CN1742118A - Tin-containing plating bath - Google Patents
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- CN1742118A CN1742118A CN 200480002699 CN200480002699A CN1742118A CN 1742118 A CN1742118 A CN 1742118A CN 200480002699 CN200480002699 CN 200480002699 CN 200480002699 A CN200480002699 A CN 200480002699A CN 1742118 A CN1742118 A CN 1742118A
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Abstract
The tin-containing plating bath according to the present invention is characterized by containing: a soluble stannous salt, or a mixture of at least 1 soluble salt selected from copper salt, bismuth salt, silver salt, indium salt, zinc salt, nickel salt, cobalt salt and antimony salt and the soluble stannous salt, and (b) an aliphatic sulfonic acid selected from alkanesulfonic acid and at least 1 of alkylbenzenesulfonic acid, wherein the aliphatic sulfonic acid is a purified aliphatic sulfonic acid containing a sulfur compound as an impurity and having a sulfur atom and a chlorine atom in the molecule, and the sulfur compound is contained in a trace amount or less. The use of the plating bath of the present invention enables the formation of a tin plating film or a tin alloy plating film excellent in reflow properties (reflow) and plating film appearance.
Description
Technical field
The present invention relates to the aliphatic sulfonic is the tin plating bath or the tin alloy plating bath of acid basis.
Background technology
Contain with alkansulfonic acids such as methylsulfonic acid, ethyl sulfonic acid, propanesulfonic acid; Alkanol sulfonic acids such as 2-hydroxyethylsulfonic acid, 2-hydroxypropyl sulfonic acid; Organic sulfonic acids such as aromatic sulphonic acid such as p-Phenylsulfonic acid are the tin plating bath or the tin alloy plating bath of acid basis, because draining is handled easily, the solvability excellence of pink salt, are widely used all the time.
Such organic sulfonic acid, particularly be in the tin plating bath and tin alloy plating bath of acid basis with aliphatic sulfonics such as widely used alkansulfonic acids, exist certain contact between the characteristic of the purity of aliphatic sulfonic and the plated film that obtains, even propose the low impurity that contains of purity of aliphatic sulfonic, whether can bring the problem of bad influence to be suggested micro-ly to the plated film characteristic.
Te Kaiping 10-204252 communique points out, in the method for making with the hydrogen peroxide oxidation alkyl sulfhydryl, the such reaction intermediate of also residual disulphide, polluting goods (paragraph 5).Open then, make alkyl sulfhydryl and hydroperoxidations such as thiomethyl alcohol, sulfur alcohol, 2 mercapto ethanol, when making alkansulfonic acid or alkanol sulfonic acids, add in reactive tank with usage quantity and to have the above H of 50 weight % greater than the chemical theory amount
2O
2The aqueous hydrogen peroxide solution of concentration, supply with alkyl sulfhydryl continuously with the low temperature below 50 ℃, through 3～20 hours maturation period, the distillation of seething with excitement under the normal pressure is handled the back, reaction solution is contacted with anion ion exchange body, by this method, obtain highly purified alkansulfonic acid or alkanol sulfonic acids (with reference to claim, the paragraph 9～11 of this communique) with high yield low cost.This method is to make alkyl sulfhydryl and hydroperoxidation, making in the process of alkansulfonic acid, greater than chemical theory amount, more the hydrogen peroxide that uses, temperature of reaction is decided to be low temperature, the maturation period is set, distill, utilize complicated processing such as anion ion exchange body processing again by the boiling under the combination normal pressure, make the method for high purity alkansulfonic acid.The document shows, the high purity alkansulfonic acid that obtains, by with (methyl) acrylic acid esterification, can be used as reactive emulsifier and use.The independent polymkeric substance of alkansulfonic acid or the multipolymer of alkansulfonic acid and vinyl monomer are also disclosed, can be used for various uses such as agglutinant, dispersion agent, tackifier, also can be used as additives such as tin plating bath, scolding tin plating bath in addition and use (with reference to the paragraph 2 of this communique).
In addition, the spy opens the 2001-64249 communique and discloses, method (with reference to paragraph 3) as the method for making of in the past alkansulfonic acid, the oxidation of enumerating mercaptan (alkyl sulfhydryl), the hydrolysis of alkyl sulfonyl halogenation thing, oxidation of dimethyl disulphide etc., make by these in the past the alkansulfonic acid aqueous solution that obtains of method for making contact with basic anion exchange resin, mainly reduce the process for purification of the sulfuric acid containing ratio in the alkansulfonic acid.Point out then, alkansulfonic acid, particularly methylsulfonic acid, in the plating of conducting metal, be suitable for, but the sulfuric acid contained as impurity is deleterious in the plating of conducting metal, in addition, by with the contacting of basic anion exchange resin, can reduce the sulfuric acid containing ratio (with reference to paragraph 2～5) in the alkansulfonic acid significantly.
Summary of the invention
The present invention studies in view of the present situation of above-mentioned conventional art, its main purpose is, in the tin plating bath or tin alloy plating bath that with the aliphatic sulfonic are acid basis, relation between the plated film characteristic of further discussing the purity of aliphatic sulfonic and obtaining provides the tin plating bath or the tin alloy plating bath that can form the plated film with excellent specific property.
The inventor, the result who furthers investigate repeatedly by achieving the above object, discovery is in the aliphatic sulfonic of alkansulfonic acid etc., contain from the various oxidation of sulfur compound impurities of manufacture method but in these sulphur compounds, have only special components such as α-chlorine dimethyl sulfone, dimethyl disulphide that electroplating characteristic is had bad influence, there are not influence in the sulphur compound beyond this special component, for example dimethyl sulfone etc. to electroplating characteristic.Then, commercially available alkansulfonic acid one is applied specific refining separate modes such as concentrating under reduced pressure, just can get rid of the specific sulphur compound that electroplating characteristic is applied bad influence effectively, the refining alkansulfonic acid that obtains is not used for the acid basis of tin plating bath or tin alloy plating bath as additive, just can improve levelling property again (reflowability), plated film outward appearance of plated film etc. greatly, so far finish the present invention.
That is, the invention provides following tin-containing plating bath.
1. tin-containing plating bath is characterized in that, is containing
(a) solubility tin salt or be selected from least a kind of soluble salt in mantoquita, bismuth salt, silver salt, indium salt, zinc salt, nickel salt, cobalt salt and the antimonic salt and the mixture of solubility tin salt,
And
(b) be selected from the tin-containing plating bath of at least a kind of aliphatic sulfonic in alkansulfonic acid and the alkanol sulfonic acids,
This aliphatic sulfonic has content of sulphur compounds that Oxidation Number forms for the compound of sulphur atom+4 below and compound that intramolecularly has sulphur atom and the chlorine atom corps family sulfonic acid below micro-by intramolecularly.
2. as above-mentioned 1 described tin-containing plating bath, it is dimethyl disulphide for the compound of the sulphur atom below+4 that intramolecularly has Oxidation Number, and the content of this compound in plating bath is less than 200ppm.
3. as above-mentioned 1 described tin-containing plating bath, it is first thiosulfonic acid S-methyl esters for the compound of the sulphur atom below+4 that intramolecularly has Oxidation Number, and the content of this compound in plating bath is less than 4ppm.
4. as above-mentioned 1 described tin-containing plating bath, the compound that intramolecularly has sulphur atom and chlorine atom is α-chlorine dimethyl sulfone, and the content of this compound in plating bath is less than 4ppm.
5. as above-mentioned 1 described tin-containing plating bath, the compound that intramolecularly has sulphur atom and chlorine atom is Alpha-Methyl sulphonyl-α, α-dichloro dimethyl sulfone, and the content of this compound in plating bath is less than 4ppm.
6. as above-mentioned 1 described tin-containing plating bath, it is dimethyl disulphide and first thiosulfonic acid S-methyl esters for the compound of sulphur atom below+4 that intramolecularly has Oxidation Number, the compound that intramolecularly has sulphur atom and chlorine atom is α-chlorine dimethyl sulfone and Alpha-Methyl sulphonyl-α, α-dichloro dimethyl sulfone
Be selected from dimethyl disulphide, first thiosulfonic acid S-methyl esters, α-chlorine dimethyl sulfone and Alpha-Methyl sulphonyl α, the sulfide more than 2 kinds in α-dichloro dimethyl sulfone is present in the plating bath,
The total content of this sulfide in plating bath is less than 2ppm.
7. as above-mentioned 1 described tin-containing plating bath, corps family sulfonic acid is made with extra care with the aliphatic sulfonic that obtained by wet oxidation alkyl sulfhydryl or dialkyl disulphides or by the aliphatic sulfonic that hydrolysis alkyl sulfuryl halide obtains and is obtained.
8. as above-mentioned 1 described tin-containing plating bath, corps family sulfonic acid makes aliphatic sulfonic contact sorbent material, the processing of enforcement solid phase extractions and obtains.
9. as above-mentioned 1 described tin-containing plating bath, corps family sulfonic acid makes aliphatic sulfonic be contacted with sorbent material, applies solid phase extractions and handle and obtain.
10. as above-mentioned 9 described tin-containing plating baths, the solid phase extractions processing that corps family sulfonic acid is to use the sorbent material of identical or different kind to implement more than 2 times obtains.
11. as above-mentioned 1 described tin-containing plating bath, corps family sulfonic acid is implemented concentrating under reduced pressure processing and solid phase extractions processing to aliphatic sulfonic, combination and is obtained.
12. as above-mentioned 1 described tin-containing plating bath, alkansulfonic acid is a methylsulfonic acid.
13. a method that forms projection is characterized in that, uses above-mentioned 1 described plating bath to form projection.
Tin-containing plating bath of the present invention, contain the solubility tin salt individually or contain at least a kind of soluble salt being selected from mantoquita, bismuth salt, silver salt, indium salt, zinc salt, nickel salt, cobalt salt and the antimonic salt and the solubility tin salt, as the plated metal composition, contain at least a kind of aliphatic sulfonic being selected from alkansulfonic acid and the alkanol sulfonic acids, as acid basis.
In the aliphatic sulfonic as the acid basis use,, can use with chemical formula: C as alkansulfonic acid
nH
2n+1SO
3The material of H (for example n=1～11) expression.As the object lesson of such alkansulfonic acid, can enumerate methylsulfonic acid, ethyl sulfonic acid, 1-propanesulfonic acid, 2-propanesulfonic acid, 1-fourth sulfonic acid, 2-fourth sulfonic acid, penta sulfonic acid etc.
In addition, as alkanol sulfonic acids, can use with chemical formula: C
mH
2m+1-CH (OH)-C
pH
2p-SO
3The material of H (for example m=0～6, p=1～5) expression.As the object lesson of such alkanol sulfonic acids, can enumerate 2-hydroxyethyl-1-sulfonic acid (hydroxyethylsulfonic acid), 2-hydroxypropyl-1-sulfonic acid (2-propyl alcohol sulfonic acid), 2-hydroxyl butyl-1-sulfonic acid, 2-hydroxyl amyl group-1-sulfonic acid, 1-hydroxypropyl-2-sulfonic acid, 3-hydroxypropyl-1-sulfonic acid, 4-hydroxyl butyl-1-sulfonic acid, 2-hydroxyl hexyl-1-sulfonic acid etc.The typical example of alkanol sulfonic acids is 2-hydroxyethyl-1-sulfonic acid.
Above-mentioned alkansulfonic acid and alkanol sulfonic acids, can a kind individually or mix more than 2 kinds and use.Wherein, preference chain alkyl sulfonic acid, preferred especially methylsulfonic acid.
The aliphatic sulfonic that uses as acid basis, particularly as the manufacture method in the past of alkansulfonic acid, be known that the method (for example by chlorine and water or by the method for hydrogen peroxide oxidation) of wet oxidation alkyl sulfhydryl, but in the method, the possibility that generates dimethyl disulphide is arranged in the intermediate stage.Open above-mentioned spy and also to point out the such reaction intermediate of residual disulphide (with reference to the paragraph 5 of the document 5) in the flat 10-204252 communique.In addition, in the method for wet oxidation dialkyl disulphides, unreacted dialkyl disulphides has possibility residual in resultant, for example, a wet oxidation dimethyl disulphide, the possibility of the remaining unreacted dimethyl disulphide of trace is just arranged in the resultant methylsulfonic acid.Even also have in the method for hydrolysis alkyl sulfuryl halide, except that the object aliphatic sulfonic, have trace to sneak into the possibility of the sulfide of various halogen atoms as impurity.About this point, same possibility is also arranged with the method for chlorine and Water type oxidation of alkyl mercaptan.
Like this, in aliphatic sulfonic, as impurity, according to its manufacture method, contain the possibility of various sulphur compounds.
Contained impurity in the aliphatic sulfonic before the inventor separates with dichloromethane extraction is refining is with liquid chromatograph on the mixtures of impurities that obtains, assert each isolate by various analytical instrument.Then, make in the aliphatic sulfonic of new separation and purification and contain these each isolates micro-ly, will contain these isolates and make tin plating bath or tin alloy plating bath as the aliphatic sulfonic of impurity as acid basis, the characteristic of the plated film that investigation obtains.Consequently, in the contained sulphur compound of impurity, the conclusion of finding have pair electroplating characteristic to bring the composition of bad influence and not bringing the composition of bad influence should pay close attention to like this.Then, after specific two kinds of compositions that electroplating characteristic had a Different Effects, finding out has the common feature in the composition that brings bad influence.Promptly find out, in the sulphur compound that is contained as impurity, particularly (A) intramolecularly have Oxidation Number for the compound of sulphur atom+4 below and (B) intramolecularly have the compound of sulphur atom and chlorine atom, bring bad influence to the characteristic of the plated film that obtains from tin plating bath and tin alloy plating bath.
Therefore, among the present invention, must make (A) intramolecularly have Oxidation Number for the compound of the sulphur atom below+4 and (B) content of intramolecularly with compound of sulphur atom and chlorine atom be zero or micro-purified aliphatic sulfonic like this use as acid basis.At this moment, the contained above-claimed cpd (A) and the total amount of compound (B) in the corps family sulfonic acid, the concentration in the plating bath when adding in plating bath is preferably the amount less than 200ppm.
Use the few corps family sulfonic acid of such specific impurities content, the tin plated film that obtains or the characteristic of tin alloy plated film, particularly levelling property (reflowability), plated film outward appearance become very good again.
Have the compound of Oxidation Number for the sulphur atom below+4 as above-mentioned (A) intramolecularly, particularly, the Oxidation Number of sulphur atom is for being not the compound of maximum rating, promptly meaning that sulphur atom does not become the compound of octet structure completely.As the object lesson of such sulphur compound, can enumerate with the compound (1) of following structural formula (a) expression and the compound of representing with structural formula (b) (2).
(1) dimethyl disulphide
CH
3-S-S-CH
3 (a)
(2) first thiosulfonic acid S-methyl esters
In addition, have the object lesson of the compound of sulphur atom and chlorine atom, can enumerate with the compound (3) of following structural formula (c) expression with the compound (4) of structural formula (d) expression as (B) intramolecularly.
(3) α-chlorine dimethyl sulfone
(4) Alpha-Methyl sulphonyl-α, α-dichloro dimethyl sulfone
In addition, in aliphatic sulfonic, except that above-mentioned impurity, the Oxidation Number that contains sulphur atoms such as dimethyl sulfone is for example also arranged for the possibility of the compound of high state but this compound does not bring bad influence to electroplating characteristic.Have again, in the aliphatic sulfonic, according to manufacture method, the possibility that contains other various impurity arranged.Therefore, in having the various impurity of possibility, particularly only be conceived to (A) intramolecularly have Oxidation Number for the compound of sulphur atom below+4 and (B) intramolecularly have the compound of sulphur atom and chlorine atom, by reducing the content of these impurity, can improve the characteristic of plated film greatly, this is not easy to predict.
In the aliphatic sulfonic contained by (A) intramolecularly have Oxidation Number for the compound of the sulphur atom below+4 and (B) intramolecularly have the content of the impurity that the compound of sulphur atom and chlorine atom forms, most preferably by all not measurable zero-dose of various analytical instrument, but if to the electroplating characteristic of tin or tin alloy, particularly the levelling property again (reflowability) and the plated film outward appearance of plated film are not brought the scope of bad influence, can be contained trace yet.Such allowance is according to the kind of impurity and difference.In above-mentioned compound, to the bad influence of plated film, α-chlorine dimethyl sulfone maximum, secondly be Alpha-Methyl sulphonyl-α, α-dichloro dimethyl sulfone is bigger, and dimethyl disulphide and first thiosulfonic acid S-methyl esters have the tendency littler than the bad influence of these compounds.
About concrete allowed band, as the concentration in the plating bath, dimethyl disulphide is preferably less than 200ppm, and first thiosulfonic acid S-methyl esters is preferably less than 4ppm.In addition, α-chlorine dimethyl sulfone and Alpha-Methyl sulphonyl-α, α-dichloro dimethyl sulfone is respectively preferably less than 4ppm.
Have again, in above-mentioned sulphur compound (1)～(4), during the coexistence of most compositions, can think owing to the synergism of these compositions, the bad influence of electroplating characteristic is increased.Therefore, be selected from dimethyl disulphide, thiomethyl alcohol sulfonic acid S-methyl esters, α-chlorine dimethyl sulfone and Alpha-Methyl sulphonyl-α, the sulphur compound in α-dichloro dimethyl sulfone, when containing more than 2 kinds in plating bath, the total concentration of these compounds is preferably less than 2ppm.
As from aliphatic sulfonic, remove (A) intramolecularly have Oxidation Number for the compound of sulphur atom below+4 and (B) intramolecularly have sulphur atom and chlorine atom compound, obtain the method for corps family sulfonic acid, can adopt concentrating under reduced pressure processing, solid phase extractions processing etc.
In these methods, it is under reduced pressure the heat stoste of aliphatic sulfonic, the processing of concentrated stoste that concentrating under reduced pressure is handled.
Preferred reduced pressure according to the kind of the aliphatics sulfone of methylsulfonic acid, 2-hydroxyethylsulfonic acid etc. and difference, for example, methylsulfonic acid, can be the pressure of 0.13～6.6kPa, preferred 0.66～3.9kPa.
How many decompression conditions of heating down also has difference according to the kind of aliphatics sulfone, and for example, methylsulfonic acid can be 50～100 ℃, can make the temperature rising edge make with extra care, also can keep suitable temperature to heat at leisure in the limit.
The concentrating under reduced pressure time generally is 1～10 hour, preferred 3～8 hours, but can suitably shorten or time expand according to the kind of aliphatic sulfonic.
In addition, the stoste of so-called aliphatic sulfonic can be used commercially available aliphatic sulfonic and with its material after concentrating of suitably heating under normal pressure in advance etc.
In the heat stoste of next processing of decompression, just evaporate impurity or the low boiling point component of removing the stoste expeditiously from stoste, do not evaporate and aliphatic sulfonic is concentrated in the remaining debris, the purity of aliphatic sulfonic improves.
It is the processing that makes aliphatic sulfonic contact sorbent material, removes impurity from aliphatic sulfonic that solid phase extractions is handled.
As sorbent material, can use the known sorbent material of gac, silica gel, activated alumina, atlapulgite, zeolite, porous polymer etc.For example, as gac, if through the charing and the operation of compose living, can use material arbitrarily.About porous polymer, typical example is that the multipolymer with vinylbenzene and Vinylstyrene is the porous polymer of parent, as commercially available product, can enumerate An Polaite (production of Supelco company).
These sorbent materials have big surface-area, are the solids that has the porous structure of a lot of fine pores of nano-order sizes in inside.
In solid phase extractions is handled, in advance with this sorbent material of filling behind the clean sorbent materials such as methyl alcohol, deionized water, in the upright post that is provided with, with suitable flow velocity aliphatic sulfonic is added drop-wise on the post, if in the stoste of aliphatic sulfonic contained impurity etc. to be adsorbed agent absorption just passable.Thus, the contained impurity of aliphatic sulfonic is removed, and can obtain highly purified corps family sulfonic acid.The flow velocity of the aliphatic sulfonic in the post can suitably be regulated according to the kind of the kind of aliphatic sulfonic, stationary phase sorbent material and consumption thereof etc.
Solid phase extractions is handled and also can be carried out repeatedly on several times ground.At this moment, as sorbent material, can use same sorbent material or also can use different types of sorbent material.For example, after dripping aliphatic sulfonic as first operation, in the post of the porous polymer of filling organic class sorbent material, drip the aliphatic sulfonic that first operation obtains as second operation, in the post of having filled same porous polymer, can carry out the extraction in 2 stages.Again as required, also can carry out multistage extraction.In addition, drip aliphatic sulfonic as first operation, in the post of having filled mineral-type sorbent materials such as gac, silica gel after, as second operation, in the post of having filled porous polymer, drip aliphatic sulfonic that first operation obtains, can carry out the extraction in 2 stages.Again as required, also can carry out multistage extraction.
In addition, also can applicable combination implement concentrating under reduced pressure processing and solid phase extractions processing to aliphatic sulfonic.
For example, after the stoste of following concentration aliphatic sulfonic is heated in decompression, can in the post of filling sorbent material, drip the aliphatic sulfonic that obtains, extract processing.
Can also make up the solid phase extractions of concentrating under reduced pressure processing and some operations handles.At this moment, solid phase extractions is handled to concentrate in the front and back that concentrating under reduced pressure is handled and is carried out, also can carry out with the separated position (that is the order of solid phase extractions-concentrating under reduced pressure-solid phase extractions) of carrying the concentrating under reduced pressure processing secretly.
In addition, above-mentioned spy opens the 2001-64249 communique and discloses the anionite-exchange resin that uses the functional group who imports quaternary ammonium salt base etc. in the parent of being made up of polymkeric substance, the method for the sulfuric acid containing ratio in the reduction alkansulfonic acid.This method is compared with the method for using above-mentioned sorbent material, is to remove the visibly different method of object.
Tin-containing plating bath of the present invention, as the metallizing composition, be the tin plating bath that contains tin salt individually, or as metallizing, contain the unleaded tin alloy plating bath of the mixture of at least a kind of soluble salt being selected from mantoquita, bismuth salt, silver salt, indium salt, zinc salt, nickel salt, cobalt salt and the antimonic salt and solubility tin salt.
Wherein, tin electroplating bath, contain the solubility tin salt and, as required, also contain the plating bath of various additives such as antioxidant, stablizer, tensio-active agent, gloss-imparting agent, semi-gloss agent, pH regulator agent again as the aliphatic sulfonic of liquid base, as necessary composition.
Tin alloy electric plating is bathed, be contain be selected from metal ingredient that at least a kind of soluble salt in mantoquita, bismuth salt, silver salt, indium salt, zinc salt, nickel salt, cobalt salt and the antimonic salt and solubility tin salt form, and as the aliphatic sulfonic of basal liquid, as necessary composition, unleaded plating bath like this, more as required, be also contain prevent plating bath decompose, with outside the stablizer that promotes tin and other metal to separate out jointly to be purpose etc., contain the plating bath of the various additives that are similar to the additive in the tin plating bath.
In the composition that in above-mentioned tin electroplating bath and tin alloy electric plating bath, adds,, can enumerate the tin salt of organic sulfonic acids such as methylsulfonic acid, ethyl sulfonic acid, 2-propyl alcohol sulfonic acid, sulfo-succinic acid, p-Phenylsulfonic acid as the solubility tin salt; Stannous fluoboric acid, stannous sulfate, tin protoxide, tin protochloride, sodium stannate, potassium stannate etc.
As forming the soluble salt of the special metal beyond the lead of alloy, can use and in bath, generate Cu with tin
+, Cu
2+, Ag
+, Bi
3+, In
3+, Zn
2+, Ni
2+, Co
2+, Co
3+And Sb
3+The inorganic salt, organic salt etc. of each metal ion species.These soluble salts can be independent a kind or mix more than 2 kinds and use.
In these soluble salts,, can exemplify copper sulfate, cupric chloride, cupric oxide, copper carbonate, neutralized verdigris, cupric pyrophosphate, cupric oxalate etc. as soluble copper salt.As soluble silver salt, can exemplify the organic sulfonic acid silver of methylsulfonic acid silver, ethyl sulfonic acid silver, 2-propyl alcohol sulfonic acid silver etc.; Silver cyanide, silver fluoborate, Sulfuric acid disilver salt, silver sulfite, silver carbonate, sulfo-succinic acid silver, Silver Nitrate, silver citrate, silver tartrate, glyconic acid silver, silver oxalate, silver suboxide, Silver monoacetate etc.As soluble bismuth salt, can exemplify the bismuth salt of bismuth sulfate, bismuth oxide, bismuth chloride, bismuth bromide, Bismuth trinitrate, organic sulfonic acid, the bismuth salt of sulfo-succinic acid etc.As solubility indium salt, can exemplify indium chloride, Indium sesquioxide, organic sulfonic acid indium etc.As soluble zinc salt, can exemplify zinc chloride, zinc sulfate, zinc oxide, organic sulfonic acid zinc, sulfo-succinic acid zinc etc.As soluble nickel salt, can exemplify the nickel salt of single nickel salt, nickelous chloride, nickel ammonium sulfate, nickel oxide, nickel acetate, organic sulfonic acid etc.As the solubility cobalt salt, can exemplify the cobalt salt of rose vitriol, cobalt chloride, organic sulfonic acid etc.As the solubility antimonic salt, can exemplify antimony chloride, fluoroboric acid antimony, organic sulfonic acid antimony etc.
In the tin electroplating bath, the content of solubility tin salt, as Sn
2+Ionic weight, preferred 1～200g/l, more preferably 3～100g/l.
In addition, in the tin electroplating bath, the content of solubility tin salt is as Sn
2+Ionic weight be 1～200g/l, other the content of soluble metallic salt as metal ingredient amount, preferred 0.1～100g/l, the content of solubility tin salt is as Sn
2+Ionic weight is that 3～100g/l, other the content of soluble metallic salt are more preferably 0.5～50g/l as the metal ingredient amount.
Be selected from the alkansulfonic acid in tin plating bath or the tin alloy plating bath and the concentration of at least a kind of aliphatic sulfonic in the alkanol sulfonic acids, preferred 1～500g/l, more preferably 1～200g/l.
Tin of the present invention or tin alloy plating bath can be used in the scope of pH arbitrarily of acidity～neutrality or alkalescence.General, the Sn in the plating bath
2+Be stable under acidity but near neutrality, become unstable easily.Therefore, when near the pH scope neutral is used plating bath of the present invention, in neutral range, for making Sn
2+Stabilization, prevent to produce the purpose that white precipitate, plating bath decompose, it is effective making it to contain coordination agent.
As coordination agent, can use hydroxycarboxylic acid, poly carboxylic acid, monocarboxylic acid, these sour salt.As object lesson, can enumerate glyconic acid, citric acid, glucoheptose, glucono-lactone, glucoheptose lactone, formic acid, acetate, propionic acid, butyric acid, xitix, oxalic acid, propanedioic acid, succsinic acid, oxyacetic acid, oxysuccinic acid, tartrate, diglycollic acid, these sour salt etc.Wherein, preferred glyconic acid, citric acid, glucoheptose, glucono-lactone, glucoheptose lactone, these sour salt.
In addition, quadrol, ethylenediamine tetraacetic acid (EDTA) (EDTA), diethylenetriamine pentaacetic acid (DTPA), nitrilotriacetic acid(NTA) (NTA), imine oxalic acid (IDA), imines dipropionic acid (IDP), hydroxyethylethylene diamine tri-acetic acid (HEDTA), triethylenetetraaminehexaacetic acid (TTHA), two (ethylenedioxybis) (ethamine) of ethylenedioxy-N, N, N ', N '-tetraacethyl, Padil class, nitrilo trimethylammonium sulfonic acid, 1-hydroxyl ethane-1, the 1-disulfonic acid, the salt that these are sour etc. also are effective as coordination agent.
Coordination agent can be independent a kind or mix more than 2 kinds and use.
About the concentration of the coordination agent in tin plating bath or the tin alloy plating bath, there is no particular limitation but be preferably 1～20mol/l usually.
The purpose of antioxidant is in order to prevent the Sn in the plating bath
2+Oxidation, can use ortho phosphorous acid or its salt, xitix or its salt, Resorcinol, catechol, Resorcinol, Phloroglucinol, cresol sulfonic acid or its salt, sulfocarbolic acid or its salt, catechol sulfonic acid or its salt, Resorcinol sulfonic acid or its salt, hydrazine etc.Antioxidant can be independent a kind or mix more than 2 kinds and use.
About the concentration of the antioxidant in tin plating bath or the tin alloy plating bath, there is no particular limitation but be preferably 0.01～20g/l usually.
The purpose of stablizer is particularly for the stabilization of tin alloy plating bath or prevent separating out jointly of the metal that decomposes, make tin and form alloy etc., can use the known stablizer of hydroxycarboxylic acid etc. of the sulfocompound, cyanogen compound, citric acid etc. of Thiourea, thiosulphate, sulphite, thioglycol, Thiovanic acid, the poly-ethylate of thioglycol, acetylcysteine etc.Stablizer can be independent a kind or mix more than 2 kinds and use.
About the concentration of the stablizer in tin plating bath or the tin alloy plating bath, there is no particular limitation but be preferably 0.01～100g/l usually.
Tensio-active agent is to give plated film, in the improvement of outward appearance, compactness, smoothness, tackiness etc., can use the various tensio-active agents of nonionic class, anionic species, both sexes, cationic etc. usually.
As the anionic species tensio-active agent, can enumerate alkyl-sulphate, polyoxyethylene alkyl ether sulfate salt, polyoxyethylene alkylphenyl ether sulfate salt, alkylbenzene sulfonate, sulfonated alkyl naphathalene etc.As the cationic tensio-active agent, can enumerate list～trialkyl amine salt, dimethyl dialkyl ammonium salt, trimethylalkyl ammonium salt etc.
As nonionic class tensio-active agent, can enumerate C
1～C
20Alkanol, phenol, naphthols, bisphenols, C
1～C
25Alkylphenol, arylalkyl phenol, C
1～C
25Alkyl naphthol, C
1～C
25Alkoxyl group phosphoric acid (salt), sorbitan ester, polyalkylene glycol, at C
1～C
22Aliphatic amides etc. are gone up the oxyethane (EO) of 2～300 moles of addition condensations and/or the condenses that propylene oxide (PO) obtains.
As amphoterics, can enumerate carboxybetaine, sultaine, imidazolinium betaine, aminocarboxylic acid etc.
Tensio-active agent can be independent a kind or mix more than 2 kinds and use.About the surfactant concentrations in tin plating bath or the tin alloy plating bath, there is no particular limitation but be preferably 0.01～50g/l usually.
As gloss-imparting agent and semi-gloss agent, can use phenyl aldehyde, o-chlorobenzaldehyde, 2,4, the various aldehyde of 6-tri chlorobenzaldehyde, m-chlorobenzaldehyde, p-nitrobenzaldehyde, p-hydroxy benzaldehyde, furfural, 1-naphthaldehyde, 2-naphthaldehyde, 2-hydroxyl-1-naphthaldehyde, 3-acenaphthene and aldehyde, benzyl acetone, pyridyl acetone, furfuryl acetone, phenylacrolein, aubepine, salicylic aldehyde, crotonic aldehyde, propenal, glutaraldehyde, paraldehyde, Vanillin etc.; The benzothiazoles of benzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole, 2-mercaptobenzothiazole etc.; Triazine, imidazoles, indoles, quinoline, 2-vinyl pyridine, aniline, phenanthrolene, new cuprous spirit, pyridine carboxylic acid, Thiourea, N-(3-hydroxy butylidene)-p-sulfanilic acid, N-butylidene sulfanilic acid, N-cinnyl subunit sulfanilic acid, 2,4-diamino-6-(2 '-methylimidazolyl (1 ')) ethyl-1,3,5-triazine, 2,4-diamino-6-(2 '-ethyl-4-methylimidazole base (1 ')) ethyl-1,3,5-triazine, 2,4-diamino-6-(2 '-undecyl imidazole base (1 ')) ethyl-1,3,5-triazine, salol etc.
Gloss-imparting agent and semi-gloss agent, according to the state of desired plated film, can be independent a kind or mix more than 2 kinds and use.About the concentration of gloss-imparting agent in tin plating bath or the tin alloy plating bath and semi-gloss agent, there is no particular limitation but be preferably 0.01～100g/l usually.
As the pH regulator agent, can use the various acid of hydrochloric acid, sulfuric acid etc.; The various alkali of ammoniacal liquor, potassium hydroxide, sodium hydroxide etc.The monocarboxylic acid class of formic acid, acetate, propionic acid etc.; The di-carboxylic acid class of boric acid class, phosphoric acid class, oxalic acid, succsinic acid etc.; The hydroxy acid class of lactic acid, tartrate etc. etc. also is effective.
As conductive salt, can use sodium salt, sylvite, magnesium salts, ammonium salt, amine salt of sulfuric acid, hydrochloric acid, phosphoric acid, thionamic acid, sulfonic acid etc. etc., the shared situation of also useful above-mentioned pH regulator agent.The content of conductive salt can be 0～100g/l usually.
Tin plating bath of the present invention or tin alloy plating bath can all be applicable to barrel plating, rack plating, high-speed and continuous plating, not have any plating method of hanging (rackless) plating etc.
The plating condition of using tin plating bath of the present invention or tin alloy plating bath also is arbitrarily, and for example to bathe temperature be more than 0 ℃, be preferably 10～50 ℃, and cathode current density can be 0.001～100A/dm
2, be preferably 0.01～30A/dm
2
Tin plating bath of the present invention or tin alloy plating bath also go for electroless plating.This moment is also same with plating, compares with the plating bath of using aliphatic sulfonic in the past, on tin plated film or tin alloy plated film, can give excellent levelling property again (reflowability), plated film outward appearance.During electroless plating was bathed, in order to promote the replacement(metathesis)reaction with the ground metal of copper, copper alloy etc., the coordination agent that contains Thiourea etc. was useful.
As mentioned above, tin plating bath of the present invention and tin alloy plating bath contain the few corps family sulfonic acid of the content of specific impurities as acid basis, and by the plated film that these plating bath form, levelling property (reflowability), plated film outward appearance etc. become very good again.
The corps family sulfonic acid that the content of the specific impurities of using in plating bath of the present invention is few, the such miscellaneous refining step that does not need the spy to open to put down in writing in the flat 10-204252 communique, can handle with concentrating under reduced pressure, solid phase extractions handles the better simply process for purification of geometric ratio and obtains, can obtain with industrial very favorable method.
In addition, use tin plating bath of the present invention or tin alloy plating bath, when printed base plate, TAB (TapeAutomated Bonding Carrier) (being with automatic bonding carrier) etc. form projection, comparing with using plating bath in the past, is not the chevron shape etc. that hinders the such following minister of substrate densification, the projection that can successfully form suitable mushroom shaped.
Tin plating bath of the present invention or tin alloy plating bath can be applicable to form tin plated film or tin alloy plated film well on the electronic component of for example semiconductor device, printed base plate, flexible printed board, thin-film carrier, terminal stud, switch, resistance, variable resistor, electrical condenser, film, inductor block, electroregulator, crystal oscillator, lead-in wire etc.
Description of drawings
Fig. 1 is the liquid chromatogram of the methylsulfonic acid before and after the enforcement separation and purification is handled in the refining example 2 of aftermentioned, and Figure 1A is that liquid chromatogram, the Figure 1B before making with extra care is the liquid chromatogram after making with extra care.
Embodiment
Below, alkansulfonic acid is handled by concentrating under reduced pressure and solid phase extractions is handled refining example is described successively, contains the tin plated film that obtains through the embodiment of the tin plating bath of the alkansulfonic acid of these refinement treatment and tin alloy plating bath and from these plating bath and levelling property again (reflowability) the evaluation test example and the ocular estimate of tin alloy plated film tested routine.
In addition, in the alkansulfonic acid before refining, contain various oxidation of sulfur compound impurities micro-ly, in the separation identification test example of these sulphur compounds of narration, make in handle tin plating bath that the refining alkansulfonic acid that obtains is an acid basis and tin alloy plating bath with concentrating under reduced pressure and contain isolating sulphur compound micro-ly, these sulphur compounds of explanation investigation are to the result of plated film appearance effects in the lump.
The refining example of＜alkansulfonic acid 〉
In the following refining example 1～8, refining example 1 is the example of being handled by concentrating under reduced pressure, refining example 2～3rd is that the solid phase extractions that sorbent material uses is handled the example that produces with the organic polymer, refining example 4 is to be the example of the solid phase extractions processing of sorbent material use with the gac, refining example 5 is to be the example of 2 sections solid phase extractions processing of sorbent material use with the organic polymer, making with extra care example 6 is to be the example of 2 sections solid phase extractions processing of sorbent material use with organic polymer and gac, refining example 7～8th, 2 sections refining examples of processing of combination concentrating under reduced pressure and solid phase extractions processing.
(1) the refining example of handling by concentrating under reduced pressure 1
In 4 mouthfuls of flasks, add the commercially available aqueous methane sulfonic acid stoste of concentration 60%, assemble water distilling apparatus with liebig's condensing tube (Liebig condenser) and fractionation with curved tube, eggplant shape flask.
Then, the limit is reduced pressure 5mmHg, limit at room temperature to begin to concentrate, make at leisure temperature to rise to the liquid temperature is 100 ℃, carries out about 5 hours concentrating under reduced pressure, obtains the methylsulfonic acid of concentration 96% with vacuum pump.
(2) the refining example of handling by solid phase extractions 2
In the 500ml beaker, add 100.0g styrene diethylene benzene copoly mer (An Polaite XAD2, Supelco company produce), add under 500ml methyl alcohol (superfine), the room temperature stir about after 1 hour, discarded supernatant liquor, repeat 3 same operations with methyl alcohol.Then, stir after 10 minutes under adding 500ml distilled water, the room temperature, discard supernatant liquor, repeat 5 same operations with distilled water.Then remove the adjusting operation of moisture, end sorbent material by filtration under diminished pressure.
At the uncovered post filling 10g of diameter 5cm * long 40cm glass wool, fill 100g and finish the styrene diethylene benzene copoly mer of above-mentioned adjusting operation, load the 10g glass wool from it.
The flow velocity that this post is divided with 5ml/ drips the commercially available methylsulfonic acid (concentration 70%) of 300g, obtains the methylsulfonic acid of concentration 70.0%.
In addition, as above-mentioned ground, An Polaite XAD2 is a sorbent material, and the deacidite of opening 2001-64249 number use with the spy is different.
(3) the refining example of handling by solid phase extractions 3
Use the styrene diethylene benzene copoly mer (Sepabeads SP207, Mitsubishi Chemical Ind produce) of bromination to be sorbent material, other to regulate operation and abstraction process with the same condition of refining example 2, the flow velocity that divides with 5ml/ on this post drips the commercially available methylsulfonic acid (concentration 70%) of 300g, obtains the methylsulfonic acid of concentration 70.0%.
(4) the refining example of handling by solid phase extractions 4
Add commercially available methylsulfonic acid (concentration 70.0%) of 500g and 50g gac (productions of Northeast chemical company) in the 500ml beaker, stir after 5 hours, the strainer filtration under diminished pressure of usefulness glass fibre, obtains the methylsulfonic acid of concentration 70.0% at recovery filtrate.
(5) the refining example of handling by 2 sections solid phase extractions 5
By with the same operation of refining example 2, be sorbent material, regulate operation and abstraction process that with styrene diethylene benzene copoly mer (An Polaite XAD2) flow velocity that divides with 5ml/ at this post drips the commercially available methylsulfonic acid (concentration 70%) of 300g, obtains the methylsulfonic acid of concentration 70.0%.
Re-use the same post of the An Polaite XAD2 that fill to implement regulates, again carry out solid phase extractions, obtain the methylsulfonic acid of concentration 70.0%.
(6) the refining example of handling by 2 sections solid phase extractions 6
By with the same operation of refining example 3, be sorbent material, regulate operation and abstraction process that with the styrene diethylene benzene copoly mer (Sepabeads SP207) of bromination the flow velocity that divides with 5ml/ at this post drips the commercially available methylsulfonic acid (concentration 70%) of 300g, obtains the methylsulfonic acid of concentration 70.0%.
Re-use the same post of having filled gac, again carry out solid phase extractions, obtain the methylsulfonic acid of concentration 70.0%.
(7) the refining example 7 that the combination concentrating under reduced pressure is handled and solid phase extractions is handled
In 4 mouthfuls of flasks, the aqueous methane sulfonic acid that adds concentration 60%, with curved tube, eggplant shape flask assembling water distilling apparatus, the limit is reduced pressure the 5mmHg limit to begin to concentrate, make at leisure temperature to rise to the liquid temperature in room temperature is 100 ℃, carries out about 5 hours concentrating under reduced pressure, obtains the methylsulfonic acid of concentration 96% with vacuum pump with liebig's condensing tube (Liebig condenser) and fractionation.
On the other hand, at the uncovered post filling 10g of diameter 5cm * long 40cm glass wool, fill 100g and implement the styrene diethylene benzene copoly mer (An Polaite XAD2) of above-mentioned adjusting operation, load the 10g glass wool from it.
The flow velocity that this post is divided with 5ml/ drips the above-mentioned methylsulfonic acid (concentration 96.0%) that the 300g concentrating under reduced pressure crosses, the methylsulfonic acid that obtains concentration 96.0%.
(8) the refining example 8 that the combination concentrating under reduced pressure is handled and solid phase extractions is handled
In 4 mouthfuls of flasks, the aqueous methane sulfonic acid that adds concentration 60%, assemble water distilling apparatus with liebig's condensing tube (Liebig condenser) and fractionation with curved tube, eggplant shape flask, the limit begins to concentrate in room temperature with the vacuum pump 5mmHg limit of reducing pressure, making temperature rise to the liquid temperature at leisure is 100 ℃, carry out about 5 hours concentrating under reduced pressure, obtain the methylsulfonic acid of concentration 96%.
On the other hand, at the uncovered post filling 10g of diameter 5cm * long 40cm glass wool, fill 100g and implement the brominated styrene-divinyl benzene copolymer (SepabeadsSP207) of above-mentioned adjusting operation, load the 10g glass wool from it.
The flow velocity that this post is divided with 5ml/ drips the above-mentioned methylsulfonic acid (concentration 96.0%) that the 300g concentrating under reduced pressure crosses, the methylsulfonic acid that obtains concentration 96.0%.
The refining evaluation Example of＜alkansulfonic acid that obtains by liquid chromatography 〉
With the refining example 2 handled by solid phase extractions is typical example, by the high-speed liquid phase chromatogram analysis methylsulfonic acid in stage before and after refining, based on the liquid chromatogram that obtains, carry out the refining evaluation of methylsulfonic acid.
The analysis condition of the above-mentioned high speed liquid chromatography of the chromatogram LC-10AS that use Shimadzu Seisakusho Ltd. produces is as follows.
Post: ODS-UG-3
Mobile phase: methyl alcohol: water=1: 5, phosphoric acid 2ml/l
UV analyzer: 230nm
Column temperature: 40 ℃
Flow velocity: 1ml/ branch
Figure 1A is the color atlas of the methylsulfonic acid before making with extra care, and Figure 1B is the color atlas of the methylsulfonic acid after making with extra care.
Analytical results is as follows.
*Before refining
PKNO TIME AREA HEIGHT MK IDNO CONC
1 0.957 120935 11207 92.5134
2 1.948 465 40 0.3557
4 3.029 5829 553 V 4.4587
8 5.816
3493 207 2.6722
TOTAL 130722 12008 100
*After refining
PKNO TIME AREA HEIGHT MK IDNO CONC
2 0.954 16818 3194 V 45.5893
3 1.068
20073 4880 SV
54.4107
TOTAL 36891 8073 100
Judge from these liquid chromatographies, in the stoste before methylsulfonic acid is refining, shown in Figure 1A, at hold-time=3.029 and visible absorbance peak, 5.816 place, but refining example 2 obtain refining after methylsulfonic acid in, shown in Figure 1B, these 2 absorption peaks almost disappear, and can confirm by implementing solid phase extractions to handle that the impurity in the stoste is removed effectively, methylsulfonic acid is by high purityization.At this moment, even almost the composition at the visible absorbance peak of Xiao Shiing does not reach tight special qualification,, be estimated as sulphur compound because be similar to the peak position that sulfocompound is seen more.But, a position judgment from above-mentioned disappearance peak, the spy opens in 2001-64249 number, does not have sulfuric acid what enumerate from the object component of removing of methylsulfonic acid.Therefore, in the methylsulfonic acid of the separation and purification of aliphatic sulfonic of the present invention and above-mentioned document refining, so can think because the refining mechanism of the object component difference of removing is also different.
Replace that solid phase extractions is handled, when concentrating under reduced pressure that methylsulfonic acid is implemented refining example 1 is handled, also can be before refining and the contrast of the liquid chromatography after refining confirm that same peak disappears.Judge from this result be suitable for that concentrating under reduced pressure is handled, methylsulfonic acid is also by high purityization effectively.
In addition, replace above-mentioned methylsulfonic acid, commercially available 2-hydroxyethyl-1-sulfonic acid is implemented separation and purification processing of the present invention, investigate before making with extra care and the liquid chromatography after making with extra care, demonstration is by the same tendency of the disappearance generation of absorption peak.
Then, preparation contains the tin plating bath and the tin alloy plating bath of the high purity methylsulfonic acid that above-mentioned refining example 1～8 obtains as described below.In addition, the blank of using the methylsulfonic acid of not implementing the separation and purification processing is routine routine in contrast with the example difference of using the methylsulfonic acid of not heating, carrying out at normal temperature the concentrating under reduced pressure processing.
The embodiment of＜tin class plating bath 〉
(1) embodiment 1
Make the tin plating bath with following composition
[the tin plating bath of levelling property evaluation usefulness again]
Tin protochloride (Sn
2+) 50g/l
The methylsulfonic acid 50g/l of refining example 1
Antioxidant is a small amount of
Nonionic class tensio-active agent is a small amount of
[the tin plating bath that the plated film ocular estimate is used]
Tin protochloride (Sn
2+) 80g/l
The methylsulfonic acid 150g/l of above-mentioned refining example 1
Antioxidant is a small amount of
Nonionic class tensio-active agent is a small amount of
In addition, in above-mentioned plating bath,, can contain xitix, catechol, Resorcinol etc. with the ratio of 1～10g/l,, can contain C with the ratio of 1～10g/l as nonionogenic tenside as antioxidant
1～C
20Alkanol, phenol, naphthols, C
1～C
25Alkylphenol, C
1～C
22The ethylene oxide adduct of fatty amine etc. (also identical with reference examples) at following embodiment.
(2) embodiment 2
Replace the methylsulfonic acid made from extra care example 1 and obtaining, the methylsulfonic acid that uses refining example 2 to obtain, composition in addition and content and embodiment 1 identical, making tin plating bath.
(3) embodiment 3
Replace the methylsulfonic acid made from extra care example 1 and obtaining, the methylsulfonic acid that uses refining example 3 to obtain, composition in addition and content and embodiment 1 identical, making tin plating bath.
(4) embodiment 4
Replace the methylsulfonic acid made from extra care example 1 and obtaining, the methylsulfonic acid that uses refining example 4 to obtain, composition in addition and content and embodiment 1 identical, making tin plating bath.
(5) embodiment 5
Replace the methylsulfonic acid made from extra care example 1 and obtaining, the methylsulfonic acid that uses refining example 5 to obtain, composition in addition and content and embodiment 1 identical, making tin plating bath.
(6) embodiment 6
Replace the methylsulfonic acid made from extra care example 1 and obtaining, the methylsulfonic acid that uses refining example 6 to obtain, composition in addition and content and embodiment 1 identical, making tin plating bath.
(7) embodiment 7
Replace the methylsulfonic acid made from extra care example 1 and obtaining, the methylsulfonic acid that uses refining example 7 to obtain, composition in addition and content and embodiment 1 identical, making tin plating bath.
(8) embodiment 8
Replace the methylsulfonic acid made from extra care example 1 and obtaining, the methylsulfonic acid that uses refining example 8 to obtain, composition in addition and content and embodiment 1 identical, making tin plating bath.
(9) embodiment 9
Make the tin-copper alloy plating bath with following composition
[levelling property (reflowability) is estimated the tin-copper alloy plating bath of usefulness again]
Stannous sulfate (Sn
2+) 50g/l
Copper sulfate (Cu
2+) 5g/l
The methylsulfonic acid 50g/l of refining example 7
Antioxidant is a small amount of
Nonionic class tensio-active agent is a small amount of
Stablizer is a small amount of
[the tin-copper alloy plating bath that the plated film ocular estimate is used]
Stannous sulfate (Sn
2+) 80g/l
Copper sulfate (Cu
2+) 8g/l
The methylsulfonic acid 150g/l of refining example 7
Antioxidant is a small amount of
Nonionic class tensio-active agent is a small amount of
Stablizer is a small amount of
In the above-mentioned plating bath, the kind of antioxidant and nonionic class tensio-active agent and content are as about tin plating bath record.In addition, stablizer is to be used for successfully separating out jointly tin and copper, also can use replacements such as Thiourea, nonionic class tensio-active agent (for example ethylene oxide adduct of lauryl amine etc.).
(10) embodiment 10
Replace the methylsulfonic acid made from extra care example 7 and obtaining, the methylsulfonic acid that uses refining example 8 to obtain, composition in addition and content and embodiment 9 identical, making tin-copper alloy plating bath.
(11) embodiment 11
Replace the methylsulfonic acid made from extra care example 7 and obtaining, the methylsulfonic acid that uses refining example 1 to obtain, composition in addition and content and embodiment 9 identical, making tin-copper alloy plating bath.
(12) embodiment 12
Make the tin-bismuth alloy electroplating plating bath with following composition
Stannous sulfate (Sn
2+) 80g/l
Bismuth sulfate (Bi
3+) 8g/l
The methylsulfonic acid 150g/l of refining example 1
Antioxidant is a small amount of
Nonionic class tensio-active agent is a small amount of
Stablizer is a small amount of
In the above-mentioned plating bath, the kind of antioxidant and nonionic class tensio-active agent and content are as about tin plating bath record.In addition, stablizer is to be used for successfully separating out jointly tin and bismuth, for example is the sulphur compounds of Thiourea etc.
(13) embodiment 13
Make tin-silver alloys plating bath with following composition
Tin protochloride (Sn
2+) 80g/l
Silver Nitrate (Ag
+(argent)) 8g/l
The methylsulfonic acid 150g/l of refining example 1
Antioxidant is a small amount of
Nonionic class tensio-active agent is a small amount of
Stablizer is a small amount of
In the above-mentioned plating bath, the kind of antioxidant and nonionic class tensio-active agent and content are as about tin plating bath record.In addition, stablizer is to be used for successfully separating out jointly tin and silver, for example is the sulphur compounds of Thiourea, thioglycol, Thiovanic acid, sulphite, thiosulphate etc.
(14) embodiment 14
Replace the methylsulfonic acid made from extra care example 1 and obtaining, the methylsulfonic acid that uses refining example 7 to obtain, composition in addition and content and embodiment 12 identical, making tin-bismuth alloy electroplating plating bath.
(15) embodiment 15
Replace the methylsulfonic acid made from extra care example 1 and obtaining, the methylsulfonic acid that uses refining example 8 to obtain, composition in addition and content and embodiment 12 identical, making tin-bismuth alloy electroplating plating bath.
(16) embodiment 16
Replace the methylsulfonic acid made from extra care example 1 and obtaining, the methylsulfonic acid that uses refining example 7 to obtain, composition in addition and content and embodiment 13 identical, making tin-silver alloys plating bath.
(17) embodiment 17
Replace the methylsulfonic acid made from extra care example 1 and obtaining, the methylsulfonic acid that uses refining example 8 to obtain, composition in addition and content and embodiment 13 identical, making tin-silver alloys plating bath.
(18) reference examples 1
Replace methylsulfonic acid, the former state ground making with extra care example 1 and obtain and use the commercially available methylsulfonic acid of not making refinement treatment, composition in addition and content and embodiment 1 identical, making tin plating bath.
(19) reference examples 2
The methylsulfonic acid that the refining example 1 of replacement obtains, use are not being heated down but the commercially available methylsulfonic acid that carries out the concentrating under reduced pressure processing at normal temperatures, composition in addition and content and embodiment 1 identical, making tin plating bath.
(20) reference examples 3
Replace methylsulfonic acid, the former state ground making with extra care example 7 and obtain and use the commercially available methylsulfonic acid of not making refinement treatment, composition in addition and content and embodiment 9 identical, making tin-copper alloy plating bath.
(21) reference examples 4
Replace methylsulfonic acid, the former state ground making with extra care example 1 and obtain and use the commercially available methylsulfonic acid of not making refinement treatment, composition in addition and content and embodiment 12 identical, making tin-bismuth alloy electroplating plating bath.
(22) reference examples 5
The methylsulfonic acid that the refining example 1 of replacement obtains, use are not being heated down but the methylsulfonic acid that carries out the concentrating under reduced pressure processing at normal temperatures, composition in addition and content and embodiment 12 identical, making tin-bismuth alloy electroplating plating bath.
(23) reference examples 6
Replace methylsulfonic acid, the former state ground making with extra care example 1 and obtain and use the commercially available methylsulfonic acid of not making refinement treatment, composition in addition and content and embodiment 13 identical, making tin-silver alloys plating bath.
From the electroplating film that each plating bath of the above embodiments and reference examples obtains, under than stricter usually condition, estimate again levelling property (reflowability) by following method.
Levelling property again (reflowability) the evaluation test example of＜stanniferous plated film 〉
Use each the tin plating bath and the tin-copper alloy plating bath of the foregoing description 1～10 and reference examples 1～3, to bathe temperature 30 ℃, cathode current density 20A/dm
2Condition electroplate, on the Cu plate, form tin plated film or the tin-copper alloy plated film of thickness 5 μ m.
With each test portion of forming plated film like this set the plated film outward appearance of placing on 300 ℃ the thermometal plate after place 60 seconds, visual observations, according to the levelling property again (reflowability) of following benchmark evaluation plated film.
A: plated film gloss is good, do not have gauffer and variable color.
B: plated film has fuzzy gloss slightly but does not have gauffer.
C: the plated film variable color is yellow～blueness but does not have gauffer.
D: the plated film variable color is yellow～blueness, also produces gauffer.
The above-mentioned test-results of expression in following table 1.
Table 1
| Execute example | Comparative example | ||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 1 | 2 | 3 | |
| Levelling property (reflowability) again | B | B | B | B | B | B | A | A | B | A | C | D | C |
From above result understood like that, the evaluation of levelling property (reflowability) again, reference examples 1～3rd, C～D but embodiment 1～10th, the excellent results of A～B.
In the test of levelling property (reflowability) again, be common condition in 10 seconds with 260 ℃ or some temperature heating of rising, but in this test, stricter than this, be set in the condition that plated film is easy to generate variable color and gauffer.Therefore, use in the reference examples 1～2 of the methylsulfonic acid in the past that does not carry out separation and purification processing of the present invention, on plated film, produce variable color and gauffer, but among the embodiment 1～10, although under strict like this condition, it is also roughly good still to can't see gauffer, gloss.
Can confirm with the contrast of reference examples 1 that from embodiment 1～6 in the tin plating bath, separation and purification of the present invention is handled, levelling property (reflowability) improves a lot again when not carrying out separation and purification once carrying out at alkansulfonic acid.In addition, can confirm with the contrast of reference examples 2 that in the tin alloy plating bath, separation and purification of the present invention is handled the raising of also giving again levelling property (reflowability) from embodiment 9～10.Can confirm with the contrast of reference examples 2 from embodiment 1, carry out concentrating under reduced pressure when handling at alkansulfonic acid, concentrated in the raising of levelling property (reflowability), under heating is important again.One contrast embodiment 1～6 and embodiment 7～8, judgement is that the combination concentrating under reduced pressure is handled and solid phase extractions is handled, when handling than a kind that only carries out these processing, more improves levelling property (reflowability) again.
As above like that, judgement is being in acid basis the tin plating bath and tin alloy plating bath that contain with the alkansulfonic acid that carries out separation and purification of the present invention, than the plating bath that contains the alkansulfonic acid that does not carry out separation and purification, the levelling property again (reflowability) of the plated film that obtains is enhanced and has obvious superiority.Therefore, when tin plated film that will obtain from plating bath of the present invention or tin alloy plated film are used in electronic unit etc., can be than improved galvanized reliability significantly in the past.
Then, set cathode current density, electroplate being easy to generate to burn under black and the uneven condition, estimate the outward appearance of the electroplating film that obtains from each plating bath of embodiment and reference examples than common highland.
The ocular estimate test example of＜tin class plated film 〉
Use each the tin plating bath and the tin alloy plating bath of embodiment 1～17 and reference examples 1,3～6, electroplate, go up tin plated film or the tin alloy plated film that forms thickness 10 μ m at Cu class lead frame (leadframe) with following condition.Respectively go between after observe electroplating with the magnifying glass precipitation state of plated film of end face, the generation situation of the whole plating ununiformity of visual observations lead frame (leadframe) is again estimated the quality of plated film outward appearance.
[plating condition]
Sn bathes Sn-Cu and bathes Sn-Bi bath Sn-Ag bath
The bath temperature (℃) 30 30 30 30
Current density (A/dm
2) 40 30 40 30
The metewand of plated film outward appearance is as follows
A: it is black, inhomogeneous to can't see burning on the plated film.
B: see slightly that on the lead-in wire end face burning is black, it is inhomogeneous not see.
C: see that at the lead-in wire end face burning is black, it is inhomogeneous not see.
D: almost comprehensively burn black, as seen inhomogeneous.
Following table 2 expression test-results
Table 2
| Execute example | |||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | |
| The plated film outward appearance | B | B | B | B | B | B | A | A | A | A | B | B | B |
Table 2 (continuing)
| Embodiment | Reference examples | |||||||||
| 14 | 15 | 16 | 17 | 1 | 2 | 3 | 4 | 5 | 6 | |
| The plated film outward appearance | A | A | A | A | C | - | C | C | C | C |
The evaluation of plated film outward appearance, reference examples 1,3～6th, C but embodiment 1～17th, the excellent results of A～B.
Usually, galvanized cathode current density is 10～20A/dm
2, but increase to 40～50A/dm in this test
2, be set to be easy to generate and burn black and uneven stringent condition.Therefore, use in the reference examples 1,3～6 of the methylsulfonic acid in the past that does not carry out separation and purification processing of the present invention, produce to burn and deceive.With respect to this, in embodiment 1～17, although under so strict condition, still can't see inhomogeneous, burn and blackly also roughly can't see.
Can confirm with the contrast of reference examples 1 from embodiment 1,2～7, in the tin plating bath once use the alkansulfonic acid that carried out separation and purification of the present invention and handled, the plated film outward appearance has raising greatly when not carrying out separation and purification.In addition, can confirm with the contrast of reference examples 3 that even in the tin-copper alloy plating bath, the alkansulfonic acid that has carried out separation and purification processing of the present invention is also given the improvement of plated film outward appearance from embodiment 10～11.In tin-bismuth alloy electroplating plating bath (contrast of embodiment 12,15 and reference examples 4), tin-silver alloys plating bath (contrast of embodiment 13,17 and reference examples 6), the alkansulfonic acid that has carried out separation and purification processing of the present invention is given the improvement of plated film outward appearance significantly.Can confirm with the contrast of reference examples 5 from embodiment 12, carry out concentrating under reduced pressure when handling at alkansulfonic acid, the improvement of plated film outward appearance, be important heating down.One contrast embodiment 1,2～6,11～13 and embodiment 7～10,14～17 judges that the combination concentrating under reduced pressure is handled and solid phase extractions is handled, when handling than a kind that only carries out these processing, more improves the plated film outward appearance.
As above like that, judgement is being in acid basis the tin plating bath and tin alloy plating bath that contain with the alkansulfonic acid that carries out separation and purification of the present invention, than the plating bath that contains the alkansulfonic acid that does not carry out separation and purification, the outward appearance of the plated film that obtains is enhanced and has obvious superiority.Come from this point, when tin plated film that will obtain from plating bath of the present invention or tin alloy plated film are used in electronic unit etc., can be more in the past than the reliability that improved plating significantly.
More than comprehensive obviously as can be known, the refining methylsulfonic acid that commercially available methylsulfonic acid is carried out that concentrating under reduced pressure is handled and/or solid phase extractions is handled and obtain as acid basis, adopt such tin plating bath or tin alloy plating bath to electroplate, can improve plated film outward appearance, levelling property (reflowability) etc. again.
Obtain excellent electroplating characteristic at methylsulfonic acid once carrying out these specific refining separating treatment, this is can infer by refining to separate, get rid of from methylsulfonic acid and give the impurity of bad influence to electroplating characteristic.
Therefore, by above-mentioned refining separation, the specific sulphur compound that from methylsulfonic acid, is excluded, in these sulphur compounds, confirm successively electroplating characteristic is applied the composition of bad influence and the composition of not exerting one's influence based on following test.
Separate impurities identification test example in the＜methylsulfonic acid 〉
With the commercially available methylsulfonic acid of 300ml dichloromethane extraction 100ml, after this, remove methylene dichloride with vaporizer.Then, extract except that the aqueous mixture that desolvates, obtains impurity repeatedly several times.In order to remove moisture contained in the impurity, to add 30ml methylene dichloride, 5g sodium sulfate.The decantation supernatant liquor, remove the back of desolvating, obtain the mixture of impurity with vaporizer.
In the mixture of the impurity that obtains, add 3ml methyl alcohol, use Liquid Chromatograph (Japanese analytical industry (strain) production of recirculation divergence type; The LC-908 type), measure, obtain isolate with the condition shown in following.
Post: Shodex Asahipak GS-31021G
Mobile phase: methyl alcohol
Flow velocity: 3.8ml/ branch
Detector: RI
Above-mentioned isolate uses
13C-NMR,
1The various analytical instrument identifications of H-NMR, IR, GC-MS, MS, ultimate analysis etc.
Its result is based on various analytical data, can assert following sulphur compound (1)～(5).
In addition, in following analytical data,
1The s of H-NMR refers to w unimodal, IR refers to weak peak, m refer to middle crest, s refers to strong peak.
(1) dimethyl disulphide
P&T-GC/MS：ms 94，79，61，45
(2) methyl thiosulfonic acid S-methyl esters
1H-NMR(ppm)：2.709(s，3H，-SO
2CH
3)、3.315(s，3H，-SCH
3)
IR(cm
-1)：1134.1(s，R-SO
2-R)、1305.7(m，R-SO
2-R)、1330.8(m，-S-CH
3)、1410.0(w，-S-CH
3)
(3) α-chlorine dimethyl sulfone
1H-NMR(ppm)：3.054(s，3H，-SO
2CH
3)、4.447(s，2H，-CH
2-Cl)
IR(cm
-1)：761.8(s，-CH
2-Cl)、1120.6(s，R-SO
2-R)、1245.9(m，-CH
2-Cl)、1313.4(s，R-SO
2-R)
GC/MS：ms 128、113、93、79、63、49
Ultimate analysis (C, H): (C
2H
5SO
2Cl) C:18.89%, H:3.48%
(4) Alpha-Methyl sulphonyl-α, α-dichloro dimethyl sulfone
1H-NMR(ppm)：2.920(s，3H，-SO
2CH
3)、3.369(s，3H，-SOCH
3)
13C-NMR(ppm)：36.873、39.832、105.880
IR(cm
-1)：1083.9(s，-SOCH
3)、1147.6(s，R-SO
2-R)、1321.1(s，R-SO
2-R)、1332.7(m，-SOCH
3)
Ultimate analysis (C, H, N, S, O):
(C
3H
6S
2O
3Cl
2) C：16.20％、H：2.56％、S：29.86％、O：21.54％
(5) dimethyl sulfone
1H-NMR(ppm)：2.991(s，3H，-SO
2CH
3)
IR(cm
-1)：1136.0(s，R-SO
2-R)、1298.0(s，R-SO
2-R)
In addition, from 1 liter 70% commercially available methylsulfonic acid, by dichloromethane extraction impurity, obtain the impurity concentration that exists in the methylsulfonic acid before making with extra care.Comprise and infer this result of expression, first thiosulfonic acid S-methyl esters (2) is that 1.6ppm, dimethyl sulfone (5) are 2.5ppm, with reference to the concentration that contains of dimethyl sulfone (5), can infer respectively that α-chlorine dimethyl sulfone (3) is 1.2ppm, Alpha-Methyl sulphonyl-α, α-dichloro dimethyl sulfone (4) is 2.5ppm.In addition, can think dimethyl disulphide (1) contain concentration and dimethyl sulfone (5) not too changes.
Therefore, handle 5 kinds of sulphur compounds that are added on separation in the above-mentioned test in the refining methylsulfonic acid that obtains respectively micro-ly, assert at the concentrating under reduced pressure of refining example 1, preparation is tin plating bath and the tin alloy plating bath that impurity contains with each sulphur compound.The quality of the electroplating film outward appearance that evaluation obtains from these plating bath is about each sulphur compound, to carry out electroplating characteristic be infectious composition or the judgement of the composition that does not have bad influence test.
＜sulphur compound is to the judgement test example of the degree of influence of electroplating characteristic 〉
Below respectively tin plating bath, tin-bismuth alloy electroplating plating bath, tin-silver alloys plating bath are illustrated successively.
(1) tin plating bath
Make the tin plating bath of following composition
Tin protochloride (Sn
2+) 60g/l
The methylsulfonic acid 106g/l of refining example 1
Nonionic class tensio-active agent 10g/l
The anionic species tensio-active agent is a small amount of
Antioxidant is a small amount of
In the above-mentioned plating bath,, use the poly-ethylate of bis-phenol as nonionic class tensio-active agent.In addition, as the anionic species tensio-active agent, make it to contain the sodium dibutyl naphthalene sulfonate of 2g/l, as antioxidant, make it to contain the xitix of 1g/l.
Then, in above-mentioned tin plating bath, be added on isolating sulphur compound (1)～(5) in the above-mentioned test respectively separately, in addition, with 1 pair 1 weight ratio and when adding sulphur compound (3) and (4), make interpolation change in concentration in this plating bath respectively in 0～5ppm (variation of every 1ppm ground), 10ppm, 50ppm, 100ppm, 200ppm.
Then, use the different tin plating bath of interpolation concentration of each sulphur compound, bathing temperature 40 ℃, cathode current density 20A/dm
2, negative electrode moves the condition that 6m/ divides, and goes up the tin plated film that forms thickness 10 μ m at Cu class lead frame (leadframe).To the plated film that obtains, with the same operation of ocular estimate test example of above-mentioned plated film, when observing the precipitation state of the end face coating that respectively goes between with magnifying glass, visual observations lead frame (leadframe) all the plated film gauffers the generation situation, estimate the quality of plated film outward appearance.
The metewand of plated film outward appearance is as follows.
A: during all surfaces of plated film is long-pending is good surface appearance more than 60%.
B: during all surfaces of plated film is long-pending is good surface appearance more than 40～60%.
C: being less than 40% during all surfaces of plated film is long-pending is good surface appearance.
Represent test-results in the following table.Compound (1) is that dimethyl disulphide, compound (2) are that first thiosulfonic acid S-methyl esters, compound (3) are that α-chlorine dimethyl sulfone, compound (4) are Alpha-Methyl sulphonyl-α, and α-dichloro dimethyl sulfone, compound (5) are dimethyl sulfone.
(5) (1) (2) (3) (4) (3)+(4)
0ppm A A A A A A
1ppm A A A A A B
2ppm A A B B B C
3ppm A A B B B C
4ppm A A C C C C
5ppm A A C C C C
10ppm A A C C C C
50ppm A A C C C C
100ppm A B C C C C
200ppm A C C C C C
Judge that from above result dimethyl sulfone (5) is even sneak into 200ppm, also without detriment to the outward appearance of plated film, electroplating characteristic is not exerted an influence.
In addition, dimethyl disulphide (1), the evaluation the when evaluation of the plated film outward appearance during 200ppm is C, 100ppm (more than the 100ppm, less than 200ppm) is B.Therefore, from confirming also that with the contrast of dimethyl sulfone (5) dimethyl disulphide (1) has bad influence to electroplating characteristic.
In addition, first thiosulfonic acid S-methyl esters (2), α-chlorine dimethyl sulfone (3), Alpha-Methyl sulphonyl-α, α-dichloro dimethyl sulfone (4), the ocular estimate when being respectively 4ppm is B when being C, 3ppm (more than the 3ppm, less than 4ppm).Can confirm that from this result similarly there is bad influence compound (2)～(4) to electroplating characteristic with compound (1).In addition, judge that compound (2)～(4) safe level in plating bath is lower than compound (1), exist, also electroplating characteristic had bad influence even in bath, surpass denier ground.
If when being conceived to exist jointly between the sulphur compound, when for example compound (3) or (4) exist with 2ppm separately, ocular estimate is B, but the total concentration when coexisting state is once becoming 2ppm, estimating and drop to C again.In addition, in coexisting state, the evaluation when adding up to concentration to be 1ppm (being more than the 1ppm, less than 2ppm) is B.Can confirm that from these results compound (3) and (4) are compared during with Individual existence respectively, even same concentration, ocular estimate are also poor in coexisting state.Therefore judge that some sulphur compound one coexistences more promote the decline of electroplating characteristic because of its synergism.
As above like that, in the tin plating bath that with the methylsulfonic acid is acid basis, can confirm the various sulphur compounds that in methylsulfonic acid, exist as impurity, not that it is all influential to electroplating characteristic, exist electroplating characteristic not have the such compound of dimethyl sulfone (5) that influences, have only specific compound that electroplating characteristic is had bad influence.As mentioned above, clear and definite is compound (1)～(4) to the infectious composition of electroplating characteristic, be intramolecularly have Oxidation Number for the compound of the sulphur atom+4 below, reach the so important point of compound that has sulphur atom and chlorine atom simultaneously.
In addition, even between compound (1)～(4), intensity (being the safe level in the plating bath) difference to the electroplating characteristic influence, in the condition that in bath, exists with separate constituent, the safe level of compound (1) is less than 200ppm, and the safe level that can infer compound (3)～(4) is less than 4ppm.Can confirm, be not to coexist in plating bath, more promote the tendency that electroplating characteristic descends because of its synergism with some compositions individually again.The condition that coexists in bath more than 2 kinds of compound (1)～(4) can be inferred it and be added up to safe level to be reduced to below the 2ppm.
(2) tin-bismuth alloy electroplating plating bath
Make the tin-bismuth alloy electroplating plating bath with following composition
Stannous sulfate (Sn
2+) 80g/l
Bismuth sulfate (Bi
3+) 8g/l
The methylsulfonic acid 150g/l of refining example 1
Nonionic class tensio-active agent is a small amount of
Antioxidant is a small amount of
In the above-mentioned plating bath, as nonionic class tensio-active agent, make it to contain the poly-ethylate of nonylphenol of 5g/l, as antioxidant, make it to contain the xitix of 1g/l.
Then, in above-mentioned tin-bismuth alloy electroplating plating bath, with the same adding conditional of above-mentioned tin plating bath, estimate the outward appearance of adding the electroplating film of isolating sulphur compound (1)～(5) in above-mentioned test.Promptly, to sulphur compound (1)～(5), with concentration in plating bath of the range of 0ppm～200ppm, separately or and land used add, with plating condition on Cu class lead frame (leadframe) the formation tin-bismuth alloy electroplating plated film same, estimate the quality of electroplating film outward appearance with the tin plating bath.Metewand is identical during with above-mentioned tin bath.
Represent test-results in following table.
(5) (1) (2) (3) (4) (3)+(4)
0ppm A A A A A A
5ppm A A A A A B
10ppm A A A A B C
50ppm A A B B C C
100ppm A A C C C C
200ppm A B C C C C
Judge that from this result dimethyl sulfone (5) is even sneak into 200ppm, also without detriment to the outward appearance of plated film, electroplating characteristic is not exerted an influence.
With respect to this, because the plated film outward appearance of sneaking into, make of compound (1)～(4) descends, so can confirm has bad influence to electroplating characteristic.Influence to the plating characteristic is different because of the kind of compound, judge with tendency similarly to be in the tin plating bath, to the influence of electroplating characteristic be that compound (1) is little, compound (4) big, compound (2)～(3) are between (1) and (4).
As above like that, in the tin-bismuth alloy electroplating plating bath that with the methylsulfonic acid is acid basis, can confirm the various sulphur compounds that in methylsulfonic acid, exist as impurity, be not that it is all influential to electroplating characteristic, have the such compound of dimethyl sulfone (5) that electroplating characteristic not have influence, opposite, intramolecularly has Oxidation Number to be the compound of the sulphur atom below+4 and to have sulphur atom and the compound of chlorine atom has the so important point of bad influence to electroplating characteristic.
In addition, same during with the tin plating bath, judge have compound (1)～(4) not to be individually but some compositions when coexisting as plating bath, because of synergism more can promote the tendency that electroplating characteristic descends.
In addition, can confirm in the tin-bismuth alloy electroplating plating bath that the safe level of compound (1)～(4) that electroplating characteristic is applied bad influence is big during than the tin plating bath.To compound (1) because relatively in the tin plating bath ocular estimate during 200ppm be that the ocular estimate during 200ppm is B in C, the tin-bismuth alloy electroplating plating bath, so even have the possibility that also is evaluated as B greater than 200ppm.In addition, to compound (4) because relatively in the tin plating bath ocular estimate during 10ppm be that the ocular estimate during 10ppm is B in C, the tin-bismuth alloy electroplating plating bath, so neither C and be evaluated as the possibility of B greater than 10ppm even have.Like this, can confirm that the safe level of each compound in bath is that the tin-bismuth alloy electroplating plating bath is bigger than tin plating bath.
Therefore, can infer when these specific sulphur compounds are present in the bath as impurity, big when reducing the resistance ratios tin plating bath of electroplating characteristic in the tin-bismuth alloy electroplating plating bath, also be difficult to occur bad influence even increase impurity concentration to plating bath than tin plating bath.
(3) tin-silver alloys plating bath
Make tin-silver alloys plating bath with following composition
Tin protochloride (Sn
2+) 80g/l
Silver Nitrate (Ag
+) 8g/l
The methylsulfonic acid 150g/l of refining example 1
Stablizer 40g/l
Nonionic class tensio-active agent is a small amount of
Antioxidant is a small amount of
In above-mentioned tin-silver alloys plating bath, the kind of nonionic class tensio-active agent and antioxidant and content are identical during with above-mentioned tin-bismuth alloy electroplating plating bath.In addition, use the poly-ethylate (Thioglycol polyethoxylate) of thioglycol as stablizer.
In above-mentioned tin-silver alloys plating bath, with the same adding conditional of above-mentioned tin plating bath, estimate the outward appearance of adding the electroplating film of isolating sulphur compound (1)～(5) in above-mentioned test.Promptly, to sulphur compound (1)～(5), with the concentration in the range plating bath of 0ppm～200ppm, independent or also land used interpolation, with plating condition on Cu class lead frame (leadframe) the formation tin-silver alloys plated film same, estimate the quality of electroplating film outward appearance with the tin plating bath.Metewand is identical during with above-mentioned tin bath.
Represent test-results in following table.
(5) (1) (2) (3) (4) (3)+(4)
0ppm A A A A A A
5ppm A A A A A C
10ppm A A B B B C
50ppm A A C C C C
100ppm A A C C C C
200ppm A B C C C C
Judge from this result, for dimethyl sulfone (5), even sneak into 200ppm, also do not damage the outward appearance of plated film, to not influence of electroplating characteristic.
With respect to this since compound (1)～(4) thus the outward appearance of sneaking into, make plated film descend and can confirm that electroplating characteristic is had bad influence.To the influence of electroplating characteristic, according to the kind of compound and difference, judge with the tendency of tin plating bath in the same manner, little to influence, the compound (1) of plating characteristic, compound (2)～(4) are bigger than compound (1).
As described above, even in the tin-silver alloys plating bath that with the methylsulfonic acid is acid basis, contained sulphur compound in methylsulfonic acid as impurity, not that it is all influential to electroplating characteristic, there not be the such compound of dimethyl sulfone (5) of influence to exist to the plating characteristic, on the contrary, to have Oxidation Number be the compound of the sulphur atom below+4 and only have sulphur atom and the compound of chlorine atom becomes clear and definite to the infectious vital point of electroplating characteristic at intramolecularly.
In addition, similarly, judging has compound (1)～(4) not to be individually but some compositions when coexisting in plating bath, because of synergism further promotes the tendency that electroplating characteristic descends during with the tin plating bath.
In addition, can confirm in tin-silver alloys plating bath, big during than the tin plating bath to the safe level of the infectious compound of electroplating characteristic (1)～(4), little during than the tin-bismuth alloy electroplating plating bath.When for example there is 200ppm in compound (1) in bath, is B in the ocular estimate of tin-silver alloys plating bath but is C, when there is 10ppm in compound (4) in bath, is B in the ocular estimate of tin-silver alloys plating bath but is C in the tin plating bath in the tin plating bath.Like this, the safe level of each compound in bath, tin-silver alloys plating bath is bigger than tin plating bath.In addition, when there are 10ppm in compound (2) or (3) in bath, because tin-ocular estimate of silver alloys in bathing be B but be A in tin-bismuth alloy electroplating is bathed, so it is big to assert that safe level in the bath of each compound, ratio tin-silver alloys that tin-bismuth alloy electroplating is bathed are bathed.
By more than, when these specific sulphur compounds exist as impurity, the resistance that the electroplating characteristic in confirming tin-silver alloys bathed descends, big, little tendency when bathing when having than tin-bismuth alloy electroplating than the tin plating bath.Therefore, when tin-silver alloys is bathed, even can infer than tin plating bath impurity concentration and increase, also be difficult to occur bad influence to electroplating characteristic, and than tin-bismuth alloy electroplating plating bath bad influence appears easily.
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| CN115161725A (en) * | 2022-06-23 | 2022-10-11 | 南通赛可特电子有限公司 | Semi-bright electro-acidic tinning additive, preparation method and application |
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