JP2014130824A - Conductive powder, conductive material containing the same, and manufacturing method of conductive particle - Google Patents
Conductive powder, conductive material containing the same, and manufacturing method of conductive particle Download PDFInfo
- Publication number
- JP2014130824A JP2014130824A JP2014019019A JP2014019019A JP2014130824A JP 2014130824 A JP2014130824 A JP 2014130824A JP 2014019019 A JP2014019019 A JP 2014019019A JP 2014019019 A JP2014019019 A JP 2014019019A JP 2014130824 A JP2014130824 A JP 2014130824A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- palladium
- particles
- electroless
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 228
- 239000000843 powder Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 239000004020 conductor Substances 0.000 title claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 353
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 342
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 176
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 174
- 238000007747 plating Methods 0.000 claims abstract description 145
- 239000011162 core material Substances 0.000 claims abstract description 69
- 238000000576 coating method Methods 0.000 claims abstract description 36
- 239000011248 coating agent Substances 0.000 claims abstract description 34
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 33
- 239000011574 phosphorus Substances 0.000 claims abstract description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011164 primary particle Substances 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 136
- 238000000034 method Methods 0.000 claims description 61
- 239000003638 chemical reducing agent Substances 0.000 claims description 58
- 239000007771 core particle Substances 0.000 claims description 52
- 239000007864 aqueous solution Substances 0.000 claims description 42
- 239000002270 dispersing agent Substances 0.000 claims description 41
- -1 palladium ions Chemical class 0.000 claims description 33
- 239000002002 slurry Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 33
- 229910001453 nickel ion Inorganic materials 0.000 claims description 31
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 30
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- 239000011347 resin Substances 0.000 claims description 26
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- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000002280 amphoteric surfactant Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 239000010931 gold Substances 0.000 abstract description 25
- 229910052737 gold Inorganic materials 0.000 abstract description 24
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 23
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- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 13
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
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- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
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- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、導電性粉体及びそれを含む導電性材料に関する。また本発明は、導電性粒子の製造方法に関する。 The present invention relates to a conductive powder and a conductive material including the same. The present invention also relates to a method for producing conductive particles.
従来、導電性接着剤、異方性導電膜、異方性導電接着剤等に用いられている導電性粉体としては、ニッケル、銅、銀、金、はんだ等の金属粉末；カーボン粉末やカーボン繊維、カーボンフレーク等のカーボン系材料；樹脂粒子の表面を無電解ニッケルめっきして、ニッケルを被覆した導電性粒子が知られている。 Conventionally, conductive powders used for conductive adhesives, anisotropic conductive films, anisotropic conductive adhesives, and the like include metal powders such as nickel, copper, silver, gold, and solder; carbon powder and carbon Carbon-based materials such as fibers and carbon flakes; conductive particles in which the surfaces of resin particles are electroless nickel-plated and coated with nickel are known.
これらの導電性粉体のうち、樹脂粒子の表面にニッケルを被覆した導電性粒子は、ニッケル皮膜が酸化されやすく、このために経時的に電気抵抗が増加することがある。また、更に導電性を高めることを目的として、通常、ニッケル皮膜上に貴金属である金めっき皮膜を更に形成させて使用される。 Among these conductive powders, the conductive particles in which the surfaces of the resin particles are coated with nickel are likely to oxidize the nickel film, and the electrical resistance may increase with time. Further, for the purpose of further improving the conductivity, a gold plating film that is a noble metal is usually formed on the nickel film.
金は高価であることから、他の貴金属を金の代替として使用することが検討されている。例えばパラジウムを最外層とする導電性粉体が提案されている（特許文献１〜３参照。）。しかしながら、最外層が金めっき皮膜である導電性粒子と同等の特性を有しているとは言い難い。 Since gold is expensive, the use of other precious metals as an alternative to gold is being considered. For example, a conductive powder having palladium as an outermost layer has been proposed (see Patent Documents 1 to 3). However, it cannot be said that the outermost layer has the same characteristics as the conductive particles that are gold-plated films.
したがって本発明の目的は、前述した従来技術の金めっき層の最外層を有する導電性粉体と同等又はそれ以上の特性を有する導電性粉体を提供することにある。 Accordingly, an object of the present invention is to provide a conductive powder having characteristics equal to or higher than those of the conductive powder having the outermost gold plating layer of the prior art described above.
前記の目的を達成すべく本発明者らは鋭意検討した結果、パラジウム又はパラジウム皮膜の表面から突出し、かつ該皮膜と連続体となっている突起部を有し、該突起部の高さ、更にはその個数等の突起部の特性を特定範囲に調製したパラジウム被覆粒子を用いること、パラジウム又はパラジウム合金皮膜として実質的にリンを含有しないか、又はリン含有量を特定範囲以下に調整した皮膜を用いること、更に導電性粉体として実質的に凝集粒子が存在しない導電性粉体を調製すること、によって最外層が金めっき皮膜である導電性粒子からなる導電性粉体と同等又はそれ以上の優れた導電性及び電気信頼性を有するものになることを知見した。 As a result of intensive studies by the present inventors to achieve the above object, the present invention has a protrusion protruding from the surface of palladium or a palladium film and being continuous with the film, the height of the protrusion, Use palladium-coated particles whose number of protrusions and other characteristics are adjusted within a specific range, or a palladium or palladium alloy film that does not substantially contain phosphorus or that has a phosphorus content adjusted to a specific range or less. And by preparing a conductive powder that is substantially free of agglomerated particles as a conductive powder, the outermost layer is equivalent to or more than a conductive powder composed of conductive particles having a gold plating film. It has been found that it has excellent electrical conductivity and electrical reliability.
本発明は前記知見に基づきなされたもので、芯材粒子の表面にニッケル又はニッケル合金皮膜が形成されたニッケル被覆粒子表面に、更にパラジウム又はパラジウム合金皮膜が形成された導電性粒子からなる導電性粉体であって、
前記導電性粒子は、パラジウム又はパラジウム合金皮膜表面から突出し、かつ該パラジウム又はパラジウム合金皮膜と連続体になっている、高さが５０ｎｍ以上である突起部を粒子１個当たり５個以上有し、
前記パラジウム又はパラジウム合金皮膜中のリン含有量が３重量％以下であり、
前記導電性粉体においては、前記導電性粒子のうち、一次粒子が占める割合が、導電性粉体の重量に対して８５重量％以上であることを特徴とする導電性粉体を提供するものである。
The present invention has been made on the basis of the above findings, and is made of conductive particles comprising nickel-coated particle surfaces on which nickel or nickel alloy coatings are formed on the surface of core particles, and further comprising conductive particles formed with palladium or palladium alloy coatings. Powder,
The conductive particles have 5 or more protrusions per particle protruding from the surface of the palladium or palladium alloy coating and being continuous with the palladium or palladium alloy coating and having a height of 50 nm or more,
The phosphorus content in the palladium or palladium alloy film is 3% by weight or less,
The conductive powder provides a conductive powder characterized in that the proportion of primary particles in the conductive particles is 85% by weight or more based on the weight of the conductive powder. It is.
また本発明は、芯材粒子の表面に、ニッケル又はニッケル合金皮膜が形成され、該皮膜の表面から突出し、かつ該皮膜と連続体になっている、高さが５０ｎｍ以上である突起部を粒子１個当たり５個以上有するニッケル被覆粒子を、分散剤の存在下に、下記の（Ｄ１）ないし（Ｄ３）のいずれかの方法で、無電解パラジウムめっき処理することを特徴とする導電性粒子の製造方法を提供するものである。
（Ｄ１）純パラジウムめっき浴で還元型無電解パラジウムめっき処理する方法。
（Ｄ２）還元剤として次亜リン酸又はその塩を用いる還元型無電解パラジウムめっき処理において、パラジウムイオンに対する還元剤のモル比を０．１〜１００として還元型無電解パラジウムめっき処理する方法。
（Ｄ３）置換型無電解パラジウムめっき処理する方法。
Further, the present invention provides a projecting portion having a height of 50 nm or more, wherein a nickel or nickel alloy film is formed on the surface of the core particle, protrudes from the surface of the film, and is continuous with the film. Electroconductive palladium plating treatment is carried out by electroless palladium plating by any one of the following methods (D1) to (D3) in the presence of a dispersing agent: 5 nickel-coated particles each having 5 or more particles A manufacturing method is provided.
(D1) A method of reducing electroless palladium plating in a pure palladium plating bath.
(D2) A method of reducing electroless palladium plating in a reducing electroless palladium plating treatment using hypophosphorous acid or a salt thereof as a reducing agent, wherein the molar ratio of the reducing agent to palladium ions is 0.1 to 100.
(D3) A method of performing substitutional electroless palladium plating.
本発明の導電性粉体は、最外層として金めっき皮膜を有する従来技術の導電性粒子からなる導電性粉体と同等又はそれ以上の導電性と、電気信頼性を有するものである。また本発明の製造方法によれば、そのような導電性粉体を容易に製造することができる。 The conductive powder of the present invention has electrical conductivity that is equal to or higher than that of a conductive powder made of conductive particles of the prior art having a gold plating film as the outermost layer, and electrical reliability. Moreover, according to the manufacturing method of this invention, such electroconductive powder can be manufactured easily.
以下、本発明をその好ましい実施形態に基づき説明する。本発明の導電性粉体は、芯材粒子の表面にニッケル又はニッケル合金皮膜（以下、これらを総称して単に「ニッケル皮膜」という。）が形成されたニッケル被覆粒子表面に、更にパラジウム又はパラジウム合金皮膜（以下、これらを総称して単に「パラジウム皮膜」という。）が形成されてなるものである。そして、本発明の導電性粉体は、パラジウム皮膜の表面から突出した突起部を多数有している点に特徴の一つを有している。以下、この突起部について説明する。 Hereinafter, the present invention will be described based on preferred embodiments thereof. The conductive powder according to the present invention further comprises palladium or palladium on the surface of nickel-coated particles in which nickel or a nickel alloy film (hereinafter collectively referred to as “nickel film”) is formed on the surface of the core particles. An alloy film (hereinafter collectively referred to simply as “palladium film”) is formed. And the electroconductive powder of this invention has one of the characteristics in having many protrusion parts which protruded from the surface of the palladium membrane | film | coat. Hereinafter, this protrusion will be described.
本発明において、導電性粒子における個々の突起部は、パラジウム皮膜と連続体になっており、突起部の最外層は少なくともパラジウム皮膜から構成されている。ここで言う「連続体」とは、パラジウム皮膜と突起部との間に、継ぎ目等の一体感を損なうような部位が存在しないことを意味する。したがって、例えば芯材粒子上にパラジウム皮膜を形成し、その上に突起部形成用のコア粒子を付着させ、該コア粒子を成長の起点として形成された突起部は、パラジウム皮膜と連続体になっていないので、本発明に言う連続体に含まれない。突起部がパラジウム皮膜と連続体になっていることで、突起部の強度が確保されるので、導電性粉体の使用時に圧力が加わっても突起部が破損しづらくなる。その結果、良好な導電性を得ることができる。 In the present invention, each protrusion in the conductive particle is a continuous body with the palladium film, and the outermost layer of the protrusion is composed of at least a palladium film. The term “continuous body” as used herein means that there is no portion between the palladium film and the protrusion that impairs the sense of unity such as a joint. Therefore, for example, a palladium film is formed on the core material particles, and core particles for forming the protrusions are adhered thereon, and the protrusions formed using the core particles as a starting point of growth become a continuous body with the palladium film. Therefore, it is not included in the continuum referred to in the present invention. Since the protrusions are continuous with the palladium film, the strength of the protrusions is ensured, so that the protrusions are not easily damaged even when pressure is applied during use of the conductive powder. As a result, good conductivity can be obtained.
本発明の導電性粉体における突起部は、特定以上の高さを有するものが特定範囲で存在していることも特徴の一つである。すなわち本発明の導電性粉体は、高さが５０ｎｍ以上の突起部を粒子１個当たり５個以上有するものである。高さが５ｎｍ以上の突起部の粒子１個当たりの個数の上限値は、１０００個以下にすることが好ましい。この理由は、突起部が多すぎると、突起部と突起部との間隔が狭くなり、突起としての効果が低下する可能性があるためである。特に、高さが５０ｎｍ以上の突起部の数が、粒子１個当たり５〜３００個であると、導電性が特に優れたものになる点で好ましい。 It is one of the characteristics that the protrusion part in the electroconductive powder of this invention has what has a height more than specific in the specific range. That is, the conductive powder of the present invention has 5 or more protrusions having a height of 50 nm or more per particle. The upper limit of the number of protrusions having a height of 5 nm or more per particle is preferably 1000 or less. The reason for this is that if there are too many protrusions, the distance between the protrusions and the protrusions becomes narrow, and the effect as protrusions may be reduced. In particular, it is preferable that the number of protrusions having a height of 50 nm or more is 5 to 300 per particle because the conductivity is particularly excellent.
高さが５０ｎｍ以上の突起部は、粒子の表面から概ね放射状に延びる細長い突起であることが好ましい。該突起部はそのアスペクト比が好ましくは１．０以上、更に好ましくは１．１以上であることが好ましい。この理由は、本発明の導電性粉体を用いて電極の導通をとる場合、電極の表面には薄い酸化皮膜が自然に形成されていたり、あるいは意図的に電極の酸化皮膜を形成したりする場合があるところ、突起部のアスペクト比が大きいと、この酸化皮膜を容易に突き破ることができるためであると考えられる。また、導電性粉体を用いて異方導電フィルムを形成した場合には、突起部のアスペクト比が大きいと、樹脂排除性が高くなるので、導電性が高くなると考えられる。このように、突起部のアスペクト比を１．０以上とすることで、すなわち突起部の形状を細長くすることで、導電性が非常に高くなることが、本発明者らの検討の結果判明した。特に、後述する実施例における実施例１〜７と実施例８〜１０との対比から明らかなように、突起部のアスペクト比が１．０以上であると、高温・高湿下に長期間保存した後の導電性の低下が効果的に抑制される。本発明者らの知る限り、突起部のアスペクト比を１以上とすることは容易でない。従来の導電性粉体における突起部は、言わばずんぐりとした形状を有している。アスペクト比の上限値は、突起部に圧力が加わったときに破損しやすくなる傾向があることから、３．０以下とすることが好ましい。このようなアスペクト比の大きな突起部を有する導電性粒子は、例えば後述する方法によって製造することができる。 The protrusions having a height of 50 nm or more are preferably elongated protrusions extending radially from the surface of the particle. The protrusions preferably have an aspect ratio of 1.0 or more, more preferably 1.1 or more. The reason for this is that when conducting the electrode using the conductive powder of the present invention, a thin oxide film is naturally formed on the surface of the electrode, or an oxide film of the electrode is intentionally formed. In some cases, it is considered that this oxide film can be easily broken if the aspect ratio of the protrusion is large. Moreover, when an anisotropic conductive film is formed using conductive powder, if the aspect ratio of the protrusions is large, the resin exclusion property becomes high, so that the conductivity is considered to be high. As a result of the examination by the present inventors, it was found that the conductivity becomes very high by setting the aspect ratio of the protrusions to 1.0 or more, that is, by elongating the shape of the protrusions. . In particular, as is apparent from the comparison between Examples 1 to 7 and Examples 8 to 10 in the examples described later, when the aspect ratio of the protrusion is 1.0 or more, it is stored for a long time under high temperature and high humidity. The decrease in conductivity after the treatment is effectively suppressed. As far as the present inventors know, it is not easy to set the aspect ratio of the protrusions to 1 or more. The protrusion in the conventional conductive powder has a so-called stubby shape. The upper limit of the aspect ratio is preferably set to 3.0 or less because it tends to break when pressure is applied to the protrusion. Such conductive particles having protrusions with a large aspect ratio can be produced by, for example, a method described later.
本発明におけるアスペクト比とは、突起部の高さＨと突起部の基部における突起部の幅Ｄとの比、すなわちＨ／Ｄで定義される値である。この定義から明らかなように、アスペクト比は突起部の細長さの尺度となるものであり、その値が大きいほど突起部が細長い形状をしていることを意味する。このアスペクト比は、突起部の高さが５０ｎｍ以上である突起部の平均値を示す。 The aspect ratio in the present invention is a ratio defined by the ratio between the height H of the protrusion and the width D of the protrusion at the base of the protrusion, that is, H / D. As is clear from this definition, the aspect ratio is a measure of the slenderness of the protrusion, and the larger the value, the more the protrusion has an elongated shape. This aspect ratio indicates an average value of the protrusions having a protrusion height of 50 nm or more.
上述のアスペクト比の測定方法は次のとおりである。電子顕微鏡によって導電性粉体における個々の粒子を拡大観察する。１つの粒子について少なくとも１個の突起部について、その基部の長さＤ及び高さＨを測定する。この場合、観察像において粒子の中央に存在する突起部よりも、むしろ粒子の周縁に存在する突起部を測定対象とすることが、寸法の正確な測定の点から重要である。このような測定を少なくとも２０個の異なる粒子を対象として行う。このようにして得られた複数のアスペクト比のデータを算術平均し、その値をアスペクト比とする。なお、突起部の横断面は異方性が小さい形状（例えばほぼ円形）をしているので、粒子の観察角度によって突起部の基部の長さＤの値が変わってしまう懸念は小さい。 The above aspect ratio measurement method is as follows. The individual particles in the conductive powder are magnified and observed with an electron microscope. The length D and height H of the base are measured for at least one protrusion for each particle. In this case, it is important from the viewpoint of accurate measurement of dimensions that the projections present at the periphery of the particles are measured rather than the projections present at the center of the particles in the observed image. Such a measurement is performed on at least 20 different particles. The data of a plurality of aspect ratios thus obtained are arithmetically averaged, and the value is used as the aspect ratio. In addition, since the cross section of the protrusion has a shape with small anisotropy (for example, substantially circular), there is little concern that the value of the length D of the base of the protrusion varies depending on the observation angle of the particles.
突起部のアスペクト比は上述のとおりであるところ、該突起部の基部の長さＤそれ自体及び突起部の高さＨそれ自体は、基部の長さＤについては０．０５〜０．５μｍ、特に０．１〜０．４μｍであることが好ましく、高さＨについては０．０５〜０．５μｍ、特に０．１〜０．４μｍであることが好ましい。突起部の基部の長さＤ及び突起部の高さＨがこの範囲内であると、導電性が更に一層向上する。 The aspect ratio of the protrusion is as described above, and the base length D of the protrusion and the height H of the protrusion itself are 0.05 to 0.5 μm for the base length D, In particular, the thickness is preferably 0.1 to 0.4 μm, and the height H is preferably 0.05 to 0.5 μm, particularly preferably 0.1 to 0.4 μm. When the length D of the base of the protrusion and the height H of the protrusion are within this range, the conductivity is further improved.
高さが５０ｎｍ以上である突起部は、粒子１個当たり上述の数存在していればよく、そのような突起部に加えて、導電性粒子中に高さが５０ｎｍ以下の突起部が存在することは、本発明において何ら妨げられない。尤も、高さが５０ｎｍ以下の突起部が多数存在すると、突起部と突起部との間隔が狭くなり、突起としての効果が低下する可能性があることから、アスペクト比が上述した範囲を満たす突起部の割合は、全突起部の数に対して好ましくは４０％以上、更に好ましくは４５％以上、一層好ましくは５０％以上とする。 The number of protrusions having a height of 50 nm or more is sufficient as long as the number described above is present per particle, and in addition to such protrusions, there are protrusions having a height of 50 nm or less in the conductive particles. This is not hindered in the present invention. However, if there are a large number of protrusions with a height of 50 nm or less, the distance between the protrusions becomes narrow and the effect as a protrusion may be reduced. Therefore, the protrusion whose aspect ratio satisfies the above range. The ratio of the part is preferably 40% or more, more preferably 45% or more, and still more preferably 50% or more with respect to the total number of protrusions.
本発明の導電性粉体は、パラジウム皮膜に含まれるリン（Ｐ）の含有量によって特徴付けられる。詳細には、本発明者らの検討の結果、パラジウム皮膜中にリンが３重量％より多く含有されると、導電性、更には電気信頼性に影響することが判明した。したがって本発明では、パラジウム皮膜中のリン含有量を３重量％以下、好ましくは２重量％以下とする。リン含有量の下限値に特に制限はなく、小さければ小さいほど好ましい。パラジウム皮膜中のリン含有量は、後述する実施例に記載の方法で測定される。 The conductive powder of the present invention is characterized by the content of phosphorus (P) contained in the palladium film. Specifically, as a result of the study by the present inventors, it has been found that if the palladium film contains more than 3% by weight of phosphorus, the conductivity and further the electrical reliability are affected. Therefore, in the present invention, the phosphorus content in the palladium film is 3% by weight or less, preferably 2% by weight or less. There is no restriction | limiting in particular in the lower limit of phosphorus content, and it is so preferable that it is small. The phosphorus content in the palladium film is measured by the method described in Examples described later.
パラジウム皮膜の下側に位置するニッケル皮膜に関しては、該皮膜中に含まれるリン含有量に特に制限はない。 Regarding the nickel film located on the lower side of the palladium film, the phosphorus content contained in the film is not particularly limited.
パラジウム皮膜の厚みに関しては、これが薄すぎると導電性粉体が十分な導電性を示しにくくなり、逆に厚すぎると芯材粒子の表面から剥離しやすくなる。これらの観点から、突起部が存在しない部位におけるパラジウム皮膜の厚みは、５〜５００ｎｍであることが好ましく、１０〜３００ｎｍであることが好ましい。 Regarding the thickness of the palladium film, if it is too thin, it becomes difficult for the conductive powder to exhibit sufficient conductivity, and conversely if it is too thick, it tends to peel from the surface of the core particles. From these viewpoints, the thickness of the palladium film in the portion where no protrusion is present is preferably 5 to 500 nm, and more preferably 10 to 300 nm.
ニッケル皮膜は、パラジウム皮膜と同様に、薄すぎると導電性能が不十分である場合があり、逆に厚すぎると粒子が凝集しやすくなる傾向にあることから、その厚みを１０〜３００ｎｍ、特に５０〜２５０ｎｍとすることが好ましい。 Similar to the palladium film, the nickel film may have insufficient conductive performance if it is too thin. Conversely, if the nickel film is too thick, the particles tend to aggregate. It is preferable to set it to ˜250 nm.
導電性粒子におけるパラジウム皮膜の厚み及びニッケル皮膜の厚みは、後述する実施例に記載の方法で測定される。 The thickness of the palladium film and the thickness of the nickel film in the conductive particles are measured by the method described in Examples described later.
パラジウム皮膜の下側に位置するニッケル皮膜は、芯材粒子の表面を被覆してニッケル被覆粒子を形成している。このニッケル被覆粒子は、芯材粒子を無電解ニッケルめっき処理して、該芯材粒子の表面にニッケル皮膜を形成すると同時に突起部も形成したものであることが好ましい。このようにして形成された突起部は、一層破損しづらいものになるからである。この観点から、本発明の導電性粉体においては、個々の粒子における突起部は、ニッケル又はニッケル合金からなる突起部芯体と、該芯体の表面を被覆するパラジウム又はパラジウム合金からなる突起部被覆層から構成されていることが好ましい。突起部がこのような構造である場合、突起部芯体は、パラジウム皮膜の下側に位置するニッケル皮膜と連続体になっていることが好ましい。また、突起部被覆層は、パラジウム皮膜と連続体になっていることが好ましい。 The nickel coating located on the lower side of the palladium coating coats the surface of the core material particles to form nickel-coated particles. The nickel-coated particles are preferably obtained by subjecting the core material particles to electroless nickel plating to form a nickel film on the surface of the core material particles and at the same time forming protrusions. This is because the protrusion formed in this way is more difficult to break. From this point of view, in the conductive powder of the present invention, the protrusions in the individual particles include a protrusion core made of nickel or a nickel alloy, and a protrusion made of palladium or a palladium alloy covering the surface of the core. It is preferable that it is comprised from the coating layer. When the protrusion has such a structure, it is preferable that the protrusion core is a continuous body with the nickel film located below the palladium film. Moreover, it is preferable that the protrusion part coating layer is a continuous body with the palladium film.
前記のニッケル皮膜によって被覆されている芯材粒子としては、後述するように各種の材質からなるものを用いることができる。特に芯材粒子として、樹脂粒子を用いると、得られる導電性粉体の粒度分布がシャープになり、また圧縮回復特性に優れる観点から特に好ましい。 As the core particles coated with the nickel film, those made of various materials can be used as will be described later. In particular, when resin particles are used as the core particles, the particle size distribution of the obtained conductive powder becomes sharp and is particularly preferable from the viewpoint of excellent compression recovery characteristics.
本発明の導電性粉体においては、個々の粒子の形状は球形であることが好ましい。ここで言う粒子の形状とは、突起部を除いた粒子の形状のことである。粒子が球形であることと、突起部を有していることに起因して、本発明の導電性粉体は、その導電性が高いものとなる。 In the conductive powder of the present invention, the shape of each particle is preferably spherical. The particle shape referred to here is the particle shape excluding the protrusions. Due to the spherical shape of the particles and the protrusions, the conductive powder of the present invention has high conductivity.
また本発明の導電性粉体は、先に述べた突起部の個数との関係において、後述するコールターカウンター法から求められる平均粒径が１〜５０μｍ、特に１〜４０μｍ、とりわけ１．５〜３０μｍである導電性粒子から構成されることが好ましい。この範囲の粒径の導電性粒子となすことで、粒子１個当たりの突起部の数と突起部の密度とがバランスして、導電性を高くすることが容易となる。 The conductive powder of the present invention has an average particle size of 1 to 50 μm, particularly 1 to 40 μm, particularly 1.5 to 30 μm, which is determined by the Coulter counter method described later, in relation to the number of protrusions described above. It is preferable that it is comprised from the electroconductive particle which is. By forming conductive particles having a particle size in this range, the number of protrusions per particle and the density of the protrusions are balanced, and it becomes easy to increase the conductivity.
導電性粒子は、その粒径が小さくなると凝集しやすい傾向にある。凝集が起こると、導電性粒子を用いた異方導電フィルムが短絡を起こしやすいという不都合がある。また、凝集をほぐすために粉砕等の処理を施すと、パラジウム皮膜及び／又はニッケル皮膜が剥離して導電性低下の原因となる。この観点から、本発明の導電性粉体においては、個々の粒子の分散性を高めることが重要である。そこで本発明の導電性粉体においては、導電性粒子のうち、一次粒子が占める割合が、導電性粉体の重量に対して８５重量％以上、好ましくは９０重量％以上、更に好ましくは９２重量％以上になっている。導電性粒子の分散性を高めるためには、例えば後述する方法に従い導電性粒子を製造すればよい。一次粒子が占める割合は次の方法で測定される。導電性粉体０．１ｇを１００ｍＬの水に入れ超音波ホモジナイザーで１分間分散させる。次いで、コールターカウンター法によって粒度分布を測定する。その結果から、一次粒子の重量割合を算出する。 Conductive particles tend to agglomerate as the particle size decreases. When aggregation occurs, there is an inconvenience that an anisotropic conductive film using conductive particles easily causes a short circuit. Further, when a treatment such as pulverization is performed to loosen the agglomeration, the palladium film and / or the nickel film is peeled off, resulting in a decrease in conductivity. From this viewpoint, it is important to improve the dispersibility of individual particles in the conductive powder of the present invention. Therefore, in the conductive powder of the present invention, the proportion of the primary particles in the conductive particles is 85% by weight or more, preferably 90% by weight or more, more preferably 92% by weight with respect to the weight of the conductive powder. % Or more. In order to improve the dispersibility of the conductive particles, for example, the conductive particles may be produced according to a method described later. The proportion of primary particles is measured by the following method. 0.1 g of conductive powder is placed in 100 mL of water and dispersed with an ultrasonic homogenizer for 1 minute. Next, the particle size distribution is measured by a Coulter counter method. From the result, the weight ratio of the primary particles is calculated.
導電性粒子におけるパラジウム皮膜は金属パラジウム又はパラジウム合金から構成されている。パラジウム合金には、例えばパラジウム−リン合金が含まれる。パラジウム−リン合金は、後述する導電性粉体の製造において、パラジウムの還元剤として次亜リン酸ナトリウムを用いた場合に生じる合金である。 The palladium film on the conductive particles is made of metallic palladium or a palladium alloy. The palladium alloy includes, for example, a palladium-phosphorus alloy. The palladium-phosphorus alloy is an alloy produced when sodium hypophosphite is used as a reducing agent for palladium in the production of conductive powder described later.
また、導電性粒子におけるニッケル皮膜は、金属ニッケル又はニッケル合金から構成されている。ニッケル合金には、例えばニッケル−リン合金が含まれる。ニッケル−リン合金も、後述する導電性粉体の製造において、ニッケルの還元剤として次亜リン酸ナトリウムを用いた場合に生じる合金である。 Further, the nickel coating on the conductive particles is made of metallic nickel or a nickel alloy. The nickel alloy includes, for example, a nickel-phosphorus alloy. A nickel-phosphorus alloy is also an alloy produced when sodium hypophosphite is used as a nickel reducing agent in the production of conductive powder described later.
次に、本発明の導電性粉体の好適な製造方法について説明する。本製造方法では、芯材粒子の表面に、ニッケル又はニッケル合金皮膜が形成され、該皮膜の表面から突出し、かつ該皮膜と連続体になっている、高さが５０ｎｍ以上である突起部を粒子１個当たり５個以上有するニッケル被覆粒子（以下、「ニッケル被覆粒子」と単に呼ぶ。）を、分散剤の存在下に、下記の（Ｄ１）ないし（Ｄ３）のいずれかの方法で、無電解パラジウムめっき処理する。
（Ｄ１）純パラジウムめっき浴で還元型無電解パラジウムめっき処理する方法。
（Ｄ２）還元剤として次亜リン酸又はその塩を用いる還元型無電解パラジウムめっき処理において、パラジウムイオンに対する還元剤のモル比を０．１〜１００として還元型無電解パラジウムめっき処理する方法。
（Ｄ３）置換型無電解パラジウムめっき処理する方法。
Next, the suitable manufacturing method of the electroconductive powder of this invention is demonstrated. In this production method, a nickel or nickel alloy film is formed on the surface of the core particle, protrudes from the surface of the film, and is a continuous body with the film. In the presence of a dispersant, nickel-coated particles having 5 or more particles per particle (hereinafter simply referred to as “nickel-coated particles”) are electrolessly treated by any of the following methods (D1) to (D3). Treat with palladium plating.
(D1) A method of reducing electroless palladium plating in a pure palladium plating bath.
(D2) A method of reducing electroless palladium plating in a reducing electroless palladium plating treatment using hypophosphorous acid or a salt thereof as a reducing agent, wherein the molar ratio of the reducing agent to palladium ions is 0.1 to 100.
(D3) A method of performing substitutional electroless palladium plating.
ニッケル被覆粒子は、以下の（ｂ１）及び（ｂ２）の２つのうちのいずれかの方法で得られるものであると、突起部の強度が強く導電性粉体の使用時に圧力が加わっても突起部が破損しづらくなり、その結果、良好な導電性を得ることができる観点から好ましい。 When the nickel-coated particles are obtained by any one of the following methods (b1) and (b2), the protrusions have a high strength even when pressure is applied during use of the conductive powder. This is preferable from the viewpoint of making it difficult for the portion to be damaged and, as a result, obtaining good conductivity.
（ｂ１）
分散剤及びニッケルイオンを含む無電解ニッケルめっき浴と、表面に貴金属が担持された芯材粒子とを混合して、該芯材粒子の表面にニッケル初期薄膜層を形成するに際し、ニッケルイオンの濃度が０．０００１〜０．００８モル／リットルに調整された該無電解ニッケルめっき浴１リットルに対して、表面積の総和が１〜１５ｍ2となるような量の該芯材粒子を用いるＡ１工程と、
Ａ１工程において得られた、ニッケル初期薄膜層を有する前記芯材粒子、及び前記分散剤を含む水性スラリーを、該分散剤の分散効果が発現するｐＨ範囲に維持しつつ、該水性スラリーに、１時間当たりのニッケルの析出量が２５〜１００ｎｍとなる量に相当する量のニッケルイオン及び還元剤を経時的に添加するＡ２工程を有する方法（以下、「ｂ１の製造法」と呼ぶ。）。
(B1)
When an electroless nickel plating bath containing a dispersant and nickel ions is mixed with core material particles having a noble metal supported on the surface, a nickel initial thin film layer is formed on the surface of the core material particles. Step A1 using the core particles in such an amount that the total surface area is 1 to 15 m 2 with respect to 1 liter of the electroless nickel plating bath adjusted to 0.0001 to 0.008 mol / liter. ,
While maintaining the aqueous slurry containing the core particle having the nickel initial thin film layer and the dispersant obtained in the step A1 in a pH range in which the dispersing effect of the dispersant is expressed, A method having an A2 step of adding nickel ions and a reducing agent in an amount corresponding to an amount of nickel deposited per hour of 25 to 100 nm (hereinafter referred to as “production method of b1”).
（ｂ２）
芯材粒子の水性スラリーを分散剤、ニッケル塩、還元剤、錯化剤などを含んだ無電解ニッケルめっき浴に添加し、無電解ニッケルめっき処理するＢ１工程、次いで該無電解ニッケルめっき浴に、無電解ニッケルめっき液の構成成分を少なくとも２液に分離して、それぞれを同時にかつ経時的に添加する無電解ニッケルめっき処理するＢ２工程とを有する方法（以下、「ｂ２の製造法」と呼ぶ。）。
(B2)
An aqueous slurry of core material particles is added to an electroless nickel plating bath containing a dispersant, a nickel salt, a reducing agent, a complexing agent, etc., and B1 step for electroless nickel plating treatment, and then to the electroless nickel plating bath, A method (hereinafter referred to as “a manufacturing method of b2”) including a B2 step of separating the components of the electroless nickel plating solution into at least two solutions and adding each of them simultaneously and over time to the electroless nickel plating treatment. ).
前記ｂ１及びｂ２の製造法で用いる芯材粒子の形状は、目的とする導電性粒子の形状に大きく影響する。先に述べたとおり、芯材粒子の表面を被覆するニッケル皮膜の厚み及びパラジウム皮膜は薄いものなので、芯材粒子の形状がほとんどそのまま導電性粒子の形状に反映される。導電性粒子が球形であることが好ましいことは先に述べたとおりであるので、芯材粒子の形状も球形であることが好ましい。 The shape of the core particles used in the production methods b1 and b2 greatly affects the shape of the target conductive particles. As described above, since the nickel coating and the palladium coating covering the surface of the core particles are thin, the shape of the core particles is almost directly reflected in the shape of the conductive particles. Since it is preferable that the conductive particles have a spherical shape as described above, the shape of the core particles is also preferably a spherical shape.
芯材粒子が球形である場合、芯材粒子の粒径は目的とする導電性粒子の粒径に大きく影響する。先に述べたとおり、芯材粒子の表面を被覆するニッケル皮膜及びパラジウム皮膜の厚みは薄いものなので、芯材粒子の粒径がほとんど導電性粒子の粒径に反映される。この観点から、芯材粒子の粒径は、目的とする導電性粒子の粒径と同程度とすることができる。具体的にはコールターカウンター法によって求められる平均粒径が１〜５０μｍ、特に１〜４０μｍ、とりわけ１．５〜３０．０μｍであることが好ましい。 When the core material particles are spherical, the particle size of the core material particles greatly affects the particle size of the target conductive particles. As described above, since the nickel coating and the palladium coating covering the surface of the core material particles are thin, the particle size of the core material particle is almost reflected in the particle size of the conductive particles. From this viewpoint, the particle diameter of the core particles can be set to be approximately the same as the particle diameter of the target conductive particles. Specifically, the average particle size determined by the Coulter counter method is preferably 1 to 50 μm, more preferably 1 to 40 μm, and particularly preferably 1.5 to 30.0 μm.
前述の方法によって測定された芯材粉体の粒度分布には幅がある。一般に、粉体の粒度分布の幅は、下記式（１）で示される変動係数により表わされる。
変動係数（％）＝（標準偏差／平均粒径）×１００ （１）
この変動係数が大きいことは分布に幅があることを示し、一方、変動係数が小さいことは粒度分布がシャープであることを示す。本発明では、芯材粒子として、この変動係数が３０％以下、特に２０％以下、とりわけ１０％以下のものを使用することが好ましい。この理由は、本発明の導電性粒子を異方導電フィルム中の導電粒子として用いた場合に、接続に有効な寄与割合が高くなるという利点があるからである。
There is a range in the particle size distribution of the core powder measured by the method described above. Generally, the width of the particle size distribution of the powder is represented by a coefficient of variation represented by the following formula (1).
Coefficient of variation (%) = (standard deviation / average particle diameter) × 100 (1)
A large coefficient of variation indicates that the distribution is wide, while a small coefficient of variation indicates that the particle size distribution is sharp. In the present invention, it is preferable to use the core particles having a coefficient of variation of 30% or less, particularly 20% or less, particularly 10% or less. This is because, when the conductive particles of the present invention are used as the conductive particles in the anisotropic conductive film, there is an advantage that the effective contribution ratio for connection is increased.
芯材粒子の具体例としては、無機物として、金属（合金も含む）、ガラス、セラミックス、シリカ、カーボン、金属又は非金属の酸化物（含水物も含む）、アルミノ珪酸塩を含む金属珪酸塩、金属炭化物、金属窒化物、金属炭酸塩、金属硫酸塩、金属リン酸塩、金属硫化物、金属酸塩、金属ハロゲン化物及び炭素などが挙げられる。有機物としては、天然繊維、天然樹脂、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、ポリブテン、ポリアミド、ポリアクリル酸エステル、ポリアクリロニトリル、ポリアセタール、アイオノマー、ポリエステルなどの熱可塑性樹脂、アルキッド樹脂、フェノール樹脂、尿素樹脂、メラミン樹脂、ベンゾグアナミン樹脂、メラミン樹脂、キシレン樹脂、シリコーン樹脂、エポキシ樹脂又はジアリルフタレート樹脂などが挙げられる。これらは単独でも使用でき又は２種以上の混合物として使用してもよい。 Specific examples of the core particles include, as inorganic substances, metals (including alloys), glass, ceramics, silica, carbon, metal or non-metal oxides (including hydrates), metal silicates including aluminosilicates, Examples thereof include metal carbide, metal nitride, metal carbonate, metal sulfate, metal phosphate, metal sulfide, metal acid salt, metal halide, and carbon. Organic materials include natural fibers, natural resins, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polybutene, polyamide, polyacrylate, polyacrylonitrile, polyacetal, ionomer, polyester, and other thermoplastic resins, alkyd resins, phenol resins, urea Examples thereof include resins, melamine resins, benzoguanamine resins, melamine resins, xylene resins, silicone resins, epoxy resins, and diallyl phthalate resins. These may be used alone or in a mixture of two or more.
また、芯材粒子のその他の物性は、特に制限されるものではないが、芯材粒子が樹脂粒子である場合は、下記の式（２）で定義されるＫの値が、２０℃において１０ｋｇｆ／ｍｍ2〜１００００ｋｇｆ／ｍｍ2の範囲であり、かつ１０％圧縮変形後の回復率が２０℃において１％〜１００％の範囲であることが好ましい。これらの物性値を満足することで、電極どうしを圧着するときに電極を傷つけることなく、電極と十分に接触させることができるからである。
Ｋ値（ｋｇｆ／ｍｍ2）＝（３／√２）×Ｆ×Ｓ-3/2×Ｒ-1/2・・・（２）
式（２）で示されるＦ及びＳは、微小圧縮試験機ＭＣＴＭ−５００（（株）島津製作所製）で測定したときの、それぞれ該微球体の１０％圧縮変形における荷重値（ｋｇｆ）及び圧縮変位（ｍｍ）であり、Ｒは該微球体の半径（ｍｍ）である。
The other physical properties of the core particles are not particularly limited, but when the core particles are resin particles, the value of K defined by the following formula (2) is 10 kgf at 20 ° C. / Mm 2 to 10000 kgf / mm 2 , and the recovery rate after 10% compression deformation is preferably in the range of 1% to 100% at 20 ° C. This is because, by satisfying these physical property values, the electrodes can be sufficiently brought into contact with each other without being damaged when the electrodes are crimped together.
K value (kgf / mm 2 ) = (3 / √2) × F × S −3/2 × R −1/2 (2)
F and S represented by the formula (2) are the load value (kgf) and compression in 10% compression deformation of the microsphere, respectively, when measured with a micro compression tester MCTM-500 (manufactured by Shimadzu Corporation). Displacement (mm), and R is the radius (mm) of the microsphere.
芯材粒子は、その表面が貴金属イオンの捕捉能を有するか、又は貴金属イオンの捕捉能を有するように表面改質されることが好ましい。貴金属イオンは、パラジウムや銀のイオンであることが好ましい。貴金属イオンの捕捉能を有するとは、貴金属イオンをキレート又は塩として捕捉し得ることを言う。例えば芯材粒子の表面に、アミノ基、イミノ基、アミド基、イミド基、シアノ基、水酸基、ニトリル基、カルボキシル基などが存在する場合には、該芯材粒子の表面は貴金属イオンの捕捉能を有する。貴金属イオンの捕捉能を有するように表面改質する場合には、例えば特開昭６１−６４８８２号公報記載の方法を用いることができる。 It is preferable that the surface of the core particle is modified so that the surface thereof has a precious metal ion capturing ability or a precious metal ion capturing ability. The noble metal ions are preferably palladium or silver ions. Having a noble metal ion scavenging ability means that the noble metal ion can be captured as a chelate or salt. For example, when an amino group, an imino group, an amide group, an imide group, a cyano group, a hydroxyl group, a nitrile group, a carboxyl group, or the like is present on the surface of the core particle, the surface of the core particle is capable of capturing noble metal ions. Have In the case of modifying the surface so as to have the ability to trap noble metal ions, for example, a method described in JP-A-61-64882 can be used.
このような芯材粒子を用い、その表面に貴金属を担持させる。具体的には、芯材粒子を塩化パラジウムや硝酸銀のような貴金属塩の希薄な酸性水溶液に分散させる。これによって貴金属イオンを粒子の表面に捕捉させる。貴金属塩の濃度は粒子の表面積１ｍ2当り１×１０-7〜１×１０-2モルの範囲で充分である。貴金属イオンが捕捉された芯材粒子は系から分離され水洗される。引き続き、芯材粒子を水に懸濁させ、これに還元剤を加えて貴金属イオンの還元処理を行う。これによって芯材粒子の表面に貴金属を坦持させる。還元剤としては、例えば次亜リン酸ナトリウム、水酸化ほう素ナトリウム、水素化ほう素カリウム、ジメチルアミンボラン、ヒドラジン、ホルマリン等が用いられる。 Using such core material particles, a noble metal is supported on the surface. Specifically, the core material particles are dispersed in a dilute acidic aqueous solution of a noble metal salt such as palladium chloride or silver nitrate. This traps noble metal ions on the surface of the particles. The concentration of the noble metal salt is sufficiently in the range of 1 × 10 −7 to 1 × 10 −2 mol per 1 m 2 of the particle surface area. The core particles in which the noble metal ions are captured are separated from the system and washed with water. Subsequently, the core material particles are suspended in water, and a reducing agent is added to the suspension so that noble metal ions are reduced. As a result, the noble metal is supported on the surface of the core particles. As the reducing agent, for example, sodium hypophosphite, sodium boron hydroxide, potassium borohydride, dimethylamine borane, hydrazine, formalin and the like are used.
貴金属イオンを芯材粒子の表面に捕捉させる前に、錫イオンを粒子の表面に吸着させる感受性化処理を施してもよい。錫イオンを粒子の表面に吸着させるには、例えば表面改質処理された芯材粒子を塩化第一錫の水溶液に投入し所定時間撹拌すればよい。 Before capturing the noble metal ions on the surface of the core material particles, a sensitization treatment for adsorbing the tin ions on the surface of the particles may be performed. In order to adsorb the tin ions on the surface of the particles, for example, the surface-treated core material particles may be put into an aqueous solution of stannous chloride and stirred for a predetermined time.
以下、前記ｂ１の製造方法について更に詳しく説明する。本製造方法は、（１）芯材粒子の表面にニッケル初期薄膜層を形成するＡ１工程と、（２）Ａ１工程で得られた粒子を原料として用い、目的とする導電性粒子を形成するＡ２工程の２工程に大別される。以下、それぞれの工程について説明する。 Hereinafter, the production method of b1 will be described in more detail. In this production method, (1) A1 step of forming a nickel initial thin film layer on the surface of core material particles, and (2) A2 of forming target conductive particles using the particles obtained in A1 step as raw materials. It is roughly divided into two processes. Hereinafter, each process will be described.
Ａ１工程においては、分散剤及びニッケルイオンを含む無電解ニッケルめっき浴と、表面に貴金属が担持された芯材粒子とを混合して、芯材粒子の表面にニッケル初期薄膜層を形成する。 In step A1, an electroless nickel plating bath containing a dispersant and nickel ions is mixed with core material particles having a noble metal supported on the surface to form a nickel initial thin film layer on the surface of the core material particles.
前述した芯材粒子を、分散剤及びニッケルイオンを含む無電解ニッケルめっき浴と混合する。無電解ニッケルめっき浴は水を媒体とする溶液であり、それに含まれる分散剤としては、例えば非イオン界面活性剤、両性イオン界面活性剤及び／又は水溶性高分子が挙げられる。非イオン界面活性剤としては、ポリエチレングリコール、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテルなどのポリオキシアルキレンエーテル系の界面活性剤を用いることができる。両性イオン界面活性剤としては、アルキルジメチル酢酸ベタイン、アルキルジメチルカルボキシメチル酢酸ベタイン、アルキルジメチルアミノ酢酸ベタインなどのベタイン系の界面活性剤を用いることができる。水溶性高分子としては、ポリビニルアルコール、ポリビニルピロリジノン、ヒドロキシエチルセルロースなどを用いることができる。分散剤の使用量は、その種類にもよるが、一般に、液体（無電解ニッケルめっき浴）の体積に対して０．５〜３０ｇ／Ｌである。特に、分散剤の使用量が液体（無電解ニッケルめっき浴）の体積に対して１〜１０ｇ／Ｌの範囲であると、ニッケル皮膜の密着性が向上する観点から好ましい。 The core material particles described above are mixed with an electroless nickel plating bath containing a dispersant and nickel ions. The electroless nickel plating bath is a solution using water as a medium, and examples of the dispersant contained therein include a nonionic surfactant, a zwitterionic surfactant, and / or a water-soluble polymer. As the nonionic surfactant, polyoxyalkylene ether surfactants such as polyethylene glycol, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and the like can be used. As the zwitterionic surfactant, a betaine surfactant such as alkyldimethylacetic acid betaine, alkyldimethylcarboxymethylacetic acid betaine, and alkyldimethylaminoacetic acid betaine can be used. As the water-soluble polymer, polyvinyl alcohol, polyvinyl pyrrolidinone, hydroxyethyl cellulose and the like can be used. The amount of the dispersant used is generally 0.5 to 30 g / L with respect to the volume of the liquid (electroless nickel plating bath) although it depends on the type. In particular, the amount of the dispersant used is preferably in the range of 1 to 10 g / L with respect to the volume of the liquid (electroless nickel plating bath) from the viewpoint of improving the adhesion of the nickel film.
無電解ニッケルめっき浴に含まれるニッケルイオンは、そのニッケル源として水溶性ニッケル塩が用いられる。水溶性ニッケル塩としては、硫酸ニッケルや塩化ニッケルを用いることができるが、これに限定されるものではない。無電解ニッケルめっき浴に含まれるニッケルイオンの濃度は０．０００１〜０．００８モル／リットル、特に０．０００１〜０．００５モル／リットルであることが好ましい。 For nickel ions contained in the electroless nickel plating bath, a water-soluble nickel salt is used as the nickel source. As the water-soluble nickel salt, nickel sulfate or nickel chloride can be used, but is not limited thereto. The concentration of nickel ions contained in the electroless nickel plating bath is preferably 0.0001 to 0.008 mol / liter, particularly preferably 0.0001 to 0.005 mol / liter.
無電解ニッケルめっき浴には、上述の成分の他に還元剤を含有させることができる。還元剤としては、先に述べた貴金属イオンの還元に用いられているものと同様のものを用いることができる。無電解ニッケルめっき浴における還元剤の濃度は４×１０-4〜２．０モル／リットル、特に２．０×１０-3〜０．２モル／リットルであることが好ましい。 In addition to the above-described components, the electroless nickel plating bath can contain a reducing agent. As the reducing agent, those similar to those used for the reduction of the noble metal ions described above can be used. The concentration of the reducing agent in the electroless nickel plating bath is preferably 4 × 10 −4 to 2.0 mol / liter, particularly 2.0 × 10 −3 to 0.2 mol / liter.
無電解ニッケルめっき浴には、更に錯化剤を含有させておいてもよい。錯化剤を含有させることで、めっき液の分解が抑制されるという有利な効果が奏される。錯化剤としては、有機カルボン酸又はその塩、例えばクエン酸、ヒドロキシ酢酸、酒石酸、リンゴ酸、乳酸若しくはグルコン酸又はそのアルカリ金属塩やアンモニウム塩が挙げられる。これらの錯化剤は１種又は２種類以上用いることができる。無電解ニッケルめっき浴における錯化剤の濃度は、０．００５〜６モル／リットル、特に０．０１〜３モル／リットルであることが好ましい。 The electroless nickel plating bath may further contain a complexing agent. By containing the complexing agent, an advantageous effect that the decomposition of the plating solution is suppressed is exhibited. Examples of the complexing agent include organic carboxylic acids or salts thereof such as citric acid, hydroxyacetic acid, tartaric acid, malic acid, lactic acid or gluconic acid, or alkali metal salts or ammonium salts thereof. These complexing agents can be used alone or in combination of two or more. The concentration of the complexing agent in the electroless nickel plating bath is preferably 0.005 to 6 mol / liter, particularly 0.01 to 3 mol / liter.
前処理が施された芯材粒子と無電解ニッケルめっき浴とを混合する方法に特に制限はない。例えば無電解ニッケルめっき浴を、ニッケルイオンの還元が可能な温度に加熱しておき、その状態下に、前処理が施された芯材粒子を無電解ニッケルめっき浴中に投入することができる。この操作によって、ニッケルイオンが還元し、還元によって生じたニッケルが芯材粒子の表面に初期薄膜層を形成する。初期薄膜層は、その厚みが０．１〜１０ｎｍ、特に０．１〜５ｎｍとなるように形成されることが好ましい。この時点では、突起部はまだ形成されていない。 There is no particular limitation on the method of mixing the pretreated core material particles and the electroless nickel plating bath. For example, the electroless nickel plating bath can be heated to a temperature at which nickel ions can be reduced, and the pretreated core material particles can be put into the electroless nickel plating bath. By this operation, nickel ions are reduced, and nickel produced by the reduction forms an initial thin film layer on the surface of the core material particles. The initial thin film layer is preferably formed to have a thickness of 0.1 to 10 nm, particularly 0.1 to 5 nm. At this point, the protrusion has not yet been formed.
Ａ１工程において重要な点は、無電解ニッケルめっき浴中に含まれるニッケルイオンの量と、投入する芯材粒子の量との関係である。具体的には、ニッケルイオンの濃度が０．０００１〜０．００８モル／リットル、好ましくは０．０００１〜０．００５モル／リットルに調整された無電解ニッケルめっき浴１リットルに対して、表面積の総和が１〜１５ｍ2、好ましくは２〜８ｍ2となるような量の芯材粒子を用いる。これによって、上述の厚みを有する初期薄膜層を容易に形成することができる。また、ニッケルイオンの量と芯材粒子の量との関係を上述のとおりにすることで、初期薄膜層が形成された芯材粒子どうしの凝集を効果的に防止することができる。このことは、芯材粒子の粒径が小さい場合、例えば粒径が３μｍ以下である場合に特に有効である。 An important point in the step A1 is the relationship between the amount of nickel ions contained in the electroless nickel plating bath and the amount of core material particles to be introduced. Specifically, the surface area of the electroless nickel plating bath is adjusted to a nickel ion concentration of 0.0001 to 0.008 mol / liter, preferably 0.0001 to 0.005 mol / liter. The amount of the core particles is such that the total is 1 to 15 m 2 , preferably 2 to 8 m 2 . Thereby, the initial thin film layer having the above-described thickness can be easily formed. In addition, by making the relationship between the amount of nickel ions and the amount of core material particles as described above, aggregation of the core material particles on which the initial thin film layer is formed can be effectively prevented. This is particularly effective when the particle diameter of the core material particles is small, for example, when the particle diameter is 3 μm or less.
ニッケルイオンの還元が完了したら、次いでＡ２工程を行う。Ａ２工程は、Ａ１工程の引き続きで行い、Ａ１工程で得られたニッケル初期薄膜層を有する芯材粒子を液体から分離する等の操作は行わない。したがって、ニッケル初期薄膜層を有する芯材粒子を含む水性スラリー中には、Ａ１工程において添加した分散剤が残存している。Ａ２工程においては、Ａ１工程で得られたニッケル初期薄膜層を有する芯材粒子、及びＡ１工程で用いた分散剤を含む水性スラリーに、ニッケルイオン及び還元剤を経時的に添加する。「経時的に添加」とは、ニッケルイオン及び還元剤を一括して添加することを除外する趣旨であり、ある一定の時間にわたってニッケルイオン及び還元剤を連続的に又は断続的に添加することを意図している。この場合、ニッケルイオン及び還元剤の添加のタイミングは完全に一致していてもよく、あるいはニッケルイオンの添加が先行し、還元剤の添加がそれに続いてもよい。その逆でもよい。更に、添加の終点においては、ニッケルイオンの添加の終了が先行し、還元剤の添加の終了がそれに続いてもよい。その逆でもよい。 When the reduction of nickel ions is completed, step A2 is then performed. The A2 step is performed after the A1 step, and the operation such as separation of the core particles having the nickel initial thin film layer obtained in the A1 step from the liquid is not performed. Therefore, the dispersant added in the step A1 remains in the aqueous slurry containing the core particles having the nickel initial thin film layer. In step A2, nickel ions and a reducing agent are added over time to the aqueous slurry containing the core material particles having the nickel initial thin film layer obtained in step A1 and the dispersant used in step A1. “Adding over time” is intended to exclude adding nickel ions and a reducing agent all at once, and adding nickel ions and a reducing agent continuously or intermittently over a certain period of time. Intended. In this case, the timing of adding the nickel ions and the reducing agent may be completely the same, or the addition of nickel ions may precede and the addition of the reducing agent may follow. The reverse is also possible. Further, at the end point of addition, the end of the addition of nickel ions may precede, and the end of the addition of the reducing agent may follow. The reverse is also possible.
Ａ２工程で用いるニッケルイオンのニッケル源としては、Ａ１工程で用いたニッケル源と同様のものを用いることができる。還元剤についても同様である。 As the nickel source of nickel ions used in step A2, the same nickel source as used in step A1 can be used. The same applies to the reducing agent.
Ａ２工程においては、ニッケルイオンの還元によって、先ず液中に微小なニッケルの核粒子を生成させ、その核粒子をＡ１工程で得られたニッケル初期薄膜層を有する芯材粒子の表面に付着させ、付着した核粒子を起点としてこれを成長させて、ニッケルからなる突起部芯体を形成する。この方法を採用することで、粒子どうしの凝集を効果的に防止することができ、かつ高さが５０ｎｍ以上でアスペクト比が１以上の突起部を容易に形成することができる。 In step A2, by reducing nickel ions, first, fine nickel core particles are generated in the liquid, and the core particles are attached to the surface of the core material particles having the nickel initial thin film layer obtained in step A1, The deposited core particles are grown as starting points to form a protruding portion core made of nickel. By adopting this method, aggregation of particles can be effectively prevented, and a protrusion having a height of 50 nm or more and an aspect ratio of 1 or more can be easily formed.
Ａ２工程におけるニッケルイオンの還元においては、水性スラリーを、Ａ１工程で添加した分散剤（この分散剤はＡ２工程においても残存している）の分散効果が発現するｐＨ範囲に維持することが重要である。これによって、粒子どうしの凝集を効果的に防止することができる。ｐＨの調整には、水性スラリーのｐＨを監視しながら各種鉱酸等の酸又は水酸化ナトリウム等のアルカリを水性スラリーに添加すればよい。ｐＨの調整範囲は、使用する分散剤に応じて適切な値を採用すればよい。分散剤として例えば非イオン界面活性剤を用いる場合には、水性スラリーのｐＨを５〜１０の範囲に維持することが好ましい。分散剤として両性イオン界面活性剤を用いる場合には、水性スラリーのｐＨを５〜８の範囲に維持することが好ましい。分散剤として水溶性高分子を用いる場合にも、水性スラリーのｐＨを５〜８の範囲に維持することが好ましい。 In the reduction of nickel ions in step A2, it is important to maintain the aqueous slurry in a pH range in which the dispersing effect of the dispersant added in step A1 (this dispersant remains in step A2) is exhibited. is there. Thereby, aggregation of particles can be effectively prevented. To adjust the pH, an acid such as various mineral acids or an alkali such as sodium hydroxide may be added to the aqueous slurry while monitoring the pH of the aqueous slurry. The pH adjustment range may be an appropriate value depending on the dispersant used. For example, when a nonionic surfactant is used as the dispersant, it is preferable to maintain the pH of the aqueous slurry in the range of 5 to 10. When using a zwitterionic surfactant as the dispersant, it is preferable to maintain the pH of the aqueous slurry in the range of 5-8. Even when a water-soluble polymer is used as the dispersant, it is preferable to maintain the pH of the aqueous slurry in the range of 5 to 8.
Ａ２工程におけるニッケルイオンの還元においては、水性スラリーに添加するニッケルイオンの量及び還元剤の量も重要である。これによって、アスペクト比の高い突起部芯体を首尾よく形成することが可能となる。具体的な条件としては、水性スラリーに、１時間当たりのニッケルの析出量が２５〜１００ｎｍ、好ましくは４０〜６０ｎｍとなる量に相当する量のニッケルイオン及び還元剤を経時的に添加する。このような添加の条件を採用することで、ニッケルの析出が、初期薄膜層よりも核粒子において優先的に生じるようになり、アスペクト比の高い突起部芯体が容易に形成される。 In the reduction of nickel ions in step A2, the amount of nickel ions and the amount of reducing agent added to the aqueous slurry are also important. This makes it possible to successfully form a projection core having a high aspect ratio. As specific conditions, nickel ions and a reducing agent in an amount corresponding to the amount of precipitation of nickel per hour of 25 to 100 nm, preferably 40 to 60 nm are added to the aqueous slurry over time. By adopting such an addition condition, nickel precipitates preferentially occur in the core particles over the initial thin film layer, and a protrusion core having a high aspect ratio can be easily formed.
ニッケルイオン及び還元剤の添加においては、水性スラリーを所定温度に加熱して、還元剤によるニッケルイオンの還元が円滑に進行するようにしてもよい。ニッケルイオン及び還元剤の添加においては、水性スラリーを攪拌しておき、還元したニッケルの付着が均一に生じるようにしてもよい。このようにして、目的とするニッケル被覆粒子が得られる。 In the addition of nickel ions and a reducing agent, the aqueous slurry may be heated to a predetermined temperature so that the reduction of nickel ions by the reducing agent proceeds smoothly. In the addition of nickel ions and a reducing agent, the aqueous slurry may be stirred so that the reduced nickel adheres uniformly. In this way, the desired nickel-coated particles are obtained.
次に、前記ｂ２の製造方法について更に詳しく説明する。本製造方法におけるＢ１工程は、芯材粒子の水性スラリーと、分散剤、ニッケル塩、還元剤及び錯化剤などを含んだ無電解ニッケルめっき浴とを混合する無電解ニッケルめっき工程である。かかるＢ１工程では、芯材粒子上へのニッケル皮膜の形成と同時にめっき浴の自己分解が起こる。この自己分解は、芯材粒子の近傍で生じるため、ニッケル皮膜の形成時に自己分解物が芯材粒子表面上に捕捉されることによって、微小突起の核が生成し、それと同時にニッケル皮膜の形成がなされる。生成した微小突起の核を基点として、突起部芯体が成長する。 Next, the production method of b2 will be described in more detail. Step B1 in this production method is an electroless nickel plating step in which an aqueous slurry of core material particles is mixed with an electroless nickel plating bath containing a dispersant, a nickel salt, a reducing agent, a complexing agent, and the like. In the B1 process, the plating bath self-decomposes simultaneously with the formation of the nickel film on the core particles. Since this self-decomposition occurs in the vicinity of the core particle, when the nickel film is formed, the self-decomposed product is trapped on the surface of the core particle, thereby generating nuclei of microprojections and at the same time forming the nickel film. Made. The protrusion core body grows with the core of the generated fine protrusion as a base point.
Ｂ１工程では、前述した芯材粒子を好ましくは１〜５００ｇ／Ｌ、更に好ましくは５〜３００ｇ／Ｌの範囲で水に十分に分散させ、水性スラリーを調製する。分散操作は、通常攪拌、高速攪拌又はコロイドミル若しくはホモジナイザーのような剪断分散装置を用いて行うことができる。また、分散操作に超音波を併用してもかまわない。必要に応じ、分散操作においては界面活性剤などの分散剤を添加する場合もある。次いで、ニッケル塩、還元剤、錯化剤及び各種添加剤などを含んだ無電解ニッケルめっき浴に、分散操作を行った芯材粒子の水性スラリーを添加し、無電解めっきＢ１工程を行う。 In the step B1, the above-described core material particles are preferably sufficiently dispersed in water in a range of preferably 1 to 500 g / L, more preferably 5 to 300 g / L to prepare an aqueous slurry. The dispersing operation can be usually performed using stirring, high-speed stirring, or a shearing dispersion device such as a colloid mill or a homogenizer. Further, ultrasonic waves may be used in combination with the dispersion operation. If necessary, a dispersing agent such as a surfactant may be added in the dispersing operation. Next, an aqueous slurry of the core material particles subjected to the dispersion operation is added to an electroless nickel plating bath containing a nickel salt, a reducing agent, a complexing agent, various additives, and the like, and the electroless plating B1 step is performed.
前述した分散剤としては、例えば非イオン界面活性剤、両性イオン界面活性剤及び／又は水溶性高分子が挙げられる。非イオン界面活性剤としては、ポリエチレングリコール、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテルなどのポリオキシアルキレンエーテル系の界面活性剤を用いることができる。両性イオン界面活性剤としては、アルキルジメチル酢酸ベタイン、アルキルジメチルカルボキシメチル酢酸ベタイン、アルキルジメチルアミノ酢酸ベタインなどのベタイン系の界面活性剤を用いることができる。水溶性高分子としては、ポリビニルアルコール、ポリビニルピロリジノン、ヒドロキシエチルセルロースなどを用いることができる。これらの分散剤は、１種又は２種以上を組み合わせて用いることができる。分散剤の使用量は、その種類にもよるが、一般に、液体（無電解ニッケルめっき浴）の体積に対して０．５〜３０ｇ／Ｌである。特に、分散剤の使用量が液体（無電解ニッケルめっき浴）の体積に対して１〜１０ｇ／Ｌの範囲であると、ニッケル皮膜の密着性が一層向上する観点から好ましい。 Examples of the dispersant described above include nonionic surfactants, zwitterionic surfactants, and / or water-soluble polymers. As the nonionic surfactant, polyoxyalkylene ether surfactants such as polyethylene glycol, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and the like can be used. As the zwitterionic surfactant, a betaine surfactant such as alkyldimethylacetic acid betaine, alkyldimethylcarboxymethylacetic acid betaine, and alkyldimethylaminoacetic acid betaine can be used. As the water-soluble polymer, polyvinyl alcohol, polyvinyl pyrrolidinone, hydroxyethyl cellulose and the like can be used. These dispersants can be used alone or in combination of two or more. The amount of the dispersant used is generally 0.5 to 30 g / L with respect to the volume of the liquid (electroless nickel plating bath) although it depends on the type. In particular, the amount of the dispersant used is preferably in the range of 1 to 10 g / L with respect to the volume of the liquid (electroless nickel plating bath) from the viewpoint of further improving the adhesion of the nickel film.
ニッケル塩としては、例えば塩化ニッケル、硫酸ニッケル又は酢酸ニッケルなどが用いられ、その濃度は０．１〜５０ｇ／Ｌの範囲とすることが好ましい。還元剤としては、例えば次亜燐酸ナトリウム、ジメチルアミンボラン、水素化ホウ素ナトリウム、水素化ホウ素カリウム又はヒドラジンなどが用いられ、その濃度は０．１〜５０ｇ／Ｌの範囲であることが好ましい。錯化剤としては、例えばクエン酸、ヒドロキシ酢酸、酒石酸、リンゴ酸、乳酸、グルコン酸若しくはそのアルカリ金属塩やアンモニウム塩などのカルボン酸（塩）、グリシンなどのアミノ酸、エチレンジアミン、アルキルアミンなどのアミン酸、その他のアンモニウム、ＥＤＴＡ又はピロリン酸（塩）など、ニッケルイオンに対し錯化作用のある化合物が使用され、これらは１種又は２種以上であってもよい。その濃度は好ましくは１〜１００ｇ／Ｌ、更に好ましくは５〜５０ｇ／Ｌの範囲である。この段階での好ましい無電解ニッケルめっき浴のｐＨは、４〜１４の範囲である。無電解ニッケルめっき反応は、芯材粒子の水性スラリーを添加すると速やかに始まり、水素ガスの発生を伴う。無電解めっきＢ１工程は、その水素ガスの発生が完全に認められなくなった時点をもって終了とする。 As the nickel salt, for example, nickel chloride, nickel sulfate, nickel acetate or the like is used, and the concentration is preferably in the range of 0.1 to 50 g / L. As the reducing agent, for example, sodium hypophosphite, dimethylamine borane, sodium borohydride, potassium borohydride or hydrazine is used, and the concentration is preferably in the range of 0.1 to 50 g / L. Examples of complexing agents include citric acid, hydroxyacetic acid, tartaric acid, malic acid, lactic acid, gluconic acid or carboxylic acids (salts) such as alkali metal salts and ammonium salts thereof, amino acids such as glycine, and amines such as ethylenediamine and alkylamine. A compound having a complexing action with respect to nickel ions, such as acid, other ammonium, EDTA, or pyrophosphoric acid (salt) is used, and these may be used alone or in combination of two or more. The concentration is preferably in the range of 1 to 100 g / L, more preferably 5 to 50 g / L. The pH of the preferred electroless nickel plating bath at this stage is in the range of 4-14. The electroless nickel plating reaction starts rapidly when an aqueous slurry of core particles is added, and is accompanied by the generation of hydrogen gas. The electroless plating B1 step ends when the generation of the hydrogen gas is not completely recognized.
次いでＢ２工程においては、前記のＢ１工程に続けて、（ｉ）ニッケル塩、還元剤及びアルカリのうちの１種を含む第１の水溶液と、残りの２種を含む第２の水溶液を用いるか、又は（ii）ニッケル塩を含む第１の水溶液と、還元剤を含む第２の水溶液と、アルカリを含む第３の水溶液とを用い、これらの水溶液をそれぞれを同時にかつ経時的に、Ｂ１工程の液に添加して無電解ニッケルめっきを行う。これらの液を添加すると再びめっき反応が始まるが、その添加量を調整することによって、形成されるニッケル皮膜を所望の膜厚に制御することができる。無電解ニッケルめっき液の添加終了後、水素ガスの発生が完全に認められなくなってから暫く液温を保持しながら攪拌を継続して反応を完結させる。 Next, in step B2, whether (i) a first aqueous solution containing one of a nickel salt, a reducing agent, and an alkali and a second aqueous solution containing the remaining two are used following the step B1. Or (ii) using a first aqueous solution containing a nickel salt, a second aqueous solution containing a reducing agent, and a third aqueous solution containing an alkali, each of these aqueous solutions being simultaneously and over time, step B1 Electroless nickel plating is added to the above solution. When these solutions are added, the plating reaction starts again. By adjusting the amount of addition, the formed nickel film can be controlled to a desired film thickness. After completion of the addition of the electroless nickel plating solution, the reaction is completed by continuing stirring while maintaining the solution temperature for a while after generation of hydrogen gas is not completely observed.
前記の（ｉ）の場合には、ニッケル塩を含む第１の水溶液と、還元剤及びアルカリを含む第２の水溶液とを用いることが好ましいが、この組み合わせに限られない。この場合には、第１の水溶液には還元剤及びアルカリは含まれず、第２の水溶液にはニッケル塩は含まれない。ニッケル塩及び還元剤としては、先に述べたものを用いることができる。アルカリとしては、例えば水酸化ナトリウムや水酸化カリウム等のアルカリ金属の水酸化物を用いることができる。前記の（ii）の場合についても同様である。 In the case of (i), it is preferable to use a first aqueous solution containing a nickel salt and a second aqueous solution containing a reducing agent and an alkali, but the present invention is not limited to this combination. In this case, the first aqueous solution contains no reducing agent and alkali, and the second aqueous solution contains no nickel salt. As the nickel salt and the reducing agent, those described above can be used. As the alkali, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be used. The same applies to the case (ii).
前記の（ii）の場合には、第１〜第３の水溶液にニッケル塩、還元剤及びアルカリがそれぞれ含まれ、かつ各水溶液には当該成分以外の他の２成分は含まれない。 In the case of (ii) above, the first to third aqueous solutions each contain a nickel salt, a reducing agent, and an alkali, and each aqueous solution contains no other two components other than the components.
（ｉ）及び（ii）の場合のいずれであっても、水溶液中のニッケル塩の濃度は５０〜４００ｇ／Ｌ、特に１００〜３００ｇ／Ｌであることが好ましい。還元剤の濃度は５０〜１０００ｇ／Ｌ、特に５０〜９００ｇ／Ｌであることが好ましい。アルカリの濃度は１０〜３００ｇ／Ｌ、特に２０〜２５０ｇ／Ｌであることが好ましい。 In any case of (i) and (ii), the concentration of the nickel salt in the aqueous solution is preferably 50 to 400 g / L, particularly preferably 100 to 300 g / L. The concentration of the reducing agent is preferably 50 to 1000 g / L, particularly 50 to 900 g / L. The alkali concentration is preferably 10 to 300 g / L, more preferably 20 to 250 g / L.
Ｂ２工程は、Ｂ１工程の終了後に連続して行うが、これに代えて、Ｂ１工程とＢ２工程とを断続して行ってもよい。この場合には、Ｂ１工程の終了後、濾過などの方法によって芯材粒子とめっき液とを分別し、新たに芯材粒子を水に分散させて水性スラリーを調製し、そこに錯化剤を好ましくは１〜１００ｇ／Ｌ、更に好ましくは５〜５０ｇ／Ｌの濃度範囲で溶解した水溶液を添加し、分散剤を好ましくは０．５〜３０ｇ／Ｌ、更に好ましくは１〜１０ｇ／Ｌの範囲で溶解し水性スラリーを調製して、該水性スラリーに前記の各水溶液を添加するＢ２工程を行う方法でもよい。このようにして目的とするニッケル被覆粒子が得られる。 Although B2 process is continuously performed after completion | finish of B1 process, it may replace with this and may perform B1 process and B2 process intermittently. In this case, after completion of the B1 step, the core material particles and the plating solution are separated by a method such as filtration, and the core material particles are newly dispersed in water to prepare an aqueous slurry, and the complexing agent is added thereto. Preferably, an aqueous solution dissolved in a concentration range of 1 to 100 g / L, more preferably 5 to 50 g / L is added, and the dispersant is preferably 0.5 to 30 g / L, more preferably 1 to 10 g / L. Alternatively, a method may be used in which an aqueous slurry is prepared by dissolution in step B2, and the step B2 is performed in which the aqueous solutions are added to the aqueous slurry. In this way, the desired nickel-coated particles are obtained.
なお、ｂ１及びｂ２の製造方法において、ニッケル被覆粒子を、ボールミルを用いた粉砕工程に付することもできる。この粉砕工程に付することによって、単分散したニッケル被覆粒子を得ることができ、また、該単分散したニッケル被覆粒子を後述する無電解パラジウムめっき処理することによって、個々の粒子の粒子表面に均一なパラジウムめっき皮膜を形成することができ、また導電性粉体の重量に対する一次粒子が占める割合を、無電解パラジウムめっき処理後において、上述した範囲内に更に容易に設定することができる。 In addition, in the manufacturing method of b1 and b2, nickel covering particle | grains can also be attached | subjected to the grinding | pulverization process using a ball mill. By subjecting to this pulverization step, monodispersed nickel-coated particles can be obtained, and by subjecting the monodispersed nickel-coated particles to electroless palladium plating, which will be described later, the particle surfaces of the individual particles are uniform. A ratio of primary particles to the weight of the conductive powder can be easily set within the above-described range after the electroless palladium plating treatment.
本発明において、ｂ１の製造方法は、芯材粒子の大きさ等にかかわらず、有効に用いることができるが、特に芯材粒子の平均粒径が１〜１０μｍの微粒な芯材粒子に対して無電解ニッケルめっきして、突起部芯体を有するニッケル被覆粒子を得る場合に、特に有効な方法である。一方、ｂ２の製造方法は３〜５０μｍの比較的大きな芯材粒子に対して無電解ニッケルめっきして、突起部芯体を有するニッケル被覆粒子を得る場合に、特に有効な方法である。 In the present invention, the production method of b1 can be used effectively regardless of the size or the like of the core particles, but particularly for fine core particles having an average particle diameter of 1 to 10 μm. This is a particularly effective method when electroless nickel plating is performed to obtain nickel-coated particles having a protrusion core. On the other hand, the production method of b2 is a particularly effective method when electroless nickel plating is performed on relatively large core material particles of 3 to 50 μm to obtain nickel-coated particles having a protrusion core.
このようにして得られたニッケル被覆粒子を、分散剤の存在下に、下記の（Ｄ１）ないし（Ｄ３）のいずれかの方法で、無電解パラジウムめっき処理することにより、目的とする導電性粉体を得ることができる。
（Ｄ１）純パラジウムめっき浴で還元型無電解パラジウムめっき処理する方法。
（Ｄ２）還元剤として次亜リン酸又はその塩を用いる還元型無電解パラジウムめっき処理において、パラジウムイオンに対する還元剤のモル比を０．１〜１００として還元型無電解パラジウムめっき処理する方法。
（Ｄ３）置換型無電解パラジウムめっき処理する方法。
The nickel-coated particles thus obtained are subjected to electroless palladium plating in the presence of a dispersant by any of the following methods (D1) to (D3), whereby the intended conductive powder is obtained. You can get a body.
(D1) A method of reducing electroless palladium plating in a pure palladium plating bath.
(D2) A method of reducing electroless palladium plating in a reducing electroless palladium plating treatment using hypophosphorous acid or a salt thereof as a reducing agent, wherein the molar ratio of the reducing agent to palladium ions is 0.1 to 100.
(D3) A method of performing substitutional electroless palladium plating.
前記（Ｄ１）及び（Ｄ２）の還元型無電解パラジウムめっき方法は、めっき液中のパラジウムイオンを還元剤の働きによって、ニッケル皮膜上にパラジウムを析出させるものである。そして、（Ｄ１）のめっき方法では、還元剤として、例えばギ酸化合物を使用することで、無電解パラジウムめっき皮膜として純度が９９重量％以上のものが得られる。一方、（Ｄ２）の還元型無電解パラジウムめっき方法では、還元剤として次亜燐酸又はその塩を使用することで、パラジウム−リン合金からなるめっき皮膜が得られる。 The reduced electroless palladium plating methods (D1) and (D2) are those in which palladium ions in a plating solution are deposited on a nickel film by the action of a reducing agent. In the plating method (D1), for example, by using a formic acid compound as the reducing agent, an electroless palladium plating film having a purity of 99% by weight or more can be obtained. On the other hand, in the reduced electroless palladium plating method (D2), a plating film made of a palladium-phosphorus alloy can be obtained by using hypophosphorous acid or a salt thereof as a reducing agent.
以下に、（Ｄ１）の純パラジウムめっき浴で還元型無電解パラジウムめっき処理する方法について説明する。純パラジウムめっき浴は、パラジウム化合物、還元剤及び錯化剤を必須成分として含有する水溶液からなる。本発明では、該純パラジウムめっき浴へ、分散剤及び前記ニッケル被覆粒子を含有させ還元型無電解パラジウムめっき処理を行う。 A method for reducing electroless palladium plating in the pure palladium plating bath (D1) will be described below. The pure palladium plating bath is composed of an aqueous solution containing a palladium compound, a reducing agent and a complexing agent as essential components. In the present invention, a reducing electroless palladium plating treatment is performed by containing a dispersant and the nickel-coated particles in the pure palladium plating bath.
前記パラジウム化合物としては、めっき液に可溶であって、所定の濃度の水溶液が得られるものであれば特に制限はない。例えば、硫酸パラジウム、塩化パラジウム、硝酸パラジウム、酢酸パラジウム、ジクロロジエチレンジアミンパラジウム、テトラアミンパラジウムジクロライド等の水溶性パラジウム化合物等が挙げられる。これらは１種又は２種以上で用いることができる。また、パラジウム化合物として、パラジウムを溶液化したパラジウム溶液を用いることもできる。パラジウム溶液としては、例えば、ジクロロジエチレンジアミンパラジウム溶液やテトラアンミンパラジウムジクロライド溶液を使用することができる。純パラジウムめっき浴におけるパラジウム化合物の含有量は、パラジウムとして好ましくは０．１〜３０ｇ／Ｌ、更に好ましくは０．３〜１０ｇ／Ｌである。 The palladium compound is not particularly limited as long as it is soluble in the plating solution and can obtain an aqueous solution having a predetermined concentration. Examples thereof include water-soluble palladium compounds such as palladium sulfate, palladium chloride, palladium nitrate, palladium acetate, dichlorodiethylenediamine palladium, tetraamine palladium dichloride, and the like. These can be used alone or in combination of two or more. Further, as the palladium compound, a palladium solution obtained by dissolving palladium can be used. As the palladium solution, for example, a dichlorodiethylenediamine palladium solution or a tetraammine palladium dichloride solution can be used. The content of the palladium compound in the pure palladium plating bath is preferably 0.1 to 30 g / L, more preferably 0.3 to 10 g / L as palladium.
還元剤はギ酸又はその塩が用いられる。純パラジウムめっき浴における還元剤の含有量は、好ましくは０．１〜１００ｇ／Ｌ、更に好ましくは１〜５０ｇ／Ｌである。 Formic acid or a salt thereof is used as the reducing agent. The content of the reducing agent in the pure palladium plating bath is preferably 0.1 to 100 g / L, more preferably 1 to 50 g / L.
錯化剤としては、例えばエチレンジアミン、ジエチレントリアミン等のアミン類；エチレンジアミンジ酢酸、エチレンジアミンテトラ酢酸、ジエチレントリアミンペンタ酢酸等のアミノポリカルボン酸、これらのナトリウム塩、カリウム塩、アンモニウム塩等；グリシン、アラニン、イミノジ酢酸、ニトリロトリ酢酸、Ｌ−グルタミン酸、Ｌ−グルタミン酸２酢酸、Ｌ−アスパラギン酸、タウリン等のアミノ酸、これらのナトリウム塩、カリウム塩、アンモニウム塩等；アミノトリメチレンホスホン酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸、エチレンジアミンテトラメチレンホスホン酸、これらのアンモニウム塩、カリウム塩、ナトリウム塩等を配合することができる。錯化剤は１種単独又は２種以上混合して用いることができる。純パラジウムめっき浴における錯化剤の含有量は、０．５〜１００ｇ／Ｌ程度とすることが好ましく、５〜５０ｇ／Ｌ程度とすることが一層好ましい。 Examples of complexing agents include amines such as ethylenediamine and diethylenetriamine; aminopolycarboxylic acids such as ethylenediaminediacetic acid, ethylenediaminetetraacetic acid, and diethylenetriaminepentaacetic acid; sodium salts, potassium salts, and ammonium salts thereof; glycine, alanine, and iminodi Amino acids such as acetic acid, nitrilotriacetic acid, L-glutamic acid, L-glutamic acid diacetic acid, L-aspartic acid and taurine, sodium salts, potassium salts and ammonium salts thereof; aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1, 1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, ammonium salts, potassium salts, sodium salts thereof and the like can be blended. Complexing agents can be used alone or in combination of two or more. The content of the complexing agent in the pure palladium plating bath is preferably about 0.5 to 100 g / L, and more preferably about 5 to 50 g / L.
分散剤としては、例えば非イオン界面活性剤、両性イオン界面活性剤及び水溶性高分子が挙げられる。非イオン界面活性剤としては、ポリエチレングリコール、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテルなどのポリオキシアルキレンエーテル系の界面活性剤を用いることができる。両性イオン界面活性剤としては、アルキルジメチル酢酸ベタイン、アルキルジメチルカルボキシメチル酢酸ベタイン、アルキルジメチルアミノ酢酸ベタインなどのベタイン系の界面活性剤を用いることができる。水溶性高分子としては、ポリビニルアルコール、ポリビニルピロリジノン、ヒドロキシエチルセルロースなどを用いることができる。分散剤の使用量は、その種類にもよるが、一般に、液体（純パラジウムめっき浴）の体積に対して０．５〜３０ｇ／Ｌである。特に分散剤の使用量が液体（純パラジウムめっき浴）の体積に対して１〜１０ｇ／Ｌの範囲であると、パラジウム皮膜の密着性が向上し、更に凝集粒子の生成を抑制する効果が高くなる観点から好ましい。 Examples of the dispersant include nonionic surfactants, zwitterionic surfactants, and water-soluble polymers. As the nonionic surfactant, polyoxyalkylene ether surfactants such as polyethylene glycol, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and the like can be used. As the zwitterionic surfactant, a betaine surfactant such as alkyldimethylacetic acid betaine, alkyldimethylcarboxymethylacetic acid betaine, and alkyldimethylaminoacetic acid betaine can be used. As the water-soluble polymer, polyvinyl alcohol, polyvinyl pyrrolidinone, hydroxyethyl cellulose and the like can be used. The amount of the dispersant used is generally 0.5 to 30 g / L with respect to the volume of the liquid (pure palladium plating bath) although it depends on the type. In particular, when the amount of the dispersant used is in the range of 1 to 10 g / L with respect to the volume of the liquid (pure palladium plating bath), the adhesion of the palladium film is improved and the effect of suppressing the formation of aggregated particles is high. From the viewpoint of
前記無電解パラジウムめっき反応のｐＨは、３〜１０、特に４〜７であると、安定した析出速度が得られるので好ましい。ｐＨ調整には、例えば硫酸、塩酸、水酸化ナトリウム、アンモニア水等を使用することができる。反応温度は２０〜９０℃、特に４０〜８０℃であると、平滑で緻密な皮膜が得られる観点から好ましい。 The pH of the electroless palladium plating reaction is preferably 3 to 10, particularly 4 to 7 because a stable deposition rate can be obtained. For pH adjustment, for example, sulfuric acid, hydrochloric acid, sodium hydroxide, aqueous ammonia and the like can be used. The reaction temperature is preferably 20 to 90 ° C, particularly 40 to 80 ° C, from the viewpoint of obtaining a smooth and dense film.
なお、純パラジウムめっき浴は、安定剤等の常用の添加剤が含有されていてもよい。そのような添加剤を含有する純パラジウムめっき浴としては例えば、日本カニゼン株式会社、小島化学薬品株式会社、中央化学産業株式会社等から市販されている市販品を用いてもよい。 The pure palladium plating bath may contain conventional additives such as stabilizers. As a pure palladium plating bath containing such an additive, for example, a commercial product commercially available from Nippon Kanisen Co., Ltd., Kojima Chemical Co., Ltd., Chuo Chemical Sangyo Co., Ltd. or the like may be used.
次に、（Ｄ２）の還元剤として次亜リン酸又はその塩を用いる還元型無電解パラジウムめっき方法について説明する。（Ｄ２）のめっき浴としては、パラジウム−リンめっき浴が用いられる。該パラジウム−リンめっき浴は、パラジウム化合物、次亜リン酸又はその塩の還元剤及び錯化剤を必須成分として含有する水溶液からなる。本発明では、該パラジウム−リンめっき浴と、分散剤及び前記ニッケル被覆粒子とを混合して、還元型無電解パラジウムめっき処理を行う。 Next, a reduced electroless palladium plating method using hypophosphorous acid or a salt thereof as the reducing agent (D2) will be described. As the plating bath (D2), a palladium-phosphorus plating bath is used. The palladium-phosphorous plating bath is composed of an aqueous solution containing a reducing agent and a complexing agent of a palladium compound, hypophosphorous acid or a salt thereof as essential components. In the present invention, the palladium-phosphorous plating bath, a dispersant and the nickel-coated particles are mixed to perform a reduced electroless palladium plating treatment.
パラジウム化合物、還元剤、錯化剤及び分散剤としては、前述した（Ｄ１）の還元型無電解パラジウムめっき方法と同じものを、同様な添加量で用いることができる。 As the palladium compound, the reducing agent, the complexing agent, and the dispersing agent, the same method as the reducing electroless palladium plating method (D1) described above can be used in the same amount.
（Ｄ２）の還元型パラジウムめっき方法では、パラジウムイオンに対する還元剤の配合量を特定範囲に調整することで、パラジウム皮膜中のリン含有量が調整される。通常、パラジウム皮膜中のリン含有量は、パラジウムイオンに対する還元剤の次亜リン酸又はその塩の配合量が多くなるにしたがって多くなる。（Ｄ２）の還元型無電解パラジウムめっきでは、パラジウムイオンに対する還元剤のモル比を、従来に比べて低い範囲に設定することが好ましい。すなわち、パラジウムイオンに対する還元剤のモル比を０．１〜１００に設定して還元型無電解パラジウムめっき処理することで、パラジウム皮膜中のリン含有量を３重量％以下、好ましくは０．５〜３重量％に調整する。パラジウムイオンに対する還元剤の添加量がモル比で０．１より小さくなると、析出速度が低下し実用的でなく、一方、１００より大きくなると、前述したようにパラジウム皮膜中のリン含有量が５重量％より大きくなり、リン含有量が３重量％以下のパラジウム皮膜が得られない。特に、本発明では、パラジウムイオンに対する還元剤のモル比が１〜３０の範囲であることが好ましい。 In the reduced palladium plating method of (D2), the phosphorus content in the palladium film is adjusted by adjusting the blending amount of the reducing agent with respect to palladium ions to a specific range. Usually, the phosphorus content in the palladium film increases as the amount of the reducing agent hypophosphorous acid or its salt added to the palladium ions increases. In the reduced electroless palladium plating of (D2), it is preferable to set the molar ratio of the reducing agent to palladium ions in a lower range than in the past. That is, by setting the molar ratio of the reducing agent to palladium ions to 0.1 to 100 and performing the reduced electroless palladium plating treatment, the phosphorus content in the palladium film is 3 wt% or less, preferably 0.5 to Adjust to 3% by weight. When the addition amount of the reducing agent with respect to palladium ions is less than 0.1 in terms of molar ratio, the deposition rate decreases and is not practical. On the other hand, when it exceeds 100, the phosphorus content in the palladium film is 5 wt. %, And a palladium film having a phosphorus content of 3% by weight or less cannot be obtained. In particular, in the present invention, the molar ratio of the reducing agent to palladium ions is preferably in the range of 1-30.
前記無電解パラジウム−リンめっき反応のｐＨは、好ましくは５〜１０、更に好ましくは５．５〜９とする。ｐＨをこの範囲内に設定することで、めっき液の安定性が高くなり、またパラジウム皮膜にクラック等の欠陥が発生しづらくなる。ｐＨの調整には、例えば硫酸、塩酸、水酸化ナトリウム、アンモニア水等を使用することができる。反応温度が２５〜８０℃、特に４０〜７０℃であると平滑で緻密な皮膜が得られる観点から好ましい。 The pH of the electroless palladium-phosphorous plating reaction is preferably 5 to 10, more preferably 5.5 to 9. By setting the pH within this range, the stability of the plating solution is increased, and defects such as cracks are less likely to occur in the palladium film. For adjusting the pH, for example, sulfuric acid, hydrochloric acid, sodium hydroxide, aqueous ammonia and the like can be used. A reaction temperature of 25 to 80 ° C., particularly 40 to 70 ° C., is preferable from the viewpoint of obtaining a smooth and dense film.
なお、パラジウム−リンめっき浴には安定剤等の常用の添加剤が含有されていてもよい。そのような添加剤を含有するパラジウム−リンめっき浴としては例えば、小島化学薬品株式会社、石原薬品株式会社等で市販されている市販品を用いてもよい。 The palladium-phosphorous plating bath may contain conventional additives such as stabilizers. As the palladium-phosphorus plating bath containing such an additive, for example, commercially available products available from Kojima Chemical Co., Ltd., Ishihara Pharmaceutical Co., Ltd., etc. may be used.
次いで、（Ｄ３）の置換型無電解パラジウムめっき方法について説明する。（Ｄ３）の置換型無電解パラジウムめっき処理する方法では、パラジウムイオンとニッケルイオンとの置換反応により置換型無電解パラジウムめっきしてニッケル被覆粒子にパラジウムめっき皮膜を形成する。 Next, the substitutional electroless palladium plating method (D3) will be described. In the substitution type electroless palladium plating method (D3), substitution type electroless palladium plating is performed by a substitution reaction of palladium ions and nickel ions to form a palladium plating film on the nickel-coated particles.
置換型無電解パラジウムめっき浴は、パラジウム化合物及び錯化剤を必須成分として含有する水溶液からなる。本発明では、該置換型無電解パラジウムめっき浴へ分散剤及び前記ニッケル被覆粒子を含有させて置換型無電解パラジウムめっき処理を行う。 The substitutional electroless palladium plating bath is composed of an aqueous solution containing a palladium compound and a complexing agent as essential components. In the present invention, the substitutional electroless palladium plating treatment is performed by adding a dispersant and the nickel-coated particles to the substitutional electroless palladium plating bath.
パラジウム化合物、錯化剤及び分散剤は、前述した（Ｄ１）の還元型無電解パラジウムめっき方法と同じものを同様な添加量で用いることができる。パラジウム化合物として、特にテトラアンミンパラジウム塩を用いた場合には、緻密なパラジウム皮膜が得られるので好ましい。 As the palladium compound, the complexing agent and the dispersing agent, the same ones as in the reducing electroless palladium plating method of (D1) described above can be used in the same addition amount. In particular, when a tetraammine palladium salt is used as the palladium compound, a dense palladium film is obtained, which is preferable.
置換型無電解パラジウムめっき反応を、ｐＨ３〜１０、特に４〜８で行うと、平滑で緻密な皮膜が得られやすいので好ましい。ｐＨ調整には、例えば硫酸、塩酸、水酸化ナトリウム、アンモニア水等を使用することができる。反応温度は２５〜８０℃、特に３０〜７０℃であることが、反応速度が実用的な程度に速くなり、また緻密なパラジウム皮膜が得られやすい点から好ましい。 It is preferable to perform the substitutional electroless palladium plating reaction at a pH of 3 to 10, particularly 4 to 8 because a smooth and dense film can be easily obtained. For pH adjustment, for example, sulfuric acid, hydrochloric acid, sodium hydroxide, aqueous ammonia and the like can be used. The reaction temperature is preferably 25 to 80 ° C., particularly 30 to 70 ° C., because the reaction rate is increased to a practical level and a dense palladium film is easily obtained.
前記（Ｄ１）〜（Ｄ３）のめっき反応終了後、常法により濾過分離、乾燥して、導電性粉体を得る。必要により、導電性粉体を、前記ニッケル被覆粒子の製法で述べた、ボールミルを用いた粉砕工程に付することもできる。この粉砕工程に付することによって、導電性粉体の重量に対する一次粒子が占める割合を、上述した範囲内に更に容易に設定することができる。 After the plating reactions (D1) to (D3) are completed, the powder is separated by filtration and dried by a conventional method to obtain conductive powder. If necessary, the conductive powder can be subjected to a pulverization step using a ball mill described in the method for producing the nickel-coated particles. By attaching | subjecting to this grinding | pulverization process, the ratio for which the primary particle accounts with respect to the weight of electroconductive powder can be set still more easily in the range mentioned above.
このようにして得られた本発明の導電性粒子は、例えば異方導電フィルム（ＡＣＦ）やヒートシールコネクタ（ＨＳＣ）、液晶ディスプレーパネルの電極を駆動用ＬＳＩチップの回路基板へ接続するための導電材料などとして好適に使用される。特に、本発明の導電性粉体は、導電性接着剤の導電性フィラーとして好適に用いられる。 The conductive particles of the present invention thus obtained are, for example, conductive for connecting the electrodes of anisotropic conductive film (ACF), heat seal connector (HSC), and liquid crystal display panel to the circuit board of the driving LSI chip. It is suitably used as a material. In particular, the conductive powder of the present invention is suitably used as a conductive filler of a conductive adhesive.
前記の導電性接着剤は、導電性基材が形成された２枚の基板間に配置され、加熱加圧によって前記導電性基材を接着して導通する異方導電性接着剤として好ましく用いられる。この異方導電性接着剤は、本発明の導電性粒子と接着剤樹脂とを含む。接着剤樹脂としては、絶縁性で、かつ接着剤樹脂として用いられているものであれば、特に制限なく使用できる。熱可塑性樹脂及び熱硬化性のいずれであってもよく、加熱によって接着性能が発現するものが好ましい。そのような接着剤樹脂には、例えば熱可塑性タイプ、熱硬化性タイプ、紫外線硬化タイプ等がある。また、熱可塑性タイプと熱硬化性タイプとの中間的な性質を示す、いわゆる半熱硬化性タイプ、熱硬化性タイプと紫外線硬化タイプとの複合タイプ等がある。これらの接着剤樹脂は被着対象である回路基板等の表面特性や使用形態に合わせて適宜選択できる。特に、熱硬化性樹脂を含んで構成される接着剤樹脂が、接着後の材料的強度に優れる点から好ましい。 The conductive adhesive is preferably used as an anisotropic conductive adhesive that is disposed between two substrates on which a conductive base material is formed, and adheres and conducts the conductive base material by heating and pressing. . This anisotropic conductive adhesive contains the conductive particles of the present invention and an adhesive resin. Any adhesive resin can be used without particular limitation as long as it is insulative and used as an adhesive resin. Either a thermoplastic resin or a thermosetting resin may be used, and those that exhibit adhesive performance by heating are preferred. Examples of such an adhesive resin include a thermoplastic type, a thermosetting type, and an ultraviolet curing type. In addition, there are so-called semi-thermosetting types that exhibit intermediate properties between thermoplastic types and thermosetting types, combined types of thermosetting types and ultraviolet curing types, and the like. These adhesive resins can be appropriately selected according to the surface characteristics and usage pattern of the circuit board or the like to be attached. In particular, an adhesive resin including a thermosetting resin is preferable from the viewpoint of excellent material strength after bonding.
接着剤樹脂としては、具体的には、エチレン−酢酸ビニル共重合体、カルボキシル変性エチレン−酢酸ビニル共重合体、エチレン−イソブチルアクリレート共重合体、ポリアミド、ポリイミド、ポリエステル、ポリビニルエーテル、ポリビニルブチラール、ポリウレタン、ＳＢＳブロック共重合体、カルボキシル変性ＳＢＳ共重合体、ＳＩＳ共重合体、ＳＥＢＳ共重合体、マレイン酸変性ＳＥＢＳ共重合体、ポリブタジエンゴム、クロロプレンゴム、カルボキシル変性クロロプレンゴム、スチレン−ブタジエンゴム、イソブチレン−イソプレン共重合体、アクリロニトリル−ブタジエンゴム（以下、ＮＢＲと表す。）、カルボキシル変性ＮＢＲ、アミン変性ＮＢＲ、エポキシ樹脂、エポキシエステル樹脂、アクリル樹脂、フェノール樹脂又はシリコーン樹脂などから選ばれる１種又は２種以上の組み合わせにより得られるものを主剤として調製されたものが挙げられる。これらのうち、熱可塑性樹脂としては、スチレン−ブタジエンゴムやＳＥＢＳなどがリワーク性に優れるので好ましい。熱硬化性樹脂としては、エポキシ樹脂が好ましい。これらのうち接着力が高く、耐熱性、電気絶縁性に優れ、しかも溶融粘度が低く、低圧力で接続が可能であるという利点から、エポキシ樹脂が最も好ましい。 Specific examples of the adhesive resin include ethylene-vinyl acetate copolymer, carboxyl-modified ethylene-vinyl acetate copolymer, ethylene-isobutyl acrylate copolymer, polyamide, polyimide, polyester, polyvinyl ether, polyvinyl butyral, and polyurethane. , SBS block copolymer, carboxyl-modified SBS copolymer, SIS copolymer, SEBS copolymer, maleic acid-modified SEBS copolymer, polybutadiene rubber, chloroprene rubber, carboxyl-modified chloroprene rubber, styrene-butadiene rubber, isobutylene- Isoprene copolymer, acrylonitrile-butadiene rubber (hereinafter referred to as NBR), carboxyl-modified NBR, amine-modified NBR, epoxy resin, epoxy ester resin, acrylic resin, phenol resin or Those obtained by one or more combinations selected from such recone resins those prepared as main agent. Of these, as the thermoplastic resin, styrene-butadiene rubber, SEBS, and the like are preferable because of their excellent reworkability. As the thermosetting resin, an epoxy resin is preferable. Of these, epoxy resins are most preferred because of their advantages of high adhesive strength, excellent heat resistance and electrical insulation, low melt viscosity, and connection at low pressure.
前記のエポキシ樹脂としては、１分子中に２個以上のエポキシ基を有する多価エポキシ樹脂であれば、一般に用いられているエポキシ樹脂が使用可能である。具体的なものとしては、フェノールノボラック、クレゾールノボラック等のノボラック樹脂、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡＤ、レゾルシン、ビスヒドロキシジフェニルエーテル等の多価フェノール類、エチレングリコール、ネオペンチルグリコール、グリセリン、トリメチロールプロパン、ポリプロピレングリコール等の多価アルコール類、エチレンジアミン、トリエチレンテトラミン、アニリン等のポリアミノ化合物、アジピン酸、フタル酸、イソフタル酸等の多価カルボキシ化合物等とエピクロルヒドリン又は２−メチルエピクロルヒドリンを反応させて得られるグリシジル型のエポキシ樹脂が例示される。また、ジシクロペンタジエンエポキサイド、ブタジエンダイマージエポキサイド等の脂肪族及び脂環族エポキシ樹脂等が挙げられる。これらは単独で又は２種以上混合して使用することができる。 As the epoxy resin, a generally used epoxy resin can be used as long as it is a polyvalent epoxy resin having two or more epoxy groups in one molecule. Specific examples include novolak resins such as phenol novolak and cresol novolak, polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, resorcin, and bishydroxydiphenyl ether, ethylene glycol, neopentyl glycol, glycerin, and trimethylolpropane. Obtained by reacting polychlorohydric alcohols such as polypropylene glycol, polyamino compounds such as ethylenediamine, triethylenetetramine, and aniline, polycarboxyl compounds such as adipic acid, phthalic acid, and isophthalic acid with epichlorohydrin or 2-methylepichlorohydrin. A glycidyl type epoxy resin is exemplified. Moreover, aliphatic and alicyclic epoxy resins such as dicyclopentadiene epoxide and butadiene dimer epoxide are listed. These can be used alone or in admixture of two or more.
なお、上述した各種の接着樹脂は、不純物イオン（ＮａやＣｌ等）や加水分解性塩素などが低減された高純度品を用いることが、イオンマイグレーションの防止の観点から好ましい。 In addition, it is preferable from the viewpoint of prevention of ion migration that the various adhesive resins described above use high-purity products in which impurity ions (such as Na and Cl) and hydrolyzable chlorine are reduced.
異方導電性接着剤における本発明の導電性粒子の使用量は、接着剤樹脂成分１００重量部に対し通常０．１〜３０重量部、好ましくは０．５〜２５重量部、より好ましくは１〜２０重量部である。導電性粒子の使用量がこの範囲内にあることにより、接続抵抗や溶融粘度が高くなることが抑制され、接続信頼性を向上させ、接続の異方性を十分に確保することができる。 The amount of the conductive particles of the present invention used in the anisotropic conductive adhesive is usually 0.1 to 30 parts by weight, preferably 0.5 to 25 parts by weight, more preferably 1 to 100 parts by weight of the adhesive resin component. ~ 20 parts by weight. When the amount of the conductive particles used is within this range, an increase in connection resistance and melt viscosity is suppressed, connection reliability is improved, and connection anisotropy can be sufficiently secured.
前記の異方導電性接着剤には、上述した導電性粒子及び接着剤樹脂の他に、当該技術分野において、公知の添加剤を配合することができ、その配合量も当該技術分野において公知の範囲内とすることができる。他の添加剤としては、例えば粘着付与剤、反応性助剤、エポキシ樹脂硬化剤、金属酸化物、光開始剤、増感剤、硬化剤、加硫剤、劣化防止剤、耐熱添加剤、熱伝導向上剤、軟化剤、着色剤、各種カップリング剤又は金属不活性剤などを例示することができる。 In addition to the above-described conductive particles and adhesive resin, the anisotropic conductive adhesive can be blended with known additives in the technical field, and the blending amount is also known in the technical field. Can be within range. Other additives include, for example, tackifiers, reactive auxiliaries, epoxy resin curing agents, metal oxides, photoinitiators, sensitizers, curing agents, vulcanizing agents, deterioration inhibitors, heat resistant additives, heat Examples thereof include a conductivity improver, a softener, a colorant, various coupling agents, or a metal deactivator.
粘着付与剤としては、例えばロジン、ロジン誘導体、テルペン樹脂、テルペンフェノール樹脂、石油樹脂、クマロン−インデン樹脂、スチレン系樹脂、イソプレン系樹脂、アルキルフェノール樹脂、キシレン樹脂などが挙げられる。反応性助剤すなわち架橋剤としては、例えばポリオール、イソシアネート類、メラミン樹脂、尿素樹脂、ウトロピン類、アミン類、酸無水物、過酸化物などが挙げられる。エポキシ樹脂硬化剤としては、１分子中に２個以上の活性水素を有するものであれば特に制限なく使用できる。具体的なものとしては、例えばジエチレントリアミン、トリエチレンテトラミン、メタフェニレンジアミン、ジシアンジアミド、ポリアミドアミン等のポリアミノ化合物；無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、無水ピロメリット酸等の有機酸無水物；フェノールノボラック、クレゾールノボラック等のノボラック樹脂等が挙げられる。これらは単独で又は２種以上混合して使用することができる。また、用途や必要に応じて潜在性硬化剤を用いてもよい。使用できる潜在性硬化剤としては、例えば、イミダゾール系、ヒドラジド系、三フッ化ホウ素−アミン錯体、スルホニウム塩、アミンイミド、ポリアミンの塩、ジシアンジアミド等及びこれらの変性物が挙げられる。これらは単独で又は２種以上の混合体として使用できる。 Examples of the tackifier include rosin, rosin derivatives, terpene resins, terpene phenol resins, petroleum resins, coumarone-indene resins, styrene resins, isoprene resins, alkylphenol resins, xylene resins and the like. Examples of the reactive assistant, that is, the crosslinking agent include polyols, isocyanates, melamine resins, urea resins, utropines, amines, acid anhydrides and peroxides. As an epoxy resin hardening | curing agent, if it has two or more active hydrogens in 1 molecule, it can be especially used without a restriction | limiting. Specific examples include polyamino compounds such as diethylenetriamine, triethylenetetramine, metaphenylenediamine, dicyandiamide, and polyamideamine; organic acid anhydrides such as phthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, and pyromellitic anhydride. Products: novolak resins such as phenol novolac and cresol novolak. These can be used alone or in admixture of two or more. Moreover, you may use a latent hardening | curing agent as needed and a use. Examples of latent curing agents that can be used include imidazole series, hydrazide series, boron trifluoride-amine complexes, sulfonium salts, amine imides, polyamine salts, dicyandiamide, and the like and modified products thereof. These can be used alone or as a mixture of two or more.
前記の異方導電性接着剤は、通常、当業者間において広く使用されている製造装置を用い、本発明の導電性粒子及び接着剤樹脂並びに必要に応じ硬化剤や各種添加剤を配合し、接着剤樹脂が熱硬化性樹脂の場合は有機溶媒中で混合することにより、熱可塑性樹脂の場合は接着剤樹脂の軟化点以上の温度で、具体的には好ましくは約５０〜１３０℃程度、更に好ましくは約６０〜１１０℃程度で溶融混練することにより製造される。このようにして得られた異方導電性接着剤は、塗布してもよいし、フィルム状にして適用してもよい。 The anisotropic conductive adhesive is usually prepared by using a manufacturing apparatus widely used among those skilled in the art, and blends the conductive particles and adhesive resin of the present invention and, if necessary, curing agents and various additives, In the case where the adhesive resin is a thermosetting resin, by mixing in an organic solvent, in the case of a thermoplastic resin, at a temperature equal to or higher than the softening point of the adhesive resin, specifically preferably about 50 to 130 ° C, More preferably, it is produced by melt-kneading at about 60 to 110 ° C. The anisotropic conductive adhesive thus obtained may be applied or applied in the form of a film.
以下、実施例により本発明を更に詳細に説明する。しかしながら本発明の範囲は、かかる実施例に制限されない。特に断らない限り、「％」は「重量％」を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to such examples. Unless otherwise specified, “%” means “% by weight”.
〔ニッケル被覆粒子試料Ｎ１の調製〕
（１）Ａ１工程
真比重が１．１の球状スチレン−シリカ複合樹脂〔平均粒径３μｍ、（株）日本触媒製、商品名ソリオスター、変動係数（Ｃ．Ｖ）３．２％〕を芯材粒子（１Ｌあたりの表面積の総和５．４６ｍ2）として用いた。その９ｇを、４００ｍＬのコンディショナー水溶液（ローム・アンド・ハース電子材料製の「クリーナーコンディショナー２３１」）に攪拌しながら投入した。コンディショナー水溶液の濃度は４０ｍｌ／Ｌであった。引き続き、液温６０℃で超音波を与えながら３０分間攪拌して芯材粒子の表面改質及び分散処理を行った。水溶液を濾過し、一回リパルプ水洗した芯材粒子を２００ｍＬのスラリーにした。このスラリーへ塩化第一錫水溶液２００ｍｌを投入した。この水溶液の濃度は５×１０-3ｍｏｌ／Ｌであった。常温で５分攪拌し、錫イオンを芯材粒子の表面に吸着させる感受性化処理を行った。引き続き水溶液を濾過し、１回リパルプ水洗した。次いで芯材粒子を４００ｍｌのスラリーにし、６０℃に維持した。超音波を併用してスラリーを攪拌しながら、０．１１ｍｏｌ／Ｌの塩化パラジウム水溶液２ｍＬを添加した。そのままの攪拌状態を５分間維持させ、芯材粒子の表面にパラジウムイオンを捕捉させる活性化処理を行った。
[Preparation of nickel-coated particle sample N1]
(1) Process A1 Spherical styrene-silica composite resin (average particle size 3 μm, manufactured by Nippon Shokubai Co., Ltd., trade name: Soliostar, coefficient of variation (C.V): 3.2%) having a true specific gravity of 1.1 is the core Used as material particles (total surface area of 5.46 m 2 per liter). 9 g of the solution was added to 400 mL of an aqueous conditioner solution (“Cleaner Conditioner 231” manufactured by Rohm and Haas Electronic Materials) with stirring. The concentration of the conditioner aqueous solution was 40 ml / L. Subsequently, the core material particles were surface-modified and dispersed by stirring for 30 minutes while applying ultrasonic waves at a liquid temperature of 60 ° C. The aqueous solution was filtered and the core particles washed once with repulp water were made into 200 mL slurry. 200 ml of stannous chloride aqueous solution was added to this slurry. The concentration of this aqueous solution was 5 × 10 −3 mol / L. The mixture was stirred at room temperature for 5 minutes to carry out a sensitization treatment for adsorbing tin ions on the surface of the core material particles. Subsequently, the aqueous solution was filtered and washed once with repulp water. The core particles were then made into 400 ml slurry and maintained at 60 ° C. While stirring the slurry using ultrasonic waves, 2 mL of a 0.11 mol / L palladium chloride aqueous solution was added. The state of stirring as it was was maintained for 5 minutes, and an activation treatment for capturing palladium ions on the surface of the core particles was performed.
次いで、２０ｇ／Ｌの酒石酸ナトリウム、５．４ｇ／Ｌの次亜リン酸ナトリウム、硫酸ニッケル六水和物（無水換算で０．４５ｇ／Ｌ）、ポリエチレングリコール５ｇ／Ｌを溶解した水溶液からなる無電解めっき浴３Ｌを７０℃に昇温し、この無電解めっき浴に、パラジウムを担持した芯材粒子９ｇを投入し、Ａ１工程を開始した。５分間攪拌し水素の発泡が停止するのを確認し、Ａ１工程を完了させた。 Next, 20 g / L sodium tartrate, 5.4 g / L sodium hypophosphite, nickel sulfate hexahydrate (0.45 g / L in anhydrous conversion), and an aqueous solution in which polyethylene glycol 5 g / L is dissolved. The temperature of the electrolytic plating bath 3L was raised to 70 ° C., and 9 g of core material particles supporting palladium were introduced into the electroless plating bath, and the A1 step was started. After stirring for 5 minutes, it was confirmed that hydrogen foaming stopped, and Step A1 was completed.
（２）Ａ２工程
２２４ｇ／Ｌ硫酸ニッケル水溶液と、２１０ｇ／Ｌの次亜リン酸ナトリウム及び８０ｇ／Ｌの水酸化ナトリウムを含む混合水溶液とをそれぞれ３００ｍＬ用い、これらをＡ１工程で得られた芯材粒子のスラリーに、定量ポンプによって連続的に分別添加し、無電解めっきＡ２工程を開始した。添加速度はいずれも２．５ｍＬ／分とした。なお、滴下開始時から滴下終了までのｐＨは５．８〜６．２で、１時間当たりのニッケル析出量は４８ｎｍであった。液を全量添加した後、７０℃の温度を保持しながら５分攪拌を継続した。次いで液を濾過し、濾過物を３回洗浄した後、１００℃の真空乾燥機で乾燥してニッケル−リン合金皮膜を有するニッケル被覆粒子試料Ｎ１を得た。
(2) Step A2 Using a 224 g / L nickel sulfate aqueous solution and a mixed aqueous solution containing 210 g / L sodium hypophosphite and 80 g / L sodium hydroxide, 300 mL each, these were used in the A1 step. The slurry was continuously added to the particle slurry by a metering pump, and the electroless plating A2 step was started. The addition rate was 2.5 mL / min. The pH from the start of dropping to the end of dropping was 5.8 to 6.2, and the amount of nickel deposited per hour was 48 nm. After all the liquid was added, stirring was continued for 5 minutes while maintaining the temperature at 70 ° C. Next, the liquid was filtered, and the filtrate was washed three times, and then dried with a vacuum dryer at 100 ° C. to obtain a nickel-coated particle sample N1 having a nickel-phosphorus alloy film.
〔ニッケル被覆粒子試料Ｎ２の調製〕
（１）Ｂ１工程
Ｎ１作製時に用いた芯材粒子をＡ１工程と同様の表面改質処理を行い、芯材表面にパラジウムを捕捉させる活性化処理を行った。次いで、２０ｇ／Ｌの酒石酸ナトリウム、４．５ｇ／Ｌの硫酸ニッケル六水和物、５．４ｇ／Ｌの次亜リン酸ナトリウム、及び５ｇ／Ｌのポリエチレングリコールを溶解した水溶液からなる無電解めっき浴３Ｌを７０℃に昇温し、この無電解めっき浴にパラジウムを担持した芯材粒子９ｇを投入し、Ｂ１工程を開始した。５分間攪拌し水素の発泡が停止するのを確認し、Ｂ１工程を完了させた。
[Preparation of nickel-coated particle sample N2]
(1) Step B1 The core material particles used in the production of N1 were subjected to the same surface modification treatment as in Step A1, and an activation treatment for capturing palladium on the surface of the core material was performed. Then, electroless plating comprising an aqueous solution in which 20 g / L sodium tartrate, 4.5 g / L nickel sulfate hexahydrate, 5.4 g / L sodium hypophosphite, and 5 g / L polyethylene glycol are dissolved. The temperature of the bath 3L was raised to 70 ° C., and 9 g of core material particles supporting palladium were introduced into the electroless plating bath, and the B1 step was started. After stirring for 5 minutes, it was confirmed that hydrogen foaming stopped, and Step B1 was completed.
（２）Ｂ２工程
２２４ｇ／Ｌの硫酸ニッケル水溶液と、２１０ｇ／Ｌの次亜リン酸ナトリウム及び８０ｇ／Ｌの水酸化ナトリウムを含む混合水溶液とをそれぞれ３００ｍＬ用い、これらをＢ１工程で得られた芯材粒子のスラリーに、定量ポンプによって連続的に分別添加し、無電解めっきＢ２工程を開始した。添加速度はいずれも２．５ｍＬ／分とした。液を全量添加した後、７０℃の温度を保持しながら５分攪拌を継続した。次いで液を濾過し、濾過物を３回洗浄した後、１００℃の真空乾燥機で乾燥してニッケル−リン合金皮膜を有するニッケル被覆粒子試料Ｎ２を得た。
(2) Step B2 Using a 224 g / L nickel sulfate aqueous solution and a mixed aqueous solution containing 210 g / L sodium hypophosphite and 80 g / L sodium hydroxide, 300 mL each, these were used in the B1 step. The slurry was continuously added to the slurry of the material particles by a metering pump, and the electroless plating B2 step was started. The addition rate was 2.5 mL / min. After all the liquid was added, stirring was continued for 5 minutes while maintaining the temperature at 70 ° C. Next, the liquid was filtered, and the filtrate was washed three times, and then dried with a vacuum dryer at 100 ° C. to obtain a nickel-coated particle sample N2 having a nickel-phosphorus alloy film.
〔ニッケル被覆粒子Ｎ３の調製（比較品）〕
Ｎ１作製時に用いた芯材粒子に対してＡ１工程と同様の表面改質処理を行い、芯材表面にパラジウムを捕捉した後、６５℃に加温した２０ｇ／Ｌの酒石酸ナトリウム及び５ｇ／Ｌのポリエチレングリコールの入った水溶液３Ｌに攪拌しながら投入し、充分に攪拌分散させて水性スラリーを調製した後、２２４ｇ／Ｌ硫酸ニッケル水溶液と、２１０ｇ／Ｌの次亜リン酸ナトリウム及び８０ｇ／Ｌの水酸化ナトリウムを含む混合水溶液とをそれぞれ３００ｍＬ用いた。添加速度はそれぞれ５ｍＬ／分とした。液を全量添加した後、７０℃の温度を保持しながら５分攪拌を継続した。次いで液を濾過し、濾過物を３回洗浄した後、１００℃の真空乾燥機で乾燥してニッケル−リン合金皮膜を有するニッケル被覆粒子試料Ｎ３を得た。この方法で平滑性に優れた皮膜が得られた。
[Preparation of nickel-coated particles N3 (comparative product)]
The core particles used in the production of N1 were subjected to the same surface modification treatment as in step A1, and after capturing palladium on the surface of the core material, 20 g / L sodium tartrate heated to 65 ° C. and 5 g / L An aqueous slurry was prepared by stirring and dispersing into 3 L of an aqueous solution containing polyethylene glycol and sufficiently stirring and dispersing, and then a 224 g / L nickel sulfate aqueous solution, 210 g / L sodium hypophosphite and 80 g / L water. 300 mL each of the mixed aqueous solution containing sodium oxide was used. The addition rate was 5 mL / min. After all the liquid was added, stirring was continued for 5 minutes while maintaining the temperature at 70 ° C. Next, the liquid was filtered, and the filtrate was washed three times, and then dried with a vacuum dryer at 100 ° C. to obtain a nickel-coated particle sample N3 having a nickel-phosphorus alloy film. A film excellent in smoothness was obtained by this method.
〔ニッケル被覆粒子Ｎ４の調製（比較品）〕
Ｎ１作製時に用いた芯材粒子に対してＡ１工程と同様の表面改質処理を行い、芯材表面にパラジウムを捕捉させる活性化処理を行った。次いで、めっき液中にポリエチレングリコールを添加しない以外はＮ２作製時と同様の操作を行い、ニッケル−リン合金皮膜を有するニッケル被覆粒子試料Ｎ４を得た。
[Preparation of nickel-coated particles N4 (comparative product)]
A surface modification treatment similar to that in the step A1 was performed on the core material particles used in the production of N1, and an activation treatment for capturing palladium on the core material surface was performed. Next, a nickel-coated particle sample N4 having a nickel-phosphorus alloy film was obtained by performing the same operation as that for producing N2 except that polyethylene glycol was not added to the plating solution.
〔ニッケル被覆粒子の物性評価〕
ニッケル被覆粒子Ｎ１〜Ｎ４の平均粒径、ニッケル皮膜の厚み、ニッケル皮膜の密着性をそれぞれ測定・評価した。また、高さが５０ｎｍ以上の突起部芯体の個数、高さが５０ｎｍの突起部芯体のアスペクト比をそれぞれ測定した。各物性評価は次の方法によって行った。それらの結果を表１に示す。
[Evaluation of properties of nickel-coated particles]
The average particle diameter of the nickel-coated particles N1 to N4, the thickness of the nickel film, and the adhesion of the nickel film were measured and evaluated. The number of protrusion cores having a height of 50 nm or more and the aspect ratio of the protrusion core having a height of 50 nm were measured. Each physical property evaluation was performed by the following method. The results are shown in Table 1.
〔ニッケル皮膜の厚み〕
ニッケル被覆粒子を王水に浸漬してニッケル皮膜を溶解し、皮膜成分をＩＣＰ又は化学分析し、以下の式（３）及び(４)からニッケル皮膜の厚みを算出した。
Ａ＝[（ｒ＋ｔ）3―ｒ3]ｄ1／ｒ3ｄ2 （３）
Ａ＝Ｗ／（１００−Ｗ） （４）
式中、ｒは芯材粒子の半径（μｍ）、ｔはニッケル皮膜の厚み、ｄ1はニッケル皮膜の比重、ｄ2は芯材粒子の比重、Ｗはニッケル含有率（重量％）である。
[Thickness of nickel coating]
The nickel-coated particles were immersed in aqua regia to dissolve the nickel film, the film components were analyzed by ICP or chemical analysis, and the thickness of the nickel film was calculated from the following formulas (3) and (4).
A = [(r + t) 3 −r 3 ] d 1 / r 3 d 2 (3)
A = W / (100-W) (4)
In the formula, r is the radius (μm) of the core particles, t is the thickness of the nickel coating, d 1 is the specific gravity of the nickel coating, d 2 is the specific gravity of the core particles, and W is the nickel content (% by weight).
〔突起部芯体の個数及びアスペクト比〕
ＳＥＭを用い、ニッケル被覆粒子を３００００倍に拡大して１０視野を観察し、ニッケル被覆粒子１個が有する高さ５０ｎｍ以上の突起部芯体の個数、及び高さ５０ｎｍ以上の突起部芯体についてアスペクト比の平均値を算出した。
[Number of protrusion cores and aspect ratio]
Using SEM, enlarge the nickel-coated particles to 30000 times and observe 10 fields of view. About the number of protrusion cores with a height of 50 nm or more and the protrusion core with a height of 50 nm or more that one nickel-coated particle has The average aspect ratio was calculated.
〔ニッケル皮膜の密着性〕
１００ｍＬのビーカーにニッケル被覆粒子２ｇ及び直径１ｍｍのジルコニアビーズ９０ｇを入れ、更にトルエンを１０ｍＬ入れた。攪拌装置で１０分攪拌した後、ジルコニアビーズとスラリーを分離し乾燥させた。乾燥後のニッケル被覆粒子を、ＳＥＭを用いて２０００倍に拡大して１０視野を観察し、攪拌によって生じた剥離片の個数の平均値を算出した。剥離片の個数１０個未満を○とし、１０〜３０個を△、３０個超を×とした。
[Nickel film adhesion]
In a 100 mL beaker, 2 g of nickel-coated particles and 90 g of zirconia beads having a diameter of 1 mm were added, and further 10 mL of toluene was added. After stirring for 10 minutes with a stirrer, the zirconia beads and the slurry were separated and dried. The nickel-coated particles after drying were magnified 2000 times using SEM, 10 fields of view were observed, and the average value of the number of peeled pieces generated by stirring was calculated. The number of peeled pieces of less than 10 was evaluated as ◯, 10-30 as Δ, and more than 30 as X.
〔実施例１ないし３〕
１０ｇ／ＬのＥＤＴＡ−２Ｎａ、１０ｇ／Ｌのクエン酸―２Ｎａ及び２０ｇ／Ｌのテトラアンミンパラジウム塩酸塩（Ｐｄ（ＮＨ3）4Ｃｌ2）溶液（パラジウムとして２ｇ／Ｌ）、カルボキシメチルセルロース（分子量２５００００、エーテル化度０．９）１００ｐｐｍからなる無電解パラジウムめっき液を調製した。このパラジウムめっき液０．６５リットル（実施例１）、１．３リットル（実施例２）、２．６リットル（実施例３）を７０℃に加熱した。これを攪拌しながら、前記で得られたニッケル被覆粒子試料（Ｎ１）１０ｇを添加した。これによって粒子の表面に無電解めっき処理を行った。処理時間は６０分とした。処理の完了後、液を濾過し、濾過物を３回リパルプした。次いで１１０℃の真空乾燥機で乾燥した。このようにして、ニッケル−リン合金皮膜上にパラジウムめっき被覆処理を施した。
[Examples 1 to 3]
10 g / L EDTA-2Na, 10 g / L citric acid-2Na and 20 g / L tetraamminepalladium hydrochloride (Pd (NH 3 ) 4 Cl 2 ) solution (2 g / L as palladium), carboxymethylcellulose (molecular weight 250,000, An electroless palladium plating solution consisting of 100 ppm of etherification degree 0.9) was prepared. 0.65 liters (Example 1), 1.3 liters (Example 2) and 2.6 liters (Example 3) of this palladium plating solution were heated to 70 ° C. While stirring this, 10 g of the nickel-coated particle sample (N1) obtained above was added. Thus, electroless plating treatment was performed on the surface of the particles. The processing time was 60 minutes. After completion of the treatment, the liquid was filtered and the filtrate was repulped three times. Subsequently, it dried with the 110 degreeC vacuum dryer. In this way, the palladium plating coating treatment was performed on the nickel-phosphorus alloy film.
〔実施例４〕
１０ｇ／Ｌのエチレンジアミン、１０ｇ／Ｌのギ酸ナトリウム及び２０ｇ／Ｌのテトラアンミンパラジウム塩酸塩（Ｐｄ（ＮＨ3）4Ｃｌ2）溶液（パラジウムとして２ｇ／Ｌ）、カルボキシメチルセルロース（分子量２５００００、エーテル化度０．９）１００ｐｐｍからなる無電解純パラジウムめっき液を調製した。このパラジウムめっき液１．３Ｌを７０℃に加熱し、これを攪拌しながら前記で得られたニッケル被覆粒子試料（Ｎ１）１０ｇを添加した。これによって粒子の表面に無電解めっき処理を行った。処理時間は３０分とした。処理の完了後、液をろ別し、以後は実施例１と同様の工程を行い、ニッケル−リン合金皮膜上にパラジウムめっき被覆処理を施した。
Example 4
10 g / L ethylenediamine, 10 g / L sodium formate and 20 g / L tetraamminepalladium hydrochloride (Pd (NH 3 ) 4 Cl 2 ) solution (2 g / L as palladium), carboxymethylcellulose (molecular weight 250,000, degree of etherification 0 .9) An electroless pure palladium plating solution consisting of 100 ppm was prepared. The palladium plating solution 1.3 L was heated to 70 ° C., and 10 g of the nickel-coated particle sample (N1) obtained above was added while stirring the solution. Thus, electroless plating treatment was performed on the surface of the particles. The processing time was 30 minutes. After completion of the treatment, the liquid was filtered off, and thereafter, the same process as in Example 1 was performed, and a palladium-plating coating treatment was performed on the nickel-phosphorus alloy film.
〔実施例５〕
１０ｇ／Ｌのエチレンジアミン、５０ｇ／Ｌの次亜リン酸ナトリウム及び２０ｇ／Ｌのテトラアンミンパラジウム塩酸塩Ｐｄ（ＮＨ3）4Ｃｌ2）溶液（パラジウムとして２ｇ／Ｌ）、カルボキシメチルセルロース（分子量２５００００、エーテル化度０．９）１００ｐｐｍからなる無電解パラジウム−リンめっき液を調整した。このパラジウムめっき液１．３Ｌを５０℃に加熱し、これを攪拌しながら上記で得られたニッケル被覆粒子試料（Ｎ１）１０ｇを添加した。これによって粒子の表面に無電解めっき処理を行った。処理時間は３０分とした。処理の完了後、液をろ別し、以後は実施例１と同様の工程を行い、ニッケル−リン合金皮膜上にパラジウムめっき被覆処理を施した。
Example 5
10 g / L ethylenediamine, 50 g / L sodium hypophosphite and 20 g / L tetraamminepalladium hydrochloride Pd (NH 3 ) 4 Cl 2 ) solution (2 g / L as palladium), carboxymethylcellulose (molecular weight 250,000, etherification) An electroless palladium-phosphorous plating solution consisting of 100 ppm was prepared. The palladium plating solution 1.3 L was heated to 50 ° C., and 10 g of the nickel-coated particle sample (N1) obtained above was added while stirring the solution. Thus, electroless plating treatment was performed on the surface of the particles. The processing time was 30 minutes. After completion of the treatment, the liquid was filtered off, and thereafter, the same process as in Example 1 was performed, and a palladium-plating coating treatment was performed on the nickel-phosphorus alloy film.
〔実施例６及び７〕
次亜リン酸ナトリウムの濃度を１０ｇ／Ｌ（実施例６）２５ｇ／Ｌ(実施例７)とする以外は実施例５と同様の操作を行い、ニッケル合金皮膜上にパラジウム−リンめっき被覆処理を施した。
[Examples 6 and 7]
The same operation as in Example 5 was carried out except that the concentration of sodium hypophosphite was 10 g / L (Example 6) and 25 g / L (Example 7), and a palladium-phosphorus plating coating treatment was performed on the nickel alloy film. gave.
〔実施例８ないし１０〕
ニッケル被覆粒子をＮ２にする以外は実施例２、実施例４、実施例５と同様の操作を行い、ニッケル−リン合金皮膜上にパラジウム−リンめっき被覆処理を施した。
[Examples 8 to 10]
Except for changing the nickel-coated particles to N2, the same operations as in Example 2, Example 4, and Example 5 were performed, and the nickel-phosphorus alloy film was subjected to a palladium-phosphorus plating coating treatment.
〔比較例１ないし３〕
ニッケル被覆粒子をＮ３にする以外は実施例２、実施例４、実施例５と同様の操作を行い、ニッケル−リン合金皮膜上にパラジウムめっき被覆又はパラジウム−リンめっき被覆処理を施した。
[Comparative Examples 1 to 3]
Except for changing the nickel-coated particles to N3, the same operations as in Example 2, Example 4, and Example 5 were performed, and the nickel-phosphorus alloy film was subjected to palladium plating coating or palladium-phosphorus plating coating treatment.
〔比較例４ないし６〕
ニッケル被覆粒子をＮ４にする以外は実施例２、実施例４、実施例５と同様の操作を行い、ニッケル−リン合金皮膜上にパラジウムめっき被覆又はパラジウム−リンめっき被覆処理を施した。
[Comparative Examples 4 to 6]
Except for changing the nickel-coated particles to N4, the same operations as in Example 2, Example 4, and Example 5 were performed, and the nickel-phosphorus alloy film was subjected to palladium plating coating or palladium-phosphorus plating coating treatment.
〔比較例７〕
次亜リン酸ナトリウムの濃度を２００ｇ／Ｌとする以外は実施例５と同様の操作を行い、ニッケル合金皮膜上にパラジウム−リンめっき被覆処理を施した。
[Comparative Example 7]
The same operation as in Example 5 was performed except that the concentration of sodium hypophosphite was 200 g / L, and a palladium-phosphorous plating coating treatment was performed on the nickel alloy film.
〔参考例１（金めっき）〕
１０ｇ／ＬのＥＤＴＡ−４Ｎａ、１０ｇ／Ｌのクエン酸―２Ｎａ及び２．９ｇ／Ｌのシアン化金カリウム（Ａｕとして２．０ｇ／Ｌ）からなる無電解金めっき液を調製した。この金めっき液２リットルを７９℃に加熱し、これを攪拌しながら、ニッケル被覆粒子Ｎ１１０ｇを添加した。これによって粒子の表面に無電解めっき処理を行った。処理時間は２０分とした。処理の完了後、液を濾過し、濾過物を３回リパルプした。次いで１１０℃の真空乾燥機で乾燥した。このようにして、ニッケル−リン合金皮膜上に金めっき被覆処理を施した。
[Reference Example 1 (Gold plating)]
An electroless gold plating solution consisting of 10 g / L EDTA-4Na, 10 g / L citric acid-2Na and 2.9 g / L potassium gold cyanide (2.0 g / L as Au) was prepared. 2 liters of this gold plating solution was heated to 79 ° C., and while stirring this, 110 g of nickel-coated particles N was added. Thus, electroless plating treatment was performed on the surface of the particles. The processing time was 20 minutes. After completion of the treatment, the liquid was filtered and the filtrate was repulped three times. Subsequently, it dried with the 110 degreeC vacuum dryer. In this way, a gold plating coating treatment was performed on the nickel-phosphorus alloy film.
〔導電性粉体の物性評価〕
実施例、比較例及び参考例で得られた導電性粒子の平均粒径、ニッケル皮膜の厚み、パラジウム皮膜の厚み、金皮膜の厚み、パラジウム皮膜中のリン含有量、高さ５０ｎｍ以上の突起部の個数、高さ５０ｎｍ以上の突起部のアスペクト比、一次粒子が占める割合をそれぞれ測定・評価した。それらの結果を、以下の表２に示す。また、パラジウム皮膜又は金皮膜の密着性、導電性、ショートの発生（電気信頼性）、抵抗値をそれぞれ測定・評価した。それらの結果を、以下の表３に示す。なお、導電性粒子の粒径、高さ５０ｎｍ以上の突起部の個数、高さ５０ｎｍ以上の突起部のアスペクト比、パラジウム皮膜又は金皮膜の密着性は前記ニッケル被覆粒子と同様な方法で測定・評価した。また、ニッケル皮膜の厚み、パラジウム皮膜又は金皮膜の厚み、パラジウム皮膜中のリン含有量、導電性、ショートの発生（電気信頼性）、抵抗値は以下のように測定・評価した。
[Evaluation of physical properties of conductive powder]
Average particle diameter of conductive particles obtained in Examples, Comparative Examples and Reference Examples, nickel coating thickness, palladium coating thickness, gold coating thickness, phosphorus content in palladium coating, protrusions with a height of 50 nm or more , The aspect ratio of protrusions having a height of 50 nm or more, and the proportion of primary particles were measured and evaluated. The results are shown in Table 2 below. Further, the adhesion, conductivity, occurrence of short circuit (electrical reliability), and resistance value of the palladium film or gold film were measured and evaluated. The results are shown in Table 3 below. The particle diameter of conductive particles, the number of protrusions with a height of 50 nm or more, the aspect ratio of protrusions with a height of 50 nm or more, and the adhesion of a palladium film or gold film were measured by the same method as for the nickel-coated particles. evaluated. Further, the thickness of the nickel film, the thickness of the palladium film or the gold film, the phosphorus content in the palladium film, the conductivity, the occurrence of a short circuit (electrical reliability), and the resistance value were measured and evaluated as follows.
〔パラジウムめっき又は金めっき後のニッケル皮膜の厚み〕
導電性粒子を王水に浸漬して金属皮膜を溶解し、皮膜成分をＩＣＰ又は化学分析し、以下の式（５）及び(６)からニッケル皮膜の厚みを算出した。
Ａ＝[（ｒ＋ｔ）3―ｒ3]ｄ1／ｒ3ｄ2 （５）
Ａ＝Ｗ／（１００−Ｘ） （６）
式中、ｒは芯材粒子の半径（μｍ）、ｔはニッケル皮膜の厚み、ｄ1はニッケル皮膜の比重、ｄ2は芯材粒子の比重、Ｗはニッケル含有率（重量％）Ｘは金又はパラジウムの含有率である。
[Thickness of nickel film after palladium plating or gold plating]
The conductive particles were immersed in aqua regia to dissolve the metal film, the film components were analyzed by ICP or chemical analysis, and the thickness of the nickel film was calculated from the following formulas (5) and (6).
A = [(r + t) 3 −r 3 ] d 1 / r 3 d 2 (5)
A = W / (100-X) (6)
Where r is the radius of the core particle (μm), t is the thickness of the nickel coating, d 1 is the specific gravity of the nickel coating, d 2 is the specific gravity of the core particles, W is the nickel content (wt%) X is the gold Or it is the content rate of palladium.
〔金皮膜・パラジウム皮膜の厚み〕
導電性粒子を王水に浸漬して、ニッケル、金又はパラジウム皮膜を溶解し皮膜成分をＩＣＰ又は化学分析し、以下の（７）及び（８）から金又はパラジウム皮膜の厚みを算出した。
Ｂ＝[（ｒ＋ｔ＋ｕ）3−（ｒ＋ｔ）3]ｄ3／（ｒ＋ｔ）3ｄ4 （７）
Ｂ＝Ｘ（１００−Ｘ） （８）
式中、ｕは金、又はパラジウムの厚み、ｄ3は金、又はパラジウム皮膜の比重、ｄ4はＮｉ品の比重、Ｘは金、又はパラジウムの含有率（重量％）である。ここで、Ｎｉ品の比重ｄ4は計算式を使用している。比重は以下の（９）の計算式を用いて算出した。
ｄ4＝１００／[（Ｗ／ｄ1）＋（１００−Ｗ）／ｄ2] （９）
[Gold film / palladium film thickness]
The conductive particles were immersed in aqua regia, the nickel, gold or palladium film was dissolved, the film components were subjected to ICP or chemical analysis, and the thickness of the gold or palladium film was calculated from the following (7) and (8).
B = [(r + t + u) 3 − (r + t) 3 ] d 3 / (r + t) 3 d 4 (7)
B = X (100-X) (8)
In the formula, u is the thickness of gold or palladium, d 3 is the specific gravity of gold or palladium film, d 4 is the specific gravity of Ni product, and X is the content (% by weight) of gold or palladium. Here, a calculation formula is used for the specific gravity d 4 of the Ni product. The specific gravity was calculated using the following formula (9).
d 4 = 100 / [(W / d 1 ) + (100−W) / d 2 ] (9)
〔パラジウム皮膜中のリン含有量〕
パラジウム被覆前のニッケル粒子を王水に浸漬してニッケル皮膜を溶解し皮膜成分をＩＣＰ又は化学分析し、金属化率を算出した。更にパラジウム被覆後の粒子のニッケル、パラジウム皮膜を溶解後皮膜成分をＩＣＰ又は化学分析し、金属化率を算出し、以下の式によりパラジウム皮膜中のリン含有率を算出した。
ニッケル被覆粒子中のリン含有量（ｇ）
Ｃ＝Ｖ×Ｙ1／１００ （１０）
パラジウム被覆粒子中のリン含有量（ｇ）
Ｄ＝Ｖ／（１−Ｗ／１００）×Ｙ2／１００ （１１）
パラジウム被覆粒子中のパラジウム含有量（ｇ）
Ｅ＝Ｖ／（１−Ｗ／１００）−Ｖ （１２）
よってパラジウム皮膜中のリン含有率Ｅ（重量％）は
Ｆ＝（Ｄ−Ｃ）／（Ｄ−Ｃ＋Ｅ）×１００ （１３）
ここで、Ｖはパラジウム処理前のニッケル被覆粒子の重量（ｇ）、Ｙ1はニッケル被覆粒子のリン含有率（重量％）、Ｙ2はパラジウム被覆粒子のリン含有率（重量％）、Ｗはパラジウムの金属化率である。ただし、ここで、ニッケル皮膜からのニッケル及びリンの溶出は非常に少なかったため０として計算した。
[Phosphorus content in phosphorus]
The nickel particles before palladium coating were immersed in aqua regia to dissolve the nickel film, and the film components were analyzed by ICP or chemical analysis to calculate the metallization rate. Further, after dissolving the nickel and palladium films of the palladium-coated particles, the film components were analyzed by ICP or chemical analysis to calculate the metallization rate, and the phosphorus content in the palladium film was calculated by the following formula.
Phosphorus content in nickel-coated particles (g)
C = V × Y 1/100 (10)
Phosphorus content in palladium-coated particles (g)
D = V / (1-W / 100) × Y 2/100 (11)
Palladium content in palladium-coated particles (g)
E = V / (1-W / 100) -V (12)
Accordingly, the phosphorus content E (% by weight) in the palladium film is F = (D−C) / (D−C + E) × 100 (13)
Here, V is the weight (g) of the nickel-coated particles before the palladium treatment, Y 1 is the phosphorus content (wt%) of the nickel-coated particles, Y 2 is the phosphorus content (wt%) of the palladium-coated particles, and W is It is the metallization rate of palladium. However, since the elution of nickel and phosphorus from the nickel film was very small, it was calculated as 0.
〔導電性、ショートの発生（電気信頼性）、抵抗値〕
エポキシ樹脂１００部、硬化剤１５０部、トルエン７０部を混合し、絶縁性接着剤を調製した。これに導電性粒子１５部を配合してペーストを得た。バーコーターを用い、このペーストをシリコーン処理ポリエステルフィルム上に塗布し乾燥させた。得られた塗工フィルムを用い、全面をアルミニウムで蒸着したガラスと５０μｍピッチに銅パターンを形成したポリイミドフィルム基板との間の接続を行った。そして電極間の導通抵抗を測定することで、導電性粒子の導電性を評価した。評価は抵抗値２Ω以下を○とし、２〜５Ωを△、５Ω以上を×とした。また、ショート発生の有無も観察した。更に８５℃・８５％ＲＨの条件で５００ｈ保持後に測定した抵抗値も測定した。
[Conductivity, occurrence of short circuit (electrical reliability), resistance value]
100 parts of epoxy resin, 150 parts of curing agent, and 70 parts of toluene were mixed to prepare an insulating adhesive. This was mixed with 15 parts of conductive particles to obtain a paste. This paste was applied onto a silicone-treated polyester film and dried using a bar coater. Using the obtained coated film, connection was made between glass whose surface was vapor-deposited with aluminum and a polyimide film substrate having a copper pattern formed on a 50 μm pitch. And the electroconductivity of electroconductive particle was evaluated by measuring the conduction | electrical_connection resistance between electrodes. In the evaluation, a resistance value of 2Ω or less was evaluated as ◯, 2-5Ω was evaluated as Δ, and 5Ω or more was evaluated as ×. In addition, the presence or absence of occurrence of a short circuit was also observed. Furthermore, the resistance value measured after holding for 500 hours under the conditions of 85 ° C. and 85% RH was also measured.
Claims (11)
前記導電性粒子は、パラジウム又はパラジウム合金皮膜表面から突出し、かつ該パラジウム又はパラジウム合金皮膜と連続体になっている、高さが５０ｎｍ以上である突起部を粒子１個当たり５個以上有し、
前記パラジウム又はパラジウム合金皮膜中のリン含有量が３重量％以下であり、
前記導電性粉体においては、前記導電性粒子のうち、一次粒子が占める割合が、導電性粉体の重量に対して８５重量％以上であることを特徴とする導電性粉体。 Conductive powder composed of conductive particles in which palladium or palladium alloy film is further formed on the surface of nickel-coated particles in which nickel or nickel alloy film is formed on the surface of core particles,
The conductive particles have 5 or more protrusions per particle protruding from the surface of the palladium or palladium alloy coating and being continuous with the palladium or palladium alloy coating and having a height of 50 nm or more,
The phosphorus content in the palladium or palladium alloy film is 3% by weight or less,
In the conductive powder, the proportion of primary particles in the conductive particles is 85% by weight or more based on the weight of the conductive powder.
（Ｄ１）純パラジウムめっき浴で還元型無電解パラジウムめっき処理する方法。
（Ｄ２）還元剤として次亜リン酸又はその塩を用いる還元型無電解パラジウムめっき処理において、パラジウムイオンに対する還元剤のモル比を０．１〜１００として還元型無電解パラジウムめっき処理する方法。
（Ｄ３）置換型無電解パラジウムめっき処理する方法。 A protrusion core having a height of 50 nm or more, which is formed of a nickel or nickel alloy film on the surface of the core particle, protrudes from the surface of the film, and is continuous with the film, per particle. A method for producing conductive particles, comprising subjecting five or more nickel-coated particles to electroless palladium plating in the presence of a dispersant by any of the following methods (D1) to (D3).
(D1) A method of reducing electroless palladium plating in a pure palladium plating bath.
(D2) A method of reducing electroless palladium plating in a reducing electroless palladium plating treatment using hypophosphorous acid or a salt thereof as a reducing agent, wherein the molar ratio of the reducing agent to palladium ions is 0.1 to 100.
(D3) A method of performing substitutional electroless palladium plating.
該芯材粒子を用いるＡ１工程と、
Ａ１工程において得られた、ニッケル初期薄膜層を有する前記芯材粒子、及び前記分散剤を含む水性スラリーを、該分散剤の分散効果が発現するｐＨ範囲に維持しつつ、該水性スラリーに、１時間当たりのニッケルの析出量が２５〜１００ｎｍとなる量に相当する量のニッケルイオン及び還元剤を経時的に添加するＡ２工程と、
を行い、前記ニッケル被覆粒子を得る請求項７記載の製造方法。 When an electroless nickel plating bath containing a dispersant and nickel ions is mixed with the core material particles having a noble metal supported on the surface, a nickel initial thin film layer is formed on the surface of the core material particles. Step A1 using the core particles in such an amount that the total surface area is 1 to 15 m 2 with respect to 1 liter of the electroless nickel plating bath whose concentration is adjusted to 0.0001 to 0.008 mol / liter. When,
While maintaining the aqueous slurry containing the core particle having the nickel initial thin film layer and the dispersant obtained in the step A1 in a pH range in which the dispersing effect of the dispersant is expressed, An A2 step of adding nickel ions and a reducing agent in an amount corresponding to the amount of precipitation of nickel per hour of 25 to 100 nm;
The manufacturing method according to claim 7, wherein the nickel-coated particles are obtained.
（ｉ）ニッケル塩、還元剤及びアルカリのうちの１種を含む第１の水溶液と、残りの２種を含む第２の水溶液を用いるか、又は（ii）ニッケル塩を含む第１の水溶液と、還元剤を含む第２の水溶液と、アルカリを含む第３の水溶液とを用い、これらの水溶液をそれぞれを同時にかつ経時的に、Ｂ１工程の液に添加して無電解ニッケルめっき処理するＢ２工程と、
を行い、前記ニッケル被覆粒子を得る請求項７記載の製造方法。 B1 step of mixing the aqueous slurry of the core material particles with an electroless nickel plating bath containing a dispersant, a nickel salt, a reducing agent and a complexing agent, and electroless nickel plating treatment;
(I) a first aqueous solution containing one of a nickel salt, a reducing agent and an alkali, and a second aqueous solution containing the remaining two, or (ii) a first aqueous solution containing a nickel salt, The B2 step of using the second aqueous solution containing the reducing agent and the third aqueous solution containing the alkali and adding these aqueous solutions to the solution of the B1 step simultaneously and over time to perform electroless nickel plating. When,
The manufacturing method according to claim 7, wherein the nickel-coated particles are obtained.
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