TWI613321B - Aqueous copper colloidal catalyst solution for electroless copper plating and electroless copper plating method - Google Patents

Aqueous copper colloidal catalyst solution for electroless copper plating and electroless copper plating method Download PDF

Info

Publication number
TWI613321B
TWI613321B TW104103873A TW104103873A TWI613321B TW I613321 B TWI613321 B TW I613321B TW 104103873 A TW104103873 A TW 104103873A TW 104103873 A TW104103873 A TW 104103873A TW I613321 B TWI613321 B TW I613321B
Authority
TW
Taiwan
Prior art keywords
acid
copper
catalyst solution
solution
colloidal
Prior art date
Application number
TW104103873A
Other languages
Chinese (zh)
Other versions
TW201531591A (en
Inventor
内田衛
田中薫
川端愛
Original Assignee
石原化學股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 石原化學股份有限公司 filed Critical 石原化學股份有限公司
Publication of TW201531591A publication Critical patent/TW201531591A/en
Application granted granted Critical
Publication of TWI613321B publication Critical patent/TWI613321B/en

Links

Classifications

    • 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
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • 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
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
    • C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • 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
    • 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
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • 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
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • 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
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • 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
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
    • C23C18/206—Use of metal other than noble metals and tin, e.g. activation, sensitisation with metals
    • 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
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • C23C18/38—Coating with copper

Abstract

本發明提供含有(A)可溶性銅鹽、(B)還原劑和(C)膠體穩定劑，上述成分(A)和(C)的含量重量比率為特定比率，不含表面活性劑、或表面活性劑的含量抑制在極少量的化學鍍銅用水系銅膠體催化劑溶液及化學鍍銅方法。該化學鍍銅方法通過將非導電性基板浸漬在含表面活性劑的液體中進行吸附促進預處理後，使用化學鍍銅用水系銅膠體催化劑溶液對非導電性基板進行催化劑賦予，再進行化學鍍銅，使得催化劑溶液的經時穩定性良好。由於在通過吸附促進預處理增強催化劑活性後，進行催化劑賦予、化學鍍膜，因此析出的銅被膜的均勻性優異並可和防止析出色斑。根據本發明，可提高水系銅催化劑溶液的經時穩定性，對經催化劑賦予的非導電性基板實施化學鍍銅，獲得均勻且無色斑銅被膜。 The present invention provides (A) a soluble copper salt, (B) a reducing agent, and (C) a colloidal stabilizer. The content ratio of the above components (A) and (C) is a specific ratio, and does not contain a surfactant or a surface active agent. The content of the agent is inhibited by a very small amount of electroless copper plating aqueous copper colloidal catalyst solution and electroless copper plating method. In the electroless copper plating method, the non-conductive substrate is immersed in a surfactant-containing liquid to perform adsorption promotion pretreatment, and then the non-conductive substrate is subjected to catalyst application using an electroless copper plating aqueous copper colloid catalyst solution, and then electroless plating is performed. Copper makes the catalyst solution have good stability over time. Since the catalyst is added and the electroless plating is performed after the catalyst is promoted by the adsorption-promoting pretreatment, the uniformity of the precipitated copper film is excellent and the precipitation is excellent. According to the present invention, it is possible to improve the temporal stability of the aqueous copper catalyst solution, and to perform electroless copper plating on the non-conductive substrate provided by the catalyst to obtain a uniform and colorless copper film.

Description

化學鍍銅用之水系銅膠體催化劑溶液及化學鍍銅方法 Water-based copper colloidal catalyst solution for electroless copper plating and electroless copper plating method

本發明涉及一種在對非導電性基板實施化學鍍銅時，用於進行作為預處理的催化劑賦予的水系銅膠體催化劑溶液及化學鍍銅方法，提供銅催化劑溶液的經時穩定性優異，並能夠形成均勻性良好和無色斑外觀的銅被膜的化學鍍銅用水系銅膠體催化劑溶液及化學鍍銅方法。 The present invention relates to a water-based copper colloidal catalyst solution and an electroless copper plating method for performing a copper plating as a pretreatment when performing electroless copper plating on a non-conductive substrate, and provides an excellent copper catalyst solution with time stability and capable of An electroless copper-based copper colloidal catalyst solution and an electroless copper plating method for forming a copper film having good uniformity and no color appearance.

在以銅或銅合金制基板為代表的導電性基板，或者以玻璃-環氧樹脂、玻璃-聚醯亞胺樹脂、環氧樹脂、聚醯亞胺樹脂、聚碳酸酯樹脂、ABS樹脂、PET樹脂等樹脂基板為代表、包括玻璃基板、陶瓷基板等的非導電性基板上實施化學鍍銅時，通常使用的方法是：首先，使鈀、銀、鉑等貴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銅液使基板上析出銅被膜。 Conductive substrate typified by a copper or copper alloy substrate, or glass-epoxy resin, glass-polyimine resin, epoxy resin, polyimide resin, polycarbonate resin, ABS resin, PET When electroless copper plating is performed on a non-conductive substrate including a resin substrate such as a resin or a glass substrate or a ceramic substrate, a method in which a noble metal such as palladium, silver or platinum is adsorbed on a substrate to form a catalyst core is generally used. Then, a copper film is deposited on the substrate by means of the electroless copper plating solution by means of the catalyst core.

另一方面，還有使用價格低廉的銅、鎳、鈷等特定金屬而不使用貴金屬催化劑的催化劑賦予方法，該方法的基本原理是，在該特定金屬的催化劑溶液中，用還原劑處理可溶性金屬鹽，生成金屬的膠體粒子，並將其作為催化劑核。 On the other hand, there is also a catalyst imparting method using a low-cost specific metal such as copper, nickel or cobalt without using a noble metal catalyst, the basic principle of which is to treat the soluble metal with a reducing agent in the catalyst solution of the specific metal. The salt forms a colloidal particle of the metal and serves as a catalyst core.

其中，水系銅膠體催化劑溶液的現有技術列舉如下。 Among them, the prior art of the aqueous copper colloidal catalyst solution is as follows.

(1)專利文獻1(日本特開H02-093076號公報，三晃特殊金屬株式會社)：添加可溶性銅鹽、分散劑、配位劑，利用還原劑進行還元處理後添加穩定劑，製成用於化學鍍銅的微細的銅催化劑溶液。上述分散劑為明膠、非離子型表面活性劑，配位劑為二羧酸、羥基羧酸(oxycarboxylic acid)等，還原劑為硼氫化鈉、二甲胺硼烷(dimethylamine borane)等。穩定劑為次磷酸鈉、二甲胺硼烷等。另外，在實施例4(第4頁左上欄)中，將被鍍物浸漬在含有硫酸銅、明膠、硼氫化鈉和次磷酸鹽的催化劑溶液中，然後實施化學鍍銅。 (1) Patent Document 1 (Japanese Laid-Open Patent Publication No. H02-093076, Sanwa Special Metal Co., Ltd.): a soluble copper salt, a dispersant, and a complexing agent are added, and a stabilizer is added after a reductant treatment, and a stabilizer is added thereto. A fine copper catalyst solution for electroless copper plating. The dispersing agent is gelatin or a nonionic surfactant, the complexing agent is a dicarboxylic acid, a oxycarboxylic acid or the like, and the reducing agent is sodium borohydride or dimethylamine borane. The stabilizer is sodium hypophosphite, dimethylamine borane or the like. Further, in Example 4 (the upper left column of page 4), the object to be plated was immersed in a catalyst solution containing copper sulfate, gelatin, sodium borohydride and hypophosphite, and then electroless copper plating was carried out.

(2)專利文獻2(日本特開H10-229280號公報，奧野製藥工業株式會社)：對被鍍物賦予由銅鹽、陰離子型表面活性劑和還原劑組成的化學鍍膜用催化劑，實施化學鍍銅後，再實施電鍍銅(請求項1~2、段落42)。在銅催化劑溶液的具體例即製造例2(段落52)中，催化劑溶液包含由硫酸銅和氨形成的銅胺配合物、陰離子型表面活性劑、以及硼氫化鈉(還原劑)。 (2) Patent Document 2 (Japanese Laid-Open Patent Publication No. H10-229280, Okuno Pharmaceutical Co., Ltd.): Electroless plating is applied to a catalyst for electroless plating comprising a copper salt, an anionic surfactant, and a reducing agent. After copper, electroplated copper is applied (requests 1~2, paragraph 42). In a specific example of the copper catalyst solution, Production Example 2 (paragraph 52), the catalyst solution contains a copper amine complex formed of copper sulfate and ammonia, an anionic surfactant, and sodium borohydride (reducing agent).

(3)專利文獻3(日本特開H07-197266號公報、日本LeaRonal株式會社)：使用氧化銅(I)膠體催化劑溶液對基板進行催化劑賦予，然後將基板浸漬到包含銅鹽、還原劑和配位劑的溶液中，在基板上直接鍍銅。上述催化劑賦予後的溶液中雖然包含配位劑、還原劑，但上述催化劑溶液的組成不明。 (3) Patent Document 3 (JP-A-H07-197266, Japan LeaRonal Co., Ltd.): a catalyst is applied to a substrate using a copper (I) colloidal catalyst solution, and then the substrate is immersed in a copper salt, a reducing agent, and a compound. In the solution of the dopant, copper is directly plated on the substrate. Although the complex solution and the reducing agent are contained in the solution after the catalyst is supplied, the composition of the catalyst solution is unknown.

(4)專利文獻4(日本特開2011-225929號公報、關東學院大學)：專利文獻4公開了包含一價銅鹽、次磷酸鹽和氯離子(請求項1)、或者進一步包含有機或無機還原劑(胺硼烷類、硼氫化合物、甲酸等)的催化劑溶 液的製備方法(權利要求1~3)，以及使用含有表面活性劑(陽離子型、陰離子型、兩性、非離子型，段落56)的調節劑對被鍍物進行預處理，再用催化劑溶液進行催化劑處理的化學鍍膜方法(請求項8~9)。上述化學鍍膜的種類為銅、鎳、金等，優選為化學鍍銅(段落70)。另外，專利文獻4還記載了如果在上述調節劑中特別使用陽離子型表面活性劑，則吸附在被鍍物上的表面活性劑的親水基帶負電，上述一價銅離子易於吸附，獲得均勻地吸附有銅離子的催化劑化被鍍物(段落58)。 (4) Patent Document 4 (JP-A-2011-225929, Kanto College University): Patent Document 4 discloses the inclusion of a monovalent copper salt, a hypophosphite, and a chloride ion (claim 1), or further contains an organic or inorganic Catalyst dissolution of reducing agent (amine borane, boron hydride, formic acid, etc.) a method for preparing a liquid (claims 1 to 3), and pretreating the object to be plated using a regulator containing a surfactant (cationic, anionic, amphoteric, nonionic, paragraph 56), and then using a catalyst solution Catalyst-treated electroless plating method (requests 8 to 9). The type of the electroless plating film is copper, nickel, gold or the like, and is preferably electroless copper plating (paragraph 70). Further, Patent Document 4 discloses that if a cationic surfactant is particularly used in the above-mentioned regulator, the hydrophilic group of the surfactant adsorbed on the object to be plated is negatively charged, and the monovalent copper ion is easily adsorbed to obtain uniform adsorption. A catalyst plated with copper ions (paragraph 58).

(5)專利文獻5(日本特表2013-522476號公報，Enthone,Incorporated)：專利文獻5記載了使用含有貴金屬/金屬-膠體(例如，鈀/錫的膠體溶液)的活化劑溶液對非導電性基板進行處理，接著，與包含銅鹽等金屬鹽溶液、該金屬離子的配位元劑和還原劑的導電體溶液接觸後，進行化學鍍膜和電鍍的非導電性基板的直接金屬化法(段落1、13)。上述導電體溶液的金屬鹽被活化劑溶液的金屬還元，例如活化劑溶液的二價錫(氧化性陽離子)作用於導電體溶液的二價銅離子(還元性陽離子)，隨著錫被氧化成四價，二價銅離子被還元成金屬銅(段落24、29)。在實施例1中，記載了使用含有鈀-錫系膠體的活化劑分散液對ABS塑膠基板進行活化處理後，再使用包含酒石酸(配位劑)、次磷酸鹽(或者次磷酸鹽和羥甲基磺酸鹽，還原劑)、以及銅鹽和鋰鹽等的導電體溶液進行處理(段落65、段落66的表1)。 (5) Patent Document 5 (Japanese Patent Publication No. 2013-522476, Enthone, Incorporated): Patent Document 5 describes the use of an activator solution containing a noble metal/metal-colloid (for example, a palladium/tin colloidal solution) for non-conducting The substrate is treated, and then, after being contacted with a metal salt solution such as a copper salt, a coordination agent of the metal ion, and a conductor solution of the reducing agent, a direct metallization method of the electroless plating and electroplating of the non-conductive substrate is performed ( Paragraphs 1, 13). The metal salt of the above conductor solution is acted upon by a metal reductor of the activator solution, such as divalent tin (oxidative cation) of the activator solution, to the divalent copper ion (returnive cation) of the electroconductor solution, as the tin is oxidized The tetravalent, divalent copper ion is reverted to metallic copper (paragraphs 24, 29). In Example 1, it is described that an ABS plastic substrate is activated by using an activator dispersion containing a palladium-tin colloid, and then a tartaric acid (coordinating agent), a hypophosphite (or a hypophosphite and a hydroxyl group) is used. The base sulfonate, reducing agent), and a conductor solution of a copper salt and a lithium salt are treated (paragraph 65 of Table 65 and paragraph 66).

現有技術文獻： Prior art literature:

[專利文獻] [Patent Literature]

專利文獻1：日本特開H02-093076號公報 Patent Document 1: Japanese Patent Publication No. H02-093076

專利文獻2：日本特開H10-229280號公報 Patent Document 2: Japanese Patent Laid-Open Publication No. H10-229280

專利文獻3：日本特開H07-197266號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. H07-197266

專利文獻4：日本特開2011-225929號公報 Patent Document 4: Japanese Laid-Open Patent Publication No. 2011-225929

專利文獻5：日本特開2013-522476號公報 Patent Document 5: Japanese Laid-Open Patent Publication No. 2013-522476

然而，雖然上述水系催化劑溶液的基本原理是使用還原劑對可溶性金屬鹽進行處理生成金屬微細粒子，但實際上，以上述專利文獻的催化劑溶液為代表的很多催化劑溶液在經時穩定性方面存在問題，不易長時間順暢地保持催化劑賦予和化學鍍膜作業的連續性。 However, although the basic principle of the above aqueous catalyst solution is to treat a soluble metal salt using a reducing agent to form fine metal particles, in practice, many catalyst solutions typified by the catalyst solution of the above-mentioned patent document have problems in stability over time. It is not easy to maintain the continuity of catalyst application and electroless plating work for a long time.

另外，即使在使用銅催化劑溶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、鍍膜產生色斑、或者均勻性惡劣等問題。 In addition, even if the electroless plating film is applied to the non-conductive substrate after the catalyst is applied using the copper catalyst solution, there is a problem that precipitation is difficult, cracks occur in the coating film due to partial deposition of the film, color unevenness in the plating film, or poor uniformity.

本發明所要解決的技術問題在於，提高水系銅催化劑溶液的經時穩定性，並且對經催化劑賦予的非導電性基板實施化學鍍銅，得到均勻且無色斑的銅被膜。 The technical problem to be solved by the present invention is to improve the temporal stability of the aqueous copper catalyst solution, and to perform electroless copper plating on the non-conductive substrate provided by the catalyst to obtain a copper film which is uniform and has no color unevenness.

本發明人從例如專利文獻1中為保持銅的還元狀態而使用穩定劑的情況出發，首先構思通過向催化劑溶液中添加對銅鹽具有配位功能的成分，使膠體粒子穩定化。 The present inventors first proposed to stabilize the colloidal particles by adding a component having a coordination function to the copper salt to the catalyst solution, for example, in the case where the stabilizer is used to maintain the reductive state of the copper.

並且，還獲得了通過向銅催化劑溶液中添加使銅鹽穩定的羥基羧酸類、氨基羧酸類等膠體穩定劑，並調整銅鹽與穩定劑的混合比率，能夠改善經時穩定性的見解。隨後，獲得了表面活性劑的存在對經時穩定 性具有惡劣影響，即使添加其含量也應該僅限於極少量的見解。另外，還獲得了特定的水溶性聚合物的存在對經時穩定性有很大幫助等見解。 Further, by adding a colloidal stabilizer such as a hydroxycarboxylic acid or an aminocarboxylic acid which stabilizes the copper salt to the copper catalyst solution, and adjusting the mixing ratio of the copper salt and the stabilizer, it is possible to improve the stability over time. Subsequently, the presence of the surfactant is obtained to stabilize over time. Sex has a bad influence, and even if it is added, it should be limited to a very small amount of insight. In addition, it has been obtained that the presence of a specific water-soluble polymer greatly contributes to the stability over time.

在這些見解的基礎上首次發現，如果在使用銅催化劑溶液對基板進行催化劑賦予之前，著重進行將基板浸漬在含有由表面活性劑組成的吸附促進劑的液體中這一預處理，則在進行催化劑賦予之際催化劑活性提高，由化學鍍銅所得的析出被膜的均勻性、以及防止被膜外觀色斑的發生方面非常優異，從而完成了本發明。 Based on these findings, it was first discovered that if the pretreatment of the substrate is carried out in a liquid containing an adsorption promoter composed of a surfactant before the catalyst is applied to the substrate using a copper catalyst solution, the catalyst is carried out. The present invention has been completed in that the catalyst activity is increased, the uniformity of the precipitated film obtained by electroless copper plating, and the occurrence of the appearance of the coating film are excellent.

即，本發明第一方面是一種用於與實施化學鍍銅的非導電性基板接觸進行催化劑賦予的化學鍍銅用水系銅膠體催化劑溶液，其含有：(A)可溶性銅鹽、(B)還原劑、以及(C)選自一元羧酸類、羥基羧酸類、氨基羧酸類、以及多元羧酸類的膠體穩定劑的至少一種；上述成分(A)與(C)的含量莫耳比為A：C=1：0.03~1：35；且不含表面活性劑、或者表面活性劑的含量為950mg/L以下。 That is, the first aspect of the present invention is an electroless copper-based copper-based colloidal catalyst solution for contact with a non-conductive substrate subjected to electroless copper plating, which comprises: (A) a soluble copper salt, and (B) reduction. And (C) at least one selected from the group consisting of monocarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, and colloidal stabilizers of polycarboxylic acids; the molar ratio of the above components (A) and (C) is A: C =1: 0.03 to 1:35; and no surfactant or surfactant content of 950 mg/L or less.

本發明第二方面是一種用於與實施化學鍍銅的非導電性基板接觸進行催化劑賦予的化學鍍銅用水系銅膠體催化劑溶液，其含有：(A)可溶性銅鹽、(B)還原劑、以及(C)選自一元羧酸類、羥基羧酸類、氨基羧酸類、多元羧酸類的膠體穩定劑的至少一種；上述成分(A)與(C)的含量莫耳比為A：C=1：0.03~1：35；且含有合成類水溶性聚合物。 A second aspect of the present invention is an electroless copper-based copper-based colloidal catalyst solution for use in contact with a non-conductive substrate for performing electroless copper plating, comprising: (A) a soluble copper salt, (B) a reducing agent, And (C) at least one selected from the group consisting of monocarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, and polycarboxylic acids; the molar ratio of the above components (A) and (C) is A: C = 1: 0.03~1:35; and contains synthetic water-soluble polymer.

本發明第三方面是，在上述本發明第二方面中，合成類水溶性聚合物為選自聚乙二醇、聚丙二醇、聚乙烯吡咯烷酮、聚乙烯醇、聚丙烯醯胺、以及聚乙烯亞胺中的至少一種的化學鍍銅用水系銅膠體催化劑溶 液。 According to a third aspect of the present invention, in the second aspect of the present invention, the synthetic water-soluble polymer is selected from the group consisting of polyethylene glycol, polypropylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, and polyethylene. Electroless copper plating of at least one of amines dissolved in water-based copper colloid catalyst liquid.

本發明第四方面是，在上述本發明第一至三方面中，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、亞磺酸類中的至少一種的化學鍍銅用水系銅膠體催化劑溶液。 According to a fourth aspect of the present invention, in the first to third aspects of the present invention, the reducing agent (B) is selected from the group consisting of a boron hydride compound, an amine borane, a hypophosphorous acid, an aldehyde, an ascorbic acid, a hydrazine, and a polyhydric phenol. An electroless copper-based copper colloidal catalyst solution of at least one of a class, a polyhydric naphthol, a phenolsulfonic acid, a naphtholsulfonic acid, and a sulfinic acid.

本發明第五方面是，在上述本發明第一至四方面任一面中，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、以及它們的鹽中的至少一種的化學鍍銅用水系銅膠體催化劑溶液。 According to a fifth aspect of the present invention, in any one of the first to fourth aspects of the present invention, 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, and citric acid. An electroless copper-based copper colloidal catalyst solution of at least one of lauric acid, myristic acid, palmitic acid, stearic acid, and a salt thereof.

本發明第六方面是，在上述本發明第一至五方面的任一面中，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、以及它們的鹽中的至少一種的化學鍍銅用水系銅膠體催化劑溶液。 According to a sixth aspect of the present invention, in any one of the first to fifth aspects of the present invention, the hydroxycarboxylic acid (C) is selected from the group consisting of citric acid, tartaric acid, malic acid, gluconic acid, glucoheptonic acid, glycolic acid, and lactic acid. , electroless copper plating of at least one of trioxy butyric acid, ascorbic acid, isocitric acid, hydroxymalonic acid, glyceric acid, hydroxybutyric acid, leucine, citrylic acid, and salts thereof A copper colloidal catalyst solution.

本发明第七方面是，在上述本发明第一至六方面的任一面中，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、谷氨酸、二羧甲基谷氨酸(dicarboxy methyl glutamate)、鳥氨酸、半胱氨酸、N,N-二(2-羥 乙基)谷氨酸、(S,S)-乙二胺琥珀酸、以及它們的鹽中的至少一種的化學鍍銅用水系銅膠體催化劑溶液。 According to a seventh aspect of the present invention, in any one of the first to sixth aspects of the present invention, the aminocarboxylic acid (C) is selected from the group consisting of hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and triethylene glycol. Tetraamine hexaacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, ammoniatriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, iminodipropionic acid, 1,3-propanediamine 1,3-propanediamine tetraacetic acid, 1,3-diamino-2-hydroxypropane tetraacetic acid, glycol ether diamine tetraacetic acid, isophthalic acid Aminetetraacetic acid, 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid, diaminopropionic acid, glutamic acid, dicarboxymethyl glutamate, avian ammonia Acid, cysteine, N,N-di(2-hydroxyl An electroless copper-based copper colloidal catalyst solution of at least one of ethyl)glutamic acid, (S,S)-ethylenediamine succinic acid, and a salt thereof.

本發明第八方面是，在上述本發明第一至七方面的任一面，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、中康酸以及它們的鹽中的至少一種的化學鍍銅用水系銅膠體催化劑溶液。 According to an eighth aspect of the invention, the polycarboxylic acid (C) is selected from the group consisting of succinic acid, glutaric acid, malonic acid, adipic acid, oxalic acid, and Malay. An electroless copper-based copper colloidal catalyst solution of at least one of acid, citraconic acid, itaconic acid, mesaconic acid, and a salt thereof.

本發明第九方面是一種化學鍍銅方法，其包括：(a)吸附促進步驟(預處理步驟)，將非導電性基板浸漬在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、以及兩性表面活性劑的吸附促進劑中的至少一種的液體中；(b)催化劑賦予步驟，將非導電性基板浸漬在上述本發明第一至八方面任一面的水系銅膠體催化劑溶液中，使銅膠體粒子吸附在基板表面上；以及(c)化學鍍膜步驟，使用化學鍍銅液在經吸附處理的上述基板上形成銅被膜。 A ninth aspect of the invention is an electroless copper plating method comprising: (a) an adsorption promoting step (pretreatment step), immersing the non-conductive substrate in a film containing a non-ionic surfactant, a cationic surfactant, a liquid of at least one of an anionic surfactant and an adsorption promoter of an amphoteric surfactant; (b) a catalyst-imparting step of immersing the non-conductive substrate on the water-based copper of any one of the first to eighth aspects of the present invention described above In the colloidal catalyst solution, the copper colloid particles are adsorbed on the surface of the substrate; and (c) the electroless plating step, the copper film is formed on the adsorbed substrate by using an electroless copper plating solution.

本發明第十方面是步驟(a)的吸附促進劑為陽離子型表面活性劑和/或兩性表面活性劑的化學鍍銅方法。 In a tenth aspect of the invention, the adsorption promoter of the step (a) is an electroless copper plating method of a cationic surfactant and/or an amphoteric surfactant.

在本發明的銅膠體催化劑溶液中，含有對銅鹽起配合作用的膠體穩定劑，通過規定該穩定劑與銅鹽的比率，並且含有聚乙二醇、聚乙烯吡咯烷酮、聚乙烯醇等特定的水溶性聚合物，或者反而不含表面活性劑，亦或是僅含極少量上述特定的水溶性聚合物，可以顯著提高液體的經時穩定性。 In the copper colloidal catalyst solution of the present invention, a colloidal stabilizer containing a compounding action for a copper salt is provided, and a ratio of the stabilizer to the copper salt is specified, and a specific polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol or the like is contained. The water-soluble polymer, or instead of a surfactant, or only a very small amount of the above specific water-soluble polymer, can significantly improve the stability of the liquid over time.

附帶說明，在上述專利文獻1的金屬體含有液(即催化劑溶液)中，不含對銅鹽起配合作用的成分。另外，在專利文獻1的實施例4(第4頁左 上欄~右上欄)的催化劑溶液中，含有1000mg/L作為分散劑的明膠，或者在上述專利文獻2的製造例2(段落52)的催化劑溶液中，含有1000mg/L陰離子型表面活性劑，其含量均超過了本發明1的催化劑溶液中表面活性劑規定量的上限。 Incidentally, in the metal body-containing liquid (that is, the catalyst solution) of Patent Document 1, the component that does not act on the copper salt is not contained. In addition, in the fourth embodiment of Patent Document 1 (page 4 left) In the catalyst solution of the upper column to the upper right column, gelatin containing 1000 mg/L as a dispersing agent or 1000 mg/L of an anionic surfactant in the catalyst solution of Production Example 2 (paragraph 52) of Patent Document 2 described above, The content thereof exceeds the upper limit of the predetermined amount of the surfactant in the catalyst solution of the present invention 1.

本發明的基本原理是，在對非導電性基板賦予上述銅膠體催化劑後再進行化學鍍銅，但作為該催化劑賦予的預處理或預備處理，著重進行將非導電性基板浸漬在含有表面活性劑的液體中的吸附促進處理，通過依次進行該吸附促進步驟、催化劑賦予步驟、以及化學鍍銅步驟，能夠增強催化劑賦予時的催化劑活性，改善由化學鍍膜所析出的銅被膜的均勻性，並且有效防止被膜的色斑發生。 The basic principle of the present invention is to perform electroless copper plating after applying the copper colloid catalyst to a non-conductive substrate. However, as a pretreatment or preliminary treatment to be applied to the catalyst, the non-conductive substrate is mainly immersed in a surfactant-containing surfactant. In the adsorption promotion treatment in the liquid, by sequentially performing the adsorption promotion step, the catalyst application step, and the electroless copper plating step, the catalyst activity at the time of catalyst application can be enhanced, and the uniformity of the copper film deposited by the electroless plating film can be improved and effective. Prevent the occurrence of stains on the film.

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銅用水系銅膠體催化劑溶液，其含有(A)可溶性銅鹽、(B)還原劑、以及(C)膠體穩定劑，上述成分(A)與(C)的含量莫耳比為特定比率，不含表面活性劑、或者僅含極少量的表面活性劑。本發明的第二方面是，代替將含有表面活性劑的情況排除、或者將表面活性劑的含量抑制在規定量以下的第一方面發明，含有合成類水溶性聚合物的水系銅膠體催化劑溶液。本發明的協力廠商面是，使用上述第一或第二方面發明的催化劑溶液的化學鍍銅方法，該方法預先用含有表面活性劑的液體對非導電性基板進行吸附促進處理，然後利用上述催化劑溶液進行催化劑賦予後再進行化學 鍍銅。 A first aspect of the present invention is an electroless copper-based copper-based colloidal catalyst solution for carrying out catalyst application in contact with a non-conductive substrate, comprising (A) a soluble copper salt, (B) a reducing agent, and (C) a colloidal stabilization The content of the above components (A) and (C) is a specific ratio, does not contain a surfactant, or contains only a very small amount of a surfactant. According to a second aspect of the present invention, in addition to the case where the surfactant is contained or the surfactant is contained in a predetermined amount or less, the aqueous copper colloid catalyst solution containing the synthetic water-soluble polymer is contained. The co-manufacturer of the present invention is an electroless copper plating method using the catalyst solution of the first or second aspect of the invention, which preliminarily adsorbs a non-conductive substrate with a liquid containing a surfactant, and then uses the above catalyst The solution is subjected to catalyst and then chemically Copper plating.

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、聚碳酸酯樹脂、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。 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. Glass substrate, ceramic substrate, and the like.

上述本發明1的水系銅膠體催化劑溶液的基本組成為：(A)可溶性銅鹽、(B)還原劑、以及(C)膠體穩定劑。 The basic composition of the aqueous copper colloidal catalyst solution of the above invention 1 is (A) a soluble copper 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一價或二價銅離子的可溶性鹽則可以使用任意的可溶性鹽，沒有特別限制，也不排除難溶性鹽。具體而言，可列舉出硫酸銅、氧化銅、氯化銅、焦磷酸銅、碳酸銅；或乙酸銅、乙二酸銅和檸檬酸銅等羧酸銅鹽；或者甲磺酸銅和羥基乙磺酸銅等有機磺酸銅鹽等，優選為硫酸銅、檸檬酸銅、甲磺酸銅。 The soluble salt (A) may be any soluble salt as long as it is a soluble salt which generates monovalent or divalent copper ions in an aqueous solution, and is not particularly limited, and does not exclude a poorly soluble salt. Specific examples thereof include copper sulfate, copper oxide, copper chloride, copper pyrophosphate, and copper carbonate; or copper carboxylate salts such as copper acetate, copper oxalate, and copper citrate; or copper methanesulfonate and hydroxyethyl b. The copper sulfonate such as copper sulfonate or the like is preferably copper sulfate, copper citrate or copper methanesulfonate.

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。 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 acid and 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.

上述膠體穩定劑(C)為在鍍浴中形成銅配合物的化合物，起到保證催化劑溶液的經時穩定性的功能。 The above-mentioned colloidal stabilizer (C) is a compound which forms a copper complex in a plating bath, and functions to ensure the stability of the catalyst solution 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、以及多元羧酸類。 The colloidal stabilizer (C) is selected from the group consisting of monocarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, and polycarboxylic acids.

上述一元羧酸類選自甲酸、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、以及其等之鹽等。 The monocarboxylic acid 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 the like.

上述羥基羧酸類選自檸檬酸、酒石酸、蘋果酸、葡萄糖酸、葡庚糖酸、乙醇酸、乳酸、三羥基丁酸、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、以及其等之鹽等。 The above hydroxycarboxylic acid is selected from the group consisting of citric acid, tartaric acid, malic acid, gluconic acid, glucoheptonic acid, glycolic acid, lactic acid, trihydroxybutyric acid, ascorbic acid, isocitric acid, hydroxymalonic acid, glyceric acid, hydroxybutyric acid, Leucine, citramalic acid, and the like.

上述氨基羧酸類選自乙二胺四乙酸(EDTA)、羥乙基乙二胺三乙酸(HEDTA)、二亞乙基三胺五乙酸(DTPA)、三亞乙基四胺六乙酸(TTHA)、乙二胺四丙酸、氨三乙酸(NTA)、亞氨基二乙酸(IDA)、亞氨基二丙酸(IDP)、羥乙基亞氨基二乙酸、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、谷氨酸、二羧甲基谷氨酸、鳥氨酸、半胱氨酸、N,N-二(2-羥乙基)谷氨酸、(S,S)-乙二胺琥珀酸以及其等之鹽等。 The above aminocarboxylic acid is selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), and triethylenetetramine hexaacetic acid (TTHA). Ethylenediaminetetrapropionic acid, ammonia triacetic acid (NTA), iminodiacetic acid (IDA), iminodipropionic acid (IDP), hydroxyethyliminodiacetic acid, 1,3-propanediaminetetraacetic acid, 1 ,3-diamino-2-hydroxypropanetetraacetic acid, glycol ether diaminetetraacetic acid, m-phenylenediaminetetraacetic acid, 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid , diaminopropionic acid, glutamic acid, dicarboxymethylglutamate, ornithine, cysteine, N,N-bis(2-hydroxyethyl)glutamic acid, (S,S)-B Diamine succinic acid, salts thereof, and the like.

上述多元羧酸類選自琥珀酸、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等。 The polycarboxylic acid is selected from the group consisting of succinic acid, glutaric acid, malonic acid, adipic acid, oxalic acid, maleic acid, citraconic acid, itaconic acid, mesaconic acid, and the like.

本發明的銅膠體催化劑溶液為水系，因此液體溶劑限定為水和/或親水性醇，排除了有機溶劑(包括親油性醇)的單獨使用。 The copper colloidal catalyst solution of the present invention is an aqueous system, and thus the liquid solvent is limited to water and/or a hydrophilic alcohol, and the use of an organic solvent (including a lipophilic alcohol) alone is excluded.

另外，關於該催化劑溶液，由於在中性附近催化劑活性容易降低，因此優選催化劑溶液的pH值在除中性區域以外的酸性側或鹼性側，具體而言pH1~6和8~12較為適合，優選為pH2~5和8~11。 Further, in the catalyst solution, since the catalyst activity is likely to decrease in the vicinity of neutrality, it is preferred that the pH of the catalyst solution be on the acidic side or the alkaline side other than the neutral region, specifically, pH 1 to 6 and 8 to 12 are suitable. Preferably, it is pH 2~5 and 8~11.

水系銅膠體催化劑溶液中可以單獨使用或並用上述可溶性銅鹽(A)，其含量為0.005~1莫耳/L，優選為0.05~0.5莫耳/L，更優選為0.04~0.2莫耳/L。 The aqueous copper colloidal catalyst solution may be used singly or in combination with the above soluble copper salt (A) in an amount of 0.005 to 1 mol/L, preferably 0.05 to 0.5 mol/L, more preferably 0.04 to 0.2 mol/L. .

上述還原劑(B)可以單獨使用或並用，其含量為0.005~1莫耳/L，優選為0.05~0.5莫耳/L。還原劑的含量若小於適當量則銅鹽的還元作用 降低，反之若過多則化學鍍膜所析出的銅被膜均質性可能會降低。 The above reducing agent (B) may be used singly or in combination, and its content is 0.005 to 1 mol/L, preferably 0.05 to 0.5 mol/L. If the content of the reducing agent is less than the appropriate amount, the reductive effect of the copper salt If it is too much, the copper film homogenization precipitated by the electroless plating film may be lowered.

上述膠體穩定劑(C)可以單獨使用或並用，其含量為0.005~2莫耳/L、優選為0.05~1.5莫耳/L。 The above-mentioned colloidal stabilizer (C) may be used singly or in combination, and its content is 0.005 to 2 mol/L, preferably 0.05 to 1.5 mol/L.

另外，在水系膠體催化劑溶液中，上述(A)和(C)的含量莫耳比為A：C=1：0.03~1：35，優選為A：C=1：0.5~1：24。如果膠體穩定劑(C)的相對含量過少，則催化劑溶液的經時穩定性降低，進而成為由化學鍍膜所得的銅被膜發生析出不良的主要原因。反之，如果膠體穩定劑(C)的含量過多，則損害催化劑溶液的經時穩定性，使所得的銅被膜的品質降低(參照後述試驗例)。 Further, in the aqueous colloidal catalyst solution, the molar ratio of the above (A) and (C) is A: C = 1: 0.03 to 1: 35, preferably A: C = 1: 0.5 to 1: 24. When the relative content of the colloidal stabilizer (C) is too small, the stability with time of the catalyst solution is lowered, and further, the copper film obtained by the electroless plating film is poorly precipitated. On the other hand, when the content of the colloidal stabilizer (C) is too large, the stability of the catalyst solution over time is impaired, and the quality of the obtained copper coating film is lowered (see the test example described later).

在水系膠體催化劑溶液中，上述(A)和(B)的含量莫耳比為A：B=1：0.05~1：6，優選為A：B=1：0.1~1：5。 In the aqueous colloidal catalyst solution, the molar ratio of the above (A) and (B) is A:B = 1:0.05 to 1:6, preferably A:B = 1:0.1 to 1:5.

在製備該催化劑溶液之際，由於從還原劑向銅離子順暢地供給電子，因此基本上是耗費時間將還原劑溶液緩慢地滴入含有可溶性銅鹽(以及膠體穩定劑)的溶液中進行製備。例如，將5~50℃(優選為10~40℃)的還原劑溶液滴入銅鹽溶液中，攪拌20~1200分鐘(優選為30~300分鐘)，製成催化劑溶液。應予說明，在催化劑溶液的製備中，也不排除將可溶性銅鹽溶液滴入還原劑溶液中。 In the preparation of the catalyst solution, since electrons are smoothly supplied from the reducing agent to the copper ions, it is basically time-consuming to prepare the reducing agent solution by slowly dropping it into a solution containing a soluble copper 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 copper salt solution, and stirred for 20 to 1200 minutes (preferably 30 to 300 minutes) to prepare a catalyst solution. It should be noted that in the preparation of the catalyst solution, it is not excluded to drip the soluble copper salt solution into the reducing agent solution.

在本發明的催化劑溶液中，通過還原劑的作用由可溶性銅鹽生成的銅膠體粒子的適當平均粒徑為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 copper colloid particles formed from the soluble copper salt by the action of the reducing agent have an appropriate average particle diameter of from 1 to 250 nm, preferably from 1 to 120 nm, more preferably from 1 to 100 nm.

如果銅膠體粒子的平均粒徑為250nm以下，則可以推測出在將非導電性基板浸漬於催化劑溶液中的情況下，膠體粒子會進入基板的微 細凹凸面的凹處，通過緻密地吸附或掛住等錨固效果，促進對基板表面賦予銅膠體核。反之，如果平均粒徑大於250nm，則不但會由於凝集、沉澱或分離等而難以獲得穩定的銅膠體，而且也無法期待錨固效果，因此只能對基板表面局部賦予銅膠體粒子，或者可能會賦予不良。 When the average particle diameter of the copper colloidal particles is 250 nm or less, it is presumed that in the case where the non-conductive substrate is immersed in the catalyst solution, the colloidal particles enter the micro-substrate. The concave portion of the fine concave and convex surface promotes the adhesion of the copper colloid core to the surface of the substrate by densely adsorbing or hanging the anchoring effect. On the other hand, if the average particle diameter is more than 250 nm, it is difficult to obtain a stable copper colloid due to aggregation, precipitation, separation, etc., and an anchoring effect cannot be expected. Therefore, only copper colloidal particles may be locally applied to the surface of the substrate, or may be imparted. bad.

在本發明1的水系銅膠體催化劑溶液中，需要不含表面活性劑，或者將表面活性劑的含量抑制在950mg/L以下。 In the aqueous copper colloidal catalyst solution of the present invention 1, it is necessary to contain no surfactant or to suppress the content of the surfactant to 950 mg/L or less.

如果催化劑溶液中含有表面活性劑，則催化劑活性可能會降低，優選不添加表面活性劑。但是，在表面活性劑的含量僅為950mg/L以下的極少量的情況下，不會對催化劑活性產生太惡劣的影響，優選為700mg/L以下。 If the catalyst solution contains a surfactant, the catalyst activity may be lowered, preferably without adding a surfactant. However, when the content of the surfactant is only a very small amount of 950 mg/L or less, the catalyst activity is not too badly affected, and is preferably 700 mg/L or less.

上述表面活性劑為非離子型表面活性劑、兩性表面活性劑、陽離子型表面活性劑、或陰離子型表面活性劑等各種表面活性劑，特別不優選兩性表面活性劑、陽離子型表面活性劑、陰離子型表面活性劑、或低分子的非離子型表面活性劑。 The above surfactant is a surfactant such as a nonionic surfactant, an amphoteric surfactant, a cationic surfactant, or an anionic surfactant, and particularly preferably an amphoteric surfactant, a cationic surfactant, or an anion. Type surfactant, or low molecular weight nonionic surfactant.

作為上述非離子型表面活性劑，可列舉出：在C1~C20脂肪醇、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 C1 to C20 fatty alcohols, phenols, naphthols, bisphenols, (poly) C1 to C25 alkylphenols, (poly)arylalkylphenols, and C1~. Addition condensation of C25 alkyl naphthol, C1~C25 alkoxylated phosphoric acid (salt), sorbitan ester, polyalkylene glycol, C1~C22 fatty amine, C1~C22 fatty decylamine, etc. 2~300 A compound of Moth ethylene oxide (EO) and/or propylene oxide (PO), a C1 to C25 alkoxylated phosphoric acid (salt), or the like.

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, Cetyldimethylbenzylammonium salt, octadecyldimethylbenzylammonium salt, trimethylbenzylammonium salt, triethylbenzylammonium salt, dimethyldiphenylammonium salt, benzyl Dimethylphenyl ammonium salt, cetyl pyridinium salt, lauryl pyridinium salt, lauryl pyridinium 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，可列舉出羧基甜菜堿、咪唑啉甜菜堿、磺基甜菜堿、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. The amphoteric surfactant may, for example, be a carboxy betain, an imidazolium betain, a sulfo bee, or 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.

本發明第二方面的水系銅膠體催化劑溶液的基本組成與本發明1的水系銅膠體催化劑溶液相同，以(A)可溶性銅鹽、(B)還原劑、以及(C)膠體穩定劑作為必須成分，成分(A)與(C)的混合比的必要條件也與本發明第一方面相同。 The basic composition of the aqueous copper colloidal catalyst solution of the second aspect of the present invention is the same as that of the aqueous copper colloidal catalyst solution of the present invention 1, and (A) a soluble copper salt, (B) a reducing agent, and (C) a colloidal stabilizer are essential components. The necessary conditions for the mixing ratio of the components (A) and (C) are also the same as those of the first aspect of the invention.

在本發明第二方面的催化劑溶液中，代替將表面活性劑含量為零的情況排除、或者將表面活性劑的含量抑制在極少量以下的本發明第一方面的必要條件，以含有合成類水溶性聚合物為特徵。 In the catalyst solution of the second aspect of the present invention, instead of the case where the surfactant content is zero, or the content of the surfactant is suppressed to a minimum amount, the necessary conditions of the first aspect of the present invention are contained in a synthetic water-soluble solution. The polymer is characterized.

如果催化劑溶液中含有該合成類水溶性聚合物，則膠體粒子的分散性提高，由此在化學鍍銅之際，有助於均勻性優異且無色斑的銅被膜的析出。 When the synthetic water-soluble polymer is contained in the catalyst solution, the dispersibility of the colloidal particles is improved, thereby contributing to the precipitation of the copper film having excellent uniformity and no color unevenness at the time of electroless copper plating.

上述合成類水溶性聚合物是指排除明膠、澱粉等天然來源的水溶性聚合物之意，而不排除半合成類的羧甲基纖維素(CMC)、甲基纖維素(MC)等纖維素衍生物。 The above synthetic water-soluble polymer means to exclude a water-soluble polymer of natural origin such as gelatin or starch, and does not exclude semi-synthetic cellulose such as carboxymethyl cellulose (CMC) or methyl cellulose (MC). derivative.

本發明第二方面中催化劑溶液的含有對象即合成類水溶性聚合物，在與本發明第一方面的催化劑溶液中不含有或含量受抑制的物件即表面活性劑的關係中，屬於其中的成分可能會有部分重複，但是在本發明中二者為不同概念。 The composition of the catalyst solution according to the second aspect of the present invention, that is, the synthetic water-soluble polymer, which is a component which is not contained in the catalyst solution of the first aspect of the invention or which is inhibited, that is, a surfactant There may be some duplication, but in the present invention the two are different concepts.

由於在本發明第二方面的催化劑溶液中，含有水溶性聚合物以外的成分並不是必要條件，因此例如無論是否含有表面活性劑均可，但基本上由於本發明第一方面的關係，優選不含表面活性劑。 Since the component other than the water-soluble polymer is not a necessary condition in the catalyst solution of the second aspect of the present invention, for example, whether or not a surfactant is contained, basically, due to the relationship of the first aspect of the present invention, it is preferred not to Contains surfactants.

如本發明第三方面所示，作為上述合成類水溶性聚合物，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。 As shown in the third aspect of the present invention, examples of the synthetic water-soluble polymer include polyethylene glycol (PEG), polypropylene glycol (PPG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), and poly. A acrylamide (PAM), a polyethyleneimine (PEI), a polyacrylate, etc. are especially preferable, and high molecular weight PEG, PVP, PVA, etc. are especially preferable.

合成類水溶性聚合物可以單獨使用或並用，其相對於催化劑溶液的含量為0.05~100g/L，優選為0.5~50g/L，進一步優選為1.0~30g/L。 The synthetic water-soluble polymer may be used singly or in combination, and its content with respect to the catalyst solution is 0.05 to 100 g/L, preferably 0.5 to 50 g/L, and more preferably 1.0 to 30 g/L.

本發明第九方面是使用上述水系銅膠體催化劑溶液的化學鍍膜方法，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)化學鍍銅步驟。 A ninth aspect of the present invention is an electroless plating method using the above aqueous copper colloid catalyst solution, which is sequentially combined by the following three steps: (a) an adsorption promoting step; (b) a catalyst imparting step; and (c) an electroless copper plating step.

上述吸附促進步驟(a)可以視為步驟(b)的催化劑賦予的預處理(預備處理)步驟，是將非導電性基板浸漬在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、兩性表面活性劑的吸附促進劑中的至少一種的液體中的步驟，通過使基板與含有表面活性劑的液體接觸，可以提高基板表面的濕潤性，增強催化劑活性，並促進下一步驟中銅膠體催化劑的吸附。 The adsorption promoting step (a) may be regarded as a pretreatment (pre-treatment) step imparted by the catalyst of the step (b), which comprises immersing the non-conductive substrate in a non-ionic surfactant, a cationic surfactant, The step of the liquid of at least one of the anionic surfactant and the amphoteric surfactant adsorption promoter can improve the wettability of the substrate surface, enhance the catalyst activity, and promote the substrate by contacting the substrate with the surfactant-containing liquid. Adsorption of the copper colloidal catalyst in the next step.

在吸附促進步驟中，需要使非導電性基板與含有表面活性劑的液體接觸，因此基本上是浸漬在液體中，但也可以將含有表面活性劑的液體噴霧在基板上、或用刷毛塗布在基板上。 In the adsorption promoting step, it is necessary to bring the non-conductive substrate into contact with the liquid containing the surfactant, so that it is substantially immersed in the liquid, but the liquid containing the surfactant may be sprayed on the substrate or coated with bristles. On the substrate.

如本發明第十方面所示，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為合適，尤其更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，則會進一步增加吸附促進效果。 As shown in the tenth aspect of the present invention, 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 increased.

在本發明第一或第二方面的催化劑溶液中，還原劑作用於可溶性銅鹽所生成的銅膠體粒子的zeta電位為負值，因此例如若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，使得下一步驟中銅膠體粒子對基板的吸附效率增加。 In the catalyst solution according to the first or second aspect of the present invention, the zeta potential of the copper colloid particles formed by the reducing agent acting on the soluble copper salt is negative, so that, for example, the non-conductive substrate is contacted with the cationic surfactant. After the treatment, the substrate is easily positively charged, so that the adsorption efficiency of the copper colloid particles on the substrate in the next step is increased.

表面活性劑的具體例，如作為上述本發明第一方面的催化劑溶液中排除或抑制物件所描述的表面活性劑的說明所示。 Specific examples of the surfactant are as shown in the description of the surfactant described in the above-mentioned catalyst solution of the first aspect of the present invention to exclude or inhibit the article.

表面活性劑的含量為0.05~100g/L，優選為0.5~50g/L。優選含有表面活性劑的液體的溫度為15~70℃左右，浸漬時間為0.5~20分鐘左右。結束吸附促進處理的非導電性基板用純水洗滌後，乾燥或不乾燥，進入下一步催化劑賦予步驟(b)。 The content of the surfactant is 0.05 to 100 g/L, preferably 0.5 to 50 g/L. The temperature of the liquid containing the surfactant is preferably about 15 to 70 ° C, and the immersion time is about 0.5 to 20 minutes. The non-conductive substrate that has finished the adsorption-promoting treatment is washed with pure water, dried or not dried, and proceeds to the next catalyst-imparting step (b).

在催化劑賦予步驟中，將非導電性基板浸漬在上述水系銅膠體催化劑溶液中，使銅膠體粒子吸附在基板表面上。 In the catalyst application step, the non-conductive substrate is immersed in the aqueous copper colloid catalyst solution to adsorb the copper colloid particles on the surface of the substrate.

該催化劑溶液的液溫為10~70℃、浸漬時間為0.1~20分鐘左右，進行浸漬處理之際，在將基板靜置於催化劑溶液的狀態下進行浸漬即可，但也可以進行攪拌或揺動。 The liquid temperature of the catalyst solution is 10 to 70 ° C, and the immersion time is about 0.1 to 20 minutes. When the immersion treatment is performed, the substrate may be immersed in a state where the substrate is left in the catalyst solution, but may be stirred or kneaded. move.

浸漬於催化劑溶液中的非導電性基板用純水洗滌後，乾燥或不乾燥，進入化學鍍銅步驟(c)。 The non-conductive substrate immersed in the catalyst solution is washed with pure water, dried or not dried, and is subjected to an electroless copper plating step (c).

化學鍍銅採用與現有技術同樣的處理即可，沒有特別限制。化學鍍銅液的液溫通常為15~70℃、優選為20~60℃。 The electroless copper plating may be the same as the prior art, and is not particularly limited. The liquid temperature of the electroless copper plating solution is usually 15 to 70 ° C, preferably 20 to 60 ° C.

鍍銅液的攪拌可以採用空氣攪拌、快速液流攪拌、利用攪拌葉片等進行的機械攪拌等。 The stirring of the copper plating liquid can be carried out by air stirring, rapid liquid agitation, mechanical stirring using a stirring blade or the like.

化學鍍銅液的組成沒有特別限制，可以使用公知的鍍銅液。 The composition of the electroless copper plating solution is not particularly limited, and a known copper plating solution can be used.

化學鍍銅液基本上含有可溶性銅鹽、還原劑和配位劑，或者還可以進一步含有表面活性劑或pH調節劑等各種添加劑、或者酸。 The electroless copper plating solution basically contains a soluble copper salt, a reducing agent, and a complexing agent, or may further contain various additives such as a surfactant or a pH adjuster, or an acid.

關於可溶性銅鹽，如上述對銅膠體催化劑溶液的描述所示。 Regarding the soluble copper salt, as described above for the copper colloidal catalyst solution.

關於化學鍍銅液中所含的還原劑，也如上述對銅膠體催化劑溶液的描述所示，以甲醛(甲醛水)為代表、包括次磷酸類、亞磷酸類、胺硼烷類、硼氫類、乙醛酸等，優選為甲醛水。 The reducing agent contained in the electroless copper plating solution is also represented by formaldehyde (formaldehyde water), including hypophosphorous acid, phosphorous acid, amine borane, and boron hydrogen, as described above for the copper colloidal catalyst solution. A class, glyoxylic acid or the like is preferably formalin.

關於化學鍍銅液中所含的配位劑，也包括與上述銅膠體催化劑溶液中描述的膠體穩定劑共通的部分，具體而言為：乙二胺四乙酸(EDTA)、二亞乙基三胺五乙酸(DTPA)、三亞乙基四胺六乙酸(TTHA)、羥乙基乙二胺三乙酸(HEDTA)、氨三乙酸(NTA)、亞氨基二乙酸(IDA)等氨基羧酸類；乙二胺、四亞甲基二胺、六亞甲基二胺、二亞乙基三胺、四亞乙基五胺、五亞乙基六胺等多胺類；單乙醇胺、二乙醇胺、三乙醇胺等氨基醇類；檸檬酸、酒石酸、乳酸、蘋果酸等羥基羧酸類；巰基乙酸、谷氨酸等。 The complexing agent contained in the electroless copper plating solution also includes a portion common to the colloidal stabilizer described in the above copper colloidal catalyst solution, specifically: ethylenediaminetetraacetic acid (EDTA), diethylene three Amino carboxylic acid such as amine pentaacetic acid (DTPA), triethylenetetramine hexaacetic acid (TTHA), hydroxyethyl ethylenediamine triacetic acid (HEDTA), ammonia triacetic acid (NTA), iminodiacetic acid (IDA); Polyamines such as diamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, etc.; monoethanolamine, diethanolamine, triethanolamine Amino alcohols; hydroxycarboxylic acids such as citric acid, tartaric acid, lactic acid, malic acid; thioglycolic acid, glutamic acid, and the like.

在化學鍍銅液中，可以含有有機酸和無機酸、或其鹽作為液體的基礎成分。 In the electroless copper plating solution, an organic acid and an inorganic acid, or a salt thereof may be contained as a base component of the liquid.

作為上述無機酸，可列舉出硫酸、焦磷酸、氟硼酸等。另外，作為有機酸，可列舉出乙醇酸或酒石酸等羥基羧酸、甲磺酸或2-羥基乙磺酸等有機磺酸等。 Examples of the inorganic acid include sulfuric acid, pyrophosphoric acid, and fluoroboric acid. Further, examples of the organic acid include a hydroxycarboxylic acid such as glycolic acid or tartaric acid, an organic sulfonic acid such as methanesulfonic acid or 2-hydroxyethanesulfonic acid, 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、銅膠體催化劑溶液、以及化學鍍銅液的製備在內的化學鍍銅方法的實施例進行說明，並且依次對銅膠體催化劑溶液的經時穩定性試驗例、上述實施例中所得的析出銅被膜的外觀評價試驗例進行說明。 Hereinafter, an example of an electroless copper plating method including the adsorption promoter-containing liquid, the copper colloidal catalyst solution, and the preparation of the electroless copper plating solution of the present invention will be described, and the copper colloidal catalyst solution is sequentially stabilized with time. An example of the evaluation of the appearance of the precipitated copper film obtained in the above test examples and the above examples will be described.

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.

《化學鍍銅方法的實施例》 "Example of Electroless Copper Plating Method"

在下列實施例1~18中，實施例7是在銅膠體催化劑溶液中含有極少量表面活性劑的例子，實施例1~4、實施例8~12和實施例18是在催化劑溶液中不含表面活性劑的離子，實施例5~6、實施例9和實施例13~17是在催化劑溶液中含有合成類水溶性聚合物的例子。 In the following Examples 1 to 18, Example 7 is an example in which a very small amount of a surfactant is contained in a copper colloidal catalyst solution, and Examples 1 to 4, Examples 8 to 12, and Example 18 are contained in a catalyst solution. Surfactant ions, Examples 5 to 6, Example 9, and Examples 13 to 17 are examples in which a synthetic water-soluble polymer is contained in a catalyst solution.

實施例1是在催化劑溶液中使用檸檬酸作為膠體穩定劑，使用硼氫化鈉作為還原劑的例子。以下，以實施例1為基礎，實施例2是降低膠體穩定劑的含量的例子，實施例3是增加膠體穩定劑的含量的例子，實施例4是降低還原劑的含量的例子，實施例8是改變膠體穩定劑的種類和含量的例子，實施例9是改變還原劑的種類和催化劑溶液的液溫的例子。另外，以實施例9為基礎，實施例10~11、15是改變可溶性銅鹽的例子，實施例12是改變膠體穩定劑的例子。 Example 1 is an example in which citric acid was used as a colloidal stabilizer in a catalyst solution and sodium borohydride was used as a reducing agent. Hereinafter, based on Example 1, Example 2 is an example of reducing the content of the colloidal stabilizer, Example 3 is an example of increasing the content of the colloidal stabilizer, and Example 4 is an example of reducing the content of the reducing agent, and Example 8 An example of changing the kind and content of the colloidal stabilizer, and Example 9 is an example of changing the kind of the reducing agent and the liquid temperature of the catalyst solution. Further, based on Example 9, Examples 10 to 11 and 15 are examples in which a soluble copper salt is changed, and Example 12 is an example in which a colloidal stabilizer is changed.

如上所述，實施例7是以實施例1為基礎，含有極少量非離子型表面活性劑，並改變膠體穩定劑的種類和催化劑溶液的pH值的例子。 As described above, Example 7 is an example in which a very small amount of a nonionic surfactant is contained on the basis of Example 1, and the kind of the colloidal stabilizer and the pH of the catalyst solution are changed.

此外，以實施例1為基礎，實施例5是在催化劑溶液中含有聚乙烯吡咯烷酮(PVP)的例子，實施例6同樣是含有聚乙二醇(PEG)的例子，實施例9和實施例14是含有PVP(改變平均分子量)的例子，實施例13是含有聚乙烯亞胺(PEI)的例子，實施例15是含有聚丙烯醯胺(PAM)的例子。 Further, based on Example 1, Example 5 is an example in which polyvinylpyrrolidone (PVP) is contained in a catalyst solution, and Example 6 is also an example containing polyethylene glycol (PEG), and Example 9 and Example 14 are the same. It is an example containing PVP (changing average molecular weight), Example 13 is an example containing polyethyleneimine (PEI), and Example 15 is an example containing polypropylene decylamine (PAM).

實施例1~15是催化劑溶液的pH值在酸性側的例子，而實施例16~18是催化劑溶液的pH值在鹼性側的例子。附帶說明，pH值的調整使用10~20%左右的硫酸、或氫氧化鈉。 Examples 1 to 15 are examples in which the pH of the catalyst solution is on the acidic side, and Examples 16 to 18 are examples in which the pH of the catalyst solution is on the alkaline side. Incidentally, the pH is adjusted by using about 10 to 20% of sulfuric acid or sodium hydroxide.

另一方面，在下列比較例1~6中，比較例1是在催化劑溶液中不含膠體穩定劑的空白例，比較例2是在催化劑溶液中膠體穩定劑相對於銅鹽的相對含量比低於本發明1~2中規定量下限的例子，比較例3是該含量比率超過本發明1~2中規定量上限的例子，比較例4是在催化劑溶液中表面活性劑的含量超過本發明1中抑制規定量的例子，比較例5是該催化劑溶液中表面活性劑的含量大於比較例4的例子，比較例6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 6, Comparative Example 1 is a blank example in which no colloidal stabilizer is contained in the catalyst solution, and Comparative Example 2 is a low relative ratio of the colloidal stabilizer to the copper salt in the catalyst solution. In the examples of the lower limit of the amount specified in the inventions 1 to 2, the comparative example 3 is an example in which the content ratio exceeds the upper limit of the amount specified in the first to second embodiments of the present invention, and the comparative example 4 is such that the content of the surfactant in the catalyst solution exceeds the present invention. In the example in which the predetermined amount is suppressed, Comparative Example 5 is an example in which the content of the surfactant in the catalyst solution is larger than that in Comparative Example 4, and Comparative Example 6 is a blank example in which the electroless plating step is directly performed from the catalyst application step without the adsorption promoting step.

另外，前述專利文獻1的實施例4在催化劑溶液中含有明膠作為分散劑，而比較例7是在催化劑溶液中含有天然來源的水溶性聚合物即明膠，而不含本發明2中規定的合成類水溶性聚合物的例子，可以視為上述專利文獻1的參照例。 Further, in Example 4 of Patent Document 1, the gelatin was contained as a dispersing agent in the catalyst solution, and Comparative Example 7 contained gelatin which is a water-soluble polymer of natural origin in the catalyst solution, and did not contain the synthesis specified in the present invention 2. An example of the water-soluble polymer can be considered as a reference example of the above-mentioned Patent Document 1.

(1)實施例1 (1) Embodiment 1

(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.

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

聚氧化亞烷基側鏈癸基醚：1g/L Polyoxyalkylene side chain decyl ether: 1g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / 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

向調整為pH4.0的25℃的上述銅溶液中滴入還原劑溶液，攪拌45分鐘，製成水系銅膠體催化劑溶液。 The reducing agent solution was dropped into the above copper solution adjusted to pH 4.0 at 25 ° C, and stirred for 45 minutes to prepare an aqueous copper colloidal catalyst solution.

上述催化劑溶液的各成分的莫耳比如下所示： The moir of each component of the above catalyst solution is as follows:

銅鹽：膠體穩定劑=1：3，銅鹽：還原劑=1：1 Copper salt: colloidal stabilizer = 1:3, copper salt: reducing agent = 1:1

生成的銅膠體粒子的平均粒徑為約10nm。 The resulting copper colloidal particles had an average particle diameter of about 10 nm.

(c)化學鍍銅液的製備 (c) Preparation of electroless copper plating solution

按照下列組成製成化學鍍銅液浴(建浴)。用下述氫氧化鈉調整該鍍液的pH值。 An electroless copper plating bath (built bath) was prepared according to the following composition. The pH of the plating solution was adjusted with the following sodium hydroxide.

[化學鍍銅液] [Chemical copper plating solution]

硫酸銅五水合物(作為Cu2+)：2.0g/L Copper sulfate pentahydrate (as Cu 2+ ): 2.0g/L

甲醛：5.0g/L Formaldehyde: 5.0g/L

EDTA：30.0g/L EDTA: 30.0g/L

氫氧化鈉：9.6g/L Sodium hydroxide: 9.6g/L

餘量：純水 Balance: pure water

pH(20℃)：12.8 pH (20 ° C): 12.8

(d)化學鍍銅的處理條件 (d) Processing conditions for electroless copper plating

首先，將非導電性基板即雙面覆銅玻璃-環氧樹脂基板(松下電工株式會社制的FR-4、板厚：1.0mm)作為試樣基板。然後，使用上述(a)的吸附促進劑對試樣基板進行吸附促進後，浸漬在上述(b)的催化劑溶液中進行催化劑賦予，再使用上述(c)的鍍液進行化學鍍銅。具體而言，將上述試樣基板在50℃、2分鐘的條件下浸漬於上述含有吸附促進劑的液體中，然後用純水洗滌。接著，將實施吸附促進處理(預處理)後的試樣基板在25℃、10分鐘的條件下浸漬於上述銅膠體催化劑溶液中，然後用純水洗滌。然後，將實施催化劑賦予後的試樣基板在50℃、10分鐘的條件下浸漬於上述化學鍍銅液中，實施化學鍍膜，在試樣基板上形成銅被膜後，用純水洗滌，乾燥。 First, a non-conductive substrate, that is, a double-sided copper-clad glass-epoxy substrate (FR-4 manufactured by Matsushita Electric Works Co., Ltd., thickness: 1.0 mm) was used as a sample substrate. Then, the sample substrate is adsorbed and accelerated by using the adsorption accelerator of the above (a), and then immersed in the catalyst solution of the above (b) to carry out catalyst application, and the plating solution of the above (c) is used for electroless copper plating. Specifically, the sample substrate was immersed in the above-mentioned liquid containing an adsorption promoter at 50 ° C for 2 minutes, and then washed with pure water. Next, the sample substrate subjected to the adsorption acceleration treatment (pretreatment) was immersed in the copper colloidal catalyst solution at 25 ° C for 10 minutes, and then washed with pure water. Then, the sample substrate to which the catalyst was applied was immersed in the electroless copper plating solution at 50 ° C for 10 minutes to form a copper plating film on the sample substrate, and then washed with pure water and dried.

(2)實施例2(實施例1的膠體穩定劑減少的例子) (2) Example 2 (Example of reduction of colloidal stabilizer of 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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示： Based on the above Example 1, the liquid and copper colloidal catalyst solution containing the adsorption promoter were prepared according to the following composition, in addition to the preparation method of the copper colloidal catalyst solution or the electroless copper plating solution and the processing conditions of each step and Example 1 the same. Incidentally, the molars of the respective components of the above catalyst solution are as follows:

銅鹽：膠體穩定劑=1：0.2，銅鹽：還原劑=1：1 Copper salt: colloidal stabilizer = 1:0.2, copper salt: reducing agent = 1:1

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

氯化十二烷基二甲基苄基銨：5g/L Dodecyldimethylbenzylammonium chloride: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

檸檬酸：0.04莫耳/L Citric acid: 0.04 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

向調整為pH4.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成的銅膠體粒子的平均粒徑為約15nm。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 4.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 15 nm.

(3)實施例3(實施例1的膠體穩定劑增加的例子) (3) Example 3 (Example of increase in colloidal stabilizer of 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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示： Based on the above Example 1, the liquid and copper colloidal catalyst solution containing the adsorption promoter were prepared according to the following composition, in addition to the preparation method of the copper colloidal catalyst solution or the electroless copper plating solution and the processing conditions of each step and Example 1 the same. Incidentally, the molars of the respective components of the above catalyst solution are as follows:

銅鹽：膠體穩定劑=1：15，銅鹽：還原劑=1：1 Copper salt: colloidal stabilizer = 1:15, copper salt: reducing agent = 1:1

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

十二烷基二甲氨基乙酸甜菜鹼：5g/L Dodecyldimethylaminoacetic acid betaine: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

檸檬酸：3.0莫耳/L Citric acid: 3.0 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

向調整為pH4.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成的銅膠體粒子的平均粒徑為約12nm。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 4.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 12 nm.

(4)實施例4(實施例1的還原劑減少的例子) (4) Example 4 (Example of reduction of reducing agent of 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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示： Based on the above Example 1, the liquid and copper colloidal catalyst solution containing the adsorption promoter were prepared according to the following composition, in addition to the preparation method of the copper colloidal catalyst solution or the electroless copper plating solution and the processing conditions of each step and Example 1 the same. Incidentally, the molars of the respective components of the above catalyst solution are as follows:

銅鹽：膠體穩定劑=1：4，銅鹽：還原劑=1：0.05 Copper salt: colloidal stabilizer = 1:4, copper salt: reducing agent = 1:0.05

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

聚氧化亞烷基側鏈癸基醚：1g/L Polyoxyalkylene side chain decyl ether: 1g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

檸檬酸：0.8莫耳/L Citric acid: 0.8 mol / L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.01莫耳/L Sodium borohydride: 0.01 mol/L

向調整為pH4.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成的銅膠體粒子的平均粒徑為約25nm。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 4.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 25 nm.

(5)實施例5(實施例1的還原劑增加的例子) (5) Example 5 (Example of increase of reducing agent of 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銅 膠體催化劑溶液，除此之外，銅膠體催化劑溶液或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示： Based on the above Example 1, the liquid and copper containing the adsorption promoter were prepared according to the following composition. In addition to the colloidal catalyst solution, the preparation method of the copper colloidal catalyst solution or the electroless copper plating solution and the treatment conditions of the respective steps are the same as in the first embodiment. Incidentally, the molars of the respective components of the above catalyst solution are as follows:

銅鹽：膠體穩定劑=1：4，銅鹽：還原劑=1：2.25 Copper salt: colloidal stabilizer = 1:4, copper salt: reducing agent = 1: 2.25

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

檸檬酸：0.8莫耳/L Citric acid: 0.8 mol / L

聚乙烯吡咯烷酮(平均分子量40000)：2.0g/L Polyvinylpyrrolidone (average molecular weight 40000): 2.0g/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.45莫耳/L Sodium borohydride: 0.45 m / L

向調整為pH4.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成的銅膠體粒子的平均粒徑為約8nm。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 4.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 8 nm.

(6)實施例6(實施例1的膠體穩定劑、還原劑減少，攪拌時間增加的例子) (6) Example 6 (Example in which the colloidal stabilizer and the reducing agent of Example 1 are reduced and the stirring time is increased)

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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液(但攪拌時間除外)或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示： Based on the above Example 1, the liquid and copper colloidal catalyst solution containing the adsorption promoter are prepared according to the following composition, in addition to the preparation method of the copper colloidal catalyst solution (except for the stirring time) or the electroless copper plating solution, and the steps of the respective steps. The processing conditions were the same as in Example 1. Incidentally, the molars of the respective components of the above catalyst solution are as follows:

銅鹽：膠體穩定劑=1：3、銅鹽：還原劑=1：0.5 Copper salt: colloidal stabilizer = 1:3, copper salt: reducing agent = 1:0.5

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

氯化十二烷基二甲基苄基銨：5g/L Dodecyldimethylbenzylammonium chloride: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

檸檬酸：0.6莫耳/L Citric acid: 0.6 mol/L

聚乙二醇(平均分子量10000)：1.0g/L Polyethylene glycol (average molecular weight 10000): 1.0g / L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.1莫耳/L Sodium borohydride: 0.1 mol/L

向調整為pH4.0的25℃的銅溶液中滴入還原劑溶液，攪拌60分鐘。 生成的銅膠體粒子的平均粒徑為約30nm。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 4.0, and stirred for 60 minutes. The resulting copper colloidal particles had an average particle diameter of about 30 nm.

(7)實施例7(實施例1的膠體穩定劑改變、量改變、pH改變、向催化劑溶液中添加表面活性劑的例子) (7) Example 7 (Example of change of colloidal stabilizer in Example 1, change in amount, change in pH, and addition of a surfactant to a catalyst solution)

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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液(但pH條件除外)或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 Based on the above Example 1, a liquid and copper colloidal catalyst solution containing an adsorption promoter is prepared according to the following composition, in addition to the preparation method of the copper colloidal catalyst solution (except pH conditions) or the electroless copper plating solution, and the steps of each step. The processing conditions were the same as in Example 1. In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：3.5，銅鹽：還原劑=1：1 Copper salt: colloidal stabilizer = 1:3.5, copper salt: reducing agent = 1:1

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

十二烷基二甲氨基乙酸甜菜鹼：5g/L Dodecyldimethylaminoacetic acid betaine: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

葡萄糖酸：0.7莫耳/L Gluconic acid: 0.7 mol/L

聚氧乙烯-苯乙烯化苯基醚(EO10莫耳)：0.2g/L Polyoxyethylene-styrenated phenyl ether (EO10 mol): 0.2g/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L

向調整為pH3.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成的銅膠體粒子的平均粒徑為約17nm。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 3.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 17 nm.

(8)實施例8(實施例1的膠體穩定劑改變、量改變的例子)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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液(但攪拌條件除外)或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。 (8) Example 8 (Example of change of colloidal stabilizer and amount of change of Example 1) Based on the above Example 1, a liquid and a copper colloidal catalyst solution containing an adsorption promoter were prepared according to the following composition, in addition to copper The preparation method of the colloidal catalyst solution (except for the stirring conditions) or the electroless copper plating solution and the treatment conditions of the respective steps are the same as in the first embodiment.

應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：3，銅鹽：還原劑=1：1 Copper salt: colloidal stabilizer = 1:3, copper salt: reducing agent = 1:1

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

氯化十二烷基二甲基苄基銨：5g/L Dodecyldimethylbenzylammonium chloride: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

乙醇酸：0.6莫耳/L Glycolic 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

向調整為pH4.0的25℃的銅溶液中滴入還原劑溶液，攪拌90分鐘。生成的銅膠體粒子的平均粒徑為約15nm。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 4.0, and stirred for 90 minutes. The resulting copper colloidal particles had an average particle diameter of about 15 nm.

(9)實施例9(實施例1的還原劑改變、浴溫改變的例子) (9) Example 9 (Example of change of reducing agent and change of bath temperature in 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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液(但銅溶液的液溫條件除外)或化學鍍銅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 liquid and copper colloidal catalyst solution containing an adsorption promoter is prepared according to the following composition, in addition to the copper colloidal catalyst solution (except for the liquid temperature condition of the copper solution) or the preparation method of the electroless copper plating solution The processing conditions of the respective steps are the same as in the first embodiment.

應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：3，銅鹽：還原劑=1：0.5 Copper salt: colloidal stabilizer = 1:3, copper salt: reducing agent = 1:0.5

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

聚氧化亞烷基側鏈癸基醚：1g/L Polyoxyalkylene side chain decyl ether: 1g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

檸檬酸：0.6莫耳/L Citric acid: 0.6 mol/L

聚乙烯吡咯烷酮(分子量300000)：1.0g/L Polyvinylpyrrolidone (molecular weight 300,000): 1.0g/L

[還原劑溶液] [Reducing agent solution]

二甲胺硼烷：0.1莫耳/L Dimethylamine borane: 0.1 mol/L

向調整為pH4.0的35℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。 生成的銅膠體粒子的平均粒徑為約45nm。 The reducing agent solution was dropped into a copper solution of 35 ° C adjusted to pH 4.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 45 nm.

(10)實施例10(實施例9的可溶性銅鹽改變的例子) (10) Example 10 (Example of change of soluble copper salt of Example 9)

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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液(但pH和銅溶液的液溫條件除外)或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 Based on the above Example 1, a liquid and copper colloidal catalyst solution containing an adsorption promoter was prepared according to the following composition, in addition to the preparation of the copper colloidal catalyst solution (except for the liquid temperature conditions of pH and copper solution) or the electroless copper plating solution. The method and the processing conditions of the respective steps are the same as in the first embodiment. In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：4，銅鹽：還原劑=1：0.5 Copper salt: colloidal stabilizer = 1:4, copper salt: reducing agent = 1:0.5

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

氯化十二烷基二甲基苄基銨：5g/L Dodecyldimethylbenzylammonium chloride: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

甲磺酸銅(作為Cu2+)：0.2莫耳/L Copper methanesulfonate (as Cu 2+): 0.2 mole / L

檸檬酸：0.8莫耳/L Citric acid: 0.8 mol / L

[還原劑溶液] [Reducing agent solution]

二甲胺硼烷：0.1莫耳/L Dimethylamine borane: 0.1 mol/L

向調整為pH3.0的35℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成的銅膠體粒子的平均粒徑為約16nm。 The reducing agent solution was dropped into a copper solution of 35 ° C adjusted to pH 3.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 16 nm.

(11)實施例11(實施例9的可溶性銅鹽改變的例子) (11) Example 11 (Example of change of soluble copper salt of Example 9)

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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液(但pH和銅溶液的液溫條件 除外)或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 Based on the above Example 1, a liquid and copper colloidal catalyst solution containing an adsorption promoter was prepared according to the following composition, in addition to the copper colloidal catalyst solution (but the liquid temperature conditions of the pH and the copper solution) The method for preparing the electroless copper plating solution and the processing conditions of the respective steps are the same as those in the first embodiment. In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：3.5，銅鹽：還原劑=1：0.75 Copper salt: colloidal stabilizer = 1:3.5, copper salt: reducing agent = 1:0.75

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

檸檬酸銅2.5水合物(作為Cu2+)：0.2莫耳/L Copper citrate 2.5 hydrate (as Cu 2+): 0.2 mole / L

檸檬酸：0.7莫耳/L Citric acid: 0.7 mol/L

[還原劑溶液] [Reducing agent solution]

二甲胺硼烷：0.15莫耳/L Dimethylamine borane: 0.15 mol/L

向調整為pH5.0的35℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成的銅膠體粒子的平均粒徑為約14nm。 The reducing agent solution was dropped into a copper solution of 35 ° C adjusted to pH 5.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 14 nm.

(12)實施例12(實施例9的膠體穩定劑改變的例子) (12) Example 12 (Example of change of colloidal stabilizer of Example 9)

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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液(但銅溶液的液溫條件除外)或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 Based on the above Example 1, a liquid and copper colloidal catalyst solution containing an adsorption promoter is prepared according to the following composition, in addition to the copper colloidal catalyst solution (except for the liquid temperature condition of the copper solution) or the preparation method of the electroless copper plating solution The processing conditions of the respective steps are the same as in the first embodiment. In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：2，銅鹽：還原劑=1：0.5 Copper salt: colloidal stabilizer = 1:2, copper salt: reducing agent = 1:0.5

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

十二烷基二甲氨基乙酸甜菜堿：5g/L Dodecyldimethylaminoacetate beet pulp: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

葡萄糖酸：0.4莫耳/L Gluconic acid: 0.4 mol/L

[還原劑溶液] [Reducing agent solution]

二甲胺硼烷：0.1莫耳/L Dimethylamine borane: 0.1 mol/L

向調整為pH4.0的35℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成的銅膠體粒子的平均粒徑為約20nm。 The reducing agent solution was dropped into a copper solution of 35 ° C adjusted to pH 4.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 20 nm.

(13)實施例13(添加水溶性聚合物的情況) (13) Example 13 (in the case of adding a water-soluble polymer)

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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 Based on the above Example 1, the liquid and copper colloidal catalyst solution containing the adsorption promoter were prepared according to the following composition, in addition to the preparation method of the copper colloidal catalyst solution or the electroless copper plating solution and the processing conditions of each step and Example 1 the same. In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：4，銅鹽：還原劑=1：1 Copper salt: colloidal stabilizer = 1:4, copper salt: reducing agent = 1:1

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

檸檬酸：0.8莫耳/L Citric acid: 0.8 mol / L

聚乙烯亞胺：1.5g/L Polyethyleneimine: 1.5g/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L

向調整為pH4.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成的銅膠體粒子的平均粒徑為約17nm。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 4.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 17 nm.

(14)實施例14(添加水溶性聚合物的情況) (14) Example 14 (in the case of adding a water-soluble polymer)

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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 Based on the above Example 1, the liquid and copper colloidal catalyst solution containing the adsorption promoter were prepared according to the following composition, in addition to the preparation method of the copper colloidal catalyst solution or the electroless copper plating solution and the processing conditions of each step and Example 1 the same. In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：4，銅鹽：還原劑=1：1 Copper salt: colloidal stabilizer = 1:4, copper salt: reducing agent = 1:1

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

檸檬酸：0.8莫耳/L Citric acid: 0.8 mol / L

聚乙烯吡咯烷酮(分子量300000)：1.0g/L Polyvinylpyrrolidone (molecular weight 300,000): 1.0g/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L

向調整為pH4.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。 生成的銅膠體粒子的平均粒徑為約15nm。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 4.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 15 nm.

(15)實施例15(改變可溶性銅鹽、添加水溶性聚合物的情況)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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 (15) Example 15 (Change of soluble copper salt, addition of water-soluble polymer) Based on the above Example 1, a liquid and copper colloidal catalyst solution containing an adsorption promoter was prepared according to the following composition, in addition to copper colloid The preparation method of the catalyst solution or the electroless copper plating solution and the treatment conditions of the respective steps are the same as in the first embodiment. In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：4，銅鹽：還原劑=1：1 Copper salt: colloidal stabilizer = 1:4, copper salt: reducing agent = 1:1

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

乙酸銅-水合物(作為Cu2+)：0.2莫耳/L Copper acetate-hydrate (as Cu 2+ ): 0.2 mol/L

檸檬酸：0.8莫耳/L Citric acid: 0.8 mol / L

聚丙烯醯胺：0.5g/L Polyacrylamide: 0.5g/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L

向調整為pH4.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成的銅膠體粒子的平均粒徑為約22nm。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 4.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 22 nm.

(16)實施例16(實施例1的pH增加的例子) (16) Example 16 (Example of pH increase of 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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液(但pH條件除外)或化學鍍銅 液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 Based on the above Example 1, a liquid and copper colloidal catalyst solution containing an adsorption promoter was prepared according to the following composition, in addition to the copper colloidal catalyst solution (except pH conditions) or electroless copper plating. The preparation method of the liquid and the treatment conditions of the respective steps were the same as in the first embodiment. In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：3，銅鹽：還原劑=1：0.5 Copper salt: colloidal stabilizer = 1:3, copper salt: reducing agent = 1:0.5

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

聚氧化亞烷基側鏈癸基醚：1g/L Polyoxyalkylene side chain decyl ether: 1g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

乙二胺四乙酸：0.6莫耳/L Ethylenediaminetetraacetic acid: 0.6 mol/L

聚乙烯吡咯烷酮(分子量300000)：1.0g/L Polyvinylpyrrolidone (molecular weight 300,000): 1.0g/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.1莫耳/L Sodium borohydride: 0.1 mol/L

向調整為pH9.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成的銅膠體粒子的平均粒徑為約18nm。 The reducing agent solution was dropped into a 25 ° C copper solution adjusted to pH 9.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 18 nm.

(17)實施例17(實施例1的pH增加的例子) (17) Example 17 (Example of pH increase of 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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液(但pH條件除外)或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 Based on the above Example 1, a liquid and copper colloidal catalyst solution containing an adsorption promoter is prepared according to the following composition, in addition to the preparation method of the copper colloidal catalyst solution (except pH conditions) or the electroless copper plating solution, and the steps of each step. The processing conditions were the same as in Example 1. In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：4，銅鹽：還原劑=1：1 Copper salt: colloidal stabilizer = 1:4, copper salt: reducing agent = 1:1

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

聚氧化亞烷基側鏈癸基醚：1g/L Polyoxyalkylene side chain decyl ether: 1g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

氨三乙酸：0.8莫耳/L Ammoniatriacetic acid: 0.8 mol/L

聚丙烯醯胺：1.0g/L Polyacrylamide: 1.0g/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

向調整為pH10.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成的銅膠體粒子的平均粒徑為約15nm。 The reducing agent solution was dropped into a 25 ° C copper solution adjusted to pH 10.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 15 nm.

(18)實施例18(實施例1的pH增加的例子) (18) Example 18 (Example of pH increase of 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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液(但pH條件除外)或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 Based on the above Example 1, a liquid and copper colloidal catalyst solution containing an adsorption promoter is prepared according to the following composition, in addition to the preparation method of the copper colloidal catalyst solution (except pH conditions) or the electroless copper plating solution, and the steps of each step. The processing conditions were the same as in Example 1. In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：3，銅鹽：還原劑=1：0.5 Copper salt: colloidal stabilizer = 1:3, copper salt: reducing agent = 1:0.5

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

二亞乙基三胺五乙酸：0.6莫耳/L Diethylenetriamine pentaacetic acid: 0.6 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

向調整為pH10.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成的銅膠體粒子的平均粒徑為約20nm。 The reducing agent solution was dropped into a 25 ° C copper solution adjusted to pH 10.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 20 nm.

(19)比較例1(催化劑溶液中沒有穩定劑的情況) (19) Comparative Example 1 (in the case where there is no stabilizer in the catalyst solution)

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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 Based on the above Example 1, the liquid and copper colloidal catalyst solution containing the adsorption promoter were prepared according to the following composition, in addition to the preparation method of the copper colloidal catalyst solution or the electroless copper plating solution and the processing conditions of each step and Example 1 the same. In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：0，銅鹽：還原劑=1：1 Copper salt: colloidal stabilizer = 1:0, copper salt: reducing agent = 1:1

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 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

向調整為pH4.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成銅膠體粒子，但發生凝集、沉澱。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 4.0, and stirred for 45 minutes. Copper colloidal particles are formed, but aggregation and precipitation occur.

(20)比較例2(銅與穩定劑之比在最小限度之外的情況) (20) Comparative Example 2 (the case where the ratio of copper to stabilizer is outside the minimum)

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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 Based on the above Example 1, the liquid and copper colloidal catalyst solution containing the adsorption promoter were prepared according to the following composition, in addition to the preparation method of the copper colloidal catalyst solution or the electroless copper plating solution and the processing conditions of each step and Example 1 the same. In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：0.01，銅鹽：還原劑=1：1 Copper salt: colloidal stabilizer = 1:0.01, copper salt: reducing agent = 1:1

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

檸檬酸：0.002莫耳/L Citric acid: 0.002 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

向調整為pH4.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成銅膠體粒子，但發生凝集、沉澱。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 4.0, and stirred for 45 minutes. Copper colloidal particles are formed, but aggregation and precipitation occur.

(21)比較例3(銅與穩定劑之比在最大限度之外的情況) (21) Comparative Example 3 (the ratio of copper to stabilizer is outside the maximum)

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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液或化學鍍銅液的製備方法 以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 Based on the above Example 1, a liquid and copper colloidal catalyst solution containing an adsorption promoter is prepared according to the following composition, in addition to the preparation method of the copper colloidal catalyst solution or the electroless copper plating solution The processing conditions of the respective steps are the same as in the first embodiment. In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：36，銅鹽：還原劑=1：1 Copper salt: colloidal stabilizer = 1:36, copper salt: reducing agent = 1:1

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+): 0.2 mole / L

乳酸：7.2莫耳/L Lactic acid: 7.2 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

向調整為pH4.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。未生成銅膠體粒子。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 4.0, and stirred for 45 minutes. No copper colloidal particles were formed.

(22)比較例4(實施例1的催化劑溶液中表面活性劑的含量超過本申請規定值的例子) (22) Comparative Example 4 (Example in which the content of the surfactant in the catalyst solution of Example 1 exceeds the value specified in the present application)

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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 Based on the above Example 1, the liquid and copper colloidal catalyst solution containing the adsorption promoter were prepared according to the following composition, in addition to the preparation method of the copper colloidal catalyst solution or the electroless copper plating solution and the processing conditions of each step and Example 1 the same. In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：4，銅鹽：還原劑=1：1 Copper salt: colloidal stabilizer = 1:4, copper salt: reducing agent = 1:1

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

聚氧化亞烷基側鏈癸基醚：1g/L Polyoxyalkylene side chain decyl ether: 1g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

檸檬酸：0.8莫耳/L Citric acid: 0.8 mol / L

聚氧乙烯-辛基苯基醚(EO15莫耳)：1.0g/L Polyoxyethylene-octylphenyl ether (EO15 Molar): 1.0g/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L

向調整為pH4.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成的銅膠體粒子的平均粒徑為約15nm。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 4.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 15 nm.

(23)比較例5(實施例1的催化劑溶液中含有大量表面活性劑的例子) (23) Comparative Example 5 (Example of a large amount of surfactant contained in the catalyst solution of 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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 Based on the above Example 1, the liquid and copper colloidal catalyst solution containing the adsorption promoter were prepared according to the following composition, in addition to the preparation method of the copper colloidal catalyst solution or the electroless copper plating solution and the processing conditions of each step and Example 1 the same. In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：4，銅鹽：還原劑=1：1 Copper salt: colloidal stabilizer = 1:4, copper salt: reducing agent = 1:1

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

聚氧化亞烷基側鏈癸基醚：1g/L Polyoxyalkylene side chain decyl ether: 1g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

檸檬酸：0.8莫耳/L Citric acid: 0.8 mol / L

聚氧乙烯-辛基苯基醚(EO15莫耳)：8.0g/L Polyoxyethylene-octylphenyl ether (EO15 Mo): 8.0g/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L

向調整為pH4.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成銅膠體粒子，但發生凝集、沉澱。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 4.0, and stirred for 45 minutes. Copper colloidal particles are formed, but aggregation and precipitation occur.

(24)比較例6(實施例1的步驟中沒有吸附促進步驟的空白例)以上述實施例1為基礎，省略吸附促進步驟的例子，按照下列組成製備銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示。 (24) Comparative Example 6 (blank example in which there is no adsorption promoting step in the step of Example 1) Based on the above-described Example 1, the example of the adsorption promoting step was omitted, and a copper colloidal catalyst solution was prepared according to the following composition, The preparation method of the copper colloidal catalyst solution or the electroless copper plating solution and the treatment conditions of the respective steps are the same as in the first embodiment. In addition, the molar of each component of the said catalyst solution is shown below.

銅鹽：膠體穩定劑=1：4，銅鹽：還原劑=1：1 Copper salt: colloidal stabilizer = 1:4, copper salt: reducing agent = 1:1

(a)銅膠體催化劑溶液的製備 (a) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

檸檬酸：0.8莫耳/L Citric acid: 0.8 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

向調整為pH4.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成的銅膠體粒子的平均粒徑為約17nm。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 4.0, and stirred for 45 minutes. The resulting copper colloidal particles had an average particle diameter of about 17 nm.

(25)比較例7(催化劑溶液中添加明膠的情況) (25) Comparative Example 7 (in the case where gelatin was added to the catalyst solution)

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銅膠體催化劑溶液，除此之外，銅膠體催化劑溶液或化學鍍銅液的製備方法以及各步驟的處理條件與實施例1相同。應予說明，上述催化劑溶液的各成分的莫耳比如下所示： Based on the above Example 1, the liquid and copper colloidal catalyst solution containing the adsorption promoter were prepared according to the following composition, in addition to the preparation method of the copper colloidal catalyst solution or the electroless copper plating solution and the processing conditions of each step and Example 1 the same. Incidentally, the molars of the respective components of the above catalyst solution are as follows:

銅鹽：膠體穩定劑=1：4，銅鹽：還原劑=1：1 Copper salt: colloidal stabilizer = 1:4, copper salt: reducing agent = 1:1

(a)含有吸附促進劑的液體的製備 (a) Preparation of a liquid containing an adsorption promoter

[含有吸附促進劑的液體] [Liquid containing adsorption promoter]

二烯丙胺聚合物的季銨鹽：5g/L Quaternary ammonium salt of diallylamine polymer: 5g/L

(b)銅膠體催化劑溶液的製備 (b) Preparation of copper colloidal catalyst solution

[銅溶液] [copper solution]

硫酸銅(作為Cu2+)：0.2莫耳/L Copper sulfate (as Cu 2+ ): 0.2 m / L

檸檬酸：0.8莫耳/L Citric acid: 0.8 mol / L

明膠：1.0g/L Gelatin: 1.0g/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.2莫耳/L Sodium borohydride: 0.2 mol/L

向調整為pH4.0的25℃的銅溶液中滴入還原劑溶液，攪拌45分鐘。生成銅膠體粒子，但發生凝集、沉澱。 The reducing agent solution was dropped into a copper solution of 25 ° C adjusted to pH 4.0, and stirred for 45 minutes. Copper colloidal particles are formed, but aggregation and precipitation occur.

《催化劑溶液經時穩定性試驗例》 "Test method for stability of catalyst solution over time"

由此，對於上述實施例1~18和比較例1~7中製成的各銅膠體催化劑溶 液，按照下列標準評價膠體穩定性的優劣： Thus, the respective copper colloid catalysts prepared in the above Examples 1 to 18 and Comparative Examples 1 to 7 were dissolved. Liquid, evaluate the strength of colloidal stability according to 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.

《由化學鍍銅析出的銅被膜的外觀評價試驗例》 "Example of Evaluation of Appearance Evaluation of Copper Film Deposited by Electroless Copper Plating"

接著，對於由上述實施例1~18和比較例1~7的化學鍍銅方法所得的化學鍍銅被膜，按照下列標準目視評價被膜外觀的優劣： Next, with respect to the electroless copper plating film obtained by the electroless copper plating methods of the above Examples 1 to 18 and Comparative Examples 1 to 7, the appearance of the film was visually evaluated according to the following criteria:

◎：鍍銅被膜均勻無色斑。 ◎: The copper plating film is uniform and has no color spots.

○：鍍銅被膜出現色斑。 ○: A stain appeared on the copper plating film.

△：鍍銅被膜出現局部未析出(鍍膜裂縫)。 △: The copper plating film was partially precipitated (coating crack).

×：銅被膜未析出。 ×: The copper 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.

《關於銅膠體催化劑溶液的經時穩定性和被膜外觀的試驗結果》 "Test Results on Time Stability of Copper Colloidal Catalyst Solution and Appearance of Film"

Figure TWI613321BD00001
Figure TWI613321BD00001

Figure TWI613321BD00002
Figure TWI613321BD00002

《催化劑溶液的經時穩定性和鍍膜外觀的綜合評價》 "Comprehensive Evaluation of Time Stability of Catalyst Solution and Appearance of Coating"

在銅膠體催化劑溶液缺乏膠體穩定劑的比較例1中，催化劑溶液的經時穩定性惡劣，而且即使在與催化劑溶液接觸後對非導電性基板實施化學鍍膜也未析出銅被膜。 In Comparative Example 1 in which the copper colloidal catalyst solution lacked the colloidal stabilizer, the stability of the catalyst solution with time was poor, and the copper film was not deposited even after the electroless plating was applied to the non-conductive substrate after contact with the catalyst solution.

另外，對於膠體穩定劑與銅鹽之比，如果膠體穩定劑的相對量過少則如比較例2所示，仍然是催化劑溶液的經時穩定性惡劣，而且在化學鍍膜中也未析出銅被膜。這一點在膠體穩定劑的相對量過多的情況下也同樣，如比較例3所示，催化劑溶液的經時穩定性惡劣，在化學鍍膜中也未析出銅被膜。 Further, as for the ratio of the colloidal stabilizer to the copper salt, if the relative amount of the colloidal stabilizer is too small, as shown in Comparative Example 2, the stability of the catalyst solution over time is still poor, and no copper film is precipitated in the electroless plating film. This is also the case when the relative amount of the colloidal stabilizer is too large. As shown in Comparative Example 3, the stability of the catalyst solution with time is poor, and no copper film is deposited in the electroless plating film.

在不經吸附促進處理即對非導電性基板進行催化劑賦予，實施化學鍍銅的比較例6中，雖然催化劑溶液的經時穩定性與實施例相同，但析出的銅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，銅膠體粒子在基板上的吸附比實施例惡劣。 In Comparative Example 6 in which electroless copper plating was performed without performing the adsorption promoting treatment, and the electroless copper plating was carried out, the stability of the catalyst solution was the same as in the examples, but the precipitated copper film was partially precipitated. From the "coating crack" generated, it was judged that the adsorption promotion pretreatment was not performed before the catalyst was supplied, so that the catalyst activity was insufficient, and the adsorption of the copper colloidal particles on the substrate was inferior to that of the examples.

另一方面，在吸附促進預處理後，進行催化劑賦予處理，然後再實施化學鍍銅的實施例1~18中，催化劑溶液的經時穩定性均良好，由化 學鍍膜析出的銅被膜大致無色斑且均勻性優異。 On the other hand, in Examples 1 to 18 in which the catalyst-imparting treatment was carried out after the adsorption-promoted pretreatment, and then electroless copper plating was performed, the catalyst solution exhibited good stability over time. The copper film deposited by the plating film has substantially no color spots and is excellent in uniformity.

該實施例1~18與上述比較例1相比可知，為了獲得無色斑且均勻性優異的銅被膜，催化劑溶液中不但含有銅鹽和還原劑，還必須含有膠體穩定劑。另外，實施例1~18與比較例2~3相比，可以判斷出只含有膠體穩定劑並不足以獲得無色斑且均勻性優異的銅被膜，適當的膠體穩定劑與銅鹽的含量比也很重要。 In each of Examples 1 to 18, as compared with Comparative Example 1, it was found that in order to obtain a copper film having no color unevenness and excellent uniformity, the catalyst solution contained not only a copper salt and a reducing agent but also a colloidal stabilizer. Further, in Examples 1 to 18, compared with Comparative Examples 2 to 3, it was found that a copper film containing only a colloidal stabilizer and having no color unevenness and excellent uniformity, and a content ratio of a suitable colloidal stabilizer to copper salt It is also very important.

在催化劑溶液的表面活性劑的含量超過本發明1的抑制規定量的比較例4中，出現因化學鍍膜中析出的銅被膜局部未析出而產生的“鍍膜裂縫”。並且，在催化劑溶液的表面活性劑的含量大於比較例4的比較例5中，化學鍍膜中未析出銅被膜。與此相對，在將表面活性劑抑制在本發明1的規定量以下的極少量的實施例7中，化學鍍膜中未產生鍍膜裂縫等，順利地析出銅被膜(但被膜出現色斑)。 In Comparative Example 4 in which the content of the surfactant in the catalyst solution exceeded the predetermined amount of inhibition of the present invention 1, a "coating crack" which was caused by partial precipitation of the copper film deposited in the electroless plating film occurred. Further, in the comparative example 5 of the catalyst solution in which the content of the surfactant of the catalyst solution was larger, no copper film was deposited in the electroless plating film. On the other hand, in the example 7 in which the surfactant was suppressed to a predetermined amount or less of the predetermined amount of the present invention, no plating crack or the like was formed in the electroless plating film, and the copper film was smoothly deposited (however, the film was stained).

另外，在催化劑溶液不含表面活性劑的實施例1~4、實施例8~12和實施例18中，當然析出了無色斑且均勻性優異的銅被膜。也就是說，如果催化劑溶液中添加的表面活性劑超過了本發明的規定值，則銅膠體催化劑溶液的催化劑活性降低，化學鍍膜中所得的銅被膜產生鍍膜裂縫，進而若表面活性劑的含量過多，則銅膠體催化劑溶液的催化劑活性消失，不會析出銅被膜。因此，只有在將表面活性劑的含量抑制在極少量的情況下，銅被膜才會順利地析出，但是催化劑溶液的活性會隨著催化劑溶液中表面活性劑的含量的增加而降低，所以可以判斷出為了保持銅膠體催化劑溶液的催化劑活性，優選基板上不添加表面活性劑。 Further, in Examples 1 to 4, Examples 8 to 12, and Example 18 in which the catalyst solution contained no surfactant, a copper film having no color unevenness and excellent uniformity was naturally precipitated. That is, if the surfactant added to the catalyst solution exceeds the value specified in the present invention, the catalyst activity of the copper colloidal catalyst solution is lowered, and the copper film obtained in the electroless plating film is cracked, and if the surfactant is excessively contained. Then, the catalyst activity of the copper colloidal catalyst solution disappears, and the copper film is not precipitated. Therefore, the copper film can be smoothly precipitated only when the content of the surfactant is suppressed to a very small amount, but the activity of the catalyst solution decreases as the content of the surfactant in the catalyst solution increases, so it can be judged. In order to maintain the catalyst activity of the copper colloidal catalyst solution, it is preferred that no surfactant is added to the substrate.

另外，在催化液含有作為天然來源的水溶性聚合物的代表例的 明膠的比較例7中，催化劑溶液的經時穩定性惡劣，因此在進行化學鍍膜之際，所得的銅被膜出現局部未析出的“鍍膜裂縫”。另一方面，在催化劑溶液含有合成類水溶性聚合物的實施例5~6和實施例13~17中，析出了無色斑且均勻性優異的銅被膜，由此可以證明為了獲得優異的實用水準的銅被膜，即使在水溶性聚合物中也需要選擇合成類的聚合物。 In addition, the catalytic liquid contains a representative example of a water-soluble polymer as a natural source. In Comparative Example 7 of gelatin, the stability of the catalyst solution with time was poor. Therefore, when the electroless plating was performed, the obtained copper film showed a "coating crack" which was not precipitated locally. On the other hand, in Examples 5 to 6 and Examples 13 to 17 in which the catalyst solution contained the synthetic water-soluble polymer, a copper film having no color unevenness and excellent uniformity was precipitated, and it was confirmed that excellent practicality was obtained. A standard copper film requires the selection of a synthetic polymer even in a water-soluble polymer.

接著，對實施例1~18進行詳細討論。 Next, Examples 1 to 18 will be discussed in detail.

以實施例1為基準，對與其它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，使用將硫酸銅作為銅鹽、硼氫化鈉作為還原劑、檸檬酸作為膠體穩定劑的催化劑溶液進行催化劑賦予，然後實施化學鍍銅的例子，催化劑溶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，化學鍍膜中所得的銅被膜均勻性優異，未出現析出色斑。 The relative evaluation with the other examples will be described based on the first embodiment. First, Example 1 is a pretreatment of a non-conductive substrate using an adsorption promoter containing a quaternary ammonium salt of a cationic surfactant, that is, a diallylamine polymer, using copper sulfate as a copper salt and sodium borohydride as a reducing agent. The catalyst solution of citric acid as a colloidal stabilizer is subjected to catalyst application, and then an example of electroless copper plating is carried out. The stability of the catalyst solution over time is good, and no precipitation or decomposition occurs even after one month after the bath is established, and in the electroless plating film, The obtained copper film was excellent in uniformity, and excellent spots were not observed.

實施例2是與實施例1相比，膠體穩定劑相對於銅鹽的含量比下降的例子；實施例4是與實施例1相比，還原劑的含量減少的例子；實施例5是還原劑的含量增加的例子；實施例8是膠體穩定劑從實施例1的檸檬酸變為乙醇酸的例子。對實施例2、4、5、8中催化劑溶液的經時穩定性和鍍膜的外觀分別進行了實施例1同樣的評價。 Example 2 is an example in which the content ratio of the colloidal stabilizer to the copper salt is decreased as compared with Example 1. Example 4 is an example in which the content of the reducing agent is reduced as compared with Example 1, and Example 5 is a reducing agent. An example of an increase in the content; Example 8 is an example in which the colloidal stabilizer is changed from the citric acid of Example 1 to glycolic acid. The same evaluation of Example 1 was carried out for each of Examples 2, 4, 5 and 8 with respect to the temporal stability of the catalyst solution and the appearance of the coating film.

實施例9是相對於實施例1將還原劑從實施例1的硼氫化鈉變為二甲胺硼烷，並增加催化劑溶液溫度的例子，對催化劑溶液的經時穩定性和鍍膜的外觀進行了與實施例1同樣的評價。實施例10是將甲磺酸作為銅鹽的例子，實施例11是將氯化銅作為銅鹽的例子，對催化劑溶液的經時穩定 性和鍍膜的外觀進行了於實施例1同樣的評價。 Example 9 is an example in which the reducing agent was changed from sodium borohydride of Example 1 to dimethylamine borane with respect to Example 1, and the temperature of the catalyst solution was increased, and the stability of the catalyst solution and the appearance of the coating film were carried out. The same evaluation as in Example 1 was carried out. Example 10 is an example in which methanesulfonic acid is used as a copper salt, and Example 11 is an example in which copper chloride is used as a copper salt, and the catalyst solution is stabilized with time. The appearance and the appearance of the coating were evaluated in the same manner as in Example 1.

如上所述，在催化劑溶液不含表面活性劑的實施例1~4、實施例8~12和實施例18中，鍍膜均勻性優異，也未出現色斑。另外，在表面活性劑只存在本發明1的規定量以下的極少量的實施例7中，化學鍍膜中未產生鍍膜裂縫等，雖然順利析出銅被膜，但被膜出現析出色斑。 As described above, in Examples 1 to 4, Examples 8 to 12, and Example 18 in which the catalyst solution contained no surfactant, the coating film was excellent in uniformity and no color unevenness occurred. In addition, in the case where the surfactant was present in a very small amount of the predetermined amount or less of the predetermined amount of the first aspect of the invention, no crack or the like was formed in the electroless plating film, and the copper film was deposited smoothly, but the film was excellent in speckle.

在催化劑溶液中作為水溶性聚合物含有PVP(平均分子量4萬)的實施例5、同樣含有PEG的實施例6、含有PEI的實施例13、含有PVP(平均分子量30萬)的實施例9和14、含有PAM的實施例15中，對催化劑溶液的經時穩定性和鍍膜的外觀分別進行了與實施例1同樣的評價。 Example 5 containing PVP (average molecular weight of 40,000) as a water-soluble polymer in the catalyst solution, Example 6 containing PEG in the same manner, Example 13 containing PEI, and Example 9 containing PVP (average molecular weight: 300,000) and 14. In Example 15 containing PAM, the same evaluation as in Example 1 was carried out for the temporal stability of the catalyst solution and the appearance of the plating film.

相對於將催化劑溶液設定為pH4.0的實施例1，在pH3的實施例10、pH5的實施例11、pH9的實施例16、pH10的實施例17~18中，對催化劑溶液的經時穩定性和鍍膜的外觀分別進行了與實施例1同樣的評價。 With respect to Example 1 in which the catalyst solution was set to pH 4.0, in Example 10 at pH 3, Example 11 at pH 5, Example 16 at pH 9, and Examples 17 to 18 at pH 10, the catalyst solution was stabilized with time. The same evaluation as in Example 1 was carried out for each of the properties and the appearance of the coating.

Claims (8)

一種用於與實施化學鍍銅的非導電性基板接觸進行催化劑賦予的化學鍍銅用水系銅膠體催化劑溶液，其特徵在於，所述化學鍍銅用水系銅膠體催化劑溶液由以下成分所組成：(A)可溶性銅鹽、(B)還原劑、以及(C)選自一元羧酸類、羥基羧酸類、氨基羧酸類、多元羧酸類的膠體穩定劑的至少一種；所述成分(A)與(C)的含量莫耳比為A：C=1：0.03~1：35；且所述化學鍍銅用水系銅膠體催化劑溶液不含表面活性劑。 An aqueous copper-based copper colloidal catalyst solution for chemical copper plating in contact with a non-conductive substrate for performing electroless copper plating, characterized in that the electroless copper-based copper-based colloidal catalyst solution is composed of the following components: A) at least one of a soluble copper salt, (B) a reducing agent, and (C) a colloidal stabilizer selected from the group consisting of monocarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, and polycarboxylic acids; the components (A) and (C) The molar ratio of the molar ratio is A: C = 1: 0.03 to 1: 35; and the electroless copper plating copper colloidal catalyst solution does not contain a surfactant. 如請求項1所述之化學鍍銅用水系銅膠體催化劑溶液，其特徵在於，所述還原劑(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、亞磺酸類中的至少一種。 The electroless copper-based copper-based colloidal catalyst solution according to claim 1, 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 an ascorbic acid. At least one of an anthracene, a polyhydric phenol, a polyhydric naphthol, a phenolsulfonic acid, a naphtholsulfonic acid, and a sulfinic acid. 如請求項1所述之化學鍍銅用水系銅膠體催化劑溶液，其特徵在於，所述一元羧酸類(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 electroless copper-based copper colloidal catalyst solution according to claim 1, wherein the monocarboxylic acid (C) is selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, and octanoic acid. At least one of citric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and the like. 如請求項1所述之化學鍍銅用水系銅膠體催化劑溶液，其特徵在於，所述羥基羧酸類(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、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、以及其等之鹽中的至少一種。 The electroless copper-based copper colloidal catalyst solution according to claim 1, wherein the hydroxycarboxylic acid (C) is selected from the group consisting of citric acid, tartaric acid, malic acid, gluconic acid, glucoheptonic acid, and glycolic acid. At least one of lactic acid, trihydroxybutyric acid, ascorbic acid, isocitric acid, hydroxymalonic acid, glyceric acid, hydroxybutyric acid, leucine, citramalic acid, and the like. 如請求項1所述之化學鍍銅用水系銅膠體催化劑溶液，其特徵在於，所述氨基羧酸類(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、1,3-二氨基-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、谷氨酸、二羧甲 基谷氨酸、鳥氨酸、半胱氨酸、N,N-二(2-羥乙基)谷氨酸、(S,S)-乙二胺琥珀酸、以及其等之鹽中的至少一種。 The electroless copper-based copper colloidal catalyst solution according to claim 1, wherein the aminocarboxylic acid (C) is selected from the group consisting of hydroxyethylethylenediaminetriacetic acid and diethylenetriaminepentaacetic acid. Triethylenetetramine hexaacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, ammoniatriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, iminodipropionic acid, 1,3-propane Amine tetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol ether diamine tetraacetic acid, m-phenylenediaminetetraacetic acid, 1,2-cyclohexanediamine-N,N,N ' N ' -tetraacetic acid, diaminopropionic acid, glutamic acid, dicarboxymethylglutamate, ornithine, cysteine, N,N-bis(2-hydroxyethyl)glutamic acid, (S And S)-ethylenediamine succinic acid, and at least one of the salts thereof. 如請求項1所述之化學鍍銅用水系銅膠體催化劑溶液，其特徵在於，所述多元羧酸類(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 electroless copper-based copper colloidal catalyst solution according to claim 1, wherein the polycarboxylic acid (C) is selected from the group consisting of succinic acid, glutaric acid, malonic acid, adipic acid, and oxalic acid. At least one of maleic acid, citraconic acid, itaconic acid, mesaconic acid, and the like. 一種化學鍍銅方法，其特徵在於，所述化學鍍銅方法包括：(a)吸附促進步驟(預處理步驟)，將非導電性基板浸漬在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、以及兩性表面活性劑的吸附促進劑中的至少一種的液體中；(b)催化劑賦予步驟，將所述非導電性基板浸漬在如請求項1~6中任一項之水系銅膠體催化劑溶液中，使銅膠體粒子吸附在基板表面上；以及(c)化學鍍膜步驟，使用化學鍍銅液在經吸附處理的所述基板上形成銅被膜。 An electroless copper plating method, characterized in that: the electroless copper plating method comprises: (a) an adsorption promoting step (pretreatment step), immersing the non-conductive substrate in a surface containing a non-ionic surfactant, a cationic surface a liquid of at least one of an active agent, an anionic surfactant, and an adsorption promoter for an amphoteric surfactant; (b) a catalyst imparting step of immersing the non-conductive substrate in any of claims 1 to 6 In the aqueous copper colloidal catalyst solution, the copper colloid particles are adsorbed on the surface of the substrate; and (c) the electroless plating step, the copper film is formed on the adsorbed substrate by using an electroless copper plating solution. 如請求項7所述之化學鍍銅方法，其特徵在於，所述步驟(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 electroless copper plating method according to claim 7, wherein the adsorption promoter of the step (a) is a cationic surfactant and/or an amphoteric surfactant.
TW104103873A 2014-02-07 2015-02-05 Aqueous copper colloidal catalyst solution for electroless copper plating and electroless copper plating method TWI613321B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014022271A JP6145681B2 (en) 2014-02-07 2014-02-07 Aqueous copper colloid catalyst solution for electroless copper plating and electroless copper plating method
JP2014-022271 2014-02-07

Publications (2)

Publication Number Publication Date
TW201531591A TW201531591A (en) 2015-08-16
TWI613321B true TWI613321B (en) 2018-02-01

Family

ID=53777715

Family Applications (1)

Application Number Title Priority Date Filing Date
TW104103873A TWI613321B (en) 2014-02-07 2015-02-05 Aqueous copper colloidal catalyst solution for electroless copper plating and electroless copper plating method

Country Status (5)

Country Link
JP (1) JP6145681B2 (en)
KR (2) KR20150113111A (en)
CN (1) CN105121701B (en)
TW (1) TWI613321B (en)
WO (1) WO2015118907A1 (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6735981B2 (en) * 2016-04-08 2020-08-05 石原ケミカル株式会社 Electroless copper plating method and method of manufacturing printed wiring board using the method
CN107434240A (en) * 2016-05-25 2017-12-05 迈奇曼德（北京）科技有限责任公司 A kind of method for producing oxygen through suitable for portable oxygenerator
JP6343787B1 (en) * 2017-06-01 2018-06-20 石原ケミカル株式会社 Copper colloid catalyst solution for electroless copper plating and electroless copper plating method
CN109112585A (en) * 2017-06-22 2019-01-01 海门市源美美术图案设计有限公司 A kind of roller copper plating bath
CN107586989B (en) * 2017-08-15 2019-08-30 中南大学 A kind of copper base high temperature self lubricating composite material
US10294569B2 (en) * 2017-10-06 2019-05-21 Rohm And Haas Electronic Materials Llc Stable electroless copper plating compositions and methods for electroless plating copper on substrates
CN109536934A (en) * 2018-12-25 2019-03-29 杭州东方表面技术有限公司 A kind of metallize for nonmetallic surface adjusts the processing solution of process
TWI764121B (en) * 2019-04-04 2022-05-11 德商德國艾托特克公司 A method for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization
CN110042372B (en) * 2019-05-07 2021-06-29 广东东硕科技有限公司 Novel use of sulfonic aromatic compounds
CN110385443A (en) * 2019-07-28 2019-10-29 长春黄金研究院烟台贵金属材料研究所有限公司 A kind of preparation method of acid system Nanometer Copper colloidal sol
CN110670050B (en) * 2019-10-24 2021-11-12 深圳市松柏实业发展有限公司 Chemical copper plating activating solution and preparation method thereof
CN113684473B (en) * 2021-07-26 2023-04-25 广州三孚新材料科技股份有限公司 Electroless copper plating solution for plastics and preparation method thereof
CN113737159A (en) * 2021-08-30 2021-12-03 广东东硕科技有限公司 Pre-immersion liquid for inhibiting copper surface chemical plating and diffusion plating and preparation method and application thereof
CN114346254B (en) * 2022-01-21 2023-08-18 重庆科技学院 Method for preparing nanometer copper powder in eutectic ionic liquid
JP7214936B1 (en) 2022-02-22 2023-01-31 悦雄 野村 Antibacterial/antiviral composition and method for producing the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020069788A1 (en) * 2000-10-24 2002-06-13 Shipley Company, L.L.C. Plating catalysts and electronic packaging substrates plated therewith
US20050016416A1 (en) * 2003-07-23 2005-01-27 Jon Bengston Stabilizer for electroless copper plating solution
JP2011225929A (en) * 2010-04-19 2011-11-10 Kanto Gakuin Univ Surface Engineering Research Institute Catalyst solution used in electroless plating method, method for preparing the catalyst solution, electroless plating method using the catalyst solution, and plated product with metal layer including metallic film formed by using the electroless plating method

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6123762A (en) * 1984-07-09 1986-02-01 Nec Corp Copper colloidal catalytic solution for electroless plating and its manufacture
JP2001325831A (en) * 2000-05-12 2001-11-22 Bando Chem Ind Ltd Metal colloid solution, conductive ink, conductive coating and conductive coating forming base film
GB0025989D0 (en) * 2000-10-24 2000-12-13 Shipley Co Llc Plating catalysts
JP4493942B2 (en) * 2003-06-26 2010-06-30 旭化成イーマテリアルズ株式会社 Cuprous oxide colloidal dispersion
JP2006322729A (en) * 2005-05-17 2006-11-30 Sumitomo Metal Mining Co Ltd Analyzing method of quantitative form of fatty acid in inorganic colloid solution
US8591636B2 (en) * 2010-12-14 2013-11-26 Rohm And Haas Electronics Materials Llc Plating catalyst and method
TWI546409B (en) * 2011-11-14 2016-08-21 Ishihara Chemical Co Ltd Electroless copper plating solution and electroless copper plating method
JP6047713B2 (en) * 2012-05-11 2016-12-21 石原ケミカル株式会社 Electroless copper plating method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020069788A1 (en) * 2000-10-24 2002-06-13 Shipley Company, L.L.C. Plating catalysts and electronic packaging substrates plated therewith
US20050016416A1 (en) * 2003-07-23 2005-01-27 Jon Bengston Stabilizer for electroless copper plating solution
JP2011225929A (en) * 2010-04-19 2011-11-10 Kanto Gakuin Univ Surface Engineering Research Institute Catalyst solution used in electroless plating method, method for preparing the catalyst solution, electroless plating method using the catalyst solution, and plated product with metal layer including metallic film formed by using the electroless plating method

Also Published As

Publication number Publication date
KR101807696B1 (en) 2017-12-11
KR20150113111A (en) 2015-10-07
TW201531591A (en) 2015-08-16
WO2015118907A1 (en) 2015-08-13
JP2015147987A (en) 2015-08-20
JP6145681B2 (en) 2017-06-14
CN105121701A (en) 2015-12-02
KR20170059493A (en) 2017-05-30
CN105121701B (en) 2018-09-28

Similar Documents

Publication Publication Date Title
TWI613321B (en) Aqueous copper colloidal catalyst solution for electroless copper plating and electroless copper plating method
TWI621736B (en) Nickle colloidal catalyst solution for electroless nickle or nickle alloy plating and electroless nickle or nickle alloy plating method
TWI684673B (en) Copper colloidal catalyst solution for electroless copper plating and electroless copper plating method
TWI597384B (en) Electroless nickel or electroless nickel alloy pretreatment solution and plating method
KR102322950B1 (en) Copper colloidal catalyst solution for electroless copper plating, electroless copper plating method, and manufacturing method of copper plating substrate
TWI546409B (en) Electroless copper plating solution and electroless copper plating method
JP6843455B1 (en) Nickel colloid catalyst solution for electroless nickel or nickel alloy plating and electroless nickel or nickel alloy plating method
JP6858425B1 (en) Nickel colloid catalyst solution for electroless nickel or nickel alloy plating and electroless nickel or nickel alloy plating method
JP6735981B2 (en) Electroless copper plating method and method of manufacturing printed wiring board using the method
JP2023008598A (en) Electroless nickel or nickel alloy plating method