JP5505149B2 - Conductive particles, method for producing the same, and anisotropic conductive adhesive - Google Patents
Conductive particles, method for producing the same, and anisotropic conductive adhesive Download PDFInfo
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- JP5505149B2 JP5505149B2 JP2010157923A JP2010157923A JP5505149B2 JP 5505149 B2 JP5505149 B2 JP 5505149B2 JP 2010157923 A JP2010157923 A JP 2010157923A JP 2010157923 A JP2010157923 A JP 2010157923A JP 5505149 B2 JP5505149 B2 JP 5505149B2
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- 239000002245 particle Substances 0.000 title claims description 142
- 239000000853 adhesive Substances 0.000 title claims description 25
- 230000001070 adhesive effect Effects 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229920000877 Melamine resin Polymers 0.000 claims description 74
- 229920005989 resin Polymers 0.000 claims description 70
- 239000011347 resin Substances 0.000 claims description 70
- 239000010409 thin film Substances 0.000 claims description 45
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 39
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- 238000001179 sorption measurement Methods 0.000 claims description 39
- -1 melamine compound Chemical class 0.000 claims description 30
- 238000007772 electroless plating Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- 238000009833 condensation Methods 0.000 claims description 19
- 238000007747 plating Methods 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000010408 film Substances 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000007547 defect Effects 0.000 description 8
- 239000004640 Melamine resin Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229920006332 epoxy adhesive Polymers 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 150000002940 palladium Chemical class 0.000 description 3
- 239000013034 phenoxy resin Substances 0.000 description 3
- 229920006287 phenoxy resin Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- ZMWGBPZJULKORQ-UHFFFAOYSA-N 2-[(4,6-diamino-1,3,5-triazin-2-yl)amino]ethanol Chemical compound NC1=NC(N)=NC(NCCO)=N1 ZMWGBPZJULKORQ-UHFFFAOYSA-N 0.000 description 1
- MNGSQDSFUODZAR-UHFFFAOYSA-N 2-[[4,6-bis(2-hydroxyethylamino)-1,3,5-triazin-2-yl]amino]ethanol Chemical compound OCCNC1=NC(NCCO)=NC(NCCO)=N1 MNGSQDSFUODZAR-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101100345589 Mus musculus Mical1 gene Proteins 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 description 1
- SYDYRFPJJJPJFE-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(N(CO)CO)=NC(N(CO)CO)=N1 SYDYRFPJJJPJFE-UHFFFAOYSA-N 0.000 description 1
- SUPOBRXPULIDDX-UHFFFAOYSA-N [[4-amino-6-(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound NC1=NC(NCO)=NC(NCO)=N1 SUPOBRXPULIDDX-UHFFFAOYSA-N 0.000 description 1
- WEAJVJTWVRAPED-UHFFFAOYSA-N [[4-amino-6-[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound NC1=NC(N(CO)CO)=NC(N(CO)CO)=N1 WEAJVJTWVRAPED-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Description
本発明は、樹脂粒子の表面に金属薄膜が形成された導電粒子に関する。 The present invention relates to conductive particles in which a metal thin film is formed on the surface of resin particles.
異方性導電フィルムに配合される比較的潰れやすい導電粒子として、樹脂粒子の表面に無電解メッキ金属薄膜を形成したものが広く使用されている。このような導電粒子における樹脂粒子と無電解メッキ金属薄膜との間の密着性を向上させるために、樹脂粒子の表面をクロム酸や過マンガン酸などの強力な酸化剤で樹脂粒子の表面を粗化することが行われている。 As conductive particles that are relatively easily crushed in an anisotropic conductive film, those in which an electroless plated metal thin film is formed on the surface of resin particles are widely used. In order to improve the adhesion between the resin particles and the electroless plated metal thin film in such conductive particles, the surface of the resin particles is roughened with a strong oxidizing agent such as chromic acid or permanganic acid. It has been done.
しかし、このような酸化剤は重金属を含むため、環境負荷が大きく、導電粒子に残留した場合に導電粒子が適用される電子デバイスの性能に悪影響を及ぼすことが懸念される。そこで、そのような酸化剤を使用せずに、樹脂粒子と無電解メッキ金属薄膜との間の密着性を向上させるために、樹脂粒子の表面をメラミン樹脂で被覆し、メラミン樹脂被膜上に無電解メッキ金属薄膜を形成することが提案されている（特許文献１）。 However, since such an oxidizing agent contains heavy metals, there is a concern that the environmental load is large, and when it remains on the conductive particles, it adversely affects the performance of the electronic device to which the conductive particles are applied. Therefore, in order to improve the adhesion between the resin particles and the electroless plating metal thin film without using such an oxidizing agent, the surface of the resin particles is coated with a melamine resin, and the melamine resin coating is not coated. It has been proposed to form an electroplated metal thin film (Patent Document 1).
しかしながら、無電解メッキ薄膜を形成する前に、樹脂粒子の表面にメラミン樹脂被膜を形成した場合、樹脂粒子表面の一部が無電解メッキ金属薄膜で被覆されていない導電粒子が少なからず存在するという問題があった。また、無電解メッキ処理により、導電粒子が凝集し、一次粒子（単一粒子）で存在している割合が低下するという問題があった。このような問題を伴う導電粒子は、異方性導電接着剤用途に不向きなものである。 However, when the melamine resin coating is formed on the surface of the resin particles before forming the electroless plating thin film, there are not a few conductive particles in which part of the resin particle surface is not coated with the electroless plating metal thin film. There was a problem. In addition, there is a problem that the electroconductive plating aggregates the conductive particles and the ratio of primary particles (single particles) is reduced. Conductive particles with such problems are unsuitable for anisotropic conductive adhesive applications.
本発明の目的は、上述した従来の問題を解決しようとするものであり、樹脂粒子表面の一部が無電解メッキ金属薄膜で被覆されていない導電粒子の割合を極力抑制し、しかも凝集せずに一次粒子（単一粒子）で存在している割合が高く、異方性導電接着剤用途に適した導電粒子を提供することである。 An object of the present invention is to solve the above-described conventional problems, and suppresses the proportion of conductive particles in which a part of the resin particle surface is not coated with an electroless plating metal thin film as much as possible, and does not aggregate. The ratio of primary particles (single particles) is high, and conductive particles suitable for anisotropic conductive adhesive applications are provided.
本発明者らは、メラミン樹脂に代えて、メラミン樹脂の原料であって加熱により自己縮合しうるメラミン化合物を、樹脂粒子の表面に吸着させ、その後で無電解メッキ金属薄膜を形成した導電粒子が、無電解メッキ金属薄膜で被覆されていない割合が非常に低く、しかも、単一粒子率が高いものであることを見出し、本発明を完成させるに至った。 Instead of the melamine resin, the present inventors have adsorbed a melamine compound, which is a raw material of the melamine resin, which can be self-condensed by heating, on the surface of the resin particles, and then the conductive particles formed with an electroless plated metal thin film The inventors have found that the proportion not covered with the electroless-plated metal thin film is very low and that the single particle ratio is high, and have completed the present invention.
即ち、本発明は、加熱により自己縮合しうるメラミン化合物を吸着させるメラミン吸着処理が表面に施された樹脂粒子と、その表面に形成された無電解メッキ金属薄膜とからなる導電粒子を提供する。 That is, the present invention provides conductive particles comprising resin particles having a melamine adsorption treatment for adsorbing a melamine compound capable of self-condensation by heating, and an electroless plated metal thin film formed on the surface.
また、本発明は、加熱により自己縮合しうるメラミン化合物を吸着させるメラミン吸着処理が表面に施された樹脂粒子と、その表面に形成された無電解メッキ金属薄膜とからなる導電粒子の製造方法であって、
樹脂粒子の表面に対し、加熱により自己縮合しうるメラミン化合物を吸着させるメラミン吸着処理工程、
メラミン吸着処理が施された樹脂粒子の表面に、無電解メッキ促進用の触媒を析出させる触媒化処理工程、及び
触媒化処理工程が施された樹脂粒子の表面に、無電解メッキにより金属薄膜を形成する無電解メッキ処理工程
を有することを特徴とする製造方法を提供する。
The present invention also relates to a method for producing conductive particles comprising resin particles having a melamine adsorption treatment for adsorbing a melamine compound capable of self-condensation by heating, and an electroless plated metal thin film formed on the surface. There,
A melamine adsorption treatment process for adsorbing a melamine compound capable of self-condensation by heating to the surface of the resin particles;
A catalyst treatment process for depositing a catalyst for promoting electroless plating on the surface of resin particles subjected to melamine adsorption treatment, and a metal thin film formed on the surface of resin particles subjected to the catalyst treatment process by electroless plating There is provided a manufacturing method characterized by having an electroless plating process to be formed.
更に、本発明は、加熱により自己縮合しうるメラミン化合物を吸着させるメラミン吸着処理が表面に施された樹脂粒子と、その表面に形成された無電解メッキ金属薄膜とからなる導電粒子が、絶縁性接着剤中に分散してなる異方性導電接着剤を提供する。 Furthermore, the present invention provides a conductive particle comprising a resin particle having a melamine adsorption treatment for adsorbing a melamine compound capable of self-condensation by heating, and an electroless plated metal thin film formed on the surface. Provided is an anisotropic conductive adhesive dispersed in an adhesive.
本発明の導電粒子は、樹脂粒子の表面に無電解メッキ金属薄膜が形成されたものであるが、その樹脂粒子として、加熱により自己縮合しうるメラミン化合物を吸着させるメラミン吸着処理が表面に施されたものを使用する。このため、樹脂粒子表面の一部が無電解メッキ金属薄膜で被覆されていない導電粒子の割合が極力抑制され、しかも凝集せずに一次粒子（単一粒子）で存在している導電粒子の割合が高くなる。 The conductive particles of the present invention are obtained by forming an electroless plated metal thin film on the surface of resin particles, and the resin particles are subjected to melamine adsorption treatment for adsorbing melamine compounds that can be self-condensed by heating. Use the same thing. For this reason, the ratio of the conductive particles in which a part of the resin particle surface is not coated with the electroless plating metal thin film is suppressed as much as possible, and the ratio of the conductive particles existing as primary particles (single particles) without agglomeration. Becomes higher.
＜導電粒子＞
本発明の導電粒子は、加熱により自己縮合しうるメラミン化合物を吸着させるメラミン吸着処理が表面に施された樹脂粒子と、その表面に形成された無電解メッキ金属薄膜とから構成されている。
<Conductive particles>
The conductive particles of the present invention are composed of resin particles having a melamine adsorption treatment for adsorbing a melamine compound that can be self-condensed by heating, and an electroless plated metal thin film formed on the surface.
（樹脂粒子）
本発明の導電粒子を構成する樹脂粒子としては、加熱により自己縮合しうるメラミン化合物を吸着させるメラミン吸着処理が表面に施された樹脂粒子を使用する。ここで、自己縮合しうるメラミン化合物とは、加熱により自己縮合してメラミン樹脂に変化しうる状態のメラミン化合物であり、例えば、メラミンのアミノ基の窒素原子にメチロール基や２−ヒドロキシエチル基が１〜６個結合した化合物が挙げられる。具体的には、モノメチロールメラミン、ジメチロールメラミン、テトラメチロールメラミン、ペンタメチロールメラミン、ヘキサメチロールメラミン等のメチロールメラミン、Ｎ−（２−ヒドロキシエチル）メラミン、Ｎ，Ｎ′−ビス（２−ヒドロキシエチル）メラミン、Ｎ，Ｎ′，Ｎ″−トリス（２−ヒドロキシエチル）メラミン等のエチロールメラミンを挙げることができる。中でも、無電解メッキ金属薄膜を安定的に形成できる点からメチロールメラニン、特にトリメチロールメラミンを好ましく使用することができる。
(Resin particles)
As the resin particles constituting the conductive particles of the present invention, resin particles having a surface subjected to melamine adsorption treatment for adsorbing a melamine compound capable of self-condensation by heating are used. Here, the self-condensable melamine compound is a melamine compound that can be self-condensed by heating to change into a melamine resin. For example, a methylol group or 2-hydroxyethyl group is present on the nitrogen atom of the amino group of melamine. The compound which 1-6 pieces couple | bonded is mentioned. Specifically, methylol melamine such as monomethylol melamine, dimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, N- (2-hydroxyethyl) melamine, N, N′-bis (2-hydroxyethyl) ) Ethylol melamine such as melamine, N, N ′, N ″ -tris (2-hydroxyethyl) melamine, etc. Among them, methylol melanin, especially trimethyl melanin is particularly preferable because it can stably form an electroless plated metal thin film. Methylol melamine can be preferably used.
メラミン吸着処理としては、導電粒子の製造方法に関し後述するように、例えば、メラミン化合物の水溶液に樹脂粒子を投入し、１〜１０時間撹拌する処理が挙げられる。この際、必要に応じ加熱してもよいが、メラミン化合物の自己縮合が生じる温度にまで加熱することは避ける必要がある。メラミン吸着処理を施した樹脂粒子は、メラミン化合物の水溶液から濾別し、水で洗浄後、メラミン化合物の自己縮合が生じないように乾燥しておくことができる。 Examples of the melamine adsorption treatment include a treatment in which resin particles are added to an aqueous solution of a melamine compound and stirred for 1 to 10 hours, as will be described later with respect to the method for producing conductive particles. At this time, heating may be performed as necessary, but it is necessary to avoid heating to a temperature at which self-condensation of the melamine compound occurs. The resin particles subjected to the melamine adsorption treatment can be filtered from an aqueous solution of the melamine compound, washed with water, and then dried so as not to cause self-condensation of the melamine compound.
このようなメラミン化合物の樹脂粒子の吸着量に関し、吸着量のコントロールは、主としてメラミン吸着処理液中のメラミン化合物濃度、処理温度、処理時間により行うことができる。一般に、吸着量が少なすぎると無電解メッキ金属薄膜に欠損部分が増大する傾向があり、多すぎるとメッキ金属の析出を阻害する傾向があるので、そのような弊害が生じないように吸着量をコントロールすることが好ましい。 Regarding the adsorption amount of the resin particles of such a melamine compound, the adsorption amount can be controlled mainly by the concentration of the melamine compound in the melamine adsorption treatment solution, the treatment temperature, and the treatment time. In general, if the amount of adsorption is too small, there is a tendency for defects to increase in the electroless plated metal thin film. If the amount is too large, the deposition of plating metal tends to be inhibited. It is preferable to control.
導電粒子のコアとなる樹脂粒子の材料としては、従来の異方性導電接着剤に配合されている金属被覆樹脂粒子を構成している樹脂材料を適用することができる。例えば、メラミン樹脂、スチレン樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリエステル樹脂、アクリル樹脂等を挙げることができる。 As the material of the resin particles that serve as the core of the conductive particles, a resin material constituting the metal-coated resin particles blended in the conventional anisotropic conductive adhesive can be applied. For example, melamine resin, styrene resin, polyimide resin, polyamide resin, polyester resin, acrylic resin, and the like can be given.
導電粒子のコアとなる樹脂粒子の粒径は、導電粒子の使用目的（例えば、異方性導電接着剤用の導電粒子、導電性接着剤用の導電粒子、電磁波シールドシート用の導電粒子等）によるが、例えば導電粒子を異方性導電接着剤に配合する場合には、０．５〜１０μｍ、好ましくは２〜５μｍである。 The particle size of the resin particles serving as the core of the conductive particles is the purpose of use of the conductive particles (for example, conductive particles for anisotropic conductive adhesive, conductive particles for conductive adhesive, conductive particles for electromagnetic wave shielding sheet, etc.) However, for example, when the conductive particles are blended in the anisotropic conductive adhesive, the thickness is 0.5 to 10 μm, preferably 2 to 5 μm.
なお、本発明の導電粒子を構成する樹脂粒子は、メラミン吸着処理に続いて触媒化処理が施されていることが好ましい。これにより、無電解メッキ金属薄膜の形成速度を速め、密着性を向上させることができる。 In addition, it is preferable that the resin particle which comprises the electrically-conductive particle of this invention is subjected to the catalyst treatment after the melamine adsorption treatment. Thereby, the formation speed of an electroless-plated metal thin film can be increased, and adhesiveness can be improved.
触媒化処理としては、従来の無電解メッキで行われている触媒化処理を適用することができる。 As the catalyzing treatment, a catalyzing treatment performed by conventional electroless plating can be applied.
触媒化処理によりパラジウムを析出させた場合の析出量に関し、析出量のコントロールは、主として触媒化処理液中のパラジウム化合物の種類や濃度、触媒化処理温度、還元剤の種類や濃度により行うことができる。一般に、析出量が少なすぎると無電解メッキ金属薄膜に欠損部分が増大する傾向があり、多すぎても析出量に見合った効果が得られず、触媒化処理コストが増大する傾向があるので、そのような弊害が生じないように析出量をコントロールすることが好ましい。 Regarding the amount of precipitation when palladium is precipitated by the catalytic treatment, the amount of precipitation is controlled mainly by the type and concentration of the palladium compound in the catalytic treatment solution, the catalytic treatment temperature, and the type and concentration of the reducing agent. it can. Generally, if the amount of precipitation is too small, the electroless plating metal thin film tends to have a defect portion, and if it is too much, an effect commensurate with the amount of precipitation cannot be obtained, and the catalytic treatment cost tends to increase. It is preferable to control the amount of precipitation so as not to cause such harmful effects.
（無電解メッキ金属薄膜）
本発明の導電粒子を構成する無電解メッキ金属薄膜としては、無電解メッキにより形成された金薄膜、ニッケル薄膜、胴薄膜、銀薄膜、パラジウム薄膜等を例示することができる。中でも、異方性導電接続信頼性の観点からニッケル薄膜を好ましく使用することができる。
(Electroless plated metal thin film)
Examples of the electroless plating metal thin film constituting the conductive particles of the present invention include a gold thin film, a nickel thin film, a body thin film, a silver thin film, a palladium thin film, and the like formed by electroless plating. Among these, a nickel thin film can be preferably used from the viewpoint of anisotropic conductive connection reliability.
無電解メッキ金属薄膜の膜厚としては、使用する金属種により異なるが、薄すぎると無電解メッキ金属薄膜の欠損部分が増大する傾向にあり、そのような欠損部分を有する導電粒子を異方性導電接着剤に適用すると導通信頼性が低下する傾向がある。厚すぎると導電粒子が凝集し易くなる傾向があるので、好ましくは１０〜５００ｎｍ、より好ましくは４０〜２００ｎｍである。 The film thickness of the electroless plated metal thin film varies depending on the type of metal used, but if it is too thin, there is a tendency for the defective part of the electroless plated metal thin film to increase, and the conductive particles having such a defective part are anisotropic. When applied to a conductive adhesive, the conduction reliability tends to decrease. If the thickness is too thick, the conductive particles tend to aggregate, so the thickness is preferably 10 to 500 nm, more preferably 40 to 200 nm.
無電解メッキ金属薄膜の形成は、従来の無電解メッキ法に準じて行うことができる。 The electroless plating metal thin film can be formed according to a conventional electroless plating method.
＜導電粒子の製造方法＞
本発明の導電粒子は、以下に説明するように、メラミン吸着処理工程、触媒化処理工程及び無電解メッキ処理工程を有する製造方法により好ましく製造することができる。以下に工程毎に説明する。なお、触媒化処理工程を省略した場合でも、樹脂粒子の表面に無電解メッキ金属薄膜を形成することができるが、樹脂粒子に対する無電解メッキ金属薄膜の密着性が低下することが懸念されるので、省略しない方が好ましい。
<Method for producing conductive particles>
As will be described below, the conductive particles of the present invention can be preferably produced by a production method having a melamine adsorption treatment step, a catalyst treatment step and an electroless plating treatment step. Below, it demonstrates for every process. Even when the catalytic treatment step is omitted, an electroless plated metal thin film can be formed on the surface of the resin particles, but there is a concern that the adhesion of the electroless plated metal thin film to the resin particles may be reduced. It is preferable not to omit it.
（メラミン吸着処理工程）
メラミン吸着処理工程は、樹脂粒子の表面に対し、加熱により自己縮合しうるメラミン化合物を吸着させる工程である。このようなメラミン化合物を樹脂粒子の表面に吸着させる手法としては、自己縮合させないように吸着させることができる手法であれば適用することができる。例えば、このようなメラニン化合物の溶液（好ましくは水溶液）に樹脂粒子を浸漬することが挙げられる。
(Melamine adsorption treatment process)
The melamine adsorption treatment step is a step of adsorbing a melamine compound that can be self-condensed by heating on the surface of the resin particles. As a technique for adsorbing such a melamine compound on the surface of the resin particles, any technique that can adsorb so as not to cause self-condensation can be applied. For example, the resin particles are immersed in a solution (preferably an aqueous solution) of such a melanin compound.
例えば、メラミン化合物としてトリメチロールメラミンを使用した場合、好ましくは精製水１Ｌにトリメチロールメラミン５〜１０ｇと、樹脂粒子１０〜２０ｇとを投入し、１〜３時間撹拌する処理を例示することができる。この際、加熱してもよいが、トリメチロールメラミンの自己縮合が生じる温度（１００℃以上）にまで加熱することは避ける必要がある。通常は２０〜６０℃である。メラミン吸着処理を施した樹脂粒子は、メラミン化合物の水溶液から濾別し、水洗後、メラミン化合物の自己縮合が生じないように自然乾燥すればよい。 For example, when trimethylol melamine is used as the melamine compound, it is preferable to add 5 to 10 g of trimethylol melamine and 10 to 20 g of resin particles to 1 L of purified water and stir for 1 to 3 hours. . At this time, although heating may be performed, it is necessary to avoid heating to a temperature (100 ° C. or higher) at which self-condensation of trimethylolmelamine occurs. Usually, it is 20-60 degreeC. The resin particles subjected to the melamine adsorption treatment may be filtered from an aqueous solution of the melamine compound, washed with water, and then naturally dried so that self-condensation of the melamine compound does not occur.
（触媒化処理工程）
触媒化処理工程は、メラミン吸着処理が施された樹脂粒子の表面に、無電解メッキ促進用の触媒を析出させる工程である。触媒化処理としては、従来の無電解メッキで行われている触媒化処理を適用することができる。この場合、処理温度は、加熱により自己縮合しうるメラミン化合物の自己縮合を生じさせない温度である。例えば、センシタイジング−アクチベーティング法やキャタライジング−アクセラレーティング法により触媒金属、好ましくはパラジウムを適用して樹脂表面に析出させる処理を例示することができる。
(Catalysis process)
The catalyst treatment step is a step of depositing a catalyst for accelerating electroless plating on the surface of the resin particles subjected to the melamine adsorption treatment. As the catalyzing treatment, a catalyzing treatment performed by conventional electroless plating can be applied. In this case, the treatment temperature is a temperature that does not cause self-condensation of the melamine compound that can be self-condensed by heating. For example, a treatment in which a catalyst metal, preferably palladium, is applied to the resin surface by a sensitizing-activating method or a catalyzing-accelrating method can be exemplified.
（センシタイジング−アクチベーティング法）
メラミン吸着処理が施された樹脂粒子を、センシタイザー液に５〜８０℃で１０秒〜１０分間浸漬し、水洗し、次いでアクチベーター液に５〜８０℃で１０秒〜１０分間浸漬する。アクチベーター液から樹脂粒子を濾別して水洗し乾燥する。センシタイザー液及びアクチベーター液としては公知のものが使用できる。例えば、センシタイザー液の具体例としては、塩化第１錫５〜５０ｇ／ｌ（リットル）と塩酸（塩化水素換算）５〜５０ｇ／ｌとを含有する水溶液を挙げることができる。また、アクチベーター液としては、パラジウム塩０．０５〜１．０ｇ／ｌを含有する水溶液が挙げられる。ここで、パラジウム塩としては、塩化パラジウム、塩化パラジウムナトリウム、塩化パラジウムカリウム、テトラアンミン塩化パラジウムなどを挙げることができる。
(Sensitizing-activating method)
The resin particles subjected to the melamine adsorption treatment are immersed in a sensitizer solution at 5 to 80 ° C. for 10 seconds to 10 minutes, washed with water, and then immersed in an activator solution at 5 to 80 ° C. for 10 seconds to 10 minutes. The resin particles are filtered off from the activator solution, washed with water and dried. Known sensitizer liquids and activator liquids can be used. For example, specific examples of the sensitizer liquid include an aqueous solution containing 5 to 50 g / l of stannous chloride and 5 to 50 g / l of hydrochloric acid (in terms of hydrogen chloride). Moreover, as an activator liquid, the aqueous solution containing 0.05-1.0 g / l of palladium salt is mentioned. Here, examples of the palladium salt include palladium chloride, sodium palladium chloride, potassium palladium chloride, and tetraammine palladium chloride.
（キャタライジング−アクセラレーティング法）
メラミン吸着処理が施された樹脂粒子を、５〜８０℃で１０秒〜５０分間、キャタライザー液に浸し、水洗し、ついで５〜８０℃で１０秒〜５０分間、アクセラレーター液に浸漬する。アクセラレーター液から樹脂粒子を濾別して水洗し乾燥する。キャタライザー液及びアクセラレーター液としては公知のものが使用できる。例えば、キャタライザー液としては、塩化第１錫５〜５０ｇ／ｌと上述したようなパラジウム塩０．０５〜１．０ｇ／ｌと塩酸（塩化水素換算）５〜５０ｇ／ｌとを含有するコロイド液が挙げられ、また、アクセラレーター液としては、塩酸が挙げられる。
(Catalyzing-Accelerating method)
The resin particles subjected to the melamine adsorption treatment are immersed in a catalyzer solution at 5 to 80 ° C. for 10 seconds to 50 minutes, washed with water, and then immersed in an accelerator solution at 5 to 80 ° C. for 10 seconds to 50 minutes. The resin particles are filtered off from the accelerator liquid, washed with water and dried. A well-known thing can be used as a catalyzer liquid and an accelerator liquid. For example, as a catalyzer solution, a colloid solution containing 5 to 50 g / l stannous chloride, 0.05 to 1.0 g / l palladium salt as described above, and 5 to 50 g / l hydrochloric acid (in terms of hydrogen chloride). Moreover, hydrochloric acid is mentioned as an accelerator liquid.
その他に、触媒化処理工程としては、メラミン吸着処理が施された樹脂粒子１０ｇを、塩化パラジウム水溶液（０．５〜１．０ｇ／ｌ）２００〜４００ｍｌに投入した後、５０〜７０℃で５秒〜２０分加熱撹拌し、その後、次亜リン酸水溶液（３０〜６０ｇ／ｌ）５０〜２００ｍｌを加入し、更に１０〜３０分間撹拌を続け、パラジウムを析出させる処理が挙げられる。 In addition, as a catalyst treatment step, 10 g of resin particles subjected to the melamine adsorption treatment are put into 200 to 400 ml of an aqueous palladium chloride solution (0.5 to 1.0 g / l), and then 5 at 50 to 70 ° C. For example, there is a treatment in which the mixture is heated and stirred for 2 to 20 minutes, and then added with 50 to 200 ml of a hypophosphorous acid aqueous solution (30 to 60 g / l) and further stirred for 10 to 30 minutes to precipitate palladium.
（無電解メッキ処理工程）
無電解メッキ処理工程は、触媒化処理工程が施された樹脂粒子の表面に、無電解メッキにより金属薄膜を形成しする工程であり、従来より公知の無電解銅メッキ、ニッケルメッキ、金メッキ、銀メッキ、錫メッキなどを使用目的に応じて、選択することできる。中でも、無電解ニッケルメッキを好ましく適用することができる。このような無電解メッキ処理工程を経ることにより本発明の導電粒子を得ることができる。
(Electroless plating process)
The electroless plating treatment step is a step of forming a metal thin film by electroless plating on the surface of the resin particles that have been subjected to the catalytic treatment step. Conventionally known electroless copper plating, nickel plating, gold plating, silver Plating, tin plating, etc. can be selected according to the purpose of use. Among these, electroless nickel plating can be preferably applied. The conductive particles of the present invention can be obtained through such an electroless plating process.
＜異方性導電接着剤＞
以上説明した本発明の導電粒子は、異方性導電接着剤に配合する導電粒子として好ましく適用することができる。即ち、この異方性導電接着剤は、上述した、加熱により自己縮合しうるメラミン化合物を吸着させるメラミン吸着処理が表面に施された樹脂粒子の表面に無電解メッキ金属薄膜を形成してなる導電粒子を、異方性導電接着剤中に５〜１２容量％となるように、絶縁性接着剤に公知の分散手法により分散したものである。通常、ペースト状接着剤、あるいはフィルムに成形して異方性導電フィルムとして使用される。
<Anisotropic conductive adhesive>
The conductive particles of the present invention described above can be preferably applied as conductive particles to be blended in an anisotropic conductive adhesive. That is, the anisotropic conductive adhesive is formed by forming an electroless plating metal thin film on the surface of the resin particles on which the melamine adsorption treatment for adsorbing the melamine compound capable of self-condensation by heating is performed. The particles are dispersed in the insulating adhesive by a well-known dispersion method so as to be 5 to 12% by volume in the anisotropic conductive adhesive. Usually, it is formed into a paste-like adhesive or a film and used as an anisotropic conductive film.
絶縁性接着剤としては、従来公知の絶縁性接着剤を適用することができ、好ましくは、熱硬化型エポキシ系接着剤を使用することができる。そのような熱硬化型エポキシ系接着剤は、膜形成樹脂、液状エポキシ樹脂（硬化成分）、硬化剤、シランカップリング剤等の構成成分を公知の方法で均一に混合することにより調製することができる。これらの構成成分は、接着層に求める特性等に応じて公知のものから適宜選択して使用することができる。 A conventionally well-known insulating adhesive can be applied as the insulating adhesive, and a thermosetting epoxy adhesive can be preferably used. Such a thermosetting epoxy adhesive can be prepared by uniformly mixing components such as a film-forming resin, a liquid epoxy resin (curing component), a curing agent, and a silane coupling agent by a known method. it can. These components can be appropriately selected from known ones according to the characteristics required for the adhesive layer.
膜形成樹脂としては、フェノキシ樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、飽和ポリエステル樹脂、ウレタン樹脂、ブタジエン樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリオレフィン樹脂等を挙げることができ、これらの２種以上を併用することができる。これらの中でも、製膜性、加工性、接続信頼性の観点から、フェノキシ樹脂を好ましく使用することができる。 Examples of the film-forming resin include phenoxy resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, urethane resin, butadiene resin, polyimide resin, polyamide resin, polyolefin resin, and the like. be able to. Among these, a phenoxy resin can be preferably used from the viewpoint of film forming property, workability, and connection reliability.
液状エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ノボラック型エポキシ樹脂、それらの変性エポキシ樹脂、脂環式エポキシ樹脂などを挙げることができ、これらの２種以上を併用することができる。 Examples of liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, modified epoxy resins thereof, and alicyclic epoxy resins, and these two or more types should be used in combination. Can do.
硬化剤としては、ポリアミン、イミダゾール等のアニオン系硬化剤やスルホニウム塩などのカチオン系硬化剤、フェノール系硬化剤等の潜在性硬化剤を挙げることができる。 Examples of the curing agent include anionic curing agents such as polyamine and imidazole, cationic curing agents such as sulfonium salts, and latent curing agents such as phenolic curing agents.
シランカップリング剤としては、エポキシ系シランカップリング剤、アクリル系シランカップリング剤等を挙げることができる。これらのシランカップリング剤は、主としてアルコキシシラン誘導体である。 Examples of the silane coupling agent include an epoxy silane coupling agent and an acrylic silane coupling agent. These silane coupling agents are mainly alkoxysilane derivatives.
熱硬化型エポキシ系接着剤には、必要に応じて充填剤、軟化剤、促進剤、老化防止剤、着色剤（顔料、染料）、有機溶剤、イオンキャッチャー剤などを配合することができる。 If necessary, the thermosetting epoxy adhesive may contain a filler, a softener, an accelerator, an anti-aging agent, a colorant (pigment, dye), an organic solvent, an ion catcher agent, and the like.
本発明の導電粒子は、異方性導電接着剤の他、等方性導電接着剤、磁性シールド剤に使用する導電粒子に適用することができる。 The conductive particles of the present invention can be applied to conductive particles used for isotropic conductive adhesives and magnetic shielding agents in addition to anisotropic conductive adhesives.
以下、発明を実施例により具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to examples.
実施例１
（メラミン吸着処理）
平均粒径３．０μｍのポリメチルメタクリレート（ＰＭＭＡ）粒子（ＭＸ−３００、総研化学（株））１０ｇを、２Ｌコニカルビーカー中の精製水１Ｌに投入し、更にメチロールメラミン（ニカレジンＳ−２６０、日本カーバイド工業（株））５ｇを投入し、６０℃で３時間撹拌することによりメラミン吸着処理を行った。時間経過後、樹脂粒子を濾過により回収し、水で洗浄し、自然乾燥した。
Example 1
(Melamine adsorption treatment)
10 g of polymethylmethacrylate (PMMA) particles (MX-300, Soken Chemical Co., Ltd.) having an average particle size of 3.0 μm were introduced into 1 L of purified water in a 2 L conical beaker, and further methylolmelamine (Nical Resin S-260, Japan). Carbide Industry Co., Ltd. (5 g) was added and the mixture was stirred at 60 ° C. for 3 hours for melamine adsorption treatment. After a lapse of time, the resin particles were collected by filtration, washed with water, and air dried.
（触媒化処理）
メラミン吸着処理を施した樹脂粒子（約１０ｇ）を、表面処理剤としてアミン系界面活性剤を１０ｇ／ｌの割合で溶解しているイオン交換水１Ｌに投入し撹拌しながら６０℃に昇温した。そこへ塩化パラジウム水溶液（１ｇ／Ｌ）を２５０ｍｌを投入し、６０℃で１０分間撹拌した。次いで、次亜リン酸水溶液（６０ｇ／Ｌ）２００ｍｌを投入し、更に３０分間撹拌を続け、表面にパラジウムが析出した樹脂粒子を含有するスラリー液を得た。
(Catalytic treatment)
The resin particles (about 10 g) subjected to the melamine adsorption treatment were added to 1 L of ion-exchanged water in which an amine-based surfactant was dissolved at a rate of 10 g / l as a surface treatment agent, and the temperature was raised to 60 ° C. while stirring. . Thereto, 250 ml of palladium chloride aqueous solution (1 g / L) was added and stirred at 60 ° C. for 10 minutes. Next, 200 ml of an aqueous hypophosphorous acid solution (60 g / L) was added, and stirring was further continued for 30 minutes to obtain a slurry liquid containing resin particles having palladium deposited on the surface.
（無電解メッキ処理）
メラミン吸着処理、続いて触媒化処理を施した樹脂粒子を含有するスラリー液にイオン交換水を添加することにより全量を５Ｌとし、そのスラリー液に酒石酸ナトリウム濃度が８ｇ／Ｌとなるように酒石酸ナトリウムを添加し、６０℃に昇温させた。この混合液に、１４５ｇ／Ｌ濃度の次亜リン酸ナトリウムと６０ｇ／Ｌ濃度の水酸化ナトリウムとを含む還元液６００ｍＬと、１００ｇ／Ｌ濃度の硫酸ニッケル水溶液６００ｍＬとを、定量ポンプでそれぞれ３ｍｌ／分の速度で滴下した。還元液と硫酸ニッケル水溶液との滴下終了後、ニッケルイオンの還元に伴って発生する水素の発泡が治まるまで撹拌を続けた。発泡が治まった後、樹脂粒子の表面に無電解ニッケルメッキ薄膜が形成された導電粒子を濾別し、水で洗浄後、１００℃の真空乾燥器中で乾燥した。得られた導電粒子のニッケル薄膜の平均膜厚は８０〜１００ｎｍであった。
(Electroless plating treatment)
Ion exchange water is added to the slurry liquid containing the resin particles subjected to melamine adsorption treatment and then catalyzed treatment to make the total volume 5 L, and the sodium tartrate concentration in the slurry liquid is 8 g / L. Was added and the temperature was raised to 60 ° C. To this mixed solution, 600 mL of a reducing solution containing 145 g / L sodium hypophosphite and 60 g / L sodium hydroxide, and 600 mL of 100 g / L nickel sulfate aqueous solution were each 3 ml / Added dropwise at a rate of minutes. After completion of the dropwise addition of the reducing solution and the nickel sulfate aqueous solution, stirring was continued until the bubbling of hydrogen generated along with the reduction of nickel ions subsided. After the foaming had subsided, the conductive particles having the electroless nickel plating thin film formed on the surface of the resin particles were filtered off, washed with water, and dried in a vacuum dryer at 100 ° C. The average film thickness of the nickel thin film of the obtained conductive particles was 80 to 100 nm.
比較例１
メラミン吸着処理を行わなかった以外は、実施例１と同様の操作により比較例１の導電粒子を得た。
Comparative Example 1
Conductive particles of Comparative Example 1 were obtained by the same operation as Example 1 except that the melamine adsorption treatment was not performed.
比較例２
メラミン吸着処理を行った後、触媒化処理前に、樹脂粒子を、トリメチロールメラミンの加熱により自己縮合が生じてしまう１５０℃という温度で６時間乾燥処理をしたこと以外は、実施例１と同様の操作により比較例２の導電粒子を得た。
Comparative Example 2
After performing the melamine adsorption treatment and before the catalyst treatment, the resin particles were the same as in Example 1 except that the resin particles were subjected to a drying treatment at a temperature of 150 ° C. for 6 hours due to heating of trimethylolmelamine. As a result, the conductive particles of Comparative Example 2 were obtained.
＜評価＞
実施例１及び比較例１、２の導電粒子について、メッキ成膜欠陥率とメッキ粒子凝集状態とを以下に説明するように試験・評価した。得られた結果を表１に示す。
<Evaluation>
For the conductive particles of Example 1 and Comparative Examples 1 and 2, the plating film formation defect rate and the plating particle aggregation state were tested and evaluated as described below. The obtained results are shown in Table 1.
（メッキ成膜欠陥率）
倍率１０００倍の走査電子顕微鏡（ＪＳＭ−６５１０Ａ、日本電子（株））により、１０００個の導電粒子を観察し、粒子表面積の５０％以上にわたってメッキ剥れが観察された導電粒子の割合（欠陥率）を求めた。実用上、欠陥率は１．０％以下であることが望まれる。
(Plating film deposition defect rate)
1000 conductive particles were observed with a scanning electron microscope (JSM-6510A, JEOL Ltd.) at a magnification of 1000 times, and the proportion of conductive particles in which plating peeling was observed over 50% or more of the particle surface area (defect rate) ) In practice, the defect rate is desirably 1.0% or less.
（単一粒子率）
粒子像解析装置（ＦＰＩＡ３０００、シスメックス社）を用いて、凝集していない一次粒子の割合（単一粒子率）を求めた。
(Single particle ratio)
Using a particle image analyzer (FPIA3000, Sysmex Corporation), the ratio of primary particles not aggregated (single particle ratio) was determined.
表１からわかるように、実施例１の導電粒子は、実用上問題のない、レベルの低いメッキ成膜欠陥率と高い単一粒子率とを示した。他方、比較例１及び２の導電粒子は、実用上問題のある、レベルの高いメッキ成膜欠陥率と低い単一粒子率とを示した。 As can be seen from Table 1, the conductive particles of Example 1 exhibited a low level of plating film formation defect rate and a high single particle rate that had no practical problems. On the other hand, the conductive particles of Comparative Examples 1 and 2 exhibited a high level of plating film formation defect rate and a low single particle rate, which had practical problems.
実施例２
実施例１で得られた導電粒子２０質量部、フェノキシ樹脂（ＹＰ５０、東都化成（株））３０質量部、液状エポキシ樹脂（ＥＰ−８２８、三菱化学（株））３０質量部、イミダゾール系硬化剤（ＨＸ３９４１ＨＰ、旭化成（株））３０質量部とを均一に混合し、この混合物を、バーコータを用いて剥離フィルム状に塗布し、８０℃で５分間プレベークすることにより異方性導電フィルムを作製した。得られた異方性導電フィルムを、千鳥配置された金バンプを有する試験用ＩＣチップ（バンプサイズ１８００μｍ２、バンプ高さ１５μｍ、外側バンプ列と内側バンプ列間の距離２０μｍ、各列内のバンプ間の距離２０μｍ）と、対応するガラス基板との間に挟持させ、加熱加圧ヘッドにて２００℃で圧力６０ＭＰａで５秒間の加熱加圧を行った。その際の外側バンプと内側バンプの導通抵抗（Ω）を常法に従って測定した。いずれも１Ω以下であり、良好な導通であった。
Example 2
20 parts by mass of conductive particles obtained in Example 1, 30 parts by mass of phenoxy resin (YP50, Toto Kasei Co., Ltd.), 30 parts by mass of liquid epoxy resin (EP-828, Mitsubishi Chemical Co., Ltd.), imidazole curing agent (HX3941HP, Asahi Kasei Co., Ltd.) 30 parts by mass were uniformly mixed, and this mixture was applied to a release film using a bar coater, and prebaked at 80 ° C. for 5 minutes to produce an anisotropic conductive film. . The obtained anisotropic conductive film was used as a test IC chip (bump size 1800 μm 2 , bump height 15 μm, distance between outer bump row and inner bump row 20 μm, bumps in each row, with staggered gold bumps. And a corresponding glass substrate, and was heated and pressed at 200 ° C. and a pressure of 60 MPa for 5 seconds with a heating and pressing head. The conduction resistance (Ω) between the outer and inner bumps at that time was measured according to a conventional method. All were 1Ω or less, and good conduction was obtained.
本発明の導電粒子は、樹脂粒子の表面に無電解メッキ金属薄膜が形成されたものであるが、その樹脂粒子として、加熱により自己縮合しうるメラミン化合物を吸着させるメラミン吸着処理が表面に施されたものを使用する。このため、樹脂粒子表面の一部が無電解メッキ金属薄膜で被覆されていない導電粒子の割合が極力抑制され、しかも凝集せずに一次粒子（単一粒子）で存在している導電粒子の割合が高くなる。よって、異方性導電接着剤に配合する導電粒子として有用である。 The conductive particles of the present invention are obtained by forming an electroless plated metal thin film on the surface of resin particles, and the resin particles are subjected to melamine adsorption treatment for adsorbing melamine compounds that can be self-condensed by heating. Use the same thing. For this reason, the ratio of the conductive particles in which a part of the resin particle surface is not coated with the electroless plating metal thin film is suppressed as much as possible, and the ratio of the conductive particles existing as primary particles (single particles) without agglomeration. Becomes higher. Therefore, it is useful as conductive particles to be blended in the anisotropic conductive adhesive.
Claims (11)
樹脂粒子の表面に対し、加熱により自己縮合しうるメラミン化合物を吸着させるメラミン吸着処理工程、
メラミン吸着処理が施された樹脂粒子の表面に、無電解メッキ促進用の触媒を析出させる触媒化処理工程、及び
触媒化処理工程が施された樹脂粒子の表面に、無電解メッキにより金属薄膜を形成する無電解メッキ処理工程
を有することを特徴とする製造方法。 A method for producing conductive particles comprising a resin particle having a melamine adsorption treatment for adsorbing a melamine compound capable of self-condensation by heating, and an electroless plated metal thin film formed on the surface,
A melamine adsorption treatment process for adsorbing a melamine compound capable of self-condensation by heating to the surface of the resin particles;
A catalyst treatment process for depositing a catalyst for promoting electroless plating on the surface of resin particles subjected to melamine adsorption treatment, and a metal thin film formed on the surface of resin particles subjected to the catalyst treatment process by electroless plating A manufacturing method comprising an electroless plating treatment step to be formed.
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