acid groups in one molecule and no ester bond in the molecule, and Z or a salt thereof may be contained singly or in combination. The total content is preferably 0. OlgZL or more. 0. Less than OlgZL, the effect is small. On the other hand, there is no upper limit of the content because the properties do not deteriorate even if the content is too high, but the content is more preferably 0.01 to 500 g / L due to cost problems. More preferably, 0.1 to: LOOgZL.
[0023] また、一分子内に 2個以上のホスホン酸基を有する化合物の方力 一分子内にホス ホン酸基が 1個の化合物より、詳細なメカニズムは不明であるが、耐酸化性能が優れ ることが判明した。一分子内のホスホン酸基の数は、コスト的な問題から 2〜6が好ま しい。  [0023] In addition, the force of a compound having two or more phosphonic acid groups in one molecule is more detailed than that of a compound having one phosphonic acid group in one molecule. It turned out to be excellent. The number of phosphonic acid groups in one molecule is preferably 2 to 6 because of cost issues.
一分子内に 2個以上のホスホン酸基を持ち、分子内にエステル結合を含まない化 合物、及び Z又はその塩としては、例えば下記一般式 (1)、 （11)、 （III)で示される化 合物、及び Z又はそのアルカリ金属塩、アンモ-ゥム塩、ァミン化合物との塩が挙げ られる。 As a compound having two or more phosphonic acid groups in one molecule and not containing an ester bond in the molecule, and Z or a salt thereof, for example, in the following general formulas (1), (11), (III) And compounds with Z or alkali metal salts thereof, ammonium salts, and amine compounds. It is done.
[0024] [化 5]  [0024] [Chemical 5]
Figure imgf000009_0001
Figure imgf000009_0001
(式 (I)中、 〜 3及び 〜丫3は各々同一もしくは異なってもよぐ水素原子、又は 炭素数 1〜5の低級アルキル基を表す。 ) (Formula (in I), ~ 3 and ~丫3 each represent the same or different and Yogu hydrogen atom, or a lower alkyl group of 1 to 5 carbon atoms.)
[化 6]  [Chemical 6]
(式 (II)中、
Figure imgf000009_0002
R2及び R4は、各々同一もしくは異なってもよぐ以下の基 (A)を表し 、 R3は、以下の基 (A)、又は炭素数 1〜5の低級アルキル基を表し、 nは 1〜3の整数 を表す。 (In the formula (II),
Figure imgf000009_0002
R 2 and R 4 each represent the following group (A), which may be the same or different, R 3 represents the following group (A), or a lower alkyl group having 1 to 5 carbon atoms, n is Represents an integer from 1 to 3.
[化 7]  [Chemical 7]
Figure imgf000009_0003
基 (A)中、 X1、及び Y1は、一般式 (I)における定義と同じである。 )
Figure imgf000009_0003
In the group (A), X 1 and Y 1 are the same as defined in the general formula (I). )
[0026] [ィ匕 8] (式 (III)中、 Xは水素原子、又は炭素数 1〜5の低級アルキル基を表し、 Yは水素原[0026] [8] (In the formula (III), X represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms; Y represents a hydrogen atom;
〇 o p =l O p = l
子、炭素数 1〜5の低級ア Yc xllルキル基、水酸基、又はアミノ基を表す。 )  Child, a lower alkyl group having 1 to 5 carbon atoms, Yc xll alkyl group, hydroxyl group, or amino group. )
[0027] 上記一般式 (I)で表される化 ◦ 0p H I合物としては、二トリロトリスメチレンホスホン酸等がェ 業的に入手可能なため特に好ましい。 [0027] As the compound represented by the above general formula (I): 0pH I compound, nitrilotrismethylene phosphonic acid and the like are particularly preferable because they are commercially available.
同様に、上記一般式 (II)で表される化合物としては、エチレンジアミンテトラキスメチ レンホスホン酸、ジエチレントリァミンペンタキスメチレンホスホン酸等が特に好ましぐ 上記一般式（III)で表される化合物としては、 1ーヒドロキシェタン 1, 1ージホスホン 酸等が特に好ましい。  Similarly, as the compound represented by the above general formula (II), ethylenediaminetetrakismethylenephosphonic acid, diethylenetriamine pentakismethylenephosphonic acid, etc. are particularly preferred as the compound represented by the above general formula (III). 1-hydroxyethane 1,1-diphosphonic acid is particularly preferred.
[0028] 上記化合物のアルカリ金属塩としては、ナトリウム塩、カリウム塩等が好ましぐァミン 化合物との塩としては、トリェチルアミン塩ゃトリエタノールアミン塩等が好まし!/、。  [0028] The alkali metal salt of the above compound is preferably a sodium salt, potassium salt or the like. The salt with an amine compound is preferably a triethylamine salt or a triethanolamine salt!
[0029] 炭素数 6〜10のアルキル基を有するリン酸エステルとしては、モノアルキルエステ ル、ジアルキルエステルが好ましぐモノアルキルエステルとジアルキルエステルの混 合物であってもよ!/、。製造上モノアルキルエステルとジアルキルエステルの混合物で 得られる場合は、分離する必要はなぐ混合物のまま用いることができ、混合物の場 合は、いかなる割合の混合物であってもよい。上記リン酸エステルとしては、例えば、 モノへキシルリン酸エステル、ジへキシルリン酸エステル、モノ 2—ェチルへキシルリ ン酸エステル、ジ 2—ェチルへキシルリン酸エステル、モノォクチルリン酸エステル、 ジォクチルリン酸エステル、モノイソデシルリン酸エステル、ジイソデシルリン酸エステ ル等が好ましい。含有量は、酸化防止剤中 0. 01〜： LOOgZLが好ましぐより好ましく は、 0. 1〜： LOg/Lである。含有量が 0. Olg/L未満であると、被膜生成が不十分で あり、 lOOgZLを超えて含有すると、液の安定性が著しく低下する。  [0029] The phosphate ester having an alkyl group having 6 to 10 carbon atoms may be a mixture of a monoalkyl ester and a dialkyl ester, preferably a monoalkyl ester or a dialkyl ester! /. When it is obtained as a mixture of monoalkyl ester and dialkyl ester in production, it can be used as it is without separation, and in the case of a mixture, it may be a mixture in any proportion. Examples of the phosphate ester include monohexyl phosphate ester, dihexyl phosphate ester, mono 2-ethylhexyl phosphate ester, di-2-ethylhexyl phosphate ester, monooctyl phosphate ester, dioctyl phosphate ester, monoiso Decyl phosphate ester, diisodecyl phosphate ester and the like are preferable. The content of the antioxidant is preferably from 0.01 to LOOgZL, more preferably from 0.1 to LOg / L. When the content is less than 0. Olg / L, the film formation is insufficient, and when it exceeds lOOgZL, the stability of the liquid is remarkably lowered.
[0030] また、酸化防止剤中の、一分子内に 2個以上のホスホン酸基を持ち、分子内にエス テル結合を含まない化合物 (A)と、炭素数 6〜： L0のアルキル基を有するリン酸エステ ル (B)の割合は、重量比で、 A: B= 1 : 2〜1 : 0. 01が好ましぐより好ましくは、 1 : 1 〜1 :0. 1である。一分子内に 2個以上のホスホン酸基を持ち、分子内にエステル結 合を含まない化合物 (A)と、炭素数 6〜： L0のアルキル基を有するリン酸エステル (B) の比 (AZB)が 1Z2未満であると、耐湿酸化防止性能が低下し、 100を超えると、耐 熱酸ィ匕防止性能が低下する。 [0030] In addition, a compound (A) having two or more phosphonic acid groups in one molecule and no ester bond in the molecule, and an alkyl group having 6 to 10 carbon atoms in the antioxidant. The ratio of the phosphoric ester (B) to be contained is, by weight ratio, A: B = 1: 2 to 1: 0.01, more preferably 1: 1. ~ 1: 0: 1. Ratio of compound (A) having two or more phosphonic acid groups in one molecule and no ester bond in the molecule to phosphate ester (B) having an alkyl group of 6 to: L0 (AZB ) Is less than 1Z2, the anti-oxidation performance against moisture decreases, and when it exceeds 100, the anti-oxidation performance against heat and oxidation deteriorates.
[0031] 本発明の酸ィ匕防止剤は、一分子内に 2個以上のホスホン酸基を持ち分子内にエス テル結合を含まない化合物、及び Z又はその塩と、炭素数 6〜 10のアルキル基を有 するリン酸エステルを水系溶媒に溶解して用いることができる。水系溶媒としては、溶 解度、コストを考慮すると水が好ましいが、水以外にアルコール類、グリコール類、ケ トン類等が含有されて 、ても良 、。 [0031] The anti-oxidation agent of the present invention comprises a compound having two or more phosphonic acid groups in one molecule and containing no ester bond in the molecule, Z or a salt thereof, and 6 to 10 carbon atoms. A phosphate ester having an alkyl group can be used by dissolving in an aqueous solvent. As the aqueous solvent, water is preferable in consideration of solubility and cost, but alcohols, glycols, ketones and the like may be contained in addition to water.
[0032] また、本発明の水系酸化防止剤は、 pHを 5以下に調整することにより、被処理表面 の耐酸ィ匕性が更に向上することを見出した。酸ィ匕防止剤の pHは、素材等への影響 を鑑み、より好ましくは ρΗ1〜5である。 pH調整剤としては、一般的に入手可能な酸 、アルカリが使用可能である。  [0032] Further, it has been found that the aqueous antioxidant of the present invention further improves the acid resistance of the surface to be treated by adjusting the pH to 5 or less. The pH of the anti-oxidation agent is more preferably ρΗ1 to 5 in view of the influence on the material and the like. As the pH adjuster, generally available acids and alkalis can be used.
[0033] 更に、水系酸ィ匕防止剤に界面活性剤を 0. 01〜10gZL添加することにより、被処 理表面の耐酸ィ匕性がよりいつそう向上する。界面活性剤の添加量が 0. OlgZL未満 であったり、 lOgZLを超えて添加しても耐酸ィ匕性の向上効果が得られない。界面活 性剤の添加量は、好ましくは 0. 1〜： LOg/Lである。  [0033] Further, by adding 0.01 to 10 g ZL of a surfactant to the water-based anti-oxidation agent, the acid resistance of the surface to be treated is further improved. Even if the addition amount of the surfactant is less than 0. OlgZL or exceeds 1OgZL, the effect of improving acid resistance cannot be obtained. The addition amount of the surfactant is preferably 0.1 to LOg / L.
界面活性剤としては、市販のァ-オン系、カチオン系、ノ-オン系、及び両性界面 活性剤の 1種もしくは 2種以上を適宜選択して使用することができる。  As the surfactant, one or more of commercially available ion-based, cationic, non-ionic, and amphoteric surfactants can be appropriately selected and used.
ァ-オン系界面活性剤としては、硫酸エステル塩型、スルホン酸塩型、リン酸エステ ル塩型、スルホサクシネート型等力 カチオン系界面活性剤としては、四級アンモ- ゥム塩型、アミン塩型等力 ノ-オン系界面活性剤としては、高級アルコールェチレ ンオキサイド付カ卩物、高級アルコールプロピレンオキサイド付カ卩物、アルキルフエノー ルエチレンオキサイド付加物、ポリオキシエチレンポリオキシプロピレンブロックポリマ 一、エチレンジァミンのポリオキシエチレンポリオキシプロピレンブロックポリマー、高 級脂肪族ァミンのエチレンオキサイド付加物、脂肪族アミドのエチレンオキサイド付カロ 物等が、両性界面活性剤としては、アミノ酸型、ベタイン型等が好ましい。  As the cationic surfactant, sulfate ester type, sulfonate salt type, phosphate ester salt type, sulfosuccinate type, etc. As the cationic surfactant, quaternary ammonium salt type, Amine salt type isotropic non-ionic surfactants include: products with higher alcohol ethylene oxide, products with higher alcohol propylene oxide, alkylphenol ethylene oxide adducts, polyoxyethylene polyoxypropylene Block polymers 1, ethyleneoxyamine polyoxyethylene polyoxypropylene block polymers, higher aliphatic amine amine oxide adducts, aliphatic amide ethylene oxide carbonates, etc., are amphoteric surfactants such as amino acid type and betaine type. Etc. are preferred.
[0034] pHを 5以下の範囲で使用する際は、ァ-オン系、ノ-オン系の 1種もしくは 2種以上 を適宜選択して使用することが好ましい。中でも、ノニオン系界面活性剤では、ポリエ チレングリコール型が特に好ましぐ高級アルコールエチレンオキサイド付加物、高級 アルコールプロピレンオキサイド付カ卩物、アルキルフエノールエチレンオキサイド付カロ 物、ポリオキシエチレンポリオキシプロピレンブロックポリマー等を特に好ましく用いる ことができる、また、ァ-オン系界面活性剤では、硫酸エステル塩型、リン酸エステル 塩型が特に好ましい。 [0034] When the pH is used in the range of 5 or less, one or more of one-on or two-on Is preferably selected and used. Among nonionic surfactants, the higher glycol ethylene oxide adducts, higher alcohol propylene oxide adducts, alkyl phenol ethylene oxide adducts, polyoxyethylene polyoxypropylene block polymers are particularly preferred for the polyethylene glycol type. Etc. can be particularly preferably used. In addition, as the ionic surfactant, a sulfate ester salt type and a phosphate ester salt type are particularly preferable.
[0035] また、本発明の酸化防止剤は、所望の性能を付与させる目的で本来の性質を損な わない範囲の量の添加剤を含んでいてもよい。添加剤としては、防腐剤、 pH緩衝剤 等が挙げられ、これらは従来公知のものを用いることができる。  [0035] Further, the antioxidant of the present invention may contain an additive in an amount within a range that does not impair the original properties for the purpose of imparting desired performance. Examples of additives include preservatives and pH buffering agents, and conventionally known additives can be used.
[0036] 本発明の酸ィ匕防止剤を用いて錫または錫合金を表面処理するには、錫または錫合 金の表面に被膜を形成する方法であればよぐ例えば、錫または錫合金を単に酸ィ匕 防止剤に浸漬させる方法、酸化防止剤を、シャワー、又はエアードコータ、ブレードコ ータ、ロッドコータ、ナイフコータ、グラビアコータ、リバースコータ、キャストコータなど の装置を用いて塗布する方法が挙げられる。  [0036] In order to surface-treat tin or a tin alloy using the anti-oxidation agent of the present invention, any method that forms a film on the surface of tin or tin alloy may be used. For example, tin or tin alloy may be used. Examples include a method of simply immersing in an antioxidant, a method of applying an antioxidant using a shower or a device such as an air coater, blade coater, rod coater, knife coater, gravure coater, reverse coater, cast coater, etc. .
表面処理する際の酸化防止剤の温度は、 15〜80°Cが好ましぐより好ましくは 30 〜70°Cである。  The temperature of the antioxidant during the surface treatment is preferably 15 to 80 ° C, more preferably 30 to 70 ° C.
[0037] 本発明の酸ィ匕防止剤で表面処理をする錫または錫合金の形状は、線状、板 '帯' 箔状、粒状、粉末状等いずれの形状であってもよぐ本発明の酸化防止剤は、電子 部品、はんだボール、はんだ粉末等を処理することができる。  [0037] The tin or tin alloy surface-treated with the anti-oxidation agent of the present invention may have any shape such as a linear shape, a plate 'strip' foil shape, a granular shape, and a powder shape. This antioxidant can treat electronic components, solder balls, solder powder, and the like.
本発明の酸化防止剤を用い、電子部品の接続端子部の導体表面に錫または錫合 金めつきを施した後に、表面処理することにより、耐酸化性に優れ、はんだ濡れ性、 耐ゥイスカー性、潤滑性が良好な電子部品とすることができる。尚、本発明における 電子部品としては、基板も含むものである。  Using the antioxidant of the present invention, the surface of the conductor of the connection terminal portion of the electronic component is tinned or tin-plated and then surface-treated to provide excellent oxidation resistance, solder wettability, and whisker resistance. An electronic component with good lubricity can be obtained. The electronic component in the present invention includes a substrate.
本発明の酸ィ匕防止剤で処理された錫合金を用いたはんだボールは、耐酸化性に 優れ、電気的接続部材であるボールグリッドアレイとして、また、電子部品に配置し、 これを回路基板に接続した実装品として良好に用いることができる。  A solder ball using a tin alloy treated with the anti-oxidation agent of the present invention has excellent oxidation resistance and is disposed as a ball grid array as an electrical connection member or in an electronic component. It can be used favorably as a mounted product connected to.
[0038] また、錫合金粉末を本発明の酸化防止剤を用いて処理し、これに粘着剤、活性剤 、チクソトロピック剤、界面活性剤、溶剤等を含むフラックスを加えてはんだペーストと して用いることもできる。このはんだペーストは、耐酸化性、耐ゥイスカー性に優れる。 上記粘着剤、活性剤、チクソトロピック剤、界面活性剤、溶剤としては従来公知のもの を用いることができる。 [0038] Further, a tin alloy powder is treated with the antioxidant of the present invention, and a flux containing an adhesive, an activator, a thixotropic agent, a surfactant, a solvent, and the like is added to the solder paste. It can also be used. This solder paste is excellent in oxidation resistance and whisker resistance. Conventionally known pressure-sensitive adhesives, activators, thixotropic agents, surfactants and solvents can be used.
実施例  Example
[0039] 次に本発明を実施例によって説明する力 本発明はこれらの実施例によって限定 されるものではない。  [0039] Next, the present invention will be described by way of examples. The present invention is not limited to these examples.
[0040] 実施例 1〜8、及び比較例 1〜8 [0040] Examples 1 to 8 and Comparative Examples 1 to 8
表 1に示すように、一分子内に 2個以上のホスホン酸基を持ち、分子内にエステル 結合を含まない化合物又はその塩と、炭素数 6〜 10のアルキル基を有するリン酸ェ ステルを有効成分とする水溶液を 8種類調製した (実施例 1〜8)。  As shown in Table 1, a compound or salt thereof having two or more phosphonic acid groups in one molecule and no ester bond in the molecule, and a phosphate ester having an alkyl group having 6 to 10 carbon atoms. Eight types of aqueous solutions as active ingredients were prepared (Examples 1 to 8).
また、比較例として、表 2に示すように 6種類の水溶液を実施例と同様に調整した（ 比較例 1〜6)。比較例 7は酸化防止剤未処理とするため酸化防止剤を調製していな い。また、比較例 8として、実施例 2の溶液のへキシルリン酸エステルをォレイルリン酸 エステルと変えた力 茶褐色に懸濁し、有効成分が完全に溶解しな力つた。  Moreover, as a comparative example, as shown in Table 2, six types of aqueous solutions were prepared in the same manner as in the examples (Comparative Examples 1 to 6). Since Comparative Example 7 was not treated with antioxidant, no antioxidant was prepared. Further, as Comparative Example 8, the power obtained by changing the hexyl phosphate of the solution of Example 2 to oleyl phosphate was suspended in brown, and the active ingredient was completely dissolved.
尚、表 1及び表 2中の、へキシルリン酸エステル、 2—ェチルへキシルリン酸エステ ル、イソデシルリン酸エステル、ブチルリン酸エステルは、すべてモノアルキルリン酸 エステルとジアルキルリン酸エステルの混合物である。  In Tables 1 and 2, hexyl phosphate ester, 2-ethylhexyl phosphate ester, isodecyl phosphate ester and butyl phosphate ester are all mixtures of monoalkyl phosphate ester and dialkyl phosphate ester.
[0041] [表 1] [0041] [Table 1]
実施例 有効成分 pHExamples Active ingredient pH
1 二トリロトリスメチレンホスホン酸： 1 g/L 2 へキシルリン酸エステル: 0.5g/L 1 Nitrilotrismethylenephosphonic acid: 1 g / L 2 Hexyl phosphate: 0.5 g / L
2 二トリロトリスメチレンホスホン酸： 1 /L 2 へキシルリン酸エステル: 0.5g/L  2 Nitrilotrismethylenephosphonic acid: 1 / L 2 Hexyl phosphate: 0.5g / L
天然ラウリルアルコールプロピレンオキサイド 12モル付加物'.1 g/L  Natural lauryl alcohol propylene oxide 12 mole adduct '.1 g / L
3 ジエチレントリァミンペンタキスメチレンホスホン酸： 1 g/L 2 へキシルリン酸エステル： 0.5g/L  3 Diethylenetriaminepentakismethylenephosphonic acid: 1 g / L 2 Hexyl phosphate: 0.5 g / L
4 ジエチレントリアミンペンタキスメチレンホスホン酸： 1 g/L 2 へキシルリン酸エステル： 0.5g/L  4 Diethylenetriaminepentakismethylenephosphonic acid: 1 g / L 2 Hexyl phosphate: 0.5 g / L
天然ラウリルアルコールプロピレンオキサイド 12モル付加物： 1 g/L  Natural lauryl alcohol propylene oxide 12 mol adduct: 1 g / L
5 ジエチレントリアミンペンタキスメチレンホスホン酸： 1 g/L 2 へキシルリン酸エステル: 0.5g/L  5 Diethylenetriaminepentakismethylenephosphonic acid: 1 g / L 2 Hexyl phosphate: 0.5 g / L
ノニルフエノールエチレンオキサイド 12モル付加物： 1 g/L  Nonylphenol ethylene oxide 12 mol adduct: 1 g / L
6 1 -ヒドロキシェタン- U -ジホスホン酸： 1 g/L 2 6 1-Hydroxyethane-U-diphosphonic acid: 1 g / L 2
2-ェチルへキシルリン酸エステル： 0.5g/L 2-Ethylhexyl phosphate: 0.5g / L
天然ラウリルアルコールプロピレンオキサイド 12モル付加物： 1 g/L  Natural lauryl alcohol propylene oxide 12 mol adduct: 1 g / L
7 ニド J口 Wスメチレンホスホン酸： 1 g/L 2 イソデシルリン酸エステル： 0.5g/L  7 Nido J mouth W Smethylenephosphonic acid: 1 g / L 2 Isodecyl phosphate: 0.5 g / L
天然ラウリルアルコールプロピレンオキサイド 12モル付加物： 1 g/L  Natural lauryl alcohol propylene oxide 12 mol adduct: 1 g / L
8 二トリロトリスメチレンホスホン酸 K塩： 1 g/し 6 へキシルリン酸エステル： 0.5g/L  8 Nitrilotrismethylenephosphonic acid K salt: 1 g / s 6 Hexyl phosphate: 0.5 g / L
天然ラウリルアルコールプロピレンオキサイド 12付加物： 1 g/L 2] Natural lauryl alcohol propylene oxide 12 adduct: 1 g / L 2]
比較例 有効成分 pHComparative example Active ingredient pH
1 二トリロトリスメチレンホスホン酸： 1 g/L 21 Nitrilotrismethylenephosphonic acid: 1 g / L 2
2 二トリロトリスメチレンホスホン酸： 1 g/L 2 2 Nitrilotrismethylenephosphonic acid: 1 g / L 2
天然ラウリルアルコールプロピレンオキサイド 12モル付加物： 1 g/L  Natural lauryl alcohol propylene oxide 12 mol adduct: 1 g / L
3 二トリロトリスメチレンホスホン酸： 1 g/L 2  3 Nitrilotrismethylenephosphonic acid: 1 g / L 2
ブチルリン酸エステル: 0.5g/L  Butyl phosphate: 0.5g / L
天然ラウリルアルコールプロピレンオキサイド 12モル付加物： 1 g/L  Natural lauryl alcohol propylene oxide 12 mol adduct: 1 g / L
4 ジエチレントリアミンペンタキスメチレンホスホン酸： 1 g/L 2 4 Diethylenetriaminepentakismethylenephosphonic acid: 1 g / L 2
5 ジエチレントリアミンペンタキスメチレンホスホン酸： 1 g/L 2 5 Diethylenetriaminepentakismethylenephosphonic acid: 1 g / L 2
天然ラウリルアルコールプロピレンオキサイド 12モル付加物 1 g/L  Natural lauryl alcohol propylene oxide 12 mol adduct 1 g / L
6 二トリロトリスメチレンホスホン酸 K塩： 1 g/L 6  6 Nitryltrismethylenephosphonic acid K salt: 1 g / L 6
天然ラウリルアルコールプロピレンオキサイド 12モル付加物： 1 g/L  Natural lauryl alcohol propylene oxide 12 mol adduct: 1 g / L
7 未処理  7 Unprocessed
[0043] 他方、銅材（C1020P、 10mm X 25mm X 0. 2 mm)に対し、以下の前処理を行つ た。 On the other hand, the following pretreatment was performed on a copper material (C1020P, 10 mm × 25 mm × 0.2 mm).
アルカリ電解脱脂 (常温、 15 A/dm2,約 30秒程度処理)→水洗→酸浸漬（10%硫 酸、常温、 5秒)→水洗→化学研磨 (CPB— 40、常温、 1分浸漬)→水洗→酸浸漬（1 0%硫酸、常温、 5秒)→水洗 Alkaline electrolytic degreasing (room temperature, 15 A / dm 2 , treatment for about 30 seconds) → water washing → acid immersion (10% sulfuric acid, room temperature, 5 seconds) → water washing → chemical polishing (CPB-40, room temperature, 1 minute immersion) → Washing → Acid soaking (10% sulfuric acid, room temperature, 5 seconds) → Washing
この基材に対し、膜厚約 5 mの錫めつきを行った（めっき浴:ティンコート K (日鉱メ タルプレーティング (株)製）、めっき条件：陰極電流密度 2AZdm2、温度 20°C、液流 動及び力ソード揺動めつき)。 This substrate was tinned with a thickness of about 5 m (plating bath: Tincoat K (manufactured by Nikko Metal Plating Co., Ltd.)), plating conditions: cathode current density 2AZdm 2 , temperature 20 ° C , Liquid flow and force sword rocking).
[0044] この錫めつきを施した基材 (以下 Sn基材)を、上記の酸化防止剤に、浴温 60°Cで 1 0秒間浸漬した後、水洗し、乾燥させたものを試験基板とした。 [0044] This tinned base material (hereinafter referred to as "Sn base material") was immersed in the above antioxidant for 10 seconds at a bath temperature of 60 ° C, then washed with water and dried to obtain a test substrate. It was.
これらの試験基板に対し、以下の評価を行った。表 3および表 4に試験結果を示す  The following evaluations were performed on these test substrates. Table 3 and Table 4 show the test results.
[0045] 耐熱酸化性 [0045] Thermal oxidation resistance
これらの試験基板を、 220°Cに保持した電気炉において、大気雰囲気で 1時間熱 処理した後、鉛フリーはんだとのはんだ濡れ性 (ゼロクロスタイム）をメニスコグラフ法 で以下の測定条件に基づき測定した。  These test boards were heat-treated in an electric furnace maintained at 220 ° C for 1 hour in the air atmosphere, and then solder wettability (zero cross time) with lead-free solder was measured by the meniscograph method based on the following measurement conditions .
装置；ソルダーチェッカー SAT— 2000 (レス力製） はんだ槽;すず:銀:銅 = 96. 5 : 3 : 0. 5 (浴温 245°C) Equipment: Solder Checker SAT-2000 (Less Power) Solder bath; Tin: Silver: Copper = 96.5: 3: 0.5 (Bath temperature 245 ° C)
フラックス； NA- 200 (タムラ化研製）  Flux; NA-200 (Tamura Chemical Research)
浸漬深さ； 2mm  Immersion depth: 2mm
浸漬速度； 4mm/sec .  Immersion speed: 4mm / sec.
浸漬時間； 5sec.  Immersion time: 5 sec.
評価基準は、以下のとおりである。  The evaluation criteria are as follows.
◎：ゼロクロスタイム 1秒未満  A: Zero cross time less than 1 second
〇：ゼロクロスタイム 1秒以上 3秒未満  ○: Zero crossing time 1 second or more and less than 3 seconds
△：ゼロクロスタイム 3秒以上 5秒未満  Δ: Zero crossing time 3 seconds or more and less than 5 seconds
X：ゼロクロスタイム 5秒以上  X: Zero cross time 5 seconds or more
[0046] 耐湿酸化性 [0046] Moisture oxidation resistance
これらの試験基板に対し、 PCT処理（温度 105°C、湿度 100%の密閉釜内にて 16 時間放置）を施した後、鉛フリーはんだとのはんだ濡れ性 (ゼロクロスタイム）をメニス コグラフ法で耐熱酸ィ匕性の項と同様に測定した。  These test boards were PCT-treated (temperature standing at 105 ° C, humidity 100% for 16 hours), and solder wettability (zero cross time) with lead-free solder was measured by meniscograph method. The measurement was performed in the same manner as the term of heat resistance and acidity.
評価基準は、以下のとおりである。  The evaluation criteria are as follows.
◎：ゼロクロスタイム 1秒未満  A: Zero cross time less than 1 second
〇：ゼロクロスタイム 1秒以上 3秒未満  ○: Zero crossing time 1 second or more and less than 3 seconds
△：ゼロクロスタイム 3秒以上 5秒未満  Δ: Zero crossing time 3 seconds or more and less than 5 seconds
X：ゼロクロスタイム 5秒以上  X: Zero cross time 5 seconds or more
[0047] 耐ゥイスカー性 [0047] Whisker resistance
基板を、温度 85°C、湿度 85%の恒温恒湿雰囲気下において、 24時間放置した。 その後、基板を充分に乾燥した後、走査型電子顕微鏡 (SEM)にて表面観察したと ころ、実施例、比較例ともゥイスカーの発生は見られな力つた。  The substrate was left for 24 hours in a constant temperature and humidity atmosphere at a temperature of 85 ° C and a humidity of 85%. Thereafter, after the substrate was sufficiently dried, the surface was observed with a scanning electron microscope (SEM). As a result, no whisker was generated in any of the examples and comparative examples.
また、ボール荷重試験（サンプルに 150gのボールの荷重を室温下で 7日間かけた 後、ゥイスカーの発生長さを顕微鏡で観察)も実施した。  In addition, a ball load test was performed (a sample was subjected to a 150 g ball load at room temperature for 7 days, and then the length of the whisker was observed with a microscope).
評価基準は、以下のとおりである。  The evaluation criteria are as follows.
〇：10 未満  ○: Less than 10
Α : 10 μ m以上〜 20 μ m未満 X : 20 /ζ πι以上 Α: 10 μm or more and less than 20 μm X: 20 / ζ πι or more
[0048] 静摩擦係数 [0048] Static friction coefficient
試験基板の表面の潤滑性を、静摩擦係数により評価した。  The lubricity of the surface of the test substrate was evaluated by the coefficient of static friction.
図 1に示すようにサンプル上に接触子を置き、徐々に傾けていき、滑り落ちた角度 より摩擦係数を測定した (静摩擦係数 =tan Θ )。  As shown in Fig. 1, a contactor was placed on the sample, gradually tilted, and the coefficient of friction was measured from the sliding angle (static coefficient of friction = tan Θ).
[0049] [表 3] [0049] [Table 3]
Figure imgf000017_0001
Figure imgf000017_0001
[0050] [表 4] [0050] [Table 4]
Figure imgf000017_0002
実施例 9〜16、及び比較例 9〜 15
Figure imgf000017_0002
Examples 9-16 and Comparative Examples 9-15
燐青銅フープ材（18mm X 100mm)に対し、以下の前処理を行った。  The following pretreatment was performed on a phosphor bronze hoop material (18 mm × 100 mm).
アルカリ電解脱脂 (常温、 15 A/dm2,約 30秒程度処理)→水洗→酸浸漬（10%硫 酸、常温、 5秒)→水洗→化学研磨 (CPB— 40、常温、 1分浸漬)→水洗→酸浸漬（1Alkaline electrolytic degreasing (room temperature, 15 A / dm 2 , treatment for about 30 seconds) → water washing → acid immersion (10% sulfuric acid, room temperature, 5 seconds) → water washing → chemical polishing (CPB-40, room temperature, 1 minute immersion) → Washing → Acid soaking (1
0%硫酸、常温、 5秒)→水洗 (0% sulfuric acid, room temperature, 5 seconds) → Washed with water
この基材に対し、膜厚約 の Sn— 9%Znめっきを行った（めっき浴：日鉱メタル プレーティング (株)製、めっき条件：陰極電流密度 3AZdm2、温度 35°C、 pH4. 0、 液流動及び力ソード揺動めつき）。 The base material was Sn-9% Zn plated with a film thickness (plating bath: Nikko Metal) Plating Co., Ltd., plating conditions: cathode current density 3AZdm 2 , temperature 35 ° C, pH 4.0, liquid flow and force sword swinging).
[0052] 実施例 1〜8及び比較例 1〜6で調製した溶液に対し、前記の Sn— Znめっきを施し た基材 (以下 Sn— Zn基材)を、 40°Cで 1分間浸漬した後、水洗し、ドライヤーにて乾 燥させたものを試験基板とした (実施例 9〜16、比較例 9〜14)。また未処理の基材 を比較例 15の試験基板とした。これらの試験基板に対し、実施例 1〜8及び比較例 1 〜7と同様に評価を行った。表 5および表 6に試験結果を示す。  [0052] Into the solutions prepared in Examples 1 to 8 and Comparative Examples 1 to 6, the Sn-Zn plated substrate (hereinafter referred to as Sn-Zn substrate) was immersed at 40 ° C for 1 minute. Thereafter, the substrate was washed with water and dried with a dryer to obtain test substrates (Examples 9 to 16, Comparative Examples 9 to 14). The untreated base material was used as a test substrate of Comparative Example 15. These test substrates were evaluated in the same manner as in Examples 1 to 8 and Comparative Examples 1 to 7. Tables 5 and 6 show the test results.
[0053] [表 5]  [0053] [Table 5]
Figure imgf000018_0001
Figure imgf000018_0001
[0054] [表 6] 耐ゥイス力一性 [0054] [Table 6] One-piece resistance to whistling
比較例 溶液 耐熱酸化性 耐湿酸化性 静摩擦係数  Comparative example Solution Thermal oxidation resistance Moist oxidation resistance Static coefficient of friction
(ボール荷重試験）  (Ball load test)
9 比較例 1 厶 Δ X 0.4 9 Comparative Example 1 厶 Δ X 0.4
1 0 比較例 2 o 〇 Δ 0.41 0 Comparative example 2 o ○ Δ 0.4
1 1 比較例 3 o O △ 0.41 1 Comparative example 3 o O △ 0.4
1 2 比較例 4 Δ Δ X 0.41 2 Comparative Example 4 Δ Δ X 0.4
1 3 比較例 5 O O △ 0.41 3 Comparative Example 5 O O △ 0.4
1 4 比較例 6 X Δ X 0.41 4 Comparative Example 6 X Δ X 0.4
1 5 未処理 X X X 0.4 1 5 Raw X X X 0.4

Claims

請求の範囲 [1] 一分子内に 2個以上のホスホン酸基を持ち、分子内にエステル結合を含まない化 合物、及び Z又はその塩と、炭素数 6〜 10のアルキル基を有するリン酸エステルとを 含むことを特徴とする錫および錫合金の水系酸化防止剤。 [2] 前記水系酸ィ匕防止剤の pHが 5以下であることを特徴とする請求の範囲第 1項記載 の錫および錫合金の水系酸化防止剤。 [3] 更に界面活性剤を 0. 01gZL〜10gZL含有することを特徴とする請求の範囲第 1 XI 項または第 2項記載の錫および錫合金の水系酸化防止剤。 〇= [4] 前記一分子内に 2個以上のホスホン酸基を持ち、分子内にエステル結合を含まな い化合物、及び Z又はその塩が下記式 (1)、 （Π)又は (III)で表される化合物、及び Z又はそのアルカリ金属塩、アンモニゥム塩、又はアミンィ匕合物との塩であることを特 徴とする請求の範囲第 1項〜第 3項のいずれか一項に記載の錫および錫合金の水 系酸化防止剤。 Claims [1] A compound having two or more phosphonic acid groups in one molecule and no ester bond in the molecule, and a phosphorus having Z or a salt thereof and an alkyl group having 6 to 10 carbon atoms An aqueous antioxidant for tin and tin alloys, characterized by comprising an acid ester. [2] The aqueous antioxidant for tin and tin alloy according to [1], wherein the pH of the aqueous antioxidant is 5 or less. [3] The tin- and tin-alloy aqueous antioxidant according to item 1 XI or claim 2, further comprising 0.01 gZL to 10 gZL of a surfactant. ○ = [4] A compound having two or more phosphonic acid groups in one molecule and no ester bond in the molecule, and Z or a salt thereof are represented by the following formula (1), (Π) or (III) The compound represented by the formula (I) and a salt with Z or an alkali metal salt, an ammonium salt, or an amine compound thereof, according to any one of claims 1 to 3. An aqueous antioxidant of tin and tin alloys.
[化 1]  [Chemical 1]
Figure imgf000019_0001
Figure imgf000019_0001
(式 (I)中、 〜 3及び 〜丫3は各々同一もしくは異なってもよぐ水素原子、又は 炭素数 1〜5の低級アルキル基を表す。 ) (Formula (in I), ~ 3 and ~丫3 each represent the same or different and Yogu hydrogen atom, or a lower alkyl group of 1 to 5 carbon atoms.)
[化 2]  [Chemical 2]
R1 (Π)R 1 (Π)
Figure imgf000019_0002
Figure imgf000019_0002
(式 (II)中、
Figure imgf000019_0003
R2及び R4は、各々同一もしくは異なってもよぐ以下の基 (A)を表し 、 Rは、以下の基 (A)、又は炭素数 1〜5の低級アルキル基を表し、 nは 1〜3の整数 を表す。 (In the formula (II),
Figure imgf000019_0003
R 2 and R 4 represent the following groups (A) which may be the same or different: , R represents the following group (A) or a lower alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 3.
[化 3] Y I [Chemical 3] Y I
Figure imgf000020_0001
〇 o p =l A)
Figure imgf000020_0001
〇 op = l A)
ol 基 (A)中、 X1、及び Y1は、一般式 (I)における定義と同じである。 ) In the ol group (A), X 1 and Y 1 are the same as defined in the general formula (I). )
[化 4]  [Chemical 4]
Figure imgf000020_0002
Figure imgf000020_0002
(式 (III)中、 Xは水素原子、又は炭素数 1〜5の低級アルキル基を表し、 Yは水素原 子、炭素数 1〜5の低級アルキル基、水酸基、又はアミノ基を表す。 ) (In formula (III), X represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms, and Y represents a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms, a hydroxyl group, or an amino group.)
[5] 請求の範囲第 1項〜第 4項のいずれか一項に記載の水系酸ィ匕防止剤を用いて錫 または錫合金の表面を処理することを特徴とする表面処理方法。 [5] A surface treatment method characterized by treating the surface of tin or a tin alloy with the aqueous acid / antioxidation agent according to any one of claims 1 to 4.
[6] 電子部品の接続端子部の導体表面に、錫または錫合金めつきを施した後に、請求 の範囲第 1項〜第 4項のいずれか一項に記載の水系酸ィヒ防止剤を用いて表面処理 を行ったことを特徴とする電子部品。 [6] The aqueous acid proof inhibitor according to any one of claims 1 to 4 is applied after tin or tin alloy plating is applied to the conductor surface of the connection terminal portion of the electronic component. An electronic component characterized by using a surface treatment.
[7] 請求の範囲第 1項〜第 4項のいずれか一項に記載の水系酸ィ匕防止剤を用いて表 面処理を行った錫合金を用いたことを特徴とするはんだボールもしくははんだ粉末。 [7] A solder ball or a solder characterized by using a tin alloy that has been surface-treated with the aqueous acid / anti-oxidation agent according to any one of claims 1 to 4 Powder.
[8] 請求の範囲第 7項に記載のはんだボールを電気的接続部材として用いたことを特 徴とするボールグリッドアレイ。  [8] A ball grid array characterized in that the solder balls according to claim 7 are used as electrical connection members.
[9] 請求の範囲第 7項に記載のはんだボールを電子部品に配置し、これを回路基板に 接続したことを特徴とする実装品。 [9] A mounted product comprising the solder ball according to claim 7 placed on an electronic component and connected to a circuit board.
[10] 請求の範囲第 7項に記載のはんだ粉末を用いたことを特徴とするはんだペースト。 [10] A solder paste characterized by using the solder powder according to claim 7.
[11] 請求の範囲第 10項に記載のはんだペーストを用いたことを特徴とする実装品。 [11] A mounted product using the solder paste according to claim 10.
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Publication number Priority date Publication date Assignee Title
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JP2012506488A (en) * 2008-10-21 2012-03-15 アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング Post-treatment composition for increasing the corrosion resistance of a metal or metal alloy surface
WO2012118075A1 (en) * 2011-03-02 2012-09-07 千住金属工業株式会社 Flux
JP2012255205A (en) * 2011-05-13 2012-12-27 C Uyemura & Co Ltd Post-treatment agent for tin or tin alloy plating film, and method for treating tin or tin alloy plating film
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1046385A (en) * 1996-08-02 1998-02-17 Daiwa Kasei Kenkyusho:Kk Electric and electronic circuit parts
JP2004137574A (en) * 2002-10-18 2004-05-13 Nikko Materials Co Ltd SURFACE TREATMENT AGENT AND SURFACE TREATMENT METHOD FOR Sn ALLOY
JP2005206860A (en) * 2004-01-21 2005-08-04 Ebara Udylite Kk Agent for removing/preventing discoloration of plated tin or tin alloy film

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005296860A (en) 2004-04-14 2005-10-27 Nitto Denko Corp Filter medium of air filter

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1046385A (en) * 1996-08-02 1998-02-17 Daiwa Kasei Kenkyusho:Kk Electric and electronic circuit parts
JP2004137574A (en) * 2002-10-18 2004-05-13 Nikko Materials Co Ltd SURFACE TREATMENT AGENT AND SURFACE TREATMENT METHOD FOR Sn ALLOY
JP2005206860A (en) * 2004-01-21 2005-08-04 Ebara Udylite Kk Agent for removing/preventing discoloration of plated tin or tin alloy film

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JP2012506488A (en) * 2008-10-21 2012-03-15 アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング Post-treatment composition for increasing the corrosion resistance of a metal or metal alloy surface
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JP4601670B2 (en) 2010-12-22
TWI327605B (en) 2010-07-21

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