WO2013046731A1 - Acidic aqueous composition for tin plating - Google Patents
Acidic aqueous composition for tin plating Download PDFInfo
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- WO2013046731A1 WO2013046731A1 PCT/JP2012/050775 JP2012050775W WO2013046731A1 WO 2013046731 A1 WO2013046731 A1 WO 2013046731A1 JP 2012050775 W JP2012050775 W JP 2012050775W WO 2013046731 A1 WO2013046731 A1 WO 2013046731A1
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- plating
- group
- tin
- aqueous composition
- acidic aqueous
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
- C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
- C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
Definitions
- the present invention relates to an acidic aqueous composition for tin-based plating, in particular, tin plating.
- tin-based plating is used as a general term for plating made of tin and plating made of tin alloy.
- the plating made of tin includes the case of containing metals other than tin at the impurity level, and is also referred to as "tin plating".
- Tin-based plating is widely used for contact parts and solder connection parts in electric / electronic parts such as semiconductor chip parts, quartz oscillators, capacitors, connector pins, lead frames, and printed circuit boards.
- bright plating is inherently suitable for the above applications because it has the advantage of being less prone to wrinkles and superior in solder wettability than matte plating.
- the deterioration of the appearance of the film is a phenomenon in which the thickness of the tin-based plating is locally varied by receiving the heat treatment.
- the unevenness of the plating caused by the fluctuation may give the appearance of a wavy or wood-like pattern.
- a base for plating such as nickel
- an intermetallic compound of tin and a base metal may be exposed. In this case, the solder wettability of the exposed portion is extremely reduced, and the electrical / electronic component in which such an exposed portion is generated may be a target for disposal.
- Patent Document 1 (a) a stannous salt and either a stannous salt and a salt of a metal selected from copper, bismuth, silver, indium, zinc, nickel, cobalt, and antimony.
- the above aliphatic sulfonic acid (b) is A purified aliphatic sulfonic acid in which a sulfur compound as an impurity other than a sulfonic acid is eliminated to zero concentration or reduced to a trace concentration, and the sulfur compound as the impurity has a sulfur atom undergoing oxidation in the molecule
- Patent Document 2 a) a step of plating a tin film on a substrate surface; b) the tin film on the substrate surface is selected from the group consisting of glycine and L-arginine before reflow treatment
- a method of surface treatment of a tin-plated film is proposed, which comprises the steps of: treating with an aqueous solution containing one or more amino acids; and c) reflowing the tin film.
- Patent Document 2 adds an additional step of treating with an aqueous solution containing a specific amino acid. This results in an increase in the cost of producing electrical and electronic components.
- the present invention can suppress the influence on the cost while suppressing the occurrence of the above-mentioned deterioration of the film appearance in the obtained plating, an acidic water-based composition for tin plating
- the task is to provide.
- One aspect of the present invention provided to solve the above problems is selected from the group consisting of a water-soluble stannous-containing substance, and a nonionic surfactant and an ionic surfactant having a polyoxyalkylene group. It contains one or more surfactants, a gloss component consisting of an aromatic carbonyl compound, and a gloss adjuvant consisting of a pyridine derivative in which at least one of the 2- and 4-positions is substituted by an electron-withdrawing group It is an acidic water system constituent for tin plating characterized by the above.
- the above-mentioned acidic water system composition may further contain one or two or more kinds of phenanthroline compounds.
- the electron withdrawing group may be one or more selected from the group consisting of a vinyl group, a carboxyl group and a pyridyl group.
- the above pyridine derivative may contain one or two of 4-vinylpyridine and 4-pyridinecarboxylic acid, and may contain 2,2'-bipyridine.
- an acidic water-based composition capable of forming tin plating in which the occurrence of the deterioration of the film appearance is suppressed while suppressing the influence on the cost.
- Acidic aqueous composition for tin plating provides, as one embodiment, one or a member selected from the group consisting of a water-soluble stannous-containing substance, a nonionic surfactant and an ionic surfactant having a polyoxyalkylene group.
- Tin plating containing two or more surfactants, a gloss component comprising an aromatic carbonyl compound, and a gloss adjuvant comprising a pyridine derivative in which at least one of the 2- and 4-positions is substituted by an electron-withdrawing group
- the term “surface having gloss” means that the center line average roughness (hereinafter abbreviated as “surface roughness”) Ra of 0.6 ⁇ m or less among the parameters relating to the surface roughness. Means If the surface roughness Ra is 0.5 ⁇ m or less, it can be said that the surface has excellent gloss.
- the maximum height Rmax which is one of the parameters of surface roughness
- the maximum height Rmax on the surface after reflow is greater than the thickness of tin plating. It can be said that it is a large surface. Describing this point in concrete terms, when the printed circuit board on which tin plating of about 3 ⁇ m thickness is formed is allowed to stand at 260 ° C. for 1 minute to reproduce the reflow, the above-mentioned appearance of the coating deteriorates. On the generated surface, the maximum height Rmax may be 10 to 40 ⁇ m.
- the acidic water-based composition for tin plating (hereinafter, also referred to as "plating solution") according to the present embodiment contains a water-soluble stannous-containing substance.
- the “water-soluble stannous-containing substance” refers to a substance consisting of one or more selected from the group consisting of a divalent cation of tin (Sn 2+ ) and a water-soluble substance containing the same.
- stannous sulfate As a source material for supplying a water-soluble stannous-containing substance to a plating solution (in the present embodiment, it is also referred to as a "stannic tin source"), stannous sulfate, stannous chloride, stannous borofluoride, etc.
- Inorganic based stannous acid stannous alkanol sulfonate such as stannous isethionate, stannous methane sulfonate, stannous alkane sulfonate such as stannous ethane sulfonate, stannous phenol sulfonate, Examples include stannous acid sulfonates such as stannous cresol sulfonate, stannous acid citrate such as stannous acid citrate and stannous acid acetate. These may be used alone or in combination of two or more.
- the tin equivalent content of the water-soluble stannous material in the plating solution according to the present embodiment is preferably 5 g / L or more and 200 g / L or less, and more preferably 30 g / L or more and 100 g / L or less . If the content of the water-soluble stannous material is excessively low, the tin plating can not be deposited. On the other hand, when the content of the water-soluble stannous material is excessively high, there is concern that the coverage of the plating may be reduced based on the increase in the viscosity of the plating solution.
- the blending amount of the first tin source becomes excessively high, the water-soluble stannous-containing substance dissolved in the plating solution in the plating solution and the stannous source in the solid state in the plating solution Will be included. At this time, the content of the water-soluble stannous-containing substance in the plating solution depends on the solubility of the stannous source.
- the plating solution according to the present embodiment contains one or more surfactants selected from the group consisting of nonionic surfactants and ionic surfactants having a polyoxyalkylene group. .
- nonionic surfactants include polyoxyalkylene alkyl phenol ether, polyoxyalkylene higher alcohol ether, polyoxyalkylene- ⁇ - or ⁇ -naphthol ether, polyoxyalkylene-mono-, di- or tri-styrenated phenol ether
- examples thereof include polyoxyethylene-polyoxypropylene-block polymer, polyoxyethylene-polyoxypropylene condensate of ethinone diamine, polyoxyalkylene addition alkylamine, and polyoxyalkylene addition alkylamide. These may be used alone or in combination of two or more.
- anionic surfactants such as alkyl phenoxy polyoxy alkylene ethyl sulfonic acid and its salt, higher alcohol polyoxy alkylene ethyl sulfonic acid and its salt, N, N- Cationic surfactants such as dipolyoxyalkylene-N, N-dialkylammonium hydrochloride are exemplified. These may be used alone or in combination of two or more.
- the content of the above surfactant is not limited. When the content is excessively small, it is difficult to obtain gloss in the obtained plating. On the other hand, when the content of the surfactant is excessively large, there is a concern that the foaming becomes active and the plating can not be performed unless the defoaming agent is used.
- a preferable example of the content of the above-mentioned surfactant is 0.5 g / L or more and 40 g / L or less.
- the plating solution according to the present embodiment may contain a surfactant other than the above-described surfactant.
- surfactants include cationic surfactants and amphoteric surfactants.
- cationic surfactants include N-monoalkyl-N-trimethylammonium salts, N, N-dialkyl-N-dimethylammonium salts, N-alkyl-isoquinolinium salts and 1-alkyl-1-hydroxyethyl -Imidazolium salts are mentioned.
- Specific examples of amphoteric surfactants include 1-hydroxyethyl-1-carboxyalkylene-2-alkylimidazolium betaine, and N, N-dimethyl-N-alkyl betaine.
- the total content of surfactants contained in the plating solution according to the present embodiment is not particularly limited, but is preferably in the range of 0.5 g / L to 80 g / L, preferably 1 g / L to 50 g / L. Is more preferable.
- the plating solution according to the present embodiment contains a gloss component composed of an aromatic carbonyl compound.
- an aromatic carbonyl compound an aromatic aldehyde, an aromatic ketone, etc. are illustrated.
- aromatic aldehydes include benzaldehyde, o-chlorobenzaldehyde, tolualdehyde, anisaldehyde, cinnamaldehyde, 2,5-dimethoxybenzaldehyde, and 1- or 2-naphthaldehyde.
- aromatic ketones benzylideneacetone and alkylnaphthyl ketones are exemplified.
- the content of the above gloss component is not limited. When the content of the gloss component is excessively small, it is not possible to provide gloss to the obtained plating. If the content of the gloss component is excessively large, it may be set appropriately in consideration of the decrease in the stability of the plating solution.
- the preferable range of the content is 0.005 g / L (5 ppm) or more and 5 g / L or less, and more preferably 0.01 g / L (10 ppm) or more and 2 g / L or less.
- the plating solution which concerns on this embodiment contains the gloss adjuvant which consists of a pyridine derivative with which at least one of the 2-position and 4-position was substituted by the electron withdrawing group.
- gloss adjuvants are also referred to as "pyridine gloss adjuvants".
- pyridine gloss adjuvants As an electron withdrawing group which gives a pyridine type glossiness adjuvant, halogen atoms, such as a vinyl group, a carboxyl group, a tosyl group, chlorine, a cyano group, a benzoyl group, an acetyl group, a pyridyl group, etc. are illustrated. Among these, vinyl and carboxyl are preferable electron-withdrawing groups.
- 4-vinylpyridine and 4-pyridinecarboxylic acid are particularly preferred pyridine-based gloss adjuvants.
- a pyridine type gloss adjuvant it is preferable to make content of a pyridine type gloss adjuvant into 0.005 g / L (5 ppm) or more and 0.2 g / L (200 ppm) or less. If the content of the pyridine-based gloss adjuvant is excessively small, there is a concern that the effect containing the same can not be obtained. On the other hand, when the content of the pyridine-based gloss adjuvant is excessively large, the balance with other additive components is lost, and a desired appearance (for example, gloss) can not be obtained, or the deposition rate of plating decreases. Are concerned.
- the plating solution according to the present embodiment contains a component for enhancing the conductivity of the plating solution (hereinafter, also referred to as "electrolyte component").
- electrolyte component a component for enhancing the conductivity of the plating solution.
- the type of electrolyte component is not particularly limited.
- Inorganic acids such as sulfuric acid, hydrochloric acid, boric acid and borohydrofluoric acid; alkanol sulfonic acids such as isethionic acid; alkane sulfonic acids such as methane sulfonic acid; sulfonic acids such as aromatic sulfonic acids such as phenol sulfonic acid; and acetic acid
- alkanol sulfonic acids such as isethionic acid
- alkane sulfonic acids such as methane sulfonic acid
- sulfonic acids such as aromatic sulfonic acids such as phenol sulfonic acid
- acetic acid examples thereof include acids such as carboxylic acids such as citric acid, malic acid and tartaric acid, and salts such as ammonium salts, sodium salts and potassium salts of these acids, and these may be used alone or a plurality of types may be used. May be Among these, sulfonic acids and / or
- the content of the electrolyte component is not limited, and should be appropriately set based on the current density in plating and the like. If an example of the range of the content is mentioned, it is 50 g / L or more and 300 g / L or less as free acid conversion content.
- the plating solution which concerns on this embodiment contains at least 1 type of phenanthroline type-compound in one preferable aspect.
- phenanthroline compound is used as a generic term for fused aromatic compounds in which two of the 14 carbons constituting the fused ring of phenanthrene are substituted with nitrogen and derivatives thereof.
- the obtained tin plating has a small surface roughness Ra immediately after plating. For this reason, it is suppressed that surface roughness Ra is increased until it generate
- phenanthroline compounds 1,10-phenanthroline, 2,9-dimethylphenanthroline, 3,4,7,8-tetramethylphenanthroline, 4,7-dihydroxyphenanthroline, 4,7-diphenyl-1,10 -Phenanthroline (vasophenanthroline), 4,7-diphenyl-2,9-dimethylphenanthroline (basokuproin), 4,7-diphenyl-1,10-phenanthroline disulfonic acid and its salt (bathophenanthroline disulfonic acid and its salt), And 4,7-diphenyl-2,9-dimethyl-1,10-phenanthroline-disulfonic acid and its salts (basokuproin disulfonic acid and its salts).
- the phenanthroline compound which the plating solution concerning this embodiment contains may be one type, and may be two or more types. Further, the content of the phenanthroline compound is not limited, but from the viewpoint of stably obtaining the effect, when it is contained, it is preferable to contain 0.0001 g / L or more (0.1 ppm), 0.001 g / L ( It is more preferable to contain 1 ppm or more. On the other hand, when the phenanthroline compound is excessively contained, the decrease in the deposition rate of the plating becomes remarkable, so the upper limit is preferably about 1 g / L, and more preferably 0.1 g / L or less.
- the plating solution according to the present embodiment may further contain an antioxidant and a defoaming agent, if necessary.
- An antioxidant is for suppressing that the tin primary ion in a plating solution is oxidized, and catechol, hydroquinone, etc. are illustrated.
- the content thereof is not limited, but a preferable example is 0.05 g / L or more and 20 g / L or less, and more preferably 0.1 g / L or more and 15 g / L or less.
- the solvent of the plating solution according to the present embodiment contains water as a main component.
- a solvent other than water an organic solvent having high solubility in water, such as alcohol, ether, or ketone may be mixed.
- the ratio is preferably 10% by volume or less with respect to the total solvent.
- the plating solution according to the present embodiment is acidic. In a preferred embodiment, it is strongly acidic and its pH is usually 1 or less.
- the plating solution can be set to a desired pH by adjusting the amount added as an acid when containing the above-mentioned electrolyte component.
- the plating conditions of the plating solution according to the present embodiment are not particularly limited. Preferred embodiments for each condition are as follows.
- the current density in applications of electric and electronic parts in which the occurrence of the above-mentioned appearance of the coating becomes a problem is usually 10 A / dm 2 or less, and often 7 A / dm 2 or less. From the viewpoint of stably imparting gloss to the obtained plating, it is preferably 3 A / dm 2 or more, and more preferably 5 A / dm 2 or more.
- the plating temperature is not particularly limited. Usually, it implements in 20 degreeC or more and 50 degrees C or less. Since a change in temperature may lead to a change in plating appearance, the control range of the plating temperature is preferably about 5 ° C.
- the integrated current amount is not particularly limited. If the accumulated current amount is excessively small, the base metal made of nickel or the like can not be sufficiently covered, and there is a concern that the solder wettability can not be improved. On the other hand, when the accumulated current amount is excessively large, it is disadvantageous from the economical point of view.
- the range of the integrated current amount should be appropriately set in consideration of these.
- Example 1 (1) Preparation of Plating Solution Plating solutions 1 to 7 shown in Table 1 were prepared.
- the plating substrate is an open frame printed circuit board in which an electric nickel plating (sulfamic acid bath, 1 ⁇ m) is formed on a wiring made of Cu 1020, which has been cleaned and activated by a known method.
- Current density 5, 10, 15A / dm 2
- Plating temperature 25 ° C (Control range: ⁇ 1 ° C)
- Integrated current 300 A ⁇ sec / dm 2
- Other plating conditions Stirring (rotation at 500 rpm with a stirrer), Rocking (5 m / min at cathode rocker)
- the surface roughness Ra of the plating surface at an arbitrary position of the printed circuit board after plating was measured.
- the measurement length was 1354 ⁇ m, and the average value of three measurement results was obtained.
- the measurement is performed so that the region is included in the measurement range as much as possible.
- the printed circuit board after reflow was observed.
- the plating was performed such that the area where the above-mentioned film appearance deterioration has occurred is included in the measurement range as much as possible.
- the surface roughness Ra at the part was measured.
- the measurement length was 1354 ⁇ m, and the average value of three measurement results was obtained.
- the obtained surface roughness Ra after reflow is judged as good (with gloss) when Ra is 0.6 ⁇ m or less at all current densities, and the result that the surface roughness Ra becomes more than 0.6 ⁇ m is at least When one was included, it was determined to be defective (no gloss). Further, among the results judged to be good based on the above criteria, the surface roughness Ra after plating and after reflow when the current density is 5 A / dm 2 in consideration of the recent plating conditions is 0. When it became 5 micrometers or less, it determined with especially favorable.
- Example 2 The plating solutions 8 to 10 shown in Table 3 were prepared. The plating treatment and the reflow test similar to Example 1 were performed using each of the obtained plating solutions 8 to 10, and the results were evaluated in the same manner as in Example 1.
- plating solution 1 The following matters were confirmed by comparison between plating solution 1 and plating solution 8. That is, the surface roughness Ra after plating decreases by containing the phenanthroline compound. As a result, the surface roughness Ra is sufficiently smaller than 0.5 ⁇ m even after reflow, and excellent gloss is obtained. Moreover, it was confirmed by comparison of the plating solution 1, the plating solution 9, and the plating solution 10 that generation
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Abstract
Provided is an acidic aqueous composition for tin plating, whereby it becomes possible to prevent the occurrence of the deterioration in coating film appearance in a plated product thereof while eliminating the influence on cost. The acidic aqueous composition for tin plating comprises: a water-soluble tin (II)-containing substance; at least one surfactant selected from the group consisting of a nonionic surfactant and an ionic surfactant having a polyoxyalkylene group; a glossy component comprising an aromatic carbonyl compound; and a glossy aid comprising a pyridine derivative in which position-2 and/or position-4 is substituted by an electron-withdrawing group.
Description
本発明は、スズ系めっき用、特にスズめっき用酸性水系組成物に関する。
本発明において、「スズ系めっき」なる用語は、スズからなるめっきおよびスズ合金からなるめっきの総称として用いられる。ここで、スズからなるめっきとはスズ以外の金属を不純物レベルで含有する場合も含むものとし、「スズめっき」ともいう。 The present invention relates to an acidic aqueous composition for tin-based plating, in particular, tin plating.
In the present invention, the term "tin-based plating" is used as a general term for plating made of tin and plating made of tin alloy. Here, the plating made of tin includes the case of containing metals other than tin at the impurity level, and is also referred to as "tin plating".
本発明において、「スズ系めっき」なる用語は、スズからなるめっきおよびスズ合金からなるめっきの総称として用いられる。ここで、スズからなるめっきとはスズ以外の金属を不純物レベルで含有する場合も含むものとし、「スズめっき」ともいう。 The present invention relates to an acidic aqueous composition for tin-based plating, in particular, tin plating.
In the present invention, the term "tin-based plating" is used as a general term for plating made of tin and plating made of tin alloy. Here, the plating made of tin includes the case of containing metals other than tin at the impurity level, and is also referred to as "tin plating".
スズ系めっきは、半導体チップ部品、水晶発振子、コンデンサ、コネクタピン、リードフレーム、プリント回路基板などの電気・電子部品における接点部やはんだ接続部に広く使用されている。スズ系めっきのうち、光沢めっきは、無光沢めっきに比べて、疵がつきにくい、はんだ濡れ性に優れるといった利点を有しているため、上記用途に本来適している。
Tin-based plating is widely used for contact parts and solder connection parts in electric / electronic parts such as semiconductor chip parts, quartz oscillators, capacitors, connector pins, lead frames, and printed circuit boards. Among tin-based plating, bright plating is inherently suitable for the above applications because it has the advantage of being less prone to wrinkles and superior in solder wettability than matte plating.
しかしながら、電気・電子部品は、その製造の過程でリフロー処理などの加熱処理を経る場合があるところ、従来技術に係る光沢めっきはこのような加熱処理を経るとめっきに皮膜外観の劣化が発生しやすいという問題点を有する。ここで、この皮膜外観の劣化は、加熱処理を受けることによってスズ系めっきの厚さが局所的に変動する現象である。その変動によって生じためっきの凹凸は波状や木目状の模様の外観をもたらすことがある。しかも、めっきの凹部においてはめっきの下地(ニッケルなど)やスズと下地金属との金属間化合物が露出する場合がある。この場合にはその露出部分のはんだ濡れ性が極端に低下してしまい、そのような露出部分が生じた電気・電子部品は廃棄対象となることもある。
However, while electric and electronic parts may undergo heat treatment such as reflow treatment in the process of their production, bright plating according to the prior art causes deterioration of the film appearance in the plating after such heat treatment. It has the problem of being easy. Here, the deterioration of the appearance of the film is a phenomenon in which the thickness of the tin-based plating is locally varied by receiving the heat treatment. The unevenness of the plating caused by the fluctuation may give the appearance of a wavy or wood-like pattern. In addition, in the plating recess, a base for plating (such as nickel) or an intermetallic compound of tin and a base metal may be exposed. In this case, the solder wettability of the exposed portion is extremely reduced, and the electrical / electronic component in which such an exposed portion is generated may be a target for disposal.
このようなはんだ濡れ性の低下ももたらす皮膜外観の劣化の発生を抑制するべく様々な技術が提案されている。
例えば、特許文献1には、(a)第一スズ塩と、第一スズ塩及び銅、ビスマス、銀、インジウム、亜鉛、ニッケル、コバルト、アンチモンから選ばれた金属の塩とのいずれかよりなる可溶性塩と、(b)アルカンスルホン酸、アルカノールスルホン酸よりなる群から選ばれた脂肪族スルホン酸の少なくとも一種を含有するスズ及びスズ合金メッキ浴において、上記脂肪族スルホン酸(b)が、同スルホン酸以外の不純物としてのイオウ化合物をゼロ濃度に排除するか、微量濃度にまで低減した精製脂肪族スルホン酸であって、上記不純物としてのイオウ化合物が、分子内に酸化途上のイオウ原子を有する化合物と、分子内にイオウ原子と塩素原子を併有する化合物との少なくとも一種である、スズ及びスズ合金の脂肪族スルホン酸メッキ浴が提案されている。 Various techniques have been proposed to suppress the occurrence of the deterioration of the film appearance which also causes such a decrease in solder wettability.
For example, according to Patent Document 1, (a) a stannous salt and either a stannous salt and a salt of a metal selected from copper, bismuth, silver, indium, zinc, nickel, cobalt, and antimony. In the tin and tin alloy plating bath containing a soluble salt and at least one aliphatic sulfonic acid selected from the group consisting of (b) alkanesulfonic acid and alkanolsulfonic acid, the above aliphatic sulfonic acid (b) is A purified aliphatic sulfonic acid in which a sulfur compound as an impurity other than a sulfonic acid is eliminated to zero concentration or reduced to a trace concentration, and the sulfur compound as the impurity has a sulfur atom undergoing oxidation in the molecule Aliphatic sulfonic acid plating baths of tin and tin alloys, which are at least one of a compound and a compound having both sulfur and chlorine atoms in the molecule It is draft.
例えば、特許文献1には、(a)第一スズ塩と、第一スズ塩及び銅、ビスマス、銀、インジウム、亜鉛、ニッケル、コバルト、アンチモンから選ばれた金属の塩とのいずれかよりなる可溶性塩と、(b)アルカンスルホン酸、アルカノールスルホン酸よりなる群から選ばれた脂肪族スルホン酸の少なくとも一種を含有するスズ及びスズ合金メッキ浴において、上記脂肪族スルホン酸(b)が、同スルホン酸以外の不純物としてのイオウ化合物をゼロ濃度に排除するか、微量濃度にまで低減した精製脂肪族スルホン酸であって、上記不純物としてのイオウ化合物が、分子内に酸化途上のイオウ原子を有する化合物と、分子内にイオウ原子と塩素原子を併有する化合物との少なくとも一種である、スズ及びスズ合金の脂肪族スルホン酸メッキ浴が提案されている。 Various techniques have been proposed to suppress the occurrence of the deterioration of the film appearance which also causes such a decrease in solder wettability.
For example, according to Patent Document 1, (a) a stannous salt and either a stannous salt and a salt of a metal selected from copper, bismuth, silver, indium, zinc, nickel, cobalt, and antimony. In the tin and tin alloy plating bath containing a soluble salt and at least one aliphatic sulfonic acid selected from the group consisting of (b) alkanesulfonic acid and alkanolsulfonic acid, the above aliphatic sulfonic acid (b) is A purified aliphatic sulfonic acid in which a sulfur compound as an impurity other than a sulfonic acid is eliminated to zero concentration or reduced to a trace concentration, and the sulfur compound as the impurity has a sulfur atom undergoing oxidation in the molecule Aliphatic sulfonic acid plating baths of tin and tin alloys, which are at least one of a compound and a compound having both sulfur and chlorine atoms in the molecule It is draft.
また、特許文献2には、a)基体表面上にスズ皮膜をめっきする工程;b)基体表面上の該スズ皮膜を、リフロー処理する前に、グリシンおよびL-アルギニンからなる群から選択される1以上のアミノ酸を含む水溶液で処理する工程;およびc)該スズ皮膜をリフロー処理する工程を含むスズめっき皮膜の表面処理方法が提案されている。
Further, in Patent Document 2, a) a step of plating a tin film on a substrate surface; b) the tin film on the substrate surface is selected from the group consisting of glycine and L-arginine before reflow treatment A method of surface treatment of a tin-plated film is proposed, which comprises the steps of: treating with an aqueous solution containing one or more amino acids; and c) reflowing the tin film.
しかしながら、特許文献1に開示されるめっき浴は、そのめっき浴に大量に含有される脂肪族スルホン酸を高度に精製しておく必要がある。このため、めっき浴の生産コストの大幅な上昇は避けられない。スズ系めっきは低コストであることが他のめっき、例えば金めっきなどの貴金属系めっきに対する有利な点であることから、スズ系めっきが高コストではその価値は著しく低下してしまう。
However, in the plating bath disclosed in Patent Document 1, it is necessary to highly refine aliphatic sulfonic acid contained in a large amount in the plating bath. For this reason, a significant increase in the production cost of the plating bath can not be avoided. Since tin-based plating is an advantage over other plating, for example, precious metal-based plating such as gold plating, tin-based plating is significantly reduced in value at high cost.
また、特許文献2に開示される方法は、特定のアミノ酸を含有する水溶液で処理する工程が追加されることになる。このため、電気・電子部品の生産コストの上昇をもたらしてしまう。
In addition, the method disclosed in Patent Document 2 adds an additional step of treating with an aqueous solution containing a specific amino acid. This results in an increase in the cost of producing electrical and electronic components.
このため、コストに与える影響を小さくしつつ、上記の皮膜外観の劣化の発生を抑制する手段が望まれている。
For this reason, a means to suppress generation | occurrence | production of said film appearance deterioration is desired, making the influence which it has on cost small.
本発明は、このような技術背景を鑑み、コストに与える影響を抑制しつつ、得られためっきにおける上記の皮膜外観の劣化の発生を抑制することが可能な、スズめっき用酸性水系組成物を提供することを課題とする。
In view of such technical background, the present invention can suppress the influence on the cost while suppressing the occurrence of the above-mentioned deterioration of the film appearance in the obtained plating, an acidic water-based composition for tin plating The task is to provide.
上記課題を解決するために提供される本発明の一態様は、水溶性第一スズ含有物質と、非イオン性界面活性剤およびポリオキシアルキレン基を有するイオン性界面活性剤からなる群から選ばれる一種または二種以上の界面活性剤と、芳香族カルボニル化合物からなる光沢成分と、2位および4位の少なくとも一つが電子求引性基により置換されたピリジン誘導体からなる光沢補助剤とを含有することを特徴とするスズめっき用酸性水系組成物である。
One aspect of the present invention provided to solve the above problems is selected from the group consisting of a water-soluble stannous-containing substance, and a nonionic surfactant and an ionic surfactant having a polyoxyalkylene group. It contains one or more surfactants, a gloss component consisting of an aromatic carbonyl compound, and a gloss adjuvant consisting of a pyridine derivative in which at least one of the 2- and 4-positions is substituted by an electron-withdrawing group It is an acidic water system constituent for tin plating characterized by the above.
上記の酸性水系組成物は、フェナントロリン系化合物の一種または二種以上をさらに含んでいてもよい。
The above-mentioned acidic water system composition may further contain one or two or more kinds of phenanthroline compounds.
上記の電子求引性基がビニル基、カルボキシル基およびピリジル基からなる群から選ばれる一種または二種以上であってもよい。
The electron withdrawing group may be one or more selected from the group consisting of a vinyl group, a carboxyl group and a pyridyl group.
上記のピリジン誘導体は、4-ビニルピリジンおよび4-ピリジンカルボン酸の一種または二種を含んでもよいし、2,2’-ビピリジンを含んでもよい。
The above pyridine derivative may contain one or two of 4-vinylpyridine and 4-pyridinecarboxylic acid, and may contain 2,2'-bipyridine.
上記の発明によれば、コストに与える影響を抑制しつつ、上記の皮膜外観の劣化の発生が抑制されたスズめっきを形成可能な酸性水系組成物を提供することが実現される。
According to the above invention, it is realized to provide an acidic water-based composition capable of forming tin plating in which the occurrence of the deterioration of the film appearance is suppressed while suppressing the influence on the cost.
1.スズめっき用酸性水系組成物
本発明は一実施形態として、水溶性第一スズ含有物質と、非イオン性界面活性剤およびポリオキシアルキレン基を有するイオン性界面活性剤からなる群から選ばれる一種または二種以上の界面活性剤と、芳香族カルボニル化合物からなる光沢成分と、2位および4位の少なくとも一つが電子求引性基により置換されたピリジン誘導体からなる光沢補助剤とを含有するスズめっき用酸性水系組成物を提供する。かかる組成物を用いて適切な条件においてめっきを行えば、上記の皮膜外観の劣化の発生が抑制された光沢外観を有するスズめっきが得られる。 1. Acidic aqueous composition for tin plating The present invention provides, as one embodiment, one or a member selected from the group consisting of a water-soluble stannous-containing substance, a nonionic surfactant and an ionic surfactant having a polyoxyalkylene group. Tin plating containing two or more surfactants, a gloss component comprising an aromatic carbonyl compound, and a gloss adjuvant comprising a pyridine derivative in which at least one of the 2- and 4-positions is substituted by an electron-withdrawing group An acidic aqueous composition for use in When plating is performed under appropriate conditions using such a composition, tin plating having a glossy appearance with the occurrence of the above-mentioned deterioration of the film appearance being suppressed can be obtained.
本発明は一実施形態として、水溶性第一スズ含有物質と、非イオン性界面活性剤およびポリオキシアルキレン基を有するイオン性界面活性剤からなる群から選ばれる一種または二種以上の界面活性剤と、芳香族カルボニル化合物からなる光沢成分と、2位および4位の少なくとも一つが電子求引性基により置換されたピリジン誘導体からなる光沢補助剤とを含有するスズめっき用酸性水系組成物を提供する。かかる組成物を用いて適切な条件においてめっきを行えば、上記の皮膜外観の劣化の発生が抑制された光沢外観を有するスズめっきが得られる。 1. Acidic aqueous composition for tin plating The present invention provides, as one embodiment, one or a member selected from the group consisting of a water-soluble stannous-containing substance, a nonionic surfactant and an ionic surfactant having a polyoxyalkylene group. Tin plating containing two or more surfactants, a gloss component comprising an aromatic carbonyl compound, and a gloss adjuvant comprising a pyridine derivative in which at least one of the 2- and 4-positions is substituted by an electron-withdrawing group An acidic aqueous composition for use in When plating is performed under appropriate conditions using such a composition, tin plating having a glossy appearance with the occurrence of the above-mentioned deterioration of the film appearance being suppressed can be obtained.
本実施形態において、「光沢」を有する表面とは、表面粗さに係るパラメータのうち、中心線平均粗さ(以下、「表面粗さ」と略称する。)Raが0.6μm以下であることを意味する。表面粗さRaが0.5μm以下であれば優れた光沢を有する表面といえる。
In the present embodiment, the term “surface having gloss” means that the center line average roughness (hereinafter abbreviated as “surface roughness”) Ra of 0.6 μm or less among the parameters relating to the surface roughness. Means If the surface roughness Ra is 0.5 μm or less, it can be said that the surface has excellent gloss.
また、表面粗さのパラメータの一つである最大高さRmaxを用いて上記の皮膜外観の劣化が発生した表面を表現すれば、リフロー後の表面における最大高さRmaxがスズめっきの厚さよりも大きい表面であるといえる。この点を具体的に数値で説明すれば、3μm程度の厚さのスズめっきが形成されたプリント基板を260℃で1分間静置してリフローを再現したときに、上記の皮膜外観の劣化が発生した表面では、最大高さRmaxが10~40μmとなる場合もある。
In addition, if the surface where the above-mentioned film appearance deterioration occurs is expressed using the maximum height Rmax which is one of the parameters of surface roughness, the maximum height Rmax on the surface after reflow is greater than the thickness of tin plating. It can be said that it is a large surface. Describing this point in concrete terms, when the printed circuit board on which tin plating of about 3 μm thickness is formed is allowed to stand at 260 ° C. for 1 minute to reproduce the reflow, the above-mentioned appearance of the coating deteriorates. On the generated surface, the maximum height Rmax may be 10 to 40 μm.
(1)水溶性第一スズ含有物質
本実施形態に係るスズめっき用酸性水系組成物(以下、「めっき液」ともいう。)は水溶性第一スズ含有物質を含む。「水溶性第一スズ含有物質」とは、スズの二価の陽イオン(Sn2+)およびこれを含有する水溶性物質からなる群から選ばれる一種または二種以上からなる物質をいう。 (1) Water-soluble stannous-containing substance The acidic water-based composition for tin plating (hereinafter, also referred to as "plating solution") according to the present embodiment contains a water-soluble stannous-containing substance. The “water-soluble stannous-containing substance” refers to a substance consisting of one or more selected from the group consisting of a divalent cation of tin (Sn 2+ ) and a water-soluble substance containing the same.
本実施形態に係るスズめっき用酸性水系組成物(以下、「めっき液」ともいう。)は水溶性第一スズ含有物質を含む。「水溶性第一スズ含有物質」とは、スズの二価の陽イオン(Sn2+)およびこれを含有する水溶性物質からなる群から選ばれる一種または二種以上からなる物質をいう。 (1) Water-soluble stannous-containing substance The acidic water-based composition for tin plating (hereinafter, also referred to as "plating solution") according to the present embodiment contains a water-soluble stannous-containing substance. The “water-soluble stannous-containing substance” refers to a substance consisting of one or more selected from the group consisting of a divalent cation of tin (Sn 2+ ) and a water-soluble substance containing the same.
水溶性第一スズ含有物質をめっき液に供給する原料物質(本実施形態において、「第一スズ源」ともいう。)として、硫酸第一スズ、塩化第一スズ、ホウフッ化第一スズ等の無機系酸第一スズ;イセチオン酸第一スズなどのアルカノールスルホン酸第一スズ、メタンスルホン酸第一スズ、エタンスルホン酸第一スズ等のアルカンスルホン酸第一スズ;フェノールスルホン酸第一スズ、クレゾールスルホン酸第一スズ等の芳香族系スルホン酸第一スズ、クエン酸第一スズ、酢酸第一スズ等のカルボン酸第一スズなどが例示される。これらは単独で用いてもよいし、複数種類を組み合わせて用いてもよい。
As a source material for supplying a water-soluble stannous-containing substance to a plating solution (in the present embodiment, it is also referred to as a "stannic tin source"), stannous sulfate, stannous chloride, stannous borofluoride, etc. Inorganic based stannous acid: stannous alkanol sulfonate such as stannous isethionate, stannous methane sulfonate, stannous alkane sulfonate such as stannous ethane sulfonate, stannous phenol sulfonate, Examples include stannous acid sulfonates such as stannous cresol sulfonate, stannous acid citrate such as stannous acid citrate and stannous acid acetate. These may be used alone or in combination of two or more.
本実施形態に係るめっき液における水溶性第一スズ含有物質のスズ換算含有量は、5g/L以上200g/L以下とすることが好ましく、30g/L以上100g/L以下とすることがさらに好ましい。水溶性第一スズ含有物質の含有量が過度に低い場合にはスズめっきを析出させることができなくなる。一方、水溶性第一スズ含有物質の含有量が過度に高い場合には、めっき液の粘度が高くなったことに基づいてめっきの付きまわり性が低下することが懸念される。なお、第一スズ源の配合量が過度に高くなると、めっき液中にはめっき液に溶解した状態にある水溶性第一スズ含有物質とめっき液中で固体の状態にある第一スズ源とが含まれることとなる。このとき、水溶性第一スズ含有物質のめっき液中の含有量は第一スズ源の溶解度に依存する。
The tin equivalent content of the water-soluble stannous material in the plating solution according to the present embodiment is preferably 5 g / L or more and 200 g / L or less, and more preferably 30 g / L or more and 100 g / L or less . If the content of the water-soluble stannous material is excessively low, the tin plating can not be deposited. On the other hand, when the content of the water-soluble stannous material is excessively high, there is concern that the coverage of the plating may be reduced based on the increase in the viscosity of the plating solution. If the blending amount of the first tin source becomes excessively high, the water-soluble stannous-containing substance dissolved in the plating solution in the plating solution and the stannous source in the solid state in the plating solution Will be included. At this time, the content of the water-soluble stannous-containing substance in the plating solution depends on the solubility of the stannous source.
(2)界面活性剤
本実施形態に係るめっき液は、非イオン性界面活性剤およびポリオキシアルキレン基を有するイオン性界面活性剤からなる群から選ばれる一種または二種以上の界面活性剤を含む。 (2) Surfactant The plating solution according to the present embodiment contains one or more surfactants selected from the group consisting of nonionic surfactants and ionic surfactants having a polyoxyalkylene group. .
本実施形態に係るめっき液は、非イオン性界面活性剤およびポリオキシアルキレン基を有するイオン性界面活性剤からなる群から選ばれる一種または二種以上の界面活性剤を含む。 (2) Surfactant The plating solution according to the present embodiment contains one or more surfactants selected from the group consisting of nonionic surfactants and ionic surfactants having a polyoxyalkylene group. .
非イオン性界面活性剤としては、ポリオキシアルキレンアルキルフェノールエーテル、ポリオキシアルキレン高級アルコールエーテル、ポリオキシアルキレン-α-またはβ-ナフトールエーテル、ポリオキシアルキレン-モノ-、ジ-またはトリ-スチレン化フェノールエーテル、ポリオキシエチレン-ポリオキシプロピレン-ブロックポリマー、エチノンジアミンのポリオキシエチレン-ポリオキシプロピレン縮合物、ポリオキシアルキレン付加アルキルアミン、ポリオキシアルキレン付加アルキルアミド等が例示される。これらは単独で用いてもよいし、複数種類を組み合わせて用いてもよい。
Examples of nonionic surfactants include polyoxyalkylene alkyl phenol ether, polyoxyalkylene higher alcohol ether, polyoxyalkylene-α- or β-naphthol ether, polyoxyalkylene-mono-, di- or tri-styrenated phenol ether Examples thereof include polyoxyethylene-polyoxypropylene-block polymer, polyoxyethylene-polyoxypropylene condensate of ethinone diamine, polyoxyalkylene addition alkylamine, and polyoxyalkylene addition alkylamide. These may be used alone or in combination of two or more.
ポリオキシアルキレン基を有するイオン性界面活性剤としては、アルキルフェノキシポリオキシアルキレンエチルスルホン酸およびその塩、高級アルコールのポリオキシアルキレンエチルスルホン酸およびその塩等のアニオン性界面活性剤、N,N-ジポリオキシアルキレン-N,N-ジアルキルアンモニウム塩酸塩等のカチオン性界面活性剤が例示される。これらは単独で用いてもよいし、複数種類を組み合わせて用いてもよい。
As the ionic surfactant having a polyoxyalkylene group, anionic surfactants such as alkyl phenoxy polyoxy alkylene ethyl sulfonic acid and its salt, higher alcohol polyoxy alkylene ethyl sulfonic acid and its salt, N, N- Cationic surfactants such as dipolyoxyalkylene-N, N-dialkylammonium hydrochloride are exemplified. These may be used alone or in combination of two or more.
上記の界面活性剤の含有量は限定されない。当該含有量が過度に少ない場合には得られためっきに光沢が得られにくくなる。一方、界面活性剤の含有量が過度に多い場合には発泡が盛んになって消泡剤を用いなければめっきを行うことが不可能になることが懸念される。上記の界面活性剤の含有量の好ましい一例を挙げれば、0.5g/L以上40g/L以下である。
The content of the above surfactant is not limited. When the content is excessively small, it is difficult to obtain gloss in the obtained plating. On the other hand, when the content of the surfactant is excessively large, there is a concern that the foaming becomes active and the plating can not be performed unless the defoaming agent is used. A preferable example of the content of the above-mentioned surfactant is 0.5 g / L or more and 40 g / L or less.
本実施形態に係るめっき液は上記の界面活性剤以外の界面活性剤を含有してもよい。そのような界面活性剤として、カチオン性界面活性剤、両性界面活性剤が例示される。カチオン性界面活性剤の具体例として、N-モノアルキル-N-トリメチルアンモニウム塩、N,N-ジアルキル-N-ジメチルアンモノウム塩、N-アルキル-イソキノリニウム塩および1-アルキル-1-ヒドロキシエチル-イミダゾリウム塩が挙げられる。両性界面活性剤の具体例として、1-ヒドロキシエチル-1-カルボキシアルキレン-2-アルキルイミダゾリウムベタイン、およびN,N-ジメチル-N-アルキルベタインが挙げられる。
The plating solution according to the present embodiment may contain a surfactant other than the above-described surfactant. Examples of such surfactants include cationic surfactants and amphoteric surfactants. Specific examples of cationic surfactants include N-monoalkyl-N-trimethylammonium salts, N, N-dialkyl-N-dimethylammonium salts, N-alkyl-isoquinolinium salts and 1-alkyl-1-hydroxyethyl -Imidazolium salts are mentioned. Specific examples of amphoteric surfactants include 1-hydroxyethyl-1-carboxyalkylene-2-alkylimidazolium betaine, and N, N-dimethyl-N-alkyl betaine.
本実施形態に係るめっき液が含有する界面活性剤の合計含有量は特に限定されないが、0.5g/L以上80g/L以下の範囲で用いられることが好ましく、1g/L以上50g/L以下であればさらに好ましい。
The total content of surfactants contained in the plating solution according to the present embodiment is not particularly limited, but is preferably in the range of 0.5 g / L to 80 g / L, preferably 1 g / L to 50 g / L. Is more preferable.
(3)光沢成分
本実施形態に係るめっき液は芳香族カルボニル化合物からなる光沢成分を含有する。
芳香族カルボニル化合物としては、芳香族アルデヒド、芳香族ケトンなどが例示される。 (3) Gloss Component The plating solution according to the present embodiment contains a gloss component composed of an aromatic carbonyl compound.
As an aromatic carbonyl compound, an aromatic aldehyde, an aromatic ketone, etc. are illustrated.
本実施形態に係るめっき液は芳香族カルボニル化合物からなる光沢成分を含有する。
芳香族カルボニル化合物としては、芳香族アルデヒド、芳香族ケトンなどが例示される。 (3) Gloss Component The plating solution according to the present embodiment contains a gloss component composed of an aromatic carbonyl compound.
As an aromatic carbonyl compound, an aromatic aldehyde, an aromatic ketone, etc. are illustrated.
芳香族アルデヒドの具体例として、ベンズアルデヒド、o-クロルベンズアルデヒド、トルアルデヒド、アニスアルデヒド、シンナムアルデヒド、2,5-ジメトキシベンズアルデヒド、および1-または2-ナフトアルデヒドが例示される。芳香族ケトンの具体例として、ベンジリデンアセトンおよびアルキルナフチルケトンが例示される。
Specific examples of aromatic aldehydes include benzaldehyde, o-chlorobenzaldehyde, tolualdehyde, anisaldehyde, cinnamaldehyde, 2,5-dimethoxybenzaldehyde, and 1- or 2-naphthaldehyde. As specific examples of aromatic ketones, benzylideneacetone and alkylnaphthyl ketones are exemplified.
上記の光沢成分の含有量は限定されない。光沢成分の含有量が過度に少ない場合には得られるめっきに光沢を付与することができなくなる。光沢成分の含有量が過度に多い場合にはめっき液の安定性が低下することを考慮して適宜設定すればよい。好ましい含有量の範囲は0.005g/L(5ppm)以上5g/L以下であり、0.01g/L(10ppm)以上2g/L以下とすればさらに好ましい。
The content of the above gloss component is not limited. When the content of the gloss component is excessively small, it is not possible to provide gloss to the obtained plating. If the content of the gloss component is excessively large, it may be set appropriately in consideration of the decrease in the stability of the plating solution. The preferable range of the content is 0.005 g / L (5 ppm) or more and 5 g / L or less, and more preferably 0.01 g / L (10 ppm) or more and 2 g / L or less.
(4)光沢補助剤
本実施形態に係るめっき液は、2位および4位の少なくとも一つが電子求引性基により置換されたピリジン誘導体からなる光沢補助剤を含有する。以下、かかる光沢補助剤を「ピリジン系光沢補助剤」ともいう。ピリジン系光沢補助剤を与える電子求引性基として、ビニル基、カルボキシル基、トシル基、塩素などのハロゲン原子、シアノ基、ベンゾイル基、アセチル基、ピリジル基などが例示される。これらの中でも、ビニル基およびカルボキシル基が好ましい電子求引性基である。したがって、4-ビニルピリジンおよび4-ピリジンカルボン酸が特に好ましいピリジン系光沢補助剤である。 (4) Gloss adjuvant The plating solution which concerns on this embodiment contains the gloss adjuvant which consists of a pyridine derivative with which at least one of the 2-position and 4-position was substituted by the electron withdrawing group. Hereinafter, such gloss adjuvants are also referred to as "pyridine gloss adjuvants". As an electron withdrawing group which gives a pyridine type glossiness adjuvant, halogen atoms, such as a vinyl group, a carboxyl group, a tosyl group, chlorine, a cyano group, a benzoyl group, an acetyl group, a pyridyl group, etc. are illustrated. Among these, vinyl and carboxyl are preferable electron-withdrawing groups. Thus, 4-vinylpyridine and 4-pyridinecarboxylic acid are particularly preferred pyridine-based gloss adjuvants.
本実施形態に係るめっき液は、2位および4位の少なくとも一つが電子求引性基により置換されたピリジン誘導体からなる光沢補助剤を含有する。以下、かかる光沢補助剤を「ピリジン系光沢補助剤」ともいう。ピリジン系光沢補助剤を与える電子求引性基として、ビニル基、カルボキシル基、トシル基、塩素などのハロゲン原子、シアノ基、ベンゾイル基、アセチル基、ピリジル基などが例示される。これらの中でも、ビニル基およびカルボキシル基が好ましい電子求引性基である。したがって、4-ビニルピリジンおよび4-ピリジンカルボン酸が特に好ましいピリジン系光沢補助剤である。 (4) Gloss adjuvant The plating solution which concerns on this embodiment contains the gloss adjuvant which consists of a pyridine derivative with which at least one of the 2-position and 4-position was substituted by the electron withdrawing group. Hereinafter, such gloss adjuvants are also referred to as "pyridine gloss adjuvants". As an electron withdrawing group which gives a pyridine type glossiness adjuvant, halogen atoms, such as a vinyl group, a carboxyl group, a tosyl group, chlorine, a cyano group, a benzoyl group, an acetyl group, a pyridyl group, etc. are illustrated. Among these, vinyl and carboxyl are preferable electron-withdrawing groups. Thus, 4-vinylpyridine and 4-pyridinecarboxylic acid are particularly preferred pyridine-based gloss adjuvants.
ピリジン系光沢補助剤の含有量は、0.005g/L(5ppm)以上0.2g/L(200ppm)以下とすることが好ましい。ピリジン系光沢補助剤の含有量が過度に少ない場合にはこれを含有させた効果を得ることができなくなることが懸念される。一方、ピリジン系光沢補助剤の含有量が過度に多い場合には他の添加成分とのバランスが崩れ、所望の外観(例えば光沢)が得られなくなったり、めっきの析出速度が低下したりすることが懸念される。
It is preferable to make content of a pyridine type gloss adjuvant into 0.005 g / L (5 ppm) or more and 0.2 g / L (200 ppm) or less. If the content of the pyridine-based gloss adjuvant is excessively small, there is a concern that the effect containing the same can not be obtained. On the other hand, when the content of the pyridine-based gloss adjuvant is excessively large, the balance with other additive components is lost, and a desired appearance (for example, gloss) can not be obtained, or the deposition rate of plating decreases. Are concerned.
(5)その他の成分
本実施形態に係るめっき液は、上記の成分に加えて、めっき液の導電性を高めるための成分(以下、「電解質成分」ともいう。)を含有する。電解質成分の種類は特に限定されない。硫酸、塩酸、ホウ酸、ホウフッ化水素酸等の無機酸;イセチオン酸等のアルカノールスルホン酸、メタンスルホン酸等のアルカンスルホン酸、フェノールスルホン酸等の芳香族系スルホン酸などのスルホン酸;および酢酸、クエン酸、リンゴ酸、酒石酸等のカルボン酸などの酸ならびにこれら酸のアンモニウム塩、ナトリウム塩、カリウム塩等の塩が例示され、これらは単独で用いられてもよいし、複数種類が用いられてもよい。これらの中でもスルホン酸および/またはスルホン酸塩が好ましい。 (5) Other components In addition to the above components, the plating solution according to the present embodiment contains a component for enhancing the conductivity of the plating solution (hereinafter, also referred to as "electrolyte component"). The type of electrolyte component is not particularly limited. Inorganic acids such as sulfuric acid, hydrochloric acid, boric acid and borohydrofluoric acid; alkanol sulfonic acids such as isethionic acid; alkane sulfonic acids such as methane sulfonic acid; sulfonic acids such as aromatic sulfonic acids such as phenol sulfonic acid; and acetic acid Examples thereof include acids such as carboxylic acids such as citric acid, malic acid and tartaric acid, and salts such as ammonium salts, sodium salts and potassium salts of these acids, and these may be used alone or a plurality of types may be used. May be Among these, sulfonic acids and / or sulfonates are preferred.
本実施形態に係るめっき液は、上記の成分に加えて、めっき液の導電性を高めるための成分(以下、「電解質成分」ともいう。)を含有する。電解質成分の種類は特に限定されない。硫酸、塩酸、ホウ酸、ホウフッ化水素酸等の無機酸;イセチオン酸等のアルカノールスルホン酸、メタンスルホン酸等のアルカンスルホン酸、フェノールスルホン酸等の芳香族系スルホン酸などのスルホン酸;および酢酸、クエン酸、リンゴ酸、酒石酸等のカルボン酸などの酸ならびにこれら酸のアンモニウム塩、ナトリウム塩、カリウム塩等の塩が例示され、これらは単独で用いられてもよいし、複数種類が用いられてもよい。これらの中でもスルホン酸および/またはスルホン酸塩が好ましい。 (5) Other components In addition to the above components, the plating solution according to the present embodiment contains a component for enhancing the conductivity of the plating solution (hereinafter, also referred to as "electrolyte component"). The type of electrolyte component is not particularly limited. Inorganic acids such as sulfuric acid, hydrochloric acid, boric acid and borohydrofluoric acid; alkanol sulfonic acids such as isethionic acid; alkane sulfonic acids such as methane sulfonic acid; sulfonic acids such as aromatic sulfonic acids such as phenol sulfonic acid; and acetic acid Examples thereof include acids such as carboxylic acids such as citric acid, malic acid and tartaric acid, and salts such as ammonium salts, sodium salts and potassium salts of these acids, and these may be used alone or a plurality of types may be used. May be Among these, sulfonic acids and / or sulfonates are preferred.
電解質成分の含有量は限定されず、めっきにおける電流密度などに基づいて適宜設定されるべきものである。その含有量の範囲の一例を挙げれば、遊離酸換算含有量として50g/L以上300g/L以下である。
The content of the electrolyte component is not limited, and should be appropriately set based on the current density in plating and the like. If an example of the range of the content is mentioned, it is 50 g / L or more and 300 g / L or less as free acid conversion content.
また、本実施形態に係るめっき液は、好ましい一態様において、少なくとも一種のフェナントロリン系化合物を含有する。「フェナントロリン化合物」なる用語は、フェナントレンの縮合環を構成する14個の炭素のうち2つを窒素で置換した縮合芳香族化合物およびその誘導体の総称として用いられる。フェナントロリン化合物を含有することにより、得られたスズめっきはめっき直後の表面粗さRaが小さくなる。このため、リフロー後に上記の皮膜外観の劣化の発生に至るまで表面粗さRaが増大することが抑制される。
Moreover, the plating solution which concerns on this embodiment contains at least 1 type of phenanthroline type-compound in one preferable aspect. The term "phenanthroline compound" is used as a generic term for fused aromatic compounds in which two of the 14 carbons constituting the fused ring of phenanthrene are substituted with nitrogen and derivatives thereof. By containing the phenanthroline compound, the obtained tin plating has a small surface roughness Ra immediately after plating. For this reason, it is suppressed that surface roughness Ra is increased until it generate | occur | produces deterioration of said film | membrane external appearance after reflow.
フェナントロリン化合物の具体例を示せば、1,10‐フェナントロリン、2,9‐ジメチルフェナントロリン、3,4,7,8‐テトラメチルフェナントロリン、4,7‐ジヒドロキシフェナントロリン、4,7‐ジフェニル‐1,10‐フェナントロリン(バソフェナントロリン)、4,7‐ジフェニル‐2,9‐ジメチルフェナントロリン(バソクプロイン)、4,7‐ジフェニル‐1,10‐フェナントロリン‐ジスルホン酸およびその塩(バソフェナントロリンジスルホン酸およびその塩)、ならびに4,7‐ジフェニル‐2,9‐ジメチル‐1,10‐フェナントロリン‐ジスルホン酸およびその塩(バソクプロインジスルホン酸及びその塩)が挙げられる。
As specific examples of phenanthroline compounds, 1,10-phenanthroline, 2,9-dimethylphenanthroline, 3,4,7,8-tetramethylphenanthroline, 4,7-dihydroxyphenanthroline, 4,7-diphenyl-1,10 -Phenanthroline (vasophenanthroline), 4,7-diphenyl-2,9-dimethylphenanthroline (basokuproin), 4,7-diphenyl-1,10-phenanthroline disulfonic acid and its salt (bathophenanthroline disulfonic acid and its salt), And 4,7-diphenyl-2,9-dimethyl-1,10-phenanthroline-disulfonic acid and its salts (basokuproin disulfonic acid and its salts).
本実施形態に係るめっき液が含有するフェナントロリン化合物は一種であってもよいし、二種以上であってもよい。また、フェナントロリン化合物の含有量は限定されないが、その効果を安定的に得る観点から、含有させる場合には0.0001g/L以上(0.1ppm)含有させることが好ましく、0.001g/L(1ppm)以上含有させることがさらに好ましい。一方、フェナントロリン化合物を過度に含有させるとめっきの析出速度の低下が顕著となるため、1g/L程度を上限とすることが好ましく、0.1g/L以下とすることがさらに好ましい。
The phenanthroline compound which the plating solution concerning this embodiment contains may be one type, and may be two or more types. Further, the content of the phenanthroline compound is not limited, but from the viewpoint of stably obtaining the effect, when it is contained, it is preferable to contain 0.0001 g / L or more (0.1 ppm), 0.001 g / L ( It is more preferable to contain 1 ppm or more. On the other hand, when the phenanthroline compound is excessively contained, the decrease in the deposition rate of the plating becomes remarkable, so the upper limit is preferably about 1 g / L, and more preferably 0.1 g / L or less.
本実施形態に係るめっき液は、必要に応じて、酸化防止剤や消泡剤をさらに含有してもよい。酸化防止剤はめっき液中のスズ第一イオンが酸化されることを抑制するためのものであり、カテコール、ハイドロキノンなどが例示される。その含有量は限定されないが、好ましい一例を挙げれば0.05g/L以上20g/L以下であり、0.1g/L以上15g/L以下とすればさらに好ましい。
The plating solution according to the present embodiment may further contain an antioxidant and a defoaming agent, if necessary. An antioxidant is for suppressing that the tin primary ion in a plating solution is oxidized, and catechol, hydroquinone, etc. are illustrated. The content thereof is not limited, but a preferable example is 0.05 g / L or more and 20 g / L or less, and more preferably 0.1 g / L or more and 15 g / L or less.
(6)溶媒、pH
本実施形態に係るめっき液の溶媒は水を主成分とする。水以外の溶媒としてアルコール、エーテル、ケトンなど水への溶解度が高い有機溶媒を混在させてもよい。この場合には、めっき液全体の安定性および廃液処理への負荷の緩和の観点から、その比率は全溶媒に対して10体積%以下とすることが好ましい。 (6) Solvent, pH
The solvent of the plating solution according to the present embodiment contains water as a main component. As a solvent other than water, an organic solvent having high solubility in water, such as alcohol, ether, or ketone may be mixed. In this case, from the viewpoint of the stability of the entire plating solution and the reduction of the load on waste liquid treatment, the ratio is preferably 10% by volume or less with respect to the total solvent.
本実施形態に係るめっき液の溶媒は水を主成分とする。水以外の溶媒としてアルコール、エーテル、ケトンなど水への溶解度が高い有機溶媒を混在させてもよい。この場合には、めっき液全体の安定性および廃液処理への負荷の緩和の観点から、その比率は全溶媒に対して10体積%以下とすることが好ましい。 (6) Solvent, pH
The solvent of the plating solution according to the present embodiment contains water as a main component. As a solvent other than water, an organic solvent having high solubility in water, such as alcohol, ether, or ketone may be mixed. In this case, from the viewpoint of the stability of the entire plating solution and the reduction of the load on waste liquid treatment, the ratio is preferably 10% by volume or less with respect to the total solvent.
本実施形態に係るめっき液は酸性である。好ましい一態様においては強酸性であり、そのpHは通常1以下である。前述の電解質成分を含有させるにあたり、酸として加える量を調整することによって、めっき液を所望のpHに設定することができる。
The plating solution according to the present embodiment is acidic. In a preferred embodiment, it is strongly acidic and its pH is usually 1 or less. The plating solution can be set to a desired pH by adjusting the amount added as an acid when containing the above-mentioned electrolyte component.
2.めっき条件
本実施形態に係るめっき液のめっき条件は特に限定されない。各条件についての好ましい態様は次のとおりである。 2. Plating Conditions The plating conditions of the plating solution according to the present embodiment are not particularly limited. Preferred embodiments for each condition are as follows.
本実施形態に係るめっき液のめっき条件は特に限定されない。各条件についての好ましい態様は次のとおりである。 2. Plating Conditions The plating conditions of the plating solution according to the present embodiment are not particularly limited. Preferred embodiments for each condition are as follows.
(1)電流密度
上記の皮膜外観の劣化の発生が問題となるような電気・電子部品用途における電流密度は通常10A/dm2以下であり、7A/dm2以下とされる場合が多い。得られためっきに光沢を安定的に付与する観点からは、3A/dm2以上とすることが好ましく、5A/dm2以上とすればさらに好ましい。 (1) Current Density The current density in applications of electric and electronic parts in which the occurrence of the above-mentioned appearance of the coating becomes a problem is usually 10 A / dm 2 or less, and often 7 A / dm 2 or less. From the viewpoint of stably imparting gloss to the obtained plating, it is preferably 3 A / dm 2 or more, and more preferably 5 A / dm 2 or more.
上記の皮膜外観の劣化の発生が問題となるような電気・電子部品用途における電流密度は通常10A/dm2以下であり、7A/dm2以下とされる場合が多い。得られためっきに光沢を安定的に付与する観点からは、3A/dm2以上とすることが好ましく、5A/dm2以上とすればさらに好ましい。 (1) Current Density The current density in applications of electric and electronic parts in which the occurrence of the above-mentioned appearance of the coating becomes a problem is usually 10 A / dm 2 or less, and often 7 A / dm 2 or less. From the viewpoint of stably imparting gloss to the obtained plating, it is preferably 3 A / dm 2 or more, and more preferably 5 A / dm 2 or more.
(2)めっき温度
めっき温度は特に限定されない。通常、20℃以上50℃以下の範囲で実施される。温度の変動はめっき外観の変化をもたらす場合があるため、めっき温度の管理幅は5℃程度とすることが好ましい。 (2) Plating temperature The plating temperature is not particularly limited. Usually, it implements in 20 degreeC or more and 50 degrees C or less. Since a change in temperature may lead to a change in plating appearance, the control range of the plating temperature is preferably about 5 ° C.
めっき温度は特に限定されない。通常、20℃以上50℃以下の範囲で実施される。温度の変動はめっき外観の変化をもたらす場合があるため、めっき温度の管理幅は5℃程度とすることが好ましい。 (2) Plating temperature The plating temperature is not particularly limited. Usually, it implements in 20 degreeC or more and 50 degrees C or less. Since a change in temperature may lead to a change in plating appearance, the control range of the plating temperature is preferably about 5 ° C.
(3)積算電流量
積算電流量は特に限定されない。積算電流量が過度に少ない場合にはニッケルなどからなる下地金属を十分に覆うことができず、はんだ濡れ性を向上させることができなくなることが懸念される。一方、積算電流量が過度に多い場合には経済的な観点から不利となる。積算電流量の範囲は、これらを考慮して適宜設定されるべきものである。 (3) Integrated current amount The integrated current amount is not particularly limited. If the accumulated current amount is excessively small, the base metal made of nickel or the like can not be sufficiently covered, and there is a concern that the solder wettability can not be improved. On the other hand, when the accumulated current amount is excessively large, it is disadvantageous from the economical point of view. The range of the integrated current amount should be appropriately set in consideration of these.
積算電流量は特に限定されない。積算電流量が過度に少ない場合にはニッケルなどからなる下地金属を十分に覆うことができず、はんだ濡れ性を向上させることができなくなることが懸念される。一方、積算電流量が過度に多い場合には経済的な観点から不利となる。積算電流量の範囲は、これらを考慮して適宜設定されるべきものである。 (3) Integrated current amount The integrated current amount is not particularly limited. If the accumulated current amount is excessively small, the base metal made of nickel or the like can not be sufficiently covered, and there is a concern that the solder wettability can not be improved. On the other hand, when the accumulated current amount is excessively large, it is disadvantageous from the economical point of view. The range of the integrated current amount should be appropriately set in consideration of these.
以下、本発明の効果を実施例に基づいて説明するが、本発明はこれに限定されるものではない。
Hereinafter, although the effect of the present invention is explained based on an example, the present invention is not limited to this.
(実施例1)
(1)めっき液の調製
表1に示されるめっき液1~7を調製した。 Example 1
(1) Preparation of Plating Solution Plating solutions 1 to 7 shown in Table 1 were prepared.
(1)めっき液の調製
表1に示されるめっき液1~7を調製した。 Example 1
(1) Preparation of Plating Solution Plating solutions 1 to 7 shown in Table 1 were prepared.
(2)めっき処理
得られためっき液1~7のそれぞれを用いて、下記のめっき条件にてめっきを行った。なお、めっきの基板は、Cu1020からなる配線上に電気ニッケルめっき(スルファミン酸浴、1μm)が形成されたオープンフレームのプリント基板であって、公知の方法で洗浄・活性化を行ったものとした。
電流密度:5、10、15A/dm2
めっき温度:25℃ (管理幅:±1℃)
積算電流量:300A・sec/dm2
その他のめっき条件:攪拌あり(攪拌子にて500rpmで回転)、揺動あり(カソードロッカにて5m/分) (2) Plating treatment Plating was performed using the obtained plating solutions 1 to 7 under the following plating conditions. The plating substrate is an open frame printed circuit board in which an electric nickel plating (sulfamic acid bath, 1 μm) is formed on a wiring made of Cu 1020, which has been cleaned and activated by a known method. .
Current density: 5, 10, 15A / dm 2
Plating temperature: 25 ° C (Control range: ± 1 ° C)
Integrated current: 300 A · sec / dm 2
Other plating conditions: Stirring (rotation at 500 rpm with a stirrer), Rocking (5 m / min at cathode rocker)
得られためっき液1~7のそれぞれを用いて、下記のめっき条件にてめっきを行った。なお、めっきの基板は、Cu1020からなる配線上に電気ニッケルめっき(スルファミン酸浴、1μm)が形成されたオープンフレームのプリント基板であって、公知の方法で洗浄・活性化を行ったものとした。
電流密度:5、10、15A/dm2
めっき温度:25℃ (管理幅:±1℃)
積算電流量:300A・sec/dm2
その他のめっき条件:攪拌あり(攪拌子にて500rpmで回転)、揺動あり(カソードロッカにて5m/分) (2) Plating treatment Plating was performed using the obtained plating solutions 1 to 7 under the following plating conditions. The plating substrate is an open frame printed circuit board in which an electric nickel plating (sulfamic acid bath, 1 μm) is formed on a wiring made of Cu 1020, which has been cleaned and activated by a known method. .
Current density: 5, 10, 15A / dm 2
Plating temperature: 25 ° C (Control range: ± 1 ° C)
Integrated current: 300 A · sec / dm 2
Other plating conditions: Stirring (rotation at 500 rpm with a stirrer), Rocking (5 m / min at cathode rocker)
(3)リフロー試験
上記のめっき処理により得られたスズめっきが形成されたプリント基板を、260℃に保持されたホットプレート上に1分間静置して、リフローさせた。 (3) Reflow Test The printed circuit board on which the tin plating obtained by the above-mentioned plating treatment was formed was allowed to stand on a hot plate maintained at 260 ° C. for 1 minute to be reflowed.
上記のめっき処理により得られたスズめっきが形成されたプリント基板を、260℃に保持されたホットプレート上に1分間静置して、リフローさせた。 (3) Reflow Test The printed circuit board on which the tin plating obtained by the above-mentioned plating treatment was formed was allowed to stand on a hot plate maintained at 260 ° C. for 1 minute to be reflowed.
(4)評価
めっき後のプリント基板の任意の位置におけるめっき面の表面粗さRaを測定した。測定長さは1354μmであり、3箇所の測定結果の平均値を求めた。なお、電流密度が大きい場合などにおいて表面が粗面化している領域がある場合には、その領域が可能な限り測定範囲内に含まれるようにして測定を行った。
また、リフロー後のプリント基板を観察した。観察の結果、上記の皮膜外観の劣化が発生している場合には、上記の皮膜外観の劣化が発生している領域が可能な限り測定範囲内に含まれるようにして、めっきが施された部分における表面粗さRaを測定した。測定長さは1354μmであり、3箇所の測定結果の平均値を求めた。
得られたリフロー後の表面粗さRaについて、全ての電流密度においてRaが0.6μm以下の場合には良好(光沢あり)と判定し、表面粗さRaが0.6μm超となる結果を少なくとも一つ含む場合には不良(光沢なし)と判定した。また、上記の基準に基づき良好と判定された結果のうち、近時のめっき条件を考慮して、電流密度を5A/dm2としたときにおけるめっき後およびリフロー後の表面粗さRaが0.5μm以下となる場合には、特に良好と判定した。 (4) Evaluation The surface roughness Ra of the plating surface at an arbitrary position of the printed circuit board after plating was measured. The measurement length was 1354 μm, and the average value of three measurement results was obtained. In the case where there is a region where the surface is roughened, for example, when the current density is large, the measurement is performed so that the region is included in the measurement range as much as possible.
Moreover, the printed circuit board after reflow was observed. As a result of observation, in the case where the above-mentioned deterioration of the film appearance has occurred, the plating was performed such that the area where the above-mentioned film appearance deterioration has occurred is included in the measurement range as much as possible. The surface roughness Ra at the part was measured. The measurement length was 1354 μm, and the average value of three measurement results was obtained.
The obtained surface roughness Ra after reflow is judged as good (with gloss) when Ra is 0.6 μm or less at all current densities, and the result that the surface roughness Ra becomes more than 0.6 μm is at least When one was included, it was determined to be defective (no gloss). Further, among the results judged to be good based on the above criteria, the surface roughness Ra after plating and after reflow when the current density is 5 A / dm 2 in consideration of the recent plating conditions is 0. When it became 5 micrometers or less, it determined with especially favorable.
めっき後のプリント基板の任意の位置におけるめっき面の表面粗さRaを測定した。測定長さは1354μmであり、3箇所の測定結果の平均値を求めた。なお、電流密度が大きい場合などにおいて表面が粗面化している領域がある場合には、その領域が可能な限り測定範囲内に含まれるようにして測定を行った。
また、リフロー後のプリント基板を観察した。観察の結果、上記の皮膜外観の劣化が発生している場合には、上記の皮膜外観の劣化が発生している領域が可能な限り測定範囲内に含まれるようにして、めっきが施された部分における表面粗さRaを測定した。測定長さは1354μmであり、3箇所の測定結果の平均値を求めた。
得られたリフロー後の表面粗さRaについて、全ての電流密度においてRaが0.6μm以下の場合には良好(光沢あり)と判定し、表面粗さRaが0.6μm超となる結果を少なくとも一つ含む場合には不良(光沢なし)と判定した。また、上記の基準に基づき良好と判定された結果のうち、近時のめっき条件を考慮して、電流密度を5A/dm2としたときにおけるめっき後およびリフロー後の表面粗さRaが0.5μm以下となる場合には、特に良好と判定した。 (4) Evaluation The surface roughness Ra of the plating surface at an arbitrary position of the printed circuit board after plating was measured. The measurement length was 1354 μm, and the average value of three measurement results was obtained. In the case where there is a region where the surface is roughened, for example, when the current density is large, the measurement is performed so that the region is included in the measurement range as much as possible.
Moreover, the printed circuit board after reflow was observed. As a result of observation, in the case where the above-mentioned deterioration of the film appearance has occurred, the plating was performed such that the area where the above-mentioned film appearance deterioration has occurred is included in the measurement range as much as possible. The surface roughness Ra at the part was measured. The measurement length was 1354 μm, and the average value of three measurement results was obtained.
The obtained surface roughness Ra after reflow is judged as good (with gloss) when Ra is 0.6 μm or less at all current densities, and the result that the surface roughness Ra becomes more than 0.6 μm is at least When one was included, it was determined to be defective (no gloss). Further, among the results judged to be good based on the above criteria, the surface roughness Ra after plating and after reflow when the current density is 5 A / dm 2 in consideration of the recent plating conditions is 0. When it became 5 micrometers or less, it determined with especially favorable.
表2に示されるように、めっき液1から3については、少なくともリフロー後の表面粗さRaは電流密度にかかわらず0.6μm以下の光沢となり、上記の皮膜外観の劣化が発生しなかった。特に、めっき液1および2については、5A/dm2のときの表面粗さRaが0.5μm以下となった。
一方、めっき液4から6については、リフロー後の表面粗さRaは0.6μmを超える場合があり、上記の皮膜外観の劣化が発生した。 As shown in Table 2, with respect to plating solutions 1 to 3, at least the surface roughness Ra after reflow was 0.6 μm or less regardless of the current density, and the above-mentioned appearance of the film did not deteriorate. In particular, for plating solutions 1 and 2, the surface roughness Ra at 5 A / dm 2 was 0.5 μm or less.
On the other hand, for the plating solutions 4 to 6, the surface roughness Ra after reflow may exceed 0.6 μm in some cases, and the above-mentioned deterioration of the film appearance occurred.
一方、めっき液4から6については、リフロー後の表面粗さRaは0.6μmを超える場合があり、上記の皮膜外観の劣化が発生した。 As shown in Table 2, with respect to plating solutions 1 to 3, at least the surface roughness Ra after reflow was 0.6 μm or less regardless of the current density, and the above-mentioned appearance of the film did not deteriorate. In particular, for plating solutions 1 and 2, the surface roughness Ra at 5 A / dm 2 was 0.5 μm or less.
On the other hand, for the plating solutions 4 to 6, the surface roughness Ra after reflow may exceed 0.6 μm in some cases, and the above-mentioned deterioration of the film appearance occurred.
(実施例2)
表3に示されるめっき液8~10を調製した。得られためっき液8~10のそれぞれを用いて、実施例1と同様のめっき処理およびリフロー試験を行い、それらの結果を実施例1の場合と同様の方法で評価した。 (Example 2)
The plating solutions 8 to 10 shown in Table 3 were prepared. The plating treatment and the reflow test similar to Example 1 were performed using each of the obtained plating solutions 8 to 10, and the results were evaluated in the same manner as in Example 1.
表3に示されるめっき液8~10を調製した。得られためっき液8~10のそれぞれを用いて、実施例1と同様のめっき処理およびリフロー試験を行い、それらの結果を実施例1の場合と同様の方法で評価した。 (Example 2)
The plating solutions 8 to 10 shown in Table 3 were prepared. The plating treatment and the reflow test similar to Example 1 were performed using each of the obtained plating solutions 8 to 10, and the results were evaluated in the same manner as in Example 1.
めっき液1とめっき液8との対比により次の事項が確認された。すなわち、フェナントロリン化合物を含有させることによってめっき後の表面粗さRaが小さくなる。その結果、リフロー後においても表面粗さRaは0.5μmよりも十分に小さくなって、優れた光沢が得られる。
また、めっき液1、めっき液9およびめっき液10の対比により、ピリジン系光沢補助剤の含有量を100ppmとしても十分に上記の皮膜外観の劣化の発生を抑制できることが確認された。 The following matters were confirmed by comparison between plating solution 1 and plating solution 8. That is, the surface roughness Ra after plating decreases by containing the phenanthroline compound. As a result, the surface roughness Ra is sufficiently smaller than 0.5 μm even after reflow, and excellent gloss is obtained.
Moreover, it was confirmed by comparison of the plating solution 1, the plating solution 9, and the plating solution 10 that generation | occurrence | production of deterioration of said film | membrane external appearance can fully be suppressed, even if content of a pyridine type glossiness adjuvant is 100 ppm.
また、めっき液1、めっき液9およびめっき液10の対比により、ピリジン系光沢補助剤の含有量を100ppmとしても十分に上記の皮膜外観の劣化の発生を抑制できることが確認された。 The following matters were confirmed by comparison between plating solution 1 and plating solution 8. That is, the surface roughness Ra after plating decreases by containing the phenanthroline compound. As a result, the surface roughness Ra is sufficiently smaller than 0.5 μm even after reflow, and excellent gloss is obtained.
Moreover, it was confirmed by comparison of the plating solution 1, the plating solution 9, and the plating solution 10 that generation | occurrence | production of deterioration of said film | membrane external appearance can fully be suppressed, even if content of a pyridine type glossiness adjuvant is 100 ppm.
Claims (5)
- 水溶性第一スズ含有物質と、
非イオン性界面活性剤およびポリオキシアルキレン基を有するイオン性界面活性剤からなる群から選ばれる一種または二種以上の界面活性剤と、
芳香族カルボニル化合物からなる光沢成分と、
2位および4位の少なくとも一つが電子求引性基により置換されたピリジン誘導体からなる光沢補助剤とを含有すること
を特徴とするスズめっき用酸性水系組成物。 A water-soluble stannous-containing substance,
One or more surfactants selected from the group consisting of nonionic surfactants and ionic surfactants having a polyoxyalkylene group,
A gloss component comprising an aromatic carbonyl compound,
An acidic aqueous composition for tin plating comprising: a gloss auxiliary comprising a pyridine derivative in which at least one of 2- and 4-positions is substituted by an electron-withdrawing group. - フェナントロリン系化合物の一種または二種以上を含む請求項1記載のめっき用酸性水系組成物。 The acidic aqueous composition for plating according to claim 1, which contains one or more of phenanthroline compounds.
- 前記電子求引性基がビニル基、カルボキシル基およびピリジル基からなる群から選ばれる一種または二種以上である、請求項1または2記載のめっき用酸性水系組成物。 The acidic aqueous composition for plating according to claim 1 or 2, wherein the electron withdrawing group is one or more selected from the group consisting of a vinyl group, a carboxyl group and a pyridyl group.
- 前記ピリジン誘導体は、4-ビニルピリジンおよび4-ピリジンカルボン酸の一種または二種を含む請求項1または2記載のめっき用酸性水系組成物。 The acidic aqueous composition for plating according to claim 1 or 2, wherein the pyridine derivative contains one or two of 4-vinylpyridine and 4-pyridinecarboxylic acid.
- 前記ピリジン誘導体が2,2’-ビピリジンを含む請求項1または2記載のめっき用酸性水系組成物。 The acidic aqueous composition for plating according to claim 1 or 2, wherein the pyridine derivative comprises 2,2'-bipyridine.
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WO2019181906A1 (en) * | 2018-03-20 | 2019-09-26 | 三菱マテリアル株式会社 | Tin or tin-alloy plating solution and bump forming method |
JP2019173162A (en) * | 2018-03-26 | 2019-10-10 | 三菱マテリアル株式会社 | Tin or tin alloy plating solution and method of forming bumps using the solution |
US11053600B2 (en) | 2018-03-20 | 2021-07-06 | Mitsubishi Materials Corporation | Tin or tin alloy plating solution and bump forming method |
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US20150122661A1 (en) * | 2013-11-05 | 2015-05-07 | Rohm And Haas Electronic Materials Llc | Plating bath and method |
US20150122662A1 (en) * | 2013-11-05 | 2015-05-07 | Rohm And Haas Electronic Materials Llc | Plating bath and method |
US9809892B1 (en) * | 2016-07-18 | 2017-11-07 | Rohm And Haas Electronic Materials Llc | Indium electroplating compositions containing 1,10-phenanthroline compounds and methods of electroplating indium |
CN111206272B (en) * | 2020-02-25 | 2021-08-10 | 广州三孚新材料科技股份有限公司 | Plating solution additive and plating solution for electroplating matte tin on heterojunction cell, and preparation method and application of plating solution additive and plating solution |
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