[go: up one dir, main page]

EP3178969B1 - Bain de placage d'alliage de cuivre-étain - Google Patents

Bain de placage d'alliage de cuivre-étain Download PDF

Info

Publication number
EP3178969B1
EP3178969B1 EP15829133.6A EP15829133A EP3178969B1 EP 3178969 B1 EP3178969 B1 EP 3178969B1 EP 15829133 A EP15829133 A EP 15829133A EP 3178969 B1 EP3178969 B1 EP 3178969B1
Authority
EP
European Patent Office
Prior art keywords
copper
compound
plating
amount
tin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP15829133.6A
Other languages
German (de)
English (en)
Other versions
EP3178969A4 (fr
EP3178969A1 (fr
Inventor
Takamitsu TSUJIMOTO
Toshimitsu Nagao
Kenji Hara
Junichi Katayama
Kuniaki Otsuka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Okuno Chemical Industries Co Ltd
Original Assignee
Okuno Chemical Industries Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Okuno Chemical Industries Co Ltd filed Critical Okuno Chemical Industries Co Ltd
Publication of EP3178969A1 publication Critical patent/EP3178969A1/fr
Publication of EP3178969A4 publication Critical patent/EP3178969A4/fr
Application granted granted Critical
Publication of EP3178969B1 publication Critical patent/EP3178969B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin

Definitions

  • the present invention relates to a copper-tin alloy plating bath.
  • Nickel plating has been widely used in electroplating. However, there are indications that nickel plating has a nickel allergy problem such that the metallic element (nickel) contained in the plating film causes skin rashes or inflammation. There is thus a need for a technique that replaces nickel plating.
  • copper-tin alloys are known to have a white appearance and film properties that are comparable to those of nickel. For this reason, copper-tin alloy plating is drawing attention as an alternative to nickel plating.
  • Cyanide ion-containing plating baths have been used for copper-tin alloy plating, but are problematic in terms of the work environment and wastewater treatment regulations.
  • pyrophosphate baths e.g., Patent Literature 1 to 3
  • acidic baths e.g., Patent Literature 4 and 5
  • non-cyanide cyanide-ion-free
  • copper-tin alloy baths copper-tin alloy baths.
  • a pyrophosphate bath compared with the case in which a cyanide bath is used, the formed plating film has high internal stress, and therefore, cracks are generated during plating, thus making it difficult to thicken the plating film.
  • US 2005/263403 A1 discloses a method for electrodeposition of bronzes, with which the substrate to be coated is plated in an acid electrolyte that contains at least tin and copper ions, an alkylsulfonic acid and a wetting agent, and the preparation of such an electrolyte.
  • US 2004/035714 A1 relates to an electrolyte and a method for depositing tin-copper alloy layers.
  • EP 1 591 563 A1 describes a tin-containing plating bath.
  • a primary object of the present invention is to provide a copper-tin alloy plating bath that allows for film thickening without using cyanide ions, and that can also be applied to barrel plating.
  • the present inventors conducted extensive research to achieve the above object, and found that a copper-tin alloy plating bath that allows for film thickening without using cyanide ions and that can also be applied to barrel plating can be obtained by using a specific sulfur-containing compound and a specific hydroxyl group-containing aromatic compound.
  • the present invention has been accomplished through further research based on this finding.
  • the copper-tin alloy plating bath of the present invention since, regarding the copper-tin alloy plating bath of the present invention, the current density has a small influence on the alloy ratio compared with the case in which hitherto known acidic baths are used, the copper-tin alloy plating bath of the present invention can also be applied to barrel plating with a large variation in the current density. Moreover, a plating film having an excellent bright appearance can be obtained by a nonionic surfactant, and an aromatic ketone or an aromatic aldehyde comprised in the aqueous solution of the copper-tin alloy plating bath.
  • Fig. 1 is a diagram showing the relationship between the current density of a copper-tin alloy plating bath and the copper content of a plating film.
  • the copper-tin alloy plating bath of the present invention is described in detail below.
  • the copper-tin alloy plating bath of the present invention comprises an aqueous solution containing a water-soluble copper compound and a water-soluble divalent tin compound as metal sources, a sulfur-containing compound represented by formula (1): R-(CH 2 ) l -S-(CH 2 ) m -S-(CH 2 ) n -R (1), wherein R is H, OH, or SO 3 Na, and l, m, and n are each independently an integer of 0 to 3, as a complexing agent, and a hydroxyl group-containing aromatic compound.
  • the water-soluble copper compound which is a copper ion source, is not particularly limited as long as it is a water-soluble compound containing divalent copper as a copper component.
  • Specific examples of water-soluble copper compounds include copper(II) chloride, copper(II) sulfate, copper(II) nitrate, copper(II) carbonate, copper(II) oxide, copper(II) acetate, copper(II) methanesulfonate, copper(II) sulfamate, copper(II) fluoride, copper(II) 2-hydroxyethanesulfonate, copper(II) 2-hydroxypropanesulfonate, copper(II) pyrophosphate, and the like.
  • copper(II) sulfate is preferable.
  • These water-soluble copper compounds can generally be used singly, or in a combination of two or more.
  • the concentration of the water-soluble copper compound is such that the copper ion concentration is 1 to 60 g/L, and preferably 10 to 40 g/L.
  • the water-soluble divalent tin compound which is a tin ion source, is not particularly limited as long as it is a water-soluble compound containing divalent tin as a tin component.
  • Specific examples of water-soluble divalent tin compounds include stannous chloride, stannous sulfate, stannous acetate, stannous pyrophosphate, stannous methanesulfonate, stannous sulfamate, stannous gluconate, stannous tartrate, stannous oxide, stannous fluoroborate, stannous 2-hydroxyethanesulfonate, stannous 2-hydroxypropanesulfonate, and the like.
  • stannous sulfate is preferable.
  • These water-soluble divalent tin compounds can generally be used singly, or in a combination of two or more.
  • the concentration of the water-soluble divalent tin compound is such that the divalent tin ion concentration is 5 to 40 g/L, and preferably 5 to 25 g/L.
  • the proportions of the water-soluble copper compound and the water-soluble divalent tin compound are preferably such that the copper:tin ratio (metal component molar ratio) is 1:0.1 to 0.6, and more preferably such that the copper:tin ratio (metal component molar ratio) is 1:0.1 to 0.3.
  • a significant feature of the present invention is that a sulfur-containing compound represented by formula (1): R-(CH 2 ) l -S-(CH 2 ) m -S-(CH 2 ) n -R (1), wherein R is H, OH, or SO 3 Na, and l, m, and n are each independently an integer of 0 to 3 is used as a complexing agent.
  • Specific examples of sulfur-containing compounds represented by formula (1) include methanedithiol, 1,2-ethanedithiol, 1,3-propanedithiol, 3,6-dithia-1,8-octanediol, bis-(sodium sulfopropyl)-disulfide, and the like.
  • 3,6-dithia-1,8-octanediol and bis-(sodium sulfopropyl)-disulfide, both of which have little odor, are preferable from the viewpoint of the work environment, and 3,6-dithia-1,8-octanediol is more preferable.
  • These sulfur-containing compounds can generally be used singly, or in a combination of two or more.
  • the concentration of the complexing agent is 5 to 500 g/L, and preferably 80 to 320 g/L.
  • a hydroxyl group-containing aromatic compound is used.
  • hydroxyl group-containing aromatic compounds include compounds in which a benzene ring or a furan ring is substituted with one or more hydroxyl groups.
  • Compounds having a benzene ring are preferable from the viewpoint of the work environment and solution stability.
  • Specific examples of hydroxyl group-containing aromatic compounds include phenol, catechol, hydroquinone, resorcinol, pyrogallol, p -cresolsulfonic acid, ascorbic acid, erythorbic acid; alkali metal salts thereof; and the like.
  • alkali metals include sodium, potassium, and the like.
  • Preferred hydroxyl group-containing aromatic compounds are phenol, catechol, hydroquinone, resorcinol, pyrogallol, p -cresolsulfonic acid, sodium ascorbate, and sodium erythorbate. These hydroxyl group-containing aromatic compounds are considered to have the action of reducing divalent copper ions (Cu 2+ ) to monovalent copper ions (Cu 1+ ), and are considered to aid copper ions and the complexing agent in forming a complex. These hydroxyl group-containing aromatic compounds can generally be used singly, or in a combination of two or more. The concentration of the hydroxyl group-containing aromatic compound is 1 to 50 g/L, and preferably 5 to 30 g/L.
  • the amounts of the complexing agent and the hydroxyl group-containing aromatic compound are such that relative to 1 mol/L of copper, the amount of the complexing agent is preferably 2 mol/L or more, and the amount of the hydroxyl group-containing aromatic compound is preferably 1 mol/L or more.
  • acids constituting the base of the copper-tin alloy plating bath include a wide variety of known organic acids and inorganic acids.
  • organic acids include methanesulfonic acid, ethanesulfonic acid, 2-propanolsulfonic acid, 2-sulfoacetic acid, 2-sulfopropionic acid, 3-sulfopropionic acid, sulfosuccinic acid, sulfomethylsuccinic acid, sulfofumaric acid, sulfomaleic acid, 2-sulfobenzoic acid, 3-sulfobenzoic acid, 4-sulfobenzoic acid, 5-sulfosalicylic acid, 4-sulfophthalic acid, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, phenolsulfonic acid, and the like.
  • inorganic acids include sulfuric acid, hydrochloric acid, sulfamic acid, and the like.
  • sulfuric acid, methanesulfonic acid, sulfosuccinic acid, and the like are preferable.
  • These acids can generally be used singly, or in a combination of two or more.
  • the concentration of the acid is 10 to 400 g/L, and preferably 150 to 200 g/L.
  • the copper-tin alloy plating bath is generally in a weakly acidic to strongly acidic pH range. More specifically, the pH of the solution of the plating bath is adjusted to 4.5 or less. An overly high pH is not preferable because if the pH is overly high, the obtained plating film will have insufficient smoothness.
  • Examples of usable pH adjusting agents include various acids, such as hydrochloric acid and sulfuric acid; various bases, such as ammonium hydroxide, sodium hydroxide, and potassium hydroxide; and the like.
  • a pH buffer may be added to reduce variation in the pH of the plating bath. As the pH buffer, a known pH buffer can be used.
  • pH buffers include sodium or potassium acetate, sodium, potassium, or ammonium borate, sodium or potassium formate, sodium or potassium tartrate, sodium, potassium, or ammonium dihydrogen phosphate, and the like. These pH adjusting agents and pH buffers can generally be used singly, or in a combination of two or more.
  • the plating bath contains a surfactant, and a leveler. Further, the plating bath may contain additives, such as high molecular compounds, if necessary.
  • high molecular compounds examples include polyethylene glycol and the like.
  • the surfactant is at least one nonionic surfactant selected from the group consisting of polyoxyethylene alkylamines, polyoxyalkylene phenyl ethers, and polyoxyalkylene naphthyl ethers.
  • the concentration of the high molecular compound can be in the range of 0.01 to 100 g/L, and preferably 0.1 to 40 g/L.
  • the surfactant is present in an amount of 0.1 to 40 g/L.
  • Levelers are additives that improve smoothness and brightness.
  • the leveler is at least one aromatic ketone or aromatic aldehyde selected from the group consisting of benzalacetone, cinnamaldehyde, ⁇ -methylcinnamaldehyde, ⁇ -hexylcinnamaldehyde, ⁇ -amylcinnamaldehyde, cuminaldehyde, benzaldehyde, and anisaldehyde.
  • aromatic ketone or aromatic aldehyde selected from the group consisting of benzalacetone, cinnamaldehyde, ⁇ -methylcinnamaldehyde, ⁇ -hexylcinnamaldehyde, ⁇ -amylcinnamaldehyde, cuminaldehyde, benzaldehyde, and anisaldehyde.
  • the leveler is present in the plating bath in a concentration of 0.01 to 10 g/L.
  • a surfactant and a leveler are used in combination.
  • the combined use of a surfactant and a leveler can expand the current-density region in which a bright plating film is obtained. This enables a plating film obtained from the plating bath of the present invention to have more excellent smoothness and higher brightness.
  • a combination of a surfactant and a leveler a combination of a nonionic surfactant, and an aromatic ketone or an aromatic aldehyde is used.
  • the nonionic surfactant is preferably a polyoxyethylene alkylamine.
  • a plating film having excellent bright appearance can be obtained by the nonionic surfactant, and the aromatic ketone or the aromatic aldehyde comprised in the aqueous solution of the plating bath.
  • a surfactant and a leveler are used in combination, wherein the concentration of the surfactant is 0.1 to 40 g/L, the concentration of the leveler is 0.01 to 10 g/L, and the surfactant:leveler ratio is 1:1 to 100:1.
  • Additives other than the additives mentioned above such as stress-reducing agents, conductive auxiliary agents, antifoaming agents, and brighteners, may be suitably selected and added to the plating bath, if necessary.
  • stress-reducing agents include naphtholsulfonic acid, saccharin, sodium 1,5-naphthalenedisulfonate, and the like. These can be used singly, or in a combination of two or more.
  • conductive auxiliary agents include hydrochloric acid, sulfuric acid, acetic acid, nitric acid, sulfamic acid, pyrophosphoric acid, boric acid, and like acids; ammonium salts, sodium salts, potassium salts, and organic amine salts thereof; and the like. These can be used singly, or in a combination of two or more.
  • antifoaming agents and brighteners commercially available antifoaming agents and brighteners for copper plating, tin plating, copper-tin alloy plating, and general plating can be suitably selected and used.
  • the bath preparation method for the plating bath of the present invention is not particularly limited.
  • the target plating solution can be obtained by dissolving a water-soluble copper compound and a water-soluble divalent tin compound in an aqueous solution in which an acid such as sulfuric acid is dissolved; adding a complexing agent and a reducing agent thereto; adding additives of the present invention thereto and, if necessary, adding other additives thereto; and, finally, adjusting the pH to a predetermined pH.
  • the plating bath of the present invention can be used in known plating methods, and can also be applied to barrel plating, in which the variation in current density is large.
  • the bath temperature is preferably in the range of 5 to 40°C.
  • the cathode current density can also be appropriately determined according to the plating solution used, type of object to be plated, etc.
  • a cathode current density of 0.1 to 3 A/dm 2 is preferable.
  • the anode may be any known anode that can be used for copper-tin alloy plating, such as a soluble anode (e.g., a tin anode, a phosphorus-containing copper anode, an oxygen-free copper anode, or a copper-tin alloy anode) or an insoluble anode (e.g., a stainless anode, a carbon anode, a lead anode, a lead-tin alloy anode, a lead-antimony alloy anode, a platinum anode, a titanium anode, a titanium-platinum anode, or an oxide coated anode, such as an iridium-oxide-coated titanium electrode).
  • a soluble anode e.g., a tin anode, a phosphorus-containing copper anode, an oxygen-free copper anode, or a copper-tin alloy anode
  • an insoluble anode e.g
  • the cathode is an object to be plated that is described below.
  • the method for copper-tin alloy plating of the present invention is a method in which electrolysis is performed using an object to be plated as a cathode in the copper-tin alloy plating bath described above.
  • the copper-tin alloy plating film described above is formed on the surface of an article to be plated by the above plating method.
  • the alloy composition of the obtained film is such that the Cu:Sn weight ratio is 95:5 to 5:95, and the alloy composition can be easily changed by varying the Cu concentration or the Sn concentration in the plating solution.
  • the article to be plated is not particularly limited as long as the surface is conductive and smooth. Examples of such articles include home appliances, faucet fittings, sundry articles, decorations, clothing accessories, and the like.
  • the copper-tin alloy plating bath of the present invention can be suitably used for plating for clothing accessories or decorations; and plating for, for example, electronic or electric components. However, this does not limit applications to other purposes.
  • Plating treatment was performed using plating baths having the compositions shown in Tables 1 to 6 below under the following conditions to individually form plating films on objects to be plated.
  • Tables 1 to 6 show the state of each plating solution, wherein the examples are reference examples, and the properties of each of the plating films formed as described above.
  • the evaluation methods for the properties are as follows.
  • Solution state The state of each solution was visually confirmed.
  • Solution stability After being allowed to stand for 24 hours, each plating solution was visually confirmed.
  • Plating appearance and occurrence of cracking Plating appearance and occurrence of cracking were observed with a digital microscope.
  • Cu:Sn ratio The Cu:Sn ratio was evaluated with a fluorescent X-ray film thickness measurement apparatus.
  • Example 3 which is a reference example, and Comparative Examples 11 and 12
  • plating treatment was performed at current densities of 0.01, 0.1, 0.5, 1, 2, and 3 A/dm 2 , and the copper content of the formed plating films was determined.
  • Fig. 1 shows the results.
  • Tables 1 to 5 reveal that no precipitates were formed in the plating baths of Examples 1 to 50 which are reference examples; that the solution state was stable, especially in the plating baths of Examples 1 to 5, 10 to 31, 34 to 42, and 45 to 50 which are reference examples; and that crack-free plating films were obtained by plating.
  • a copper-tin alloy plating film having any ratio can be obtained by adjusting the metal concentration in the plating solution.
  • Tables 3 to 5 show that adding a surfactant or a leveler to the plating solution improves brightness of a plating appearance, and that a plating appearance having excellent brightness can be obtained by adding both a surfactant and a leveler to the plating solution.
  • Fig. 1 shows that in the plating bath of Example 3, which is a reference example, the current density has a small influence on the alloy ratio as compared with the case of a hitherto known acidic bath (Comparative Example 12).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Claims (4)

  1. Bain de placage d'alliage de cuivre-étain, comprenant une solution aqueuse ayant un pH de 4,5 ou moins, la solution aqueuse contenant un composé du cuivre bivalent soluble dans l'eau, un composé de l'étain bivalent soluble dans l'eau, un composé soufré représenté par la formule (1) :

            R-(CH2)l-S-(CH2)m-S-(CH2)n-R     (1),

    où R est H, OH ou SO3Na, et l, m et n sont chacun indépendamment un entier allant de 0 à 3,
    un composé aromatique contenant un groupe hydroxyle, un tensioactif et un agent nivelant,
    le tensioactif étant au moins un tensioactif non ionique choisi parmi le groupe consistant en des polyoxyéthylène-alkylamines, des polyoxyalkylène-phényléthers et des polyoxyalkylène-naphtyléthers,
    l'agent nivelant étant au moins une cétone aromatique ou un aldéhyde aromatique choisi parmi le groupe consistant en de la benzalacétone, du cinnamaldéhyde, de l'a-méthylcinnamaldéhyde, de l'a-hexylcinnamaldéhyde, de l'a-amylcinnamaldéhyde, du cuminaldéhyde, du benzaldéhyde et de l'anisaldéhyde,
    le composé du cuivre bivalent soluble dans l'eau étant présent en une quantité telle que la quantité des ions cuivre bivalents se situe dans l'intervalle allant de 1 à 60 g/litre,
    le composé de l'étain bivalent soluble dans l'eau étant présent en une quantité telle que la quantité des ions étain bivalents se situe dans l'intervalle allant de 5 à 40 g/litre,
    le composé soufré étant présent en une quantité située dans l'intervalle allant de 5 à 500 g/litre,
    le composé aromatique contenant un hydroxyle étant présent en une quantité située dans l'intervalle allant de 1 à 50 g/litre,
    le tensioactif étant présent en une quantité située dans l'intervalle allant de 0,1 à 40 g/litre,
    l'agent nivelant étant présent en une quantité située dans l'intervalle allant de 0,01 à 10 g/litre, et le rapport tensioactif:agent nivelant allant de 1:1 à 100:1.
  2. Bain de placage d'alliage cuivre-étain selon la revendication 1, où le composé soufré est au moins un membre du groupe consistant en du méthanedithiol, du 1,2-éthane-dithiol, du 1,3-propanedithiol, du 3,6-dithia-1,8-octanediol, et du bis(sulfopropyl de sodium)disulfure.
  3. Bain de placage d'alliage cuivre-étain selon la revendication 1 ou 2, où le composé aromatique contenant un groupe hydroxyle est au moins un membre du groupe consistant en du phénol, du catéchol, de l'hydroquinone, du résorcinol, du pyrogallol, de l'acide p-crésolsufonique, de l'ascorbate de sodium et de l'érythorbate de sodium.
  4. Procédé de placage d'alliage cuivre-étain, le procédé comprenant la réalisation d'une électrolyse à l'aide d'un objet à plaquer comme cathode dans le bain de placage d'alliage cuivre-étain selon l'une quelconque des revendications 1 à 3.
EP15829133.6A 2014-08-08 2015-07-28 Bain de placage d'alliage de cuivre-étain Active EP3178969B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014162294 2014-08-08
PCT/JP2015/071330 WO2016021439A1 (fr) 2014-08-08 2015-07-28 Bain de placage d'alliage de cuivre-étain

Publications (3)

Publication Number Publication Date
EP3178969A1 EP3178969A1 (fr) 2017-06-14
EP3178969A4 EP3178969A4 (fr) 2017-12-27
EP3178969B1 true EP3178969B1 (fr) 2020-01-01

Family

ID=55263710

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15829133.6A Active EP3178969B1 (fr) 2014-08-08 2015-07-28 Bain de placage d'alliage de cuivre-étain

Country Status (7)

Country Link
US (1) US20170204528A1 (fr)
EP (1) EP3178969B1 (fr)
JP (1) JP6048712B2 (fr)
CN (1) CN106661752B (fr)
CA (1) CA2957587C (fr)
TW (1) TWI641729B (fr)
WO (1) WO2016021439A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019052355A (ja) * 2017-09-15 2019-04-04 上村工業株式会社 電解Ｓｎ又はＳｎ合金めっき液及びＳｎ又はＳｎ合金めっき物の製造方法
JP6645609B2 (ja) * 2018-07-27 2020-02-14 三菱マテリアル株式会社 錫合金めっき液
CN110205659B (zh) * 2019-07-17 2020-06-16 广州三孚新材料科技股份有限公司 一种电镀锡添加剂及其制备方法
CN120485893A (zh) * 2025-06-18 2025-08-15 东强（连州）铜箔有限公司 一种超高精细化pcb用高强度vlp铜箔及其制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3871013B2 (ja) * 1998-11-05 2007-01-24 上村工業株式会社 錫−銅合金電気めっき浴及びそれを使用するめっき方法
EP1325175B1 (fr) * 2000-09-20 2005-05-04 Dr.Ing. Max Schlötter GmbH & Co. KG Electrolyte et procede pour deposer des couches d'alliages etain-cuivre
EP1408141B1 (fr) * 2002-10-11 2014-12-17 Enthone Inc. Methode et électrolyte pour la deposition galvanique des bronzes
JP4441726B2 (ja) * 2003-01-24 2010-03-31 石原薬品株式会社 スズ又はスズ合金の脂肪族スルホン酸メッキ浴の製造方法
US20060260948A2 (en) * 2005-04-14 2006-11-23 Enthone Inc. Method for electrodeposition of bronzes
JP5419021B2 (ja) * 2008-11-11 2014-02-19 ユケン工業株式会社 ジンケート型亜鉛めっき浴
EP2221396A1 (fr) * 2008-12-31 2010-08-25 Rohm and Haas Electronic Materials LLC Compositions de dépôt électrique à l'alliage d'étain sans plomb et procédés
JP5313773B2 (ja) * 2009-06-04 2013-10-09 三菱伸銅株式会社 めっき付き銅条材及びその製造方法
JP6133056B2 (ja) * 2012-12-27 2017-05-24 ローム・アンド・ハース電子材料株式会社 スズまたはスズ合金めっき液

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
JP6048712B2 (ja) 2016-12-21
CA2957587A1 (fr) 2016-02-11
TW201612362A (en) 2016-04-01
CN106661752A (zh) 2017-05-10
WO2016021439A1 (fr) 2016-02-11
CA2957587C (fr) 2019-03-05
EP3178969A4 (fr) 2017-12-27
US20170204528A1 (en) 2017-07-20
TWI641729B (zh) 2018-11-21
EP3178969A1 (fr) 2017-06-14
JPWO2016021439A1 (ja) 2017-04-27
HK1232261A1 (zh) 2018-01-05
CN106661752B (zh) 2021-08-10

Similar Documents

Publication Publication Date Title
TWI404834B (zh) 青銅之電鍍方法
JP4249438B2 (ja) 銅―錫合金めっき用ピロリン酸浴
EP1874982B1 (fr) Methode d'electrodeposition de bronzes
EP2551382B1 (fr) Substrats revêtus d'argent résistants aux températures élevées
US9145617B2 (en) Adhesion promotion of cyanide-free white bronze
US20100038254A1 (en) Tin electroplating solution and tin electroplating method
CN102162110A (zh) 一种甲基磺酸盐镀锡电解液及钢带或钢板的镀锡方法
EP3178969B1 (fr) Bain de placage d'alliage de cuivre-étain
TWI548782B (zh) 無氰化物之酸性消光銀電鍍組成物及方法
CN102046852A (zh) 用于铜-锡合金无氰化物沉积的含焦磷酸盐的镀液
CN1703540A (zh) 电沉积铜的方法
US20090159453A1 (en) Method for silver plating
JPH02301588A (ja) 錫，鉛，錫―鉛合金電気めっき浴及び電気めっき方法
JP2015206074A (ja) 銅錫合金めっき液およびこれを用いた銅錫合金のめっき方法
JP4283256B2 (ja) 金属の電解析出方法
CN101649474A (zh) 铜-锡合金镀膜、非氰系铜-锡合金镀液以及采用该镀液的镀覆方法
HK1232261B (zh) 铜-锡合金镀敷浴
US2757134A (en) Zinc cyanide electrolyte
WO2025142000A1 (fr) Solution d'électrodéposition et procédé d'électrodéposition d'un article par dépôt électrolytique l'utilisant
JPS6312954B2 (fr)

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20170202

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602015044851

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C25D0003600000

Ipc: C25D0003580000

A4 Supplementary search report drawn up and despatched

Effective date: 20171129

RIC1 Information provided on ipc code assigned before grant

Ipc: C25D 3/60 20060101ALI20171123BHEP

Ipc: C25D 3/58 20060101AFI20171123BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20180706

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20190723

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: OKUNO CHEMICAL INDUSTRIES CO., LTD.

RIN1 Information on inventor provided before grant (corrected)

Inventor name: NAGAO, TOSHIMITSU

Inventor name: OTSUKA, KUNIAKI

Inventor name: KATAYAMA, JUNICHI

Inventor name: TSUJIMOTO, TAKAMITSU

Inventor name: HARA, KENJI

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1219869

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602015044851

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200101

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200527

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200401

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200401

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200402

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200501

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602015044851

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1219869

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200101

26N No opposition filed

Effective date: 20201002

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20200728

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200728

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200731

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200731

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200728

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200728

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200101

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20220531

Year of fee payment: 8

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230517

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602015044851

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240201