TWI684673B - Copper colloidal catalyst solution for electroless copper plating and electroless copper plating method - Google Patents

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

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TWI684673B
TWI684673B TW105103759A TW105103759A TWI684673B TW I684673 B TWI684673 B TW I684673B TW 105103759 A TW105103759 A TW 105103759A TW 105103759 A TW105103759 A TW 105103759A TW I684673 B TWI684673 B TW I684673B
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acid
copper
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colloidal
catalytic solution
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TW201631208A (en
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内田衛
田中薫
田中雄也
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日商石原化學股份有限公司
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    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—
    • B01J35/30—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • 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
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde

Abstract

The present invention provides a copper colloidal catalyst solution for electroless copper plating. After pretreatment for promoting absorption by immersing a non-conductive substrate into a liquid containing surfactant, the copper colloidal catalyst solution for electroless copper plating comprising (A) soluble copper salt, (B) reducing agent, (C) colloidal stabilizer and (D) specific carbohydrate such as glucose, maltose, xylitol and sorbitol, is used to apply the non-conductive substrate with catalyst and then the electroless copper plating is conducted so that the catalyst solution is stable over time. In addition, after pretreatment to enhance the catalyst activity, and catalyst application with catalyst solution and electroless plating, an excellent and uniform copper film can be obtained.

Description

化學鍍銅用之銅膠體催化溶液及化學鍍銅方法 Copper colloidal catalytic solution for electroless copper plating and electroless copper plating method

本發明涉及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銅膠體催化溶液、使用該催化溶液的化學鍍銅方法、以及採用該方法形成的銅被膜的非導電性基板，提供能夠顯著提高銅催化溶液的經時穩定性，賦予銅被膜優異外觀的技術方案。 The present invention relates to a copper colloidal catalytic solution applied as a catalyst for pretreatment when performing electroless copper plating on a non-conductive substrate, an electroless copper plating method using the catalytic solution, and a non-copper film formed by this method. The conductive substrate provides a technical solution that can significantly improve the stability of the copper catalytic solution over time and give the copper coating an excellent appearance.

為了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，通常採用的方法是：首先使鈀、銀、鉑等貴金屬吸附在基板上作為催化劑核，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。 For conductive substrates represented by copper or copper alloy substrates, or glass-epoxy resins, glass-polyimide resins, epoxy resins, polyimide resins, polycarbonate resins, ABS resins, A resin substrate such as PET resin is representative. Electroless copper plating is performed on non-conductive substrates such as glass substrates and ceramic substrates. The usual method is: first, noble metals such as palladium, silver, and platinum are adsorbed on the substrate as a catalyst core, and then With the use of the catalyst core, a copper film is deposited on the substrate using an electroless copper plating solution.

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 that uses low-cost copper, nickel, cobalt, and other specific metals without using a precious metal catalyst. The basic principle of this method is: in the catalytic solution of the specific metal, the soluble metal is treated with a reducing agent The salt generates colloidal particles of the metal and uses it as a catalyst core.

其中，銅膠體催化溶液的現有技術列舉如下：專利文獻1公開了在添加可溶性銅鹽、分散劑(明膠、非離子型表面活性劑)、絡合劑(二羧酸、羥基羧酸(oxycarboxylic acid)等)，利用還原劑(硼氫化鈉、二甲胺硼烷(dimethylamine borane)等)進行還原處理後，再添加穩定劑(次磷酸鈉、二 甲胺硼烷等)製成用於化學鍍銅的微細的銅催化溶液。 Among them, the prior art of copper colloidal catalytic solution is listed as follows: Patent Document 1 discloses the addition of soluble copper salt, dispersant (gelatin, nonionic surfactant), and complexing agent (dicarboxylic acid, oxycarboxylic acid) Etc.), after reducing treatment with a reducing agent (sodium borohydride, dimethylamine borane, etc.), the stabilizer (sodium hypophosphite, di Methylamine borane, etc.) is made into a fine copper catalytic solution for electroless copper plating.

專利文獻2公開了對被鍍物賦予由銅鹽(製備例2中為銅胺絡合物)、陰離子型表面活性劑和還原劑組成的化學鍍用催化劑，實施化學鍍銅後，再實施電鍍銅(請求項1~2、段落42)。 Patent Document 2 discloses that an electroless plating catalyst composed of a copper salt (copper amine complex in Preparation Example 2), an anionic surfactant, and a reducing agent is applied to an object to be plated, and after electroless copper plating, electroplating is performed. Copper (requests 1~2, paragraph 42).

專利文獻3公開了使用氧化銅(I)膠體催化劑溶液對基板進行催化劑賦予後，將基板浸漬於含有銅鹽、還原劑和絡合劑的溶液中，在基板上直接鍍銅。 Patent Document 3 discloses that after a catalyst is applied to a substrate using a copper (I) colloidal catalyst solution, the substrate is immersed in a solution containing a copper salt, a reducing agent, and a complexing agent, and copper is directly plated on the substrate.

專利文獻4公開了使用含有表面活性劑(陽離子型、兩性、非離子型等，段落56)的調節劑對被鍍物進行預處理，再使用含有一價銅鹽、次磷酸鹽和氯離子、或者進而含有還原劑(胺硼烷類、硼氫化合物類等)的催化劑溶液進行催化劑處理的化學鍍銅方法(請求項8~9、段落70)。 Patent Document 4 discloses that a regulator containing a surfactant (cationic, amphoteric, nonionic, etc., paragraph 56) is used to pretreat the object to be plated, and then a monovalent copper salt, hypophosphite and chloride ion are used. Or an electroless copper plating method in which a catalyst solution containing a reducing agent (amine boranes, boron hydrides, etc.) is subjected to catalyst treatment (request items 8 to 9, paragraph 70).

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，上述一價銅離子變得易於吸附(段落58)。 Patent Document 4 also describes that if a cationic surfactant is used in particular in the above-mentioned regulator, the hydrophilic group of the surfactant adsorbed on the object is negatively charged, and the above-mentioned monovalent copper ion becomes easily adsorbed (paragraph 58).

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)的活化劑的分散液對非導電性基板進行處理，接著，與含有銅鹽溶液、絡合劑和還原劑的導電體溶液接觸後，進行化學鍍和電鍍的方法(段落1、13、24、29、65、表1)。 Patent Document 5 describes the treatment of a non-conductive substrate using a dispersion liquid containing an activator of a noble metal/metal-colloid (for example, a palladium/tin colloid solution), followed by conduction with a copper salt solution, a complexing agent, and a reducing agent After the body solution is contacted, the methods of electroless plating and electroplating are carried out (paragraphs 1, 13, 24, 29, 65, Table 1).

上述水系催化溶液的基本原理是利用還原劑處理可溶性金屬鹽生成金屬微細粒子，但實際上包括上述專利文獻1~5的催化溶液在內，該原理的催化溶液通常大多在經時穩定性方面存在問題，不易長時間平穩地保持催化劑賦予和化學鍍操作的連續性。 The basic principle of the above-mentioned aqueous catalytic solution is to use a reducing agent to treat soluble metal salts to generate fine metal particles, but in fact, including the catalytic solutions of the above Patent Documents 1 to 5, the catalytic solutions of this principle usually exist in terms of stability over time. The problem is that it is not easy to maintain the continuity of catalyst giving and electroless plating operations smoothly for a long time.

如果經時穩定性降低，則即使進行催化劑賦予實施化學鍍銅，也會出現被膜的情況，或者存在局部未析出被膜的鍍膜缺損或鍍膜產生斑紋，亦或均勻性差等問題。 If the stability over time is reduced, even if the catalyst is applied and electroless copper plating is performed, the coating may occur, or there may be a problem that the coating film is not partially deposited, the coating film is streaked, or the uniformity is poor.

例如，使用建浴初期的催化溶液處理後進行化學鍍的銅被膜 時，建浴時的經時穩定性越低被膜外觀就越差，但還需要考慮建浴後數月單位的經時穩定性。也就是說，即便在使用建浴初期的催化溶液處理的被膜外觀良好的情況下，如果使用自建浴起經過數月後的催化溶液進行處理則被膜外觀產生上述鍍膜缺損或斑紋的情況也不少，因此催化溶液的經時穩定性很重要。 For example, a copper coating that is chemically plated after being treated with a catalytic solution at the beginning of the bath At this time, the lower the stability over time when the bath is built, the worse the appearance of the coating. However, it is also necessary to consider the stability over time in units of several months after the bath is built. In other words, even if the coating treated with the catalytic solution in the initial stage of the bath is in good appearance, the coating appearance or the above-mentioned coating defects or streaks may not occur if the catalytic solution is treated with the catalytic solution after a few months from the establishment of the bath. Less, so the stability of the catalytic solution over time is important.

因此，本申請人在日本特願2014-022271號(以下稱為先申請發明)中提出了通過向銅催化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，同時調整銅鹽和該穩定劑的混合比率，並且使表面活性劑的含量為零或將其含量抑制在極少量以下，從而改善催化溶液的經時穩定性的銅膠體催化溶液。 Therefore, the applicant proposed in Japanese Patent Application No. 2014-022271 (hereinafter referred to as the first application invention) to add colloidal stabilizers such as hydroxycarboxylic acids and aminocarboxylic acids that stabilize copper salts to a copper catalytic solution, while adjusting A copper colloidal catalytic solution in which the mixing ratio of the copper salt and the stabilizer is zero or the content of the surfactant is suppressed to a very small amount or less, thereby improving the temporal stability of the catalytic solution.

若考慮到化學鍍所得銅被膜外觀的提高或處理成本的降低，則期望進一步改善催化溶液的經時穩定性。 Considering the improvement of the appearance of the copper film obtained by electroless plating or the reduction of the processing cost, it is desired to further improve the stability of the catalytic solution over time.

因此，著眼於向催化溶液中添加糖類是否會對催化溶液的經時穩定性造成影響，並且抽取包含在催化劑賦予後進行化學鍍銅時使用糖類的技術內容的專利文獻，則如下所示。 Therefore, focusing on whether the addition of saccharides to the catalytic solution will affect the stability of the catalytic solution over time, and extracting patent documents containing the technical content of using saccharides when performing electroless copper plating after the catalyst is given are as follows.

(1)專利文獻6 (1) Patent Literature 6

在非導電性基板上將金屬鹽還原進行催化劑賦予處理，再進行化學鍍銅處理的方法(請求項1、段落1)，進行上述催化劑賦予的組合物包含葡萄糖(glucose)、半乳糖、麥芽糖(maltose)、果糖(fructose)、木糖(xylose)等還原糖(請求項1、10、段落1、24)。另外，上述組合物中還可含有檸檬酸、酒石酸、蘋果酸等緩衝劑(段落19)。 A method of reducing a metal salt on a non-conductive substrate, performing a catalyst application process, and then performing an electroless copper plating process (request item 1, paragraph 1). The composition for applying the catalyst application includes glucose, galactose, and maltose ( reducing sugars such as maltose, fructose, and xylose (request items 1, 10, paragraphs 1, 24). In addition, the above composition may further contain buffering agents such as citric acid, tartaric acid, and malic acid (paragraph 19).

類似的現有文獻包括日本特開2012-127002號公報(Rohm & Haas)。 Similar existing documents include Japanese Patent Laid-Open No. 2012-127002 (Rohm & Haas).

(2)專利文獻7 (2) Patent Literature 7

在非導電性基板上將金屬鹽(銅鹽等)還原進行催化劑賦予處理，然後進行化學鍍銅處理的方法(請求項1、3、段落29、表1)，上述還 原劑可列舉出葡萄糖(段落25)。另外，通過將酒石酸、檸檬酸、琥珀酸等羧酸、蔗糖、果糖等糖類溶解於催化劑溶液中，可以提高催化劑金屬對基材表面的附著量(段落31)。 A method of reducing a metal salt (copper salt, etc.) on a non-conductive substrate to provide a catalyst-imparting treatment, and then performing an electroless copper plating treatment (requests 1, 3, paragraph 29, table 1). The original agent may include glucose (paragraph 25). In addition, by dissolving carboxylic acids such as tartaric acid, citric acid, and succinic acid, sugars such as sucrose, fructose, and the like in the catalyst solution, the amount of adhesion of the catalyst metal to the substrate surface can be increased (paragraph 31).

(3)專利文獻8 (3) Patent Literature 8

使用銀膠體催化溶液(預處理液)而非銅催化溶液進行催化劑賦予處理，然後進行化學鍍銅的方法(請求項1、35)。 A method of performing a catalyst-imparting treatment using a silver colloidal catalytic solution (pretreatment liquid) instead of a copper catalytic solution, and then performing electroless copper plating (request items 1, 35).

上述催化溶液中，除了添加檸檬酸、酒石酸、乳酸、蘋果酸等羥基羧酸以外(請求項1、3)，還可以添加纖維素及其衍生物、單糖類、多糖類及其衍生物等公知的膠體分散劑(段落46)。 In addition to hydroxycarboxylic acids such as citric acid, tartaric acid, lactic acid, and malic acid (claims 1 and 3), it is also possible to add cellulose and its derivatives, monosaccharides, polysaccharides and their derivatives to the catalytic solution Colloidal dispersant (paragraph 46).

單糖類、多糖類及其衍生物為蔗糖、甘露醇、山梨醇、甘油、糊精等(段落50)。 Monosaccharides, polysaccharides and their derivatives are sucrose, mannitol, sorbitol, glycerin, dextrin, etc. (paragraph 50).

(4)專利文獻9 (4) Patent Literature 9

對樹脂成形體製成的非導電性基板進行蝕刻處理，使其接觸含有貴金屬化合物(金、銀等)和亞錫鹽的膠體溶液，然後接觸鈀化合物的水溶液進行催化劑賦予處理，再進行化學鍍銅處理的方法(請求項1~2)。 A non-conductive substrate made of a resin molded body is etched to contact a colloidal solution containing a precious metal compound (gold, silver, etc.) and a stannous salt, and then contacted with an aqueous solution of a palladium compound for catalyst addition treatment, and then electroless plating Copper processing method (request items 1~2).

葡萄糖、山梨醇(sorbit)、纖維素、蔗糖、甘露醇(mannite)、葡萄糖酸內酯等具有還原性的糖類可以添加在化學鍍銅液中而非上述催化溶液中(段落73)。 Reducing sugars such as glucose, sorbit, cellulose, sucrose, mannite, and gluconolactone may be added to the electroless copper plating solution instead of the above-mentioned catalytic solution (paragraph 73).

(5)專利文獻10 (5) Patent Literature 10

在樹脂、陶瓷、玻璃等非導電性基板上進行蝕刻處理，使錫鹽(氯化亞錫等)附著進行感應化處理，浸漬於硝酸銀溶液中在錫上置換出銀形成錫-銀複合物，再浸漬於還原性溶液中進行活化，然後進行化學鍍銅的方法(請求項1~6、段落10、22)，上述還原性溶液中可以使用葡萄糖。 Etching is performed on non-conductive substrates such as resin, ceramics, glass, etc., and tin salts (stannous chloride, etc.) are attached for induction treatment, and immersed in a silver nitrate solution to replace silver on tin to form a tin-silver composite, A method of immersing in a reducing solution for activation and then performing electroless copper plating (requests 1 to 6, paragraphs 10 and 22). Glucose can be used in the reducing solution.

現有技術文獻： Existing technical literature:

[專利文獻] [Patent Literature]

專利文獻1：日本特開H02-093076號公報、 專利文獻2：日本特開H10-229280號公報、 專利文獻3：日本特開H07-197266號公報、 專利文獻4：日本特開2011-225929號公報、 專利文獻5：日本特開2013-522476號公報、 專利文獻6：日本特開2012-130910號公報、 專利文獻7：日本特開2003-313670號公報、 專利文獻8：日本特開2004-190042號公報、 專利文獻9：日本特開2006-299366號公報、 專利文獻10：日本特開2005-146330號公報。 Patent Document 1: Japanese Patent Laid-Open No. H02-093076, Patent Document 2: Japanese Patent Laid-Open No. H10-229280, Patent Document 3: Japanese Patent Laid-Open No. H07-197266, Patent Document 4: Japanese Patent Laid-Open No. 2011-225929, Patent Document 5: Japanese Patent Laid-Open No. 2013-522476, Patent Document 6: Japanese Patent Laid-Open No. 2012-130910, Patent Document 7: Japanese Patent Laid-Open No. 2003-313670, Patent Document 8: Japanese Patent Laid-Open No. 2004-190042, Patent Document 9: Japanese Patent Laid-Open No. 2006-299366, Patent Document 10: Japanese Patent Laid-Open No. 2005-146330.

上述專利文獻6~10中，作為預處理劑的催化溶液使用葡萄糖、果糖、麥芽糖、纖維素等糖類、或者甘露醇、山梨醇等糖醇。 In the above Patent Documents 6 to 10, sugars such as glucose, fructose, maltose, and cellulose, or sugar alcohols such as mannitol and sorbitol are used as the catalytic solution of the pretreatment agent.

但是，專利文獻9中，糖類、糖醇用於化學鍍銅液而非催化溶液。 However, in Patent Document 9, sugars and sugar alcohols are used for the electroless copper plating solution instead of the catalytic solution.

本發明所要解決的技術問題在於，在上述先申請發明的基礎上對其特徵性成分組成進行擴展，進一步提高銅膠體催化溶液的經時穩定性。 The technical problem to be solved by the present invention is to expand its characteristic composition on the basis of the above-mentioned first application invention and further improve the stability of the copper colloidal catalytic solution over time.

本發明人以上述專利文獻6~10為出發點，對添加有包含糖類、糖醇的碳水化合物(carbohydrate)的銅膠體催化溶液與其經時穩定性的關係進行了深入研究，結果發現若選擇特定碳水化合物添加到銅膠體催化溶液中，則與沒有碳水化合物的情況相比能夠有效地提高催化溶液的經時穩定性，另外還發現即使添加特定碳水化合物以外的碳水化合物上述經時穩定性也不會提高或者反而會降低，從而完成了本發明。 Based on the above Patent Documents 6 to 10, the inventors conducted an in-depth study on the relationship between the copper colloidal catalytic solution added with carbohydrates containing sugars and sugar alcohols and their stability over time, and found that if a specific carbohydrate is selected When the compound is added to the copper colloidal catalytic solution, it can effectively improve the temporal stability of the catalytic solution compared to the case without carbohydrates. In addition, it is also found that the above-mentioned temporal stability will not be affected even if a carbohydrate other than a specific carbohydrate is added. Increasing or conversely decreasing will complete the present invention.

即，本發明1是一種化學鍍銅用銅膠體催化溶液，其是用於 與實施化學鍍銅的非導電性基板接觸進行催化劑賦予的銅膠體催化溶液，含有：(A)可溶性銅鹽；(B)還原劑；(C)選自一元羧酸類、羥基羧酸類、氨基羧酸類、以及多元羧酸類中的膠體穩定劑的至少一種；以及(D)选自葡萄糖、果糖、乳糖、麥芽酚、異麥芽酮糖(isomaltulose)、木糖、山梨醇、木糖醇、甘露醇、麥芽糖醇、赤蘚糖醇、還原澱粉糖漿(reduced starch syrup)、乳糖醇、還原派拉丁糖、以及葡萄糖酸內酯中的碳水化合物的至少一種。 That is, the present invention 1 is a copper colloidal catalytic solution for electroless copper plating, which is used for A copper colloidal catalytic solution provided by a catalyst in contact with a non-conductive substrate subjected to electroless copper plating, containing: (A) soluble copper salt; (B) reducing agent; (C) selected from monocarboxylic acids, hydroxycarboxylic acids, and aminocarboxylic acids At least one of colloidal stabilizers in acids and polycarboxylic acids; and (D) selected from glucose, fructose, lactose, maltol, isomaltulose, xylose, sorbitol, xylitol, At least one of carbohydrates in mannitol, maltitol, erythritol, reduced starch syrup, lactitol, reduced palatinose, and gluconolactone.

本發明2是，在上述本發明1中，可溶性鹽(A)與膠體穩定劑(C)的含量莫耳比為A：C=1：0.03~1：35的化學鍍銅用銅膠體催化溶液。 The present invention 2 is, in the above-mentioned present invention 1, the content ratio of the soluble salt (A) and the colloid stabilizer (C) is a molar ratio A: C=1:0.03~1:35 copper colloidal catalytic solution for electroless copper plating .

本發明3是，在上述本發明1或2中，進一步含有選自聚乙二醇、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合成類水溶性聚合物的至少一種的化學鍍銅用銅膠體催化溶液。 The present invention 3 is the above-mentioned present invention 1 or 2 further containing a synthetic water-soluble material selected from polyethylene glycol, polypropylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polypropylene amide, and polyethyleneimine Copper colloidal catalytic solution for electroless copper plating of at least one of the polymers.

本發明4是，在上述本發明1~3的任一項中，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、以及亞磺酸類中的至少一種的化學鍍銅用銅膠體催化溶液。 The present invention 4 is that in any of the above-mentioned present inventions 1 to 3, the reducing agent (B) is selected from the group consisting of boron hydride compounds, amine boranes, hypophosphorous acids, aldehydes, ascorbic acids, hydrazines, and polyphenols Copper colloidal catalytic solution for electroless copper plating of at least one of the types, multi-component naphthols, phenolsulfonic acids, naphtholsulfonic acids, and sulfinic acids.

本發明5是，在上述本發明1~4的任一項中，膠體穩定劑(C)中的一元羧酸類為選自甲酸、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；羥基羧酸類為選自檸檬酸、酒石酸、蘋果酸、葡萄糖酸、葡庚糖酸、乙醇酸、乳酸、三羥基丁酸(trioxybutyric 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、以及其等之鹽中的至少一種；氨基羧酸類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、以及其等之鹽中的至少一種；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的化學鍍銅用銅膠體催化溶液。 The invention 5 is that in any one of the inventions 1 to 4 above, the monocarboxylic acids in the colloidal stabilizer (C) are selected from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, caprylic acid, At least one of capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and salts thereof; hydroxycarboxylic acids are selected from citric acid, tartaric acid, malic acid, gluconic acid, glucoheptonic acid, and ethanol At least one of acid, lactic acid, trioxybutyric acid, ascorbic acid, isocitric acid, hydroxymalonic acid, glyceric acid, hydroxybutyric acid, leucine, citracallic acid, and salts thereof; amino The carboxylic acids are selected from hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, ammoniatriacetic acid, imino Diacetic acid, hydroxyethyliminodiacetic acid, iminodipropionic acid, 1,3-propanediamine tetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid ( 1,3-diamino-2-hydroxypropane tetraacetic acid), glycol ether diamine tetraacetic acid, m-benzene Diamine tetraacetic acid, 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid, diaminopropionic acid, glutamic acid, dicarboxy methyl glutamate, bird At least one of amino acid, cysteine, N,N-bis(2-hydroxyethyl) glutamic acid, (S,S)-ethylenediamine succinic acid, and their salts; polycarboxylic acids ( C) is at least one salt 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 Copper colloidal catalytic solution for electroless copper plating.

本發明6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吸附促進劑的液體中，該吸附促進劑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中的至少一種；(b)催化劑賦予步驟，將非導電性基板浸漬在上述本發明1~5中任一項的銅膠體催化溶液中，使銅膠體粒子吸附在基板表面上；以及(c)化學鍍步驟，使用化學鍍銅液在經吸附處理的上述基板上形成銅被膜。 The present invention 6 is an electroless copper plating method, which includes: (a) an adsorption promotion step (pretreatment step), immersing a non-conductive substrate in a liquid containing an adsorption promoter selected from a non-ionic surface At least one of an active agent, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant; (b) a catalyst-imparting step, a non-conductive substrate is immersed in any of the above 1 to 5 of the present invention In the copper colloidal catalytic solution, the copper colloidal particles are adsorbed on the surface of the substrate; and (c) an electroless plating step, using an electroless copper plating solution to form a copper coating on the substrate subjected to the adsorption treatment.

本發明7是，在上述本發明6中，步驟(a)的吸附促進劑為陽離子型表面活性劑和/或兩性表面活性劑的化學鍍銅方法。 The present invention 7 is an electroless copper plating method in which the adsorption accelerator in step (a) is a cationic surfactant and/or amphoteric surfactant in the above-mentioned present invention 6.

本發明8是，採用上述本發明6或7的化學鍍銅方法形成銅被膜的非導電性基板。 The present invention 8 is a non-conductive substrate in which a copper coating is formed by the above-mentioned electroless copper plating method of the present invention 6 or 7.

上述先申請發明中，提出了將非導電性基板浸漬在含有銅鹽、還原劑和膠體穩定劑的銅催化溶液中，從而利用其催化劑活性在下一步化學鍍銅步驟中析出外觀良好的銅被膜。 In the above-mentioned first application invention, it is proposed to immerse the non-conductive substrate in a copper catalytic solution containing a copper salt, a reducing agent, and a colloidal stabilizer, so as to use its catalytic activity to precipitate a copper film with a good appearance in the next step of electroless copper plating.

本發明中，通過在該先申請發明的銅催化溶液的必須成分中進一步增加特定碳水化合物，能夠顯著提高催化溶液的經時穩定性，通過化學鍍得到外觀優異的銅被膜。 In the present invention, by further adding specific carbohydrates to the essential components of the copper catalytic solution of the first application of the invention, the temporal stability of the catalytic solution can be significantly improved, and a copper coating excellent in appearance can be obtained by electroless plating.

尤其是即使從建浴起經過數月膠體催化溶液也很穩定，因此能夠得到外觀優異的被膜，並且能夠減輕催化溶液的維護，提高化學鍍銅 的生產率。 In particular, the colloidal catalytic solution is stable even after a few months from the establishment of the bath. Therefore, a coating with excellent appearance can be obtained, the maintenance of the catalytic solution can be reduced, and the electroless copper plating can be improved. Productivity.

作為化學鍍銅的預處理，以往有使用錫-鈀等進行的催化劑賦予，而在本發明中不使用貴金屬，因此可以降低基板製造的成本，也無需將對基板賦予的鈀除去。 As a pretreatment for electroless copper plating, there has conventionally been catalyst provision using tin-palladium or the like, but no precious metals are used in the present invention, so the cost of manufacturing a substrate can be reduced without removing palladium applied to the substrate.

另外，如果在對非導電性基板進行催化劑賦予之前利用表面活性劑進行吸附促進處理，則能夠改善銅膠體催化劑的效果。尤其是如果用陽離子型活性劑進行處理，則銅膠體催化劑的效果顯著提高。 In addition, if the adsorption promoting treatment is performed with a surfactant before the catalyst is applied to the non-conductive substrate, the effect of the copper colloidal catalyst can be improved. Especially if treated with a cationic active agent, the effect of the copper colloidal catalyst is significantly improved.

本發明的第一方面是化學鍍銅用銅膠體催化溶液，其是用於與非導電性基板接觸進行催化劑賦予的銅膠體催化溶液，含有(A)可溶性銅鹽、(B)還原劑和(C)膠體穩定劑，並且還含有(D)特定碳水化合物；第二方面是使用上述第一方面的催化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，接著，使用上述催化溶液進行催化劑賦予後進行化學鍍銅；第三方面是採用第二方面的化學鍍銅方法形成銅被膜的非導電性基板。 The first aspect of the present invention is a copper colloidal catalytic solution for electroless copper plating, which is a copper colloidal catalytic solution for contacting with a non-conductive substrate to give a catalyst, and contains (A) a soluble copper salt, (B) a reducing agent and ( C) A colloidal stabilizer, and also containing (D) a specific carbohydrate; the second aspect is an electroless copper plating method using the catalytic solution of the first aspect above, which is performed on a non-conductive substrate with a liquid containing a surfactant in advance After the adsorption promotion treatment, the catalyst solution is applied using the above-mentioned catalytic solution and then electroless copper plating is performed. The third aspect is a non-conductive substrate in which a copper film is formed by the electroless copper plating method of the second aspect.

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樹脂等樹脂基板代表，包括玻璃基板、陶瓷基板等。 The above-mentioned non-conductive substrate refers to resin substrates such as glass-epoxy resin, glass-polyimide resin, epoxy resin, polyimide resin, polycarbonate resin, ABS resin, PET resin, etc., including glass Substrates, ceramic substrates, etc.

上述本發明1的銅膠體催化溶液的必須成分為(A)可溶性銅鹽、(B)還原劑、(C)膠體穩定劑以及(D)特定碳水化合物。 The essential components of the above copper colloidal catalytic solution of the present invention 1 are (A) soluble copper salt, (B) reducing agent, (C) colloidal stabilizer, and (D) specific carbohydrate.

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；或者乙酸銅、乙二酸銅和檸檬酸銅等羧酸銅鹽；亦或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。 Any soluble salt can be used as long as the above-mentioned soluble salt (A) is a soluble salt that generates monovalent or divalent copper ions in an aqueous solution, and a hardly soluble salt is not excluded. Specifically, copper sulfate, copper oxide, copper chloride, copper pyrophosphate, copper carbonate; or copper acetate, copper oxalate, copper citrate and other carboxylic acid copper salts; or copper methanesulfonate and hydroxyl group Copper ethanesulfonate Copper salts of organic sulfonic acids and the like are preferably copper sulfate, copper citrate, and 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 borohydride compounds, amine boranes, hypophosphorous acids, aldehydes, ascorbic acids, hydrazines, polyphenols, polynaphthols, phenolsulfonic acids, and naphtholsulfonic acids. , Sulfinic acid, etc. Aldehydes are formaldehyde, glyoxylic acid or its salts, and polyphenols are catechol, hydroquinone, resorcinol, pyrogallol, resorcinol, gallic acid, etc. The acids are phenolsulfonic acid, cresolsulfonic acid or their salts, and the like.

上述膠體穩定劑(C)為在鍍浴中形成銅絡合物的化合物，起到保證催化溶液的經時穩定性的功能。 The colloidal stabilizer (C) is a compound that forms a copper complex in the plating bath and functions to ensure the stability of the catalytic 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 monocarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, and polycarboxylic acids.

作為上述一元羧酸類，可列舉出甲酸、乙酸、丙酸、丁酸、戊酸、己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸以及其等之鹽等。 Examples of the monocarboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and salts thereof.

作為上述羥基羧酸類，可列舉出檸檬酸、酒石酸、蘋果酸、葡萄糖酸、葡庚糖酸、乙醇酸、乳酸、三羥基丁酸、抗壞血酸、異檸檬酸、羥基丙二酸、甘油酸、羥基丁酸、亮氨酸、檸蘋酸、以及其等之鹽等。 Examples of the aforementioned hydroxycarboxylic acids include citric acid, tartaric acid, malic acid, gluconic acid, glucoheptonic acid, glycolic acid, lactic acid, trihydroxybutyric acid, ascorbic acid, isocitric acid, hydroxymalonic acid, glyceric acid, and hydroxy Butyric acid, leucine, citracallic acid, and their salts, etc.

作為上述氨基羧酸類，可列舉出乙二胺四乙酸(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。 Examples of the aminocarboxylic acids include ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), and triethylenetetraminehexaacetic acid ( TTHA), ethylenediaminetetrapropionic acid, aminotriacetic acid (NTA), iminodiacetic acid (IDA), iminodipropionic acid (IDP), hydroxyethyliminodiacetic acid, 1,3-propanediamine Acetic 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, dicarboxymethyl glutamic acid, ornithine, cysteine, N,N-bis(2-hydroxyethyl) glutamic acid, (S,S )-Ethylenediamine succinic acid and its salts.

作為上述多元羧酸類，可列舉出琥珀酸、戊二酸、丙二酸、己二酸、乙二酸、馬來酸、檸康酸、衣康酸、中康酸、以及其等之鹽等。 Examples of the above polycarboxylic acids include succinic acid, glutaric acid, malonic acid, adipic acid, oxalic acid, maleic acid, citraconic acid, itaconic acid, mesaconic acid, and salts thereof, etc. .

本發明的膠體催化溶液具有選擇添加特定碳水化合物(D)的 特徵。 The colloidal catalytic solution of the present invention has the option of adding specific carbohydrates (D) feature.

上述碳水化合物(D)主要是為了提高膠體催化溶液的經時穩定性而添加的，選自葡萄糖(glucose)、果糖(fructose)、乳糖(lactose)、麥芽糖(maltose)、異麥芽酮糖(派拉丁糖)、木糖、山梨醇、木糖醇、甘露醇、麥芽糖醇、赤蘚糖醇、還原澱粉糖漿、乳糖醇、還原異麥芽酮糖、葡萄糖酸內酯。 The above carbohydrates (D) are mainly added to improve the stability of the colloidal catalytic solution over time, and are selected from glucose, fructose, lactose, maltose, and isomaltulose ( Palatinose), xylose, sorbitol, xylitol, mannitol, maltitol, erythritol, reduced starch syrup, lactitol, reduced isomaltulose, gluconolactone.

上述葡萄糖、果糖、木糖等屬於單糖類，葡萄糖酸內酯屬於單糖類的衍生物，乳糖、麥芽糖等屬於二糖類，山梨醇、木糖醇、甘露醇等屬於糖醇，而本發明的碳水化合物的概念包括上述糖類及其衍生物、糖醇。 The above glucose, fructose, xylose, etc. are monosaccharides, gluconolactone is a derivative of monosaccharides, lactose, maltose, etc. are disaccharides, sorbitol, xylitol, mannitol, etc. are sugar alcohols, and the carbohydrate of the present invention The concept of compounds includes the aforementioned sugars and their derivatives, sugar alcohols.

上述還原澱粉糖漿是指葡萄糖、麥芽糖等特定的上述糖類的醛基被還原成羥基的澱粉糖漿。另外，作為上述碳水化合物(D)，葡萄糖、果糖、木糖等特定的單糖類由3個以上糖苷鍵聚合而成的低聚物也同樣有效。 The reduced starch syrup refers to a starch syrup in which the aldehyde groups of specific sugars such as glucose and maltose are reduced to hydroxyl groups. In addition, as the above-mentioned carbohydrate (D), oligomers in which specific monosaccharides such as glucose, fructose, and xylose are polymerized with three or more glycosidic bonds are also effective.

另一方面，上述碳水化合物從特定成分中選擇，因此排除澱粉、糊精等。 On the other hand, the above carbohydrates are selected from specific ingredients, so starch, dextrin, etc. are excluded.

優選的碳水化合物可列舉出葡萄糖、果糖、乳糖、麥芽糖、山梨醇、木糖醇、甘露醇、葡萄糖酸內酯，大致優選糖醇。 Preferred carbohydrates include glucose, fructose, lactose, maltose, sorbitol, xylitol, mannitol, and gluconolactone, and sugar alcohols are generally preferred.

本發明的銅膠體催化溶液為水系，因此液體溶劑限定為水和/或親水性醇，排除有機溶劑(包括親油性醇)單獨使用。 The copper colloidal catalytic solution of the present invention is an aqueous system, so the liquid solvent is limited to water and/or hydrophilic alcohols, excluding organic solvents (including lipophilic alcohols) to be used alone.

另外，關於該催化溶液，由於在中性附近催化劑活性容易降低，因此優選催化溶液的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，如果pH值調整為pH2~5和8~11則銅膠體粒子易於穩定化。 In addition, regarding this catalytic solution, since the catalyst activity tends to decrease near neutrality, it is preferable that the pH value of the catalytic solution is on the acidic side or the basic side other than the neutral region, specifically pH 1 to 6 and 8 to 12 are more suitable It is preferably pH 2 to 5 and 8 to 11. If the pH value is adjusted to pH 2 to 5 and 8 to 11, the copper colloidal particles are easily stabilized.

銅膠體催化溶液中，上述可溶性銅鹽(A)可以單獨使用或並用，其含量為0.005~3莫耳/L，優選為0.05~2莫耳/L，更優選為0.04~1.2莫耳 /L。 In the copper colloidal catalytic solution, the above-mentioned soluble copper salt (A) can be used alone or in combination, and its content is 0.005 to 3 mol/L, preferably 0.05 to 2 mol/L, and more preferably 0.04 to 1.2 mol /L.

上述還原劑(B)可以單獨使用或並用，其含量為0.005~4莫耳/L，優選為0.02~3莫耳/L，更優選為0.03~2.2莫耳/L。還原劑的含量若小於適當量則銅鹽的還原作用降低，反之若過多則化學鍍所析出的銅被膜的均質性可能會降低。 The reducing agent (B) can be used alone or in combination, and its content is 0.005 to 4 mol/L, preferably 0.02 to 3 mol/L, and more preferably 0.03 to 2.2 mol/L. If the content of the reducing agent is less than the appropriate amount, the reduction effect of the copper salt is reduced, whereas if it is too much, the homogeneity of the copper film deposited by electroless plating may be reduced.

上述膠體穩定劑(C)可以單獨使用或並用，其含量為0.005~4莫耳/L，優選為0.01~2莫耳/L，更優選為0.05~1.6莫耳/L。 The colloidal stabilizer (C) can be used alone or in combination, and its content is 0.005 to 4 mol/L, preferably 0.01 to 2 mol/L, and more preferably 0.05 to 1.6 mol/L.

上述碳水化合物(D)可以單獨使用或並用，其含量為0.001~4莫耳/L，優選為0.01~3莫耳/L，更優選為0.05~2.2莫耳/L。 The above carbohydrates (D) can be used alone or in combination, and the content thereof is 0.001 to 4 mol/L, preferably 0.01 to 3 mol/L, and more preferably 0.05 to 2.2 mol/L.

在銅膠體催化溶液中，上述(A)與(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，則催化溶液的經時穩定性降低，進而也成為化學鍍所得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，則會損害催化溶液的經時穩定性，使所得銅被膜的品質下降(參照後述試驗例)。 In the copper colloidal catalytic solution, the molar ratio of the above (A) to (C) is A:C=1:0.03~1:35, preferably A:C=1:0.5~1:24. If the relative content of the colloidal stabilizer (C) is too small, the temporal stability of the catalytic solution is reduced, and it also becomes the main cause of precipitation defects of the copper coating obtained by electroless plating. Conversely, if the content of the colloidal stabilizer (C) is too large, the temporal stability of the catalytic solution will be impaired, and the quality of the resulting copper coating will be degraded (refer to the test examples described later).

在銅膠體催化溶液中，上述(A)與(B)的含量莫耳比為A：B=1：0.01~1：6，優選為A：B=1：0.05~1：4，更優選為A：B=1：0.07~1：2。 In the copper colloidal catalytic solution, the molar ratio of the above (A) to (B) is A:B=1:0.01~1:6, preferably A:B=1:0.05~1:4, more preferably A: B=1:0.07~1:2.

在銅膠體催化溶液中，上述(A)與(D)的含量莫耳比為A：D=1：0.01~1：40，優選為A：D=1：0.1~1：25，更優選為A：D=1：1~1：15。如果碳水化合物(D)的相對含量過多，則反而會使膠體催化溶液過度穩定化而喪失催化劑活性，有可能對非導電性基板的催化劑核賦予，進而對外觀良好的被膜形成造成障礙。 In the copper colloidal catalytic solution, the molar ratio of (A) to (D) above is A: D=1:0.01~1:40, preferably A:D=1:0.1~1:25, more preferably A: D=1:1~1:15. If the relative content of carbohydrates (D) is too large, the colloidal catalytic solution will be excessively stabilized and the catalyst activity will be lost, which may impart to the catalyst core of the non-conductive substrate, which may hinder the formation of a good-looking coating.

在製備該催化溶液之際，由於從還原劑向銅離子平穩地供給電子，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)，製成催化溶液。應予說明，在催化溶液的製備中，也不排除將可溶性銅鹽溶液滴入 還原劑溶液中。 When preparing the catalytic solution, since the electrons are smoothly supplied from the reducing agent to the copper ions, basically it takes time to slowly drop the reducing agent solution into the solution containing the soluble copper salt (and colloidal stabilizer) for preparation. For example, a reducing agent solution at 5 to 50°C (preferably 10 to 40°C) is dropped into the copper salt solution, and stirred for 20 to 1200 minutes (preferably 30 to 300 minutes) to prepare a catalytic solution. It should be noted that in the preparation of the catalytic solution, it is not excluded to drop the soluble copper salt solution into Reductant solution.

在本發明的催化溶液中，通過還原劑的作用由可溶性銅鹽生成的銅膠體粒子是適宜平均粒徑為1~250nm，優選為1~120nm，更優選為1~100nm的微細粒子。 In the catalytic solution of the present invention, the copper colloidal particles generated from the soluble copper salt by the action of the reducing agent are fine particles having an average average particle diameter of 1 to 250 nm, preferably 1 to 120 nm, and more preferably 1 to 100 nm.

如果銅膠體粒子的平均粒徑為250nm以下，則可以推斷將非導電性基板浸漬在催化溶液中時，膠體粒子進入基板的微細凹凸面的凹處，通過緻密地吸附或掛住等錨固效果，促進對基板表面賦予銅膠體核。反之，如果平均粒徑大於250nm，則不但會因凝聚、沉澱或分離等而難以獲得穩定的銅膠體，而且錨固效果也不理想，因此只能對基板表面局部賦予銅膠體粒子，或者有可能出現賦予不良。 If the average particle size of the copper colloidal particles is 250 nm or less, it can be inferred that when the non-conductive substrate is immersed in the catalytic solution, the colloidal particles enter the concave portions of the fine uneven surface of the substrate, and the anchoring effect such as dense adsorption or hanging, Promote the application of copper colloid cores to the substrate surface. Conversely, if the average particle size is greater than 250 nm, not only will it be difficult to obtain stable copper colloids due to aggregation, precipitation, or separation, but also the anchoring effect will be unsatisfactory. Therefore, copper colloid particles can only be locally applied to the surface of the substrate, or may appear Give bad.

本發明1的銅膠體催化溶液中可含有表面活性劑，但由於催化劑活性有可能降低，因此優選表面活性劑的含量抑制在950mg/L以下。 The copper colloidal catalytic solution of the present invention 1 may contain a surfactant. However, since the catalyst activity may be reduced, the content of the surfactant is preferably suppressed to 950 mg/L or less.

上述表面活性劑是指非離子型、兩性、陽離子型、或陰離子型的各種表面活性劑，特別不優選兩性、陽離子型、陰離子型、或低分子的非離子型表面活性劑。 The above-mentioned surfactants refer to nonionic, amphoteric, cationic, or anionic surfactants, and amphoteric, cationic, anionic, or low-molecular nonionic surfactants are not particularly preferred.

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、或者C1~C25烷氧基化磷酸(鹽)等。 Examples of the above nonionic surfactants include C1-C20 fatty alcohols, phenols, naphthols, bisphenols, (poly)C1-C25 alkylphenols, (poly)arylalkylphenols, and C1- Addition condensation of C25 alkylnaphthol, C1~C25 alkoxylated phosphoric acid (salt), sorbitan ester, polyalkylene glycol, C1~C22 fatty amine, C1~C22 fatty amide, etc. 2~300 Mole ethylene oxide (EO) and/or propylene oxide (PO) compounds, or C1-C25 alkoxylated phosphoric acid (salt), etc.

作為上述陽離子型表面活性劑，可列舉出季銨鹽或吡啶鹽等，具體而言可列舉出：十二烷基三甲基銨鹽、十八烷基三甲基銨鹽、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、十二烷基吡啶鹽、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 surfactants include quaternary ammonium salts and pyridine salts, and specific examples thereof include dodecyl trimethyl ammonium salt, octadecyl trimethyl ammonium salt, and dodecyl group. Dimethyl ethyl ammonium salt, octadecyl dimethyl ethyl ammonium salt, dimethyl benzyl dodecyl ammonium salt, hexadecyl dimethyl benzyl ammonium salt, octadecyl dimethyl Benzyl ammonium salt, trimethyl benzyl ammonium salt, triethyl benzyl ammonium salt, dimethyl diphenyl ammonium salt, benzyl dimethyl phenyl ammonium salt, cetyl pyridinium salt, twelve Alkylpyridinium salt, dodecylpyridinium salt, stearylamine acetate, laurylamine Acetate, octadecylamine acetate, etc.

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。 Examples of the anionic surfactant include alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, alkylbenzene sulfonate, [(mono, di, tri ) Alkyl] naphthalene sulfonate, etc.

作為上述兩性表面活性劑，可列舉出羧基甜菜鹼、咪唑啉甜菜鹼、磺基甜菜鹼、氨基羧酸等。另外，還可以使用環氧乙烷和/或環氧丙烷與烷基胺或二胺的縮合生成物的硫酸化或磺酸化加合物。 Examples of the amphoteric surfactants include carboxybetaine, imidazoline betaine, sulfobetaine, and aminocarboxylic acid. In addition, sulfated or sulfonated adducts of condensation products of ethylene oxide and/or propylene oxide with alkylamines or diamines can also be used.

為了提高膠體粒子的分散性，化學鍍銅時得到均勻且無斑紋的被膜，本發明的銅膠體催化溶液中可含有合成類水溶性聚合物。 In order to improve the dispersibility of colloidal particles, a uniform and non-marking coating is obtained during electroless copper plating. The copper colloidal catalytic solution of the present invention may contain a synthetic water-soluble polymer.

如果催化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，由此在化學鍍銅時，有助於析出均勻性優異且無斑紋的銅被膜。 If this synthetic water-soluble polymer is contained in the catalytic solution, the dispersibility of the colloidal particles is improved, which contributes to the precipitation of a copper film having excellent uniformity and no streaks during 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，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-mentioned synthetic water-soluble polymer refers to the exclusion of water-soluble polymers of natural origin such as gelatin and starch, but does not exclude the semi-synthetic cellulose derivatives such as carboxymethyl cellulose (CMC) and methyl cellulose (MC) .

本發明3的催化溶液的含有對象即合成類水溶性聚合物，在與上述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 catalytic solution of the present invention 3 contains synthetic water-soluble polymers. In the relationship with the above-mentioned surfactants, the components belonging to them may be partially repeated, but in the present invention, the two are different concepts.

本發明3的催化溶液中，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，即含有或不含有表面活性劑均可。 In the catalytic solution of the present invention 3, it is not necessary to include components other than the water-soluble polymer. For example, whether or not a surfactant is included, that is, whether or not the surfactant is included may be sufficient.

如本發明3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 present invention 3, examples of the synthetic water-soluble polymer include polyethylene glycol (PEG), polypropylene glycol (PPG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), and polypropylene amide. Amine (PAM), polyethyleneimine (PEI), polyacrylate, etc., particularly preferably high molecular weight PEG, PVP, PVA, etc.

合成類水溶性聚合物可以單獨使用或並用，其相對於催化溶 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。 Synthetic water-soluble polymers can be used alone or in combination. The content of the liquid 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6是使用上述銅膠體催化溶液的化學鍍方法，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。 The present invention 6 is an electroless plating method using the above copper colloidal catalytic solution, which is sequentially combined by the following three steps: (a) an adsorption promoting step, (b) a catalyst providing step, and (c) an electroless copper plating step.

上述吸附促進步驟(a)可視為步驟(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吸附促進劑的液體中的步驟，上述吸附促進劑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中的至少一種。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粒子的吸附。 The above-mentioned adsorption promotion step (a) can be regarded as a pretreatment (preliminary treatment) step given by the catalyst of step (b), which is a step of immersing the non-conductive substrate in the liquid containing the adsorption promoter, and the adsorption promoter is selected from At least one of an ionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. By contacting the substrate with a liquid containing a surfactant, the wettability of the substrate surface can be improved, the catalyst activity can be enhanced, and the adsorption of copper colloidal particles in the next step can be promoted.

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等。 In the adsorption promotion step, the non-conductive substrate needs to be in contact with the liquid containing the surfactant, so it is basically immersed in the liquid, but the liquid containing the surfactant can also be sprayed on the substrate or coated on the substrate with bristles First class.

如本發明7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，則吸附促進效果進一步增加。 As shown in the present invention 7, from the viewpoint of promoting adsorption, a positively charged cationic or amphoteric surfactant is suitable, and a cationic surfactant is more particularly preferred. In addition, if a small amount of nonionic surfactant is used in combination with the cationic surfactant, the effect of promoting the adsorption further increases.

在本發明的催化溶液中，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，下一步驟中銅膠體粒子對基板的吸附效率增加。 In the catalytic solution of the present invention, the zeta potential of the copper colloidal particles generated by the reducing agent acting on the soluble copper salt is a negative value. Therefore, for example, if a non-conductive substrate is subjected to contact treatment with a cationic surfactant, the substrate is likely to carry With positive charge, the adsorption efficiency of the copper colloidal particles to the substrate increases in the next step.

表面活性劑的具體例，如作為上述本發明1的催化溶液中排除或抑制物件所描述的表面活性劑的說明所述。 Specific examples of the surfactant are as described in the description of the surfactant described as the object of excluding or suppressing the object in the catalytic solution of the present invention 1 described above.

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。 The content of the surfactant is 0.05 to 100 g/L, preferably 0.5 to 50 g/L. Preferably, the temperature of the liquid containing the surfactant is about 15 to 70° C., and the immersion time is about 0.5 to 20 minutes.

吸附促進處理結束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)。 After the non-conductive substrate after the adsorption promotion treatment is washed with pure water, dry or not After drying, proceed to the next step of giving catalyst (b).

在催化劑賦予步驟中，將非導電性基板浸漬在上述銅膠體催化溶液中，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 above-mentioned copper colloidal catalytic solution to adsorb the copper colloidal particles on the substrate surface.

該催化溶液的液溫為5~70℃、優選為15~60℃，浸漬時間為0.1~20分鐘、優選為0.2~10分鐘，進行浸漬處理時，在將基板靜置於催化溶液中的狀態下浸漬即可，但也可以進行攪拌或揺動。 The liquid temperature of the catalytic solution is 5 to 70°C, preferably 15 to 60°C, the immersion time is 0.1 to 20 minutes, preferably 0.2 to 10 minutes, and when the immersion treatment is performed, the substrate is placed in a state of being statically placed in the catalytic solution It can be immersed under water, but it can also be stirred or stirred.

另外，如果在該催化劑賦予步驟(b)之後下一步化學鍍銅步驟(c)之前***酸洗處理步驟，則與不進行酸洗的情況相比，能夠進一步增進該催化劑活性的活度，即使對具有通孔或貫穿孔的複雜形狀的基板也能夠可靠地防止鍍銅不均勻或斷線的惡劣影響，進一步提高銅被膜的密合性。 In addition, if the pickling treatment step is inserted after the catalyst imparting step (b) and before the next electroless copper plating step (c), the activity of the catalyst activity can be further improved compared to the case without pickling, even The substrate with a complex shape having through holes or through holes can also reliably prevent the adverse effects of copper plating unevenness or wire breakage, and further improve the adhesion of the copper coating.

進行酸洗處理時，酸的濃度為10~200g/L、優選為20~100g/L，酸可使用硫酸、鹽酸等無機酸、有機磺酸、乙酸、酒石酸、檸檬酸等羧酸等有機酸。 When pickling, the acid concentration is 10 to 200 g/L, preferably 20 to 100 g/L. For the acid, inorganic acids such as sulfuric acid and hydrochloric acid, organic acids such as organic sulfonic acid, acetic acid, tartaric acid, and citric acid can be used .

酸洗的處理溫度為5~70℃、優選為15~60℃，處理時間為0.1~20分鐘、優選為0.2~10分鐘。 The treatment temperature of pickling is 5 to 70°C, preferably 15 to 60°C, and the treatment time is 0.1 to 20 minutes, preferably 0.2 to 10 minutes.

浸漬於催化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 catalytic solution is washed with pure water, dried or not dried, and then enters the electroless copper plating step (c).

化學鍍銅與現有技術同樣進行處理即可，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 processed in the same manner 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、攪拌葉片等的機械攪拌等。 The stirring of the copper plating liquid may be mechanical stirring such as air stirring, rapid liquid flow stirring, stirring blades and the like.

本發明8是採用上述化學鍍銅方法形成銅被膜的非導電性基板，是指經由本發明6的吸附促進、催化劑賦予、化學鍍而形成銅被膜的上述基板。 The present invention 8 is a non-conductive substrate for forming a copper film by the above-mentioned electroless copper plating method, and refers to the above-mentioned substrate for forming a copper film through the adsorption promotion, catalyst application, and electroless plating of the present invention 6.

非導電性基板如上所述，是指玻璃-環氧樹脂、玻璃-聚醯亞胺樹脂、環氧樹脂、聚醯亞胺樹脂等樹脂基板，或者玻璃基板、陶瓷基板等。 As described above, the non-conductive substrate refers to a resin substrate such as glass-epoxy resin, glass-polyimide resin, epoxy resin, or polyimide resin, or a glass substrate, ceramic substrate, 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 well-known copper plating solution can be used.

化學鍍銅液基本上含有可溶性銅鹽、還原劑和絡合劑，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 adjusting agent or an acid.

關於可溶性銅鹽，如上述對銅膠體催化溶液的描述所示。 Regarding the soluble copper salt, as described above for the copper colloidal catalytic 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。 Regarding the reducing agent contained in the electroless copper plating solution, as shown in the above description of the copper colloidal catalytic solution, represented by formaldehyde (formaldehyde water), including hypophosphorous acid, phosphorous acid, amine borane, boron hydrogen Type, glyoxylic acid, etc., preferably formaldehyde water.

關於化學鍍銅液中所含的絡合劑，也包括與上述銅膠體催化溶液中描述的膠體穩定劑通用的部分，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 the parts common to the colloid stabilizer described in the above copper colloidal catalytic solution, specifically: ethylenediaminetetraacetic acid (EDTA), diethylenetriamine Aminocarboxylic acids such as pentaacetic acid (DTPA), triethylenetetraminehexaacetic acid (TTHA), hydroxyethylethylenediaminetriacetic acid (HEDTA), aminotriacetic acid (NTA), and iminodiacetic acid (IDA); Polyamines such as amine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, etc.; monoethanolamine, diethanolamine, triethanolamine, etc. Amino alcohols; hydroxycarboxylic acids such as citric acid, tartaric acid, lactic acid, malic acid; thioglycolic acid, glutamic acid, etc.

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。 The electroless copper plating solution may contain organic acids, inorganic acids or salts thereof as the basic components of the liquid.

上述無機酸可列舉出硫酸、焦磷酸、氟硼酸等。另外，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. Examples of the organic acid include hydroxycarboxylic acids such as glycolic acid and tartaric acid, and organic sulfonic acids such as methanesulfonic acid and 2-hydroxyethanesulfonic acid.

[實施例] [Example]

以下，對包括本發明的含有吸附促進劑的液體、銅膠體催化溶液、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溶液的經時穩定性和上述實施例中所得銅被膜的外觀的評價試驗例進行說明。 Hereinafter, embodiments of the electroless copper plating method including the preparation of the liquid containing the adsorption accelerator of the present invention, the copper colloidal catalytic solution, and the electroless copper plating solution will be described, and the copper colloidal catalytic solution will be sequentially stabilized over time. Examples of evaluation tests of the properties and appearance of the copper coatings obtained in the above examples are 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 of course can be arbitrarily modified within the scope of the technical idea of the present invention.

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

下列實施例1~20中，實施例9~10是催化溶液中含有合成類水溶性聚合物之例，除此之外的實施例為不含該水溶性聚合物之例，實施例2~20大致是以實施例1或實施例4為基礎，改變成分等之例。 In the following Examples 1 to 20, Examples 9 to 10 are examples in which the synthetic water-soluble polymer is contained in the catalytic solution, and the other examples are examples without the water-soluble polymer, Examples 2 to 20 This is an example of changing the components and the like based on Example 1 or Example 4.

實施例1是在催化溶液中使用檸檬酸作為膠體穩定劑，使用木糖醇(糖醇)作為碳水化合物，使用硼氫化鈉和次磷酸作為還原劑之例。實施例2是以實施例1為基礎，將木糖醇的含量調整為上述通常範圍的下限之例，實施例3是將木糖醇的含量調整為上述通常範圍的上限之例。實施例4是碳水化合物使用山梨醇(糖醇)之例，同樣地實施例5是碳水化合物使用甘露醇(糖醇)之例，實施例6是碳水化合物使用葡萄糖酸內酯(單糖類的衍生物)之例，實施例7是碳水化合物使用葡萄糖(單糖類)之例，實施例8是碳水化合物使用麥芽糖(二糖類)之例。實施例9是碳水化合物使用木糖醇，合成類水溶性聚合物使用聚乙烯吡咯烷酮之例。實施例10是碳水化合物使用山梨醇，合成類水溶性聚合物使用聚乙二醇之例。實施例11是碳水化合物並用木糖醇和山梨醇之例(糖醇彼此間的並用例)，同樣地實施例12是碳水化合物並用甘露醇和葡萄糖之例(糖醇與單糖類的並用例)。實施例13是以實施例1為基礎改變可溶性銅鹽之例，實施例14是以實施例4為基礎改變可溶性銅鹽之例。實施例15~16是以實施例1為基礎改變膠體穩定劑之例，實施例17是以實施例4為基礎改變膠體穩定劑之例。實施例18是以實施例4為基礎改變還原劑之例，實施例19是以實施例5為基礎改變還原劑之例。實施例20是以實施例1為基礎將催化溶液的pH值改變至弱鹼性區之例。 Example 1 is an example of using citric acid as a colloidal stabilizer, xylitol (sugar alcohol) as a carbohydrate, and sodium borohydride and hypophosphorous acid as a reducing agent in a catalytic solution. Example 2 is based on Example 1 and adjusts the content of xylitol to the lower limit of the above normal range, and Example 3 is an example of adjusting the content of xylitol to the upper limit of the above normal range. Example 4 is an example of using sorbitol (sugar alcohol) as a carbohydrate, and similarly Example 5 is an example of using mannitol (sugar alcohol) as a carbohydrate, and example 6 is using a gluconolactone (derivation of monosaccharides) of a carbohydrate (Example), Example 7 is an example of using glucose (monosaccharides) as carbohydrates, and Example 8 is an example of using maltose (disaccharides) as carbohydrates. Example 9 is an example of using xylitol as a carbohydrate and polyvinylpyrrolidone as a synthetic water-soluble polymer. Example 10 is an example of using sorbitol as a carbohydrate and polyethylene glycol as a synthetic water-soluble polymer. Example 11 is an example in which carbohydrates are used in combination with xylitol and sorbitol (a combination of sugar alcohols with each other), and similarly Example 12 is an example in which carbohydrates are used in combination with mannitol and glucose (a combination example of sugar alcohols and monosaccharides). Example 13 is an example of changing the soluble copper salt based on Example 1, and Example 14 is an example of changing the soluble copper salt based on Example 4. Examples 15 to 16 are based on Example 1 to change the colloid stabilizer, and Example 17 are based on Example 4 to change the colloid stabilizer. Example 18 is an example of changing the reducing agent based on Example 4, and Example 19 is an example of changing the reducing agent based on Example 5. Example 20 is an example of changing the pH value of the catalytic solution to the weakly alkaline region on the basis of Example 1.

另外，實施例4和實施例11是在催化劑賦予步驟之後化學鍍銅步驟之前***酸洗步驟之例，其他實施例均不進行酸洗，依次進行吸附促進→催化劑賦予→化學鍍銅各步驟之例。 In addition, Example 4 and Example 11 are examples in which the pickling step is inserted after the catalyst-imparting step and before the electroless copper-plating step. Other examples do not perform acid-washing, and sequentially perform adsorption promotion→catalyst imparting→electroless copper-plating steps example.

另一方面，在下列比較例1~3中，比較例1是催化溶液中不含膠體穩定劑和碳水化合物這兩種成分的空白例。比較例2是催化溶液中含有 膠體穩定劑，並含有與本發明所規定的碳水化合物不同的碳水化合物(澱粉)之例。比較例3是無吸附促進步驟，直接從催化劑賦予步驟進行化學鍍步驟的空白例。 On the other hand, in the following Comparative Examples 1 to 3, Comparative Example 1 is a blank example in which the two components of colloidal stabilizer and carbohydrate are not contained in the catalytic solution. Comparative example 2 is contained in the catalytic solution Examples of colloidal stabilizers containing carbohydrates (starch) different from the carbohydrates specified in the present invention. Comparative Example 3 is a blank example in which the electroless plating step is performed directly from the catalyst application step without the adsorption promotion step.

另外，基準例依照上述先申請發明進行，因此是催化溶液中含有膠體穩定劑但不含本發明所規定的碳水化合物之例。 In addition, the reference example is based on the above-mentioned first application invention, and therefore is an example in which the catalytic solution contains the colloidal stabilizer but does not contain the carbohydrate specified in the present invention.

(1)實施例1 (1) Example 1

《吸附促進、催化劑賦予以及化學鍍的處理步驟》 "Processing steps for adsorption promotion, catalyst addition, and electroless 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FR-4、板厚：1.0mm)作為試樣基板。 First, a double-sided copper-clad glass-epoxy resin substrate (FR-4 manufactured by Matsushita Electric Works Co., Ltd., plate thickness: 1.0 mm) was used as a sample substrate.

然後，使用後述(a)的吸附促進劑對試樣基板進行吸附促進後，浸漬在後述(b)的催化溶液中進行催化劑賦予，再使用後述(c)的鍍液進行化學鍍銅。 Then, the sample substrate is subjected to adsorption promotion using an adsorption promoter described in (a) described later, and then immersed in a catalyst solution described in (b) described below to provide catalyst, and then electroless copper plating is performed using a plating solution described in (c) described later.

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溶液中，用純水洗滌。然後，將實施催化劑賦予後的試樣基板浸漬於上述化學鍍銅液中，在50℃、10分鐘的條件下實施化學鍍，在試樣基板上形成銅被膜後，用純水洗滌，乾燥。 Specifically, the sample substrate was immersed in the liquid containing the adsorption accelerator under the conditions of 50° C. and 2 minutes, and then washed with pure water. Next, the sample substrate subjected to the adsorption promotion treatment (pretreatment) was immersed in the above copper colloidal catalytic solution at 25° C. for 10 minutes, and washed with pure water. Then, the sample substrate after the catalyst application was immersed in the above-mentioned electroless copper plating solution, and electroless plating was performed under the conditions of 50° C. and 10 minutes. After the copper film was formed on the sample substrate, it was washed with pure water and dried.

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

按照下列組成製備含有吸附促進劑的液體。 The liquid containing the adsorption accelerator was prepared according to the following composition.

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

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

聚氧乙烯側鏈癸基醚：1g/L Polyoxyethylene side chain decyl ether: 1g/L

pH值：10.0 pH value: 10.0

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

木糖醇：0.3莫耳/L Xylitol: 0.3 moles/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 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，製成銅膠體催化溶液。 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 a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:3, copper salt: reducing agent=1:2.

生成的銅膠體粒子的平均粒徑為約15nm。 The average particle diameter of the generated copper colloidal particles was about 15 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)。該鍍液用後述氫氧化鈉調整pH值。 The electroless copper plating bath (built bath) was made according to the following composition. This plating solution adjusts pH value with sodium hydroxide mentioned later.

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

硫酸銅五水合物(以Cu2+計)：2.0g/L Copper sulfate pentahydrate (calculated 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值(20℃)：12.8 pH value (20℃): 12.8

(2)實施例2 (2) Example 2

以上述實施例1為基礎，按照下列組成製備銅膠體催化溶液，除此之外，含有吸附促進劑的液體、化學鍍銅液的組成、以及吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件與實施例1相同。 Based on the above Example 1, a copper colloidal catalytic solution was prepared according to the following composition, in addition to the composition of the liquid containing the adsorption promoter, the electroless copper plating solution, and the steps of adsorption promotion, catalyst addition, and electroless copper plating The conditions are the same as in Example 1.

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

木糖醇：0.001莫耳/L Xylitol: 0.001 mol/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 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，製成銅膠體催化溶液。 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 a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：0.01，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:0.01, copper salt: reducing agent=1:2.

生成的銅膠體粒子的平均粒徑為約25nm。 The average particle diameter of the generated copper colloidal particles is about 25 nm.

(3)實施例3 (3) Example 3

以上述實施例1為基礎，按照下列組成製備銅膠體催化溶液，除此之外，含有吸附促進劑的液體、化學鍍銅液的組成、以及吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件與實施例1相同。 Based on the above Example 1, a copper colloidal catalytic solution was prepared according to the following composition, in addition to the composition of the liquid containing the adsorption promoter, the electroless copper plating solution, and the steps of adsorption promotion, catalyst addition, and electroless copper plating The conditions are the same as in Example 1.

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

木糖醇：4.0莫耳/L Xylitol: 4.0 moles/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 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，製成銅膠體催化溶液。 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 a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅 鹽：碳水化合物=1：40，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper Salt: carbohydrate = 1:40, copper salt: reducing agent = 1:2.

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

(4)實施例4 (4) Example 4

依次進行吸附促進、催化劑賦予、酸洗、化學鍍銅各步驟之例。 Examples of the steps of accelerating adsorption, providing catalyst, pickling, and electroless copper plating are performed in this order.

應予說明，吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件以及化學鍍銅液的組成與實施例1相同，含有吸附促進劑的液體和銅膠體催化溶液的各製備條件如下所示。 In addition, the processing conditions of each step of the adsorption promotion, catalyst addition, electroless copper plating, and the composition of the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the liquid containing the adsorption accelerator and the copper colloidal catalytic solution are shown below.

另外，酸洗的處理條件如後述(d)所示。 In addition, the processing conditions of pickling are as shown in (d) mentioned later.

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

按照以下組成製備含有吸附促進劑的液體。 The liquid containing the adsorption accelerator was prepared according to the following composition.

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

氯化十二烷基二甲基苄基銨：5g/L Dodecyl dimethyl benzyl ammonium chloride: 5g/L

聚氧乙烯側鏈癸基醚：1g/L Polyoxyethylene side chain decyl ether: 1g/L

pH值：9.0 pH value: 9.0

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

山梨醇：0.3莫耳/L Sorbitol: 0.3 mol/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 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，製成銅膠體催化溶液。 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 a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:3, copper salt: reducing agent=1:2.

生成的銅膠體粒子的平均粒徑為約40nm。 The average particle diameter of the generated copper colloidal particles is about 40 nm.

(d)酸洗的處理條件 (d) Treatment conditions for pickling

製備50g/L的硫酸洗滌液，將經上述催化劑賦予處理後的試樣基板在45℃、1分鐘的條件下浸漬於該洗滌液中，水洗後，供給下一步化學鍍銅步驟。 A 50 g/L sulfuric acid washing liquid was prepared, and the sample substrate after the catalyst application treatment was immersed in the washing liquid at 45° C. for 1 minute, washed with water, and then subjected to the next step of electroless copper plating.

(5)實施例5 (5) Example 5

吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件以及化學鍍銅液的組成與實施例1相同，含有吸附促進劑的液體和銅膠體催化溶液的各製備條件如下所示： The processing conditions of the steps of adsorption promotion, catalyst addition, electroless copper plating, and the composition of the electroless copper plating solution are the same as in Example 1. The preparation conditions of the liquid containing the adsorption accelerator and the copper colloidal catalytic solution are as follows:

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

按照以下組成製備含有吸附促進劑的液體。 The liquid containing the adsorption accelerator was prepared according to the following composition.

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

十二烷基二甲基氨基乙酸甜菜鹼：5g/L Dodecyl dimethyl glycine betaine: 5g/L

聚氧乙烯辛基苯基醚：1g/L Polyoxyethylene octyl phenyl ether: 1g/L

pH值：10.5 pH value: 10.5

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

甘露醇：0.3莫耳/L Mannitol: 0.3 mol/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 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，製成銅膠體催化溶液。 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 a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:3, copper salt: reducing agent=1:2.

生成的銅膠體粒子的平均粒徑為約25nm。 The average particle diameter of the generated copper colloidal particles is about 25 nm.

(6)實施例6 (6) Example 6

吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件、以及含有吸附促進劑的液體和化學鍍銅液的組成與實施例1相同，銅膠體催化溶液的製備條件如下所示： The processing conditions of each step of adsorption promotion, catalyst addition, electroless copper plating, and the composition of the liquid containing the adsorption promoter and the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the copper colloidal catalytic solution are as follows:

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

葡萄糖酸內酯：0.3莫耳/L[還原劑溶液] Gluconolactone: 0.3 mol/L [reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 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，製成銅膠體催化溶液。 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 a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:3, copper salt: reducing agent=1:2.

生成的銅膠體粒子的平均粒徑為約20nm。 The average particle diameter of the generated copper colloidal particles is about 20 nm.

(7)實施例7 (7) Example 7

吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件、以及含有吸附促進劑的液體和化學鍍銅液的組成與實施例1相同，銅膠體催化溶液的製備條件如下所示。 The adsorption conditions, catalyst addition, processing conditions of each step of electroless copper plating, and the composition of the liquid containing the adsorption promoter and the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the copper colloidal catalytic solution are shown below.

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

葡萄糖：0.3莫耳/L Glucose: 0.3 mol/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 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，製成銅膠體催化溶液。 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 a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:3, copper salt: reducing agent=1:2.

生成的銅膠體粒子的平均粒徑為約15nm。 The average particle diameter of the generated copper colloidal particles was about 15 nm.

(8)實施例8 (8) Example 8

吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件以及化學鍍銅液的組成與實施例1相同，含有吸附促進劑的液體和銅膠體催化溶液的各製備條件如下所示。 The processing conditions of the steps of adsorption promotion, catalyst addition, electroless copper plating, and the composition of the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the liquid containing the adsorption accelerator and the copper colloidal catalytic solution are shown below.

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

按照以下組成製備含有吸附促進劑的液體。 The liquid containing the adsorption accelerator was prepared according to the following composition.

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

氯化十二烷基二甲基苄基銨：5g/L Dodecyl dimethyl benzyl ammonium chloride: 5g/L

聚氧乙烯辛基苯基醚：1g/L Polyoxyethylene octyl phenyl ether: 1g/L

pH值：10.5 pH value: 10.5

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

麥芽糖：0.3莫耳/L Maltose: 0.3 mol/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 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60分鐘，製成銅膠體催化溶液。 The reducing agent solution was dropped into the above copper solution adjusted to pH 4.0 at 25° C. and stirred for 60 minutes to prepare a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:3, copper salt: reducing agent=1:2.

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

(9)實施例9 (9) Example 9

吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件以及化學鍍銅液的組成與實施例1相同，含有吸附促進劑的液體和銅膠體催化溶液的各製備條件如下所示。 The processing conditions of the steps of adsorption promotion, catalyst addition, electroless copper plating, and the composition of the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the liquid containing the adsorption accelerator and the copper colloidal catalytic solution are shown below.

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

按照以下組成製備含有吸附促進劑的液體。 The liquid containing the adsorption accelerator was prepared according to the following composition.

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

十二烷基二甲基氨基乙酸甜菜堿：5g/L Dodecyl dimethyl glycine beetroot: 5g/L

聚氧乙烯辛基苯基醚：1g/L Polyoxyethylene octyl phenyl ether: 1g/L

pH值：10.0 pH value: 10.0

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

木糖醇：0.3莫耳/L Xylitol: 0.3 moles/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：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 mol/L

向調整為pH3.0的25℃的上述銅溶液中滴入還原劑溶液攪拌45分鐘，製 成銅膠體催化溶液。 The reducing agent solution was added dropwise to the copper solution at 25°C adjusted to pH 3.0 and stirred for 45 minutes to prepare Copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:3, copper salt: reducing agent=1:2.

生成的銅膠體粒子的平均粒徑為約25nm。 The average particle diameter of the generated copper colloidal particles is about 25 nm.

(10)實施例10 (10) Example 10

吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件以及化學鍍銅液的組成與實施例1相同，含有吸附促進劑的液體和銅膠體催化溶液的各製備條件如下所示。 The processing conditions of the steps of adsorption promotion, catalyst addition, electroless copper plating, and the composition of the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the liquid containing the adsorption accelerator and the copper colloidal catalytic solution are shown below.

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

按照以下組成製備含有吸附促進劑的液體。 The liquid containing the adsorption accelerator was prepared according to the following composition.

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

氯化十二烷基二甲基苄基銨：5g/L Dodecyl dimethyl benzyl ammonium chloride: 5g/L

聚氧乙烯側鏈癸基醚：1g/L Polyoxyethylene side chain decyl ether: 1g/L

pH值：10.0 pH value: 10.0

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

山梨醇：0.3莫耳/L Sorbitol: 0.3 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：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 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90分鐘，製成銅膠體催化溶液。 The reducing agent solution was dropped into the above copper solution adjusted to pH 4.0 at 25° C. and stirred for 90 minutes to prepare a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅 鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper Salt: Carbohydrate=1:3, Copper Salt: Reductant=1:2.

生成的銅膠體粒子的平均粒徑為約35nm。 The average particle diameter of the generated copper colloidal particles was about 35 nm.

(11)實施例11 (11) Example 11

依次進行吸附促進、催化劑賦予、酸洗、化學鍍銅各步驟之例。 Examples of the steps of accelerating adsorption, providing catalyst, pickling, and electroless copper plating are performed in this order.

但是，吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件、以及含有吸附促進劑的液體和化學鍍銅液的組成與實施例1相同，銅膠體催化溶液的製備條件如下所示。 However, the processing conditions of each step of the adsorption promotion, catalyst addition, electroless copper plating, and the composition of the liquid containing the adsorption promoter and the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the copper colloidal catalytic solution are shown below.

另外，酸洗的處理條件如後述(d)所示。 In addition, the processing conditions of pickling are as shown in (d) mentioned later.

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

山梨醇：0.2莫耳/L Sorbitol: 0.2 mol/L

木糖醇：0.1莫耳/L Xylitol: 0.1 mol/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 mol/L

向調整為pH4.0的35℃的上述銅溶液中滴入還原劑溶液攪拌45分鐘，製成銅膠體催化溶液。 The reducing agent solution was dropped into the above-mentioned copper solution adjusted to pH 4.0 at 35°C and stirred for 45 minutes to prepare a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:3, copper salt: reducing agent=1:2.

生成的銅膠體粒子的平均粒徑為約25nm。 The average particle diameter of the generated copper colloidal particles is about 25 nm.

(d)酸洗的處理條件 (d) Treatment conditions for pickling

製備50g/L的硫酸洗滌液，將經上述催化劑賦予處理後的試樣基板在45℃、1分鐘的條件下浸漬於該洗滌液中，水洗後，供給下一步化學鍍銅步驟。 A 50 g/L sulfuric acid washing liquid was prepared, and the sample substrate after the catalyst application treatment was immersed in the washing liquid at 45° C. for 1 minute, washed with water, and then subjected to the next step of electroless copper plating.

(12)實施例12 (12) Example 12

吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件以及化學鍍銅液的組成與實施例1相同，含有吸附促進劑的液體和銅膠體催化溶液的各製備條件如下所示。 The processing conditions of the steps of adsorption promotion, catalyst addition, electroless copper plating, and the composition of the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the liquid containing the adsorption accelerator and the copper colloidal catalytic solution are shown below.

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

按照以下組成製備含有吸附促進劑的液體。 The liquid containing the adsorption accelerator was prepared according to the following composition.

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

氯化十二烷基二甲基苄基銨：5g/L Dodecyl dimethyl benzyl ammonium chloride: 5g/L

聚氧乙烯側鏈癸基醚：1g/L Polyoxyethylene side chain decyl ether: 1g/L

pH值：8.5 pH value: 8.5

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

甘露醇：0.2莫耳/L Mannitol: 0.2 mol/L

葡萄糖：0.2莫耳/L Glucose: 0.2 mol/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 mol/L

向調整為pH3.0的35℃的上述銅溶液中滴入還原劑溶液攪拌45分鐘，製成銅膠體催化溶液。 The reducing agent solution was dropped into the above-mentioned copper solution adjusted to pH 3.0 at 35° C. for 45 minutes to prepare a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：4，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:4, copper salt: reducing agent=1:2.

生成的銅膠體粒子的平均粒徑為約15nm。 The average particle diameter of the generated copper colloidal particles was about 15 nm.

(13)實施例13 (13) Example 13

吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件、以及含有吸附促進劑的液體和化學鍍銅液的組成與實施例1相同，銅膠體催化溶液的製備 條件如下所示。 Adsorption promotion, catalyst addition, processing conditions of each step of electroless copper plating, and the composition of the liquid containing the adsorption promoter and the electroless copper plating solution are the same as in Example 1, and the preparation of the copper colloidal catalytic solution The conditions are as follows.

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

甲磺酸銅(以Cu2+計)：0.1莫耳/L Copper methanesulfonate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

木糖醇：0.3莫耳/L Xylitol: 0.3 moles/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 mol/L

向調整為pH5.0的35℃的上述銅溶液中滴入還原劑溶液攪拌45分鐘，製成銅膠體催化溶液。 The reducing agent solution was dropped into the above-mentioned copper solution adjusted to pH 5.0 at 35°C and stirred for 45 minutes to prepare a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:3, copper salt: reducing agent=1:2.

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

(14)實施例14 (14) Embodiment 14

吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件、以及含有吸附促進劑的液體和化學鍍銅液的組成與實施例1相同，銅膠體催化溶液的製備條件如下所示。 The adsorption conditions, catalyst addition, processing conditions of each step of electroless copper plating, and the composition of the liquid containing the adsorption promoter and the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the copper colloidal catalytic solution are shown below.

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

檸檬酸銅(以Cu2+計)：0.1莫耳/L Copper citrate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

山梨醇：0.3莫耳/L Sorbitol: 0.3 mol/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 mol/L

向調整為pH5.0的35℃的上述銅溶液中滴入還原劑溶液攪拌45分鐘，製成銅膠體催化溶液。 The reducing agent solution was dropped into the above-mentioned copper solution adjusted to pH 5.0 at 35°C and stirred for 45 minutes to prepare a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:3, copper salt: reducing agent=1:2.

生成的銅膠體粒子的平均粒徑為約25nm。 The average particle diameter of the generated copper colloidal particles is about 25 nm.

(15)實施例15 (15) Example 15

吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件、以及含有吸附促進劑的液體和化學鍍銅液的組成與實施例1相同，銅膠體催化溶液的製備條件如下所示。 The adsorption conditions, catalyst addition, processing conditions of each step of electroless copper plating, and the composition of the liquid containing the adsorption promoter and the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the copper colloidal catalytic solution are shown below.

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

甲酸：0.2莫耳/L Formic acid: 0.2 mol/L

木糖醇：0.3莫耳/L Xylitol: 0.3 moles/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 mol/L

向調整為pH4.0的35℃的上述銅溶液中滴入還原劑溶液攪拌45分鐘，製成銅膠體催化溶液。 The reducing agent solution was dropped into the above-mentioned copper solution adjusted to pH 4.0 at 35°C and stirred for 45 minutes to prepare a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:3, copper salt: reducing agent=1:2.

生成的銅膠體粒子的平均粒徑為約15nm。 The average particle diameter of the generated copper colloidal particles was about 15 nm.

(16)實施例16 (16) Example 16

吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件、以及含有吸附促進劑的液體和化學鍍銅液的組成與實施例1相同，銅膠體催化溶液的製備條件如下所示。 The adsorption conditions, catalyst addition, processing conditions of each step of electroless copper plating, and the composition of the liquid containing the adsorption promoter and the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the copper colloidal catalytic solution are shown below.

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

乳酸：0.2莫耳/L Lactic acid: 0.2 mol/L

木糖醇：0.3莫耳/L Xylitol: 0.3 moles/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 mol/L

向調整為pH4.0的35℃的上述銅溶液中滴入還原劑溶液攪拌45分鐘，製成銅膠體催化溶液。 The reducing agent solution was dropped into the above-mentioned copper solution adjusted to pH 4.0 at 35°C and stirred for 45 minutes to prepare a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:3, copper salt: reducing agent=1:2.

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

(17)實施例17 (17) Example 17

吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件、以及含有吸附促進劑的液體和化學鍍銅液的組成與實施例1相同，銅膠體催化溶液的製備條件如下所示。 The adsorption conditions, catalyst addition, processing conditions of each step of electroless copper plating, and the composition of the liquid containing the adsorption promoter and the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the copper colloidal catalytic solution are shown below.

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

氨三乙酸：0.2莫耳/L Ammonia triacetic acid: 0.2 mol/L

山梨醇：0.3莫耳/L Sorbitol: 0.3 mol/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 mol/L

向調整為pH4.0的35℃的上述銅溶液中滴入還原劑溶液攪拌45分鐘，製 成銅膠體催化溶液。 The reducing agent solution was added dropwise to the copper solution at 35°C adjusted to pH 4.0 and stirred for 45 minutes to prepare Copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:3, copper salt: reducing agent=1:2.

生成的銅膠體粒子的平均粒徑為約15nm。 The average particle diameter of the generated copper colloidal particles was about 15 nm.

(18)實施例18 (18) Example 18

吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件、以及含有吸附促進劑的液體和化學鍍銅液的組成與實施例1相同，銅膠體催化溶液的製備條件如下所示。 The adsorption conditions, catalyst addition, processing conditions of each step of electroless copper plating, and the composition of the liquid containing the adsorption promoter and the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the copper colloidal catalytic solution are shown below.

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

山梨醇：0.3莫耳/L Sorbitol: 0.3 mol/L

[還原劑溶液] [Reducing agent solution]

二甲胺硼烷：0.02莫耳/L Dimethylamine borane: 0.02 mol/L

抗壞血酸：0.18莫耳/L Ascorbic acid: 0.18 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，製成銅膠體催化溶液。 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 a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:3, copper salt: reducing agent=1:2.

生成的銅膠體粒子的平均粒徑為約25nm。 The average particle diameter of the generated copper colloidal particles is about 25 nm.

(19)實施例19 (19) Example 19

吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件、以及含有吸附促進劑的液體和化學鍍銅液的組成與實施例1相同，銅膠體催化溶液的製備條件如下所示。 The adsorption conditions, catalyst addition, processing conditions of each step of electroless copper plating, and the composition of the liquid containing the adsorption promoter and the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the copper colloidal catalytic solution are shown below.

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

甘露醇：0.3莫耳/L Mannitol: 0.3 mol/L

[還原劑溶液] [Reducing agent solution]

二甲胺硼烷：0.02莫耳/L Dimethylamine borane: 0.02 mol/L

抗壞血酸：0.18莫耳/L Ascorbic acid: 0.18 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，製成銅膠體催化溶液。 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 a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:3, copper salt: reducing agent=1:2.

生成的銅膠體粒子的平均粒徑為約15nm。 The average particle diameter of the generated copper colloidal particles was about 15 nm.

(20)實施例20 (20) Example 20

吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件、以及含有吸附促進劑的液體和化學鍍銅液的組成與實施例1相同，銅膠體催化溶液的製備條件如下所示。 The adsorption conditions, catalyst addition, processing conditions of each step of electroless copper plating, and the composition of the liquid containing the adsorption promoter and the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the copper colloidal catalytic solution are shown below.

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

EDTA：0.2莫耳/L EDTA: 0.2 mol/L

木糖醇：0.3莫耳/L Xylitol: 0.3 moles/L

[還原劑溶液] [Reducing agent solution]

二甲胺硼烷：0.02莫耳/L Dimethylamine borane: 0.02 mol/L

抗壞血酸：0.18莫耳/L Ascorbic acid: 0.18 mol/L

向調整為pH9.0的25℃的上述銅溶液中滴入還原劑溶液攪拌45分鐘，製成銅膠體催化溶液。 The reducing agent solution was dropped into the above copper solution adjusted to pH 9.0 at 25°C and stirred for 45 minutes to prepare a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate=1:3, copper salt: reducing agent=1:2.

生成的銅膠體粒子的平均粒徑為約30nm。 The average particle diameter of the generated copper colloidal particles is about 30 nm.

(21)比較例1 (21) Comparative Example 1

以上述實施例1為基礎，但銅膠體催化溶液中不含膠體穩定劑和碳水化合物的空白例。 Based on the above Example 1, but a blank example in which the copper colloidal catalytic solution does not contain colloidal stabilizers and carbohydrates.

即，吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件、以及含有吸附促進劑的液體和化學鍍銅液的組成與實施例1相同，銅膠體催化溶液的製備條件如下所示。 That is, the processing conditions of each step of the adsorption promotion, catalyst addition, electroless copper plating, and the composition of the liquid containing the adsorption promoter and the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the copper colloidal catalytic solution are shown below.

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 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，製成銅膠體催化溶液。 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 a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：0，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:0, copper salt: reducing agent=1:2.

生成銅膠體粒子，但發生凝聚、沉澱。 Copper colloidal particles are generated, but aggregation and precipitation occur.

(22)比較例2 (22) Comparative Example 2

以上述實施例1為基礎，銅膠體催化溶液中含有膠體穩定劑以及與本發明的規定不同的碳水化合物(澱粉)之例。 Based on the above Example 1, the copper colloidal catalytic solution contains an example of a colloidal stabilizer and a carbohydrate (starch) different from the provisions of the present invention.

即，吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件、以及含有吸附促進劑的液體和化學鍍銅液的組成與實施例1相同，銅膠體催化溶液的製備條件如下所示。 That is, the processing conditions of each step of the adsorption promotion, catalyst addition, electroless copper plating, and the composition of the liquid containing the adsorption promoter and the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the copper colloidal catalytic solution are shown below.

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

澱粉：0.3莫耳/L Starch: 0.3 mol/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 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，製成銅膠體催化溶液。 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 a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物(澱粉)=1：3，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer = 1:2, copper salt: carbohydrate (starch) = 1:3, copper salt: reducing agent = 1:2.

生成的銅膠體粒子的平均粒徑為約200nm。 The average particle diameter of the generated copper colloidal particles is about 200 nm.

(23)比較例3 (23) Comparative Example 3

以上述實施例1為基礎，省略吸附促進步驟之例。 Based on the above-mentioned Embodiment 1, the example of the adsorption promotion step is omitted.

即，不對試樣基板實施吸附促進處理，直接浸漬於實施例1的催化溶液(b)中進行催化劑賦予，進而使用實施例1的鍍液(c)進行化學鍍銅。催化劑賦予、化學鍍銅各步驟的處理條件、以及銅膠體催化溶液和化學鍍銅液的各製備條件與實施例1相同。 That is, the sample substrate was not subjected to the adsorption promotion treatment, and was directly immersed in the catalytic solution (b) of Example 1 to provide the catalyst, and then electroless copper plating was performed using the plating solution (c) of Example 1. The catalyst addition, the processing conditions of the electroless copper plating steps, and the preparation conditions of the copper colloidal catalytic solution and the electroless copper plating liquid are the same as in Example 1.

(24)基準例 (24) Reference example

依照上述先申請發明進行，因此是以上述實施例1為基礎，催化溶液中含有膠體穩定劑但不含碳水化合物之例。 In accordance with the above-mentioned first application invention, based on the above Example 1, the catalytic solution contains a colloidal stabilizer but no carbohydrates.

即，吸附促進、催化劑賦予、化學鍍銅各步驟的處理條件、以及含有吸附促進劑的液體和化學鍍銅液的組成與實施例1相同，銅膠體催化溶液的製備條件如下所示。 That is, the processing conditions of each step of the adsorption promotion, catalyst addition, electroless copper plating, and the composition of the liquid containing the adsorption promoter and the electroless copper plating solution are the same as in Example 1, and the preparation conditions of the copper colloidal catalytic solution are shown below.

(b)銅膠體催化溶液的製備 (b) Preparation of copper colloidal catalytic solution

[銅溶液] [Copper solution]

硫酸銅(以Cu2+計)：0.1莫耳/L Copper sulfate (calculated as Cu 2+ ): 0.1 mol/L

檸檬酸：0.2莫耳/L Citric acid: 0.2 mol/L

[還原劑溶液] [Reducing agent solution]

硼氫化鈉：0.02莫耳/L Sodium borohydride: 0.02 mol/L

次磷酸：0.18莫耳/L Hypophosphorous acid: 0.18 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，製成銅膠體催化溶液。 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 a copper colloidal catalytic solution.

上述催化溶液的各成分的莫耳比如下所示：銅鹽：膠體穩定劑=1：2，銅鹽：碳水化合物(澱粉)=1：0，銅鹽：還原劑=1：2。 The molar ratios of the components of the above catalytic solution are as follows: copper salt: colloidal stabilizer=1:2, copper salt: carbohydrate (starch)=1:0, copper salt: reducing agent=1:2.

生成的銅膠體粒子的平均粒徑為約30nm。 The average particle diameter of the generated copper colloidal particles is about 30 nm.

《催化溶液的經時穩定性試驗例》 "Experimental Example of Stability of Catalytic Solution"

由此，對於上述實施例1~20、比較例1~3和基準例中建浴的各銅膠體催化溶液，按照下列標準評價膠體穩定性的優劣。 Thus, for each of the copper colloidal catalytic solutions in the above-mentioned Examples 1 to 20, Comparative Examples 1 to 3, and the reference example, the quality of the colloidal stability was evaluated according to the following criteria.

◎：建浴後經過2個月以上也未發生沉澱或分解。 ◎: No precipitation or decomposition occurred more than 2 months after the bath was built.

○：建浴後1個月以上2個月以內發生沉澱或分解。 ○: Precipitation or decomposition occurred within 1 month to 2 months after the bath was established.

△：建浴後1個月內發生沉澱或分解。 △: Precipitation or decomposition occurred within 1 month after the bath was established.

×：未生成膠體粒子，或者建浴後立刻沉澱或分解。 ×: No colloidal particles were formed, or precipitated or decomposed immediately after the bath was established.

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

接著，對於上述實施例1~20、比較例1~3和基準例中建浴的各銅膠體催化溶液，按照下列標準目視評價使用建浴初期的催化溶液的情況下所得銅鍍膜外觀的優劣。 Next, for each of the copper colloidal catalyst solutions for bathing in the above Examples 1 to 20, Comparative Examples 1 to 3, and the reference example, the quality of the appearance of the copper plating film obtained by using the catalytic solution at the initial stage of bathing was visually evaluated according to the following criteria.

○：銅鍍膜均勻無斑紋。 ○: The copper plating film is uniform and free of streaks.

△：銅鍍膜出現斑紋或局部未析出(鍍膜缺損)。 △: The copper plating film has streaks or partial precipitation (defect of the plating film).

×：銅被膜未析出。 ×: The copper film did not precipitate.

應予說明，析出被膜的“斑紋”表示存在被膜緻密性或平滑性等與周圍不 同的部分。被膜的“斑紋”是與被膜的均勻性不同的觀點。 It should be noted that the “marking” of the deposited film means that the denseness or smoothness of the film is present, which is not related to the surroundings. The same part. The "marking" of the coating is different from the uniformity of the coating.

《對銅膠體催化溶液的經時穩定性和被膜外觀的試驗結果》 "Test results on the stability of copper colloidal catalytic solution over time and the appearance of the coating"

Figure 105103759-A0202-12-0037-1
Figure 105103759-A0202-12-0037-1

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

在銅膠體催化溶液不含膠體穩定劑和碳水化合物的比較例1中，催化溶液的經時穩定性差，而且在與催化溶液接觸後即使對非導電性基板實施化 學鍍也未析出銅被膜。 In Comparative Example 1 in which the copper colloidal catalytic solution did not contain colloidal stabilizers and carbohydrates, the catalytic solution had poor stability over time, and even after contacting the catalytic solution, the non-conductive substrate was chemically modified. The copper coating was not precipitated by the plating.

另一方面，在催化溶液含有膠體穩定劑而不含碳水化合物的基準例中，顯示出催化溶液建浴後經過1個月也未發生沉澱的良好經時穩定性，銅被膜的外觀良好。 On the other hand, in the reference example in which the catalytic solution contains a colloidal stabilizer and no carbohydrates, it shows good stability over time after precipitation of the catalytic solution after the bath is established, and the appearance of the copper film is good.

但是，在膠體穩定劑與碳水化合物共存的催化溶液中，使用與本發明所規定的特定碳水化合物不同的澱粉作為該碳水化合物的比較例2，經時穩定性下降使得催化溶液所生成的銅粒子不微細，形成的銅被膜出現鍍膜缺損，被膜外觀產生問題。 However, in the catalytic solution in which the colloidal stabilizer and the carbohydrate coexist, a starch different from the specific carbohydrate specified in the present invention is used as the comparative example 2 of the carbohydrate, and the stability decreases over time so that the copper particles generated by the catalytic solution It is not fine, and the formed copper film is defective in plating, and the appearance of the film is problematic.

在非導電性基板不進行吸附促進處理而直接進行催化劑賦予，再實施化學鍍銅的比較例3中，催化溶液的經時穩定性與實施例相同，但析出的銅被膜出現鍍膜缺損，因此可以判斷由於催化劑賦予之前未進行吸附促進預處理，所以催化劑活性不足，銅膠體粒子對基板的吸附與實施例相比較差。 In Comparative Example 3 where electroless copper plating was carried out without performing the adsorption promotion treatment on the non-conductive substrate, the time stability of the catalytic solution was the same as in the example, but the deposited copper film had a coating defect, so it was possible It was judged that since the catalyst was not subjected to pretreatment for adsorption promotion before the catalyst was provided, 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，在進行吸附促進預處理後，進行催化劑賦予處理，接著實施化學鍍銅的實施例1~20中，催化溶液的經時穩定性均優異，化學鍍所析出的銅被膜大致無斑紋或鍍膜缺損，呈現出優異的外觀。 On the other hand, after performing the adsorption promotion pretreatment, the catalyst addition treatment, followed by the electroless copper plating of Examples 1 to 20, the catalytic solution was excellent in stability over time, and the copper film deposited by the electroless plating was almost free of streaks Or the coating is defective, showing an excellent appearance.

上述基準例與比較例1對比可知，為了得到無斑紋或鍍膜缺損的外觀良好的銅被膜，催化溶液中不但必須含有銅鹽和還原劑，還必須含有膠體穩定劑。 The comparison between the above-mentioned reference example and Comparative Example 1 shows that in order to obtain a copper film with good appearance without streaks or coating defects, the catalytic solution must contain not only a copper salt and a reducing agent, but also a colloidal stabilizer.

另一方面，將上述實施例1~20與該基準例對比可知，為了得到外觀優異的銅被膜，需要使膠體穩定劑和本發明的特定碳水化合物共存於催化溶液中。尤其若著眼於催化溶液的經時穩定性，則基準例雖然顯示出建浴後1個月以上的穩定性評價為○，但實施例1~20的各催化溶液顯示出建浴後超過2個月的穩定性，表明對於該經時穩定性，實施例1~20的各催化溶液相對於基準例具有優勢，並具有能夠使催化溶液的維護比基準例更為簡化，從而能夠減輕化學鍍銅的處理成本的優點。 On the other hand, it can be seen from the comparison between the above Examples 1 to 20 and the reference example that in order to obtain a copper film having an excellent appearance, it is necessary to coexist the colloidal stabilizer and the specific carbohydrate of the present invention in the catalytic solution. In particular, focusing on the stability over time of the catalytic solution, although the reference example shows a stability evaluation of more than 1 month after the bath establishment, the catalytic solutions of Examples 1 to 20 show more than 2 months after the bath establishment. Stability, indicating that for this time-dependent stability, each of the catalytic solutions of Examples 1 to 20 has advantages over the reference example, and has the ability to make the maintenance of the catalytic solution more simplified than the reference example, thereby reducing the treatment of electroless copper plating Cost advantage.

另外，將使用與本發明所規定的特定碳水化合物不同的澱粉的比較例2與實施例1~20對比可知，即使在膠體穩定劑與碳水化合物共存於催化溶液中的情況下，若不選擇本發明所規定的特定碳水化合物，則不會改善催化溶液的經時穩定性，反而無法平穩地形成微細的銅膠體粒子，結果會損害被膜外觀，因此可判斷選擇特定碳水化合物對提高催化溶液的經時穩定性的重要性。 In addition, comparing Comparative Example 2 and Examples 1 to 20 using a starch different from the specific carbohydrate specified in the present invention, it can be seen that even in the case where the colloidal stabilizer and the carbohydrate coexist in the catalytic solution, if this option is not selected The specific carbohydrates specified in the invention will not improve the temporal stability of the catalytic solution, but will not form fine copper colloid particles smoothly, which will damage the appearance of the coating. Therefore, it can be judged that the selection of specific carbohydrates can improve the catalytic solution. The importance of time stability.

接著，對實施例1~20進行詳細討論。 Next, Examples 1 to 20 will be discussed in detail.

以實施例1為基礎說明與其他實施例的相對評價。首先，實施例1使用含有陽離子型表面活性劑即二烯丙胺聚合物的季銨鹽的吸附促進劑對非導電性基板進行預處理，使用以硫酸銅為銅鹽、硼氫化鈉為還原劑、檸檬酸為膠體穩定劑、木糖醇為特定碳水化合物的催化溶液進行催化劑賦予後，進行化學鍍銅之例，催化溶液的經時穩定性良好，建浴後經過2個月也未發生沉澱或分解，另外，化學鍍所得的銅被膜未出現析出斑紋或鍍膜缺損，呈現出優異的外觀。 Based on Example 1, the relative evaluation with other examples will be described. First, in Example 1, a non-conductive substrate was pretreated with an adsorption accelerator containing a quaternary ammonium salt of a diallylamine polymer, which is a cationic surfactant, using copper sulfate as a copper salt and sodium borohydride as a reducing agent. The catalytic solution of citric acid as a colloidal stabilizer and xylitol as a specific carbohydrate is given as an example of electroless copper plating. The catalytic solution has good stability over time, and no precipitation or decomposition occurs after 2 months after the bath is established. In addition, the copper coating obtained by the electroless plating did not show precipitation spots or plating defects, and exhibited an excellent appearance.

實施例2是相對於實施例1大幅減少碳水化合物的含量之例，實施例3是反之大幅增加碳水化合物的含量之例，與實施例1同樣催化溶液的經時穩定性良好，所得銅被膜呈現出優異的外觀。 Example 2 is an example in which the content of carbohydrate is greatly reduced compared to Example 1, and Example 3 is an example in which the content of carbohydrate is greatly increased. In the same way as Example 1, the stability of the catalytic solution over time is good, and the resulting copper film appears Outstanding appearance.

在碳水化合物改為山梨醇(糖醇)的實施例4、同樣改為甘露醇(糖醇)的實施例5、改為葡萄糖酸內酯(單糖類衍生物)的實施例6、改為葡萄糖(單糖類)的實施例7、改為麥芽糖(二糖類)的實施例8、改為山梨醇和木糖醇(糖醇彼此間的並用)的實施例11、甘露醇和葡萄糖(糖醇與單糖類的並用)的實施例12中，均與實施例1同樣表現出高經時穩定性和優異的被膜外觀。 Example 4 in which carbohydrate was changed to sorbitol (sugar alcohol), Example 5 in which it was also changed to mannitol (sugar alcohol), Example 6 in which it was changed to gluconolactone (monosaccharide derivative), and it was changed to glucose Example 7 of (monosaccharides), Example 8 changed to maltose (disaccharide), Example 11 changed to sorbitol and xylitol (combination of sugar alcohols with each other), mannitol and glucose (sugar alcohol and monosaccharides) In the example 12 of (combined use of ), all of them showed high stability over time and excellent appearance of the coating as in example 1.

以含有木糖醇的實施例1的催化溶液為基礎，向催化溶液中添加PVP(平均分子量4萬)作為水溶性聚合物的實施例9中，催化溶液的經時穩定性和鍍膜外觀與實施例1的評價相同。 Based on the catalytic solution of Example 1 containing xylitol, PVP (average molecular weight of 40,000) was added to the catalytic solution as a water-soluble polymer in Example 9, the time-dependent stability of the catalytic solution and the appearance and implementation of the coating The evaluation of Example 1 is the same.

以含有山梨醇的實施例4的催化溶液為基礎，向催化溶液中添 加PEG(平均分子量1萬)作為水溶性聚合物的實施例10中，催化溶液的經時穩定性和鍍膜外觀與實施例4的評價相同。 Based on the catalytic solution of Example 4 containing sorbitol, add to the catalytic solution In Example 10 in which PEG (average molecular weight 10,000) was added as a water-soluble polymer, the time-dependent stability of the catalytic solution and the appearance of the coating film were the same as the evaluation in Example 4.

另外，即使以實施例1、4或5為基礎，改變可溶性銅鹽、膠體穩定劑、還原劑(參照實施例13~19)，也表現出與各基礎實施例相同的高經時穩定性和優異的被膜外觀。 In addition, even if the soluble copper salt, colloidal stabilizer, and reducing agent (refer to Examples 13 to 19) were changed on the basis of Examples 1, 4, or 5, the same high-time stability and the same as in each basic example were exhibited. Excellent coating appearance.

相對於催化溶液設定為pH4.0的實施例1，在設定為弱鹼性側的pH9的實施例20中，同樣表現出高經時穩定性和優異的被膜外觀。 With respect to Example 1 where the catalytic solution was set to pH 4.0, Example 20 which was set to pH 9 on the weakly alkaline side also showed high stability over time and excellent film appearance.

實施例4和實施例11均為在催化劑賦予處理後進行酸洗再進行化學鍍銅處理之例，與其他實施例相比未特別出現被膜外觀上的差異，即使實施熱處理被膜面與基板之間也未發生變化，可確認高密合性。 Example 4 and Example 11 are both examples of pickling after the catalyst-imparting treatment and then electroless copper plating. Compared with other examples, there is no particular difference in the appearance of the coating, even if heat treatment is performed between the coating surface and the substrate There is no change, and high adhesion can be confirmed.

Claims (8)

一種化學鍍銅用之銅膠體催化溶液，是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銅膠體催化溶液，其特徵在於含有：(A)可溶性銅鹽；(B)還原劑；(C)選自一元羧酸類、羥基羧酸類、氨基羧酸額、以及多元羧酸類中的膠體穩定劑的至少一種；以及(D)選自葡萄糖、果糖、乳糖、麥芽酚、派拉丁糖、木糖、山梨醇、木糖醇、甘露醇、麥芽糖醇、赤蘚糖醇、還原澱粉糖漿、乳糖醇、還原派拉丁糖、以及葡萄糖酸內酯中的碳水化合物的至少一種。 A copper colloidal catalytic solution for electroless copper plating is a copper colloidal catalytic solution for contacting with a non-conductive substrate subjected to electroless copper plating for catalyst endowment, which is characterized by containing: (A) soluble copper salt; (B) reduction Agent; (C) at least one colloidal stabilizer selected from monocarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, and polycarboxylic acids; and (D) selected from glucose, fructose, lactose, maltol, pie At least one of carbohydrates in latinose, xylose, sorbitol, xylitol, mannitol, maltitol, erythritol, reduced starch syrup, lactitol, reduced palmitan, and gluconolactone. 如請求項1所述之化學鍍銅用之銅膠體催化溶液，其特徵在於，所述可溶性鹽(A)與所述膠體穩定劑(C)的含量莫耳比為A：C=1：0.03~1：35。 The copper colloidal catalytic solution for electroless copper plating according to claim 1, wherein the molar ratio of the soluble salt (A) to the colloidal stabilizer (C) is A: C=1: 0.03 ~1:35. 如請求項1或2所述之化學鍍銅用之銅膠體催化溶液，其特徵在於，所述化學鍍銅用銅膠體催化溶液還含有選自聚乙二醇、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合成類水溶性聚合物的至少一種。 The copper colloidal catalytic solution for electroless copper plating according to claim 1 or 2, characterized in that the copper colloidal catalytic solution for electroless copper plating further contains a polyethylene glycol, polypropylene glycol, polyvinylpyrrolidone, poly At least one of synthetic water-soluble polymers among vinyl alcohol, polypropylene amide, and polyethyleneimine. 如請求項1或2所述之化學鍍銅用之銅膠體催化溶液，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、以及亞磺酸類中的至少一種。 The copper colloidal catalytic solution for electroless copper plating according to claim 1 or 2, wherein the reducing agent (B) is selected from the group consisting of boron hydride compounds, amine boranes, hypophosphorous acids, aldehydes, and ascorbic acid At least one of hydrazines, polyhydric phenols, polyhydric naphthols, phenol sulfonic acids, naphthol sulfonic acids, and sulfinic acids. 如請求項1或2所述之化學鍍銅用之銅膠體催化溶液，其特徵在於， 所述膠體穩定劑(C)中的所述一元羧酸類為選自甲酸、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；所述羥基羧酸類為選自檸檬酸、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；所述氨基羧酸類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；所述多元羧酸類為選自琥珀酸、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 copper colloidal catalytic solution for electroless copper plating according to claim 1 or 2, characterized in that: The monocarboxylic acids in the colloidal stabilizer (C) are selected from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, hard acid At least one of fatty acids and salts thereof; the hydroxycarboxylic acids are selected from citric acid, tartaric acid, malic acid, gluconic acid, glucoheptonic acid, glycolic acid, lactic acid, trihydroxybutyric acid, ascorbic acid, iso At least one of citric acid, hydroxymalonic acid, glyceric acid, hydroxybutyric acid, leucine, citracallic acid, and their salts; the amino carboxylic acids are selected from hydroxyethyl ethylenediamine triacetic acid, di Ethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, ammoniatriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, iminodipropylene 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, dicarboxymethylglutamic acid, ornithine, cysteine, N,N-bis(2-hydroxyethyl At least one of glutamate, (S,S)-ethylenediamine succinic acid, and salts thereof; the polycarboxylic acids are selected from succinic acid, glutaric acid, malonic acid, adipic acid, At least one of oxalic acid, maleic acid, citraconic acid, itaconic acid, mesaconic acid, and salts thereof. 一種化學鍍銅方法，其特徵在於包括：(a)吸附促進步驟(預處理步驟)，將非導電性基板浸漬在含有吸附促進劑的液體中，所述吸附促進劑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中的至少一種；(b)催化劑賦予步驟，將非導電性基板浸漬在請求項1至5中任一項所述的銅膠體催化溶液中，使銅膠體粒子吸附在基板表面上；以及(c)化學鍍步驟，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 method of electroless copper plating, characterized in that it includes: (a) an adsorption promotion step (pretreatment step), immersing a non-conductive substrate in a liquid containing an adsorption promoter, the adsorption promoter selected from nonionic surface active At least one of an agent, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant; (b) a catalyst-imparting step of immersing the non-conductive substrate in any one of claims 1 to 5 In the copper colloidal catalytic solution, the copper colloidal particles are adsorbed on the surface of the substrate; and (c) an electroless plating step, using an electroless copper plating solution to form a copper coating on the substrate subjected to the adsorption treatment. 如請求項6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 method for electroless copper plating according to claim 6, wherein the adsorption accelerator in the step (a) is a cationic surfactant and/or an amphoteric surfactant. 一種銅被膜的非導電性基板，其係採用如請求項6或7所述之化學鍍銅方法所形成。 A copper-coated non-conductive substrate is formed by the electroless copper plating method described in claim 6 or 7.
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Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6268379B2 (en) * 2016-07-08 2018-01-31 石原ケミカル株式会社 Nickel colloidal catalyst solution for electroless nickel or nickel alloy plating and electroless nickel or nickel alloy plating method
JP6688183B2 (en) * 2016-07-15 2020-04-28 日本エレクトロプレイテイング・エンジニヤース株式会社 Pretreatment liquid for electroless plating
TWI638821B (en) * 2016-08-24 2018-10-21 李長榮化學工業股份有限公司 Metal catalyst, manufacturing method and applications thereof
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
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
CN110592564B (en) * 2019-09-29 2021-07-13 济南大学 Method for spraying mirror surface cupronickel
JP6843455B1 (en) * 2020-04-27 2021-03-17 石原ケミカル株式会社 Nickel colloid catalyst solution for electroless nickel or nickel alloy plating and electroless nickel or nickel alloy plating method
JP6858425B1 (en) * 2020-06-24 2021-04-14 石原ケミカル株式会社 Nickel colloid catalyst solution for electroless nickel or nickel alloy plating and electroless nickel or nickel alloy plating method
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
CN115418632B (en) * 2022-07-27 2023-11-17 深圳市富利特科技有限公司 High-speed high-ductility chemical copper suitable for horizontal line equipment and preparation method thereof
KR102643735B1 (en) 2023-05-08 2024-03-06 가드넥(주) Graphite sheet with excellent heat dissipation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4261747A (en) * 1978-12-06 1981-04-14 Nathan Feldstein Dispersions for activating non-conductors for electroless plating
TW200825206A (en) * 2006-08-03 2008-06-16 Basf Ag Process for application of metal layer on a substrate

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4339476A (en) * 1978-08-17 1982-07-13 Nathan Feldstein Dispersions for activating non-conductors for electroless plating
JPS6123762A (en) * 1984-07-09 1986-02-01 Nec Corp Copper colloidal catalytic solution for electroless plating and its manufacture
JPH0613753B2 (en) * 1988-09-29 1994-02-23 三晃特殊金属工業株式会社 Method for producing solution containing fine metal body used for electroless plating
JP3337802B2 (en) 1993-12-28 2002-10-28 日本リーロナール株式会社 Direct plating method by metallization of copper (I) oxide colloid
JP3890542B2 (en) 1997-02-17 2007-03-07 奥野製薬工業株式会社 Method for manufacturing printed wiring board
GB0025989D0 (en) * 2000-10-24 2000-12-13 Shipley Co Llc Plating catalysts
JP4143385B2 (en) 2002-03-05 2008-09-03 株式会社大和化成研究所 Pretreatment liquid for imparting catalyst for electroless plating, pretreatment method using the liquid, electroless plating film and / or plating coating produced using the method
JP2003313670A (en) 2002-04-22 2003-11-06 C Uyemura & Co Ltd Method for forming electroless plating film
JP3925724B2 (en) 2003-11-13 2007-06-06 株式会社黒坂鍍金工業所 Surface treatment method for non-conductive materials
JP4617445B2 (en) 2005-04-22 2011-01-26 奥野製薬工業株式会社 Plating method for resin molding
DE102010012204B4 (en) 2010-03-19 2019-01-24 MacDermid Enthone Inc. (n.d.Ges.d. Staates Delaware) Improved process for direct metallization of non-conductive substrates
JP5570285B2 (en) 2010-04-19 2014-08-13 株式会社日本表面処理研究所 Catalyst aqueous solution used in electroless plating method, method for preparing the catalyst aqueous solution, electroless plating method using the catalyst aqueous solution, and metal object to be plated provided with a metal film formed using the electroless plating method
US8591637B2 (en) 2010-12-14 2013-11-26 Rohm And Haas Electronic Materials Llc Plating catalyst and method
US8591636B2 (en) * 2010-12-14 2013-11-26 Rohm And Haas Electronics Materials Llc Plating catalyst and method
JP6013753B2 (en) * 2012-03-30 2016-10-25 タキロン株式会社 Eaves bending joint
JP6047713B2 (en) * 2012-05-11 2016-12-21 石原ケミカル株式会社 Electroless copper plating method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4261747A (en) * 1978-12-06 1981-04-14 Nathan Feldstein Dispersions for activating non-conductors for electroless plating
TW200825206A (en) * 2006-08-03 2008-06-16 Basf Ag Process for application of metal layer on a substrate

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