TWI621736B - Nickle colloidal catalyst solution for electroless nickle or nickle alloy plating and electroless nickle or nickle alloy plating method - Google Patents
Nickle colloidal catalyst solution for electroless nickle or nickle alloy plating and electroless nickle or nickle alloy plating method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
Abstract
本發明提供一種化學鍍鎳或鎳合金用鎳膠體催化劑液，將非導電性基板浸漬於含表面活性劑的液體中預先進行吸附促進處理後，使用含有(A)可溶性鎳鹽、(B)還原劑、以及(C)膠體穩定劑的化學鍍鎳用鎳膠體催化劑液對非導電性基板進行催化劑賦予，然後進行化學鍍鎳。利用吸附促進預處理增強催化劑活性後，使用經時穩定性優異的催化劑液進行催化劑賦予，再進行化學鍍膜，因此可得到無析出色斑的均勻鎳被膜。即使代替上述鍍鎳方法用於鍍鎳合金方法，也能得到均勻性優異的鎳合金被膜。 The present invention provides a nickel colloidal catalyst liquid for electroless nickel plating or nickel alloy, which comprises immersing a non-conductive substrate in a surfactant-containing liquid in advance for adsorption promotion treatment, and then using (A) soluble nickel salt and (B) reducing The electroless nickel plating of the agent and (C) colloidal stabilizer is carried out by applying a catalyst to the non-conductive substrate with a nickel colloidal catalyst liquid, followed by electroless nickel plating. After the catalyst is promoted by the adsorption-promoting pretreatment, the catalyst is applied by using a catalyst liquid having excellent stability over time, and then electroless plating is performed. Thus, a uniform nickel film having excellent speckle-free spots can be obtained. Even if it is used for the nickel plating alloy method instead of the above nickel plating method, a nickel alloy film excellent in uniformity can be obtained.
Description
本發明涉及在對非導電性基板實施化學鍍鎳或鎳合金時，用於進行作為預處理的催化劑賦予的鎳膠體催化劑液及使用該催化劑液的化學鍍鎳或鎳合金方法，提供鎳膠體催化劑液的經時穩定性優異，並可形成均勻性良好且無色斑的外觀的鎳或鎳合金被膜的化學鍍鎳或鎳合金用鎳膠體催化劑液及化學鍍鎳或鎳合金方法。 The present invention relates to a nickel colloidal catalyst liquid for carrying out a catalyst for pretreatment and an electroless nickel or nickel alloy method using the catalyst liquid for performing electroless nickel plating or a nickel alloy on a non-conductive substrate, and providing a nickel colloidal catalyst The liquid is excellent in stability over time, and can form a nickel or nickel alloy coating film of nickel or nickel alloy coating having good uniformity and no color unevenness, and a nickel colloidal catalyst liquid and an electroless nickel plating or nickel alloy method.
為了在以玻璃-環氧樹脂、玻璃-聚醯亞胺樹脂、環氧樹脂、聚醯亞胺樹脂、聚碳酸脂樹脂、ABS樹脂、PET樹脂等樹脂基板為代表、包括玻璃基板、陶瓷基板等在內的非導電性基板上實施化學鍍鎳或鎳合金，常規方法是：首先使鈀、金、銀、銅、鎳等金屬吸附在基板上成為催化劑核，然後借助該催化劑核利用化學鍍鎳或鎳合金液使基板上析出該鎳系被膜。 In order to represent a resin substrate such as glass-epoxy resin, glass-polyimine resin, epoxy resin, polyimide resin, polycarbonate resin, ABS resin, or PET resin, including glass substrate, ceramic substrate, etc. Electroless nickel plating or nickel alloy is performed on the inner non-conductive substrate. The conventional method is: first, a metal such as palladium, gold, silver, copper or nickel is adsorbed on the substrate to form a catalyst core, and then electroless nickel plating is performed by means of the catalyst core. Or the nickel alloy liquid deposits the nickel-based film on the substrate.
因此，在實施包括鍍鎳或鎳合金在內的化學鍍膜時，作為其預處理對被鍍物賦予鎳催化劑核的現有技術列舉如下。 Therefore, in the case of performing an electroless plating including nickel plating or a nickel alloy, the prior art which imparts a nickel catalyst core to the object to be plated as a pretreatment thereof is as follows.
(1)專利文獻1(日本特開2005-008936號公報，Uyemura & Co.,Ltd.) (1) Patent Document 1 (JP-A-2005-008936, Uyemura & Co., Ltd.)
一種化學鍍膜方法，包括對被鍍物的金屬材料部分賦予催化劑金屬的第一催化劑步驟、對非導電性材料部分賦予催化劑金屬的第二催化劑步驟、以及使用化學鍍浴的化學鍍膜步驟，化學鍍浴包括化學鍍鎳浴、化學鍍銅浴等(請求項1、12、段落42)。 An electroless plating method comprising a first catalyst step of imparting a catalyst metal to a metal material portion of a material to be plated, a second catalyst step of imparting a catalyst metal to a portion of the non-conductive material portion, and an electroless plating step using an electroless plating bath, electroless plating The bath includes an electroless nickel plating bath, an electroless copper plating bath, and the like (requests 1, 12, and 42).
上述第一步驟的催化劑金屬為鎳、鈀、金、銀、銅等(段落24、27)。另外，在上述第二催化劑步驟中，用鹼性催化劑金屬溶液處理後，再用還原劑液處理(段落32、38、40)，但該催化劑金屬為鎳、鈀、銀、鈷等(段落34)。 The catalyst metal of the first step described above is nickel, palladium, gold, silver, copper or the like (paragraphs 24 and 27). Further, in the second catalyst step, after treatment with a basic catalyst metal solution, treatment with a reducing agent liquid (paragraphs 32, 38, 40), but the catalyst metal is nickel, palladium, silver, cobalt, etc. (paragraph 34 ).
(2)專利文獻2(日本特開2012-130910號公報，Rohm and Haas Company) (2) Patent Document 2 (Japanese Laid-Open Patent Publication No. 2012-130910, Rohm and Haas Company)
將含有鎳、鈀、銅、銀等金屬、穩定劑(咪唑衍生物)、以及還原劑的催化劑液用於具有通孔的基板後，實施鎳、銅、銀等的化學鍍膜(請求項1、10，段落11、15、17、24、44)。 A catalyst liquid containing a metal such as nickel, palladium, copper, or silver, a stabilizer (imidazole derivative), and a reducing agent is applied to a substrate having a through hole, and then an electroless plating film of nickel, copper, silver, or the like is applied (claim 1 10, paragraphs 11, 15, 17, 24, 44).
作為優選的穩定劑為(2-氨基-2-羧基)咪唑(即組氨酸)、4,5-咪唑二羧酸、4-咪唑乙酸等(段落17)。 Preferred stabilizers are (2-amino-2-carboxy)imidazole (i.e., histidine), 4,5-imidazoledicarboxylic acid, 4-imidazoleacetic acid, and the like (Section 17).
(3)專利文獻3(日本特開2012-127002號公報，Rohm and Haas Company) (3) Patent Document 3 (Japanese Laid-Open Patent Publication No. 2012-127002, Rohm and Haas Company)
將含有鎳、鈀、銅、銀等金屬、穩定劑(吡啶衍生物)、以及還原劑的催化劑液用於具有通孔的基板後，實施鎳、銅、銀等的化學鍍膜(請求項1、6、10，段落10~11、15、23~24、44)。 A catalyst liquid containing a metal such as nickel, palladium, copper, or silver, a stabilizer (pyridine derivative), and a reducing agent is applied to a substrate having a through hole, and then an electroless plating film of nickel, copper, silver, or the like is applied (claim 1 6, 10, paragraphs 10~11, 15, 23~24, 44).
優選的穩定劑為4-二甲基吡啶、4-氨基吡啶、2-氨基-4,6-二甲基吡啶、4-氨基煙酸、2-氨基煙酸等(段落17)。 Preferred stabilizers are 4-dimethylpyridine, 4-aminopyridine, 2-amino-4,6-lutidine, 4-aminonicotinic acid, 2-aminonicotinic acid, etc. (Section 17).
(4)專利文獻4(日本特開H11-241170號公報，Okuno Chemical Industries Co.,Ltd) (4) Patent Document 4 (Japanese Patent Laid-Open Publication No. H11-241170, Okuno Chemical Industries Co., Ltd.)
將被鍍物浸漬于含有主要成分銀鹽、次要成分鎳鹽(或鐵、鈷鹽)、非離子型表面活性劑、以及還原劑的催化劑液後，使用鎳、銅等的鍍浴進行化學鍍膜(請求項1~4)。 The object to be plated is immersed in a catalyst liquid containing a main component silver salt, a minor component nickel salt (or iron, cobalt salt), a nonionic surfactant, and a reducing agent, and then subjected to chemistry using a plating bath of nickel or copper. Coating (requests 1 to 4).
通過使用上述次要成分鎳鹽(或鐵、鈷鹽)，與未配合該成分的情況相比，催化劑液的催化劑活性提高，可獲得更均勻且良好的化學鍍膜(段落19)。 By using the above-mentioned secondary component nickel salt (or iron or cobalt salt), the catalyst activity of the catalyst liquid is improved as compared with the case where the component is not blended, and a more uniform and good electroless plating film can be obtained (paragraph 19).
例如，實施例1中將被鍍物浸漬於含有銀鹽、鎳鹽、硼烷系還原劑以及非離子型表面活性劑的催化劑液後，實施化學鍍鎳或化學鍍銅(段落39~47，表1)。 For example, in Example 1, the object to be plated is immersed in a catalyst liquid containing a silver salt, a nickel salt, a borane-based reducing agent, and a nonionic surfactant, and then subjected to electroless nickel plating or electroless copper plating (paragraphs 39 to 47, Table 1).
在此情況下，催化劑核的基本成分為銀而非鎳。 In this case, the basic component of the catalyst core is silver instead of nickel.
(5)專利文獻5(日本特開2002-180110號公報，Catalysts & Chemicals Industries Co.,Ltd.) (5) Patent Document 5 (Japanese Laid-Open Patent Publication No. 2002-180110, Catalysts & Chemicals Industries Co., Ltd.)
含有電極電位低的金屬的鹽A、電極電位高的金屬的鹽B、 穩定劑、以及還原劑的金屬膠體溶液的製造方法。 a salt A containing a metal having a low electrode potential, a salt B of a metal having a high electrode potential, A method for producing a stabilizer and a metal colloidal solution of a reducing agent.
電極電位低的金屬A為鎳、金、銀、銅等(請求項4，段落10)，電極電位高的金屬B為鈀、鉑等(請求項4，段落22)。 The metal A having a low electrode potential is nickel, gold, silver, copper or the like (Requirement 4, paragraph 10), and the metal B having a high electrode potential is palladium, platinum or the like (Requirement 4, paragraph 22).
穩定劑為檸檬酸、蘋果酸、聚乙烯醇(PVA)、聚乙烯吡咯烷酮(PVP)等(段落22)。 The stabilizers are citric acid, malic acid, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), etc. (paragraph 22).
先利用還原劑將電極電位高的金屬B還原，析出金屬微粒，該金屬微粒起到粒子核的作用，金屬鹽A在該核金屬B的微粒表面被還原而析出，得到金屬膠體微粒(段落23、26)。 First, the metal B having a high electrode potential is reduced by a reducing agent to precipitate metal fine particles, and the metal fine particles function as a particle nucleus, and the metal salt A is reduced and precipitated on the surface of the fine particles of the nuclear metal B to obtain metal colloidal particles (paragraph 23) , 26).
在實施例1~3中，金屬鹽A為鎳鹽，金屬鹽B為鈀鹽。穩定劑為明膠、PVP、檸檬酸(參照表1)。 In Examples 1 to 3, the metal salt A was a nickel salt, and the metal salt B was a palladium salt. The stabilizers are gelatin, PVP, and citric acid (see Table 1).
但是，實施例中未提及化學鍍膜。 However, no electroless plating is mentioned in the examples.
現有技術文獻： Prior art literature:
[專利文獻] [Patent Literature]
專利文獻1：日本特開2005-008936號公報、 專利文獻2：日本特開2012-130910號公報、 專利文獻3：日本特開2012-127002號公報、 專利文獻4：日本特開H11-241170號公報、 專利文獻5：日本特開2002-180110號公報。 Patent Document 1: Japanese Laid-Open Patent Publication No. 2005-008936, Patent Document 2: Japanese Laid-Open Patent Publication No. 2012-130910, Patent Document 3: Japanese Laid-Open Patent Publication No. 2012-127002, Patent Document 4: Japanese Laid-Open Patent Publication No. H11-241170, Patent Document 5: Japanese Laid-Open Patent Publication No. 2002-180110.
通常，將含有可溶性金屬鹽和還原劑的催化劑液用於預處理的化學鍍膜的基本原理是，利用還原劑將可溶性金屬鹽還原成金屬微細粒子，將該金屬微粒作為鍍膜的催化劑核，但實際情況是，上述專利文獻1~5(專利文獻4中催化劑核的基本成分不是鎳而是銀)的催化劑液大多在經時穩定性方面存在問題，不易長時間平穩確保催化劑賦予與化學鍍膜的操作連續性。 In general, the basic principle of using a catalyst liquid containing a soluble metal salt and a reducing agent for pretreatment is to reduce a soluble metal salt into metal fine particles by using a reducing agent, and the metal fine particles are used as a catalyst core of a plating film, but actually In the case of the catalyst liquids of the above-mentioned Patent Documents 1 to 5 (the basic component of the catalyst core in Patent Document 4 is not nickel but silver), there is a problem in stability over time, and it is difficult to ensure the operation of the catalyst and the electroless plating for a long time. Continuity.
另外，即使用鎳催化劑液對非導電性基板進行催化劑賦予後再實施化學鍍膜，也會存在析出困難、因局部未析出被膜而產生鍍膜裂縫、或者鍍膜產生色斑、均勻性差等問題。 In addition, even if the electroless plating film is applied to the non-conductive substrate by using the nickel catalyst liquid, there is a problem that precipitation is difficult, cracks occur in the coating film due to partial deposition of the film, or the coating film is colored, and the uniformity is poor.
本發明所要解決的技術問題在於，提高鎳催化劑液的經時穩定性，並且對經催化劑賦予的非導電性基板實施化學鍍鎳，得到均勻且無色斑的鎳或鎳合金被膜。 The technical problem to be solved by the present invention is to improve the temporal stability of the nickel catalyst liquid, and to perform electroless nickel plating on the non-conductive substrate imparted by the catalyst to obtain a nickel or nickel alloy coating film which is uniform and has no color unevenness.
本發明人認為，在例如專利文獻2、3、5中，除了還原劑以外，為了保持用於賦予含鎳的催化劑核的金屬還原狀態而並用穩定劑，首先考慮在催化劑液中添加對鎳鹽具有絡合功能的成分使膠體粒子穩定，參考上述專利文獻公開的各種化合物，或者深入研究了代替該化合物的適當穩定劑。 The present inventors believe that, for example, in Patent Documents 2, 3, and 5, in addition to a reducing agent, in order to maintain a metal reducing state for imparting a nickel-containing catalyst core and to use a stabilizer together, it is first considered to add a nickel salt to the catalyst liquid. The component having a complexing function stabilizes the colloidal particles, and various compounds disclosed in the above patent documents are referred to, or a suitable stabilizer in place of the compound is intensively studied.
結果發現，通過向鎳催化劑液中添加使鎳鹽穩定的羥基羧酸類、氨基羧酸類等膠體穩定劑能夠改善經時穩定性，若可溶性鎳鹽、還原劑和穩定劑的含量適當，則會使經時穩定性更高鍍敷外觀更好。 As a result, it has been found that by adding a colloidal stabilizer such as a hydroxycarboxylic acid or an aminocarboxylic acid which stabilizes the nickel salt to the nickel catalyst liquid, the stability over time can be improved, and if the content of the soluble nickel salt, the reducing agent and the stabilizer is appropriate, Better plating stability over time.
進而，基於此見解首次發現，如果在使用鎳催化劑液對基板進行催化劑賦予之前，著重進行將基板浸漬於含有包含表面活性劑的吸附促進劑的液體中的預處理，則在進行催化劑賦予之際催化劑活性提高，由化學鍍鎳或鎳合金所得的析出被膜的均勻性、以及防止被膜產生外觀色斑的能力增強，從而完成了本發明。 Furthermore, based on this knowledge, it is found for the first time that the catalyst is applied to the liquid containing the adsorption promoter containing the surfactant before the catalyst is applied to the substrate using the nickel catalyst solution. The catalyst activity is improved, the uniformity of the precipitated film obtained by electroless nickel plating or a nickel alloy, and the ability to prevent the appearance of stains on the film are enhanced, and the present invention has been completed.
即，本發明1是一種用於與實施化學鍍鎳或鎳合金的非導電性基板接觸進行催化劑賦予的化學鍍鎳或鎳合金用鎳膠體催化劑液，其含有：(A)可溶性鎳鹽、(B)還原劑、以及(C)選自一元羧酸類、羥基羧酸類、氨基羧酸類、以及多元羧酸類中的膠體穩定劑的至少一種。 That is, the present invention 1 is a nickel colloidal catalyst liquid for electroless nickel plating or nickel alloy which is used for contact with a non-conductive substrate which is subjected to electroless nickel plating or a nickel alloy, and which contains: (A) a soluble nickel salt, ( B) at least one of a reducing agent and (C) a colloidal stabilizer selected from the group consisting of monocarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, and polycarboxylic acids.
本發明2是在上述本發明1的化學鍍鎳或鎳合金用鎳膠體催化劑液中，可溶性鎳鹽(A)的含量為0.005~1.0莫耳/L，還原劑(B)的含量為0.005~0.8莫耳/L，膠體穩定劑(C)的含量為0.015~8.0莫耳/L。 The present invention 2 is characterized in that the content of the soluble nickel salt (A) is 0.005 to 1.0 mol/L, and the content of the reducing agent (B) is 0.005 in the nickel colloidal catalyst liquid for electroless nickel plating or nickel alloy according to the first aspect of the invention. 0.8 mol/L, the content of the colloidal stabilizer (C) is 0.015 to 8.0 m/L.
本發明3是在上述本發明1或2的化學鍍鎳或鎳合金用鎳膠體催化劑液中，還原劑(B)為選自硼氫化合物、胺硼烷類、次磷酸類、醛類、抗壞血酸類、肼類、多元酚類、多元萘酚類、苯酚磺酸類、萘酚磺酸類、亞磺酸類、以及還原糖類中的至少一種。 The present invention 3 is the nickel colloidal catalyst liquid for electroless nickel plating or nickel alloy according to the first or second aspect of the invention, wherein the reducing agent (B) is selected from the group consisting of a boron hydride compound, an amine borane, a hypophosphorous acid, an aldehyde, and ascorbic acid. At least one of a steroid, a hydrazine, a polyhydric phenol, a polyhydric naphthol, a phenolsulfonic acid, a naphtholsulfonic acid, a sulfinic acid, and a reducing sugar.
本發明4是在上述本發明1~3中任一項的化學鍍鎳或鎳合金 用鎳膠體催化劑液中，一元羧酸類(C)為選自甲酸、乙酸、丙酸、丁酸、戊酸、己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、以及其等之鹽中的至少一種。 The present invention 4 is the electroless nickel plating or nickel alloy according to any one of the above inventions 1 to 3. In the nickel colloidal catalyst liquid, the monocarboxylic acid (C) is selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid. And at least one of the salts thereof.
本發明5是在上述本發明1~4中任一項的化學鍍鎳或鎳合金用鎳膠體催化劑液中，羥基羧酸類(C)為選自檸檬酸、酒石酸、蘋果酸、葡萄糖酸、葡庚糖酸、乙醇酸、乳酸、三羥基丁酸(trioxy butyric acid)、抗壞血酸、異檸檬酸、羥基丙二酸、甘油酸、羥基丁酸、亮氨酸、檸蘋酸、異抗壞血酸、以及其等之鹽中的至少一種。 The present invention 5 is the nickel colloidal catalyst liquid for electroless nickel plating or nickel alloy according to any one of the above Inventions 1 to 4, wherein the hydroxycarboxylic acid (C) is selected from the group consisting of citric acid, tartaric acid, malic acid, gluconic acid, and hydrochloric acid. Heptonic acid, glycolic acid, lactic acid, trioxy butyric acid, ascorbic acid, isocitric acid, hydroxymalonic acid, glyceric acid, hydroxybutyric acid, leucine, citramalic acid, isoascorbic acid, and At least one of the salts.
本发明6是在上述本发明1~5中任一項的化學鍍鎳或鎳合金用鎳膠體催化劑液中，氨基羧酸類(C)為選自羥乙基乙二胺三乙酸、二亞乙基三胺五乙酸、三亞乙基四胺六乙酸、乙二胺四乙酸、乙二胺四丙酸、氨三乙酸、亞氨基二乙酸、羥乙基亞氨基二乙酸、亞氨基二丙酸、1,3-丙二胺四乙酸(1,3-propanediamine tetraacetic acid)、1,3-二氨基-2-羥基丙烷四乙酸(1,3-diamino-2-hydroxypropane tetraacetic acid)、乙二醇醚二胺四乙酸、間苯二胺四乙酸、1,2-環己二胺-N,N,N’,N’-四乙酸、二氨基丙酸、以及其等之鹽中的至少一種。 The present invention is the nickel colloidal catalyst liquid for electroless nickel plating or nickel alloy according to any one of the above Inventions 1 to 5, wherein the aminocarboxylic acid (C) is selected from the group consisting of hydroxyethylethylenediaminetriacetic acid and diethylene glycol. Triamine pentaacetic acid, triethylenetetramine hexaacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, aminotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, iminodipropionic acid, 1,3-propanediamine tetraacetic acid, 1,3-diamino-2-hydroxypropane tetraacetic acid, glycol ether At least one of diaminetetraacetic acid, m-phenylenediaminetetraacetic acid, 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid, diaminopropionic acid, and the like.
氨基酸類(C)為選自谷氨酸、二羧甲基谷氨酸(dicarboxy methyl glutamate)、鳥氨酸、半胱氨酸、甘氨酸、N,N-二(2-羥乙基)甘氨酸、(S,S)-乙二胺琥珀酸、以及其等之鹽中的至少一種。 The amino acid (C) is selected from the group consisting of glutamic acid, dicarboxymethyl glutamate, ornithine, cysteine, glycine, N,N-bis(2-hydroxyethyl)glycine, At least one of (S,S)-ethylenediamine succinic acid, and a salt thereof.
本發明7是在上述本發明1~6中任一項的化學鍍鎳或鎳合金用鎳膠體催化劑液中，多元羧酸類(C)為選自琥珀酸、戊二酸、丙二酸、己二酸、乙二酸、馬來酸、檸康酸、衣康酸、中康酸、以及其等之鹽中的至少一種。 The present invention is the nickel colloidal catalyst solution for electroless nickel plating or nickel alloy according to any one of the above aspects of the present invention, wherein the polycarboxylic acid (C) is selected from the group consisting of succinic acid, glutaric acid, malonic acid, and At least one of diacid, oxalic acid, maleic acid, citraconic acid, itaconic acid, mesaconic acid, and the like.
本發明8是一種化學鍍鎳或鎳合金方法，包括：(a)吸附促進步驟，將非導電性基板浸漬於含有選自非離子型表面活性劑、陽離子型表面活性劑、陰離子型表面活性劑、兩性表面活性劑中的吸附促進劑的至少一種的液體中；(b)催化劑賦予步驟，將經吸附促進後的非導電性基板浸漬于上述本發明1~7中任一項的鎳膠體催化劑液中，使鎳膠體粒子吸附在基板 表面上；以及(c)化學鍍膜步驟，使用化學鍍鎳或鎳合金液在經催化劑賦予後的上述基板上形成鎳或鎳合金被膜。 The invention 8 is a method for electroless nickel plating or nickel alloy, comprising: (a) an adsorption promoting step of immersing a non-conductive substrate containing a surfactant selected from the group consisting of a nonionic surfactant, a cationic surfactant, and an anionic surfactant In the liquid of at least one of the adsorption promoters in the amphoteric surfactant; (b) a catalyst-imparting step of immersing the non-conductive substrate after the adsorption promotion in the above-mentioned nickel colloidal catalyst of any one of the inventions 1 to 7. In the liquid, the nickel colloid particles are adsorbed on the substrate And (c) an electroless plating step of forming a nickel or nickel alloy film on the substrate after the catalyst is applied using an electroless nickel or nickel alloy solution.
本發明9是在上述本發明8的化學鍍鎳或鎳合金方法中，步驟(a)的吸附促進劑為陽離子型表面活性劑和/或兩性表面活性劑。 The present invention 9 is the electroless nickel plating or nickel alloy method according to the eighth aspect of the invention, wherein the adsorption promoter of the step (a) is a cationic surfactant and/or an amphoteric surfactant.
本發明的鎳膠體催化劑液中，通過含有對鎳鹽有絡合作用的羥基羧酸類等特定的膠體穩定劑，能夠提高該催化劑液的經時穩定性，進而通過規定上述穩定劑或還原劑等的含量，能夠進一步顯著提高催化劑液的經時穩定性。 In the nickel colloidal catalyst liquid of the present invention, by containing a specific colloidal stabilizer such as a hydroxycarboxylic acid which is complexed with a nickel salt, the stability of the catalyst liquid over time can be improved, and the stabilizer or reducing agent can be specified. The content can further significantly improve the stability of the catalyst liquid over time.
附帶說明，上述專利文獻1的實施例1~15中，沒有第一或第二催化劑步驟中進行鎳催化劑賦予之例，另外，專利文獻2~3的實施例中也均無鎳催化劑液之例。 Incidentally, in Examples 1 to 15 of Patent Document 1, there is no example in which the nickel catalyst is applied in the first or second catalyst step, and in the examples of Patent Documents 2 to 3, there is no nickel catalyst solution. .
專利文獻4中，雖然記載了例如實施例1的催化劑液中含有銀鹽和鎳鹽，催化劑賦予後實施化學鍍鎳這一點(段落39~47、表1)，但如上所述，催化劑核的基本成分是銀而非鎳。 In Patent Document 4, for example, a silver salt and a nickel salt are contained in the catalyst liquid of Example 1, and electroless nickel plating is performed after the catalyst is applied (paragraphs 39 to 47 and Table 1). However, as described above, the catalyst core is The basic ingredient is silver instead of nickel.
另外，專利文獻5中，催化劑賦予的基本原理是兩段階的還原機理，反應機理複雜，實際操作也繁雜，而且實施例中未提及化學鍍膜。 Further, in Patent Document 5, the basic principle of catalyst application is a two-stage reduction mechanism, the reaction mechanism is complicated, and the actual operation is complicated, and the electroless plating film is not mentioned in the examples.
本發明中，基本原理是對非導電性基板賦予上述鎳膠體催化劑後再實施化學鍍鎳(或鎳合金)，但通過著重實施將非導電性基板浸漬於含表面活性劑的液體中的吸附促進處理作為該催化劑賦予的預處理，依次進行該吸附促進步驟、催化劑賦予步驟、以及化學鍍鎳(或鎳合金)步驟，能夠強化催化劑賦予時的催化劑活性，改善化學鍍膜所析出的鎳(或鎳合金)被膜的均勻性，並且良好地防止被膜色斑的發生。 In the present invention, the basic principle is to apply electroless nickel plating (or nickel alloy) to the non-conductive substrate after the nickel colloidal catalyst is applied, but the adsorption promotion of immersing the non-conductive substrate in the surfactant-containing liquid is emphasized. The pretreatment to be applied to the catalyst is carried out, and the adsorption promotion step, the catalyst application step, and the electroless nickel plating (or nickel alloy) step are sequentially performed, whereby the catalyst activity at the time of catalyst application can be enhanced, and nickel (or nickel) precipitated by the electroless plating film can be improved. The alloy) has uniformity of the film and well prevents the occurrence of film spots.
具體實施方式 detailed description
本發明的第一方面是用於與非導電性基板接觸進行催化劑 賦予的化學鍍鎳或鎳合金用鎳膠體催化劑液，含有(A)可溶性鎳鹽、(B)還原劑和(C)膠體穩定劑(相當於本發明1)；第二方面是使用上述第一方面的催化劑液的化學鍍鎳或鎳合金方法，預先用含表面活性劑的液體對非導電性基板進行吸附促進處理，接著，使用上述催化劑液在催化劑賦予後進行化學鍍膜(相當於本發明8)。 A first aspect of the invention is for use in contact with a non-conductive substrate for carrying out a catalyst The nickel colloidal catalyst solution for electroless nickel plating or nickel alloy is provided, comprising (A) a soluble nickel salt, (B) a reducing agent and (C) a colloidal stabilizer (corresponding to the invention 1); the second aspect is the use of the first In the method of electroless nickel plating or nickel alloying of the catalyst liquid, the non-conductive substrate is subjected to an adsorption promoting treatment by a liquid containing a surfactant in advance, and then the electroless plating is performed after the catalyst is applied using the catalyst liquid (corresponding to the present invention 8 ).
上述第一方面的發明中，通過使成分(A)、(B)、(C)的含量適當，能夠進一步改善催化劑液的經時穩定性。 In the first aspect of the invention, the content of the components (A), (B), and (C) is appropriately adjusted, whereby the stability of the catalyst liquid over time can be further improved.
另外，上述非導電性基板是指，以玻璃-環氧樹脂、玻璃-聚醯亞胺樹脂、環氧樹脂、聚醯亞胺樹脂、聚碳酸脂樹脂、ABS樹脂、PET樹脂等樹脂基板為代表、包括玻璃基板、陶瓷基板等。 In addition, the non-conductive substrate is represented by a resin substrate such as a glass-epoxy resin, a glass-polyimine resin, an epoxy resin, a polyimide resin, a polycarbonate resin, an ABS resin, or a PET resin. Including glass substrates, ceramic substrates, and the like.
上述本發明1的鎳膠體催化劑液的基本組成為：(A)可溶性鎳鹽、(B)還原劑、以及(C)膠體穩定劑。 The basic composition of the above nickel colloidal catalyst liquid of the present invention 1 is (A) a soluble nickel salt, (B) a reducing agent, and (C) a colloidal stabilizer.
上述可溶性鹽(A)只要是在水溶液中產生鎳離子的可溶性鹽，則可以使用任意可溶性鹽，沒有特別限制，也不排除難溶性鹽。具體而言，可列舉出硫酸鎳、氧化鎳、氯化鎳、硫酸鎳銨、乙酸鎳、硝酸鎳、碳酸鎳、氨基磺酸鎳、或者有機磺酸或羧酸的鎳鹽等。 The soluble salt (A) may be any soluble salt as long as it is a soluble salt which generates nickel ions in an aqueous solution, and is not particularly limited, and does not exclude a poorly soluble salt. Specific examples thereof include nickel sulfate, nickel oxide, nickel chloride, nickel ammonium sulfate, nickel acetate, nickel nitrate, nickel carbonate, nickel sulfamate, or a nickel salt of an organic sulfonic acid or a carboxylic acid.
作為上述還原劑(B)，可列舉出硼氫化合物、胺硼烷類、次磷酸類、醛類、抗壞血酸類、肼類、多元酚類、多元萘酚類、苯酚磺酸類、萘酚磺酸類、亞磺酸類、還原糖類等。 Examples of the reducing agent (B) include a boron hydride compound, an amine borane, a hypophosphorous acid, an aldehyde, an ascorbic acid, an anthraquinone, a polyhydric phenol, a polyhydric naphthol, a phenolsulfonic acid, and a naphtholsulfonic acid. , sulfinic acids, reducing sugars, etc.
硼氫化合物為硼氫化鈉、硼氫化鉀等；胺硼烷類為二甲胺硼烷、二乙胺硼烷等。醛類為甲醛、乙醛酸或其鹽等；多元酚類為鄰苯二酚、對苯二酚、間苯二酚、鄰苯三酚、間苯三酚、沒食子酸等；苯酚磺酸類為苯酚磺酸、甲酚磺酸或其鹽等。還原糖類為葡萄糖、果糖等。 The borohydride compound is sodium borohydride, potassium borohydride or the like; the amine borane is dimethylamine borane, diethylamine borane or the like. The aldehydes are formaldehyde, glyoxylic acid or its salts; the polyphenols are catechol, hydroquinone, resorcinol, pyrogallol, phloroglucinol, gallic acid, etc.; The acid is phenolsulfonic acid, cresolsulfonic acid or a salt thereof. The reducing sugars are glucose, fructose, and the like.
上述膠體穩定劑(C)為在鍍浴中形成鎳絡合物的化合物，起到保證催化劑液的經時穩定性的功能。 The above-mentioned colloidal stabilizer (C) is a compound which forms a nickel complex in a plating bath, and functions to ensure the stability of the catalyst liquid over time.
該膠體穩定劑(C)選自一元羧酸類、羥基羧酸類、氨基羧酸類、氨基酸類、以及多元羧酸類。 The colloidal stabilizer (C) is selected from the group consisting of monocarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, amino acids, and polycarboxylic acids.
作為上述一元羧酸類，可列舉出甲酸、乙酸、丙酸、丁酸、戊酸、己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、以及其 等之鹽等。 Examples of the monocarboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and the like. Wait for the salt and so on.
作為上述羥基羧酸類，可列舉出檸檬酸、酒石酸、蘋果酸、葡萄糖酸、葡庚糖酸、乙醇酸、乳酸、三羥基丁酸、抗壞血酸、異檸檬酸、羥基丙二酸、甘油酸、羥基丁酸、亮氨酸、檸蘋酸、異抗壞血酸、以及其等之鹽等。 Examples of the hydroxycarboxylic acid include citric acid, tartaric acid, malic acid, gluconic acid, glucoheptonic acid, glycolic acid, lactic acid, trihydroxybutyric acid, ascorbic acid, isocitric acid, hydroxymalonic acid, glyceric acid, and hydroxyl group. Butyric acid, leucine, citramalic acid, isoascorbic acid, and the like.
作為上述氨基羧酸類，可列舉出羥乙基乙二胺三乙酸、二亞乙基三胺五乙酸、三亞乙基四胺六乙酸、乙二胺四乙酸、乙二胺四丙酸、氨三乙酸、亞氨基二乙酸、羥乙基亞氨基二乙酸、亞氨基二丙酸、1,3-丙二胺四乙酸、1,3-二氨基-2-羥基丙烷四乙酸、乙二醇醚二胺四乙酸、間苯二胺四乙酸、1,2-環己二胺-N,N,N’,N’-四乙酸、二氨基丙酸、以及其等之鹽等。 Examples of the aminocarboxylic acid include hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, and ammonia trioxide. Acetic acid, iminodiacetic acid, hydroxyethyl iminodiacetic acid, iminodipropionic acid, 1,3-propanediaminetetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol ether Aminetetraacetic acid, m-phenylenediaminetetraacetic acid, 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid, diaminopropionic acid, salts thereof, and the like.
另外，作為上述氨基酸類，可列舉出谷氨酸、二羧甲基谷氨酸、鳥氨酸、半胱氨酸、甘氨酸、N,N-二(2-羥乙基)甘氨酸、(S,S)-乙二胺琥珀酸、以及其等之鹽等。 Further, examples of the amino acid include glutamic acid, dicarboxymethylglutamic acid, ornithine, cysteine, glycine, N,N-bis(2-hydroxyethyl)glycine, and (S, S). - Ethylenediamine succinic acid, and the like, and the like.
作為上述多元羧酸類，可列舉出琥珀酸、戊二酸、丙二酸、己二酸、乙二酸、馬來酸、檸康酸、衣康酸、中康酸、以及其等之鹽等。 Examples of the polyvalent carboxylic acid include succinic acid, glutaric acid, malonic acid, adipic acid, oxalic acid, maleic acid, citraconic acid, itaconic acid, mesaconic acid, and the like. .
本發明的鎳膠體催化劑液以可溶性鎳鹽(A)、還原劑(B)、膠體穩定劑(C)為必須成分，但也可以進一步含有水溶性聚合物。 The nickel colloidal catalyst liquid of the present invention contains a soluble nickel salt (A), a reducing agent (B), and a colloidal stabilizer (C) as essential components, but may further contain a water-soluble polymer.
如果催化劑液中含有水溶性聚合物，則膠體粒子的分散性提高，進而在化學鍍鎳時，可期待有助於析出均勻性優異且無色斑的鎳被膜。 When the water-soluble polymer is contained in the catalyst liquid, the dispersibility of the colloidal particles is improved, and in the case of electroless nickel plating, a nickel film which contributes to excellent precipitation uniformity and has no color unevenness can be expected.
上述水溶性聚合物基本優選為合成型聚合物，但也不排除明膠、澱粉等天然來源的水溶性聚合物、或者羧甲基纖維素(CMC)、甲基纖維素(MC)等纖維素衍生物之類的半合成型聚合物。關於該合成型水溶性聚合物，在後述與表面活性劑的關係下，部分重複也無妨。 The above water-soluble polymer is basically preferably a synthetic polymer, but does not exclude a water-soluble polymer of natural origin such as gelatin or starch, or a cellulose derivative such as carboxymethyl cellulose (CMC) or methyl cellulose (MC). Semi-synthetic polymer such as a substance. The synthetic water-soluble polymer may be partially repeated in the relationship with a surfactant to be described later.
作為上述合成型水溶性聚合物，可列舉出聚乙二醇(PEG)、聚丙二醇(PPG)、聚乙烯吡咯烷酮(PVP)、聚乙烯醇(PVA)、聚丙烯醯胺(PAM)、聚乙烯亞胺(PEI)、聚丙烯酸鹽等，特別優選高分子量的PEG、PVP、PVA等。 Examples of the synthetic water-soluble polymer include polyethylene glycol (PEG), polypropylene glycol (PPG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polypropylene decylamine (PAM), and polyethylene. An imine (PEI), a polyacrylate, or the like is particularly preferably a high molecular weight PEG, PVP, PVA or the like.
另外，本發明的鎳膠體催化劑液中，為了增加成為催化劑核的微細金屬的分散性，可以根據需要含有表面活性劑。 Further, in the nickel colloidal catalyst liquid of the present invention, in order to increase the dispersibility of the fine metal serving as the catalyst core, a surfactant may be contained as needed.
該表面活性劑可以選擇非離子型、兩性、陽離子型、或者陰離子型的各種表面活性劑。 The surfactant may be selected from various surfactants of nonionic, amphoteric, cationic or anionic.
作為上述非離子型表面活性劑，可列舉出C1~C20鏈烷醇、酚、萘酚、雙酚類、(聚)C1~C25烷基酚、(聚)芳基烷基酚、C1~C25烷基萘酚、C1~C25烷氧基化磷酸(鹽)、脫水山梨醇酯、聚亞烷基二醇、C1~C22脂肪胺、C1~C22脂肪醯胺等中加成縮合2~300莫耳環氧乙烷(EO)和/或環氧丙烷(PO)而成的化合物、C1~C25烷氧基化磷酸(鹽)等。 Examples of the nonionic surfactant include a C 1 to C 20 alkanol, a phenol, a naphthol, a bisphenol, a (poly) C 1 to C 25 alkyl phenol, and a (poly) aryl alkyl phenol. , C 1 ~ C 25 alkyl naphthol, C 1 ~ C 25 alkoxylated phosphoric acid (salt), sorbitan ester, polyalkylene glycol, C 1 ~ C 22 fatty amine, C 1 ~ C 22 A compound obtained by adding 2 to 300 mol of ethylene oxide (EO) and/or propylene oxide (PO) to a fatty guanamine or the like, and a C 1 to C 25 alkoxylated phosphoric acid (salt).
作為上述陽離子型表面活性劑，可列舉出季銨鹽或者吡啶鹽等，具體而言可列舉出：月桂基三甲基銨鹽、硬脂基三甲基銨鹽、十二烷基二甲基乙基銨鹽、十八烷基二甲基乙基銨鹽、二甲基苄基十二烷基銨鹽、十六烷基二甲基苄基銨鹽、十八烷基二甲基苄基銨鹽、三甲基苄基銨鹽、三乙基苄基銨鹽、二甲基二苯基銨鹽、苄基二甲基苯基銨鹽、十六烷基吡啶鹽、月桂基吡啶鹽、十二烷基吡啶鹽、硬脂胺乙酸鹽、月桂胺乙酸鹽、十八烷胺乙酸鹽等。 Examples of the cationic surfactant include a quaternary ammonium salt or a pyridinium salt, and specific examples thereof include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, and dodecyl dimethyl group. Ethyl ammonium salt, octadecyl dimethyl ethyl ammonium salt, dimethyl benzyl dodecyl ammonium salt, cetyl dimethyl benzyl ammonium salt, octadecyl dimethyl benzyl Ammonium salt, trimethylbenzylammonium salt, triethylbenzylammonium salt, dimethyldiphenylammonium salt, benzyldimethylphenylammonium salt, cetylpyridinium salt, lauryl pyridinium salt, Dodecylpyridine salt, stearylamine acetate, laurylamine acetate, octadecylamine acetate, and the like.
作為上述陰離子型表面活性劑，可列舉出烷基硫酸鹽、聚氧乙烯烷基醚硫酸鹽、聚氧乙烯烷基苯基醚硫酸鹽、烷基苯磺酸鹽、[(單、二、三)烷基]萘磺酸鹽等。作為上述兩性表面活性劑，可列舉出羧基甜菜鹼、咪唑啉甜菜鹼、磺基甜菜鹼、氨基羧酸等。另外，還可以使用環氧乙烷和/或環氧丙烷與烷基胺或二胺的縮合生成物的硫酸化或或磺酸化加成物。 Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkylbenzenesulfonates, and [(single, two, three). An alkyl] naphthalene sulfonate or the like. Examples of the amphoteric surfactant include a carboxybetaine, an imidazolinium betaine, a sulfobetaine, and an aminocarboxylic acid. Further, a sulfated or sulfonated adduct of a condensation product of ethylene oxide and/or propylene oxide with an alkylamine or a diamine can also be used.
在鎳膠體催化劑液中，上述可溶性鎳鹽(A)可以單獨使用或並用，其含量適宜為0.005~1.0莫耳/L，優選為0.02~0.5莫耳/L，更優選為0.05~0.3莫耳/L。 In the nickel colloidal catalyst liquid, the above soluble nickel salt (A) may be used singly or in combination, and the content thereof is suitably 0.005 to 1.0 mol/L, preferably 0.02 to 0.5 mol/L, more preferably 0.05 to 0.3 mol. /L.
如果可溶性鎳鹽(A)的含量少於適當量則有可能造成鎳被膜的膜厚不足，或被膜的均質性降低，反之，上限濃度根據溶解量等而受限制。 If the content of the soluble nickel salt (A) is less than the appropriate amount, the film thickness of the nickel film may be insufficient or the homogeneity of the film may be lowered. Conversely, the upper limit concentration is limited depending on the amount of dissolution or the like.
上述還原劑(B)可以單獨使用或並用，其含量適宜為0.005~0.8莫耳/L，優選為0.03~0.5莫耳/L、更優選為0.05~0.3莫耳/L。 The above reducing agent (B) may be used singly or in combination, and its content is suitably from 0.005 to 0.8 mol/L, preferably from 0.03 to 0.5 mol/L, more preferably from 0.05 to 0.3 mol/L.
如果還原劑的含量少於適當量則鎳鹽的還原作用降低，反之，上限濃度因溶解量等而受制限，但若過多則化學鍍膜所析出的鎳被膜 的均質性有可能降低。 If the content of the reducing agent is less than the appropriate amount, the reduction of the nickel salt is lowered. Conversely, the upper limit concentration is limited by the amount of dissolution, etc., if too large, the nickel coating deposited by the electroless plating film The homogeneity is likely to decrease.
上述膠體穩定劑(C)可以單獨使用或並用，其含量為0.015~8.0莫耳/L、優選為0.03~5.0莫耳/L、更優選為0.075~2.0莫耳/L。 The above-mentioned colloidal stabilizer (C) may be used singly or in combination, and its content is from 0.015 to 8.0 mol/L, preferably from 0.03 to 5.0 mol/L, more preferably from 0.075 to 2.0 mol/L.
如果上述膠體穩定劑的含量少於適當量，則有可能損害膠體催化劑液的經時穩定性、所得鍍膜的均勻性降低、或產生色斑。如果大於適當量，則化學鍍膜所得鎳被膜的均質性有可能降低。 If the content of the above-mentioned colloidal stabilizer is less than an appropriate amount, there is a possibility that the temporal stability of the colloidal catalyst liquid, the uniformity of the obtained plating film, or the occurrence of color unevenness may be impaired. If it is larger than an appropriate amount, the homogeneity of the nickel film obtained by electroless plating may be lowered.
另外，膠體穩定劑優選為可溶性鎳鹽含量的1.5倍以上。 Further, the colloidal stabilizer is preferably 1.5 times or more the content of the soluble nickel salt.
上述水溶性聚合物可以單獨使用或並用，其相對於催化劑液的含量適宜為0.05~100g/L。 The above water-soluble polymers may be used singly or in combination, and the content thereof is preferably 0.05 to 100 g/L with respect to the content of the catalyst liquid.
本發明的鎳膠體催化劑液可以是水系也可以是親油性醇等有機溶劑系。 The nickel colloidal catalyst liquid of the present invention may be an aqueous system or an organic solvent such as a lipophilic alcohol.
在水系的情況下，液體溶劑選自水和/或親水性醇。 In the case of a water system, the liquid solvent is selected from the group consisting of water and/or a hydrophilic alcohol.
另外，該催化劑液的pH值沒有特別限制，但優選中性、弱酸性、弱鹼性等。 Further, the pH of the catalyst liquid is not particularly limited, but is preferably neutral, weakly acidic, weakly alkaline or the like.
在製備該催化劑液時，為了從還原劑平穩地向鎳離子提供電子，基本上要花費時間將還原劑溶液緩慢滴入含有可溶性鎳鹽(和膠體穩定劑)的溶液中進行製備。例如，將5~50℃(優選為10~40℃)的還原劑溶液滴入鎳鹽溶液中攪拌20~1200分鐘(優選為30~300分鐘)，製成催化劑液。應予說明，催化劑液的製備中，也不排除將可溶性鎳鹽的溶液滴入還原劑的液體中。 In the preparation of the catalyst liquid, in order to smoothly supply electrons from the reducing agent to the nickel ions, it takes substantially time to prepare the preparation of the reducing agent solution by slowly dropping it into a solution containing a soluble nickel salt (and a colloidal stabilizer). For example, a reducing agent solution of 5 to 50 ° C (preferably 10 to 40 ° C) is dropped into a nickel salt solution and stirred for 20 to 1200 minutes (preferably 30 to 300 minutes) to prepare a catalyst liquid. Incidentally, in the preparation of the catalyst liquid, it is not excluded to drip the solution of the soluble nickel salt into the liquid of the reducing agent.
本發明的催化劑液中，在還原劑的作用下由可溶性鎳鹽生成的鎳膠體粒子是適宜平均粒徑為1~250nm、優選為1~120nm、更優選為1~100nm的微細粒子。 In the catalyst solution of the present invention, the nickel colloidal particles produced from the soluble nickel salt by the action of the reducing agent are fine particles having a suitable average particle diameter of from 1 to 250 nm, preferably from 1 to 120 nm, more preferably from 1 to 100 nm.
如果鎳膠體粒子的平均粒徑為250nm以下，則可推測出在將非導電性基板浸漬於催化劑液中的情況下，膠體粒子進入基板的微細凹凸面的凹處，通過緻密地吸附或者掛住等錨固效果，促進對基板表面賦予鎳膠體核。 When the average particle diameter of the nickel colloidal particles is 250 nm or less, it is presumed that when the non-conductive substrate is immersed in the catalyst liquid, the colloidal particles enter the concave portion of the fine uneven surface of the substrate, and are densely adsorbed or caught. The anchoring effect promotes the application of a nickel colloid core to the surface of the substrate.
本發明8是使用上述鎳膠體催化劑液的化學鍍膜方法，由以下三個步驟依次組合而成：(a)吸附促進步驟、(b)催化劑賦予步驟、(c)化學 鍍鎳或鎳合金步驟。 The present invention 8 is an electroless plating method using the above nickel colloidal catalyst liquid, which is sequentially combined by the following three steps: (a) adsorption promotion step, (b) catalyst imparting step, (c) chemistry Nickel or nickel alloying steps.
上述吸附促進步驟(a)換言之即為(b)的催化劑賦予的預處理步驟，是將非導電性基板浸漬於含有選自非離子型表面活性劑、陽離子型表面活性劑、陰離子型表面活性劑、兩性表面活性劑中的吸附促進劑的至少一種的液體中的步驟，通過使基板與含表面活性劑的液體接觸，提高基板表面的潤濕性增強催化劑活性，促進下一步驟中鎳膠體粒子的吸附。 The adsorption promoting step (a) is a pretreatment step of the catalyst of (b), in which the non-conductive substrate is immersed in a non-ionic surfactant, a cationic surfactant, an anionic surfactant. a step in a liquid of at least one of the adsorption promoters in the amphoteric surfactant, which improves the wettability of the surface of the substrate to enhance the activity of the catalyst by contacting the substrate with the liquid containing the surfactant, and promotes the nickel colloidal particles in the next step. Adsorption.
吸附促進步驟中，需要使非導電性基板與含表面活性劑的液體接觸，因此基本上浸漬於液體中，但將含表面活性劑的液體噴霧到基板上，或用刷毛塗布到基板上等也無妨。 In the adsorption promoting step, the non-conductive substrate needs to be brought into contact with the liquid containing the surfactant, so that it is substantially immersed in the liquid, but the surfactant-containing liquid is sprayed onto the substrate, or the bristles are applied to the substrate. No problem.
如本發明9所示，從促進吸附的觀點出發，帶正電荷的陽離子型或兩性表面活性劑較適合，特別優選陽離子型表面活性劑。另外，如果在陽離子型表面活性劑中並用少量非離子型表面活性劑，則吸附促進效果進一步增強。 As shown in the present invention 9, a positively charged cationic or amphoteric surfactant is suitable from the viewpoint of promoting adsorption, and a cationic surfactant is particularly preferable. Further, if a small amount of a nonionic surfactant is used in combination with the cationic surfactant, the adsorption promoting effect is further enhanced.
本發明1的催化劑液中，還原劑作用於可溶性鎳鹽生成的鎳膠體粒子zeta電位為負值，因此例如若利用陽離子型表面活性劑對非導電性基板進行接觸處理，則基板容易帶正電荷，下一步驟中鎳膠體粒子對基板的吸附效率增加。 In the catalyst liquid of the first aspect of the invention, the zeta potential of the nickel colloidal particles generated by the reducing agent acting on the soluble nickel salt is a negative value. Therefore, if the non-conductive substrate is subjected to a contact treatment with a cationic surfactant, for example, the substrate is easily positively charged. In the next step, the adsorption efficiency of the nickel colloidal particles on the substrate increases.
吸附促進步驟中表面活性劑的具體例，如上述本發明1的催化劑液中所描述的表面活性劑的記載所示。 Specific examples of the surfactant in the adsorption promoting step are shown in the description of the surfactant described in the above catalyst liquid of the present invention 1.
表面活性劑的含量為0.05~100g/L，優選為0.5~50g/L。優選該吸附促進步驟的處理溫度為15~70℃左右、浸漬時間為0.5~20分鐘左右。 The content of the surfactant is 0.05 to 100 g/L, preferably 0.5 to 50 g/L. Preferably, the treatment temperature of the adsorption promotion step is about 15 to 70 ° C, and the immersion time is about 0.5 to 20 minutes.
應予說明，優選在上述吸附促進步驟(a)之前，進一步進行除汙(desmear)處理、中和處理等預處理。 In addition, it is preferable to perform pretreatment such as desmear treatment and neutralization treatment before the adsorption promotion step (a).
結束吸附促進步驟(a)的非導電性基板用純水洗滌後，乾燥或不乾燥，轉入下一催化劑賦予步驟(b)。 The non-conductive substrate that has finished the adsorption-promoting step (a) is washed with pure water, dried or not dried, and transferred to the next catalyst-imparting step (b).
催化劑賦予步驟中，將非導電性基板浸漬於上述鎳膠體催化劑液中，使鎳膠體吸附在基板表面上。 In the catalyst application step, the non-conductive substrate is immersed in the nickel colloidal catalyst liquid to adsorb the nickel colloid on the surface of the substrate.
該催化劑液的液溫為15~95℃、優選為15~70℃，浸漬時間為0.1~20分鐘左右，pH值為3~11，進行浸漬處理時，只要將基板在靜置狀態 下浸漬於催化劑液中即可，但也可以進行攪拌或搖動。 The liquid temperature of the catalyst liquid is 15 to 95 ° C, preferably 15 to 70 ° C, the immersion time is about 0.1 to 20 minutes, and the pH is 3 to 11. When the immersion treatment is performed, the substrate is left still. The immersion in the catalyst liquid may be carried out, but stirring or shaking may also be carried out.
浸漬於催化劑液中的非導電性基板用純水洗滌後，乾燥或不乾燥，轉入化學鍍鎳或鎳合金步驟(c)。 The non-conductive substrate immersed in the catalyst liquid is washed with pure water, dried or not dried, and transferred to an electroless nickel or nickel alloy step (c).
化學鍍鎳或鎳合金與以往同樣處理即可，沒有特別限制。化學鍍鎳或鎳合金液的液溫通常為15~90℃、優選為20~70℃。 The electroless nickel plating or the nickel alloy may be treated in the same manner as in the related art, and is not particularly limited. The liquid temperature of the electroless nickel plating or nickel alloy liquid is usually 15 to 90 ° C, preferably 20 to 70 ° C.
鎳或鎳合金鍍液的攪拌可以採用空氣攪拌、快速液流攪拌、攪拌葉片等的機械攪拌等。 The stirring of the nickel or nickel alloy plating solution may be carried out by air stirring, rapid flow stirring, mechanical stirring such as stirring blades, and the like.
化學鍍鎳或鎳合金液的組成沒有特別限制，可以使用公知的鍍液。 The composition of the electroless nickel plating or nickel alloy liquid is not particularly limited, and a known plating solution can be used.
化學鍍鎳實質上為鍍鎳-磷合金、或者鍍鎳-硼合金。 Electroless nickel plating is essentially a nickel-phosphorus alloy or a nickel-boron alloy.
上述鎳合金為鎳-鈷、鎳-錫、鎳-錫-鋅等。 The nickel alloy is nickel-cobalt, nickel-tin, nickel-tin-zinc or the like.
公知的化學鍍鎳液基本上以可溶性鎳鹽和還原劑為主成分，其中含有絡合劑、pH調節劑、反應促進劑等各種添加劑。 The known electroless nickel plating liquid is mainly composed of a soluble nickel salt and a reducing agent, and contains various additives such as a complexing agent, a pH adjuster, and a reaction accelerator.
在進行化學鍍膜時，如果使用磷系還原劑(例如次磷酸鹽)，則得到鎳-磷合金鍍膜，如果使用硼系還原劑(例如，二甲胺硼烷)，則得到鎳-硼合金被膜。 When performing electroless plating, if a phosphorus-based reducing agent (for example, hypophosphite) is used, a nickel-phosphorus alloy plating film is obtained, and if a boron-based reducing agent (for example, dimethylamine borane) is used, a nickel-boron alloy coating is obtained. .
關於可溶性鎳鹽，如上述鎳膠體催化劑液的記載所示。 The soluble nickel salt is as described in the above nickel colloidal catalyst liquid.
關於上述絡合劑，也有與上述鎳膠體催化劑液所描述的膠體穩定劑共通的部分，具體而言為氨、乙二胺、焦磷酸鹽、檸檬酸、蘋果酸、乳酸、乙酸、乙二胺四乙酸(EDTA)等。 Regarding the above complexing agent, there are also a portion common to the colloidal stabilizer described in the above nickel colloidal catalyst liquid, specifically ammonia, ethylenediamine, pyrophosphate, citric acid, malic acid, lactic acid, acetic acid, ethylenediaminetetra. Acetic acid (EDTA) and the like.
[實施例] [Examples]
以下，對包括本發明的含有吸附促進劑的液體、鎳膠體催化劑液、以及化學鍍鎳或鎳合金液的製備在內的化學鍍鎳或鎳合金方法的實施例進行說明，依次說明鎳膠體催化劑液的經時穩定性試驗例、上述實施例所得的析出鎳(或鎳合金)被膜的外觀評價試驗例。 Hereinafter, examples of the method of electroless nickel plating or nickel alloy including the liquid of the adsorption promoter containing the present invention, the nickel colloidal catalyst liquid, and the electroless nickel or nickel alloy liquid will be described, and the nickel colloid catalyst will be sequentially explained. Test Example of Appearance Evaluation of Precipitated Nickel (or Nickel Alloy) Films obtained in the above Examples.
應予說明，本發明並不限於下列實施例、試驗例，當然可以在本發明的技術構思的範圍內進行任意變形。 It should be noted that the present invention is not limited to the following examples and test examples, and it is of course possible to carry out any modifications within the scope of the technical idea of the present invention.
《化學鍍鎳和鎳合金方法的實施例》 "Example of Electroless Nickel Plating and Nickel Alloy Method"
在下列實施例1~22中，實施例1~20為化學鍍鎳方法的實施例，實施例 21~22為化學鍍鎳-鈷合金方法的實施例。 In the following Examples 1 to 22, Examples 1 to 20 are examples of the electroless nickel plating method, and Examples 21 to 22 are examples of the method of electroless nickel-cobalt alloy plating.
上述實施例1是進行除汙和中和的預處理步驟後，依次實施吸附促進→催化劑賦予→化學鍍膜各步驟的化學鍍鎳方法的實施例，是吸附促進步驟的吸附促進劑為陽離子型表面活性劑和非離子型表面活性劑的混合物，催化劑賦予步驟的膠體催化劑液使用硼氫化合物作為還原劑、使用檸檬酸(羥基羧酸)作為膠體穩定劑之例。 The first embodiment is an example of an electroless nickel plating method in which each step of adsorption promotion → catalyst application → electroless plating is sequentially performed after the pretreatment step of decontamination and neutralization, and the adsorption promoter in the adsorption promotion step is a cationic surface. A mixture of an active agent and a nonionic surfactant, and a colloidal catalyst liquid for the catalyst imparting step uses a borohydride as a reducing agent and citric acid (hydroxycarboxylic acid) as a colloidal stabilizer.
上述實施例2~12和實施例15~20以實施例1為基礎，實施例2~3是改變實施例1的膠體穩定劑的含量之例，實施例4~5是改變還原劑的含量之例，實施例6是分別增加鎳鹽、還原劑和膠體穩定劑的含量之例，實施例7是將實施例1的pH值(中性)變為弱酸性之例，實施例8是將膠體穩定劑改為另一種羥基羧酸之例，實施例9是將膠體穩定劑改為多元羧酸之例，實施例10是將還原劑改為抗壞血酸之例，實施例11是將還原劑改為硼烷類之例，實施例12是改變可溶性鎳鹽的種類之例，實施例15是並用甘氨酸(氨基酸)和蘋果酸(羥基羧酸)作為膠體穩定劑之例，實施例16~17是增加鎳鹽、還原劑和膠體穩定劑的含量之例，其中，實施例17是並用硼氫化合物和抗壞血酸作為還原劑之例，實施例18是並用3種還原劑之例，實施例19~20是使用兩性表面活性劑作為吸附促進步驟的吸附促進劑之例。 The above Examples 2 to 12 and Examples 15 to 20 are based on Example 1, and Examples 2 to 3 are examples in which the content of the colloidal stabilizer of Example 1 is changed, and Examples 4 to 5 are the contents of the reducing agent. For example, Example 6 is an example in which the contents of the nickel salt, the reducing agent, and the colloidal stabilizer are respectively increased, and Example 7 is an example in which the pH value (neutral) of Example 1 is weakly acidic, and Example 8 is a colloid. The stabilizer is changed to another hydroxycarboxylic acid, the embodiment 9 is an example in which the colloidal stabilizer is changed to a polycarboxylic acid, the embodiment 10 is an example in which the reducing agent is changed to ascorbic acid, and the embodiment 11 is a modification in which the reducing agent is changed. Examples of boranes, Example 12 is an example of changing the kind of soluble nickel salt, and Example 15 is an example in which glycine (amino acid) and malic acid (hydroxycarboxylic acid) are used together as a colloidal stabilizer, and Examples 16 to 17 are added. Examples of the content of the nickel salt, the reducing agent and the colloidal stabilizer, wherein Example 17 is an example in which a boron hydride compound and ascorbic acid are used in combination as a reducing agent, and Example 18 is an example in which three kinds of reducing agents are used in combination, and Examples 19 to 20 are An amphoteric surfactant is used as an example of an adsorption promoter for the adsorption promoting step.
實施例13~14以實施例9為基礎，實施例13是改變鎳鹽種類之例，實施例14是並用硼氫化合物和次磷酸作為還原劑之例。 Examples 13 to 14 are based on Example 9, Example 13 is an example of changing the kind of nickel salt, and Example 14 is an example in which a boron hydride compound and hypophosphorous acid are used in combination as a reducing agent.
另外，如上所述，實施例21~22是化學鍍鎳-鈷合金方法的實施例，其中，實施例21在進行除汙和中和的預處理步驟後，依次實施吸附促進→催化劑賦予→化學鍍膜各步驟，預處理步驟、吸附促進步驟、催化劑賦予步驟以上述實施例1為基礎。實施例22以上述實施例21為基礎，是將鎳膠體催化劑液從實施例1改為實施例18的催化劑液之例。 Further, as described above, Examples 21 to 22 are examples of the electroless nickel-cobalt alloy method in which, in Example 21, after the pretreatment step of decontamination and neutralization, adsorption promotion→catalyst impartation→chemistry was sequentially performed. The respective steps of the coating, the pretreatment step, the adsorption promoting step, and the catalyst imparting step are based on the above-described Example 1. In Example 22, based on the above Example 21, the nickel colloidal catalyst liquid was changed from Example 1 to the catalyst liquid of Example 18.
另一方面，下列比較例1~3中，比較例1是催化劑液中不含膠體穩定劑的空白例，比較例2是催化劑液中含有可期待穩定化作用的化合物代替本發明的膠體穩定劑之例，比較例3是沒有吸附促進步驟，直接從催化劑賦予步驟進行化學鍍膜步驟的空白例。 On the other hand, in the following Comparative Examples 1 to 3, Comparative Example 1 is a blank example in which no colloidal stabilizer is contained in the catalyst liquid, and Comparative Example 2 is a catalyst containing a compound which can be expected to be stabilized in place of the colloidal stabilizer of the present invention. As an example, Comparative Example 3 is a blank example in which the electroless plating step is carried out directly from the catalyst application step without the adsorption promoting step.
(1)實施例1 (1) Embodiment 1
本發明的化學鍍鎳方法特徵在於依次實施吸附促進→催化劑賦予→化學鍍膜各步驟，而本實施例1是在吸附促進步驟之前進一步實施除汙和中和的預處理步驟之例。 The electroless nickel plating method of the present invention is characterized in that each step of adsorption promotion → catalyst application → electroless plating is sequentially performed, and this embodiment 1 is an example of a pretreatment step of further performing decontamination and neutralization before the adsorption promotion step.
即，首先在下列條件(p)下進行預處理後，在條件(a)下進行吸附促進，在條件(b)下進行催化劑賦予，然後在條件(c)下進行化學鍍鎳-磷。 Namely, first, after pretreatment under the following condition (p), adsorption promotion is carried out under the condition (a), catalyst application is carried out under the condition (b), and then electroless nickel-phosphorus is carried out under the condition (c).
(p)預處理步驟 (p) Pretreatment steps
首先，在雙面覆銅玻璃-環氧樹脂基板(Panasonic Electric Works Co.,Ltd.製FR-4，板厚：1.0mm)上，將35μm的銅箔溶解除去，除污/中和處理後的基板作為試樣基板。 First, a 35 μm copper foil was dissolved and removed on a double-sided copper-clad glass-epoxy substrate (FR-4 manufactured by Panasonic Electric Works Co., Ltd., thickness: 1.0 mm), and after decontamination/neutralization treatment The substrate serves as a sample substrate.
除汙處理液和中和處理液的組成、以及除汙/中和處理條件如下所示： The composition of the desmutting treatment liquid and the neutralization treatment liquid, and the decontamination/neutralization treatment conditions are as follows:
[除汙處理液] [Decontamination treatment liquid]
高錳酸鉀：50g/L Potassium permanganate: 50g/L
氫氧化鈉：20g/L Sodium hydroxide: 20g/L
[中和處理液] [Neutralization treatment solution]
硫酸：50g/L Sulfuric acid: 50g/L
乙二酸：10g/L Oxalic acid: 10g/L
Noigen XL-80：1g/L Noigen XL-80: 1g/L
[除汙/中和處理條件] [Decontamination/Neutralization Treatment Conditions]
將試樣基板在80℃、10分鐘的條件下浸漬於除汙處理液中，用純水洗滌。然後，在40℃、10分鐘的條件下浸漬于中和處理液中，用純水洗滌、乾燥，從而將吸附在試樣基板上的錳溶解除去。 The sample substrate was immersed in a desmutting treatment liquid at 80 ° C for 10 minutes, and washed with pure water. Then, it was immersed in the neutralization treatment liquid at 40 ° C for 10 minutes, washed with pure water, and dried to dissolve and remove manganese adsorbed on the sample substrate.
應予說明，Noigen XL-80为Dai-ichi Kogyo Seiyaku Co.,Ltd.製的非離子表面活性劑，以聚氧化烯支鏈癸基醚為主成分。 In addition, Noigen XL-80 is a nonionic surfactant manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., and has a polyoxyalkylene branched mercaptoether as a main component.
(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter
按照以下組成製備含有吸附促進劑的液體。 A liquid containing an adsorption promoter was prepared in accordance with the following composition.
[吸附促進劑] [Adsorption accelerator]
二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L
聚氧化烯支鏈癸基醚：1g/L Polyoxyalkylene branched decyl ether: 1g/L
(b)鎳催化劑液的製備 (b) Preparation of nickel catalyst solution
鎳溶液、還原劑溶液、以及鎳膠體催化劑液的製備條件如下所示。 The preparation conditions of the nickel solution, the reducing agent solution, and the nickel colloidal catalyst liquid are as follows.
[鎳溶液] [nickel solution]
硫酸鎳(以Ni2+計0.1莫耳/L)：0.1莫耳/L Nickel sulfate (0.1 mol/L in terms of Ni 2+ ): 0.1 mol/L
檸檬酸：0.3莫耳/L Citric acid: 0.3 mol/L
[還原劑溶液] [Reducing agent solution]
硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
向調整為pH值7.0的30℃鎳溶液中滴入還原劑溶液並攪拌，得到鎳膠體催化劑液。 The reducing agent solution was dropped into a 30 ° C nickel solution adjusted to pH 7.0 and stirred to obtain a nickel colloidal catalyst liquid.
(c)化學鍍鎳-磷液的製備 (c) Preparation of electroless nickel-phosphorus solution
按照以下組成製成化學鍍鎳液(建浴)。另外，該鍍液使用稀硫酸或氫氧化鈉進行pH值調整。 An electroless nickel plating solution (built bath) was prepared in accordance with the following composition. In addition, the plating solution is adjusted in pH using dilute sulfuric acid or sodium hydroxide.
[化學鍍鎳液] [Chemical nickel plating solution]
硫酸鎳六水合物(以Ni2+計)：5.6g/L Nickel sulfate hexahydrate (based on Ni 2+ ): 5.6 g / L
次磷酸鈉一水合物：30g/L Sodium hypophosphite monohydrate: 30g/L
琥珀酸：25.0g/L Succinic acid: 25.0g/L
餘量：純水 Balance: pure water
pH值(20℃)：4.6 pH (20 ° C): 4.6
(d)化學鍍鎳-磷的處理條件 (d) Treatment conditions for electroless nickel-phosphorus plating
將除汙/中和處理後的試樣基板在50℃、2分鐘的條件下浸漬於上述(a)含有吸附促進劑的液體中，用純水洗滌後，在5℃、10分鐘的條件下浸漬於上述(b)鎳膠體催化劑液中，用純水洗滌。 The sample substrate after the decontamination/neutralization treatment was immersed in the above (a) liquid containing the adsorption promoter at 50 ° C for 2 minutes, washed with pure water, and then dried at 5 ° C for 10 minutes. It was immersed in the above (b) nickel colloidal catalyst liquid, and washed with pure water.
然後，在90℃、20分鐘的條件下浸漬於上述(c)化學鍍鎳液中實施化學鍍膜，在試樣基板上形成鎳-磷被膜後，用純水洗滌，乾燥。 Then, it was immersed in the above (c) electroless nickel plating solution at 90 ° C for 20 minutes to carry out electroless plating, and a nickel-phosphorus film was formed on the sample substrate, and then washed with pure water and dried.
(2)實施例2 (2) Embodiment 2
以上述實施例1為基礎，按照下列組成製備鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above-mentioned Example 1, a nickel colloidal catalyst liquid was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
硫酸鎳(以Ni2+計0.1莫耳/L)：0.1莫耳/L Nickel sulfate (0.1 mol/L in terms of Ni 2+ ): 0.1 mol/L
檸檬酸：0.15莫耳/L Citric acid: 0.15 mol/L
[還原劑溶液] [Reducing agent solution]
硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
(3)實施例3 (3) Embodiment 3
以上述實施例1為基礎，按照下列組成製備鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above-mentioned Example 1, a nickel colloidal catalyst liquid was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
硫酸鎳(以Ni2+計0.1莫耳/L)：0.1莫耳/L Nickel sulfate (0.1 mol/L in terms of Ni 2+ ): 0.1 mol/L
檸檬酸：0.4莫耳/L Citric acid: 0.4 m / L
[還原劑溶液] [Reducing agent solution]
硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
(4)實施例4 (4) Embodiment 4
以上述實施例1為基礎，按照下列組成製備鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above-mentioned Example 1, a nickel colloidal catalyst liquid was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
硫酸鎳(以Ni2+計0.1莫耳/L)：0.1莫耳/L Nickel sulfate (0.1 mol/L in terms of Ni 2+ ): 0.1 mol/L
檸檬酸：0.3莫耳/L Citric acid: 0.3 mol/L
[還原劑溶液] [Reducing agent solution]
硼氫化鈉：0.05莫耳/L Sodium borohydride: 0.05 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
(5)實施例5 (5) Embodiment 5
以上述實施例1為基礎，按照下列組成製備鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above-mentioned Example 1, a nickel colloidal catalyst liquid was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
硫酸鎳(以Ni2+計0.1莫耳/L)：0.1莫耳/L Nickel sulfate (0.1 mol/L in terms of Ni 2+ ): 0.1 mol/L
檸檬酸：0.3莫耳/L Citric acid: 0.3 mol/L
[還原劑溶液] [Reducing agent solution]
硼氫化鈉：0.3莫耳/L Sodium borohydride: 0.3 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
(6)實施例6 (6) Embodiment 6
以上述實施例1為基礎，按照下列組成製備鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件與實施例1相同。 Based on the above Example 1, a nickel colloidal catalyst liquid was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were the same as in Example 1.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
硫酸鎳(以Ni2+計0.1莫耳/L)：0.2莫耳/L Nickel sulfate (0.1 mol/L in terms of Ni 2+ ): 0.2 mol/L
檸檬酸：0.6莫耳/L Citric acid: 0.6 mol/L
[還原劑溶液] [Reducing agent solution]
硼氫化鈉：0.4莫耳/L Sodium borohydride: 0.4 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
(7)實施例7 (7) Embodiment 7
以上述實施例1為基礎，鎳膠體催化劑液的pH值如下所示進行製備， 除此之外，鎳膠體催化劑液的組成和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 Based on the above Example 1, the pH of the nickel colloidal catalyst liquid was prepared as follows. In addition, the composition of the nickel colloidal catalyst liquid, the preparation method of the electroless nickel plating liquid, and the processing conditions of each step were set to be the same as in the first embodiment.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
與實施例1相同。 The same as in the first embodiment.
[還原劑溶液] [Reducing agent solution]
與實施例1相同。 The same as in the first embodiment.
[鎳膠體催化劑液] [Nickel colloidal catalyst solution]
向調整為pH值5.0的25℃鎳溶液中滴入還原劑溶液並攪拌，得到鎳膠體催化劑液。 The reducing agent solution was dropped into a 25 ° C nickel solution adjusted to pH 5.0 and stirred to obtain a nickel colloidal catalyst liquid.
(8)實施例8 (8) Example 8
以上述實施例1為基礎，按照下列組成製備鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above-mentioned Example 1, a nickel colloidal catalyst liquid was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
硫酸鎳(以Ni2+計0.1莫耳/L)：0.1莫耳/L Nickel sulfate (0.1 mol/L in terms of Ni 2+ ): 0.1 mol/L
蘋果酸：0.3莫耳/L Malic acid: 0.3 mol / L
[還原劑溶液] [Reducing agent solution]
硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
(9)實施例9 (9) Embodiment 9
以上述實施例1為基礎，按照下列組成製備鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above-mentioned Example 1, a nickel colloidal catalyst liquid was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
硫酸鎳(以Ni2+計0.1莫耳/L)：0.1莫耳/L Nickel sulfate (0.1 mol/L in terms of Ni 2+ ): 0.1 mol/L
琥珀酸：0.3莫耳/L Succinic acid: 0.3 mol/L
[還原劑溶液] [Reducing agent solution]
硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
(10)實施例10 (10) Embodiment 10
以上述實施例1為基礎，按照下列組成製備鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above-mentioned Example 1, a nickel colloidal catalyst liquid was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
硫酸鎳(以Ni2+計0.1莫耳/L)：0.1莫耳/L Nickel sulfate (0.1 mol/L in terms of Ni 2+ ): 0.1 mol/L
檸檬酸：0.3莫耳/L Citric acid: 0.3 mol/L
[還原劑溶液] [Reducing agent solution]
抗壞血酸：0.2莫耳/L Ascorbic acid: 0.2 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
(11)實施例11 (11) Example 11
以上述實施例1為基礎，按照下列組成製備鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above-mentioned Example 1, a nickel colloidal catalyst liquid was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
硫酸鎳(以Ni2+計0.1莫耳/L)：0.1莫耳/L Nickel sulfate (0.1 mol/L in terms of Ni 2+ ): 0.1 mol/L
檸檬酸：0.3莫耳/L Citric acid: 0.3 mol/L
[還原劑溶液] [Reducing agent solution]
二甲胺硼烷：0.2莫耳/L Dimethylamine borane: 0.2 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
(12)實施例12 (12) Example 12
以上述實施例1為基礎，按照下列組成製備鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above-mentioned Example 1, a nickel colloidal catalyst liquid was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
乙酸鎳(以Ni2+計0.1莫耳/L)：0.1莫耳/L Nickel acetate (0.1 mol/L in terms of Ni 2+ ): 0.1 mol/L
檸檬酸：0.3莫耳/L Citric acid: 0.3 mol/L
[還原劑溶液] [Reducing agent solution]
硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
(13)實施例13 (13) Example 13
以上述實施例9為基礎，按照下列組成製備鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above-mentioned Example 9, a nickel colloidal catalyst liquid was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
氨基磺酸鎳(以Ni2+計0.1莫耳/L)：0.1莫耳/L Nickel sulfamate (0.1 mol/L in terms of Ni 2+ ): 0.1 mol/L
琥珀酸：0.3莫耳/L Succinic acid: 0.3 mol/L
[還原劑溶液] [Reducing agent solution]
硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
(14)實施例14 (14) Example 14
以上述實施例9為基礎，按照下列組成製備鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above-mentioned Example 9, a nickel colloidal catalyst liquid was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
硫酸鎳(以Ni2+計0.1莫耳/L)：0.1莫耳/L Nickel sulfate (0.1 mol/L in terms of Ni 2+ ): 0.1 mol/L
琥珀酸：0.3莫耳/L Succinic acid: 0.3 mol/L
[還原劑溶液] [Reducing agent solution]
次磷酸：0.1莫耳/L Hypophosphorous acid: 0.1 mol/L
硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
(15)實施例15 (15) Example 15
以上述實施例1為基礎，按照下列組成製備鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above-mentioned Example 1, a nickel colloidal catalyst liquid was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
硫酸鎳(以Ni2+計0.1莫耳/L)：0.1莫耳/L Nickel sulfate (0.1 mol/L in terms of Ni 2+ ): 0.1 mol/L
甘氨酸：0.1莫耳/L Glycine: 0.1 mol/L
蘋果酸：0.3莫耳/L Malic acid: 0.3 mol / L
[還原劑溶液] [Reducing agent solution]
硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
(16)實施例16 (16) Embodiment 16
以上述實施例1為基礎，按照下列組成製備鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above-mentioned Example 1, a nickel colloidal catalyst liquid was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
硫酸鎳(以Ni2+計0.1莫耳/L)：0.2莫耳/L Nickel sulfate (0.1 mol/L in terms of Ni 2+ ): 0.2 mol/L
檸檬酸：0.6莫耳/L Citric acid: 0.6 mol/L
[還原劑溶液] [Reducing agent solution]
硼氫化鈉：0.3莫耳/L Sodium borohydride: 0.3 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
(17)實施例17 (17) Example 17
以上述實施例1為基礎，按照下列組成製備鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above-mentioned Example 1, a nickel colloidal catalyst liquid was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
硫酸鎳(以Ni2+計0.1莫耳/L)：0.2莫耳/L Nickel sulfate (0.1 mol/L in terms of Ni 2+ ): 0.2 mol/L
檸檬酸：0.6莫耳/L Citric acid: 0.6 mol/L
[還原劑溶液] [Reducing agent solution]
硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L
抗壞血酸：0.2莫耳/L Ascorbic acid: 0.2 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
(18)實施例18 (18) Example 18
以上述實施例1為基礎，按照下列組成製備鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above-mentioned Example 1, a nickel colloidal catalyst liquid was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
硫酸鎳(以Ni2+計0.1莫耳/L)：0.2莫耳/L Nickel sulfate (0.1 mol/L in terms of Ni 2+ ): 0.2 mol/L
檸檬酸：0.3莫耳/L Citric acid: 0.3 mol/L
[還原劑溶液] [Reducing agent solution]
硼氫化鈉：0.1莫耳/L Sodium borohydride: 0.1 mol/L
次磷酸：0.1莫耳/L Hypophosphorous acid: 0.1 mol/L
二甲胺硼烷：0.1莫耳/L Dimethylamine borane: 0.1 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
(19)實施例19 (19) Example 19
以上述實施例1為基礎，按照下列組成製備吸附促進劑，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above Example 1, an adsorption promoter was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter
按照下列組成製備含有吸附促進劑的液體。 A liquid containing an adsorption promoter was prepared in accordance with the following composition.
[吸附促進劑] [Adsorption accelerator]
月桂基二甲基氨基乙酸甜菜鹼：5g/L Lauryl dimethylaminoacetic acid betaine: 5g/L
(20)實施例20 (20) Embodiment 20
以上述實施例1為基礎，按照下列組成製備吸附促進劑，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 On the basis of the above Example 1, an adsorption promoter was prepared in accordance with the following composition, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the treatment conditions of the respective steps were set to be the same as in the first embodiment.
(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter
按照下列組成製備含有吸附促進劑的液體。 A liquid containing an adsorption promoter was prepared in accordance with the following composition.
[吸附促進劑] [Adsorption accelerator]
烷基咪唑啉甜菜鹼：5g/L Alkyl imidazoline betaine: 5g/L
聚氧化烯支鏈癸基醚：1g/L Polyoxyalkylene branched decyl ether: 1g/L
(21)實施例21 (21) Example 21
以上述實施例1為基礎，按照下列組成製備化學鍍鎳-鈷合金液，除此之外，吸附促進劑和鎳膠體催化劑液的製備方法、以及預處理、吸附促進、催化劑賦予、化學鍍膜各步驟的處理條件設定為與實施例1相同。 Based on the above Example 1, the electroless nickel-cobalt alloy solution is prepared according to the following composition, in addition to the preparation method of the adsorption promoter and the nickel colloidal catalyst liquid, as well as the pretreatment, adsorption promotion, catalyst application, and electroless plating. The processing conditions of the steps are set to be the same as in the first embodiment.
(c)化學鍍鎳-鈷合金液的製備 (c) Preparation of electroless nickel-cobalt alloy solution
[化學鍍鎳液] [Chemical nickel plating solution]
氯化鎳(以Ni2+計)：1.5g/L Nickel chloride (based on Ni 2+ ): 1.5g / L
氯化鈷(以Co2+計)：1.5g/L Cobalt chloride (calculated as Co 2+ ): 1.5g/L
酒石酸鈉：78g/L Sodium tartrate: 78g/L
鹽酸肼：68g/L Guanidine hydrochloride: 68g/L
餘量：純水 Balance: pure water
pH值(20℃)：12.0 pH (20 ° C): 12.0
(22)實施例22 (22) Example 22
上述實施例21為基礎，按照上述實施例18的組成製備鎳膠體催化劑液，除此之外，吸附促進劑和鎳膠體催化劑液的製備方法、以及預處理、吸附促進、催化劑賦予、化學鍍膜各步驟的處理條件設定為與實施例21相同。 Based on the above-mentioned Example 21, a nickel colloidal catalyst liquid is prepared according to the composition of the above-mentioned Example 18, in addition to the preparation method of the adsorption promoter and the nickel colloidal catalyst liquid, and pretreatment, adsorption promotion, catalyst application, and electroless plating. The processing conditions of the steps were set to be the same as in Example 21.
(23)比較例1 (23) Comparative Example 1
以上述實施例1為基礎，按照下列組成製備含有吸附促進劑的液體和鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 Based on the above Example 1, the liquid and the nickel colloidal catalyst liquid containing the adsorption promoter were prepared according to the following composition, and the preparation method of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the processing conditions of each step were set to The same as in the first embodiment.
即，在該比較例1中，鎳膠體催化劑液中不含膠體穩定劑。 That is, in Comparative Example 1, the colloidal stabilizer was not contained in the nickel colloidal catalyst liquid.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
硫酸鎳(以Ni2+計0.1莫耳/L)：0.1莫耳/L Nickel sulfate (0.1 mol/L in terms of Ni 2+ ): 0.1 mol/L
[還原劑溶液] [Reducing agent solution]
硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
但是，雖然生成鎳膠體粒子，但發生凝集、沉澱。 However, although nickel colloidal particles are formed, aggregation and precipitation occur.
(24)比較例2 (24) Comparative Example 2
以上述實施例1為基礎，按照下列組成製備含有吸附促進劑的液體和鎳膠體催化劑液，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 Based on the above Example 1, the liquid and the nickel colloidal catalyst liquid containing the adsorption promoter were prepared according to the following composition, and the preparation method of the nickel colloidal catalyst liquid and the electroless nickel plating liquid, and the processing conditions of each step were set to The same as in the first embodiment.
即，在該比較例2中，鎳膠體催化劑液中，代替本發明所規定的膠體穩定劑，含有可期待類似於該膠體穩定劑作用的乙醇胺。 That is, in Comparative Example 2, in the nickel colloidal catalyst liquid, instead of the colloidal stabilizer specified in the present invention, ethanolamine which is expected to function similarly to the colloidal stabilizer is contained.
(b)鎳膠體催化劑液的製備 (b) Preparation of nickel colloidal catalyst solution
[鎳溶液] [nickel solution]
硫酸鎳(Ni2+)：0.1莫耳/L Nickel sulfate (Ni2+): 0.1 mol/L
乙醇胺：0.3莫耳/L Ethanolamine: 0.3 mol / L
[還原劑溶液] [Reducing agent solution]
硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L
[鎳膠體催化劑液的製備條件] [Preparation conditions of nickel colloidal catalyst liquid]
與實施例1相同。 The same as in the first embodiment.
但是，雖然生成鎳膠體粒子，但發生凝集、沉澱。 However, although nickel colloidal particles are formed, aggregation and precipitation occur.
(20)比較例3 (20) Comparative Example 3
以上述實施例1為基礎，省略吸附促進步驟，除此之外，鎳膠體催化劑液和化學鍍鎳液的製備方法、以及各步驟的處理條件設定為與實施例1相同。 The adsorption promotion step was omitted on the basis of the above-described first embodiment, and the preparation methods of the nickel colloidal catalyst liquid and the electroless nickel plating liquid and the processing conditions of the respective steps were set to be the same as in the first embodiment.
即，將除汙/中和處理後的試樣基板在5℃、10分鐘的條件下浸漬於鎳膠體催化劑液中，用純水洗滌。 Specifically, the sample substrate after the decontamination/neutralization treatment was immersed in a nickel colloidal catalyst liquid at 5 ° C for 10 minutes, and washed with pure water.
然後，在90℃、20分鐘的條件下浸漬於上述化學鍍鎳液中實施化學鍍膜，在試樣基板上形成鎳-磷被膜後，用純水洗滌，乾燥。 Then, the electroless plating solution was immersed in the above electroless nickel plating solution at 90 ° C for 20 minutes, and a nickel-phosphorus film was formed on the sample substrate, and then washed with pure water and dried.
《催化劑液的經時穩定性試驗例》 "Example of test for stability of catalyst liquid over time"
由此，對於上述實施例1~22和比較例1~3中製備的各鎳膠體催化劑液，按照下列標準評價膠體穩定性的優劣。 Thus, the merits of the colloidal stability of each of the nickel colloidal catalyst liquids prepared in the above Examples 1 to 22 and Comparative Examples 1 to 3 were evaluated in accordance with the following criteria.
○：建浴後1個月內未發生沉澱或分解。 ○: No precipitation or decomposition occurred within 1 month after the bath was built.
×：建浴後立刻發生沉澱或分解。 ×: Precipitation or decomposition occurs immediately after the bath is built.
《經化學鍍膜析出的鎳和鎳合金被膜的外觀評價試驗例》 "Example of Evaluation of Appearance Evaluation of Nickel and Nickel Alloy Coatings Deposited by Electroless Coating"
接著，對於由上述實施例1~22和比較例1~3的各化學鍍膜方法得到的鎳或鎳合金化學鍍膜，按照下列標準目視評價被膜外觀的優劣。 Next, the nickel or nickel alloy electroless plating film obtained by each of the chemical plating methods of Examples 1 to 22 and Comparative Examples 1 to 3 was visually evaluated for the appearance of the film according to the following criteria.
○：鍍膜未出現色斑。 ○: No stain appeared on the coating.
△：鍍膜出現局部未析出(鍍膜裂縫)。 △: The coating film was partially precipitated (coating crack).
×：鍍膜未析出。 ×: The coating film was not precipitated.
應予說明，析出被膜的“色斑”表示存在被膜的緻密性或平滑性等與周囲不同的部分。被膜的“色斑”與被膜的均勻性屬於不同觀點。 In addition, the "spot" of the film to be deposited indicates that there is a portion different from the circumference such as the denseness or smoothness of the film. The "spot" of the film and the uniformity of the film belong to different viewpoints.
《對鎳膠體催化劑液的經時穩定性和被膜外觀的試驗結果》 "Test Results of Time Stability of Nickel Colloidal Catalyst and Appearance of Film"
下表為上述膠體催化劑液的經時穩定性和被膜外觀的評價試驗結果。 The following table shows the results of the evaluation of the stability of the above colloidal catalyst liquid and the appearance of the film.
《催化劑液的經時穩定性和鍍膜外觀的綜合評價》 "Comprehensive evaluation of the stability of the catalyst liquid and the appearance of the coating"
在鎳膠體催化劑液缺少膠體穩定劑的比較例1中，催化劑液的經時穩定性差，進而即使在與催化劑液接觸後對非導電性基板實施化學鍍膜也未析出鎳被膜。 In Comparative Example 1 in which the nickel colloidal catalyst liquid lacked the colloidal stabilizer, the stability of the catalyst liquid with time was poor, and even after the electroless plating was applied to the non-conductive substrate after contact with the catalyst liquid, the nickel film was not deposited.
另外，在鎳膠體催化劑液中含有可期待穩定化作用的乙醇胺代替本發明的膠體穩定劑的比較例2中，仍然是催化劑液的經時穩定性差， 進而在化學鍍膜中未析出鎳被膜。由此，可以判斷出為了使催化劑液經時穩定化，需要鎳鹽中含有還原劑，並使羥基羧酸類、氨基羧酸類等特定成分作為本發明的膠體穩定劑共存。 Further, in Comparative Example 2 containing an ethanolamine which can be expected to be stabilized in the nickel colloidal catalyst liquid in place of the colloidal stabilizer of the present invention, the stability of the catalyst liquid was still poor. Further, a nickel film was not deposited in the electroless plating film. Thus, it can be judged that in order to stabilize the catalyst liquid over time, it is necessary to contain a reducing agent in the nickel salt, and a specific component such as a hydroxycarboxylic acid or an aminocarboxylic acid is allowed to coexist as a colloidal stabilizer of the present invention.
在不經吸附促進處理即對非導電性基板進行催化劑賦予，實施化學鍍鎳的比較例3中，雖然催化劑液的經時穩定性與實施例相同，但析出的鎳被膜出現因局部未析出之處而產生的“鍍膜裂縫”，由此可判斷出由於催化劑賦予前未進行吸附促進預處理，因此催化劑活性不足，鎳膠體粒子在基板上的吸附比實施例差。 In Comparative Example 3 in which electroless nickel plating was performed on the non-conductive substrate without the adsorption-promoting treatment, the stability of the catalyst liquid was the same as in the examples, but the precipitated nickel film was partially precipitated. From the "coating crack" generated, it was judged that the adsorption promotion pretreatment was not performed before the catalyst was applied, so that the catalyst activity was insufficient, and the adsorption of the nickel colloidal particles on the substrate was inferior to that of the examples.
與此相對，在吸附促進預處理後，進行催化劑賦予處理，然後再實施化學鍍鎳的實施例1~20中，催化劑液的經時穩定性均良好，化學鍍膜所析出的鎳被膜大致無色斑且均勻性優異。 On the other hand, in Examples 1 to 20 in which the catalyst application treatment was carried out after the adsorption-promoted pretreatment, and then electroless nickel plating was performed, the stability of the catalyst liquid was good, and the nickel film deposited by the electroless plating film was substantially colorless. Excellent in spot and uniformity.
該實施例1~20與上述比較例1對比可知，為了獲得無色斑且均勻性優異的鎳被膜，催化劑液中不但含有鎳鹽和還原劑，還必須含有膠體穩定劑。 In comparison with the above Comparative Example 1, the examples 1 to 20 show that in order to obtain a nickel film having no color unevenness and excellent uniformity, the catalyst liquid contains not only a nickel salt and a reducing agent but also a colloidal stabilizer.
另外，若將實施例1~20與比較例2對比則，為了得到無色斑且均勻性優異的鎳被膜，即便添加只能期待絡合作用的化合物也不具備有效性，可判斷出本發明所規定的特定膠體穩定劑的選擇很重要。 In addition, in order to obtain a nickel film having no color unevenness and excellent uniformity, it is not effective to add a compound which can only be expected to be complexed, and it can be judged that the present invention is obtained by comparing Examples 1 to 20 with Comparative Example 2. The choice of the specific colloidal stabilizer specified is important.
另外，從實施例1~20與比較例3的對比可明確，為了對鎳被膜賦予實用且優異的外觀，在催化劑賦予前對膠體催化劑核進行吸附促進的預處理很重要。 Further, from the comparison between Examples 1 to 20 and Comparative Example 3, it is clear that in order to impart a practical and excellent appearance to the nickel film, it is important to pretreat the adsorption of the colloidal catalyst core before the catalyst is supplied.
另一方面，與上述實施例1~20(化學鍍鎳方法)同樣，化學鍍鎳-鈷合金方法的實施例21~22中化學鍍膜所析出的鎳合金被膜也無色斑且均勻性優異。 On the other hand, in the same manner as in the above-described Examples 1 to 20 (electroless nickel plating method), in the examples 21 to 22 of the electroless nickel-cobalt alloy plating method, the nickel alloy film deposited by the electroless plating film was also free from color spots and excellent in uniformity.
接著，對實施例1~22進行詳細說明。 Next, Examples 1 to 22 will be described in detail.
以實施例1為基準，對與其他實施例的相對評價進行說明。首先，實施例1是使用含有陽離子型表面活性劑即二烯丙胺聚合物的季銨鹽的吸附促進劑對非導電性基板進行預處理，使用以硫酸鎳為鎳鹽、以硼氫化合物為還原劑、以檸檬酸為膠體穩定劑的催化劑液進行催化劑賦予，然後實施化學鍍鎳之例，催化劑液的經時穩定性良好，即使建浴後經過1個月 也未發生沉澱或分解，另外，化學鍍膜所得的鎳被膜均勻性優異，未出現析出色斑。 The relative evaluation with the other examples will be described based on the first embodiment. First, in Example 1, a non-conductive substrate was pretreated with an adsorption promoter containing a quaternary ammonium salt of a cationic surfactant, that is, a diallylamine polymer, using nickel sulfate as a nickel salt and a boron hydride compound as a reduction. An agent, a catalyst solution using citric acid as a colloidal stabilizer, and a method of performing electroless nickel plating, and the stability of the catalyst liquid is good, even after one month after the bath is built. No precipitation or decomposition occurred, and the nickel film obtained by the electroless plating film was excellent in uniformity, and excellent spots were not observed.
實施例2是相對於實施例1減少催化劑液的膠體穩定劑含量之例，實施例3是相對於實施例1增加膠體穩定劑含量之例，實施例4是相對於實施例1減少催化劑液的還原劑含量之例，實施例5是增加還原劑含量之例，實施例6是增加催化劑液的鎳鹽含量、膠體穩定劑含量和還原劑含量之例，實施例16~17是增加催化劑液的鎳鹽含量、還原劑含量和膠體穩定劑含量之例，但即使在適當範圍內改變膠體穩定劑、還原劑、鎳鹽等的含量，催化劑液的經時穩定性和鍍膜外觀也均為與實施例1(或實施例9)相同的評價。 Example 2 is an example of reducing the colloidal stabilizer content of the catalyst liquid with respect to Example 1, Example 3 is an example of increasing the colloidal stabilizer content with respect to Example 1, and Example 4 is a catalyst liquid reduction with respect to Example 1. Examples of the reducing agent content, Example 5 is an example of increasing the reducing agent content, and Example 6 is an example of increasing the nickel salt content, the colloidal stabilizer content, and the reducing agent content of the catalyst liquid, and Examples 16 to 17 are examples of increasing the catalyst liquid. Examples of nickel salt content, reducing agent content and colloidal stabilizer content, but even if the content of colloidal stabilizer, reducing agent, nickel salt, etc. is changed within an appropriate range, the stability of the catalyst liquid and the appearance of the coating film are both implemented. Example 1 (or Example 9) the same evaluation.
實施例7是相對於實施例1將鎳膠體催化劑液的pH值從中性變為弱酸性之例，實施例8~9、15是相對於實施例1將催化劑液的膠體穩定劑種類改為其他羥基羧酸、多元羧酸、氨基酸類之例，實施例10~11、17~18是相對於實施例1將催化劑液的還原劑種類從次磷酸改為抗壞血酸、胺硼烷類、或者並用多種還原劑之例，實施例14是相對於實施例9同樣並用多種還原劑之例，實施例12~13是相對於實施例1改變催化劑液的鎳鹽種類之例，但即使適當改變膠體穩定劑、還原劑、鎳鹽的種類，此外即使將催化劑液的pH值變為中性~弱酸性，催化劑液的經時穩定性和鍍膜外觀也均為與實施例1(或實施例9)同樣優異的評價。 Example 7 is an example in which the pH of the nickel colloidal catalyst liquid was changed from neutral to weakly acidic with respect to Example 1, and Examples 8 to 9 and 15 were used to change the type of colloidal stabilizer of the catalyst liquid to Example 1 with respect to Example 1. Examples of the hydroxycarboxylic acid, the polyvalent carboxylic acid, and the amino acid, Examples 10 to 11, and 17 to 18 are those in which the reducing agent of the catalyst liquid is changed from hypophosphoric acid to ascorbic acid, amine borane, or a combination thereof in the first embodiment. Examples of the reducing agent, Example 14 is an example in which a plurality of reducing agents are used in the same manner as in Example 9, and Examples 12 to 13 are examples in which the type of the nickel salt of the catalyst liquid is changed with respect to Example 1, but the colloidal stabilizer is appropriately changed. The type of the reducing agent and the nickel salt, and even if the pH of the catalyst liquid is changed to neutral to weakly acidic, the stability of the catalyst liquid and the appearance of the coating film are both excellent as in the first embodiment (or the embodiment 9). evaluation of.
實施例19~20是相對於實施例1將吸附促進步驟中的處理劑從陽離子型表面活性劑(和非離子型表面活性劑)改為兩性表面活性劑之例，但即使在吸附促進步驟中使用陽離子型表面活性劑、兩性表面活性劑中的任意表面活性劑，被膜外觀的優異評價也未改變。 Examples 19 to 20 are examples in which the treating agent in the adsorption promoting step is changed from a cationic surfactant (and a nonionic surfactant) to an amphoteric surfactant with respect to Example 1, but even in the adsorption promoting step. The excellent evaluation of the appearance of the film was not changed by using any of the cationic surfactant and the amphoteric surfactant.
另一方面，實施例21~22是鍍鎳-鈷合金方法之例，若以鍍鎳方法的實施例1為基礎，經過吸附促進處理、鎳膠體催化劑液中的浸漬處理，實施化學鍍鎳合金，則與鍍鎳的情況同樣，得到均勻性優異的鎳合金被膜。 On the other hand, Examples 21 to 22 are examples of a method of plating a nickel-cobalt alloy, and based on Example 1 of a nickel plating method, an electroless nickel alloy is subjected to an adsorption promotion treatment and an immersion treatment in a nickel colloidal catalyst liquid. In the same manner as in the case of nickel plating, a nickel alloy film having excellent uniformity is obtained.
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| JP6201153B2 (en) | 2017-09-27 |
| WO2016039016A1 (en) | 2016-03-17 |
| JP2016056421A (en) | 2016-04-21 |
| CN106460179B (en) | 2019-05-10 |
| KR20170008287A (en) | 2017-01-23 |
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