TWI597384B - Electroless nickel or electroless nickel alloy pretreatment solution and plating method - Google Patents

Electroless nickel or electroless nickel alloy pretreatment solution and plating method Download PDF

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TWI597384B
TWI597384B TW102100675A TW102100675A TWI597384B TW I597384 B TWI597384 B TW I597384B TW 102100675 A TW102100675 A TW 102100675A TW 102100675 A TW102100675 A TW 102100675A TW I597384 B TWI597384 B TW I597384B
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nickel
electroless nickel
pretreatment liquid
electroless
alloy
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TW102100675A
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TW201335422A (en
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Tomio Kudo
Ei Uchida
Kaoru Tanaka
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Ishihara Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
    • C23C18/206—Use of metal other than noble metals and tin, e.g. activation, sensitisation with metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
    • C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel

Description

無電鍍鎳或無電鍍鎳合金用的前處理液及電鍍方法 Pretreatment liquid and electroplating method for electroless nickel or electroless nickel alloy

本發明是關於無電鍍鎳(electroless nickel plating)或無電鍍鎳合金(electroless nickel alloy plating)用的前處理液(pretreatment liquid)及電鍍方法(plating method)，提供一種可僅藉由使非導電性基板接觸前處理液的簡便的處理，在非導電性基板上平順地施以無電鍍鎳或無電鍍鎳合金之前處理液及電鍍方法。 The present invention relates to a pretreatment liquid and a plating method for electroless nickel plating or electroless nickel alloy plating, which can provide a non-conductivity only by The substrate is treated with a pretreatment liquid before the treatment, and the electroless nickel or electroless nickel alloy pretreatment liquid and plating method are applied smoothly on the non-conductive substrate.

為了在由玻璃環氧樹脂(glass epoxy resin)、玻璃聚醯亞胺樹脂(glass polyimide resin)、環氧樹脂(epoxy resin)、聚醯亞胺樹脂(polyimide resin)、聚碳酸酯樹脂(polycarbonate resin)、ABS樹脂(Acrylonitrile-Butadiene-Styrene resin：丙烯腈-丁二烯-苯乙烯樹脂)、PET樹脂(polyethylene terephthalate resin：聚乙烯對苯二甲酸酯樹脂)構成的樹脂基板，以及玻璃基板、陶瓷基板等的非導電性基板上施以無電鍍鎳，首先需使銀、鈀、鉑、銅等的特定的金屬吸附於該基板上並以銀、鈀、鉑、銅等的特定的金屬當作催化核(catalytic nuclei)。然後，透過無電鍍鎳液使鎳塗膜析出於賦予催化活性(catalytic activity)的非導電性基板上。 In order to be used in a glass epoxy resin, a glass polyimide resin, an epoxy resin, a polyimide resin, a polycarbonate resin a resin substrate comprising ABS resin (Acrylonitrile-Butadiene-Styrene resin), PET resin (polyethylene terephthalate resin), and a glass substrate. Electroless nickel is applied to a non-conductive substrate such as a ceramic substrate. First, a specific metal such as silver, palladium, platinum, or copper is adsorbed on the substrate, and a specific metal such as silver, palladium, platinum, or copper is used as a specific metal. Catalytic nucleus Nuclei). Then, the nickel coating film is deposited on the non-conductive substrate imparting catalytic activity through the electroless nickel plating solution.

若顯示在透過銀、鈀等的貴金屬系或銅系的藥劑對基板進行處理後，進行無電鍍鎳之習知技術，則如下所示。 The conventional technique of performing electroless nickel plating after the treatment of the substrate by a noble metal or copper-based drug such as silver or palladium is shown below.

(1)、專利文獻1 (1) Patent Document 1

使銅化合物(硫酸銅、硝酸銅等：段落9)的溶液接觸基板上，進行乾燥，浸漬於還原液(包含硼氫化合物(borohydride)、聯氨(hydrazine)等的液體：段落12)，在基板上形成銅微粒子後，進行無電鍍鎳(請求項1~4、段落13)。銅微粒子的大小一般為300nm以下，大部分為100~200nm左右(段落12)。 The solution of the copper compound (copper sulfate, copper nitrate, etc.: paragraph 9) is brought into contact with the substrate, dried, and immersed in a reducing solution (a liquid containing a borohydride or a hydrazine: paragraph 12). After the copper fine particles are formed on the substrate, electroless nickel plating is performed (requests 1 to 4, paragraph 13). The size of the copper microparticles is generally 300 nm or less, and most of them are about 100 to 200 nm (paragraph 12).

(2)、專利文獻2 (2) Patent Document 2

使用銀化合物，與具有比銀還低的氧化還原電位的金屬化合物(二價的錫、鐵、鈷或三價的鈦等；當作還原劑作用(請求項3、段落19))，與含有羧酸類、氨基羧酸(aminocarboxylic acid)類、縮合磷酸(condensed phosphoric acid)類等(當作錯合劑(complexing agent)作用)的無電電鍍用催化劑組成物，在非導電性基板上賦予銀催化劑後，在非導電性基板上進行無電鍍鎳(請求項7、段落39)。在上述無電電鍍用催化劑組成物中，在包含錯合劑的溶液中銀化合物被還原且形成有銀膠體(silver colloid)(段落12)。 A silver compound is used, and a metal compound having a lower oxidation-reduction potential than silver (divalent tin, iron, cobalt or trivalent titanium; etc.; acting as a reducing agent (request 3, paragraph 19)), and a catalyst composition for electroless plating of a carboxylic acid, an aminocarboxylic acid, a condensed phosphoric acid or the like (as a complexing agent), after a silver catalyst is applied to a non-conductive substrate Electroless nickel plating is performed on a non-conductive substrate (claim 7 and paragraph 39). In the above catalyst composition for electroless plating, a silver compound is reduced and a silver colloid is formed in a solution containing a binder (paragraph 12).

(3)、專利文獻3 (3) Patent Document 3

在非導電性基板上以鈀-錫賦予催化劑(請求項1~3、 段落28)，進行無電鍍鎳(請求項4、段落27)。 Palladium-tin is applied to the non-conductive substrate (Requests 1 to 3, Paragraph 28), electroless nickel plating (request item 4, paragraph 27).

(4)、專利文獻4~7 (4) Patent Literature 4~7

在專利文獻4中，透過包含錫離子的銀膠體將非導電性基板的表面活性化，施以無電鍍鎳(請求項1)。在專利文獻5中，透過鈀-錫將被電鍍物的表面活性化，施以無電鍍鎳(請求項1~2)。在專利文獻6中，將鈀系的電鍍介質(plating medium)塗佈於合成樹脂成型品的表面上並使其乾燥後，施以無電鍍鎳(請求項1~2、6)。在專利文獻7中，不是關於無電鍍鎳，而是關於無電鍍鎳合金的技術，在非導體的表面透過鈀賦予催化劑後，進行無電鍍銅-鎳(請求項1)。 In Patent Document 4, the surface of the non-conductive substrate is activated by a silver colloid containing tin ions, and electroless nickel plating is applied (claim 1). In Patent Document 5, the surface of the object to be plated is activated by palladium-tin, and electroless nickel plating is performed (requests 1 to 2). In Patent Document 6, a palladium-based plating medium is applied onto the surface of a synthetic resin molded article and dried, and then electroless nickel is applied (requests 1 to 2 and 6). In Patent Document 7, it is not related to electroless nickel plating, but a technique of electroless nickel plating, and electroless copper-nickel (Recommended Item 1) is carried out after passing a palladium-imparting catalyst on the surface of a non-conductor.

無電鍍鎳的前處理若不是透過上述貴金屬系而是可透過鎳系的藥劑進行處理的話，則在成本上有利。因此，若舉出不是透過貴金屬系或銅系的藥劑而是透過鎳鹽(nickel salt)等的鎳系的藥劑對非導電性基板進行處理後，施以無電鍍鎳之習知技術，則如下所示。 The pretreatment of electroless nickel plating is advantageous in terms of cost if it is treated by a nickel-based chemical agent instead of passing through the noble metal system. Therefore, the non-conductive substrate is treated by a nickel-based drug such as a nickel salt, which is not a noble metal or a copper-based agent, and is subjected to electroless nickel plating. Shown.

(1)、專利文獻8 (1) Patent Document 8

使被電鍍物(金屬、樹脂、玻璃、陶瓷；段落11)接觸包含錳鹽(manganese salt)(硫酸錳、醋酸錳、氯化錳等；段落14)的水溶液(賦予催化活性(catalytic activity)；段落16)。接著，使其接觸包含鎳鹽的水溶液，使其接觸包含還原劑的水溶液後，施以無電鍍鎳(請求項1、5、段落43)。 The electroplated material (metal, resin, glass, ceramic; paragraph 11) is contacted with an aqueous solution containing a manganese salt (manganese sulfate, manganese acetate, manganese chloride, etc.; paragraph 14) (giving a catalytic activity; Paragraph 16). Next, an aqueous solution containing a nickel salt is brought into contact with an aqueous solution containing a reducing agent, and then electroless nickel is applied (requests 1, 5, and 43).

(2)、專利文獻9 (2) Patent Document 9

使非導電性基材接觸包含鎳及銅的混合氫氧化物的膠體液並賦予催化劑，浸漬於含強還原劑的液體，對該混合氫氧化物進行還原處理。透過與無電電鍍液相同的還原劑清洗非導電性基材，不進行水洗而進行無電鍍鎳(請求項1、4)。據此，防止在對非導電性基材的表面進行水洗時產生的混合氫氧化物的氧化(段落4)。 The non-conductive substrate is brought into contact with a colloidal liquid containing a mixed hydroxide of nickel and copper, and is supplied to a catalyst, and immersed in a liquid containing a strong reducing agent, and the mixed hydroxide is subjected to a reduction treatment. The non-conductive substrate was washed with the same reducing agent as the electroless plating solution, and electroless nickel plating was performed without washing with water (Requirements 1 and 4). According to this, oxidation of the mixed hydroxide which is generated when the surface of the non-conductive substrate is washed with water is prevented (paragraph 4).

(3)、專利文獻10 (3) Patent Document 10

在具有微小的面積與深度的井(well)(段落10)使用包含鎳鹽的鹼水溶液(具體上包含硫酸鎳及硫酸銨的鹼水溶液；段落16)使鎳核產生(段落16)。將該鎳核浸漬於鎳浴或對鎳具有催化活性的金屬浴(metal bath)，形成鎳塗膜或鈷、鎳系塗膜等(段落20)(請求項1)。上述無電沈積(electroless deposition)被推測為：與一般的無電沈積其沉積機制(deposition mechanism)不同，伴隨著基板之矽等的無機物的陽極反應，鎳以特異地析出的機制進行(段落13)。 A nickel nucleus is produced in a well having a small area and depth (paragraph 10) using an aqueous alkali solution containing a nickel salt (specifically, an aqueous alkali solution containing nickel sulfate and ammonium sulfate; paragraph 16) (paragraph 16). The nickel core is immersed in a nickel bath or a metal bath having catalytic activity for nickel to form a nickel coating film or a cobalt or nickel-based coating film (paragraph 20) (claim 1). The above electroless deposition is presumed to be different from the deposition mechanism of the general electroless deposition, and the nickel is preferentially precipitated by the anodic reaction of the inorganic substance such as the substrate (paragraph 13).

[專利文獻1]日本國特開平6-256961號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 6-256961

[專利文獻2]日本國特開2004-190066號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-190066

[專利文獻3]日本國特開2001-323383號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-323383

[專利文獻4]日本國特表2004-513229號公報 [Patent Document 4] Japanese National Patent Publication No. 2004-513229

[專利文獻5]日本國特開2002-256441號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2002-256441

[專利文獻6]日本國特開平5-320922號公報 [Patent Document 6] Japanese Patent Publication No. 5-320922

[專利文獻7]日本國特公平7-091670號公報 [Patent Document 7] Japanese National Patent No. 7-091670

[專利文獻8]日本國特開2002-309375號公報 [Patent Document 8] Japanese Patent Laid-Open Publication No. 2002-309375

[專利文獻9]日本國特開2002-047574號公報 [Patent Document 9] Japanese Patent Laid-Open Publication No. 2002-047574

[專利文獻10]日本國特開2004-115839號公報 [Patent Document 10] Japanese Patent Laid-Open Publication No. 2004-115839

若查看透過鎳系的藥劑對基板上進行處理的上述習知技術的話，專利文獻8~9原理上為使鎳鹽或氧化鎳接觸基板，透過還原劑將附著於基板的鎳鹽等還原成金屬鎳並賦予催化劑的技術。即使是專利文獻10，也在鎳核的產生使用包含硫酸鎳的鹼水溶液。因此，專利文獻8~10都不是直接使用金屬鎳對基板賦予催化核。 In view of the above-described conventional technique of treating a substrate by a nickel-based drug, Patent Documents 8 to 9 basically cause a nickel salt or a nickel oxide to contact a substrate, and reduce a nickel salt or the like adhering to the substrate to a metal through a reducing agent. Nickel and the technology of the catalyst. Even in Patent Document 10, an aqueous alkali solution containing nickel sulfate is used for the production of a nickel core. Therefore, in Patent Documents 8 to 10, neither of the metal nickel is directly used to impart a catalytic core to the substrate.

當以金屬鎳對非導電性基板(例如樹脂基板)賦予催化活性時，將該基板浸漬於鎳粉末的混合液被考慮。但是，即使僅將平均粒徑為μm級(例如數十μm)的鎳粉末混合、攪拌於水或有機溶媒中，也很難成為均勻的分散相(dispersed phase)。因此，即使將樹脂基板浸漬於該混合液後，浸漬於無電鍍鎳液，鎳塗膜也不析出。 When a catalytic activity is imparted to a non-conductive substrate (for example, a resin substrate) with metallic nickel, a mixed solution in which the substrate is immersed in nickel powder is considered. However, even if only nickel powder having an average particle diameter of μm (for example, several tens of μm) is mixed and stirred in water or an organic solvent, it is difficult to form a uniform dispersed phase. Therefore, even if the resin substrate is immersed in the mixed solution and immersed in the electroless nickel plating solution, the nickel coating film does not precipitate.

本申請人先在日本國特願2011-248664號公報中提出了：藉由調製將具有250nm以下的特定粒徑的銅奈米粒子混合、攪拌並使其均勻地分散於水或有機溶媒中之前處理液，預先將非導電性基板浸漬於該前處理液後(前處理之後)，浸漬於無電鍍銅液，在基板上形成均質的銅塗膜之無電鍍銅方法。 Japanese Patent Application No. 2011-248664 proposes that the copper nanoparticles having a specific particle diameter of 250 nm or less are mixed, stirred, and uniformly dispersed in water or an organic solvent by preparation. The treatment liquid is an electroless copper plating method in which a non-conductive substrate is immersed in the pre-treatment liquid (after pre-treatment), and immersed in an electroless copper plating solution to form a homogeneous copper coating film on the substrate.

因此，構思了將使用銅奈米粒子的無電鍍銅方法的技術(以下稱為先行技術)適用於無電鍍鎳。但是，鎳的金屬 粒子的情形，微細粒子的舉動與銅奈米粒子不同。例如即使將微細化到粒徑400nm的奈米級(nano-order)的粒子混合於有機溶媒或水，得到均勻的分散相也不像銅奈米粒子般簡單。也有受到鎳粒子的含量或溶媒的種類等的影響，不容易使其均勻地分散的情形。即使使用分散劑(dispersant)該傾向也不太有變化。因此，即使將基板浸漬於混合了粒徑400nm的微細鎳粒子的液體後進行無電鍍鎳，也與μm級的鎳粉末一樣，未達到鎳塗膜的析出。 Therefore, a technique (hereinafter referred to as a prior art) in which an electroless copper plating method using copper nanoparticles is conceived is applied to electroless nickel plating. However, nickel metal In the case of particles, the behavior of fine particles is different from that of copper nanoparticles. For example, even if a nano-order particle having a particle diameter of 400 nm is mixed with an organic solvent or water, a uniform dispersed phase is not as simple as a copper nanoparticle. There is also a case where the content of the nickel particles or the type of the solvent is affected, and it is not easy to uniformly disperse. This tendency does not change even with the use of dispersant. Therefore, even if the substrate is immersed in a liquid in which fine nickel particles having a particle diameter of 400 nm are mixed, and electroless nickel plating is performed, the precipitation of the nickel coating film is not achieved as in the case of the nickel powder of the μm grade.

如此，雖然有透過還原反應在非導電性基板上賦予鎳催化劑的技術，但無直接賦予金屬鎳催化劑的技術。鎳的微細粒子顯示與銅奈米粒子不同的舉動，得到均勻的分散相不像銅奈米粒子般簡單。因此，本發明是鑑於上述習知技術的問題點，其目的為提供一種能以簡便的處理直接地賦予非導電性基板鎳催化劑，在非導電性基板的全面均質地形成良好的鎳塗膜或鎳合金塗膜之無電鍍鎳或無電鍍鎳合金用的前處理液及電鍍方法。 As described above, there is a technique of imparting a nickel catalyst to a non-conductive substrate by a reduction reaction, but there is no technique for directly imparting a metal nickel catalyst. The fine particles of nickel show a different behavior from the copper nanoparticles, and it is as simple as obtaining a uniform dispersed phase unlike copper nanoparticles. Accordingly, the present invention has been made in view of the above problems in the prior art, and an object thereof is to provide a nickel coating film which can directly impart a non-conductive substrate to a non-conductive substrate by a simple process, and which can form a uniform nickel coating film or a non-conductive substrate. Pretreatment liquid and electroplating method for electroless nickel or electroless nickel alloy for nickel alloy coating.

鎳的微細粒子顯示與銅奈米粒子不同的舉動。因此，為了達成上述目的，檢討了在前處理液的調製時，添加於溶媒的鎳粒子的粒徑的變化是否直接關係到催化活性的表現程度。當使用了μm級的鎳粉末時，即使混合於溶媒也無法得到鎳粒子的穩定的分散系。因此，即使將樹脂基板等的非導電性基板浸漬於該混合系並施以無電電鍍液，鎳塗膜也不析出。當將鎳粒子的粒徑微細化到300nm時，與400nm的情形相同，無法得到良好的分散液，無鎳塗膜的 析出。在先行技術的無電鍍銅方法中，含有於前處理液的銅奈米粒子的粒徑的容許上限值為250nm。仿照先行技術的無電鍍銅方法，更將鎳粒子的粒徑微細化，重複嘗試了前處理與無電鍍鎳。 The fine particles of nickel show a different behavior from the copper nanoparticles. Therefore, in order to achieve the above object, it is reviewed whether the change in the particle diameter of the nickel particles added to the solvent during the preparation of the pretreatment liquid is directly related to the degree of expression of the catalytic activity. When a nickel powder of a μm grade is used, a stable dispersion of nickel particles cannot be obtained even if it is mixed with a solvent. Therefore, even if a non-conductive substrate such as a resin substrate is immersed in the mixed system and an electroless plating solution is applied, the nickel coating film does not precipitate. When the particle diameter of the nickel particles is made fine to 300 nm, as in the case of 400 nm, a good dispersion liquid cannot be obtained, and the nickel-free coating film is not obtained. Precipitate. In the prior art electroless copper plating method, the allowable upper limit of the particle diameter of the copper nanoparticles contained in the pretreatment liquid is 250 nm. Following the electroless copper plating method of the prior art, the particle size of the nickel particles was further refined, and the pretreatment and the electroless nickel plating were repeatedly tried.

其結果，藉由更將鎳粒子的粒徑微細化到超過銅奈米粒子的情形的容許上限值，發現以下的點而完成了本發明。若更進一步將鎳粒子微細化，則可在非導電性基板的全面析出均質的鎳塗膜。即使是施以無電鍍鎳合金的情形，也能在非導電性基板的全面析出均質的鎳合金塗膜。而且，在調製前處理液時，使用分散劑或不使用分散劑都同樣地能析出利用電鍍形成的塗膜。 As a result, the present invention has been completed by further refining the particle diameter of the nickel particles to the allowable upper limit of the case where the copper nanoparticles are more than the copper nanoparticles. When the nickel particles are further refined, a uniform nickel coating film can be deposited on the non-conductive substrate. Even in the case of applying an electroless nickel alloy, a homogeneous nickel alloy coating film can be deposited on the non-conductive substrate. Further, when the pretreatment liquid is prepared, a coating film formed by electroplating can be precipitated in the same manner using a dispersant or a dispersant.

也就是說，本發明為一種無電鍍鎳或無電鍍鎳合金用的前處理液，接觸施以無電鍍鎳或無電鍍鎳合金的非導電性樹脂基板並進行前處理，使鎳粒子分散於溶媒中，其特徵為：前述鎳粒子的平均粒徑為1~200nm，前述鎳粒子之對該前處理液的含量為40~60重量%，直接地將前述鎳粒子賦予前述非導電性樹脂基板。 That is, the present invention is a pretreatment liquid for electroless nickel or electroless nickel alloy, and is contacted with a non-electroconductive resin substrate coated with electroless nickel or electroless nickel alloy and pretreated to disperse nickel particles in a solvent. In the above, the nickel particles have an average particle diameter of 1 to 200 nm, and the content of the nickel particles to the pretreatment liquid is 40 to 60% by weight, and the nickel particles are directly supplied to the non-conductive resin substrate.

依照上述本發明，可考慮為藉由包含於前處理液的鎳粒子的粒徑以200nm以下，對非導電性基板的表面的定錨效應(anchoring effect)顯現。可透過該定錨效應，直接地將鎳粒子催化劑賦予非導電性基板。 According to the present invention described above, it is conceivable that the anchoring effect on the surface of the non-conductive substrate is exhibited by the particle diameter of the nickel particles contained in the pretreatment liquid being 200 nm or less. The nickel particle catalyst can be directly imparted to the non-conductive substrate by the anchoring effect.

前述溶媒包含在常壓下沸點250℃以下及閃點(flash point)10℃以上的有機溶媒(organic solvent)較佳。 The solvent contains an organic solvent having a boiling point of 250 ° C or less and a flash point of 10 ° C or more at normal pressure.

有機溶媒的具體例可舉出：選自於由醇類 (alcohols)、乙二醇醚類(glycol ethers)、極性脂環烴類(polar alicyclic hydrocarbons)、醯胺類(amides)、亞碸類(sulfoxides)所組成的群中的至少一種。 Specific examples of the organic solvent include: selected from alcohols At least one of a group consisting of (alcohols), glycol ethers, polar alicyclic hydrocarbons, amides, and sulfoxides.

有機溶媒的具體例可舉出：選自於由異丙醇(isopropyl alcohol)、異丁醇(isobutyl alcohol)、3-甲氧基-3-甲基-1-丁醇(3-methoxy-3-methyl-1-butanol)、1-辛醇(1-octanol)、萜品醇(terpineol)、環己醇(cyclohexanol)、乙二醇(ethylene glycol)、丙二醇(propylene glycol)、丙二醇甲醚(propylene glycol monomethyl ether)、2-丁氧基乙酸乙酯(2-butoxyethyl acetate)、乙二醇丁醚(ethylene glycol butyl ether)、丙二醇甲醚醋酸酯(propylene glycol monomethyl ether acetate)、乙二醇***醋酸脂(diethylene glycol monoethyl ether acetate)、2-乙氧基乙酸乙酯(2-ethoxyethyl acetate)、乙二醇二乙酸酯(ethylene glycol diacetate)、N,N-二甲基甲醯胺(N,N-dimethylformamide)、二甲亞碸(dimethyl sulfoxide)、N-甲基吡咯酮(N-methyl-2-pyrolidone)、丙烯碳酸鹽(propylene carbonate)所組成的群中的至少一種。 Specific examples of the organic solvent include: isopropyl alcohol, isobutyl alcohol, 3-methoxy-3-methyl-1-butanol (3-methoxy-3) -methyl-1-butanol), 1-octanol, terpineol, cyclohexanol, ethylene glycol, propylene glycol, propylene glycol methyl ether Propylene glycol monomethyl ether), 2-butoxyethyl acetate, ethylene glycol butyl ether, propylene glycol monomethyl ether acetate, ethylene glycol ether Diethylene glycol monoethyl ether acetate, 2-ethoxyethyl acetate, ethylene glycol diacetate, N,N-dimethylformamide (N At least one selected from the group consisting of N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrolidone, and propylene carbonate.

前述溶媒包含水也可以，此情形的前處理液的pH為3.0~10.0較佳。 The solvent may be water. The pH of the pretreatment liquid in this case is preferably 3.0 to 10.0.

更包含使前述鎳粒子分散於前述溶媒中的分散劑，前述分散劑之對前述鎳粒子的含量為3~70重量%，前述分散 劑為至少具有一個磺酸基、羧基、羥基或磷酸基的分子量200~10000的化合物較佳。 Further, the present invention further includes a dispersing agent that disperses the nickel particles in the solvent, and the dispersing agent has a content of the nickel particles of 3 to 70% by weight, and the dispersion The agent is preferably a compound having a molecular weight of 200 to 10,000 having at least one sulfonic acid group, carboxyl group, hydroxyl group or phosphoric acid group.

前述分散劑的具體例可舉出：選自於由胺、聚酯、羧酸、羧酸鹽(carboxylate)、硫酸鹽(sulfate)、磺酸(sulfonic acid)、磺基琥珀酸(sulfosuccinic acid)、磷酸酯(phosphate ester)及胺、聚酯、羧酸、羧酸鹽、硫酸鹽、磺酸、磺基琥珀酸、磷酸酯的鹽，烷基銨鹽(alkyl ammonium salt)、直鏈烷基醚(straight chain alkyl ether)、聚醚(polyether)、聚氨酯(polyurethane)、聚丙烯酸酯(polyacrylate)所組成的群中的至少一種。 Specific examples of the dispersant include: an amine, a polyester, a carboxylic acid, a carboxylate, a sulfate, a sulfonic acid, or a sulfosuccinic acid. , phosphate esters and amines, polyesters, carboxylic acids, carboxylates, sulfates, sulfonic acids, sulfosuccinic acids, phosphate salts, alkyl ammonium salts, linear alkyl groups At least one of a group consisting of a straight chain alkyl ether, a polyether, a polyurethane, and a polyacrylate.

前述分散劑的具體例可舉出：選自於由聚氧乙烯苯乙烯化二苯醚硫酸銨(ammonium polyoxyethylene styrenated phenyl ether sulfate)、聚氧乙烯十三醚磷酸酯(polyoxyethylene tridecyl ether phosphate ester)、聚氧乙烯烷基醚磷酸酯單乙醇胺鹽(polyoxyethylene alkyl ether phosphate ester monoethanolamine salt)、聚氧乙烯烷基磺基琥珀酸二鈉(disodium polyoxyethylene alkyl sulfosuccinate)、直鏈型烷基苯磺酸鈉(sodium linear alkyl benzene sulfonate)、萘磺酸鈉甲醛縮合物(sodium naphthalenesulfonate formaldehyde condensate)、聚烷基多胺環氧烷加成物(polyalkylene polyamine alkylene oxide adduct)、聚烷基聚亞胺環氧烷加成物(polyalkylene polyimine alkylene oxide adduct)、聚 乙烯吡咯烷酮(polyvinylpyrrolidone)、聚乙二醇(polyethylene glycol)、聚丙二醇(polypropylene glycol)、聚乙烯醇(polyvinyl alcohol)、多磷酸(polyphosphoric acid)所組成的群中的至少一種。 Specific examples of the dispersing agent include: polyoxyethylene styrenated phenyl ether sulfate, polyoxyethylene tridecyl ether phosphate ester, and polyoxyethylene tridecyl ether phosphate ester. Polyoxyethylene alkyl ether phosphate ester monoethanolamine salt, disodium polyoxyethylene alkyl sulfosuccinate, linear sodium alkylbenzene sulfonate (sodium) Linear alkyl benzene sulfonate), sodium naphthalenesulfonate formaldehyde condensate, polyalkylene polyamine alkylene oxide adduct, polyalkylene polyalkylene oxide alkylene oxide Polyalkylene polyimine alkylene oxide adduct At least one of a group consisting of polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, and polyphosphoric acid.

施以無電鍍鎳合金時的鎳合金例如選自於由鎳銅合金、鎳鈷合金、鎳錫合金所組成的群的合金。 The nickel alloy to which the electroless nickel alloy is applied is, for example, an alloy selected from the group consisting of nickel-copper alloy, nickel-cobalt alloy, and nickel-tin alloy.

本發明為一種電鍍方法，其特徵包含：將非導電性樹脂基板浸漬於上述的前處理液，直接地使包含於該前處理液的鎳粒子催化劑賦予該非導電性樹脂基板表面上之前處理程序；在被進行了前處理的前述非導電性樹脂基板上使用無電鍍鎳液或無電鍍鎳合金液形成鎳塗膜或鎳合金塗膜之無電電鍍程序。 The present invention provides a plating method comprising: immersing a non-conductive resin substrate in the pretreatment liquid; and directly applying a nickel particle catalyst contained in the pretreatment liquid to a surface of the non-conductive resin substrate; An electroless plating process for forming a nickel coating film or a nickel alloy coating film on an electroless nickel plating solution or an electroless nickel plating alloy on the non-conductive resin substrate subjected to pretreatment.

依照上述本發明，可考慮為因包含於前處理液的鎳粒子的粒徑以200nm以下，故對非導電性基板的表面的定錨效應顯現。可透過該定錨效應，直接地將鎳粒子催化劑賦予非導電性基板。 According to the present invention described above, it is conceivable that the anchoring effect on the surface of the non-conductive substrate is exhibited because the particle diameter of the nickel particles contained in the pretreatment liquid is 200 nm or less. The nickel particle catalyst can be directly imparted to the non-conductive substrate by the anchoring effect.

如上述依照本發明，因直接地將鎳奈米粒子催化劑賦予非導電性基板，故能以簡便的處理在該非導電性基板的全面均質地形成良好的鎳塗膜或鎳合金塗膜。 According to the present invention, since the nickel nanoparticle catalyst is directly applied to the non-conductive substrate, a favorable nickel coating film or nickel alloy coating film can be formed uniformly on the non-conductive substrate in a simple manner.

圖1是比較例3之外觀照片。 1 is a photograph of the appearance of Comparative Example 3.

圖2是實施例3之外觀照片。 2 is a photograph of the appearance of Example 3.

本發明為接觸施以無電鍍鎳或無電鍍鎳合金的非導電性基板並進行前處理，以規定的濃度使適當地微細化的鎳粒子分散於溶媒中的前處理液。本發明為在將非導電性基板浸漬於該前處理液並賦予鎳的催化劑後，對該非導電性基板施以無電鍍鎳或無電鍍鎳合金的方法。 The present invention relates to a pretreatment liquid in which a non-electroconductive substrate coated with an electroless nickel or an electroless nickel alloy is subjected to pretreatment and a suitably finened nickel particle is dispersed in a solvent at a predetermined concentration. The present invention is a method in which an electroless nickel or an electroless nickel alloy is applied to the non-conductive substrate after the non-conductive substrate is immersed in the pre-treatment liquid and a catalyst for nickel is applied.

非導電性基板不限定，惟具體上是由玻璃環氧樹脂、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樹脂構成的樹脂基板，以及玻璃基板、陶瓷基板等。在本發明所謂的鍍鎳合金是意味著像鎳銅合金、鎳鈷合金等，基本上是鎳與對方的金屬的合金的電鍍。因此，例如鍍鎳磷合金及鍍鎳硼合金等因鎳的對方不是金屬，故被分類成鍍鎳。 The non-conductive substrate is not limited, but specifically, a resin substrate composed of a glass epoxy resin, a glass polyimide resin, an epoxy resin, a polyimide resin, a polycarbonate resin, an ABS resin, or a PET resin, and Glass substrate, ceramic substrate, and the like. The so-called nickel-plated alloy in the present invention means electroplating of an alloy of nickel and a metal other than nickel-copper alloy, nickel-cobalt alloy or the like. Therefore, for example, nickel-plated phosphorus alloy and nickel-plated boron alloy are classified as nickel plating because the nickel is not a metal.

前處理液是由溶媒與鎳粒子構成。此外，在前處理液的調製時，更使用分散劑或不使用分散劑均可。含有於前處理液的鎳粒子為平均粒徑：1~200nm，較佳為平均粒徑：1~150nm，更佳為平均粒徑1~130nm，最佳為平均粒徑：1~100nm的微細粒子。在以下的說明中稱本發明的鎳粒子為鎳奈米粒子。滿足該粒徑的鎳奈米粒子可容易由市面上的販賣品得到。 The pretreatment liquid is composed of a solvent and nickel particles. Further, in the preparation of the pretreatment liquid, a dispersant may be used or no dispersant may be used. The nickel particles contained in the pretreatment liquid have an average particle diameter of 1 to 200 nm, preferably an average particle diameter of 1 to 150 nm, more preferably an average particle diameter of 1 to 130 nm, and most preferably an average particle diameter of 1 to 100 nm. particle. In the following description, the nickel particles of the present invention are referred to as nickel nanoparticles. Nickel nanoparticles which satisfy this particle size can be easily obtained from commercially available products.

使用非常微細的鎳奈米粒子此點為本發明的最有特徵的部分，若以包含200nm以下的鎳奈米粒子的前處理液賦 予非導電性基板催化活性，則不限於無電鍍鎳，也能施以無電鍍鎳合金。 The use of very fine nickel nanoparticles is the most characteristic part of the invention, if it is a pretreatment liquid containing nickel nanoparticles of 200 nm or less. The electrocatalytic activity of the non-conductive substrate is not limited to electroless nickel plating, and an electroless nickel alloy can also be applied.

若鎳奈米粒子的平均粒徑超過200nm，則即使將基板浸漬於混合了鎳奈米粒子的液體，催化活性也不太能期待。因此，鎳奈米粒子的平均粒徑需為200nm以下。如此可推定在已微細化的鎳的金屬粒子中，藉由定錨效應使鎳的催化核賦予到非導電性基板的表面上被促進。 When the average particle diameter of the nickel nanoparticles exceeds 200 nm, even if the substrate is immersed in a liquid in which nickel nanoparticles are mixed, the catalytic activity is not expected. Therefore, the average particle diameter of the nickel nanoparticles is required to be 200 nm or less. As described above, it is presumed that in the metal particles of the finened nickel, the catalytic core of nickel is imparted to the surface of the non-conductive substrate by the anchoring effect.

當在分散劑的共存下將鎳奈米粒子混合於溶媒時，與不使用分散劑的情形比較容易形成分散相。使用分散劑的情形，或不使用分散劑的情形的任一種情形，在分散狀態不充分時，在調製前處理液或將基板浸漬於前處理液時，若能透過攪拌形成良好的分散相的話即可。 When the nickel nanoparticles are mixed in a solvent in the presence of a dispersing agent, it is easier to form a dispersed phase than in the case where a dispersing agent is not used. In the case of using a dispersing agent or in the case of not using a dispersing agent, when the dispersing state is insufficient, when the pretreatment liquid or the substrate is immersed in the pretreatment liquid, if a good dispersed phase can be formed by stirring, Just fine.

分散劑可零零散散地將鎳奈米粒子解膠(peptization)，可不使被解開的粒子凝聚而使其穩定地分散。該分散劑被大致區別為分子量2000~100萬的高分子分散劑、分子量未滿2000的低分子分散劑，無機分散劑。 The dispersing agent disperses the nickel nanoparticles in a pseudo-dispersion manner, so that the unwound particles can be stably dispersed without being agglomerated. The dispersant is roughly distinguished by a polymer dispersant having a molecular weight of 2,000 to 1,000,000, a low molecular dispersant having a molecular weight of less than 2,000, and an inorganic dispersant.

高分子分散劑為少量且分散作用高，可期待立體阻礙(steric hindrance)產生的排斥效應。高分子分散劑可分類成陰離子性(anionic)、陽離子性(cationic)、非離子性(nonionic)。陰離子性有多羧酸(polycarboxylic acid)系、萘磺酸甲醛縮合(naphthalenesulfonic acid-formaldehyde condensation)系等的水系用、多羧酸部分烷基酯(polycarboxylic acid partial alkyl ester)系等的有機溶媒用的高分子分散劑。陽離子性有聚烷基多 胺(polyalkylene polyamine)系等的有機溶媒系的高分子分散劑。非離子性有聚乙二醇等的水系用、聚醚系等的有機溶媒用的高分子分散劑。 The polymer dispersant is small in amount and high in dispersion, and the repulsion effect by steric hindrance can be expected. Polymer dispersants can be classified into anionic, cationic, and nonionic. An anionic organic solvent such as a polycarboxylic acid, a naphthalenesulfonic acid-formaldehyde condensation system, or a polycarboxylic acid partial alkyl ester. Polymer dispersant. Cationic polyalkylene An organic solvent-based polymer dispersant such as a polyalkylene polyamine. A non-ionic polymer dispersing agent for an organic solvent such as polyethylene glycol or the like, or a polyether-based organic solvent.

低分子的分散劑吸附於鎳奈米粒子的表面且容易濕潤的濕潤作用優良，但分散穩定化作用不及於高分子分散劑。低分子的分散劑可分類成陰離子性、陽離子性、非離子性。陰離子性有烷基磺酸(alkyl sulfonic acid)系等的水系用低分子分散劑。陽離子性有四級銨鹽(quaternary ammonium salt)系等的水系用、烷基多胺(alkyl polyamine)系等的有機溶媒用的低分子分散劑。非離子性有高級醇烯化氧(higher alcohol alkylene oxide)系等的水系用、多元醇酯(polyhydric alcohol ester)系等的有機溶媒用的低分子分散劑。無機分散劑具有在水系下之吸附於粒子表面，及靜電排斥產生的強的穩定化作用。無機分散劑有三聚磷酸鹽(tripolyphosphate)等的水系用分散劑。 The low molecular weight dispersing agent is adsorbed on the surface of the nickel nanoparticle and is excellent in wettability, but the dispersion stabilizing effect is inferior to the polymer dispersing agent. Low molecular dispersants can be classified into anionic, cationic, and nonionic. An anionic liquid-based low molecular weight dispersing agent such as an alkyl sulfonic acid system. The cationic substance is a low molecular weight dispersing agent for an organic solvent such as an aqueous system or an alkyl polyamine system such as a quaternary ammonium salt. A low molecular weight dispersing agent for an organic solvent such as a water-based or polyhydric alcohol ester which is a non-ionic high alcohol alkylene oxide system. The inorganic dispersant has a strong stabilizing effect by adsorption to the surface of the particles under water and electrostatic repulsion. The inorganic dispersant is a water-based dispersant such as tripolyphosphate.

分散劑的上位概念的具體例可舉出：胺、聚酯、羧酸、羧酸鹽、硫酸鹽、磺酸、磺基琥珀酸、磷酸、磷酸酯及胺、聚酯、羧酸、羧酸鹽、硫酸鹽、磺酸、磺基琥珀酸、磷酸、磷酸酯的鹽，烷醇基銨鹽、烷基銨鹽、直鏈烷基醚、聚醚、聚氨酯、聚丙烯酸酯、聚矽氧烷(polysiloxane)等。此情形胺包含烷基胺(alkylamine)、單胺(monoamine)、多胺(polyamine)等，磷酸類為磷酸及其鹽，磷酸包含多磷酸(polyphosphoric acid)。 Specific examples of the upper concept of the dispersing agent include amines, polyesters, carboxylic acids, carboxylates, sulfates, sulfonic acids, sulfosuccinic acids, phosphoric acid, phosphates and amines, polyesters, carboxylic acids, and carboxylic acids. Salts, sulfates, sulfonic acids, sulfosuccinic acids, phosphoric acid, phosphate salts, alkanol ammonium salts, alkyl ammonium salts, linear alkyl ethers, polyethers, polyurethanes, polyacrylates, polyoxyalkylene oxides (polysiloxane) and the like. In this case, the amine includes an alkylamine, a monoamine, a polyamine, etc., the phosphoric acid is phosphoric acid and a salt thereof, and the phosphoric acid contains polyphosphoric acid.

分散劑的中位概念的具體例可舉出：包含酸基的團聯 共聚物(block copolymer)的烷基銨鹽、高分子量酸性聚合物的烷醇基銨鹽、多官能聚合物的烷醇基銨鹽、星型構造變性聚烷氧基化物、長鏈聚氨基醯胺(long-chain polyaminoamide)與酸性聚合物的鹽、聚氨基醯胺的聚羧酸鹽(polycarboxylate)、長鏈聚氨基醯胺與極性酸酯的鹽、含羥基羧酸鹽、烷醇基氨基醯胺(alkylol aminoamide)、不飽和多羧酸聚氨基醯胺、酸性聚合物的羧酸鹽、變性丙烯酸系團聯共聚物、極性酸酯與高分子醇的組合、不飽和多羧酸聚合物、不飽和酸性多羧酸聚酯與聚矽氧烷的組合等。 Specific examples of the median concept of the dispersant include a cluster containing an acid group. Alkyl ammonium salt of block copolymer, alkanol ammonium salt of high molecular weight acidic polymer, alkanol ammonium salt of polyfunctional polymer, star structure denatured polyalkoxylate, long chain polyaminoguanidine a salt of a long-chain polyaminoamide with an acidic polymer, a polycarboxylate of polyaminoguanamine, a salt of a long-chain polyaminoguanamine and a polar acid ester, a hydroxycarboxylic acid salt, an alkyl alcohol amino group An alkylol aminoamide, an unsaturated polycarboxylic acid polyaminoamine, a carboxylate of an acidic polymer, a denatured acrylic copolymer, a combination of a polar acid ester and a high molecular alcohol, an unsaturated polycarboxylic acid polymer , a combination of an unsaturated acidic polycarboxylic acid polyester and a polyoxyalkylene.

分散劑的下位概念的具體例可舉出：聚氧乙烯苯乙烯化二苯醚硫酸銨、聚氧乙烯十三醚磷酸酯、聚氧乙烯烷基醚磷酸酯單乙醇胺鹽、聚氧乙烯烷基磺基琥珀酸二鈉、直鏈型烷基苯磺酸鈉、萘磺酸鈉甲醛縮合物、聚烷基多胺環氧烷加成物、聚烷基聚亞胺環氧烷加成物、聚乙烯吡咯烷酮、聚乙二醇、聚丙二醇、聚乙烯醇、多磷酸。 Specific examples of the subordinate concept of the dispersing agent include polyoxyethylene styrenated diphenyl ether ammonium sulfate, polyoxyethylene tridecyl ether phosphate, polyoxyethylene alkyl ether phosphate monoethanolamine salt, and polyoxyethylene alkyl group. Disodium sulfosuccinate, sodium linear alkylbenzene sulfonate, sodium naphthalene sulfonate formaldehyde condensate, polyalkyl polyamine alkylene oxide adduct, polyalkyl polyimide alkylene oxide adduct, Polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyphosphoric acid.

高分子分散劑的市面上的販賣品可舉出：SOLSPERSE 3000、SOLSPERSE 5000、SOLSPERSE 9000、SOLSPERSE 12000、SOLSPERSE 13240、SOLSPERSE 17000、SOLSPERSE 20000、SOLSPERSE 24000、SOLSPERSE 26000、SOLSPERSE 27000、SOLSPERSE 28000、SOLSPERSE 41090(以上日本路博潤公司製)；DISPERBYK101、DISPERBYK102、DISPERBYK103、DISPERBYK106、DISPERBYK108、DISPERBYK109、DISPERBYK110、DISPERBYK111、 DISPERBYK112、DISPERBYK116、DISPERBYK130、DISPERBYK140、DISPERBYK142、DISPERBYK145、DISPERBYK161、DISPERBYK162、DISPERBYK163、DISPERBYK166、DISPERBYK167、DISPERBYK168、DISPERBYK170、DISPERBYK171、DISPERBYK174、DISPERBYK180、DISPERBYK182、DISPERBYK183、DISPERBYK184、DISPERBYK185、DISPERBYK187、DISPERBYK190、DISPERBYK191、DISPERBYK192、DISPERBYK193、DISPERBYK194、DISPERBYK198、DISPERBYK199、DISPERBYK2000、DISPERBYK2001、DISPERBYK2008、DISPERBYK2009、DISPERBYK2010、DISPERBYK2012、DISPERBYK2022、DISPERBYK2025、DISPERBYK2050、DISPERBYK2070、DISPERBYK2090、DISPERBYK2091、DISPERBYK2095、DISPERBYK2096、DISPERBYK2150、DISPERBYK2155、ANTI-TERRA-U(以上日本BYK公司製)；POLYMER 100、POLYMER 120、POLYMER 150、POLYMER 400、POLYMER 401、POLYMER 402、POLYMER 403、POLYMER 450、POLYMER 451、POLYMER 452、POLYMER 453、EFKA-46、EFKA-47、EFKA-48、EFKA-49、EFKA-1501、EFKA-1502、EFKA-4540、EFKA-4550(以上EFKA化學公司製)；FLOWLEN DOPA-158、FLOWLEN DOPA-22、FLOWLEN DOPA-17、FLOWLEN G-700、FLOWLEN TG-720W、FLOWLEN-730W、FLOWLEN-740W、FLOWLEN-745W(以上共榮社化學公司製)；AJISPER-PA-111、AJISPER-PN411、 AJISPER-PB821、AJISPER-PB822、AJISPER-PB881(以上味之素公司製)；DISPARLON1210、DISPARLON2150、DISPARLON KS-860、DISPARLON KS-873N、DISPARLON7004、DISPARLON1831、DISPARLON1850、DISPARLON1860、DISPARLON DA-1401、DISPARLON PW-36、DISPARLON DN-900、DISPARLON DA-1200、DISPARLON DA-550、DISPARLON DA-7301、DISPARLON DA-325、DISPARLON DA-375、DISPARLON DA-234(以上楠本化成公司製)；SN DISPERSANT5020、SN DISPERSANT5027、SN DISPERSANT5029、SN DISPERSANT5034、SN DISPERSANT5040、SN DISPERSANT5045、SN DISPERSANT5468、SN DISPERSANT9228、SN SPARSE70、SN SPARSE2190、SN WETL、SN WET366、NOPCOSPARSE44-C、NOPCOWET50、NOPCOSANTRFA(以上SAN NOPCO公司製)；PLYSURFA215C、PLYSURFA212C、PLYSURFM208F(第一工業製藥公司製)等。 Commercially available macromolecular dispersants include: SOLSPERSE 3000, SOLSPERSE 5000, SOLSPERSE 9000, SOLSPERSE 12000, SOLSPERSE 13240, SOLSPERSE 17000, SOLSPERSE 20000, SOLSPERSE 24000, SOLSPERSE 26000, SOLSPERSE 27000, SOLSPERSE 28000, SOLSPERSE 41090 ( Above Japan Lubrizol Corporation); DISPERBYK101, DISPERBYK102, DISPERBYK103, DISPERBYK106, DISPERBYK108, DISPERBYK109, DISPERBYK110, DISPERBYK111, DISPERBYK112, DISPERBYK116, DISPERBYK130, DISPERBYK140, DISPERBYK142, DISPERBYK145, DISPERBYK161, DISPERBYK162, DISPERBYK163, DISPERBYK166, DISPERBYK167, DISPERBYK168, DISPERBYK170, DISPERBYK171, DISPERBYK174, DISPERBYK180, DISPERBYK182, DISPERBYK183, DISPERBYK184, DISPERBYK185, DISPERBYK187, DISPERBYK190, DISPERBYK191, DISPERBYK192, DISPERBYK193, DISPERBYK194, DISPERBYK198, DISPERBYK199, DISPERBYK2000, DISPERBYK2001, DISPERBYK2008, DISPERBYK2009, DISPERBYK2010, DISPERBYK2012, DISPERBYK2022, DISPERBYK2025, DISPERBYK2050, DISPERBYK2070, DISPERBYK2090, DISPERBYK2091, DISPERBYK2095, DISPERBYK2096, DISPERBYK2150, DISPERBYK2155, ANTI-TERRA-U (above Japan BYK) ; POLYMER 100, POLYMER 120, POLYMER 150, POLYMER 400, POLYMER 401, POLYMER 402, POLYMER 403, POLYMER 450, POLYMER 451, POLYMER 452, POLYMER 453, EFKA-46, EFKA-47, EFKA-48, EFKA-49, EFKA-1501, EFKA-1502, EFKA-4540, EFKA-4550 (manufactured by EFKA Chemical Co., Ltd.); FLOWLEN DOPA-1 58. FLOWLEN DOPA-22, FLOWLEN DOPA-17, FLOWLEN G-700, FLOWLEN TG-720W, FLOWLEN-730W, FLOWLEN-740W, FLOWLEN-745W (manufactured by Kyoeisha Chemical Co., Ltd.); AJISPER-PA-111, AJISPER -PN411, AJISPER-PB821, AJISPER-PB822, AJISPER-PB881 (manufactured by Ajinomoto Co., Ltd.); DISPARLON1210, DISPARLON2150, DISPARLON KS-860, DISPARLON KS-873N, DISPARLON7004, DISPARLON1831, DISPARLON1850, DISPARLON1860, DISPARLON DA-1401, DISPARLON PW- 36, DISPARLON DN-900, DISPARLON DA-1200, DISPARLON DA-550, DISPARLON DA-7301, DISPARLON DA-325, DISPARLON DA-375, DISPARLON DA-234 (manufactured by Nanben Chemical Co., Ltd.); SN DISPERSANT5020, SN DISPERSANT5027, SN DISPERSANT5029, SN DISPERSANT5034, SN DISPERSANT5040, SN DISPERSANT5045, SN DISPERSANT5468, SN DISPERSANT9228, SN SPARSE70, SN SPARSE2190, SN WETL, SN WET366, NOPCOSPARSE44-C, NOPCOWET50, NOPCOSANTRFA (made by SAN NOPCO); PLYSURFA215C, PLYSURFA212C, PLYSURFM208F (manufactured by First Industrial Pharmaceutical Co., Ltd.), etc.

例如ANTI-TERRA-250為烷醇基銨鹽系，DISPERBYK111為包含酸基的共聚物，DISPERBYK180為包含酸基的共聚物的烷基銨鹽，DISPERBYK182~185、198為聚氨酯系，DISPERBYK187、190~191、194、199、2010、2012、2015為聚丙烯酸酯系，PLYSURFA212C為磷酸酯系。 For example, ANTI-TERRA-250 is an alkyl alcohol ammonium salt system, DISPERBYK111 is a copolymer containing an acid group, DISPERBYK180 is an alkyl ammonium salt of a copolymer containing an acid group, DISPERBYK182~185, 198 is a polyurethane system, DISPERBYK187, 190~ 191, 194, 199, 2010, 2012, and 2015 are polyacrylate systems, and PLYSURFA212C is a phosphate ester system.

例如HITENOL NF-08為苯乙烯化二苯醚硫酸銨的環氧乙烷加成物(ethylene oxide adduct)，NEO-HITENOL S-70為磺基琥珀酸鹽(sulfosuccinate)的環氧乙烷加成物。DISCOALL206為聚烷基聚亞胺的環氧烷加成物，NEOGEN S-20F為苯磺酸鹽(benzenesulphonate)系。 For example, HITENOL NF-08 is an ethylene oxide adduct of styrenated diphenyl ether ammonium sulfate, and NEO-HITENOL S-70 is a sulfosuccinate ethylene oxide addition. Things. DISCOALL206 is an alkylene oxide adduct of polyalkyleneimine, NEOGEN S-20F is a benzene sulphonate system.

使用於前處理液的溶媒由安全面等的觀點，需要只有水，或只有在常壓下沸點250℃以下且閃點10℃以上的有機溶媒，或水及該有機溶媒的混合物。有機溶媒的具體例可舉出：醇類(包含乙二醇類)、醚類(包含乙二醇醚類)、酯類(包含環狀酯)、極性脂環烴類、醯胺類、亞碸類等。藉由使用鎳奈米粒子使得分散系非常穩定。由促進穩定化的觀點，溶媒以極性的有機溶媒較佳，由含氧化合物或含酸基化合物構成的極性溶媒更佳。 From the viewpoint of a safety surface or the like, the solvent used in the pretreatment liquid requires only water or an organic solvent having a boiling point of 250 ° C or less and a flash point of 10 ° C or more under normal pressure, or a mixture of water and the organic solvent. Specific examples of the organic solvent include alcohols (including ethylene glycols), ethers (including glycol ethers), esters (including cyclic esters), polar alicyclic hydrocarbons, guanamines, and sub- Ape and so on. The dispersion is very stable by using nickel nanoparticles. From the viewpoint of promoting stabilization, the solvent is preferably a polar organic solvent, and a polar solvent composed of an oxygen-containing compound or an acid group-containing compound is more preferable.

極性有機溶媒的下位概念的具體例選自於由異丙醇、異丁醇、3-甲氧基-3-甲基-1-丁醇、1-辛醇、萜品醇、環己醇、乙二醇、丙二醇、丙二醇甲醚、2-丁氧基乙酸乙酯、乙二醇丁醚、丙二醇甲醚醋酸酯、乙二醇***醋酸脂、2-乙氧基乙酸乙酯、乙二醇二乙酸酯、N,N-二甲基甲醯胺、二甲亞碸、N-甲基吡咯酮、丙烯碳酸鹽所組成的群較佳。而且，甲氧基乙酸丙酯(methoxypropyl acetate)、乙酸丁酯(butyl acetate)、二丙二醇甲醚(dipropylene glycol monomethyl ether)、三丙二醇甲醚(tripropylene glycol monomethyl ether)、乙二醇單丁醚(butyl cellosolve)等也有效。 Specific examples of the subordinate concept of the polar organic solvent are selected from the group consisting of isopropanol, isobutanol, 3-methoxy-3-methyl-1-butanol, 1-octanol, terpineol, cyclohexanol, Ethylene glycol, propylene glycol, propylene glycol methyl ether, ethyl 2-butoxyacetate, ethylene glycol butyl ether, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, 2-ethoxyethyl acetate, ethylene glycol A group consisting of diacetate, N,N-dimethylformamide, dimethyl hydrazine, N-methylpyrrolidone, and propylene carbonate is preferred. Moreover, methoxypropyl acetate, butyl acetate, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobutyl ether ( Butyl cellosolve) is also effective.

前處理液是將鎳粒子混合及攪拌於溶媒而被調製。分散劑添加於溶媒或不添加均可。當溶媒選擇水或水與極性有機溶媒的混合物時，由分散穩定性的觀點，前處理液的pH為3.0~10.0較佳，更佳為4.0~9.0。 The pretreatment liquid is prepared by mixing and stirring the nickel particles in a solvent. The dispersant may be added to the solvent or may be added. When the solvent is selected from water or a mixture of water and a polar organic solvent, the pH of the pretreatment liquid is preferably from 3.0 to 10.0, more preferably from 4.0 to 9.0, from the viewpoint of dispersion stability.

在進行攪拌時無須特別強烈地攪拌，惟鎳奈米粒子得到均勻的分散相不像銅奈米粒子般簡單，即使是使用分散劑的情形，該傾向也不太有變化。因此，在前處理液的調製時，繼續攪拌直到分散為止較佳。混合及攪拌時的液溫為常溫也可以。也可以在前處理液含有：用以防止鎳奈米粒子的表面氧化的抗氧化劑(antioxidant)、鹽酸、硫酸、醋酸、草酸等的各種酸；由氫氧化鈉、氫氧化鉀、氨水、胺等的各種鹼構成的pH調整劑(pH adjuster)，及陰離子性、陽離子性、非離子性界面活性劑(surfactant)等的各種添加劑(addition agent)。 There is no need to stir particularly strongly during the stirring, but the uniform dispersion phase of the nickel nanoparticles is not as simple as the copper nanoparticles, and the tendency does not change even in the case of using a dispersant. Therefore, in the preparation of the pretreatment liquid, it is preferred to continue stirring until dispersion. The liquid temperature during mixing and stirring may be normal temperature. The pretreatment liquid may contain: an antioxidant, a hydrochloric acid, a sulfuric acid, an acetic acid, an oxalic acid, or the like for preventing oxidation of the surface of the nickel nanoparticles; and a sodium hydroxide, potassium hydroxide, ammonia, an amine, or the like; Various pH adjusters (pH adjusters) composed of various bases, and various additive agents such as anionic, cationic, and nonionic surfactants.

鎳奈米粒子對前處理液的全量的含量為1~80重量%，5~70重量%較佳。若比1重量%少，則很難將鎳奈米粒子均勻吸附於基板，若超過80重量%，則即使使用分散劑也不容易形成穩定的分散系。當使用分散劑調製前處理液時，分散劑對鎳奈米粒子的含量也取決於分散劑的種類，為3~70重量%，3~50重量%較佳。若比3重量%少，則不容易形成穩定的分散系，若比70重量%多，則有在賦予催化劑後的鎳塗膜混入雜質之虞。 The total content of the nickel nanoparticles to the pretreatment liquid is from 1 to 80% by weight, preferably from 5 to 70% by weight. When the amount is less than 1% by weight, it is difficult to uniformly adsorb the nickel nanoparticles on the substrate, and if it exceeds 80% by weight, it is difficult to form a stable dispersion even if a dispersant is used. When the pretreatment liquid is prepared using a dispersant, the content of the dispersant to the nickel nanoparticles is also dependent on the type of the dispersant, and is preferably from 3 to 70% by weight, preferably from 3 to 50% by weight. When it is less than 3% by weight, a stable dispersion system is not easily formed, and if it is more than 70% by weight, impurities may be mixed in the nickel coating film after the catalyst is added.

可藉由使用本發明的前處理液實現以下的電鍍方法。也就是說，一種電鍍方法，包含：將非導電性基板浸漬於本發明的前處理液，使包含於該前處理液的鎳粒子催化劑賦予該非導電性基板表面上之前處理程序；在被進行了前處理的前述非導電性基板上使用無電鍍鎳液或無電鍍鎳合金液形成鎳塗膜或鎳合金塗膜之無電電鍍程序。此外除了該 等程序以外，也可以依照需要導入其他的程序。 The following plating method can be achieved by using the pretreatment liquid of the present invention. That is, a plating method includes: immersing a non-conductive substrate in the pretreatment liquid of the present invention, and applying a nickel particle catalyst contained in the pretreatment liquid to the surface of the non-conductive substrate before the processing; An electroless plating process for forming a nickel coating film or a nickel alloy coating film on the aforementioned non-conductive substrate using an electroless nickel plating solution or an electroless nickel plating alloy solution. In addition to the In addition to programs, you can also import other programs as needed.

在前處理程序中，將非導電性基板浸漬於前處理液時的液溫為10~50℃，浸漬時間為1~20分。以純水清洗浸漬於前處理液的非導電性基板後，進行乾燥，或不進行乾燥而移至無電電鍍程序。在該程序中若與以往一樣處理的話即可，無特別的限制。無電鍍鎳液或無電鍍鎳合金液的液溫為15~100℃，較佳為20~100℃。關於使用於無電鍍鎳液或無電鍍鎳合金液的攪拌法可使用空氣攪拌法、急速液流攪拌法、利用攪拌葉片(agitating blade)等進行的機械攪拌法等。 In the pretreatment process, the liquid temperature when the non-conductive substrate is immersed in the pretreatment liquid is 10 to 50 ° C, and the immersion time is 1 to 20 minutes. The non-conductive substrate immersed in the pretreatment liquid is washed with pure water, dried, or moved to an electroless plating process without drying. In the program, if it is handled as before, there is no particular limitation. The liquid temperature of the electroless nickel plating solution or the electroless nickel plating alloy liquid is 15 to 100 ° C, preferably 20 to 100 ° C. As the stirring method used for the electroless nickel plating solution or the electroless nickel plating alloy liquid, an air stirring method, a rapid liquid flow stirring method, a mechanical stirring method using an agitating blade or the like, or the like can be used.

無電鍍鎳液的組成無特別的限制，可使用眾所周知的無電鍍鎳液。無電鍍鎳液含有可溶性鎳鹽與還原劑與錯合劑。更進一步使無電鍍鎳液含有pH調整劑、界面活性劑等的各種添加劑、酸也可以。關於可溶性鎳鹽，無特別的限制，若為在水溶液中使鎳離子產生的可溶性的鹽的話，則可使用任意的可溶性鎳鹽，不溶性鹽(insoluble salt)也可以。具體上硫酸鎳、氯化鎳、硫酸銨鎳(nickel ammonium sulfate)、醋酸鎳、碳酸鎳、氨基磺酸鎳(nickel aminosulfonate)、氧化鎳、有機磺酸的鎳鹽等較佳。 The composition of the electroless nickel plating liquid is not particularly limited, and a well-known electroless nickel plating liquid can be used. Electroless nickel plating baths contain soluble nickel salts with reducing agents and complexing agents. Further, the electroless nickel plating solution may contain various additives such as a pH adjuster and a surfactant, and an acid. The soluble nickel salt is not particularly limited, and any soluble nickel salt or insoluble salt may be used as a soluble salt for causing nickel ions in an aqueous solution. Specifically, nickel sulfate, nickel chloride, nickel ammonium sulfate, nickel acetate, nickel carbonate, nickel aminosulfonate, nickel oxide, nickel salt of an organic sulfonic acid, or the like is preferred.

含有於無電鍍鎳液的還原劑可舉出：次磷酸(hypophosphorous acid)類(次磷酸及其鹽)、亞磷酸(phosphorous acid)類、胺硼烷類(二甲基胺硼烷(dimethylamine borane)等)、硼氫化物(borohydride)類等，特別是次磷酸類較佳。當使用次磷酸鈉(sodium hypophosphite)當作還原劑時，透過次磷酸鈉被氧化時放出的電子，使鎳離子被還原成金屬鎳。與此同時，也引起磷析出的反應。因此，嚴密地來說鎳磷合金塗膜析出。若將胺硼烷類(二甲基胺硼烷等)或硼氫化物類使用於還原劑，則嚴密地來說鎳硼合金塗膜析出。在本發明所謂的鎳合金包含例如鍍鎳磷合金、鍍鎳硼合金等。 Examples of the reducing agent contained in the electroless nickel plating solution include: hypophosphorous acid (phosphoric acid and its salt), phosphorous acid, and amine borane (dimethylamine borane). And the like, borohydride or the like, particularly the phosphoric acid is preferred. When using sodium hypophosphite (sodium When hypophosphite is used as a reducing agent, the electrons emitted by the oxidation of sodium hypophosphite cause the nickel ions to be reduced to metallic nickel. At the same time, it also causes a reaction of phosphorus precipitation. Therefore, the nickel-phosphorus alloy coating film is strictly precipitated. When an amine borane (such as dimethylamine borane) or a borohydride is used for the reducing agent, the nickel boron alloy coating film is precipitated. The so-called nickel alloy in the present invention contains, for example, a nickel-plated phosphorus alloy, a nickel-plated boron alloy, or the like.

含有於無電鍍鎳液的錯合劑可將無電鍍鎳液中的鎳離子形成穩定的可溶性錯合物(soluble complex)。錯合劑的具體例可舉出：醋酸、乳酸、草酸等的單羧酸(monocarboxylic acid)或多羧酸(polycarboxylic acid)；酒石酸(tartaric acid)、檸檬酸(citric acid)、蘋果酸等的氧基羧酸(oxycarboxylic acid)類、硫乙醇酸(thioglycolic acid)等的硫醇(mercaptan)類；甘胺酸(glycine)、丙胺酸(alanine)、天冬胺酸(aspartic acid)、麩胺酸(glutamic acid)等的胺基酸類；乙二胺四乙酸(EDTA：ethylenediaminetetraacetic acid)、二乙烯三胺五乙酸(DTPA：diethylenetriaminepenta-acetic acid)、三亞乙基四胺六乙酸(TTHA：triethylenetetraaminehexaacetic acid)、羥乙基乙二胺三乙酸(HEDTA：Hydroxyethyl ethylenediaminetriacetic acid)、氮基三醋酸(NTA：nitrilotriacetic acid)、亞胺二醋酸(IDA：iminodiacetic acid)等的胺基羧酸類；聯氨、乙二胺(ethylenediamine)、四亞甲二胺 (tetramethylenediamine)、六亞甲二胺(hexamethylenediamine)、二乙烯三胺(diethylenetriamine)、四乙烯戊胺(tetraethylenepentamine)、五伸乙六胺(pentaethylenehexamine)等的多胺類；單乙醇胺(monoethanolamine)、二乙醇胺(diethanolamine)、三乙醇胺(triethanolamine)等的胺醇(amino alcohol)類；氨(ammonia)等。 The complexing agent contained in the electroless nickel plating solution forms a stable soluble complex of nickel ions in the electroless nickel plating solution. Specific examples of the complexing agent include monocarboxylic acid or polycarboxylic acid such as acetic acid, lactic acid, and oxalic acid; oxygen such as tartaric acid, citric acid, and malic acid. Mercaptans such as oxycarboxylic acids and thioglycolic acids; glycine, alanine, aspartic acid, and glutamic acid Amino acids such as glutamic acid; ethylenediaminetetraacetic acid, DTPA: diethylenetriaminepenta-acetic acid, and TTHA:triethylenetetraaminehexaacetic acid , hydroxyethylethylenediamine triacetic acid (HEDTA: Hydroxyethyl ethylenediamine triacetic acid), nitrogen-based triacetic acid (NTA: nitrilotriacetic acid), imine diacetic acid (IDA: iminodiacetic acid) and other amine carboxylic acids; hydrazine, ethylene Amine (ethylenediamine), tetramethylenediamine (tetramethylenediamine), hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, polyamines, monoethanolamine, An amino alcohol such as diethanolamine or triethanolamine; ammonia or the like.

使無電鍍鎳液含有界面活性劑等的添加劑也可以。界面活性劑的具體例可舉出：聚乙二醇、聚丙二醇、聚氧乙烯-聚氧丙烯隨機共聚物(polyoxyethylene-polyoxypropylene random copolymer)、聚氧乙烯-聚氧丙烯團聯共聚物(polyoxyethylene-polyoxypropylene block copolymer)等。該等聚合物的分子量一般為500~100萬，較佳為1000~10萬的範圍內。含有於無電鍍鎳液的pH調整劑與含有於前處理液的pH調整劑一樣。 An additive such as a surfactant or the like may be used in the electroless nickel plating solution. Specific examples of the surfactant include polyethylene glycol, polypropylene glycol, polyoxyethylene-polyoxypropylene random copolymer, and polyoxyethylene-polyoxypropylene copolymer. Polyoxypropylene block copolymer) and the like. The molecular weight of the polymers is generally from 500 to 1,000,000, preferably from 1,000 to 100,000. The pH adjuster contained in the electroless nickel plating solution is the same as the pH adjuster contained in the pretreatment liquid.

以有機酸、無機酸及有機酸、無機酸的鹽之中一種以上當作無電鍍鎳液的基礎成分也可以。無機酸可舉出：硫酸、焦磷酸(pyrophosphoric acid)、氟硼酸(fluoroboric acid)等。有機酸可舉出：乙醇酸(glycolic acid)或酒石酸等的氧基羧酸、甲磺酸(methanesulfonic acid)或2-羥乙磺酸(2-hydroxyethanesulfonic acid)等的有機磺酸(organic sulfonic acid)等。 One or more of an organic acid, an inorganic acid, a salt of an organic acid or an inorganic acid may be used as a basic component of the electroless nickel plating solution. Examples of the inorganic acid include sulfuric acid, pyrophosphoric acid, and fluoroboric acid. Examples of the organic acid include an organic sulfonic acid such as an oxycarboxylic acid such as glycolic acid or tartaric acid, methanesulfonic acid or 2-hydroxyethanesulfonic acid (organic sulfonic acid). )Wait.

若以包含200nm以下的鎳奈米粒子的前處理液對非導電性基板賦予催化活性，則不限於無電鍍鎳，可施以無電鍍鎳合金。當施以無電鍍鎳合金時，在將非導電性基板浸漬於前處理液後，就會浸漬於無電鍍鎳合金液。鎳合金是意味著鎳與對方的金屬的合金，鎳合金以鎳銅合金、鎳鈷合金、鎳錫合金較佳。無電鍍鎳合金液與無電鍍鎳液一樣含有：可溶性鎳鹽、對方的金屬的可溶性鹽、還原劑、錯合劑。使無電鍍鎳合金液含有pH調整劑、界面活性劑等的各種添加劑、酸也可以。 When a pretreatment liquid containing nickel nanoparticles containing 200 nm or less is used to impart catalytic activity to a non-conductive substrate, it is not limited to electroless nickel plating, and an electroless nickel alloy can be applied. When an electroless nickel alloy is applied, the non-conductive substrate is immersed in the electroless nickel alloy solution after being immersed in the pretreatment liquid. The nickel alloy means an alloy of nickel and the other metal, and the nickel alloy is preferably a nickel-copper alloy, a nickel-cobalt alloy or a nickel-tin alloy. The electroless nickel alloy solution contains the same as the electroless nickel solution: a soluble nickel salt, a soluble salt of the other metal, a reducing agent, and a complexing agent. The electroless nickel plating alloy may contain various additives such as a pH adjuster and a surfactant, and an acid.

可溶性銅鹽可舉出：硫酸銅、氧化銅、氯化銅、碳酸銅、醋酸銅、焦磷酸銅、草酸銅等。可溶性鈷鹽可舉出：硫酸鈷、氯化鈷、有機磺酸的鈷鹽等。可溶性亞錫鹽可舉出：以甲磺酸、乙磺酸(ethanesulfonic acid)、2-丙醇磺酸(2-propanol sulfonic acid)、磺基琥珀酸、對苯酚磺酸(p-phenolsulfonic acid)等的有機磺酸的亞錫鹽為首，以及氟硼酸亞錫(stannous fluoroborate)、硫酸亞錫(stannous sulfate)、氧化亞錫(stannous oxide)、氯化亞錫(stannous chloride)、錫酸鈉(sodium stannate)、錫酸鉀(potassium stannate)等。在無電鍍鎳合金液中，因需要鎳與對方的金屬共析(eutectoid)，故使鎳及對方的金屬在無電鍍鎳合金液中一起穩定化，且調整氧化還原電位之錯合劑的選擇很重要。 Examples of the soluble copper salt include copper sulfate, copper oxide, copper chloride, copper carbonate, copper acetate, copper pyrophosphate, and copper oxalate. The soluble cobalt salt may, for example, be cobalt sulfate, cobalt chloride or a cobalt salt of an organic sulfonic acid. The soluble stannous salt can be exemplified by methanesulfonic acid, ethanesulfonic acid, 2-propanol sulfonic acid, sulfosuccinic acid, p-phenolsulfonic acid. The stannous salt of organic sulfonic acid is the first, as well as stannous fluoroborate, stannous sulfate, stannous oxide, stannous chloride, sodium stannate ( Sodium stannate), potassium stannate, etc. In the electroless nickel alloy solution, since nickel is required to eutectoid with the other metal, the nickel and the other metal are stabilized together in the electroless nickel alloy solution, and the selection of the modifier for adjusting the oxidation-reduction potential is very high. important.

如上述依照本發明，因包含於前處理液的鎳奈米粒子的粒徑以200nm以下，對非導電性基板表面的定錨效應顯 現。可透過該定錨效應，直接地將鎳奈米粒子催化劑賦予非導電性基板。據此，能以簡便的處理直接地賦予非導電性基板鎳催化劑，在非導電性基板的全面均質地形成良好的鍍鎳塗膜或鍍鎳合金塗膜。 According to the present invention, since the particle diameter of the nickel nanoparticle contained in the pretreatment liquid is 200 nm or less, the anchoring effect on the surface of the non-conductive substrate is remarkable. Now. The nickel nanoparticle catalyst can be directly imparted to the non-conductive substrate by the anchoring effect. According to this, the non-conductive substrate nickel catalyst can be directly supplied by a simple treatment, and a favorable nickel plating coating film or nickel plating alloy coating film can be formed uniformly on the non-conductive substrate.

[實施例] [Examples]

以下透過實施例更詳細地說明本發明。本發明不是被限定於上述實施形態及以下的實施例，依照申請專利範圍所示，在申請專利範圍包含有均等的範圍內的所有的變更。如以下的(A)~(D)所示，對樹脂基板施以鍍鎳及鍍鎳合金，實施了鍍鎳及鍍鎳合金的外觀評價試驗。 Hereinafter, the present invention will be described in more detail by way of examples. The present invention is not limited to the above-described embodiments and the following embodiments, and all modifications within the scope of the claims are included in the scope of the claims. As shown in the following (A) to (D), nickel plating and nickel plating alloy were applied to the resin substrate, and an appearance evaluation test of nickel plating and nickel plating alloy was performed.

在以下的各實施例中適用本發明的方法進行，在各比較例中比照該方法進行。 The method of the present invention was carried out in each of the following examples, and was carried out in accordance with the method in each comparative example.

(A)、調整前處理液，透過無電鍍鎳在樹脂基板形成鎳塗膜。 (A), the pretreatment liquid is adjusted, and a nickel coating film is formed on the resin substrate through electroless nickel plating.

(B)、進行了得到的鎳塗膜的外觀評價試驗。 (B) The appearance evaluation test of the obtained nickel coating film was performed.

(C)、調整前處理液，透過無電鍍鎳合金在樹脂基板形成鎳合金塗膜。 (C), the pretreatment liquid is adjusted, and a nickel alloy coating film is formed on the resin substrate through the electroless nickel alloy.

(D)、進行了得到的鎳合金塗膜的外觀評價試驗。 (D) The appearance evaluation test of the obtained nickel alloy coating film was performed.

(A)、鎳塗膜的形成 (A), formation of nickel coating film

形成鎳磷合金塗膜當作鎳塗膜。實施例1~16為使用分散劑調整了前處理液的例子。實施例1為前處理液的溶媒使用醇系的有機溶媒的實施例全體的基本例。實施例2為使實施例1的鎳奈米粒子的粒徑變化的例子。實施例3~4為使實施例1的鎳奈米粒子之對前處理液的含量變化的例 子。實施例5為使實施例1的分散劑的含量變化的例子。實施例6~10為使實施例1的分散劑的種類變化的例子。實施例11~13為使實施例1的有機溶媒的種類變化的例子。實施例14~15為以實施例1為基本且溶媒使用水改變分散劑的種類的例子。實施例16為以實施例1為基本且使用水與醇系的混合溶媒改變了分散劑的種類的例子。 A nickel-phosphorus alloy coating film was formed as a nickel coating film. Examples 1 to 16 are examples in which a pretreatment liquid was adjusted using a dispersant. Example 1 is a basic example of the entire example of the use of an alcohol-based organic solvent as a solvent for the pretreatment liquid. Example 2 is an example in which the particle diameter of the nickel nanoparticles of Example 1 was changed. Examples 3 to 4 are examples in which the content of the pretreatment liquid of the nickel nanoparticles of Example 1 was changed. child. Example 5 is an example in which the content of the dispersant of Example 1 was changed. Examples 6 to 10 are examples in which the kind of the dispersant of Example 1 was changed. Examples 11 to 13 are examples in which the type of the organic solvent of Example 1 was changed. Examples 14 to 15 are examples in which the type of the dispersing agent was changed based on Example 1 and the solvent was changed with water. Example 16 is an example in which the type of the dispersant was changed using Example 1 as the basic and using a mixed solvent of water and an alcohol.

實施例17~23為不使用分散劑調製了前處理液的例子。實施例17為以實施例1為基本省略了分散劑的例子。實施例18為以水當作溶媒的例子。實施例19為使用水與醇系的混合溶媒的例子。實施例20為以實施例1為基本且改變了鎳奈米粒子的粒徑的例子。實施例21~22為以實施例1為基本且改變了鎳奈米粒子之對前處理液的含量的例子。實施例23為以實施例1為基本且改變了有機溶媒的種類的例子。 Examples 17 to 23 are examples in which a pretreatment liquid was prepared without using a dispersant. Example 17 is an example in which the dispersant was omitted in the first embodiment. Example 18 is an example in which water is used as a solvent. Example 19 is an example in which a mixed solvent of water and an alcohol is used. Example 20 is an example in which the particle diameter of the nickel nanoparticles is changed based on Example 1. Examples 21 to 22 are examples in which the content of the pretreatment liquid of the nickel nanoparticles was changed in the same manner as in the first embodiment. Example 23 is an example in which the type of the organic solvent was changed based on Example 1.

比較例1~6為使用分散劑調製了前處理液的例子。比較例1~5為鎳粉末的平均粒徑比本發明的適當範圍大的例子。比較例6為鎳奈米粒子的含量比本發明的適當範圍少的例子。比較例7~8為不使用分散劑調製了前處理液的例子。比較例7為分散劑的含量比本發明的適當範圍少的例子。比較例7為鎳粉末的平均粒徑比本發明的適當範圍大，前處理液使用醇系的有機溶媒的例子。比較例8為鎳粉末的平均粒徑比本發明的適當範圍大，前處理液使用水的例子。 Comparative Examples 1 to 6 are examples in which a pretreatment liquid was prepared using a dispersant. Comparative Examples 1 to 5 are examples in which the average particle diameter of the nickel powder is larger than the appropriate range of the present invention. Comparative Example 6 is an example in which the content of the nickel nanoparticles is smaller than the appropriate range of the present invention. Comparative Examples 7 to 8 are examples in which a pretreatment liquid was prepared without using a dispersant. Comparative Example 7 is an example in which the content of the dispersant is smaller than the appropriate range of the present invention. In Comparative Example 7, the average particle diameter of the nickel powder was larger than the appropriate range of the present invention, and the pretreatment liquid was an example of an alcohol-based organic solvent. Comparative Example 8 is an example in which the average particle diameter of the nickel powder is larger than the appropriate range of the present invention, and water is used as the pretreatment liquid.

(1)、實施例1 (1), embodiment 1

首先，在以下述的條件(a)進行了樹脂基板(以下稱為基板)的預備處理，接著以條件(b)進行了前處理後，以條件(c)進行了無電鍍鎳。 First, a preliminary treatment of a resin substrate (hereinafter referred to as a substrate) was carried out under the following condition (a), and then pre-treatment was carried out under the condition (b), and then electroless nickel plating was carried out under the condition (c).

(a)、基板的預備處理程序 (a) Substrate preparation procedure

首先，在雙面貼銅的玻璃環氧樹脂基板(松下電工(股)製的FR-4、板厚：1.0mm)中，以溶解除去35μm的銅箔，進行了除膠渣處理(desmear treatment)(亦即粗糙面化處理)及中和處理者當作試樣基板。除膠渣處理液及中和處理液的組成如下所示。 First, in a double-sided copper-clad glass epoxy substrate (FR-4 manufactured by Matsushita Electric Co., Ltd., thickness: 1.0 mm), a 35 μm copper foil was dissolved and removed, and desmear treatment was performed. (ie, roughening treatment) and neutralizing processor as a sample substrate. The composition of the desmear treatment liquid and the neutralization treatment liquid is as follows.

[除膠渣處理液] [Degreased treatment liquid]

過錳酸鉀(potassium permanganate)：50g/L Potassium permanganate: 50g/L

氫氧化鈉：20g/L Sodium hydroxide: 20g/L

[中和處理液] [Neutralization treatment solution]

硫酸：50g/L Sulfuric acid: 50g/L

草酸：10g/L Oxalic acid: 10g/L

NOIGEN XL-80：1g/L NOIGEN XL-80: 1g/L

藉由以80℃、10分鐘的條件將試樣基板浸漬於除膠渣處理液中，以純水清洗。然後，以40℃、10分鐘的條件將試樣基板浸漬於中和處理液中，以純水清洗、進行乾燥，將吸附於試樣基板的錳溶解除去。此外，NOIGEN XL-80為第一工業製藥公司製的非離子界面活性劑(non-ionic surfactant)，以聚亞氧烷基支鏈癸醚(polyoxyalkylene branched decyl ether)為主成分。 The sample substrate was immersed in a desmear treatment liquid at 80 ° C for 10 minutes, and washed with pure water. Then, the sample substrate was immersed in the neutralization treatment liquid at 40 ° C for 10 minutes, washed with pure water, and dried, and the manganese adsorbed on the sample substrate was dissolved and removed. Further, NOIGEN XL-80 is a non-ionic surfactant manufactured by First Industrial Pharmaceutical Co., Ltd., and is mainly composed of polyoxyalkylene branched decyl ether.

(b)、前處理程序 (b), pre-processing procedures

接著，以以下的組成將鎳奈米粒子與分散劑混合、攪拌於有機溶媒中，調製了前處理液。 Next, the nickel nanoparticles were mixed with a dispersing agent in the following composition, and stirred in an organic solvent to prepare a pretreatment liquid.

[前處理液] [pretreatment liquid]

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-111：0.2g DISPERBYK-111: 0.2g

3-甲氧基-3-甲基-1-丁醇：7.3g 3-methoxy-3-methyl-1-butanol: 7.3g

鎳奈米粒子的粒徑為70nm，DISPERBYK-111為日本BYK公司製的分散劑，以包含酸基的共聚物為主成分。此情形，鎳奈米粒子之對液全量的含量為40%(重量基準：以下同樣)，分散劑之對鎳奈米粒子的含量為4%。 The nickel nanoparticles have a particle diameter of 70 nm, DISPERBYK-111 is a dispersant manufactured by BYK Corporation of Japan, and a copolymer containing an acid group as a main component. In this case, the content of the total amount of the nickel nanoparticles to the liquid was 40% (weight basis: the same applies hereinafter), and the content of the dispersant to the nickel nanoparticles was 4%.

(c)、無電電鍍程序 (c), electroless plating procedure

以以下的組成建立了無電鍍鎳液(一般的無電鍍鎳磷合金液)的電解浴。該電鍍液是藉由稀硫酸或氫氧化鈉進行了pH調整。 An electrolytic bath of an electroless nickel plating solution (a general electroless nickel-phosphorus alloy liquid) was established with the following composition. The plating solution is pH adjusted by dilute sulfuric acid or sodium hydroxide.

[無電鍍鎳液] [electroless nickel plating]

六水硫酸鎳(nickel(II)sulfate hexahydrate)(以Ni2+)：5.6g/L Nickel (II) sulfate hexahydrate (with Ni 2+ ): 5.6 g / L

一水次磷酸鈉(sodium hypophosphite monohydrate)：30g/L Sodium hypophosphite monohydrate: 30g/L

琥珀酸：25.0g/L Succinic acid: 25.0g/L

剩餘：純水 Remaining: pure water

pH(20℃)：4.6 pH (20 ° C): 4.6

也就是說，一邊以25℃、10分鐘的條件將進行了依照除膠渣/中和處理進行的預備處理之試樣基板攪拌，一邊浸 漬於前處理液，以純水清洗。然後，在無電鍍鎳液中以90℃、5分鐘的條件對該試樣基板施以無電電鍍，在試樣基板上形成鎳塗膜(鎳磷合金塗膜)。然後，以純水清洗該試樣基板，進行了乾燥。 In other words, while the sample substrate subjected to the preliminary treatment by the desmear/neutralization treatment was stirred at 25 ° C for 10 minutes, the sample substrate was immersed. Stab the pretreatment solution and wash it with pure water. Then, the sample substrate was subjected to electroless plating in an electroless nickel plating solution at 90 ° C for 5 minutes, and a nickel coating film (nickel phosphorus alloy coating film) was formed on the sample substrate. Then, the sample substrate was washed with pure water and dried.

(2)、實施例2 (2), embodiment 2

以實施例1為基本，以以下的組成調製了前處理液。 Based on Example 1, the pretreatment liquid was prepared in the following composition.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-111：0.2g DISPERBYK-111: 0.2g

3-甲氧基-3-甲基-1-丁醇：7.3g 3-methoxy-3-methyl-1-butanol: 7.3g

令鎳奈米粒子的粒徑為100nm。 The particle diameter of the nickel nanoparticles was 100 nm.

(3)、實施例3 (3), embodiment 3

以實施例1為基本，以以下的組成調製了前處理液。 Based on Example 1, the pretreatment liquid was prepared in the following composition.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-111：0.2g DISPERBYK-111: 0.2g

3-甲氧基-3-甲基-1-丁醇：44.8g 3-methoxy-3-methyl-1-butanol: 44.8g

鎳奈米粒子之對液全量的含量為10%。 The total amount of the nickel nanoparticle particles in the liquid is 10%.

(4)、實施例4 (4), embodiment 4

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-111：0.2g DISPERBYK-111: 0.2g

3-甲氧基-3-甲基-1-丁醇：3.1g 3-methoxy-3-methyl-1-butanol: 3.1g

鎳奈米粒子之對液全量的含量為60%。 The total amount of the nickel nanoparticle particles in the liquid is 60%.

(5)、實施例5 (5), embodiment 5

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-111：0.5g DISPERBYK-111: 0.5g

3-甲氧基-3-甲基-1-丁醇：7.0g 3-methoxy-3-methyl-1-butanol: 7.0 g

分散劑之對鎳奈米粒子的含量為10%。 The content of the dispersant to the nickel nanoparticles was 10%.

(6)、實施例6 (6), embodiment 6

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

PLYSURFA212C：0.2g PLYSURFA212C: 0.2g

3-甲氧基-3-甲基-1-丁醇：7.3g 3-methoxy-3-methyl-1-butanol: 7.3g

由實施例1變更了分散劑的種類。此外，PLYSURFA212C為第一工業製藥公司製的分散劑，以聚氧乙烯十三醚磷酸酯為主成分。 The type of the dispersant was changed by the first embodiment. Further, PLYSURFA212C is a dispersant manufactured by First Industrial Pharmaceutical Co., Ltd., and contains polyoxyethylene tridecyl phosphate as a main component.

(7)、實施例7 (7), embodiment 7

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

HITENOL NF-08：0.2g HITENOL NF-08: 0.2g

3-甲氧基-3-甲基-1-丁醇：7.3g 3-methoxy-3-methyl-1-butanol: 7.3g

由實施例1變更了分散劑的種類。此外，HITENOL NF-08為第一工業製藥公司製的分散劑，以聚氧乙烯苯乙烯化二苯醚硫酸銨為主成分。 The type of the dispersant was changed by the first embodiment. In addition, HITENOL NF-08 is a dispersant made by First Industrial Pharmaceutical Co., Ltd., which is mainly composed of polyoxyethylene styrenated diphenyl ether ammonium sulfate.

(8)、實施例8 (8), embodiment 8

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

NEO-HITENOL S-70：0.2g NEO-HITENOL S-70: 0.2g

3-甲氧基-3-甲基-1-丁醇：7.3g 3-methoxy-3-methyl-1-butanol: 7.3g

由實施例1變更了分散劑的種類。NEO-HITENOL S-70為第一工業製藥公司製的分散劑，以聚氧乙烯烷基(C12~C14烷基)磺基琥珀酸二鈉為主成分。 The type of the dispersant was changed by the first embodiment. NEO-HITENOL S-70 is a dispersant made by the First Industrial Pharmaceutical Co., Ltd., and contains polyoxyethylene alkyl (C12-C14 alkyl) sulfosuccinate disodium as the main component.

(9)、實施例9 (9), embodiment 9

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISCOALL206：0.2g DISCOALL206: 0.2g

3-甲氧基-3-甲基-1-丁醇：7.3g 3-methoxy-3-methyl-1-butanol: 7.3g

由實施例1變更了分散劑的種類。DISCOALL206為第一工業製藥公司製的分散劑，以聚烷基聚亞胺環氧烷加成物為主成分。 The type of the dispersant was changed by the first embodiment. DISCOALL 206 is a dispersant made by the First Industrial Pharmaceutical Company, which is based on a polyalkyleneimide alkylene oxide adduct.

(10)、實施例10 (10), embodiment 10

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

NEOGEN S-20F：0.2g NEOGEN S-20F: 0.2g

3-甲氧基-3-甲基-1-丁醇：7.3g 3-methoxy-3-methyl-1-butanol: 7.3g

由實施例1變更了分散劑的種類。NEOGEN S-20F為第一工業製藥公司製的分散劑，以直鏈型烷基苯磺酸鈉為主成分。 The type of the dispersant was changed by the first embodiment. NEOGEN S-20F is a dispersant made by First Industrial Pharmaceutical Co., Ltd., with linear sodium alkylbenzene sulfonate as the main component.

(11)、實施例11 (11), embodiment 11

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-111：0.2g DISPERBYK-111: 0.2g

丙二醇甲醚：7.3g Propylene glycol methyl ether: 7.3g

由實施例1變更了有機溶媒的種類。 The type of the organic solvent was changed by the first embodiment.

(12)、實施例12 (12), embodiment 12

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-111：0.2g DISPERBYK-111: 0.2g

N,N-二甲基甲醯胺：7.3g N,N-dimethylformamide: 7.3g

由實施例1變更了有機溶媒的種類。 The type of the organic solvent was changed by the first embodiment.

(13)、實施例13 (13), embodiment 13

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-111：0.2g DISPERBYK-111: 0.2g

二甲亞碸：7.3g Dimethyl hydrazine: 7.3g

由實施例1變更了有機溶媒的種類。 The type of the organic solvent was changed by the first embodiment.

(14)、實施例14 (14), embodiment 14

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-180：0.2g DISPERBYK-180: 0.2g

水：7.3g Water: 7.3g

由實施例1變更了分散劑的種類及溶媒的種類。DISPERBYK-180為日本BYK公司製的分散劑，以包含酸基的團聯共聚物的烷基銨鹽為主成分。前處理液的pH為7.0。 The type of the dispersant and the type of the solvent were changed by the first embodiment. DISPERBYK-180 is a dispersant manufactured by BYK Corporation of Japan, and contains an alkylammonium salt of an acid group-containing copolymer. The pH of the pretreatment liquid was 7.0.

(15)、實施例15 (15), embodiment 15

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

LAVELIN FD-40：0.2g LAVELIN FD-40: 0.2g

水：7.3g Water: 7.3g

由實施例1變更了分散劑的種類及溶媒的種類。LAVELIN FD-40為第一工業製藥公司製的分散劑，以萘磺酸鈉甲醛縮合物為主成分。前處理液的pH為7.0。 The type of the dispersant and the type of the solvent were changed by the first embodiment. LAVELIN FD-40 is a dispersant made by First Industrial Pharmaceutical Co., Ltd., which is based on sodium naphthalene sulfonate formaldehyde condensate. The pH of the pretreatment liquid was 7.0.

(16)、實施例16 (16), embodiment 16

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-180：0.2g DISPERBYK-180: 0.2g

純水：3.7g Pure water: 3.7g

3-甲氧基-3-甲基-1-丁醇：3.6g 3-methoxy-3-methyl-1-butanol: 3.6g

使實施例1的溶媒變化成純水/醇的混合溶媒。前處理液的pH為6.0。 The solvent of Example 1 was changed to a mixed solvent of pure water/alcohol. The pH of the pretreatment liquid was 6.0.

(17)、實施例17 (17), embodiment 17

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

3-甲氧基-3-甲基-1-丁醇：7.5g 3-methoxy-3-methyl-1-butanol: 7.5 g

實施例1的分散劑未添加。 The dispersant of Example 1 was not added.

(18)、實施例18 (18), embodiment 18

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

純水：7.5g Pure water: 7.5g

實施例1的分散劑未添加，由實施例1變更了溶劑的 種類。前處理液的pH為7.0。 The dispersant of Example 1 was not added, and the solvent was changed by Example 1. kind. The pH of the pretreatment liquid was 7.0.

(19)、實施例19 (19), embodiment 19

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

純水：3.8g Pure water: 3.8g

3-甲氧基-3-甲基-1-丁醇：3.7g 3-methoxy-3-methyl-1-butanol: 3.7 g

實施例1的分散劑未添加，使溶媒變化成純水/醇的混合溶媒。前處理液的pH為6.0。 The dispersant of Example 1 was not added, and the solvent was changed to a mixed solvent of pure water/alcohol. The pH of the pretreatment liquid was 6.0.

(20)、實施例20 (20), embodiment 20

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

3-甲氧基-3-甲基-1-丁醇：7.5g 3-methoxy-3-methyl-1-butanol: 7.5 g

實施例1的分散劑未添加，鎳奈米粒子的粒徑為100nm。 The dispersant of Example 1 was not added, and the particle diameter of the nickel nanoparticles was 100 nm.

(21)、實施例21 (21), Example 21

以實施例1為基本，以以下的組成調製了前處理液。 Based on Example 1, the pretreatment liquid was prepared in the following composition.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

3-甲氧基-3-甲基-1-丁醇：45.0g 3-methoxy-3-methyl-1-butanol: 45.0g

實施例1的分散劑未添加，鎳奈米粒子之對液全量的含量為10%。 The dispersant of Example 1 was not added, and the total amount of the nickel nanoparticles to the liquid was 10%.

(22)、實施例22 (22), embodiment 22

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

3-甲氧基-3-甲基-1-丁醇：3.3g 3-methoxy-3-methyl-1-butanol: 3.3g

實施例1的分散劑未添加，鎳奈米粒子之對液全量的含量為60%。 The dispersant of Example 1 was not added, and the total amount of the nickel nanoparticles to be used was 60%.

(23)、實施例23 (23), embodiment 23

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

N,N-二甲基甲醯胺：7.5g N,N-dimethylformamide: 7.5g

實施例1的分散劑未添加，變更了有機溶劑的種類。 The dispersant of Example 1 was not added, and the kind of the organic solvent was changed.

(24)、比較例1 (24), Comparative Example 1

以實施例1為基本，以以下的組成調製了前處理液。 Based on Example 1, the pretreatment liquid was prepared in the following composition.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-111：0.2g DISPERBYK-111: 0.2g

3-甲氧基-3-甲基-1-丁醇：7.3g 3-methoxy-3-methyl-1-butanol: 7.3g

鎳奈米粒子使用了平均粒徑10μm的粒子。 As the nickel nanoparticle, particles having an average particle diameter of 10 μm were used.

(25)、比較例2 (25), Comparative Example 2

以實施例1為基本，以以下的組成調製了前處理液。 Based on Example 1, the pretreatment liquid was prepared in the following composition.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-111：0.2g DISPERBYK-111: 0.2g

3-甲氧基-3-甲基-1-丁醇：7.3g 3-methoxy-3-methyl-1-butanol: 7.3g

鎳奈米粒子使用了平均粒徑1μm的粒子。 As the nickel nanoparticle, particles having an average particle diameter of 1 μm were used.

(26)、比較例3 (26), Comparative Example 3

以實施例1為基本，以以下的組成調製了前處理液。 Based on Example 1, the pretreatment liquid was prepared in the following composition.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-111：0.2g DISPERBYK-111: 0.2g

3-甲氧基-3-甲基-1-丁醇：7.3g 3-methoxy-3-methyl-1-butanol: 7.3g

鎳奈米粒子使用了平均粒徑400nm的粒子。 As the nickel nanoparticle, particles having an average particle diameter of 400 nm were used.

(27)、比較例4 (27), Comparative Example 4

以實施例14為基本，以以下的組成調製了前處理液。 Based on Example 14, the pretreatment liquid was prepared in the following composition.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-180：0.2g DISPERBYK-180: 0.2g

水：7.3g Water: 7.3g

鎳奈米粒子使用了平均粒徑400nm的粒子。前處理液的pH為7.0。 As the nickel nanoparticle, particles having an average particle diameter of 400 nm were used. The pH of the pretreatment liquid was 7.0.

(28)、比較例5 (28), Comparative Example 5

以實施例1為基本，以以下的組成調製了前處理液。 Based on Example 1, the pretreatment liquid was prepared in the following composition.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-111：0.2g DISPERBYK-111: 0.2g

3-甲氧基-3-甲基-1-丁醇：7.3g 3-methoxy-3-methyl-1-butanol: 7.3g

鎳奈米粒子使用了平均粒徑300nm的粒子。 As the nickel nanoparticle, particles having an average particle diameter of 300 nm were used.

(29)、比較例6 (29), Comparative Example 6

以實施例1為基本，如以下般使前處理液的組成變化。 Based on Example 1, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：1.0g Nickel Nanoparticles: 1.0g

DISPERBYK-111：0.04g DISPERBYK-111: 0.04g

3-甲氧基-3-甲基-1-丁醇：198.96g 3-methoxy-3-methyl-1-butanol: 198.96g

鎳奈米粒子之對液全量的含量為0.5%。 The total amount of the nickel nanoparticle particles in the liquid is 0.5%.

(30)、比較例7 (30), Comparative Example 7

以實施例17為基本，以以下的組成調製了前處理液。 Based on Example 17, the pretreatment liquid was prepared in the following composition.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

3-甲氧基-3-甲基-1-丁醇：7.5g 3-methoxy-3-methyl-1-butanol: 7.5 g

鎳奈米粒子使用了平均粒徑400nm的粒子。 As the nickel nanoparticle, particles having an average particle diameter of 400 nm were used.

(31)、比較例8 (31), Comparative Example 8

以實施例18為基本，以以下的組成調製了前處理液。 Based on Example 18, the pretreatment liquid was prepared in the following composition.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

純水：7.5g Pure water: 7.5g

鎳奈米粒子使用了平均粒徑400nm的粒子。前處理液的pH為7.0。 As the nickel nanoparticle, particles having an average particle diameter of 400 nm were used. The pH of the pretreatment liquid was 7.0.

(B)、鎳塗膜的外觀評價試驗 (B), appearance evaluation test of nickel coating film

針對實施例1~23及比較例1~8，以目視觀察得到的鎳塗膜的外觀，以以下的基準評價了其優劣。○：在基板的全面得到了均質的鎳塗膜。╳：鎳塗膜未析出。外觀評價的試驗結果如表1所示。 With respect to Examples 1 to 23 and Comparative Examples 1 to 8, the appearance of the nickel coating film obtained by visual observation was evaluated by the following criteria. ○: A homogeneous nickel coating film was obtained on the entire substrate. ╳: The nickel coating film did not precipitate. The test results of the appearance evaluation are shown in Table 1.

[表1] [Table 1]

(C)、鎳合金塗膜的形成 (C), formation of nickel alloy coating film

形成鎳鈷合金塗膜，當作鎳合金塗膜。實施例24~25為使用分散劑調製了前處理液的例子。實施例24為前處理液的溶媒為醇系的有機溶媒的例子。實施例25為溶媒為水的例子。實施例26~27為不使用分散劑調製了前處理液的例子。實施例26為前處理液的溶媒為醇系的有機溶媒的例子。實施例27為溶媒為水的例子。比較例9是以實施例24為基本，鎳奈米粒子的粒徑比本發明的適當範圍大的 400nm的例子。 A nickel-cobalt alloy coating film is formed and used as a nickel alloy coating film. Examples 24 to 25 are examples in which a pretreatment liquid was prepared using a dispersant. Example 24 is an example in which the solvent of the pretreatment liquid is an alcohol-based organic solvent. Example 25 is an example in which the solvent is water. Examples 26 to 27 are examples in which a pretreatment liquid was prepared without using a dispersant. Example 26 is an example in which the solvent of the pretreatment liquid is an alcohol-based organic solvent. Example 27 is an example in which the solvent is water. Comparative Example 9 is based on Example 24, and the particle diameter of the nickel nanoparticles is larger than the appropriate range of the present invention. An example of 400nm.

(1)、實施例24 (1), Example 24

首先，以下述的條件(a)進行了基板的預備處理，接著以條件(b)進行了前處理後，以條件(c)進行了無電鍍鎳。 First, the substrate was subjected to preliminary treatment under the following condition (a), and then pre-treatment was carried out under the condition (b), and then electroless nickel plating was performed under the condition (c).

(a)、基板的預備處理程序：以與前述實施例1一樣的條件，對雙面貼銅玻璃環氧基板進行了預備處理。 (a) Preparation Process of Substrate: The double-sided copper-clad epoxy substrate was subjected to preliminary treatment under the same conditions as in the above-described Example 1.

(b)、前處理程序：接著，以以下的組成將鎳奈米粒子與分散劑混合、攪拌於有機溶媒中，調製了前處理液。 (b) Pretreatment procedure: Next, the nickel nanoparticles were mixed with a dispersing agent in the following composition, and stirred in an organic solvent to prepare a pretreatment liquid.

[前處理液] [pretreatment liquid]

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-111：0.2g DISPERBYK-111: 0.2g

3-甲氧基-3-甲基-1-丁醇：7.3g 3-methoxy-3-methyl-1-butanol: 7.3g

上述鎳奈米粒子的粒徑為70nm，DISPERBYK-111為日本BYK公司製的分散劑，以包含酸基的共聚物為主成分。此情形，鎳奈米粒子之對液全量的含量為40%，分散劑之對鎳奈米粒子的含量為4%。 The nickel nanoparticles have a particle diameter of 70 nm, and DISPERBYK-111 is a dispersant manufactured by BYK Co., Ltd., and a copolymer containing an acid group as a main component. In this case, the total amount of the nickel nanoparticles is 40%, and the content of the dispersant to the nickel nanoparticles is 4%.

(c)、無電鍍鎳合金程序：以以下的組成建立了無電鍍鎳鈷合金液(一般的無電鍍鎳鈷合金液)的電解浴。該電鍍液是藉由稀硫酸或氫氧化鈉進行了pH調整。 (c) Electroless nickel plating alloy procedure: An electrolytic bath of an electroless nickel-cobalt alloy liquid (a general electroless nickel-cobalt alloy liquid) was established with the following composition. The plating solution is pH adjusted by dilute sulfuric acid or sodium hydroxide.

[無電鍍鎳鈷合金液] [electroless nickel-cobalt alloy solution]

氯化鎳(以Ni2+)：1.5g/L Nickel chloride (with Ni 2+ ): 1.5g / L

氯化鈷(以Co2+)：1.5g/L Cobalt chloride (with Co 2+ ): 1.5g / L

酒石酸鈉：78g/L Sodium tartrate: 78g/L

氫氯酸肼(hydrazine hydrochloride)：68g/L Hydrazine hydrochloride: 68g/L

剩餘：純水 Remaining: pure water

pH(20℃)：12.0 pH (20 ° C): 12.0

一邊以25℃、10分鐘的條件將進行了依照除膠渣/中和處理進行的預備處理之試樣基板攪拌，一邊浸漬於前處理液，以純水清洗。然後，在無電鍍鎳鈷合金液中以90℃、5分鐘的條件對該試樣基板施以無電電鍍，在試樣基板上形成鎳鈷合金塗膜。然後，以純水清洗該試樣基板，進行了乾燥。 While stirring the sample substrate subjected to the preliminary treatment by the desmear/neutralization treatment at 25 ° C for 10 minutes, the sample substrate was immersed in the pretreatment liquid and washed with pure water. Then, the sample substrate was subjected to electroless plating in an electroless nickel-cobalt alloy solution at 90 ° C for 5 minutes to form a nickel-cobalt alloy coating film on the sample substrate. Then, the sample substrate was washed with pure water and dried.

(2)、實施例25 (2), embodiment 25

以實施例24為基本，如以下般使前處理液的組成變化。 Based on Example 24, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-180：0.2g DISPERBYK-180: 0.2g

水：7.3g Water: 7.3g

由實施例24變更了分散劑及溶媒的種類。前處理液的pH為7.0。 The type of the dispersant and the solvent was changed in Example 24. The pH of the pretreatment liquid was 7.0.

(3)、實施例26 (3), embodiment 26

以實施例24為基本，如以下般使前處理液的組成變化。 Based on Example 24, the composition of the pretreatment liquid was changed as follows.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

3-甲氧基-3-甲基-1-丁醇：7.5g 3-methoxy-3-methyl-1-butanol: 7.5 g

實施例24的分散劑未添加。 The dispersant of Example 24 was not added.

(4)、實施例27 (4), embodiment 27

以實施例25為基本，如以下般使前處理液的組成變 化。 Based on Example 25, the composition of the pretreatment liquid is changed as follows. Chemical.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

純水：7.5g Pure water: 7.5g

實施例25的分散劑未添加。前處理液的pH為7.0。 The dispersant of Example 25 was not added. The pH of the pretreatment liquid was 7.0.

(5)、比較例9 (5), Comparative Example 9

以實施例24為基本，以以下的組成調製了前處理液。 Based on Example 24, the pretreatment liquid was prepared in the following composition.

鎳奈米粒子：5.0g Nickel Nanoparticles: 5.0g

DISPERBYK-111：0.2g DISPERBYK-111: 0.2g

3-甲氧基-3-甲基-1-丁醇：7.3g 3-methoxy-3-methyl-1-butanol: 7.3g

鎳奈米粒子使用了平均粒徑400nm的粒子。 As the nickel nanoparticle, particles having an average particle diameter of 400 nm were used.

(D)、鎳合金塗膜的外觀評價試驗 (D), appearance evaluation test of nickel alloy coating film

針對實施例24~27及比較例9，以目視觀察得到的鎳鈷合金塗膜的外觀，以以下的基準評價了其優劣。○：在基板的全面得到了均質的鎳鈷合金塗膜。╳：鎳鈷合金塗膜未析出。外觀評價的試驗結果如表2所示。 With respect to Examples 24 to 27 and Comparative Example 9, the appearance of the nickel-cobalt alloy coating film obtained by visual observation was evaluated by the following criteria. ○: A homogeneous nickel-cobalt alloy coating film was obtained on the entire substrate. ╳: The nickel-cobalt alloy coating film did not precipitate. The test results of the appearance evaluation are shown in Table 2.

(綜合評價) (Overview)

(1)、針對無電鍍鎳(實施例1~23及比較例1~8) (1) For electroless nickel plating (Examples 1 to 23 and Comparative Examples 1 to 8)

(比較例1及2)在該等比較例中，使用平均粒徑10μm、1μm的μm單位的鎳粉末。在都調製了前處理液的時間點產生凝聚、分離且明顯的相分離被認定的結果，浸漬於無電鍍鎳液後，鎳塗膜也不析出。 (Comparative Examples 1 and 2) In these comparative examples, nickel powder of μm units having an average particle diameter of 10 μm and 1 μm was used. When the pretreatment liquid was prepared, aggregation and separation occurred, and significant phase separation was confirmed. After the immersion in the electroless nickel plating solution, the nickel coating film did not precipitate.

(比較例3~5)在該等比較例中，使用400nm、300nm的nm單位的鎳奈米粒子，在分散劑的共存下調製了前處理液。與比較例1~2比較，前處理液的分散狀態某種程度改善了。但是，被判斷了浸漬於無電鍍鎳液後，鎳塗膜也不析出，不太有催化活性。圖1是比較例3的外觀照片，得知基板的全面為白色的質地面(flux line)原封不動。 (Comparative Examples 3 to 5) In these comparative examples, nickel nanoparticles having a cell diameter of 400 nm and 300 nm were used, and a pretreatment liquid was prepared in the presence of a dispersant. Compared with Comparative Examples 1 and 2, the dispersion state of the pretreatment liquid was somewhat improved. However, it was judged that the nickel coating film was not precipitated after being immersed in the electroless nickel plating solution, and it was less catalytically active. Fig. 1 is a photograph showing the appearance of Comparative Example 3, and it was found that the entire flush line of the substrate was intact.

(比較例6)在該比較例中，鎳奈米粒子的含量比本發明的適當範圍少。鎳塗膜不析出。 (Comparative Example 6) In this comparative example, the content of the nickel nanoparticles was smaller than the appropriate range of the present invention. The nickel coating film does not precipitate.

(比較例7及8)在該等比較例中，無分散劑而使用400nm的鎳奈米粒子。鎳塗膜不析出。 (Comparative Examples 7 and 8) In these comparative examples, 400 nm nickel nanoparticles were used without a dispersing agent. The nickel coating film does not precipitate.

(實施例1~23)在該等實施例中，令鎳奈米粒子的粒徑及含量等為本發明的規定範圍。實施例1~23在調製了前處理液的時間點，被分成形成了美麗的分散狀態的實施例，與分散狀態稍微後退的實施例。在各實施例中，一邊攪拌，一邊將基板浸漬於該前處理液後，對該基板施以無電鍍鎳。確認了均質的鎳塗膜遍及基板的全面析出。圖2是實施例3的外觀照片，得知基板的全面透過銀白色的塗膜覆蓋。在實施例1~23中，與比較例1~8不同，使用包含將粒徑微細化到200nm以下的鎳奈米粒子的前處理液。據此，可有效賦予基板催化活性，若進行無電電鍍，則明顯 地可在基板上的全面析出均質的鎳塗膜。 (Examples 1 to 23) In the examples, the particle diameter and content of the nickel nanoparticles were within the predetermined range of the present invention. In the examples 1 to 23, the examples in which the pretreatment liquid was prepared were divided into the examples in which the dispersed state was formed, and the dispersion state was slightly retreated. In each of the examples, the substrate was immersed in the pretreatment liquid while stirring, and then the substrate was subjected to electroless nickel plating. It was confirmed that the homogeneous nickel coating film was completely deposited throughout the substrate. Fig. 2 is a photograph showing the appearance of Example 3, showing that the substrate is completely covered with a silver-white coating film. In Examples 1 to 23, unlike Comparative Examples 1 to 8, a pretreatment liquid containing nickel nanoparticles having a particle diameter of 200 nm or less was used. According to this, the catalytic activity of the substrate can be effectively imparted, and if electroless plating is performed, it is obvious A homogeneous nickel coating film can be deposited on the substrate.

更詳細地檢討實施例1~23。使鎳奈米粒子的粒徑變化成70nm、100nm的實施例1及2的情形，在基板的全面得到了均質的鎳塗膜。即使使鎳奈米粒子的含量變化(實施例1、實施例3及實施例4)，也一樣可在基板的全面形成均質的鎳塗膜。 Examples 1 to 23 were reviewed in more detail. In the case of the examples 1 and 2 in which the particle diameter of the nickel nanoparticles was changed to 70 nm and 100 nm, a homogeneous nickel coating film was obtained on the entire substrate. Even if the content of the nickel nanoparticles is changed (Example 1, Example 3, and Example 4), a homogeneous nickel coating film can be formed on the entire substrate.

針對使用分散劑調整了前處理液的實施例1~16進行檢討。即使使分散劑對鎳奈米粒子的含量變化，鎳塗膜為均質此點也無不同(實施例1及實施例5)。即使使分散劑的種類變化，鎳塗膜為均質此點也無不同(實施例1及實施例6~10)。前處理液的溶媒僅為有機溶媒、僅為純水或純水與有機溶媒的混合物的任一個，鎳塗膜為均質此點也無不同(實施例1~16)。 Examples 1 to 16 in which the pretreatment liquid was adjusted using a dispersant were reviewed. Even if the content of the dispersant to the nickel nanoparticles was changed, the nickel coating film was homogeneous (Example 1 and Example 5). Even if the type of the dispersant was changed, the nickel coating film was not uniform (Example 1 and Examples 6 to 10). The solvent of the pretreatment liquid is only an organic solvent, and it is only pure water or a mixture of pure water and an organic solvent, and the nickel coating film is homogeneous, and there is no difference (Examples 1 to 16).

針對無分散劑而調製了前處理液的實施例17~23進行檢討。與使用分散劑調製了前處理液的實施例1~16一樣，都可在基板全面形成了均質的鎳塗膜。無分散劑的該等實施例17~23的情形，即使使鎳奈米粒子的粒徑或含量變化，鎳塗膜為均質此點也無不同。當改變前處理液的溶媒的種類時，該溶媒僅為有機溶媒、僅為水或水與有機溶媒的混合物的任一個，鎳塗膜為均質此點也無不同 Examples 17 to 23 in which the pretreatment liquid was prepared without a dispersant were reviewed. As in Examples 1 to 16 in which the pretreatment liquid was prepared using a dispersant, a homogeneous nickel coating film was formed on the entire substrate. In the case of the above Examples 17 to 23 without a dispersing agent, even if the particle diameter or content of the nickel nanoparticles were changed, the nickel coating film was homogeneous. When the type of the solvent of the pretreatment liquid is changed, the solvent is only an organic solvent, only water or a mixture of water and an organic solvent, and the nickel coating film is homogeneous.

(2)、針對無電鍍鎳合金(實施例24~27及比較例9) (2) For electroless nickel alloys (Examples 24 to 27 and Comparative Example 9)

在鎳奈米粒子的粒徑超過本發明的規定範圍的400nm的比較例9中，鎳合金塗膜未析出。在將鎳奈米粒子的粒徑及含量特定於本發明的規定範圍的實施例24~27中，在 基板的全面均質的鎳合金塗膜析出了。在該等實施例24~27中，不管分散劑的有無、溶媒為有機溶媒或水，鎳合金塗膜為均質被認定。如實施例1~23所示，若以包含200nm以下的鎳奈米粒子的前處理液，賦予非導電性基板催化活性，則可透過浸漬於無電鍍鎳液，形成均質的鎳塗膜。該無電鍍鎳方法如實施例24~27所示，被印證了也能適用於無電鍍鎳合金方法。 In Comparative Example 9 in which the particle diameter of the nickel nanoparticles exceeded 400 nm in the predetermined range of the present invention, the nickel alloy coating film was not precipitated. In Examples 24 to 27 in which the particle diameter and content of the nickel nanoparticles were specified in the predetermined range of the present invention, A fully homogeneous nickel alloy coating film of the substrate was precipitated. In the examples 24 to 27, regardless of the presence or absence of the dispersant, the solvent was an organic solvent or water, the nickel alloy coating film was considered to be homogeneous. As shown in Examples 1 to 23, when a pretreatment liquid containing nickel nanoparticles having a diameter of 200 nm or less is used to impart catalytic activity to the non-conductive substrate, it can be immersed in an electroless nickel plating solution to form a homogeneous nickel coating film. The electroless nickel plating method, as shown in Examples 24 to 27, is also confirmed to be applicable to the electroless nickel plating method.

Claims (10)

一種無電鍍鎳或無電鍍鎳合金用的前處理液，接觸施以無電鍍鎳或無電鍍鎳合金的非導電性樹脂基板並進行前處理，使鎳粒子分散於溶媒中，其特徵為：該鎳粒子的平均粒徑為1~200nm，該鎳粒子之對該前處理液的含量為40~60重量%，直接地將該鎳粒子賦予該非導電性樹脂基板。 A pretreatment liquid for electroless nickel or electroless nickel alloy, which is contacted with a non-electroconductive resin substrate coated with electroless nickel or electroless nickel alloy and pretreated to disperse nickel particles in a solvent, which is characterized in that: The nickel particles have an average particle diameter of 1 to 200 nm, and the content of the nickel particles to the pretreatment liquid is 40 to 60% by weight, and the nickel particles are directly applied to the non-conductive resin substrate. 如申請專利範圍第1項之無電鍍鎳或無電鍍鎳合金用的前處理液，其中該溶媒包含在常壓下沸點250℃以下且閃點10℃以上的有機溶媒。 The pretreatment liquid for electroless nickel or electroless nickel alloy according to claim 1, wherein the solvent comprises an organic solvent having a boiling point of 250 ° C or less and a flash point of 10 ° C or more under normal pressure. 如申請專利範圍第2項之無電鍍鎳或無電鍍鎳合金用的前處理液，其中該有機溶媒是選自於由醇類、乙二醇醚類、極性脂環烴類、醯胺類、亞碸類所組成的群中的至少一種。 The pretreatment liquid for electroless nickel or electroless nickel alloy according to claim 2, wherein the organic solvent is selected from the group consisting of alcohols, glycol ethers, polar alicyclic hydrocarbons, guanamines, At least one of the group consisting of the azaleas. 如申請專利範圍第2項之無電鍍鎳或無電鍍鎳合金用的前處理液，其中該有機溶媒是選自於由異丙醇、異丁醇、3-甲氧基-3-甲基-1-丁醇、1-辛醇、萜品醇、環己醇、乙二醇、丙二醇、丙二醇甲醚、2-丁氧基乙酸乙酯、乙二醇丁醚、丙二醇甲醚醋酸酯、乙二醇***醋酸脂、2-乙氧基乙酸乙酯、乙二醇二乙酸酯、N,N-二甲基甲醯胺、二甲亞碸、N-甲基吡咯酮、丙烯碳酸鹽所組成的群中的至少一種。 A pretreatment liquid for electroless nickel or electroless nickel alloy according to claim 2, wherein the organic solvent is selected from the group consisting of isopropanol, isobutanol, 3-methoxy-3-methyl- 1-butanol, 1-octanol, terpineol, cyclohexanol, ethylene glycol, propylene glycol, propylene glycol methyl ether, ethyl 2-butoxyacetate, ethylene glycol butyl ether, propylene glycol methyl ether acetate, Glycol ether acetate, 2-ethoxyacetic acid ethyl acetate, ethylene glycol diacetate, N,N-dimethylformamide, dimethyl hydrazine, N-methylpyrrolidone, propylene carbonate At least one of the group consisting of. 如申請專利範圍第1項至第4項中任一項之無電鍍 鎳或無電鍍鎳合金用的前處理液，其中該溶媒包含水，該前處理液的pH為3.0~10.0。 Electroless plating as in any of items 1 to 4 of the patent application scope A pretreatment liquid for nickel or electroless nickel alloy, wherein the solvent comprises water, and the pH of the pretreatment liquid is 3.0 to 10.0. 如申請專利範圍第1項至第4項中任一項之無電鍍鎳或無電鍍鎳合金用的前處理液，其中更包含使該鎳粒子分散於該溶媒中的分散劑，該分散劑之對該鎳粒子的含量為3~70重量%，該分散劑為至少具有一個磺酸基、羧基、羥基或磷酸基的分子量200~10000的化合物。 The pretreatment liquid for electroless nickel or electroless nickel alloy according to any one of claims 1 to 4, further comprising a dispersant for dispersing the nickel particles in the solvent, the dispersant The content of the nickel particles is 3 to 70% by weight, and the dispersant is a compound having a molecular weight of 200 to 10,000 having at least one sulfonic acid group, carboxyl group, hydroxyl group or phosphoric acid group. 如申請專利範圍第6項之無電鍍鎳或無電鍍鎳合金用的前處理液，其中該分散劑是選自於由胺、聚酯、羧酸、羧酸鹽、硫酸鹽、磺酸、磺基琥珀酸、磷酸酯及胺、聚酯、羧酸、羧酸鹽、硫酸鹽、磺酸、磺基琥珀酸、磷酸酯的鹽，烷基銨鹽、直鏈烷基醚、聚醚、聚氨酯、聚丙烯酸酯所組成的群中的至少一種。 The pretreatment liquid for electroless nickel or electroless nickel alloy according to claim 6 of the patent application, wherein the dispersant is selected from the group consisting of amines, polyesters, carboxylic acids, carboxylates, sulfates, sulfonic acids, and sulfonates. Succinic acid, phosphate and amine, polyester, carboxylic acid, carboxylate, sulfate, sulfonic acid, sulfosuccinic acid, phosphate salt, alkyl ammonium salt, linear alkyl ether, polyether, polyurethane And at least one of the group consisting of polyacrylates. 如申請專利範圍第6項之無電鍍鎳或無電鍍鎳合金用的前處理液，其中該分散劑是選自於由聚氧乙烯苯乙烯化二苯醚硫酸銨、聚氧乙烯十三醚磷酸酯、聚氧乙烯烷基醚磷酸酯單乙醇胺鹽、聚氧乙烯烷基磺基琥珀酸二鈉、直鏈型烷基苯磺酸鈉、萘磺酸鈉甲醛縮合物、聚烷基多胺環氧烷加成物、聚烷基聚亞胺環氧烷加成物、聚乙烯吡咯烷酮、聚乙二醇、聚丙二醇、聚乙烯醇、多磷酸所組成的群中的至少一種。 A pretreatment liquid for electroless nickel or electroless nickel alloy according to claim 6 of the patent application, wherein the dispersant is selected from the group consisting of polyoxyethylene styrenated diphenyl ether ammonium sulfate, polyoxyethylene tridecyl ether phosphate Ester, polyoxyethylene alkyl ether phosphate monoethanolamine salt, disodium polyoxyethylene alkyl sulfosuccinate, sodium linear alkylbenzene sulfonate, sodium naphthalene sulfonate formaldehyde condensate, polyalkyl polyamine ring At least one of a group consisting of an oxyalkyl adduct, a polyalkyl polyimide alkylene oxide adduct, polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, and polyphosphoric acid. 如申請專利範圍第1項至第8項中任一項之無電鍍鎳或無電鍍鎳合金用的前處理液，其中施以無電鍍鎳合金 時的鎳合金是選自於由鎳銅合金、鎳鈷合金、鎳錫合金所組成的群的合金。 An electroless nickel or electroless nickel alloy pretreatment liquid according to any one of claims 1 to 8, wherein an electroless nickel alloy is applied The nickel alloy at the time is an alloy selected from the group consisting of nickel-copper alloy, nickel-cobalt alloy, and nickel-tin alloy. 一種電鍍方法，其特徵包含：將非導電性樹脂基板浸漬於申請專利範圍第1項至第9項中任一項之前處理液，直接地使包含於該前處理液的鎳粒子催化劑賦予該非導電性樹脂基板表面上之前處理程序；以及在被進行了前處理的該非導電性樹脂基板上使用無電鍍鎳液或無電鍍鎳合金液形成鎳塗膜或鎳合金塗膜之無電電鍍程序。 An electroplating method, comprising: immersing a non-conductive resin substrate in a treatment liquid before any one of items 1 to 9 of the patent application, directly imparting a nickel particle catalyst contained in the pretreatment liquid to the non-conductive A pretreatment process on the surface of the resin substrate; and an electroless plating process for forming a nickel coating film or a nickel alloy coating film on the non-electroconductive resin substrate subjected to the pretreatment using an electroless nickel plating solution or an electroless nickel plating alloy solution.
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