JP2017031447A - Tin and tin alloy electroplating bath, method for forming electrodeposition using plating bath, and electronic component produced by the method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plating bath forming an electrodeposition excellent in the uniformity of the height of a projection electrode formed on a substrate, a lead frame, wafer or the like by tin or tin alloy electroplating.SOLUTION: Provided is a tin and tin alloy electroplating bath obtained by adding a plating bath with a crosslinking type aromatic compound (such as benzylphenyl disulfonic acid salt, diaminostilbene, dipyrrole ether, alkyl diphenyletherdisulfonic acid salt, diphenylaminedisulfonic acid salt) having a structure obtained by crosslinking with the coupling of a specified bivalent coupled group such as ether coupling of each aromatic ring or heterocyclic ring, alkylene coupling, imino coupling or the like as the fundamental skeleton.SELECTED DRAWING: None

Description

  The present invention relates to an electroplated tin and tin alloy plating bath, a method of forming an electrodeposit using the plating bath, and an electronic component manufactured by the method that can form an electrodeposit excellent in height uniformity. I will provide a.

In the case where an electrodeposit is formed by applying electroplating to an electronic component (projection electrode (bump), electrodeposition film, etc.), for example, a substrate for mounting a semiconductor chip is light, thin and small. There is a CSP (Chip Size / scale Package) type semiconductor component in which the package substrate area is miniaturized to the same extent as the semiconductor chip mounted on the substrate.
To connect the substrate and the semiconductor chip, a bump electrode is formed by filling a pad or land on the semiconductor chip or a pad, land or via body on the substrate side with tin or a tin alloy, and forming the bump electrode. A semiconductor chip is loaded.
When projecting electrodes are formed by filling with this tin or tin alloy material, there are a method in which a tin-based solder paste or solder ball is placed and then melted by heat treatment, or a method in which it is formed by electroplating. The electroplating method is suitable.

Therefore, the electrotin or tin alloy plating bath used for forming the protruding electrode is as follows.
(1) Patent Document 1
By forming a protruding electrode on a substrate by electroplating using a tin-lead alloy plating bath containing a formalin condensate of naphthalenesulfonic acid and a nonionic surfactant (claims 1, 25 to 26, paragraphs) 18) The height uniformity of the protruding electrode is increased (paragraph 27).
The tin-lead alloy plating bath may contain a nonionic surfactant.
Examples 1 and 4 disclose a tin-lead alloy plating bath containing an ethylene oxide (EO) adduct of bisphenol F (paragraphs 31 and 34).

(2) Patent documents 2 to 4
Patent Documents 2 to 4 disclose electrotin-lead alloy plating baths for forming protruding electrodes on a semiconductor wafer.
Patent Document 2 is characterized by containing a bubble removing agent, and can contain various surfactants such as nonionic surfactants and anionic surfactants (Claim 17). Examples 7 and 20 (paragraphs 40 and 53) disclose a tin-lead alloy plating bath containing an EO adduct of bisfer A.
Patent Documents 3 and 4 are characterized by containing a specific nonionic surfactant or aldolsulfanyl derivative.

(3) Patent Document 5
An electrotin-silver alloy, tin-copper alloy, and tin-bismuth alloy plating bath for forming protruding electrodes on a semiconductor element is disclosed (claim 1).
Examples 1-4 disclose a tin-silver alloy plating bath containing an EO adduct of bisfer A (paragraphs 50-53).

(4) Patent Document 6
An electrolytic tin and tin alloy plating bath for forming a protruding electrode on a substrate is disclosed, and the soluble tin salt is characterized by having a purity higher than a predetermined level (Claim 1).
Example 5 discloses a tin-silver alloy plating bath containing an EO adduct of bisfer F, and Example 8 discloses a tin-copper alloy plating bath containing an EO adduct of bisfer F, respectively. (Paragraphs 42 and 45).

(5) Patent Document 7
An electrotin-silver alloy plating bath for forming a protruding electrode is disclosed, and is characterized by containing a specific thiourea derivative, or a specific aldehyde or ketone.
The plating bath can contain a cationic surfactant (quaternary ammonium salt) (claims 6 to 7, paragraph 29).

(6) Patent Documents 8 to 10
Patent Documents 8 to 10 are electroplating baths for forming an approximate material of a tin-lead alloy plating film on parts such as protruding electrodes, chip parts, and lead frames.
Patent Document 8 relates to an electrotin plating bath, and can contain various surfactants such as nonionic surfactants and anionic surfactants (paragraphs 39 to 40).
Patent Document 9 discloses an electrotin-copper alloy plating bath, Example 3 discloses a bath containing sodium dioctylsulfosuccinate, and Example 10 discloses a bath containing an EO adduct of bispheel A (Table 1). ~ 2).

(7) Patent Document 11
Although there is no description or suggestion of application to the formation of bump electrodes, an electrolytic tin and tin alloy plating bath containing a surfactant and a predetermined alcohol derivative is disclosed.
Examples of the surfactant include nonionic surfactants and anionic surfactants (paragraph 18). Examples of nonionic surfactants include polyoxyalkylene bisphenol (paragraph 19), and anionic surfactants. Examples of the agent include alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl diphenyl ether sulfonate, polyoxyethylene alkyl phenol ether sulfate salt and the like (paragraph 21).

JP-A-2005-290505 Japanese Patent Laid-Open No. 11-229174 Japanese Patent Laid-Open No. 08-267976 Japanese Patent Application Laid-Open No. 08-078424 Japanese Patent Laying-Open No. 2015-045094 Japanese Patent Laying-Open No. 2015-036449 Special table 2009-510255 gazette JP 2007-284733 A JP 2002-080993 A JP 2001-026898 A Japanese Patent No. 3904333

When chip components such as LSI and IC are mounted on a large number of protruding electrodes formed on a substrate, to ensure the connection with the chip components, ensure the shape of the protruding electrodes, especially the uniformity of the height. is important. This also applies to the inter-substrate connection in which the substrates are connected via the protruding electrodes formed on the lands.
However, when the protruding electrodes are formed by the tin or tin alloy plating bath shown in the above-mentioned patent document, there is a situation that if the number of protruding electrodes increases, it is not easy to ensure the uniformity of the height. There is an increased risk of connection failure with the increase in the number of electrodes, the electrode pitch, and the miniaturization of dimensions.

  As described above, the present invention has a technical problem to form an electrodeposit having excellent height uniformity with respect to electrodeposits such as bump electrodes and electrodeposition films formed using an electrotin or tin alloy plating bath. To do.

  The present inventors have plated a tin or tin alloy with a crosslinkable aromatic compound having a structure in which an aromatic ring or a heterocycle is crosslinked with a specific type of bond such as an ether bond, an alkylene bond, or an imino bond as a basic skeleton. When it is contained in a bath and an electrodeposit (projection electrode or electrodeposition film) is formed by electroplating, variation in the height of the electrodeposit is suppressed, and the uniformity of the height can be secured well, and sulfide compounds, etc. It was found that the above-mentioned problems can be achieved more smoothly when a complexing agent of a specific type selected from the above is used in combination with the plating bath, and the present invention has been completed.

Invention 1 is any of (A) a stannous salt and a mixture of a stannous salt and a metal salt selected from zinc, nickel, bismuth, cobalt, indium, antimony, gold, silver, copper, and lead. Some soluble salts,
(B) an acid or a salt thereof;
(C) Cross-linked aromatic compound represented by the following general formula (1)
Za-Xa-Y-Xb-Zb (1)
(In the above formula (1), Xa and Xb represent an aromatic ring and a heterocyclic ring, and Xa and Xb may be the same or different; Y represents a linear or branched alkylene chain, alkenylene chain, alkynylene chain, these Represents a carbon chain partially substituted with carbonyl, an oxygen atom, or a nitrogen atom; Za and Zb are hydrogen, a C1-C18 alkyl group, a C1-C18 alkoxy group, a halogen, a sulfonic acid (salt) group, It represents any one of an amide group, an amino group, a quaternary ammonium base, a carboxyl group, a hydroxyl group, a nitro group, and a nitroso group, Za and Zb are each 1 to 4, and Za and Zb may be the same or different. )
And a tin alloy plating bath containing tin.

  The present invention 2 is the present invention 1, wherein in the above compound (C), Y is an alkylene chain, an alkenylene chain, an oxygen atom or a nitrogen atom, and Xa and Xb are a benzene ring, naphthalene ring, thiazole ring, pyrrole ring, Selected from the group consisting of pyridine ring, pyrazine ring, pyridazine ring, thiadiazole ring, imidazoline ring, imidazole ring, thiazoline ring, triazole ring, tetrazole ring, picoline ring, furazane ring, piperidine ring, piperazine ring, triazine ring, benzimidazole ring The electrotin and tin alloy plating bath according to claim 1, wherein the electrotin and tin alloy plating bath are provided.

  Invention 3 is the invention 2, wherein the compound (C) is dipyridylalkane, dipyridylalkanesulfonic acid, dipiperidylalkane, dipiperidylalkanesulfonic acid, dipyrrolealkane, dipyrrolealkanesulfonic acid, diimidazolylalkane, Diimidazolylalkanesulfonic acid, ditriazolylalkane, ditriazolylalkanesulfonic acid, dianilinealkane, dianilinealkanesulfonic acid, diphenylalkane, aminodiphenylalkane, diphenylalkanesulfonic acid, hydroxydiphenylalkanesulfonic acid, hydroxydiphenylalkanesulfonic acid, Aminodiphenylalkanesulfonic acid, dinaphthylalkane, aminodinaphthylalkane, dinaphthylalkanesulfonic acid, hydroxydinaphthylalkanesulfo Acid, aminodinaphthylalkanesulfonic acid, phenylalkylimidazole, phenylalkylpyridine, diaminostilbene, diaminostilbenesulfonic acid, alkylhydroxystilbene, dipyridylamine, dipyridylaminesulfonic acid, dipiperidylamine, dipiperidylaminesulfonic acid, dipyrroleamine , Dipyrroleaminesulfonic acid, diimidazolylamine, diimidazolylaminesulfonic acid, ditriazolylamine, ditriazolylaminesulfonic acid, anilineamine, dianilineaminesulfonic acid, diphenylamine, aminodiphenylamine, diphenylaminesulfonic acid, hydroxydiphenylaminesulfone Acid, aminodiphenylaminesulfonic acid, dinaphthylamine, aminodinaphthylamine, dinaphthyl Minsulfonic acid, hydroxydinaphthylaminesulfonic acid, aminodinaphthylaminesulfonic acid, dialkyldiphenylammonium salt, dialkyldinaphthylammonium salt, N, N, N ', N'-tetraalkyldiaminodiphenylamine, phenylnaphthylaminesulfonic acid, dipyridyl ether, dipyridyl ether Ether sulfonic acid, dipiperidyl ether, dipiperidyl ether sulfonic acid, dipyrrole ether, dipyrrole ether sulfonic acid, diimidazolyl ether, diimidazolyl ether sulfonic acid, ditriazolyl ether, ditriazolyl ether sulfonic acid, dianiline ether, Dianiline ether sulfonic acid, diphenyl ether, alkyl diphenyl ether, hydroxy diphenyl ether, amino diphenyl ether -Tell, alkylamino diphenyl ether, carboxydiphenyl ether, diphenyl ether sulfonic acid, alkyl diphenyl ether sulfonic acid, hydroxy diphenyl ether sulfonic acid, dinaphthyl ether, alkyl dinaphthyl ether, hydroxy dinaphthyl ether, amino dinaphthyl ether, alkylamino Dinaphthyl ether, carboxydinaphthyl ether, dinaphthyl ether sulfonic acid, alkyl dinaphthyl ether sulfonic acid, phenyl naphthyl ether, alkylphenyl naphthyl ether, hydroxyphenyl naphthyl ether, aminophenyl naphthyl ether, alkylaminophenyl naphthyl ether --Tell, carboxyphenyl naphthyl ether, phenyl naphthyl ether sulfonic acid, alkyl Two Luna naphthyl ether sulfonate, hydroxyphenyl naphthyl ether sulfonate, alkyl amino nitro ether, or an electric tin and tin alloy plating bath, characterized in that at least one selected from the group consisting of salts.

The present invention 4 provides the sulfide compound, oxycarboxylic acid, polycarboxylic acid, pyrophosphoric acid aminocarboxylic acid, polyamine selected from the following compounds (a) to (c) in any one of the present inventions 1 to 3 At least one complexing agent selected from aminoalcohols and salts thereof (a) Aliphatic sulfide compounds represented by the following formula (a) Xn-R1-S- (CH2CH2S) m-R2-Xn (a) )
(In the formula (a), R1 and R2 are C2 to C4 alkylene; X is OH, SO3H, SO3M (M is an alkali metal, ammonia or amine), NRaRb (Ra and Rb are hydrogen, C1 to C6 alkyl), CONRaRb (Ra and Rb are hydrogen, C1 to C6 alkyl) and may be bonded to any carbon atom in the alkylene chain constituting R1 and R2; m is an integer of 1 to 2; n Is an integer from 1 to 4.)
(B) Aliphatic sulfide compound represented by the following formula (b) H- (OA) n-S- (OA) n-H (b)
(In the formula (b), A is ethylene or propylene (a hydroxyl group may be bonded to the carbon atom constituting the ethylene or propylene chain); n is an integer of 1 to 25.)
(C) one or more of mono-, di- or trisulfide bonds in the molecule, or an atomic group selected from aliphatic, alicyclic, aromatic and heterocyclic rings located on both wings of the bond An electrotin and tin alloy plating bath characterized by containing an aromatic sulfide compound having at least one basic nitrogen atom in at least one of them.

  The present invention 5 further comprises at least one additive selected from surfactants, antioxidants, brighteners, semi-brighteners, and pH adjusters in any of the present inventions 1-4. It is a characteristic electrotin and tin alloy plating bath.

  The present invention 6 is a method of forming an electrodeposit made of tin or a tin alloy using the electroplating bath according to any one of the present inventions 1 to 5.

  The present invention 7 includes a glass substrate, a silicon substrate, a sapphire substrate, a wafer, a printed wiring board, a semiconductor integrated circuit, a resistor, a variable resistor, a capacitor, a filter, an inkta, a thermistor, and a crystal vibration manufactured by the method of the present invention 6 It is an electronic component selected from a child, a switch, a lead wire, and a solar cell.

In the present invention, a structure in which an aromatic ring or a heterocyclic ring is crosslinked with a specific type of bond selected from an ether bond, an alkylene bond and the like, for example, a crosslinked aromatic compound having a diphenyl ether structure as a basic skeleton is tin and Because it is contained in a tin alloy plating bath, when a large number of electrodeposits (projection electrodes and electrodeposition coatings) are formed by electroplating, variations in the height of the electrodeposits are suppressed, so that the height of the electrodeposits is uniform. Can be secured well.
Further, when a specific complexing agent such as a sulfide compound is added to the tin and tin alloy plating bath of the present invention, the uniformity of the height of the electrodeposit is further increased by improving the stability of the plating bath.
Therefore, when the tin and tin alloy plating bath of the present invention is applied to various electronic components, the heights of a large number of protruding electrodes can be satisfactorily made uniform. On the other hand, when an electrodeposited film is formed, the thickness of the film can be made uniform, and for example, a good tin-based material can be filled without generating voids when filling a via hole or the like on a substrate.

The electrolytic tin and tin alloy plating bath of Patent Document 11 can contain a surfactant (paragraph 18), and polyoxyalkylene bisphenol as an example of the listed nonionic surfactant (paragraph 19). In addition, alkyl diphenyl ether sulfonates are described as examples of the listed anionic surfactants (paragraph 21).
However, as described above, Patent Document 11 has no description or suggestion that this tin or tin alloy plating bath is applied to the formation of the protruding electrode, and examples include, for example, alkyl diphenyl ether sulfone. There is no specific description of an electroplating bath containing an acid salt.

  In the present invention, first, a structure in which an aromatic ring or a heterocyclic ring is crosslinked with a specific type of bond selected from an ether bond, an alkylene bond, an alkynylene bond, an imino bond, a quaternary ammonium bond, and the like as a basic skeleton. An electrotin and tin alloy plating bath containing the cross-linked aromatic compound C, and second, a method of forming an electrodeposit (projection electrode or electrodeposition film) using the electroplating bath, Third, an electronic component manufactured by the forming method.

One tin plating bath of the present invention contains (A) a soluble stannous salt, (B) an acid or a salt thereof, and (C) a cross-linked aromatic compound.
On the other hand, the tin alloy plating bath of the present invention includes any of (A) a stannous salt and a mixture of a metal salt selected from zinc, nickel, bismuth, cobalt, indium, antimony, gold, silver, copper, and lead. A soluble salt thereof, (B) an acid or a salt thereof, and (C) a cross-linked aromatic compound.

The tin or tin alloy plating bath of the present invention is characterized by containing the above-mentioned crosslinked aromatic compound (C). As described above, the compound (C) is represented by the following general formula (1). .
Za-Xa-Y-Xb-Zb (1)
In the general formula (1), Xa and Xb represent an aromatic ring and a heterocyclic ring, and the bridged aromatic compound (C) of the present invention is a concept including a compound having the aromatic ring and a compound having a heterocyclic ring. The aromatic ring is a benzene ring, a naphthalene ring, an anthracene ring or the like, preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.
The above heterocycle is a concept including monocyclic heterocycle and fused heterocycle, tetrazole, triazole, triazine, thiazole, thiadiazole, thiazoline, imidazole, imidazoline, quinoline, furan, morpholine, thiophene, pyridine, oxazole, oxadi Azole, pyrrole, pyrazole, pyrazine, furazane, isothiazole, isoxazole, pyrazolidine, pyrimidine, pyridazine, pyrrolidine, benzimidazole, benzothiazole, benzoxazole, indolizine, indole, isoindole, indazole, purine, isoquinoline, naphthyridine, quinoxaline , Carbazole, phenanthroline, phenazine, phenothiazine, phenothiazine, phenoxazine, phenanthridine, pyrroline, picoli Various rings such as imidazolidine, pyrazoline, piperidine, piperazine, indoline, thianthrene, preferably thiazole, pyrrole, pyridine, pyrazine, pyridazine, thiadiazole, imidazoline, imidazole, thiazoline, triazole, tetrazole, picoline, furazane, piperidine, These are various rings of piperazine, triazine, and benzimidazole.

Xa and Xb which are the aromatic ring and heterocyclic ring may be the same or different.
For example, both Xa and Xb may be benzene rings, or Xa may be a benzene ring and Xb may be a naphthalene ring. For example, sodium alkyldiphenyl ether disulfonate of Example 3 described later is the former example, and sodium alkylphenyl naphthyl ether disulfonate of Example 1 is the latter example.
Also, for example, both Xa and Xb may be pyridine rings (see dipyridylethane in Example 15), Xa may be a benzene ring and Xb may be a pyridine ring, Xa may be a pyridine ring and Xb may be an imidazole ring.

In the above general formula (1), Y is selected from a so-called carbon bond, oxygen bond, and nitrogen bond, and specifically, a linear or branched alkylene chain, alkenylene chain, alkynylene chain, or a part thereof. It is selected from a carbon chain replaced with carbonyl, an oxygen atom, and a nitrogen atom.
When Y is an oxygen atom, it means an ether bond connecting Xa and Xb. For example, the compound C contained in Examples 1 to 12, 16 to 19, 31 to 34, etc., in detail, dianiline ether of Example 16, alkyl diphenyl ether sodium disulfonate of Example 3, And diaminodiphenyl ether.

When Y is a nitrogen atom, it can take a secondary or tertiary amine structure or a quaternary ammonium salt structure.
The above secondary amine structure is an imino bond connecting Xa and Xb (that is, two bonds of nitrogen atom bridge Xa and Xb, and the remaining bond is a hydrogen atom or an alkyl group. Means a bond). For example, sodium diphenylamine disulfonate of Example 26, alkyldiaminodiphenylamine of Example 24, and the like.
In the quaternary ammonium salt structure, of the four bonds of the nitrogen atom, two bonds to the Xa and Xb aromatic rings and heterocycles, and the other two bonds are, for example, both hydrogen and alkyl groups ( This means that a counter ion such as a halogen or an alkyl sulfate anion (RSO 3 −) is coordinated to the nitrogen atom that forms a quaternary ammonium salt. For example, N-dimethyldiphenylammonium methyl sulfate of Example 27, Example 3
No. 9 sodium diphenyldimethylammonium disulfonate / chloride.

When Y is a carbon atom, it means a bond selected from a linear or branched alkylene chain, an alkenylene chain, an alkynylene chain, or a carbon chain in which a part thereof is replaced by carbonyl. The number of carbon atoms is preferably about C1 to C16.
A typical alkylene chain is a polymethylene chain, and examples thereof include a monomethylene chain, a dimethylene chain (ethylene chain), and a trimethylene chain (linear propylene chain). For example, dipyridylethane of Example 15 and sodium benzylphenyl disulfonate of Example 42.
The alkenylene chain has one or more double bonds in the carbon bond (see diaminostilbene in Example 21). Similarly, the alkynylene chain has one or more triple bonds. When Y is a carbon atom, an alkylene chain and an alkynylene chain are preferable, and a C1-C4 linear alkylene chain and a linear alkynylene chain are more preferable.
Examples of the carbon chain in which a part of the alkylene chain, alkenylene chain, or alkynylene chain is replaced with carbonyl include phenylbutyrophenone.

  Y as the crosslinked structure portion is preferably an ether bond, an alkylene bond, an alkynylene bond, an imino bond, or a quaternary ammonium salt structure, and more preferably an ether bond, an alkylene bond, an imino bond, or a quaternary ammonium salt structure.

Xa and Xb which are the aromatic ring and heterocyclic ring may be substituted with a substituent Za or Zb or may be unsubstituted (that is, Za and / or Zb is hydrogen).
Substituents Za and Zb are C1 to C18 linear or branched alkyl groups, C1 to C18 linear or branched alkoxy groups, halogen, sulfonic acid or its base, amide group, amino group, quaternary ammonium. Any of a base, a carboxyl group, a hydroxyl group, a nitro group, and a nitroso group, preferably a C1 to C18 linear or branched alkyl group, a sulfonic acid (salt) group, hydrogen, an amide group, an amino group, or a carboxyl group, An acid (salt) group, a C1-C18 straight chain alkyl group, hydrogen, a hydroxyl group, and an amino group are more preferred.
Examples of the C1-C18 alkyl group include lauryl, palmityl, stearyl and the like.
Examples of substitution of the quaternary ammonium base with a benzene ring include 4,4′-dimethylammonium diphenyl ether / methyl sulfate of Example 33, 4-nitrosomethylethyldiphenylammonium / ethyl sulfate of Example 29, and the like. .
Za and Zb are bonded to one to four aromatic rings or heterocyclic rings, respectively. Za and Zb may be the same or different. For example, when bonding to Za and Zb one by one, both Za and Zb may be a sulfonic acid group, Za may be a sulfonic acid group, and Zb may be a hydrogen or amino group.

Examples of the bridged aromatic compound (C) include dipyridylalkane, dipyridylalkanesulfonic acid, dipiperidylalkane, dipiperidylalkanedisulfonic acid, dipyrrole alkane, dipyrrolealkanedisulfonic acid, diimidazolylalkane, diimidazolylalkanesulfonic acid. , Ditriazolyl alkane, ditriazolyl alkane sulfonic acid, dianiline alkane, dianiline alkane sulfonic acid, diphenyl alkane, amino diphenyl alkane, diphenyl alkane sulfonic acid, hydroxy diphenyl alkane, hydroxy diphenyl alkane sulfonic acid, amino diphenyl alkane sulfonic acid , Dinaphthylalkane, aminodinaphthylalkane, dinaphthylalkanesulfonic acid, hydroxydinaphthylalkanesulfonic acid, Nodinaphthylalkanesulfonic acid, phenylalkylimidazole, phenylalkylpyridine, diaminostilbene, diaminostilbenesulfonic acid, alkylhydroxystilbene, dipyridylamine, dipyridylaminesulfonic acid, dipiperidylamine, dipiperidylaminesulfonic acid, dipyrroleamine, dipyrrole Aminesulfonic acid, diimidazolylamine, diimidazolylaminesulfonic acid, ditriazolylamine, ditriazolylaminesulfonic acid, anilineamine, dianilineaminesulfonic acid, diphenylamine, aminodiphenylamine, diphenylaminesulfonic acid, hydroxydiphenylaminesulfonic acid, amino Diphenylamine sulfonic acid, dinaphthylamine, aminodinaphthylamine, dinaphthylamines Phosphonic acid, hydroxydinaphthylaminesulfonic acid, aminodinaphthylaminesulfonic acid, dialkyldiphenylammonium salt, dialkyldinaphthylammonium salt, N, N, N ', N'-tetraalkyldiaminodiphenylamine, phenylnaphthylaminesulfonic acid, dipyridyl ether, dipyridyl ether Ether sulfonic acid, dipiperidyl ether, dipiperidyl ether sulfonic acid, dipyrrole ether, dipyrrole ether sulfonic acid, diimidazolyl ether, diimidazolyl ether sulfonic acid, ditriazolyl ether, ditriazolyl ether sulfonic acid, dianiline ether, Dianiline ether sulfonic acid, diphenyl ether, alkyl diphenyl ether, hydroxy diphenyl ether, amino diphenyl ether, Alkylamino diphenyl ether, carboxydiphenyl ether, diphenyl ether sulfonic acid, alkyl diphenyl ether sulfonic acid, hydroxy diphenyl ether sulfonic acid, dinaphthyl ether, alkyl dinaphthyl ether, hydroxy dinaphthyl ether, amino dinaphthyl ether, alkylamino dinaphthyl ether -Tell, carboxydinaphthyl ether, dinaphthyl ether sulfonic acid, alkyl dinaphthyl ether sulfonic acid, phenyl naphthyl ether, alkylphenyl naphthyl ether, hydroxyphenyl naphthyl ether, aminophenyl naphthyl ether, alkylaminophenyl naphthyl ether, Carboxyphenyl naphthyl ether, phenyl naphthyl ether sulfonic acid, alkylphenyl naphthalene Chill ether sulfonate, hydroxyphenyl naphthyl ether sulfonate, dialkyl amino nitro ether, or a salt thereof.
Preferably, dipyrrole alkane disulfonic acid or a salt thereof, hydroxydiphenylalkane, diphenylalkanesulfonic acid or a salt thereof, hydroxydiphenylalkanesulfonic acid or a salt thereof, alkylamino diphenyl ether, amide dipyridyl ether sulfonic acid or a salt thereof, diamide dipyridyl ether sulfone Acid or salt thereof, alkyldiphenyl ether sulfonic acid or salt thereof, diphenyl ether sulfonic acid or salt thereof, alkylamino ditriazolyl ether sulfonic acid or salt thereof, alkylphenyl naphthyl ether sulfonic acid or salt thereof, dianiline ether, dipyridylalkane, benzyl Phenylsulfonic acid or its salt, aminostilbene, diphenylamine disulfonic acid or its salt, dialkyldiphenylammoni Salt-free is preferable.

Since the structure of the crosslinked aromatic compound (C) is not relatively complicated, it is easy to obtain a commercial product.
Moreover, it is as follows when the synthesis example is shown for every bridge | crosslinking form about what is considered that acquisition is difficult among the said compounds (C).
(1) Example of Synthesis of Compound (a) 4,4′-Diaminodiphenyl Ether Having Ether Bond First, concentrated sulfuric acid used as a catalyst was added to concentrated nitric acid while cooling with water to form a mixed acid. Diphenyl ether was added to this mixed acid, and the mixture was stirred at 50 to 60 ° C. for 3 hours for nitration. After completion of the reaction, alkali treatment was performed. After evaporating the solvent under reduced pressure, it was isolated by silica gel column chromatography and recrystallized to obtain 4,4'-dinitrodiphenyl ether. The structure was confirmed by 1H-NMR spectrum.
Thereafter, 4,4′-dinitrodiphenyl ether was dissolved in ethanol and water, iron powder and ammonium chloride were added, and the mixture was stirred at 100 ° C. for amination. After completion of the reaction, the precipitate was filtered, the solvent was distilled off under reduced pressure, and the residue was isolated by silica gel column chromatography and recrystallized to obtain 4,4'-diaminodiphenyl ether. The structure was confirmed by 1H-NMR spectrum.
For example, the compound C used in Example 10 described later is the compound.
(B) Synthesis example of sodium diphenyl ether disulfonate First, diphenyl ether was added little by little to fuming sulfuric acid at 20 ° C to 30 ° C. The reaction temperature was maintained at 115 ° C. and the mixture was stirred for 24 hours to sulfonylate. After completion of the reaction, ion-exchanged water was added dropwise in an ice bath.
Thereafter, an aqueous sodium hydroxide solution was added dropwise in an ice bath. Then, the mixture was allowed to stand overnight, and the precipitate was suction filtered. The filtrate was washed with ion-exchanged water to obtain sodium diphenyl ether disulfonate as an aqueous solution. The structure was confirmed by 1H-NMR spectrum.
According to the synthesis example, for example, the compound C shown in Example 18 described later can be easily synthesized.
(C) Synthesis example of 4-phenoxybenzothiazole First, 2-chlorobenzothiazole was added little by little to a mixed solution of acetitolyl and phenol at 80 ° C., and stirred overnight to perform etherification.
After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was isolated by silica gel column chromatography and recrystallized to obtain 4-phenoxybenzothiazole. The structure was confirmed by 1H-NMR spectrum. The compound has a phenoxy group bonded to a benzothiazole ring. In other words, the benzothiazole ring and the benzene ring are connected by an ether bond.

(2) Compound having alkylene bond According to the following synthesis examples (a) to (b), for example, compound C shown in Examples 15 and 23 described later can be easily synthesized.
(A) Example of synthesis of 4,4'-dihydroxydiphenylpropane First, aluminum chloride was added to a mixed solution of 1,3-diphenylpropane, dry-dichloromethane and dichloromethylmethyl ether in small portions in an ice bath to formylate. Went. After completion of the reaction, the reaction mixture was poured into ice water, extracted with chloroform, washed with saturated brine, and dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, it was isolated by silica gel column chromatography and recrystallized to obtain 4,4'-dicarboxaldehyde diphenylpropane. The structure was confirmed by 1H-NMR spectrum.
Thereafter, ethanol and sodium borohydride were added and stirred for 3 and a half hours. After completion of the reaction, the mixture was neutralized with 1% aqueous hydrochloric acid to quench sodium borohydride, and the organic phase was washed with saturated brine and dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, recrystallization was carried out to obtain 4,4'-dihydroxydiphenylpropane. The structure was confirmed by 1H-NMR spectrum.
(B) Synthesis example of 5,5′-tert-butyl-2,2′-dimethylbibenzyl First, 4-tert-butyltoluene, dichloromethane, and chloromethylmethyl ether were added. While stirring the mixed solution, titanium tetrachloride was added dropwise in an ice bath. Then, it stirred while confirming reaction at room temperature, and Friedel-Crafts alkylation was performed. After completion of the reaction, the reaction mixture was poured into ice water to crush aluminum chloride. Thereafter, extraction was performed with an organic solvent, and the organic phase was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and distillation under reduced pressure was performed to obtain 4-tert-butylchloroxylene. The structure was confirmed by 1H-NMR.
Thereafter, a portion of iodine was added to the reaction vessel to which magnesium was added and stirred. Dry-ether was poured into the solution, and a mixed solution of iodomethane and dry-ether was added dropwise to the solution so as to be naturally refluxed. After the dropwise addition, the mixture was refluxed for 1 hour and a half in a 60 ° C. oil bath to prepare a Grignard reagent. After allowing to cool, a mixed solution of 4-tert-butylchloroxylene and dry-ether was gradually added dropwise, and then stirred while confirming the reaction in an oil bath at 40 ° C. The reaction mixture was allowed to cool after completion of the reaction, poured into ice water, made weakly acidic by adding 10% hydrochloric acid, extracted, and the organic phase was washed with saturated brine and dried over anhydrous magnesium sulfate.
The solvent was distilled off under reduced pressure, and the residue was recrystallized to obtain 5,5'-tert-butyl-2,2'-dimethylbibenzyl. The structure was confirmed by 1H-NMR.
In this compound, one benzyl group is bonded to the methylene carbon atom of the other benzyl group. In other words, the benzene ring is bonded to both carbon atoms of the ethylene chain.

(3) Compound having imino bond According to the following synthesis examples (a) to (b), for example, compound C shown in Examples 24 and 26 described later can be easily synthesized.
(A) Example of synthesis of 4,4'-dicarboxydiphenylamine First, aluminum chloride was added to a mixed solution of diphenylamine, dry-dichloromethane and dichloromethylmethyl ether in small portions in an ice bath to formify. After completion of the reaction, the reaction mixture was poured into ice water, extracted with chloroform, washed with saturated brine, and dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, it was isolated by silica gel column chromatography and recrystallized to obtain 4,4'-dicarboxaldehyde diphenylamine.
Thereafter, hydrogen peroxide was added to a mixed solution of 4,4′-dicarboxaldehyde diphenylamine and ethanol, and the mixture was stirred overnight at 50 ° C. After evaporating the solvent under reduced pressure, it was isolated by silica gel column chromatography and recrystallized to obtain 4,4'-dicarboxydiphenylamine. The structure was confirmed by 1H-NMR spectrum.
(B) Synthesis example of 4-anilinopyridine First, a mixed solution of chlorobenzene and chloroform was dropped to a mixed solution of 4-aminopyridine and chloroform at 50 ° C. or lower. Then, it stirred at 70 degreeC overnight. After completion of the reaction, ion exchange water was added. The aqueous phase was extracted and aqueous sodium hydroxide solution was added dropwise in a water bath to make the solution alkaline.
Thereafter, extraction was performed using dichloromethane, and the organic phase was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and isolated by silica gel column chromatography to obtain 4-anilinopyridine.
In this compound, the amino group of the aniline ring is bonded to the carbon atom at the 4-position of the pyridine ring. In other words, the pyridine ring and the benzene ring are bonded via the imino group.

(4) Compound having a quaternary ammonium bond First, methyl sulfate was slowly added dropwise to diphenylamine at 50 ° C. or lower for methylation. Thereafter, ion exchange water was added. An aqueous sodium hydroxide solution was added dropwise in a water bath to make the solution alkaline. Extraction was performed using dichloromethane, and the organic phase was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain N-methyldiphenylamine.
Thereafter, methyl sulfate is slowly added dropwise to N-methyldiphenylamine at 50 ° C. or lower and methylated again. The structure is confirmed by 1H-NMR, then ion-exchanged water is added, and N, N′-dimethyldiphenylammonium methyl is added in an aqueous solution. Obtained sulphate. The structure was confirmed by 1H-NMR spectrum.
If based on the said synthesis example, the compound C shown to the below-mentioned Examples 27-29 is easily compoundable, for example.

  The cross-linked aromatic compound (C) can be used singly or in combination, and the content of the tin or tin alloy plating bath is 0.0001 to 200 g / L, preferably 0.001 to 100 g / L, more preferably 0.01. ~ 50 g / L. If it is less than the appropriate range, the effect of imparting the uniformity of the height of the protruding electrode will be reduced, and even if it exceeds the appropriate range, the effect of imparting the uniformity of the height of the protruding electrode will be reduced, or the appearance of the plating film will be poor. And is a waste of cost.

  In the tin or tin alloy plating bath of the present invention, the soluble stannous salt (A) is basically a tin salt of an organic acid or an inorganic acid that generates Sn 2+ in water, specifically, stannous sulfate. , Stannous acetate, stannous borofluoride, stannous sulfamate, stannous pyrophosphate, stannous chloride, stannous gluconate, stannous tartrate, stannous oxide, sodium stannate, tin Examples include potassium acid, stannous methanesulfonate, stannous ethanesulfonate, stannous 2-hydroxyethanesulfonate, stannous 2-hydroxypropanesulfonate, and stannous sulfosuccinate.

In the specific tin alloy plating bath of the present invention 1, the metal of the tin counterpart that forms the tin alloy is selected from zinc, nickel, bismuth, cobalt, indium, antimony, gold, silver, copper, and lead.
As for the soluble salt of the other metal, for example, the soluble salt of silver includes silver acetate, silver nitrate, silver chloride, silver oxide, silver cyanide, potassium silver cyanide, silver methanesulfonate, 2-hydroxyethanesulfone. Acid silver, silver 2-hydroxypropanesulfonate, and the like.
The soluble salts of copper include copper sulfate, copper nitrate, copper carbonate, copper pyrophosphate, copper chloride, copper cyanide, copper borofluoride, copper sulfamate, copper methanesulfonate, copper 2-hydroxyethanesulfonate, 2- Examples include copper hydroxypropane sulfonate.
Soluble salts of bismuth include bismuth sulfate, bismuth gluconate, bismuth nitrate, bismuth oxide, bismuth carbonate, bismuth chloride, bismuth methanesulfonate, and bismuth 2-hydroxypropanesulfonate.
Soluble salts of indium include indium sulfamate, indium sulfate, indium borofluoride, indium oxide, indium methanesulfonate, and indium 2-hydroxypropanesulfonate.
Soluble zinc salts include zinc oxide, zinc sulfate, zinc nitrate, zinc chloride, zinc pyrophosphate, zinc cyanide, zinc methanesulfonate, zinc 2-hydroxyethanesulfonate, and zinc 2-hydroxypropanesulfonate. .
Soluble salts of antimony include antimony borofluoride, antimony chloride, potassium antimony tartrate, potassium pyroantimonate, antimony tartrate, antimony methanesulfonate, and antimony 2-hydroxypropanesulfonate.
Soluble nickel salts include nickel sulfate, nickel formate, nickel chloride, nickel sulfamate, nickel borofluoride, nickel acetate, nickel methanesulfonate, nickel 2-hydroxypropanesulfonate.
Soluble lead salts include lead acetate, lead nitrate, lead carbonate, lead borofluoride, lead sulfamate, lead methanesulfonate, lead ethanesulfonate, lead 2-hydroxyethanesulfonate, lead 2-hydroxypropanesulfonate, etc. There is.
Examples of the soluble salt of cobalt include cobalt sulfate, cobalt chloride, cobalt acetate, cobalt borofluoride, cobalt methanesulfonate, and cobalt 2-hydroxypropanesulfonate.

The total concentration of the metal soluble salt in the bath is generally 1 to 200 g / L, preferably 10 to 150 g / L in terms of metal salt.
Moreover, what is necessary is just to adjust suitably the mixing ratio of soluble stannous salt and the soluble salt of the metal of the other party which forms an alloy according to the composition ratio of the desired tin alloy plating film.

The tin alloy of the present invention is an alloy of tin and at least one metal selected from the group consisting of zinc, nickel, bismuth, cobalt, indium, antimony, gold, silver, copper, and lead. Specifically, Including binary alloys of tin-silver alloy, tin-copper alloy, tin-bismuth, tin-indium, tin-zinc, tin-antimony, tin-nickel, tin-gold, tin-cobalt, tin-lead, Tin-copper-silver alloy, tin-copper-bismuth alloy, tin-zinc-nickel, tin-bismuth-silver, tin-bismuth-lead, tin-lead-silver, tin-indium-silver, tin-nickel-cobalt, etc. Including alloys of three or more components.
From the viewpoint of bath management, the aforementioned two-component tin alloy is preferable.

In the tin or tin alloy plating bath of the present invention, the acid or salt (B) serving as the base is an organic acid, an inorganic acid, or an alkali metal salt, alkaline earth metal salt, ammonium salt, amine salt, or the like. is there.
Examples of the organic acid include organic sulfonic acid and aliphatic carboxylic acid, and examples of the inorganic acid include sulfuric acid, hydrochloric acid, borohydrofluoric acid, hydrofluoric acid, and sulfamic acid. Among these, a bath of an organic sulfonic acid or a salt thereof is preferable from the standpoint of sulfuric acid bath, tin solubility, ease of wastewater treatment, and the like.
The acid or salt thereof can be used singly or in combination, and its content is 0.1 to 10 mol / L, preferably 0.5 to 5 mol / L.

  Examples of the organic sulfonic acid include alkane sulfonic acid, alkanol sulfonic acid, sulfosuccinic acid, and aromatic sulfonic acid. As the alkane sulfonic acid, those represented by the chemical formula CnH2n + 1SO3H (for example, n = 1 to 11) are used. Specific examples include methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 2-propanesulfonic acid, 1-butanesulfonic acid, 2-butanesulfonic acid, pentanesulfonic acid, and the like.

Examples of the alkanol sulfonic acid include chemical formula CmH2m + 1-CH (OH) -CpH2p-SO3H (for example, m = 0 to 6, p = 1 to 5).
In particular, 2-hydroxyethane-1-sulfonic acid (isethionic acid), 2-hydroxypropane-1-sulfonic acid (2-propanolsulfonic acid), 3-hydroxypropane-1 -Sulfonic acid, 2-hydroxybutane-1-sulfonic acid, 2-hydroxypentane-1-sulfonic acid and the like, 1-hydroxypropane-2-sulfonic acid, 4-hydroxybutane-1-sulfonic acid, 2-hydroxy Examples include hexane-1-sulfonic acid.

The aromatic sulfonic acid is basically benzene sulfonic acid, alkyl benzene sulfonic acid, phenol sulfonic acid, naphthalene sulfonic acid, alkyl naphthalene sulfonic acid, naphthol sulfonic acid, etc., specifically, 1-naphthalene sulfonic acid, 2 -Naphthalenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, p-phenolsulfonic acid, cresolsulfonic acid, sulfosalicylic acid, nitrobenzenesulfonic acid, sulfobenzoic acid, diphenylamine-4-sulfonic acid and the like.
Among the organic sulfonic acids, methanesulfonic acid, ethanesulfonic acid, 2-propanolsulfonic acid, 2-hydroxyethanesulfonic acid, and the like are preferable.
The carboxylic acid refers to monocarboxylic acid, polycarboxylic acid, oxycarboxylic acid, aminocarboxylic acid and the like.

The electrotin and tin alloy plating bath of the present invention further includes a complexing agent selected from a specific sulfide compound, oxycarboxylic acid, polycarboxylic acid, aminocarboxylic acid, phosphonic acid and salts thereof, polyamine, and amino alcohol. It is preferable to contain (D).
The complexing agent D firstly co-deposits with tin by stabilizing various metal ions such as silver, copper, zinc, and bismuth, which form an alloy with tin, in the bath against a tin alloy plating bath. It acts to make it. Second, the tin or tin alloy plating bath of the present invention can be applied to any pH range such as acidic, neutral (including weakly acidic), and stannous ions are basically stable when acidic. However, since white precipitation is likely to occur in the vicinity of neutrality, the complexing agent D acts to stabilize Sn2 + in the vicinity of neutrality.
Among the complexing agents D, a specific sulfide compound can be expected to have the first action in a tin alloy plating bath such as a tin-silver alloy, a tin-copper alloy, a tin-gold alloy, or a tin-bismuth alloy.
On the other hand, the complexing agent D selected from oxycarboxylic acid, polycarboxylic acid, aminocarboxylic acid, pyrophosphoric acid, polyamine, aminoalcohol and salts thereof is tin-zinc alloy, tin-nickel alloy, tin-cobalt alloy, The first action can be expected in a tin alloy plating bath such as a tin-indium alloy, and the second action can be expected in a tin plating bath and all tin alloy plating baths.
However, when the complexing agent (D) is an oxycarboxylic acid, polycarboxylic acid, aminocarboxylic acid, pyrophosphoric acid or a salt thereof, the acid or salt (B) used as a base component of the plating bath The complexing agent (D) can also be used. In other words, in the plating bath adjusted to near neutrality of the present invention, the oxycarboxylic acid, polycarboxylic acid, aminocarboxylic acid, pyrophosphoric acid or salts thereof contained in the bath are the base components of the bath. It will also function as a complexing agent.
For example, gluconic acid of Example 21 which is a neutral plating bath described later, gluconate of Example 24, citric acid of Example 31, pyrophosphoric acid of Example 37, and the like are examples.

The complexing agent D comprising the sulfide compound is selected from the compounds (a) to (c) as described above.
However, the compound (a) is represented by the following formula (a).
Xn-R1-S- (CH2CH2S) m-R2-Xn (a)
The compound (b) is represented by the following formula (b).
H- (OA) n-S- (OA) n-H (b)
Among these, the sulfide compound represented by the above formula (a) is a thiaalkane type aliphatic sulfide compound, which is 3,6-dithiaoctane-1,8-diol, 3,6,9-trithiaundecane-1,11. -Diol, 4,7-dithiadecane-1,10-diol, 4,7-dithiadecane-1,2,9,10-tetraol, 4,7,10-trithiatridecane-1,13-diol, 4, 7-dithiadecane-1,10-disulfonic acid, 5,8-dithiadecane-1,12-disulfonic acid, 3,6-dithiaoctane-1,8-disulfonic acid, 5,8,11-trithiapentadecane-1,15 -Disulfonic acid, 1,8-diamino-3,6-dithiaoctane, 1,11-bis (methylamino) -3,6,9-trithiaundecane, 1,14-bis (methylamino) -3,6, 9,12-tetrathiatate Decane, 1,10-diamino-4,7-dithiadecane, 4,7-dithiadiethoxy ether, 6,9-dithiatetradecane-6,9-diethoxy-1,14-diol or salts thereof (Na, K , Amine, ammonium) and the like.
Preferably, 3,6-dithiaoctane-1,8-diol, 4,7-dithiadecane-1,10-diol, 1,10-diamino-4,7-dithiadecane, 3,6-dithiaoctane-1,8-disulfone Acid, 1,8-diamino-3,6-dithiaoctane, 4,7-dithiadecane-1,2,9,10-tetraol, and the like.

In this case, in the above formula (a), when R 1 and R 2 are both ethylene, X is OH, and the addition number m is 1,6-dithiaoctane represented by HO—CH 2 CH 2 —S—CH 2 CH 2 S—CH 2 CH 2 —OH Means 1,8-diol.
When both R1 and R2 are propylene, X is OH, and the addition number m is 1,4,7-dithiadecane-1,10-diol represented by HO-CH2CH2CH2-S-CH2CH2S-CH2CH2CH2-OH See Examples 5, 9, 14).
When R1 and R2 are both propylene, X is SO3Na, and the addition number m is 2, 4,7,10-trithiatridecane-1, represented by NaO3S-CH2CH2CH2-S- (CH2CH2S) 2-CH2CH2CH2-SO3Na, It means sodium 13-disulfonate.
When R1 = R2 = CH2CH2, X = NH2, and m = 1, H2N-CH2CH2-S-CH2CH2-S-CH2CH2-NH2 (1,8-diamino-3,6-dithiaoctane) is obtained.
For R1 = R2 = CH2CH2, X = NHCH3, m = 3, CH3HN-CH2CH2-S-CH2CH2-S-CH2CH2-S-CH2CH2-S-CH2CH2-NHCH3 (1,14-bis (methylamino) -3,6 , 9,12-tetrathiatetradecane.
In the above formula (a), the substituent X such as OH and SO3H bonded to the C2-C4 alkylene chain of R1 and R2 may be bonded to any carbon atom in the alkylene chain. In general, for example, an OH group is present at each of the first and second carbon atoms of the propylene chain (that is, R1 or R2 in the formula (a) is a C3 alkylene chain). A compound having a structure in which one bond, that is, a total of two bonds (that is, n = 2 in formula (a)) is also included in the thiaalkane type aliphatic sulfide compound represented by formula (a).

The sulfide compound represented by the above formula (b) is an oxyalkylene type aliphatic sulfide compound, and is thiobis (pentaethylene glycol), thiobis (hexaethylene glycol), thiobis (octaethylene glycol), thiobis (decaethylene). Glycol), thiobis (undecaethylene glycol), thiobis (dodecaethylene glycol), thiobis (tridecaethylene glycol), thiobis (tetradecaethylene glycol), thiobis (pentadecaethylene glycol), dithiobis (pentadecaethylene glycol), Examples thereof include thiobis (eicosaethylene glycol), thiobis (triacontaethylene glycol), and thiobis (triglycerin).
Preferred are thiobis (dodecaethylene glycol), thiobis (hexaethylene glycol), thiobis (decaethylene glycol), thiobis (eicosaethylene glycol), dithiobis (pentadecaethylene glycol), thiobis (triglycerin), and the like.
In this general formula (b), A is ethylene and propylene, and the addition molar ratio of the oxyethylene chain to the oxypropylene chain is not particularly limited, but the number of moles of the oxyethylene chain is equal to the number of moles of the oxypropylene chain. Or it is more preferable than the number of moles of the oxypropylene chain. Moreover, although the addition number n of oxyalkylene is an integer of 1-25, Preferably it is n = 3-25, More preferably, it is n = 10-20.
In the general formula (b), when A is ethylene and the addition number n is 5, it means thiobis (pentaethylene glycol) represented by H— (OCH 2 CH 2) 5 —S— (CH 2 CH 2 O) 5 —H.
When A is ethylene and the addition number n is 12, it means thiobis (dodecaethylene glycol) represented by H- (OCH2CH2) 12-S- (CH2CH2O) 12-H.
On the other hand, in the general formula (b), examples of the compound in which a hydroxyl group is bonded to the carbon atom constituting the ethylene or propylene chain A include thiobis (triglycerin).

The sulfide compound (c) is an aromatic sulfide compound and can be represented by the following general formula (c1).
Ra-[(S) x-Rb] p-[(S) y-Rc] q (c1)
(In formula (c1), x and y each represents an integer of 1 to 4; p represents 0 or an integer of 1 to 100; q represents an integer of 1 to 100.)
The aromatic sulfide compound is a compound having one or more sulfides, disulfide bonds, or the like in the molecule and one or more basic nitrogen atoms in at least one of the two wing atom groups of the bond. .
Ra and Rc representing an atomic group in the aromatic sulfide compound represent aralkyl, cycloalkyl, polycyclic cycloalkyl, aryl, polycyclic aryl, heterocyclic group, polycyclic heterocyclic group, Group Rb represents aralkylene, cycloalkylene, polycyclic cycloalkylene, arylene, polycyclic arylene, heterocyclic group, or polycyclic heterocyclic group. Specific examples of the above atomic groups include C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, cyclopentane ring group, cyclohexane ring group, benzene ring group, naphthalene ring group, phenanthrene ring group, pyridine ring group, Pyrrole ring group, pyrazine ring group, pyridazine ring group, thiazole ring group, thiadiazole ring group, imidazoline ring group, imidazole ring, thiazoline ring group, triazole ring, tetrazole ring group, picoline ring group, furazane ring group, piperidine ring group, Piperazine ring group, triazine ring, morpholine ring group, benzothiazole ring group, benzimidazole ring group, quinoline ring group, quinoxaline ring group, pteridine ring group, phenanthroline ring group, phenazine ring group, indoline ring group, perhydroindoline ring group Etc.
Since the number of sulfur bonds x and y is 1 to 4 respectively, the sulfide compound is composed of a sulfide compound, a disulfide compound, a trisulfide compound, and a tetrasulfide compound.

Moreover, the repeating number p of atomic group Rb in an aromatic sulfide compound is 0-100, and the repeating number q of atomic group Rc is 1-100.
However, when p = 0, Ra and Rc located at the end of the aromatic sulfide compound may be bonded to form a substituted or unsubstituted monocyclic or polycyclic ring. P = 1-100
In this case, Ra and Rb, Ra and Rb, or Rb and Rc are combined to form a substituted or unsubstituted monocycle or polycycle, or Ra and Rb and Rb and Rc are combined together. Substituted or unsubstituted monocyclic or polycyclic rings.
Each of Ra, Rb, and Rc may have a substituent or may be unsubstituted. Specific examples of the substituent include C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 alkoxy, C1-6 alkylthio, C1-6 alkoxy C1-6 alkyl, C1-6 alkylthio C1 6 alkyl, C1-6 alkylcarbonyl, C1-6 alkoxycarbonyl, amino, C1-6 alkylamino, C1-6 dialkylamino, carbamoyl, halogen, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, alkylsulfenyl, aryl And sulfenyl, cyano, nitro, hydroxy, carboxyl, mercapto, imino, alkylthio, arylthio, alkyldithio, aryldithio, alkyltrithio, aryltrithio, alkyltetrathio, aryltetrathio groups and the like.

The aromatic sulfide compound will be described along the general formula (c1). When p = 0, Ra = Rc = pyridine ring (abbreviated as Py), y = 2, and q = 1, Py-SS-Py (Dipyridyl disulfide), and each has a basic nitrogen atom in the pyridine ring at both ends of the disulfide bond. When p = 0, Ra = Rc = aniline ring (abbreviated as An), y = 1, q = 1, it becomes An-S-An (thiodianiline), and the aniline rings at both ends of the monosulfide bond (ie, bonded to the benzene ring) Each has a basic nitrogen atom.
When Ra = Rc = pyridine ring (abbreviated as Py), Rc = CH2CH2, x = y = 1, p = 3, q = 1, Py-SCH2CH2-SCH2CH2-SCH2CH2-S-Py (1,10-dipyridyl-1 , 4,7,10-tetrathiadecane) and has a basic nitrogen atom in each of the pyridine rings at both ends of the molecule.

Specific examples of the aromatic sulfide compound include the following compounds.
2-ethylthioaniline, dithiodianiline, 2- (2-aminoethyldithio) pyridine, 2,2'-dithiadiazolyl disulfide, 5,5'-di (1,2,3-triazolyl) disulfide 2,2'-dipyrazinyl disulfide, 2,2'-dipyridyl disulfide, 2,2'-dithiodianiline, 4,4'-dipyridyl disulfide, 2,2'-diamino-4,4'-dimethyl Diphenyl disulfide, 2,2'-dipyridazinyl disulfide, 5,5'-dipyrimidinyl disulfide, 2,2'-di (5-dimethylaminothiadiazolyl) disulfide, 5,5'-di (1- Methyltetrazolyl) disulfide, 2,2′-di (1-methylpyrrolyl) disulfide, 2-pyridyl-2-hydroxyphenyl disulfide, 2,2′-dipiperidyl disulfide, 2,2'-dipyridyl sulfide, 2,6-di (2-pyridyldithio) pyridine, 2,2'-dipiperazinyl disulfide, 2,2'-di (3,5-dihydroxypyrimidinyl) disulfide, 2,2 '-Diquinolyl disulfide, 2,2'-di {6- (2-pyridyl)} pyridyl disulfide, 2,2'-α-picolyl disulfide, 2,2'-di (8-hydroxyquinolyl) disulfide, ) 5,5'-diimidazolyl disulfide, 2,2'-dithiazolyl disulfide, 2-pyridyl-2-aminophenyl disulfide, 2-pyridyl-2-quinolyl disulfide, 2,2'-dithiazolinyl disulfide 2,2'-di (4,5-diamino-6-hydroxypyrimidinyl) disulfide, 2,2'-di (6-chloropyridyl) tetrasulfide, 2,2'-dimorpholinodisulfur 2,2'-di (8-methoxyquinolyl) disulfide, 4,4'-di (3-methoxycarbonylpyridyl) disulfide, 2-pyridyl-4-methylthiophenyl disulfide, 2-piperazyl-4-ethoxymethyl Phenyl disulfide, 2,2'-di {6- (2-pyridyldithio) pyridyl} disulfide, 2,2'-diquinoxalinyl disulfide, 2,2'-dipteridinyl disulfide, 3,3'-diph Lazanyl disulfide, 3,3'-diphenanthrolinyl disulfide, 8,8'-diquinolyl disulfide, 1,1'-diphenazinyl disulfide, 4,4'-di (3-carboxylpyridyl) trisulfide 2,2'-dithiazolinyl disulfide, 2,2'-dipicolyl disulfide, dimethylaminodiethyl disulfide, 2,2'-diperch Loindolyl disulfide, 6,6'-diimidazo [2,1-b] thiazolyl disulfide, 2,2'-di (5-nitrobenzimidazolyl) disulfide, 2,4,6-tris (2-pyridyldithio) -1,3,5-triazine, 2-aminoethyl-2'-hydroxyethyl disulfide, di (2-pyridylthio) methane, 2,4,6-tris (2-pyridyl) -1,3,5-trithiane, 5,5'-diamino-2,11-dithio [3,3] paracyclophane, 2,3-dithia-1,5-diazaindane, 2,4,6-trithia-3a, 7a-diazaindene, 1,10 -Di (2-pyridyl) -1,4,7,10-tetrathiadecane and the like.
Preferred aromatic sulfide compounds include 2,2'-dithiodianiline, 2,2'-dipyridyl disulfide, 2,6-di (2-pyridyldithio) pyridine, 4,4'-dipyridyl disulfide, 2,2 '. -Dipyridyl sulfide, 1,1'-diphenazinyl disulfide, 2,2'-dithiazolinyl disulfide and the like.

On the other hand, examples of the complexing agent D selected from the above oxycarboxylic acid, polycarboxylic acid, aminocarboxylic acid, phosphonic acid and salts thereof, polyamine, and amino alcohol include citric acid, tartaric acid, malic acid, gluconic acid, glycol Acid, diglycolic acid, glucoheptonic acid, gluconolactone, gluconoheptlactone, ascorbic acid, oxalic acid, malonic acid, succinic acid, ethylenediamine, diethylenetriamine, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotri Acetic acid (NTA), iminodiacetic acid (IDA), iminodipropionic acid (IDP), hydroxyethyl ethylenediamine triacetic acid (HEDTA), triethylenetetramine hexaacetic acid (TTHA), ethylenedioxybis (ethylamine) -N, N, N ', N'-tetraacetic acid, Examples include lysines, nitrilotrimethylphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, ethanolamine, diethanolamine, triethanolamine, or salts thereof.
Preferred compounds of the complexing agent D include citric acid, tartaric acid, gluconic acid, oxalic acid, malonic acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), iminodiacetic acid. (IDA), hydroxyethylethylenediaminetriacetic acid (HEDTA), and triethanolamine.

The complexing agent D of the present invention selected from the above aliphatic sulfide compounds, aromatic sulfide compounds, oxycarboxylic acids, polycarboxylic acids, aminocarboxylic acids and the like can be used alone or in combination.
The content of the complexing agent D composed of the above aliphatic sulfide compound and aromatic sulfide compound in the plating bath is 0.01 to 300 g / L, preferably 0.1 to 200 g / L, more preferably 0.5 to 150 g / L. L. For example, it is usually used in 4 to 10 moles relative to the total amount of gold, bismuth, silver and copper contained.
The content of the complexing agent D composed of a compound other than sulfide, such as the above oxycarboxylic acid, polycarboxylic acid, aminocarboxylic acid, etc., is suitably 0.01 to 500 g / L, preferably 0.1 to 400 g / L, more preferably 1 to 300 g / L.

The electrotin and tin alloy plating bath of the present invention further includes a surfactant, an antioxidant, a brightener, a semi-brightener, a smoothing agent, a stabilizer, a pH adjuster, a conductive salt, an antiseptic, and an antifoaming agent. Various additives such as can be contained.
For the purpose of improving the appearance, denseness, smoothness, adhesion and the like of the plating film, various surfactants such as ordinary anionic, cationic, nonionic or amphoteric surfactants can be used. In particular, nonionic surfactants are important for the formation of practical tin and tin alloy films.
Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl benzene sulfonates, and alkyl naphthalene sulfonates. As the cationic surfactant, mono-trialkylamine salt, dialkyldimethylammonium salt, alkyldimethylethylammonium salt, alkyldimethylhydroxyethylammonium salt, alkyldimethylethylammonium salt, trimethylbenzylammonium salt, alkyldimethylbenzylammonium salt, A trimethyl alkyl ammonium salt etc. are mentioned. Nonionic surfactants include C1-C20 alkanols, phenols, naphthols, bisphenols, C1-C25 alkylphenols, arylalkylphenols, C1-C25 alkylnaphthols, C1-C25 alkoxyl phosphates (salts), sorbitan esters, polyalkylene glycols. , C1-C22 aliphatic amide and the like obtained by addition condensation of 2-300 mol of ethylene oxide (EO) and / or propylene oxide (PO), ethylenediamine polyethoxylate-polypropoxylate block copolymer, and the like. Examples of amphoteric surfactants include carboxybetaine, imidazoline betaine, and aminocarboxylic acid.

Examples of the smoothing agent include β-naphthol, β-naphthol-6-sulfonic acid, β-naphthalenesulfonic acid, m-chlorobenzaldehyde, p-nitrobenzaldehyde, p-hydroxybenzaldehyde, (o-, p-) methoxybenzaldehyde, Vanillin, (2,4-, 2,6-) dichlorobenzaldehyde, (o-, p-) chlorobenzaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, 2 (4) -hydroxy-1-naphthaldehyde, 2 ( 4) -Chloro-1-naphthaldehyde, 2 (3) -thiophenecarboxaldehyde, 2 (3) -furaldehyde, 3-indolecarboxaldehyde, salicylaldehyde, o-phthalaldehyde, formaldehyde, acetaldehyde, paraaldehyde, butyraldehyde , Isobutyraldehyde, propi Onaldehyde, n-valeraldehyde, acrolein, crotonaldehyde, glyoxal, aldol, succindialdehyde, capronaldehyde, isovaleraldehyde, allylaldehyde, glutaraldehyde, 1-benzylidene-7-heptanal, 2,4-hexadienal, Cinnamaldehyde, benzylcrotonaldehyde, amine-aldehyde condensate, mesityl oxide, isophorone, diacetyl, hexanedione-3,4, acetylacetone, 3-chlorobenzylideneacetone, sub.pyridylideneacetone, sub.furfuridineacetone, sub. Tenylideneacetone, 4- (1-naphthyl) -3-buten-2-one, 4- (2-furyl) -3-buten-2-one, 4- (2-thiophenyl) -3-butene-2- On, Kurkumi Benzylideneacetylacetone, benzalacetone, acetophenone, (2,4-3,4-) dichloroacetophenone, benzylideneacetophenone, 2-cinnamylthiophene, 2- (ω-benzoyl) vinylfuran, vinylphenylketone, acrylic acid, Methacrylic acid, ethacrylic acid, ethyl acrylate, methyl methacrylate, butyl methacrylate, crotonic acid, propylene-1,3-dicarboxylic acid, cinnamic acid, (o-, m-, p-) toluidine, (o-, p-) aminoaniline, aniline, (o-, p-) chloroaniline, (2,5-3,4-) chloromethylaniline, N-monomethylaniline, 4,4'-diaminodiphenylmethane, N-phenyl- (α-, β-) naphthylamine, methylbenztriazole, 1,2,3-triazine, 1,2,4-triazine 1,3,5-triazine, 1,2,3-benztriazine, imidazole, 2-vinylpyridine, indole, quinoline, reaction product of monoethanolamine and o-vanillin, polyvinyl alcohol, catechol, hydroquinone, resorcin, polyethylene Examples include imine, disodium ethylenediaminetetraacetate, and polyvinylpyrrolidone.
Gelatin, polypeptone, N- (3-hydroxybutylidene) -p-sulfanilic acid, N-butylidenesulfanilic acid, N-cinnamoylidenesulfanilic acid, 2,4-diamino-6- (2'-methylimidazolyl) (1 ')) Ethyl-1,3,5-triazine, 2,4-diamino-6- (2'-ethyl-4-methylimidazolyl (1')) ethyl-1,3,5-triazine, 2, 4-Diamino-6- (2'-undecylimidazolyl (1 ')) ethyl-1,3,5-triazine, phenyl salicylate or benzothiazoles are also effective as a smoothing agent.
Examples of the benzothiazoles include benzothiazole, 2-methylbenzothiazole, 2-mercaptobenzothiazole, 2- (methylmercapto) benzothiazole, 2-aminobenzothiazole, 2-amino-6-methoxybenzothiazole, and 2-methyl. -5-chlorobenzothiazole, 2-hydroxybenzothiazole, 2-amino-6-methylbenzothiazole, 2-chlorobenzothiazole, 2,5-dimethylbenzothiazole, 6-nitro-2-mercaptobenzothiazole, 5-hydroxy -2-methylbenzothiazole, 2-benzothiazolethioacetic acid and the like.

  As the above-mentioned brightener or semi-brightener, there are some overlaps with the above-mentioned smoothing agent, but benzaldehyde, o-chlorobenzaldehyde, 2,4,6-trichlorobenzaldehyde, m-chlorobenzaldehyde, p-nitrobenzaldehyde, p-hydroxy. Benzaldehyde, furfural, 1-naphthaldehyde, 2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 3-acenaphthaldehyde, benzylideneacetone (benzalacetone), pyridideneacetone, furfurylideneacetone, cinnamaldehyde, anise Aldehydes such as aldehyde, salicylaldehyde, crotonaldehyde, acrolein, glutaraldehyde, paraaldehyde, vanillin, triazine, imidazole, indole, quinoline, 2-vinylpyridy Aniline, phenanthroline, neocuproine, picolinic acid, thioureas, N- (3-hydroxybutylidene) -p-sulfanilic acid, N-butylidenesulfanilic acid, N-cinnamoylidenesulfanilic acid, 2,4-diamino- 6- (2'-methylimidazolyl (1 ')) ethyl-1,3,5-triazine, 2,4-diamino-6- (2'-ethyl-4-methylimidazolyl (1')) ethyl-1, 3,5-triazine, 2,4-diamino-6- (2'-undecylimidazolyl (1 ')) ethyl-1,3,5-triazine, phenyl salicylate, or benzothiazole, 2-methylbenzothiazole 2-aminobenzothiazole, 2-amino-6-methoxybenzothiazole, 2-methyl-5-chlorobenzothiazole, 2-hydroxybenzothiazole, 2-a Roh-6-methyl-benzothiazole, 2-chloro-benzothiazole, 2,5-dimethyl benzothiazole, 5-hydroxy-2-methyl-benzothiadiazole benzothiazoles azoles such, such as saccharin.

The above-mentioned antioxidant is for the purpose of preventing the oxidation of Sn2 + in the bath. Ascorbic acid or a salt thereof, hydroquinone, catechol, resorcin, hydroquinone, phloroglucin, cresolsulfonic acid or a salt thereof, phenolsulfonic acid or a salt thereof, catechol Examples include sulfonic acid or a salt thereof, hydroquinone sulfonic acid or a salt thereof, hydroxynaphthalene sulfonic acid or a salt thereof, and hydrazine. For example, in a neutral bath, ascorbic acid or a salt thereof is preferable.
Examples of the pH adjuster include various acids such as hydrochloric acid and sulfuric acid, various bases such as aqueous ammonia, potassium hydroxide and sodium hydroxide, monocarboxylic acids such as formic acid, acetic acid and propionic acid, and boron. Dicarboxylic acids such as acids, phosphoric acids, oxalic acid and succinic acid, and oxycarboxylic acids such as lactic acid and tartaric acid are also effective.
Examples of the conductive salt include sodium salts such as sulfuric acid, hydrochloric acid, phosphoric acid, sulfamic acid, and sulfonic acid, potassium salts, magnesium salts, ammonium salts, and amine salts. is there.
Examples of the preservative include boric acid, 5-chloro-2-methyl-4-isothiazolin-3-one, benzalkonium chloride, phenol, phenol polyethoxylate, thymol, resorcin, isopropylamine, and guaiacol.
Examples of the antifoaming agent include pluronic surfactants, higher aliphatic alcohols, acetylene alcohols and polyalkoxylates thereof.

The present invention 6 is a method of forming an electrodeposit made of tin or a tin alloy using the electroplating bath of the present invention. A typical example of the electrodeposit is a bump electrode, which is formed on a wafer, a substrate, a lead frame, or the like. When a large number of protruding electrodes are formed using the tin or tin alloy plating bath of the present invention, the height uniformity of the protruding electrodes can be ensured satisfactorily.
Next, a representative example of the electrodeposit is an electrodeposition film. When a large number of electrodeposition films are formed using the tin or tin alloy plating bath of the present invention, the thickness of the film can be made uniform, and voids (voids) can be smoothly prevented by filling the via holes.
On the other hand, the present invention 7 is an electronic component manufactured by the forming method of the present invention 6, and the electronic component is a glass substrate, silicon substrate, sapphire substrate, wafer, printed wiring board, semiconductor integrated circuit, resistor, variable resistor, capacitor. , Filter, inductor, thermistor, crystal resonator, switch, lead wire, solar cell.
For example, when a protruding electrode is formed on a silicon substrate or wafer by applying the plating bath of the present invention, if attention is paid to the protruding electrode, the forming method belongs to the present invention 6 and the focused method is focused on the substrate or wafer on which the protruding electrode is formed. Then, these manufacturing methods belong to the present invention 7. Further, when an electrodeposition film is formed on a lead frame or a substrate, if attention is paid to the plating film, the formation method belongs to the present invention 6, and when attention is paid to the lead frame or the substrate on which the film is formed, these manufacturing methods are the present invention. Belonging to 7.
In the electroplating using the tin or tin alloy plating bath of the present invention, various plating methods such as barrel plating, rack plating, high-speed continuous plating, rackless plating, cup plating, and dip plating can be employed.
As electroplating conditions, the bath temperature is 0 ° C. or higher, preferably about 10 to 50 ° C., and the cathode current density is 0.001 to 40 A / dm 2, preferably 0.01 to 25 A / dm 2.
After the electroplating, the deposited tin or tin alloy is reflowed or a protruding electrode or an electrodeposition film is formed without reflowing.

Hereinafter, examples of electrotin and tin alloy plating baths of the present invention, manufacturing examples in which protruding electrodes are formed on a semiconductor substrate by electroplating using the plating bath obtained in the examples, and many obtained in the manufacturing examples For the protruding electrode groups, height uniformity evaluation test examples will be sequentially described.
The present invention is not restricted to the above-described examples, production examples, and test examples, and it is needless to say that arbitrary modifications can be made within the scope of the technical idea of the present invention.

<< Examples of electrolytic tin and tin alloy plating bath >>
Among Examples 1-45 below, Examples 1-2, 22, 27 are examples of tin plating baths, Examples 3-4, 36 are examples of tin-zinc alloy plating baths, Examples 5-16, 28- 29 is an example of a tin-silver alloy plating bath, Examples 17, 20, 25, 32-33 are examples of a tin-copper alloy plating bath, Examples 18, 23, 26, 34-35 are tin-bismuth alloy plating baths Examples 19, 21, 24, 30 to 31 are tin-indium alloy plating baths, Examples 37 to 39 are examples of tin-nickel alloy plating baths, and Examples 40 to 41 are tin-gold alloy plating baths. Examples, Examples 42 to 43 are examples of tin-cobalt alloy plating baths, and Examples 44 to 45 are examples of tin-antimony alloy plating baths.
Examples 7 to 8 and 15 are cross-linked heterocyclic compounds, and all other examples are cross-linked aromatic ring compounds.
Moreover, about the bridge | crosslinking type aromatic compound of this invention contained in a plating bath, Example 15, 20-23, 42 has an example which has a carbon bond, Examples 13, 24, 26, 35-36, 43 have an imino bond. Examples, Examples 25, 27 to 29, 39 and 45 are examples having a quaternary ammonium salt bond, and all other examples are examples having an ether bond.

On the other hand, among Comparative Examples 1 to 13, Comparative Example 1 is a blank example of a tin bath that does not contain the crosslinked aromatic compound of the present invention (compound having an ether bond), and Comparative Example 2 is a crosslinked aromatic compound of the present invention. Blank example of tin bath not containing (compound having carbon bond), Comparative Example 3 is a blank example of tin bath not containing the cross-linked aromatic compound of the present invention (compound having quaternary ammonium salt bond), Comparative Example 4 Is an example of a tin bath containing a bisphenol type nonionic surfactant in place of the cross-linked aromatic compound of the present invention.
Comparative Example 5 is a blank example of a tin-silver alloy bath that does not contain the crosslinked aromatic compound of the present invention (compound having an ether bond), and is a bisphenol type nonion instead of the crosslinked aromatic compound of the present invention. It is also an example of a tin-silver alloy bath containing an ionic surfactant. Comparative Example 6 is a blank example of a tin-silver alloy bath not containing the cross-linked aromatic compound (compound having a carbon bond) of the present invention, and Comparative Example 7 is a cross-linked aromatic compound (compound having an imino bond) of the present invention. A blank example of a tin-silver alloy bath not containing any of the above, and Comparative Example 8 is a blank example of a tin-silver alloy bath not containing the crosslinked aromatic compound of the present invention (compound having a quaternary ammonium salt bond). Comparative Example 9 is also an example of a tin-silver alloy bath containing a quaternary ammonium salt type cationic surfactant in place of the crosslinked aromatic compound of the present invention (compound having a quaternary ammonium salt bond).
Comparative Example 10 is a blank example of a tin-copper alloy bath that does not contain the crosslinked aromatic compound (compound having an ether bond) of the present invention, and is a bisphenol type nonion instead of the crosslinked aromatic compound of the present invention. It is also an example of a tin-copper alloy bath containing a surfactant. Comparative Example 11 is a blank example of a tin-copper alloy bath that does not contain the crosslinked aromatic compound of the present invention (compound having a carbon bond).
Comparative Example 12 is a blank example of a tin-zinc alloy bath not containing the crosslinked aromatic compound of the present invention (compound having an ether bond), and Comparative Example 13 is a crosslinked aromatic compound of the present invention (compound having an imino bond). It is a blank example of the tin-zinc alloy bath which does not contain.

(1) Example 1
An electrotin plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 65g / L
Methanesulfonic acid (as free acid) 100g / L
Cumylphenol polyethoxylate (EO13 mol) 10g / L
Catecholsulfonic acid 2.5 g / L
Sodium alkylphenyl naphthyl ether disulfonate 2g / L
Isopropyl alcohol 5g / L
The isopropyl alcohol (IPA) is a solvent of an alkylphenyl naphthyl ether disulfonate belonging to the cross-linked aromatic compound C of the present invention, and after dissolving the compound C in IPA, the IPA solution is used as a plating bath. To give the above composition (the same applies to the following examples and comparative examples).
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 3A / dm2

(2) Example 2
An electrotin plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 65g / L
Methanesulfonic acid (as free acid) 100g / L
Ethylenediamine polyethoxylate
-Polypropoxylate block polymer 10 g / L
Lauryldimethylethylammonium hydroxide 5g / L
Catecholsulfonic acid 2.5 g / L
Methacrylic acid 1g / L
Sodium alkylphenyl naphthyl ether disulfonate 2g / L
Isopropyl alcohol 5g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 5A / dm2

(3) Example 3
An electric tin-zinc alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 40g / L
Zinc chloride (as Zn2 +) 30g / L
Gluconic acid 100g / L
Methanesulfonic acid (as free acid) 50g / L
Poly (diallylamine) polymer 0.2 g / L
Sodium alkyldiphenyl ether disulfonate 0.2 g / L
Sodium hydroxide appropriate amount (adjusted to pH 5)
[Plating conditions]
Bath temperature: 25 ° C
Cathode current density: 2A / dm2

(4) Example 4
An electric tin-zinc alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 40g / L
Zinc methanesulfonate (as Zn2 +) 60g / L
Citric acid 100g / L
Methanesulfonic acid (as free acid) 100g / L
Trimethylbenzylammonium chloride 3g / L
Dipyrrole ether 1g / L
Ammonia water appropriate amount (adjusted to pH 5)
[Plating conditions]
Bath temperature: 25 ° C
Cathode current density: 2A / dm2

(5) Example 5
An electric tin-silver alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 85g / L
Silver methanesulfonate (as Ag +) 1.3g / L
Methanesulfonic acid (as free acid) 80g / L
3,6-dithiaoctane-1,8-diol 10 g / L
α-Naphthol polyethoxylate (EO13 mol) 10g / L
Catecholsulfonic acid 2g / L
Methacrylic acid 1g / L
Sodium alkyldiphenyl ether disulfonate 10.5 g / L
Isopropyl alcohol 3g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 10 A / dm2

(6) Example 6
An electric tin-silver alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 50g / L
Silver methanesulfonate (as Ag +) 0.3g / L
Methanesulfonic acid (as free acid) 130g / L
3,6-dithiaoctane-1,8-diol 10 g / L
Ethylenediamine polyethoxylate
-Polypropoxylate block copolymer 8g / L
Hydroquinone 0.5g / L
Diaminodiphenyl ether disulfonic acid 0.8 g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 3A / dm2

(7) Example 7
An electric tin-silver alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 80g / L
Silver methanesulfonate (as Ag +) 0.8g / L
Methanesulfonic acid (as free acid) 100g / L
4,7-ditidecane-1,10-diol 5 g / L
Glycerin polyethoxylate
-Polypropoxylate copolymer 8g / L
Resorcinol sulfonic acid 2g / L
Benzalacetone 0.05g / L
Ammonium ditriazolyl ether disulfonate 0.5 g / L
Isopropyl alcohol 3g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 6A / dm2

(8) Example 8
An electric tin-silver alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 80g / L
Silver methanesulfonate (as Ag +) 0.5g / L
Methanesulfonic acid (as free acid) 100g / L
Thiobis (triglycerin) 50g / L
Bisphenol A polyethoxylate (EO15 mol) 8g / L
Catechol 2g / L
Benzimidazolyl hydroxybenzoimidazolyl ether 0.1 g / L
Isopropyl alcohol 10g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 6A / dm2

(9) Example 9
An electric tin-silver alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 60g / L
Silver methanesulfonate (as Ag +) 0.6g / L
Methanesulfonic acid (as free acid) 100g / L
1,10-diamino-4,7-dithiadecane 10 g / L
Bisphenol A polyethoxylate (EO10 mol) 5g / L
Aminocatechol 2g / L
Diphenyl ether disulfonic acid 1g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 8A / dm2

(10) Example 10
An electric tin-silver alloy plating bath was constructed with the following composition.
Stannous hydroxyethanesulfonate (as Sn2 +) 80g / L
Silver hydroxyethanesulfonate (as Ag +) 1.5 g / L
Hydroxyethanesulfonic acid (as free acid) 80g / L
4,7-dithiadecane-1,2,9,10-tetraol 7 g / L
Bisphenol E polyethoxylate (EO15 mol) 5g / L
Potassium hydroquinonesulfonate 2g / L
Diaminodiphenyl ether 0.5g / L
Isopropyl alcohol 10g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 10 A / dm2

(11) Example 11
An electric tin-silver alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 45g / L
Silver methanesulfonate (as Ag +) 0.3g / L
Methanesulfonic acid (as free acid) 80g / L
Thiobis (dodecaethylene glycol) 80g / L
Cumylphenol polyethoxylate (EO10 mol) 5g / L
Lauryltrimethylammonium sulfate 5g / L
Catechol 2g / L
Dicarboxydiphenyl ether 1.5g / L
Methanol 3g / L
[Plating conditions]
Bath temperature: 25 ° C
Cathode current density: 4A / dm2

(12) Example 12
An electric tin-silver alloy plating bath was constructed with the following composition.
Stannous ethanesulfonate (as Sn2 +) 50g / L
Ethanesulfonic acid silver (as Ag +) 0.5g / L
Ethanesulfonic acid (as free acid) 80g / L
2,2'-dithiodianiline 15g / L
Styrenated phenol polyethoxylate (EO20 mol) 10g / L
Methyl hydroquinone 1g / L
Sodium dinaphthyl ether disulfonate 0.5 g / L
Isopropyl alcohol 10g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 4A / dm2

(13) Example 13
An electric tin-silver alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 60g / L
Silver methanesulfonate (as Ag +) 0.7g / L
Methanesulfonic acid (as free acid) 100g / L
Thiobis (decaethylene glycol) 100g / L
Ethylenediamine polyethoxylate
-Polypropoxylate block copolymer 10 g / L
Dimethylbenzyl lauryl ammonium hydroxide 1g / L
Catecholsulfonic acid 2g / L
Diaminodiphenylamine 4g / L
Isopropyl alcohol 5g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 6A / dm2

(14) Example 14
An electric tin-silver alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 80g / L
Silver methanesulfonate (as Ag +) 0.7g / L
Methanesulfonic acid (as free acid) 100g / L
4,7-dithiadecane-1,10-diol 10 g / L
Thioglycol 8g / L
β-naphthol polyethoxylate (EO 20 mol) 10 g / L
Hydroquinonesulfonic acid 2g / L
Sodium alkyldiphenyl ether disulfonate 0.5 g / L
Isopropyl alcohol 3g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 6A / dm2

(15) Example 15
An electric tin-silver alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 80g / L
Silver methanesulfonate (as Ag +) 1.0 g / L
Methanesulfonic acid (as free acid) 100g / L
Thiobis (icosaethylene glycol) 100g / L
Cumylphenol polyethoxylate (EO13 mol) 12g / L
Sodium catecholsulfonate 2g / L
1,2-dipyridylethane 1g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 12A / dm2

(16) Example 16
An electric tin-silver alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 75g / L
Silver methanesulfonate (as Ag +) 0.8g / L
Methanesulfonic acid (as free acid) 100g / L
Dithiobis (pentadecaethylene glycol) 70g / L
Bisphenol A polyethoxylate (EO15 mol) 8g / L
Styrenated phenol polyethoxylate (EO20 mol) 2g / L
Potassium hydroquinonesulfonate 2.5g / L
Dianiline ether 2g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 6A / dm2

(17) Example 17
An electric tin-copper alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 50g / L
Copper methanesulfonate (as Cu2 +) 0.7g / L
Methanesulfonic acid (as free acid) 120g / L
Thiodiglycol 10g / L
Bisphenol E polyethoxylate (EO10 mol) 5g / L
Sodium hydroquinone sulfonate 2g / L
Sodium diphenyl ether disulfonate 1g / L
Catecholsulfonic acid 2g / L
[Plating conditions]
Bath temperature: 25 ° C
Cathode current density: 2A / dm2

(18) Example 18
An electric tin-bismuth alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 15g / L
Bismuth methanesulfonate (as Bi3 +) 60g / L
Methanesulfonic acid (as free acid) 100g / L
Octylphenyl ether polyethoxylate (EO20 mol) 10g / L
Catechol 2g / L
Thiodiphenol 0.2g / L
Sodium diphenyl ether disulfonate 1g / L
In addition, the said thiodiphenol is a void inhibitor at the time of reflowing the deposited tin-bismuth alloy (the following examples are also the same).
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 3A / dm2

(19) Example 19
An electric tin-indium alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 2g / L
Indium methanesulfonate (as In3 +) 30g / L
Citric acid 200g / L
Poly (diallylamine) polymer 0.5 g / L
Sodium diphenyl ether disulfonate 0.2g / L
Sodium hydroxide appropriate amount (adjusted to pH 6)
[Plating conditions]
Bath temperature: 55 ° C
Cathode current density: 1.6 A / dm2

(20) Example 20
An electric tin-copper alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 55g / L
Copper methanesulfonate (as Cu2 +) 1.0g / L
Methanesulfonic acid (as free acid) 100g / L
Thiodiglycol 20g / L
Polyoxyethylene styrenated phenyl ether 5g / L
Potassium 4,4- (dimethylethylene) diphenylsulfonate 1g / L
Methyl catechol 5g / L
Methanol 2g / L
[Plating conditions]
Bath temperature: 25 ° C
Cathode current density: 3A / dm2

(21) Example 21
An electric tin-indium alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 5g / L
Indium methanesulfonate (as In3 +) 35g / L
Gluconic acid 250g / L
Polyoxyethylene alkylamine 3.5g / L
Diaminostilbene 0.6g / L
Sodium hydroxide appropriate amount (adjusted to pH 5)
[Plating conditions]
Bath temperature: 45 ° C
Cathode current density: 1.5 A / dm2

(22) Example 22
An electrotin plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 85g / L
Methanesulfonic acid (as free acid) 80g / L
Polyoxyethylene sorbitan monooleate 10g / L
Lauryldimethylethylammonium hydroxide 5g / L
Methoxycatechol 3g / L
Alkylhydroxystilbene 0.8g / L
Isopropyl alcohol 2g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 7A / dm2

(23) Example 23
An electric tin-bismuth alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 20g / L
Bismuth methanesulfonate (as Bi3 +) 40g / L
Methanesulfonic acid (as free acid) 150g / L
Polyvinylpyrrolidone 9g / L
Chlorocatechol 1.5g / L
2,4-diphenyl-4-methylpentane 0.4 g / L
Methanol 5g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 5A / dm2

(24) Example 24
An electric tin-indium alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 10g / L
Indium methanesulfonate (as In3 +) 50g / L
Sodium gluconate 250g / L
Polyoxyethylene styrenated phenyl ether 0.7g / L
Alkyldiaminodiphenylamine 0.2g / L
Amount of aqueous ammonia (adjusted to pH 6)
[Message
Bath temperature: 45 ° C
Cathode current density: 3.5 A / dm2

(25) Example 25
An electric tin-copper alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 60g / L
Copper methanesulfonate (as Cu2 +) 1g / L
Methanesulfonic acid (as free acid) 80g / L
Thiodiglycolic acid 8g / L
Bisphenol A polyethoxylate (EO10 mol) 10g / L
N-dimethyldiphenylammonium methyl sulfate 0.5g / L
Pyrogallol 2g / L
[Plating conditions]
Bath temperature: 35 ° C
Cathode current density: 4A / dm2

(26) Example 26
An electric tin-bismuth alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 20g / L
Bismuth methanesulfonate (as Bi3 +) 50g / L
Methanesulfonic acid (as free acid) 90g / L
Naphthalenesulfonic acid sodium formalin condensate 7g / L
Methyl pyrogallol 3g / L
Sodium diphenylamine disulfonate 1g / L
[Plating conditions]
Bath temperature: 40 ° C
Cathode current density: 4.5 A / dm2

(27) Example 27
An electrotin plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 65g / L
Methanesulfonic acid (as free acid) 100g / L
Polyoxyethylene tridecyl ether 10g / L
Catecholsulfonic acid 2.5 g / L
N-dimethyldiphenylammonium methyl sulfate 2g / L
Isopropyl alcohol 5g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 3A / dm2

(28) Example 28
An electric tin-silver alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 85g / L
Silver methanesulfonate (as Ag +) 1.3g / L
Methanesulfonic acid (as free acid) 80g / L
Dipyridyl disulfide 5g / L
Polyoxyethylene octyl phenyl ether 10g / L
Catecholsulfonic acid 2g / L
4-ethylammonium ethyl sulfate-methylethyldiphenylammonium ethyl sulfate 1.5 g / L
Isopropyl alcohol 3g / L
[Plating conditions]
Bath temperature: 25 ° C
Cathode current density: 10 A / dm2

(29) Example 29
An electric tin-silver alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 50g / L
Silver methanesulfonate (as Ag +) 0.3g / L
Methanesulfonic acid (as free acid) 130g / L
3,6-dithiaoctane-1,8-diol 10 g / L
Polyoxyalkylene phenyl ether 8g / L
Hydroquinone 0.5g / L
4-nitrosomethylethyldiphenylammonium
-Ethylsulfate 0.8g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 3A / dm2

(30) Example 30
An electric tin-indium alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 2g / L
Indium methanesulfonate (as In3 +) 30g / L
Citric acid 200g / L
Poly (diallylmethylammonium
-Methyl sulfate) polymer 0.5 g / L
4,4'-dihydroxydiphenyl ether 0.2 g / L
Sodium hydroxide appropriate amount (adjusted to pH 6)
[Plating conditions]
Bath temperature: 50 ° C
Cathode current density: 1.6 A / dm2

(31) Example 31
An electric tin-indium alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 2g / L
Indium methanesulfonate (as In3 +) 30g / L
Citric acid 200g / L
Poly (diallylmethylammonium
-Ethyl sulfate) Polymer 0.5 g / L
3,4,4'-triaminodiphenyl ether 0.2 g / L
Sodium hydroxide appropriate amount (adjusted to pH 6)
[Plating conditions]
Bath temperature: 55 ° C
Cathode current density: 1.6 A / dm2

(32) Example 32
An electric tin-copper alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 50g / L
Copper methanesulfonate (as Cu2 +) 0.7g / L
Methanesulfonic acid (as free acid) 120g / L
Thiodiglycol 10g / L
Bisphenol A polyethoxylate (EO13 mol) 5g / L
Alkyl diphenyl ether ammonium disulfonate 1g / L
Potassium hydroquinonesulfonate 2g / L
[Plating conditions]
Bath temperature: 25 ° C
Cathode current density: 2A / dm2

(33) Example 33
An electric tin-copper alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 50g / L
Copper methanesulfonate (as Cu2 +) 0.7g / L
Methanesulfonic acid (as free acid) 120g / L
Thiodiglycol 10g / L
Bisphenol E polyethoxylate (EO20 mol) 5g / L
4,4'-dimethylammonium diphenyl ether
-Methyl sulfate 1g / L
Potassium hydroquinonesulfonate 2g / L
[Plating conditions]
Bath temperature: 25 ° C
Cathode current density: 2A / dm2

(34) Example 34
An electric tin-bismuth alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 15g / L
Bismuth methanesulfonate (as Bi3 +) 60g / L
Methanesulfonic acid (as free acid) 100g / L
Octylphenyl ether polyethoxylate (EO20 mol) 10g / L
Catechol 2g / L
Thiodiphenol 0.2g / L
3,4'-di (methylamino) -4-nitrodiphenyl ether 1 g / L
[Plating conditions]
Bath temperature: 25 ° C
Cathode current density: 3A / dm2

(35) Example 35
An electric tin-bismuth alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 15g / L
Bismuth methanesulfonate (as Bi3 +) 60g / L
Methanesulfonic acid (as free acid) 100g / L
Octylphenyl ether polyethoxylate (EO20 mol) 10g / L
Catechol 2g / L
Thiodiphenol 0.2g / L
4- (dimethylamino) -4'-nitrosodiphenylamine 1 g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 3A / dm2

(36) Example 36
An electric tin-zinc alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 40g / L
Zinc methanesulfonate (as Zn2 +) 60g / L
Citric acid 100g / L
Methanesulfonic acid (as free acid) 100g / L
Trimethylbenzylammonium chloride 3g / L
N, N, N ′, N′-tetramethyldiaminodiphenylamine 1 g / L
Ammonium water appropriate amount (adjusted to pH 5)
[Plating conditions]
Bath temperature: 25 ° C
Cathode current density: 2A / dm2

(37) Example 37
An electric tin-nickel alloy plating bath was constructed with the following composition.
Stannous chloride (as Sn2 +) 30g / L
Nickel chloride (as Ni2 +) 60g / L
Glycine 75g / L
Pyrophosphate 90g / L
Sodium diphenyl ether disulfonate 0.1 g / L
Sodium hydroxide appropriate amount (adjusted to pH 7)
[Plating conditions]
Bath temperature: 55 ° C
Cathode current density: 1.5 A / dm2

(38) Example 38
An electric tin-nickel alloy plating bath was constructed with the following composition.
Stannous chloride (as Sn2 +) 45g / L
Nickel chloride (as Ni2 +) 60g / L
Glycine 30g / L
Pyrophosphate 90g / L
Catechol 2g / L
Sodium dinaphthyl ether disulfonate 0.1 g / L
Saccharin 1g / L
Sodium hydroxide appropriate amount (adjusted to pH 7)
[Plating conditions]
Bath temperature: 55 ° C
Cathode current density: 1.5 A / dm2

(39) Example 39
An electric tin-nickel alloy plating bath was constructed with the following composition.
Stannous chloride (as Sn2 +) 30g / L
Nickel chloride (as Ni2 +) 50g / L
Glycine 70g / L
Pyrophosphate 60g / L
Catechol 1g / L
Diphenyldimethylammonium
-Sodium disulfonate / chloride 0.1g / L
Saccharin 1g / L
Sodium hydroxide appropriate amount (adjusted to pH 7)
[Plating conditions]
Bath temperature: 40 ° C
Cathode current density: 0.5 A / dm2

(40) Example 40
An electric tin-gold alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 20g / L
Mercaptosuccinic acid gold (as Au +) 10g / L
Mercaptosuccinic acid 30g / L
Citric acid 50g / L
Polyethylene glycol 1g / L
Polyoxyethylene palm alcohol ether 0.5g / L
Catechol 3g / L
Sodium diphenyl ether disulfonate 0.3g / L
Potassium hydroxide appropriate amount (adjusted to pH 8)
[Plating conditions]
Bath temperature: 60 ° C
Cathode current density: 1A / dm2

(41) Example 41
An electric tin-gold alloy plating bath was constructed with the following composition.
Stannous pyrophosphate (as Sn2 +) 50g / L
Gold cyanide (as Au +) 8g / L
Potassium pyrophosphate 25g / L
Sodium diphenylamine disulfonate 0.2 g / L
Potassium hydroxide appropriate amount (adjusted to pH 8)
[Plating conditions]
Bath temperature: 35 ° C
Cathode current density: 1A / dm2

(42) Example 42
An electric tin-cobalt alloy plating bath was constructed with the following composition.
Stannous chloride (as Sn2 +) 20g / L
Cobalt chloride (as Co2 +) 60g / L
Sodium gluconate 100g / L
Sodium benzyl phenyl disulfonate 0.25g / L
Sodium hydroxide appropriate amount (adjusted to pH 2.0)
[Plating conditions]
Bath temperature: 50 ° C
Cathode current density: 1.5 A / dm2

(43) Example 43
An electric tin-cobalt alloy plating bath was constructed with the following composition.
Stannous chloride (as Sn2 +) 20g / L
Cobalt chloride (as Co2 +) 60g / L
Sodium gluconate 60g / L
Citric acid 2g / L
Sodium 2,2'-dinaphthylamine disulfonate 0.2 g / L
Sodium hydroxide appropriate amount (adjusted to pH 2.0)
[Plating conditions]
Bath temperature: 50 ° C
Cathode current density: 1.5 A / dm2

(44) Example 44
An electric tin-antimony alloy plating bath was constructed with the following composition.
1-hydroxyethane
-1,1-disulfonic acid stannous (as Sn2 +) 40 g / L
1-hydroxyethane
-1,1-disulfonic acid antimony (as Sb3 +) 8 g / L
1-hydroxyethane-1,1-disulfonic acid (as free acid) 150 g / L
Lauryl phenyl ether polyethoxylate (EO 10 mol) 0.1 g / L
Catechol 3g / L
Sodium diphenyl ether disulfonate 0.2g / L
Sodium hydroxide appropriate amount (adjusted to pH 2.0)
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 1A / dm2

(45) Example 45
An electric tin-antimony alloy plating bath was constructed with the following composition.
1-hydroxyethane
-1,1-disulfonic acid stannous (as Sn2 +) 60 g / L
1-hydroxyethane
-1,1-disulfonic acid antimony (as Sb3 +) 6 g / L
1-hydroxyethane-1,1-disulfonic acid (as free acid) 100 g / L
β-naphthol ether polyethoxylate (EO 10 mol) 10 g / L
Catechol 10g / L
Diphenyldimethylammonium
-Sodium disulfonate / chloride 0.1g / L
Sodium hydroxide appropriate amount (adjusted to pH 2.3)
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 1A / dm2

(46) Comparative Example 1
This example is based on Example 1 and does not contain the crosslinked aromatic compound of the present invention.
That is, an electrotin plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 65g / L
Methanesulfonic acid (as free acid) 100g / L
Cumylphenol polyethoxylate (EO13 mol) 10g / L
Catecholsulfonic acid 2.5 g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 3A / dm2

(47) Comparative Example 2
This example is based on Example 22 and does not contain the crosslinked aromatic compound of the present invention.
That is, an electrotin plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 85g / L
Methanesulfonic acid (as free acid) 80g / L
Polyoxyethylene sorbitan monooleate 10g / L
Lauryldimethylethylammonium hydroxide 5g / L
Methoxycatechol 3g / L
Isopropyl alcohol 2g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 7A / dm2

(48) Comparative Example 3
This example is based on Example 27 and does not contain the crosslinked aromatic compound of the present invention.
That is, an electrotin plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 65g / L
Methanesulfonic acid (as free acid) 100g / L
Polyoxyethylene tridecyl ether 10g / L
Catecholsulfonic acid 2.5 g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 3A / dm2

(49) Comparative Example 4
This is an example containing, based on Example 1, a bisphenol type nonionic surfactant in place of the cross-linked aromatic compound of the present invention.
That is, an electrotin plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 65g / L
Methanesulfonic acid (as free acid) 100g / L
Bisphenol A polyethoxylate (EO13 mol) 10g / L
Catecholsulfonic acid 2.5 g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 3A / dm2

(50) Comparative Example 5
This example is based on Example 10 and does not contain the crosslinked aromatic compound of the present invention.
That is, an electrotin-silver alloy plating bath was constructed with the following composition.
Stannous hydroxyethanesulfonate (as Sn2 +) 80g / L
Silver hydroxyethanesulfonate (as Ag +) 1.5 g / L
Hydroxyethanesulfonic acid (as free acid) 80g / L
Bis (2,3-dihydroxypropiothio) ethane 7 g / L
Bisphenol E polyethoxylate (EO15 mol) 5g / L
Potassium hydroquinonesulfonate 2g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 10 A / dm2

(51) Comparative Example 6
This example is based on Example 15 and does not contain the crosslinked aromatic compound of the present invention.
That is, an electrotin-silver alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 80g / L
Silver methanesulfonate (as Ag +) 1.0 g / L
Methanesulfonic acid (as free acid) 100g / L
Thiobis (icosaethylene glycol) 100g / L
Cumylphenol polyethoxylate (EO13 mol) 12g / L
Sodium catecholsulfonate 2g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 12A / dm2

(52) Comparative Example 7
This example is based on Example 13 and does not contain the crosslinked aromatic compound of the present invention.
That is, an electrotin-silver alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 60g / L
Silver methanesulfonate (as Ag +) 0.7g / L
Methanesulfonic acid (as free acid) 100g / L
Thiobis (hexaethylene glycol) 150g / L
Glycerin polyethoxylate
-Polypropoxylate copolymer 10 g / L
Dimethylbenzyl lauryl ammonium hydroxide 1g / L
Catecholsulfonic acid 2g / L
[Plating conditions]
Bath temperature: 30 ° C
Cathode current density: 6A / dm2

(53) Comparative Example 8
This example is based on Example 28 and does not contain the crosslinked aromatic compound of the present invention.
That is, an electrotin-silver alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 85g / L
Silver methanesulfonate (as Ag +) 1.3g / L
Methanesulfonic acid (as free acid) 80g / L
Dipyridyl disulfide 5g / L
Polyoxyethylene octyl phenyl ether 10g / L
Catecholsulfonic acid 2g / L
[Plating conditions]
Bath temperature: 25 ° C
Cathode current density: 10 A / dm2

(54) Comparative Example 9
Based on Example 28, this is an example containing a quaternary ammonium salt type cationic surfactant in place of the crosslinked aromatic compound of the present invention.
That is, an electrotin-silver alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 85g / L
Silver methanesulfonate (as Ag +) 1.3g / L
Methanesulfonic acid (as free acid) 80g / L
Dipyridyl disulfide 5g / L
Polyoxyethylene octyl phenyl ether 10g / L
Trimethylbenzylammonium chloride 3g / L
Catecholsulfonic acid 2g / L
[Plating conditions]
Bath temperature: 25 ° C
Cathode current density: 10 A / dm2

(55) Comparative Example 10
This example is based on Example 17 and does not contain the crosslinked aromatic compound of the present invention.
That is, an electric tin-copper alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 50g / L
Copper methanesulfonate (as Cu2 +) 0.7g / L
Methanesulfonic acid (as free acid) 120g / L
Thiodiglycol 10g / L
Bisphenol E polyethoxylate (EO10 mol) 5g / L
Sodium hydroquinone sulfonate 2g / L
[Plating conditions]
Bath temperature: 25 ° C
Cathode current density: 2A / dm2

(56) Comparative Example 11
This example is based on Example 20 and does not contain the crosslinked aromatic compound of the present invention.
That is, an electric tin-copper alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 55g / L
Copper methanesulfonate (as Cu2 +) 1.0g / L
Methanesulfonic acid (as free acid) 100g / L
Thiodiglycol 20g / L
Polyoxyethylene styrenated phenyl ether 5g / L
Methyl catechol 5g / L
Methanol 2g / L
[Plating conditions]
Bath temperature: 25 ° C
Cathode current density: 3A / dm2

(57) Comparative Example 12
This example is based on Example 3 and does not contain the crosslinked aromatic compound of the present invention.
That is, an electrotin-zinc alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 40g / L
Zinc chloride (as Zn2 +) 30g / L
Gluconic acid 100g / L
Methanesulfonic acid (as free acid) 50g / L
Poly (diallylamine) polymer 0.2 g / L
Sodium hydroxide appropriate amount (adjusted to pH 5)
[Plating conditions]
Bath temperature: 25 ° C
Cathode current density: 2A / dm2

(58) Comparative Example 13
This example is based on Example 36 and does not contain the crosslinked aromatic compound of the present invention.
That is, an electrotin-zinc alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn2 +) 40g / L
Zinc methanesulfonate (as Zn2 +) 60g / L
Citric acid 100g / L
Methanesulfonic acid (as free acid) 100g / L
Trimethylbenzylammonium chloride 3g / L
Ammonium water appropriate amount (adjusted to pH 5)
[Plating conditions]
Bath temperature: 25 ° C
Cathode current density: 2A / dm2

Therefore, a large number of protruding electrodes were formed using each of the electric tin or tin alloy plating baths of Examples 1 to 45 and Comparative Examples 1 to 13, and an evaluation test of the height uniformity of the protruding electrodes was performed.
<< Example in which protruding electrodes are formed by electroplating >>
By electroplating (the plating conditions are as described at the end of each example and comparative example), the protruding electrodes using the respective electrotin or tin alloy plating baths of Examples 1 to 45 and Comparative Examples 1 to 13 on the substrate Groups (about 5,000) were formed.
Regarding the electrodeposited film of tin or tin alloy constituting the protruding electrode, in Examples 1 to 45, the film appearance was uniform and the particles were dense.
On the other hand, in the comparative example, the film appearance was generally uniform, but there were cases where unevenness was observed in the film appearance.

《Example of evaluation test for bump electrode height uniformity》
For a large number of protruding electrodes formed on a silicon substrate by electroplating using the tin or tin alloy plating bath, the difference between the maximum value and the minimum value in the protruding electrode group is 1 as shown in the following formula (p). The ratio A (%) in which the numerical value of / 2 occupies the average height of the protruding electrodes was calculated, and the superiority or inferiority of the height uniformity of the protruding electrodes was quantitatively evaluated.
A = {(H (Max) −H (Min)) / 2} / H (Av) × 100 (p)
H (Av): Average height of protruding electrode group
H (Max): Maximum height in the protruding electrode group
H (Min): Minimum height in the protruding electrode group

The table below shows the test results.
Uniformity Uniformity Uniformity Example 1 4.2% Example 21 4.6% Example 41 6.5%
Example 2 3.6% Example 22 4.1% Example 42 6.5%
Example 3 2.0% Example 23 1.3% Example 43 6.5%
Example 4 2.5% Example 24 4.6% Example 44 6.0%
Example 5 4.2% Example 25 1.7% Example 45 6.0%
Example 6 2.1% Example 26 1.9%
Example 7 1.9% Example 27 4.9% Comparative Example 1 12.1%
Example 8 4.3% Example 28 4.8% Comparative Example 2 9.5%
Example 9 3.5% Example 29 3.7% Comparative Example 3 15.3%
Example 10 4.8% Example 30 5.2% Comparative Example 4 10.8%
Example 11 1.5% Example 31 5.1% Comparative Example 5 12.8%
Example 12 2.2% Example 32 3.4% Comparative Example 6 9.3%
Example 13 3.8% Example 33 2.9% Comparative Example 7 14.4%
Example 14 2.0% Example 34 3.2% Comparative Example 8 17.5%
Example 15 4.5% Example 35 2.6% Comparative Example 9 11.8%
Example 16 4.0% Example 36 3.5% Comparative Example 10 9.9%
Example 17 1.6% Example 37 6.5% Comparative Example 11 9.8%
Example 18 1.0% Example 38 5.8% Comparative Example 12 10.0%
Example 19 4.6% Example 39 5.2% Comparative Example 13 10.4%
Example 20 2.2% Example 40 6.3%

<< Evaluation of test results >>
(1) Electrotin plating bath First, in an electrotin plating bath, Comparative Example 1 is a crosslinked aromatic compound C of the present invention having an ether bond, Comparative Example 2 is a compound C having a carbon bond, and Comparative Example 3 is a quaternary ammonium salt. Although it is each blank example which does not contain the compound C which has a coupling | bonding, these Comparative Examples 1-3 are Examples 1-2, 22, and 27 containing the compound C of this invention (especially Example 1, 22, Compared with 27), the ratio A of uniformity in the comparative example was 9.5 to 15.3%, whereas the ratio A in the example was 3.6 to 4.9%.
Incidentally, the bridged aromatic compound C of the present invention includes a compound having a basic skeleton in which benzene rings are bridged by carbon bonds (Y = carbon bond, Xa, Xb = benzene ring in the general formula (1)). The compound C and the bisphenol type nonionic surfactant are common in that they have this basic skeleton.
Comparative Example 4 is an example of a tin plating bath containing the bisphenol type nonionic surfactant in place of the crosslinked aromatic compound C of the present invention. The uniformity ratio A of Comparative Example 4 is 10.8%. Met.
The compound C of the present invention includes a compound having a basic skeleton of a quaternary ammonium salt in which a benzene ring is bonded to a nitrogen atom (in the general formula (1), Y = quaternary ammonium salt bond among nitrogen bonds). , Xa, Xb = benzene ring), and the compound C is common in that it has this basic skeleton with, for example, a benzalkonium salt (that is, quaternary ammonium salt) type cationic surfactant.
Comparative Example 1 is a blank example that does not contain the compound C of the present invention. On the other hand, instead of the compound C of the present invention, an example of a tin plating bath containing the benzalkonium salt type cationic surfactant. However, the uniformity ratio A of Comparative Example 1 was 12.1%.
Therefore, in the electrotin plating bath, the uniformity ratio A (3.6 to 4.9%) of the example is remarkably smaller and higher than the comparative examples 1 to 4 (9.5 to 15.3%). It can be seen that the variation in the thickness is suppressed and the height uniformity of the protruding electrodes is excellent.

(2) Electrotin-silver alloy plating bath In the electrotin-silver alloy plating bath, Comparative Example 5 is the crosslinked aromatic compound C of the present invention having an ether bond, Comparative Example 6 is Compound C having a carbon bond, Comparative Example 7 is a compound C having an imino bond, and Comparative Example 8 is each blank example not containing the compound C having a quaternary ammonium salt bond, but these Comparative Examples 5 to 8 were carried out containing the compound C of the present invention. Compared with Examples 5-16 and 28-29 (especially Examples 10, 13, 15, 28), the comparative example A has a height uniformity ratio A of 9.3 to 17.5%. The ratio A of the examples was 1.5 to 4.8%.
Further, since the bisphenol E type nonionic surfactant contained in Comparative Example 5 has a basic skeleton common to the compound C of the present invention having a structure in which benzene rings are cross-linked by a carbon bond, as described above, Comparative Example 5 is a blank example that does not contain the compound C of the present invention. On the other hand, instead of the compound C of the present invention, a tin-silver alloy plating bath containing the bisphenol-type nonionic surfactant is used. This is also an example, and the uniformity ratio A of Comparative Example 5 was 12.8%.
Furthermore, the benzalkonium-type cationic surfactant contained in Comparative Example 9 has a benzene ring with respect to the compound C of the present invention having a structure in which benzene rings are cross-linked by a nitrogen bond of a quaternary ammonium salt. Since the quaternary ammonium salt structure is common, the comparative example 9 is an example of a tin-silver alloy plating bath containing the quaternary ammonium salt type cationic surfactant instead of the compound C of the present invention. The uniformity ratio A of Comparative Example 9 was 11.8%.
Therefore, in the electrotin-silver alloy plating bath, the uniformity ratio A (1.5 to 4.8%) of the example is significantly higher than those of Comparative Examples 5 to 9 (9.3 to 17.5%). It can be seen that it is small and has excellent height uniformity of the protruding electrodes.

(3) Electrotin-copper alloy plating bath In the electrotin-copper alloy plating bath, Comparative Example 10 does not include the cross-linked aromatic compound C of the present invention having an ether bond, and Comparative Example 11 does not include the compound C having a carbon bond. Although it is each blank example, when these Comparative Examples 10-11 are compared with Examples 17, 20, 25, 32-33 (especially Examples 17, 20) containing the compound C of the present invention, Comparative Examples The height uniformity ratio A was 9.8 to 9.9%, while the ratio A in the examples was 1.6 to 3.4%.
Moreover, since the nonionic surfactant of the bisphenol E type contained in the comparative example 10 has a basic skeleton common to the compound C of the present invention having a structure in which benzene rings are cross-linked by a carbon bond, as described above, The comparative example 10 is a blank example that does not contain the compound C of the present invention. On the other hand, instead of the compound C of the present invention, a tin-copper alloy plating bath containing the bisphenol type nonionic surfactant is used. This is also an example, and the uniformity ratio A of Comparative Example 10 was 9.9%.
Therefore, in the electric tin-copper alloy plating bath, the uniformity ratio A (1.6 to 3.4%) of the example is significantly higher than those of Comparative Examples 10 to 11 (9.8 to 9.9%). It can be seen that it is small and has excellent height uniformity of the protruding electrodes.

(4) Electro-tin-zinc alloy plating bath In the electro-tin-copper alloy plating bath, Comparative Example 12 does not include the cross-linked aromatic compound C of the present invention having an ether bond, and Comparative Example 13 does not include the compound C having an imino bond. Although it is each blank example, when these Comparative Examples 12-13 are compared with Examples 3-4 and 36 (especially Examples 3 and 36) containing the compound C of this invention, the height of a comparative example is uniform. The sex ratio A was 10.0 to 10.4%, while the ratio A in the examples was 2.0 to 3.5%.
Further, the benzalkonium-type cationic surfactant contained in Comparative Example 13 is a compound C of the present invention having a structure in which benzene rings are cross-linked by a quaternary ammonium salt type nitrogen bond, and 4 having a benzene ring. Since it is common in the quaternary ammonium salt structure, the comparative example 13 is an example of a tin-zinc alloy plating bath containing the quaternary ammonium salt type cationic surfactant instead of the compound C of the present invention, The uniformity ratio A of this comparative example 13 was 10.4%.
Therefore, in the electrotin-zinc alloy plating bath, the uniformity ratio A (2.0 to 3.5%) of the example is significantly higher than those of Comparative Examples 12 to 13 (10.0 to 10.4%). It can be seen that it is small and has excellent height uniformity of the protruding electrodes.

(5) Evaluation of electrotin and tin alloy plating bath Summarizing the above (1) to (4), the tin or tin alloy plating bath of the example containing the crosslinked aromatic compound C of the present invention is When a large number of protruding electrodes are formed on a substrate with respect to a plating bath that does not contain compound C, it has a remarkable advantage in that excellent uniformity can be secured by suppressing variations in the height of the protruding electrodes. That was proved.
Further, the compound C of the present invention having a structure in which benzene rings are cross-linked by a carbon bond has a basic skeleton in common with a bisphenol type nonionic surfactant, but as can be seen from the comparison of the above examples and comparative examples, Even if this bisphenol type nonionic surfactant is contained in the plating bath instead of the compound C of the invention, the uniformity of the height of the protruding electrode cannot be ensured, so that the present invention can ensure excellent uniformity. The superiority of the tin and tin alloy plating baths containing Compound C is apparent.
Furthermore, the compound C of the present invention having a structure in which benzene rings are cross-linked by a nitrogen bond of a quaternary ammonium salt is common to benzalkonium type cationic surfactants and the like and a quaternary ammonium salt structure having a benzene ring. As can be seen from the comparison between the above Examples and Comparative Examples, the desired purpose is achieved with the inclusion of a cationic surfactant such as a benzalkonium salt in terms of ensuring good uniformity of the height of the protruding electrode. The superiority of tin and tin alloy plating baths containing compound C of the present invention is not apparent.

On the other hand, when Examples 1-45 are examined in detail, the crosslinked aromatic compound C of the present invention is a tin plating bath, or various tins including tin-silver alloy, tin-copper alloy, tin-zinc alloy and the like. Even when applied to any of the alloy plating baths, the height uniformity of the protruding electrodes can be ensured satisfactorily.
In this case, the compound C of the present invention can exhibit its effectiveness by adding a small amount of additive to the plating bath, and there is no difference in effectiveness depending on the bath type.
Examples 7 to 8 and 15 are cross-linked heterocyclic compounds, and all other examples are cross-linked aromatic ring compounds. Even if the compound C of the present invention has either an aromatic ring or a heterocyclic ring, The uniformity of the height can be secured well, and there is no difference in effectiveness between the aromatic ring and the heterocyclic ring.
In the compound C of the present invention, the crosslinked structure of the aromatic ring or heterocyclic ring has a carbon bond such as alkylene or alkynylene (see Examples 15, 20 to 23, 42), an imino bond (Examples 13, 24, 26, 35-36, 43), quaternary ammonium salt bond (see Examples 25, 27-29, 39, 45) or ether bond (see all other examples) The uniformity of the height of the protruding electrode can be ensured satisfactorily, and there is no difference in effectiveness between the crosslinked structures selected from an ether bond, a carbon bond, and a nitrogen bond.

Claims (7)

(A) a soluble salt of any one of a stannous salt and a mixture of a metal salt selected from stannous salt and zinc, nickel, bismuth, cobalt, indium, antimony, gold, silver, copper, lead; ,
(B) an acid or a salt thereof;
(C) Cross-linked aromatic compound represented by the following general formula (1)
Za-Xa-Y-Xb-Zb (1)
(In the above formula (1), Xa and Xb represent an aromatic ring and a heterocyclic ring, and Xa and Xb may be the same or different; Y represents a linear or branched alkylene chain, alkenylene chain, alkynylene chain, these Represents a carbon chain partially substituted with carbonyl, an oxygen atom, an imino bond or a nitrogen atom forming a quaternary ammonium bond; Za and Zb are hydrogen, a C1-C18 alkyl group, a C1-C18 alkoxy group; Represents a halogen, a sulfonic acid (salt) group, an amide group, an amino group, a quaternary ammonium base, a carboxyl group, a hydroxyl group, a nitro group, or a nitroso group. And Zb may be the same or different.)
Electrotin and tin alloy plating bath containing   In the above compound (C), Y is an alkylene chain, alkenylene chain, oxygen atom, nitrogen atom, and Xa and Xb are a benzene ring, naphthalene ring, thiazole ring, pyrrole ring, pyridine ring, pyrazine ring, pyridazine ring, thiadiazole ring , An imidazoline ring, an imidazole ring, a thiazoline ring, a triazole ring, a tetrazole ring, a picoline ring, a furazane ring, a piperidine ring, a piperazine ring, a triazine ring, or a benzimidazole ring. The electrolytic tin and tin alloy plating bath according to claim 1.   The compound (C) is dipyridylalkane, dipyridylalkanesulfonic acid, dipiperidylalkane, dipiperidylalkanesulfonic acid, dipyrrolealkane, dipyrrolealkanesulfonic acid, diimidazolylalkane, diimidazolylalkanesulfonic acid, ditriazolylalkane, Ditriazolyl alkanesulfonic acid, dianiline alkane, dianiline alkanesulfonic acid, diphenylalkane, aminodiphenylalkane, diphenylalkanesulfonic acid, hydroxydiphenylalkane, hydroxydiphenylalkanesulfonic acid, aminodiphenylalkanesulfonic acid, dinaphthylalkane, amino Dinaphthylalkane, dinaphthylalkanesulfonic acid, hydroxydinaphthylalkanesulfonic acid, aminodinaphthylalkanesul Acid, phenylalkylimidazole, phenylalkylpyridine, diaminostilbene, diaminostilbenesulfonic acid, alkylhydroxystilbene, dipyridylamine, dipyridylaminesulfonic acid, dipiperidylamine, dipiperidylaminesulfonic acid, dipyrroleamine, dipyrroleaminesulfonic acid , Diimidazolylamine, diimidazolylamine sulfonic acid, ditriazolylamine, ditriazolylamine sulfonic acid, aniline amine, dianiline amine sulfonic acid, diphenylamine, aminodiphenylamine, diphenylamine sulfonic acid, hydroxydiphenylamine sulfonic acid, aminodiphenylamine sulfonic acid , Dinaphthylamine, aminodinaphthylamine, dinaphthylaminesulfonic acid, hydroxydinaphth Ruaminesulfonic acid, aminodinaphthylaminesulfonic acid, dialkyldiphenylammonium salt, dialkyldinaphthylammonium salt, N, N, N ', N'-tetraalkyldiaminodiphenylamine, phenylnaphthylaminesulfonic acid, dipyridyl ether, dipyridyl ether sulfonic acid, di Piperidyl ether, dipiperidyl ether sulfonic acid, dipyrrole ether, dipyrrole ether sulfonic acid, diimidazolyl ether, diimidazolyl ether sulfonic acid, ditriazolyl ether, ditriazolyl ether sulfonic acid, dianiline ether, dianiline ether sulfonic acid , Diphenyl ether, alkyl diphenyl ether, hydroxy diphenyl ether, amino diphenyl ether, alkylamino diphenyl ether -Tell, carboxydiphenyl ether, diphenyl ether sulfonic acid, alkyl diphenyl ether sulfonic acid, hydroxy diphenyl ether sulfonic acid, dinaphthyl ether, alkyl dinaphthyl ether, hydroxy dinaphthyl ether, aminodinaphthyl ether, alkylamino dinaphthyl ether, carboxy Dinaphthyl ether, dinaphthyl ether sulfonic acid, alkyl dinaphthyl ether sulfonic acid, phenyl naphthyl ether, alkylphenyl naphthyl ether, hydroxyphenyl naphthyl ether, aminophenyl naphthyl ether, alkylaminophenyl naphthyl ether, carboxyphenyl naphthyl ether , Phenyl naphthyl ether sulfonic acid, alkyl phenyl naphthyl ether sulfonic acid, Hydroxyphenyl-naphthyl ether sulfonate, alkyl amino nitro ether, or electrical tin and tin alloy plating bath according to claim 2, characterized in that at least one selected from the group consisting of salts. Further, a complexing agent selected from sulfide compounds selected from the following compounds (a) to (c), oxycarboxylic acids, polycarboxylic acids, aminocarboxylic acids, pyrophosphoric acids, polyamines, amino alcohols and salts thereof. At least one (a) aliphatic sulfide compound represented by the following formula (a) Xn-R1-S- (CH2CH2S) m-R2-Xn (a)
(In the formula (a), R1 and R2 are C2 to C4 alkylene; X is OH, SO3H, SO3M (M is an alkali metal, ammonia or amine), NRaRb (Ra and Rb are hydrogen, C1 to C6 alkyl), CONRaRb (Ra and Rb are hydrogen, C1 to C6 alkyl) and may be bonded to any carbon atom in the alkylene chain constituting R1 and R2; m is an integer of 1 to 2; n Is an integer from 1 to 4.)
(B) Aliphatic sulfide compound represented by the following formula (b) H- (OA) n-S- (OA) n-H (b)
(In the formula (b), A is ethylene or propylene (a hydroxyl group may be bonded to the carbon atom constituting the ethylene or propylene chain); n is an integer of 1 to 25.)
(C) one or more mono-, di- or trisulfide bonds in the molecule, or a group of atoms selected from aliphatic, alicyclic, aromatic and heterocyclic rings located on both wings of the bond The electrotin and tin alloy plating bath according to any one of claims 1 to 3, further comprising an aromatic sulfide compound having at least one basic nitrogen atom.   Furthermore, at least 1 type of additive chosen from surfactant, antioxidant, a brightener, a semi-gloss agent, and a pH adjuster is contained, The any one of Claims 1-4 characterized by the above-mentioned. Electric tin and tin alloy plating bath.   A method for forming an electrodeposit made of tin or a tin alloy using the electroplating bath according to any one of claims 1 to 5.   A glass substrate, a silicon substrate, a sapphire substrate, a wafer, a printed wiring board, a semiconductor integrated circuit, a resistor, a variable resistor, a capacitor, a filter, an inta, a thermistor, a crystal resonator, a switch, and a lead wire manufactured by the forming method according to claim 6. Electronic parts selected from solar cells.