JP2020064833A - Base particles for conductive particles and use thereof - Google Patents
Base particles for conductive particles and use thereof Download PDFInfo
- Publication number
- JP2020064833A JP2020064833A JP2018197781A JP2018197781A JP2020064833A JP 2020064833 A JP2020064833 A JP 2020064833A JP 2018197781 A JP2018197781 A JP 2018197781A JP 2018197781 A JP2018197781 A JP 2018197781A JP 2020064833 A JP2020064833 A JP 2020064833A
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- JP
- Japan
- Prior art keywords
- particles
- conductive particles
- meth
- conductive
- acrylate
- Prior art date
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- Granted
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- 239000002245 particle Substances 0.000 title claims abstract description 359
- 239000000178 monomer Substances 0.000 claims abstract description 89
- 239000004020 conductor Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 239000011246 composite particle Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 46
- 238000007747 plating Methods 0.000 abstract description 11
- 230000002776 aggregation Effects 0.000 abstract description 5
- 238000004220 aggregation Methods 0.000 abstract description 4
- 239000002585 base Substances 0.000 description 97
- -1 acryloxy group Chemical group 0.000 description 72
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 69
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 33
- 229920002554 vinyl polymer Polymers 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000011156 evaluation Methods 0.000 description 27
- 239000000463 material Substances 0.000 description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- 239000002202 Polyethylene glycol Substances 0.000 description 20
- 229920001223 polyethylene glycol Polymers 0.000 description 20
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- 229910000077 silane Inorganic materials 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 229910052700 potassium Inorganic materials 0.000 description 14
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 229920001296 polysiloxane Polymers 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 229920001451 polypropylene glycol Polymers 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- 229910052737 gold Inorganic materials 0.000 description 9
- 239000010931 gold Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 239000002609 medium Substances 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
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- 239000000839 emulsion Substances 0.000 description 6
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- 238000004519 manufacturing process Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- 239000011135 tin Substances 0.000 description 6
- 229910000990 Ni alloy Inorganic materials 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 4
- 229920001748 polybutylene Polymers 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
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- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
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- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- TXHZNLCKXHJYNX-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound COCCOCCOCCOCCOCCOCCOCCOCCOCCOC(=O)C(C)=C TXHZNLCKXHJYNX-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 150000005215 alkyl ethers Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
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- 125000002843 carboxylic acid group Chemical group 0.000 description 2
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- XDSGMUJLZDSCPA-UHFFFAOYSA-N diazanium;phenoxybenzene;sulfate Chemical class [NH4+].[NH4+].[O-]S([O-])(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 XDSGMUJLZDSCPA-UHFFFAOYSA-N 0.000 description 2
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- MKPHQUIFIPKXJL-UHFFFAOYSA-N 1,2-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(O)C(O)OC(=O)C(C)=C MKPHQUIFIPKXJL-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は導電粒子用基材粒子およびその利用に関する。 The present invention relates to base particles for conductive particles and use thereof.
従来、電子機器の組み立てにおいて、対向する多数の電極や配線間の電気的接続を行うために、異方性導電材料による接続方式が採用されている。異方性導電材料は、導電粒子をバインダー樹脂等に混合した材料である。また、異方性導電材料に用いられる導電粒子としては、金属粒子や基材とする導電粒子用基材粒子の表面を導電性金属層で被覆したものが使用されている。 2. Description of the Related Art Conventionally, in assembling an electronic device, a connection method using an anisotropic conductive material has been adopted in order to electrically connect a large number of opposing electrodes and wirings. The anisotropic conductive material is a material in which conductive particles are mixed with a binder resin or the like. In addition, as the conductive particles used for the anisotropic conductive material, metal particles or base particles for conductive particles as a base material, the surfaces of which are coated with a conductive metal layer, are used.
導電粒子として、特許文献１には、導電粒子用基材粒子の平均粒子径が０．５μｍ〜２．５μｍと小さい導電粒子が開示されている。また、特許文献２には、導電粒子用基材粒子の個数基準の平均分散粒子径が１．０μｍ〜２．５μｍと小さく、分散粒子径の個数基準の変動係数が所定の範囲である導電粒子が開示されている。 As the conductive particles, Patent Document 1 discloses conductive particles having a small average particle diameter of the base material particles for conductive particles of 0.5 μm to 2.5 μm. Further, in Patent Document 2, conductive particles in which the number-based average dispersed particle diameter of the base particles for conductive particles is as small as 1.0 μm to 2.5 μm, and the number-based variation coefficient of the dispersed particle diameter is within a predetermined range. Is disclosed.
特許文献１および２に開示される従来技術でも検討されているが、導電粒子の基材となる導電粒子用基材粒子の粒子径が小さい場合、導電粒子用基材粒子に導電性金属層をメッキする際に、導電粒子用基材粒子が凝集し、均一に導電性金属層が形成されない問題がある。また、その結果、初期抵抗値および接続信頼性に問題が生じるおそれがある。 Although studied in the related art disclosed in Patent Documents 1 and 2, when the particle size of the base particles for conductive particles, which is the base material for the conductive particles, is small, a conductive metal layer is formed on the base particles for conductive particles. At the time of plating, there is a problem that the base particles for conductive particles aggregate, and the conductive metal layer is not uniformly formed. Further, as a result, problems may occur in the initial resistance value and connection reliability.
本発明の一態様は、メッキする際に導電粒子用基材粒子が凝集せず、初期抵抗値が低く、かつ接続信頼性が高い導電粒子を作製するための、粒子径の小さな導電粒子用基材粒子およびその利用技術を提供することを目的とする。 One aspect of the present invention is a base for conductive particles having a small particle size for producing conductive particles in which base particles for conductive particles do not aggregate during plating, have a low initial resistance value, and have high connection reliability. The object is to provide wood particles and a technology for utilizing the wood particles.
本発明者は、前記の課題を解決するために鋭意検討した結果、親水性単量体に由来する構造単位を有する導電粒子用基材粒子を用いることにより、水に対する分散性に優れ、メッキの際に導電粒子用基材粒子の凝集を防止でき、その結果、初期抵抗値が低く、かつ接続信頼性が高い導電粒子を得られることを見出し、本発明を完成させた。
本発明は、以下構成を包含する。
The present inventor, as a result of extensive studies to solve the above problems, by using a base particle for conductive particles having a structural unit derived from a hydrophilic monomer, excellent dispersibility in water, plating of At the time, it was found that aggregation of the base particles for conductive particles can be prevented, and as a result, conductive particles having a low initial resistance value and high connection reliability can be obtained, and the present invention was completed.
The present invention includes the following configurations.
〔１〕平均粒子径が１．０μｍ〜２．５μｍであり、親水性単量体に由来する構造単位を有する、導電粒子用基材粒子。 [1] Base particle for conductive particles, having an average particle diameter of 1.0 μm to 2.5 μm and having a structural unit derived from a hydrophilic monomer.
〔２〕前記導電粒子用基材粒子１００重量％に対して、前記親水性単量体に由来する成分を１０〜２５重量％含む、〔１〕に記載の導電粒子用基材粒子。 [2] The base particle for conductive particles according to [1], which contains 10 to 25 wt% of a component derived from the hydrophilic monomer with respect to 100 wt% of the base particle for conductive particles.
〔３〕Ｓｉ原子を含む有機無機複合粒子である、〔１〕または〔２〕に記載の導電粒子用基材粒子。 [3] The base particle for conductive particles according to [1] or [2], which is an organic-inorganic composite particle containing a Si atom.
〔４〕〔１〕〜〔３〕のいずれか一項に記載の導電粒子用基材粒子の表面に、少なくとも一層の導電性金属層が形成されている、導電粒子。 [4] Conductive particles in which at least one conductive metal layer is formed on the surface of the base particle for conductive particles according to any one of [1] to [3].
〔５〕〔４〕に記載の導電粒子を含む、異方性導電材料。 [5] An anisotropic conductive material containing the conductive particles according to [4].
〔６〕〔４〕に記載の導電粒子と、バインダー樹脂とを含む、異方性導電ペースト。 [6] An anisotropic conductive paste containing the conductive particles according to [4] and a binder resin.
本発明の一態様によれば、メッキの際に導電粒子用基材粒子の凝集を防止でき、その結果、初期抵抗値が低く、かつ接続信頼性が高い導電粒子を提供することができる。 According to one aspect of the present invention, it is possible to prevent aggregation of the base particles for conductive particles during plating, and as a result, it is possible to provide conductive particles having a low initial resistance value and high connection reliability.
本発明の一実施形態について以下に説明するが、本発明はこれに限定されるものではない。本発明は、以下に説明する各構成に限定されるものではなく、特許請求の範囲に示した範囲で種々の変更が可能であり、異なる実施形態や実施例にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態や実施例についても本発明の技術的範囲に含まれる。また、本明細書中に記載された学術文献および特許文献の全てが、本明細書中において参考文献として援用される。また、本明細書において特記しない限り、数値範囲を表す「Ａ〜Ｂ」は「Ａ以上Ｂ以下」を意図する。 One embodiment of the present invention will be described below, but the present invention is not limited to this. The present invention is not limited to each configuration described below, various modifications are possible within the scope shown in the claims, and technical means disclosed in different embodiments and examples Embodiments and examples obtained by appropriately combining them are also included in the technical scope of the present invention. Further, all of the academic documents and patent documents described in the present specification are incorporated herein by reference. Unless otherwise specified in this specification, “A to B” representing a numerical range means “A or more and B or less”.
〔１．導電粒子用基材粒子〕
本発明の一実施形態に係る導電粒子用基材粒子（以下、単に「導電粒子用基材粒子」とも称する。）は、平均粒子径が１．０μｍ〜２．５μｍであり、親水性単量体に由来する構造単位を有するもの（親水性単量体成分をポリマーのユニットに含むもの）である。
[1. Base particle for conductive particles]
The base particles for conductive particles according to one embodiment of the present invention (hereinafter, also simply referred to as “base particles for conductive particles”) have an average particle diameter of 1.0 μm to 2.5 μm and a hydrophilic single amount. It has a structural unit derived from the body (containing a hydrophilic monomer component in a polymer unit).
本明細書中で使用される「親水性単量体」とは、水酸基、カルボン酸基、アミノ基、および／またはエチレンオキシド鎖（以下、「ＥＯ鎖」とも称する。）等の極性官能基を有するビニル系単官能単量体を意味する。「ビニル系単官能単量体」とは、１分子中に一個のビニル基を有する単量体を意図する。なお、本明細書中、「ビニル基」には、炭素−炭素二重結合のみならず、（メタ）アクリロキシ基、アリル基、イソプロペニル基、ビニルフェニル基、イソプロペニルフェニル基のような重合性炭素−炭素二重結合を有する置換基も含まれるものとする。なお、本明細書において「（メタ）アクリロイル基」、「（メタ）アクリロキシ基」、「（メタ）アクリレート」または「（メタ）アクリル」はそれぞれ、「アクリロイル基、メタクリロイル基の一方または両方」、「アクリロキシ基、メタクリロキシ基の一方または両方」、「アクリレート、メタクリレートの一方または両方」や「アクリル、メタクリルの一方または両方」を示すものとする。 The "hydrophilic monomer" used in the present specification has a polar functional group such as a hydroxyl group, a carboxylic acid group, an amino group, and / or an ethylene oxide chain (hereinafter, also referred to as "EO chain"). It means a vinyl-based monofunctional monomer. The “vinyl-based monofunctional monomer” means a monomer having one vinyl group in one molecule. In the present specification, "vinyl group" includes not only a carbon-carbon double bond but also a polymerizable group such as (meth) acryloxy group, allyl group, isopropenyl group, vinylphenyl group, isopropenylphenyl group. Substituents having a carbon-carbon double bond are also included. In the present specification, “(meth) acryloyl group”, “(meth) acryloxy group”, “(meth) acrylate” or “(meth) acryl” means “one or both of acryloyl group and methacryloyl group”, "One or both of acryloxy group and methacryloxy group", "one or both of acrylate and methacrylate" and "one or both of acryl and methacryl" are meant.
水酸基含有単官能モノマーとしては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート等のヒドロキシ基含有（メタ）アクリレート類；ｐ−ヒドロキシスチレン、等のヒドロキシ基含有スチレン類等が挙げられる。 Examples of the hydroxyl group-containing monofunctional monomer include hydroxy group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate; p-hydroxystyrene, And hydroxy group-containing styrenes and the like.
カルボン酸基含有単官能モノマーとしては、（メタ）アクリル酸、２−（メタ）アクリロイロキシエチルコハク酸、２−（メタ）アクリロイロキシエチルフタル酸等が挙げられる。 Examples of the carboxylic acid group-containing monofunctional monomer include (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, and 2- (meth) acryloyloxyethylphthalic acid.
アミノ基含有単官能モノマーとしては、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ｔ−ブチルアミノエチル（メタ）アクリレート、エチルメチルアミノエチル（メタ）アクリレート等が挙げられる。 Examples of the amino group-containing monofunctional monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate and ethylmethylaminoethyl (meth) acrylate.
ＥＯ鎖含有単官能モノマーとしては、メトキシポリメチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、メトキシポリブチレングリコール（メタ）アクリレート、オクトキシポリエチレングリコールポリプロピレングリコール（メタ）アクリレート、ラウロキシポリエチレングリコール（メタ）アクリレート、ステアロキシポリエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコールポリプロピレングリコール（メタ）アクリレート等のポリアルキレングリコールモノ（メタ）アクリレートが挙げられる。 Examples of the EO chain-containing monofunctional monomer include methoxy polymethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, methoxy polybutylene glycol (meth) acrylate, octoxy polyethylene glycol polypropylene glycol ( Polyalkylene glycol mono (meth) acrylates such as (meth) acrylate, lauroxy polyethylene glycol (meth) acrylate, stearoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol polypropylene glycol (meth) acrylate Can be mentioned.
ＥＯ鎖および水酸基含有単官能モノマーとしては、ポリメチレングリコール（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、ポリブチレングリコール（メタ）アクリレート、ポリエチレングリコールプロピレングリコール（メタ）アクリレート、ポリエチレングリコールポリプロピレングリコール（メタ）アクリレート、ポリエチレングリコールテトラメチレングリコール（メタ）アクリレート、プロピレングリコールポリブチレングリコール（メタ）アクリレート等のポリアルキレングリコールモノ（メタ）アクリレートが挙げられる。 Examples of the EO chain- and hydroxyl group-containing monofunctional monomer include polymethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polybutylene glycol (meth) acrylate, polyethylene glycol propylene glycol (meth) acrylate, Examples thereof include polyalkylene glycol mono (meth) acrylates such as polyethylene glycol polypropylene glycol (meth) acrylate, polyethylene glycol tetramethylene glycol (meth) acrylate, and propylene glycol polybutylene glycol (meth) acrylate.
前記ＥＯ鎖含有単官能モノマーの市販品としては、メトキシポリエチレングリコールメタクリレートである「ブレンマー（登録商標）ＰＭＥ−１００」、「ブレンマーＰＭＥ−２００」、「ブレンマーＰＭＥ−４００」、「ブレンマーＰＭＥ−１０００」および「ブレンマーＰＭＥ−４０００」（日油株式会社製）；オクトキシポリエチレングリコールポリプロピレングリコールメタクリレートである「ブレンマー５０ＰＯＥＰ−８００Ｂ」（日油株式会社製）；ラウロキシポリエチレングリコールメタクリレートである「ブレンマーＰＬＥ−４００」および「ブレンマーＰＬＥ−１３００」（日油株式会社製）；ステアロキシポリエチレングリコールメタクリレートである「ブレンマーＰＳＥ−４００」および「ブレンマーＰＳＥ−１３００」（日油株式会社）；フェノキシポリエチレングリコールメタクリレートである「ブレンマーＰＡＥ−１００」（日油株式会社）；フェノキシポリエチレングリコールポリプロピレングリコールメタクリレートである「ブレンマー４３ＰＡＰＥ−６００Ｂ」（日油株式会社）等が挙げられる。 As a commercial product of the EO chain-containing monofunctional monomer, methoxypolyethylene glycol methacrylate "Blemmer (registered trademark) PME-100", "Blemmer PME-200", "Blemmer PME-400", "Blemmer PME-1000" is used. And "Blenmer PME-4000" (manufactured by NOF CORPORATION); "Blenmer 50 POEP-800B" (manufactured by NOF CORPORATION) which is octoxy polyethylene glycol polypropylene glycol methacrylate; "Blenmer PLE-400 which is lauroxy polyethylene glycol methacrylate". And "Blemmer PLE-1300" (manufactured by NOF CORPORATION); "Blemmer PSE-400" and "Blemmer PSE-130" which are stearoxy polyethylene glycol methacrylates. (NOF Corporation); phenoxy polyethylene glycol methacrylate "Blenmer PAE-100" (NOF Corporation); phenoxy polyethylene glycol polypropylene glycol methacrylate "Blenmer 43PAPE-600B" (NOF Corporation) and the like. To be
前記ＥＯ鎖および水酸基含有単官能モノマーの市販品としては、ポリエチレングリコールメタクリレートである「ブレンマー（登録商標）ＰＥ−９０」、「ブレンマーＰＥ−２００」、「ブレンマーＰＥ−３５０」（日油株式会社製）；ポリプロピレングリコールメタクリレートである「ブレンマー（登録商標）ＰＰ−５００」、「ブレンマーＰＰ−８００」、「ブレンマーＰＰ−１０００」（日油株式会社製）；ポリエチレングリコールプロピレングリコールメタクリレートである「ブレンマー（登録商標）５０ＰＥＰ−３００」（日油株式会社製）；ポリエチレングリコールポリプロピレングリコールメタクリレートである「ブレンマー（登録商標）７０ＰＥＰ−３５０Ｂ」（日油株式会社製）；ポリエチレングリコールテトラメチレングリコールメタクリレートである「ブレンマー（登録商標）５５ＰＥＴ−８００」（日油株式会社製）；プロピレングリコールポリブチレングリコールメタクリレートである「ブレンマー（登録商標）１０ＰＰＢ−５００Ｂ」（日油株式会社）等が挙げられる。 Commercially available products of the EO chain and hydroxyl group-containing monofunctional monomer are polyethylene glycol methacrylates "Blemmer (registered trademark) PE-90", "Blemmer PE-200", and "Blemmer PE-350" (manufactured by NOF CORPORATION). ); Polypropylene glycol methacrylate "Blemmer (registered trademark) PP-500", "Blemmer PP-800", "Blemmer PP-1000" (manufactured by NOF CORPORATION); polyethylene glycol propylene glycol methacrylate "Blemmer (registered trademark)" Trademark) 50PEP-300 "(manufactured by NOF CORPORATION); polyethylene glycol polypropylene glycol methacrylate" Blenmer (registered trademark) 70PEP-350B "(manufactured by NOF CORPORATION); polyethylene glycol tetramethylene "Blenmer (registered trademark) 55PET-800" (manufactured by NOF CORPORATION) which is recall methacrylate; "Blenmer (registered trademark) 10PPB-500B" (NOF Corporation) which is propylene glycol polybutylene glycol methacrylate. .
前記親水性単量体は、水に対する分散性に優れた導電粒子用基材粒子を得られるという観点から、水酸基含有単官能モノマーであることが好ましい。 The hydrophilic monomer is preferably a hydroxyl group-containing monofunctional monomer from the viewpoint that base particles for conductive particles having excellent dispersibility in water can be obtained.
導電粒子用基材粒子が親水性単量体に由来する構造単位を有するかどうかは、例えば、ＩＲ分析によって、特定の官能基に対応する吸収波長の吸光度を測定することにより、評価することができる。 Whether the base particles for conductive particles have a structural unit derived from a hydrophilic monomer can be evaluated by measuring the absorbance at the absorption wavelength corresponding to a specific functional group, for example, by IR analysis. it can.
前記平均粒子径は、下記実施例に記載の方法で測定される。本発明の一実施形態において、導電粒子用基材粒子の平均粒子径は、個数基準の平均分散粒子径で、１．０μｍ〜２．５μｍである。メッキの際に凝集しにくいため、導電粒子用基材粒子の平均粒子径は、２．０μｍ〜２．５μｍであることが好ましい。導電粒子用基材粒子の平均粒子径は、実施例に記載の方法で測定することができる。 The average particle diameter is measured by the method described in Examples below. In one embodiment of the present invention, the average particle size of the base particles for conductive particles is 1.0 μm to 2.5 μm in terms of number-based average dispersed particle size. The average particle size of the base particles for conductive particles is preferably 2.0 μm to 2.5 μm because they are less likely to aggregate during plating. The average particle diameter of the base particles for conductive particles can be measured by the method described in the examples.
本発明の一実施形態に係る導電粒子用基材粒子は、導電粒子用基材粒子１００重量％に対して、前記親水性単量体に由来する成分を１０〜２５重量％含んでいてもよい。 The base particle for conductive particles according to an embodiment of the present invention may include 10 to 25 wt% of a component derived from the hydrophilic monomer with respect to 100 wt% of the base particle for conductive particles. .
前記親水性単量体に由来する成分が１０重量％未満である場合、優れた初期抵抗値および接続信頼性を達成できない。一方、前記親水性単量体に由来する成分が２５重量％を超える場合、導電粒子を作製するためのメッキ処理以前に、導電粒子用基材粒子自身の合成段階で凝集してしまう。このことから、前記導電粒子用基材粒子は、前記親水性単量体に由来する成分を１０重量％〜２５重量％含むことが好ましく、１５重量％〜２０重量％含むことがより好ましい。 When the component derived from the hydrophilic monomer is less than 10% by weight, excellent initial resistance value and connection reliability cannot be achieved. On the other hand, if the content of the component derived from the hydrophilic monomer exceeds 25% by weight, the base particles for conductive particles themselves aggregate at the stage of synthesis before the plating treatment for producing the conductive particles. From this, it is preferable that the base particle for conductive particles contains 10 wt% to 25 wt% of the component derived from the hydrophilic monomer, and more preferably 15 wt% to 20 wt%.
本発明の一実施形態において、導電粒子用基材粒子は、親水性単量体に由来する構造単位を有していればよく、親水性単量体以外のビニル系単量体に由来する構造単位を有していてもよい。また、導電粒子用基材粒子は、ビニル系単量体に由来する構造単位のみを有している粒子に限られず、後述するＳｉ原子を含む有機無機複合粒子から構成される粒子でもよい。これらの導電粒子用基材粒子を構成する材料は、単独で用いられてもよく、２種以上が併用されてもよい。 In one embodiment of the present invention, the conductive particle substrate particles may have a structural unit derived from a hydrophilic monomer, a structure derived from a vinyl-based monomer other than the hydrophilic monomer It may have a unit. The base particles for conductive particles are not limited to particles having only a structural unit derived from a vinyl-based monomer, and may be particles composed of organic-inorganic composite particles containing Si atoms described below. The materials forming the base particles for conductive particles may be used alone or in combination of two or more kinds.
親水性単量体以外のビニル系単量体としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート等のアルキル（メタ）アクリレート類；シクロプロピル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、シクロオクチル（メタ）アクリレート、シクロウンデシル（メタ）アクリレート、シクロドデシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、４−ｔ−ブチルシクロヘキシル（メタ）アクリレート等のシクロアルキル（メタ）アクリレート類；フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、トリル（メタ）アクリレート、フェネチル（メタ）アクリレート等の芳香環含有（メタ）アクリレート類；スチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、α−メチルスチレン、ｐ−ｔ−ブチルスチレン等のアルキルスチレン類、ｏ−クロロスチレン、ｍ−クロロスチレン、ｐ−クロロスチレン等のハロゲン基含有スチレン類等のスチレン系単官能モノマー；等のビニル系単官能単量体が挙げられる。本発明の一実施形態において、導電粒子用基材粒子は、１０％Ｋ値の低い導電粒子が得られやすい点で、スチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、α−メチルスチレン、ｐ−ｔ−ブチルスチレン等のアルキルスチレン類を含むことが好ましい。 Examples of vinyl-based monomers other than hydrophilic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl. (Meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl Alkyl (meth) acrylates such as (meth) acrylate; cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, cycloun Cycloalkyl (meth) acrylates such as sil (meth) acrylate, cyclododecyl (meth) acrylate, isobornyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate , Tolyl (meth) acrylate, phenethyl (meth) acrylate and other aromatic ring-containing (meth) acrylates; styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, pt-butyl. Examples thereof include vinyl monofunctional monomers such as alkyl styrenes such as styrene, halogen group-containing styrenes such as o-chlorostyrene, m-chlorostyrene and p-chlorostyrene; In one embodiment of the present invention, the base particles for conductive particles are styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-, since conductive particles having a low 10% K value are easily obtained. It is preferable to contain alkylstyrenes such as methylstyrene and pt-butylstyrene.
また、親水性単量体以外のビニル系単量体として、例えば、アリル（メタ）アクリレート等のアリル（メタ）アクリレート類；エチレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、１，１０−デカンジオールジ（メタ）アクリレート、１，３−ブチレンジ（メタ）アクリレート等のアルカンジオールジ（メタ）アクリレート；ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、デカエチレングリコールジ（メタ）アクリレート、ペンタデカエチレングリコールジ（メタ）アクリレート、ペンタコンタヘクタエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ポリテトラメチレングリコールジ（メタ）アクリレート等のポリアルキレングリコールジ（メタ）アクリレート等のジ（メタ）アクリレート類；トリメチロールプロパントリ（メタ）アクリレート等のトリ（メタ）アクリレート類；ペンタエリスリトールテトラ（メタ）アクリレート等のテトラ（メタ）アクリレート類；ジペンタエリスリトールヘキサ（メタ）アクリレート等のヘキサ（メタ）アクリレート類；ジビニルベンゼン、ジビニルナフタレン、及びこれらの誘導体等の芳香族炭化水素系架橋剤（好ましくは、ジビニルベンゼン等のスチレン系多官能モノマー）；Ｎ，Ｎ−ジビニルアニリン、ジビニルエーテル、ジビニルサルファイド、ジビニルスルホン酸等のヘテロ原子含有架橋剤；等のビニル系多官能単量体も挙げられる。「ビニル系多官能単量体」とは、１分子中に２個以上のビニル基を有する単量体を意図する。 As vinyl-based monomers other than hydrophilic monomers, for example, allyl (meth) acrylates such as allyl (meth) acrylate; ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth). Alkanes such as acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,3-butylene di (meth) acrylate Diol di (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, pentadecaethylene glycol di (meth) acrylate, pentacontahector ethylene glycol di (meth) ) Acry , Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate and other polyalkylene glycol di (meth) acrylates and other di (meth) acrylates; trimethylolpropane Tri (meth) acrylates such as tri (meth) acrylate; Tetra (meth) acrylates such as pentaerythritol tetra (meth) acrylate; Hexa (meth) acrylates such as dipentaerythritol hexa (meth) acrylate; Divinylbenzene, Aromatic hydrocarbon crosslinking agents such as divinylnaphthalene and their derivatives (preferably styrenic polyfunctional monomers such as divinylbenzene); N, N-divinylaniline, divinyl ether, divinyl Sulfide, hetero atom-containing crosslinking agents such as divinyl sulfonic acid, vinyl-type polyfunctional monomers such may be mentioned. The “vinyl-based polyfunctional monomer” means a monomer having two or more vinyl groups in one molecule.
また、本発明の一実施形態に係る導電粒子用基材粒子は、Ｓｉ原子を含む有機無機複合粒子であってもよい。 The base material particles for conductive particles according to the embodiment of the present invention may be organic-inorganic composite particles containing Si atoms.
「Ｓｉ原子を含む有機無機複合粒子」とは、シラン化合物を加水分解・縮合することで得られるポリシロキサン骨格構造、および有機質成分の単量体に由来する構造単位を有する粒子を意味する。シラン化合物としては、好ましくは（メタ）アクリロキシ基を有するシラン化合物が挙げられる。また、有機質成分の単量体としては、好ましくは上述したビニル系単量体が挙げられる。 The “organic-inorganic composite particle containing Si atom” means a particle having a polysiloxane skeleton structure obtained by hydrolyzing and condensing a silane compound and a structural unit derived from a monomer of an organic component. The silane compound preferably includes a silane compound having a (meth) acryloxy group. Moreover, as the monomer of the organic component, the above-mentioned vinyl-based monomer is preferably exemplified.
前記シラン化合物としては、特に限定はされないが、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン、テトラブトキシシラン、テトラアセトキシシラン等の４官能性シラン、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、フェニルトリメトキシシラン、メチルトリアセトキシシラン、ビニルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３，４−エポキシブチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン等の３官能基シラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジアセトキシジメチルシラン、ジフェニルジシランジオール等の２官能性シラン等を挙げることができる。これらは１種のみ用いても２種以上を併用してもよい。 The silane compound is not particularly limited, but tetrafunctional silane such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and tetraacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyl. Trimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, methyltriacetoxysilane, vinyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, γ -Trifunctional silanes such as glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diacetoxydimethylsilane, diphe Bifunctional silane such as Le disilane diol, and the like. These may be used alone or in combination of two or more.
また、前記（メタ）アクリロキシ基を有するシラン化合物としては、特に限定はされないが、例えば、γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルトリアセトキシシラン、γ−（メタ）アクリロキシエトキシプロピルトリメトキシシラン（または、γ−トリメトキシシリルプロピル−β−（メタ）アクリロキシエチルエーテルともいう）、γ−（メタ）アクリロキシプロピルメチルジメトキシシラン、γ−（メタ）アクリロキシプロピルメチルジエトキシシラン等が挙げられる。これらは１種のみ用いても２種以上を併用してもよい。 The silane compound having a (meth) acryloxy group is not particularly limited, but, for example, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- ( (Meth) acryloxypropyltriacetoxysilane, γ- (meth) acryloxyethoxypropyltrimethoxysilane (also referred to as γ-trimethoxysilylpropyl-β- (meth) acryloxyethyl ether), γ- (meth) acryl Roxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane and the like can be mentioned. These may be used alone or in combination of two or more.
本発明の一実施形態に係る導電粒子用基材粒子は、当該基材粒子の直径が１０％変位したときの圧縮弾性率（１０％Ｋ値）が６０００Ｎ／ｍｍ２以下あることが好ましく、４０００Ｎ／ｍｍ２以下であることがより好ましく、３０００Ｎ／ｍｍ２以下であることがさらに好ましい。１０％Ｋ値が低い場合、メッキの際に凝集し易く、抵抗値や接続信頼性が悪化しやすいが、本発明の一実施形態によれば、かかる問題を回避でき、異方導電接続状態における抵抗値の経時的上昇が抑えられ、優れた接続信頼性が得られる。 The base particle for conductive particles according to one embodiment of the present invention preferably has a compressive elastic modulus (10% K value) of 6000 N / mm 2 or less when the diameter of the base particle is displaced by 10%, preferably 4000 N or less. / Mm 2 or less is more preferable, and 3000 N / mm 2 or less is still more preferable. When the 10% K value is low, the particles easily aggregate during plating, and the resistance value and the connection reliability are easily deteriorated. However, according to an embodiment of the present invention, such a problem can be avoided, and the anisotropic conductive connection state can be achieved. An increase in resistance over time is suppressed, and excellent connection reliability is obtained.
〔２．導電粒子〕
本発明の一実施形態に係る導電粒子（以下、単に「導電粒子」とも称する。）は、導電粒子用基材粒子の表面に、少なくとも一層の導電性金属層が形成されている。
[2. Conductive particles]
In the conductive particles according to one embodiment of the present invention (hereinafter, also simply referred to as “conductive particles”), at least one conductive metal layer is formed on the surface of the base particles for conductive particles.
導電性金属層を構成する金属としては特に限定されないが、例えば、金、銀、銅、白金、鉄、鉛、アルミニウム、クロム、パラジウム、ニッケル、ロジウム、ルテニウム、アンチモン、ビスマス、ゲルマニウム、スズ、コバルト、インジウムおよびニッケル−リン、ニッケル−ホウ素等の金属や金属化合物、および、これらの合金等が挙げられる。これらの中でも、金、ニッケル、パラジウム、銀、銅、錫が導電性に優れた導電性微粒子となることから好ましい。また、安価な点で、ニッケル、ニッケル合金（Ｎｉ−Ａｕ、Ｎｉ−Ｐｄ、Ｎｉ−Ｐｄ−Ａｕ、Ｎｉ−Ａｇ）；銅、銅合金（ＣｕとＦｅ、Ｃｏ、Ｎｉ、Ｚｎ、Ｓｎ、Ｉｎ、Ｇａ、Ｔｌ、Ｚｒ、Ｗ、Ｍｏ、Ｒｈ、Ｒｕ、Ｉｒ、Ａｇ、Ａｕ、Ｂｉ、Ａｌ、Ｍｎ、Ｍｇ，Ｐ、Ｂからなる群から選択される少なくとも１種の金属元素との合金、好ましくはＡｇ、Ｎｉ、Ｓｎ、Ｚｎとの合金）；銀、銀合金（ＡｇとＦｅ、Ｃｏ、Ｎｉ、Ｚｎ、Ｓｎ、Ｉｎ、Ｇａ、Ｔｌ、Ｚｒ、Ｗ、Ｍｏ、Ｒｈ、Ｒｕ、Ｉｒ、Ａｕ、Ｂｉ、Ａｌ、Ｍｎ、Ｍｇ、Ｐ、Ｂからなる群から選択される少なくとも１種の金属元素との合金、好ましくはＡｇ−Ｎｉ、Ａｇ−Ｓｎ、Ａｇ−Ｚｎ）；錫、錫合金（たとえばＳｎ−Ａｇ、Ｓｎ−Ｃｕ、Ｓｎ−Ｃｕ−Ａｇ、Ｓｎ−Ｚｎ、Ｓｎ−Ｓｂ、Ｓｎ−Ｂｉ−Ａｇ、Ｓｎ−Ｂｉ−Ｉｎ、Ｓｎ−Ａｕ、Ｓｎ−Ｐｂ等）等が好ましい。 The metal constituting the conductive metal layer is not particularly limited, for example, gold, silver, copper, platinum, iron, lead, aluminum, chromium, palladium, nickel, rhodium, ruthenium, antimony, bismuth, germanium, tin, cobalt. , Indium and nickel-phosphorus, nickel-boron, and other metals and metal compounds, and alloys thereof. Among these, gold, nickel, palladium, silver, copper, and tin are preferable because they become conductive fine particles having excellent conductivity. In addition, at low cost, nickel, nickel alloys (Ni-Au, Ni-Pd, Ni-Pd-Au, Ni-Ag); copper, copper alloys (Cu and Fe, Co, Ni, Zn, Sn, In, An alloy with at least one metal element selected from the group consisting of Ga, Tl, Zr, W, Mo, Rh, Ru, Ir, Ag, Au, Bi, Al, Mn, Mg, P and B, preferably Ag, Ni, Sn, Zn alloy); silver, silver alloy (Ag and Fe, Co, Ni, Zn, Sn, In, Ga, Tl, Zr, W, Mo, Rh, Ru, Ir, Au, Bi) , Alloys with at least one metal element selected from the group consisting of Al, Mn, Mg, P and B, preferably Ag—Ni, Ag—Sn, Ag—Zn); tin, tin alloys (eg Sn— Ag, Sn-Cu, Sn-Cu-Ag, Sn-Zn, Sn-S , Sn-Bi-Ag, Sn-Bi-In, Sn-Au, Sn-Pb, etc.) and the like are preferable.
また、導電性金属層は、単層でもよいし複層であってもよい。複層の場合には、例えば、ニッケル（ニッケル合金）−金、ニッケル（ニッケル合金）−パラジウム、ニッケル（ニッケル合金）−パラジウム−金、ニッケル（ニッケル合金）−銀等の組合せが好ましく挙げられる。 Further, the conductive metal layer may be a single layer or multiple layers. In the case of multiple layers, for example, a combination of nickel (nickel alloy) -gold, nickel (nickel alloy) -palladium, nickel (nickel alloy) -palladium-gold, nickel (nickel alloy) -silver, and the like are preferable.
前記導電性金属層の厚さは、０．０１μｍ以上が好ましく、より好ましくは０．０３μｍ以上、さらに好ましくは０．０５μｍ以上であり、０．２０μｍ以下が好ましく、より好ましくは０．１８μｍ以下、さらに好ましくは０．１５μｍ以下、一層好ましくは、０．１２μｍ以下、特に好ましくは０．０８０μｍ以下である。基材とする導電粒子用基材粒子が微細な粒子径である導電粒子においては、導電性金属層の厚さが上記範囲内であれば、導電粒子を異方性導電材料として用いる際に、安定した電気的接続が維持できる。 The thickness of the conductive metal layer is preferably 0.01 μm or more, more preferably 0.03 μm or more, further preferably 0.05 μm or more, 0.20 μm or less, more preferably 0.18 μm or less, The thickness is more preferably 0.15 μm or less, still more preferably 0.12 μm or less, and particularly preferably 0.080 μm or less. In the conductive particles for which the base particles for conductive particles as the base material have a fine particle diameter, when the thickness of the conductive metal layer is within the above range, when using the conductive particles as an anisotropic conductive material, Stable electrical connection can be maintained.
導電性金属層の形成方法は特に限定されず、例えば、基材表面に無電解メッキ法、電解メッキ法等によってメッキを施す方法；基材表面に真空蒸着、イオンプレーティング、イオンスパッタリング等の物理的蒸着方法により導電性金属層を形成する方法；等が挙げられる。これらの中でも特に無電解メッキ法が、大掛かりな装置を必要とせず容易に導電性金属層を形成できる点で好ましい。 The method of forming the conductive metal layer is not particularly limited, and examples thereof include a method of plating the surface of the base material by an electroless plating method, an electrolytic plating method or the like; a physical method such as vacuum deposition, ion plating, or ion sputtering on the surface of the base material. A method of forming a conductive metal layer by a dynamic vapor deposition method; and the like. Among these, the electroless plating method is particularly preferable in that the conductive metal layer can be easily formed without requiring a large-scale device.
〔３．異方性導電材料〕
本発明の一実施形態に係る異方性導電材料（以下、単に「異方性導電材料」とも称する。）は、上述した導電粒子を含むものであればよい。
[3. Anisotropic conductive material]
The anisotropic conductive material according to one embodiment of the present invention (hereinafter, also simply referred to as “anisotropic conductive material”) may be any one containing the above-mentioned conductive particles.
異方性導電材料の形態は特に限定されず、例えば、異方性導電フィルム、異方性導電ペースト、異方性導電接着剤、異方性導電インクなど様々な形態が挙げられる。これらの異方性導電材料を相対向する基材同士や電極端子に設けることにより、良好な電気的接続が可能になる。なお、本発明の導電粒子を用いた異方性導電材料には、液晶表示素子用導通材料（導通スペーサーおよびその組成物）も含まれる。 The form of the anisotropic conductive material is not particularly limited, and examples thereof include various forms such as an anisotropic conductive film, an anisotropic conductive paste, an anisotropic conductive adhesive, and an anisotropic conductive ink. By providing these anisotropic conductive materials on the base materials facing each other and on the electrode terminals, good electrical connection can be achieved. The anisotropic conductive material using the conductive particles of the present invention also includes a conductive material for liquid crystal display devices (conductive spacer and its composition).
異方性導電材料において、導電粒子の含有量は、用途に応じて適宜決定すればよいが、例えば、異方性導電材料の全量に対して１体積％以上が好ましく、より好ましくは２体積％以上、さらに好ましくは５体積％以上であり、５０体積％以下が好ましく、より好ましくは３０体積％以下、さらに好ましくは２０体積％以下である。導電粒子の含有量が少なすぎると、充分な電気的導通が得られ難い場合があり、一方、導電粒子の含有量が多すぎると、導電粒子同士が接触してしまい、異方性導電材料としての機能が発揮され難い場合がある。 In the anisotropic conductive material, the content of the conductive particles may be appropriately determined according to the application, but for example, it is preferably 1% by volume or more, more preferably 2% by volume with respect to the total amount of the anisotropic conductive material. As described above, the content is more preferably 5% by volume or more, preferably 50% by volume or less, more preferably 30% by volume or less, and further preferably 20% by volume or less. If the content of the conductive particles is too small, it may be difficult to obtain sufficient electrical conduction, on the other hand, if the content of the conductive particles is too large, the conductive particles contact each other, as an anisotropic conductive material. It may be difficult for the function of to be exhibited.
また、本発明の一実施形態における異方性導電ペースト（以下、単に「異方性導電ペースト」とも称する。）は、上述した導電粒子と、バインダー樹脂とを含むものである。前記異方性導電ペーストは、前記導電粒子がバインダー樹脂に分散してなる。 The anisotropic conductive paste (hereinafter, also simply referred to as “anisotropic conductive paste”) according to the embodiment of the present invention includes the conductive particles described above and a binder resin. The anisotropic conductive paste is formed by dispersing the conductive particles in a binder resin.
前記バインダー樹脂としては、絶縁性の樹脂であれば特に限定されず、例えば、アクリル樹脂、エチレン−酢酸ビニル樹脂、スチレン−ブタジエンブロック共重合体等の熱可塑性樹脂；グリシジル基を有するモノマーやオリゴマーおよびイソシアネートなどの硬化剤との反応により硬化する硬化性樹脂組成物；光や熱により硬化する硬化性樹脂組成物；等が挙げられる。 The binder resin is not particularly limited as long as it is an insulating resin, and examples thereof include thermoplastic resins such as acrylic resins, ethylene-vinyl acetate resins, and styrene-butadiene block copolymers; monomers and oligomers having a glycidyl group, and A curable resin composition that is cured by reaction with a curing agent such as isocyanate; a curable resin composition that is cured by light or heat; and the like.
前記異方性導電材料におけるフィルム膜厚、ペーストや接着剤の塗工膜厚、印刷膜厚等については、使用する導電性微粒子の粒子径と、接続すべき電極の仕様とを考慮し、接続すべき電極間に導電粒子が狭持され、且つ接続すべき電極が形成された接合基板同士の空隙がバインダー樹脂層により充分に満たされるように、適宜設定することが好ましい。 Regarding the film thickness of the anisotropic conductive material, the coating thickness of the paste or adhesive, the printed film thickness, etc., the particle diameter of the conductive fine particles to be used and the specifications of the electrodes to be connected are taken into consideration. It is preferable to appropriately set such that the conductive particles are sandwiched between the electrodes to be bonded and the voids between the bonded substrates in which the electrodes to be connected are formed are sufficiently filled with the binder resin layer.
〔４．導電粒子用基材粒子の製造方法〕
前記導電粒子用基材粒子の製造方法としては、特に制限はなく、乳化重合、懸濁重合、分散重合、シード重合、ゾルゲルシード重合法等が挙げられるが、前記導電粒子用基材粒子の粒子径を所望の範囲にするには、例えば、シード重合法により導電粒子用基材粒子を合成した後、分級する方法等が好ましく採用される。導電粒子用基材粒子の合成にシード重合法を採用することにより、粒度分布の小さい導電粒子用基材粒子が得られる。さらに、合成後の導電粒子用基材粒子を分級し粗粒子を除去することにより、平均粒子径を所望の範囲に調整することができる。
[4. Method for producing base material particles for conductive particles]
The method for producing the base particles for conductive particles is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, dispersion polymerization, seed polymerization, and sol-gel seed polymerization method. In order to adjust the diameter to a desired range, for example, a method of synthesizing base particles for conductive particles by a seed polymerization method and then classifying the particles is preferably adopted. By adopting the seed polymerization method for the synthesis of the base particles for conductive particles, base particles for conductive particles having a small particle size distribution can be obtained. Furthermore, the average particle diameter can be adjusted to a desired range by classifying the base particles for conductive particles after synthesis and removing coarse particles.
前記シード重合法は、シード粒子調製工程、吸収工程および重合工程を含む。なお、例えば、ビニル系重合体のみから構成される粒子を合成する場合には、親水性単量体等のビニル系単量体からシード粒子を調製すればよく、ビニル系単量体とポリシロキサン骨格を有する材料とから構成される粒子を合成する場合には、前記シラン化合物からシード粒子（すなわち、ポリシロキサン粒子）を調製すればよい。 The seed polymerization method includes a seed particle preparation step, an absorption step and a polymerization step. Note that, for example, when synthesizing particles composed only of a vinyl-based polymer, seed particles may be prepared from a vinyl-based monomer such as a hydrophilic monomer. When synthesizing particles composed of a material having a skeleton, seed particles (that is, polysiloxane particles) may be prepared from the silane compound.
シラン化合物からシード粒子（すなわち、ポリシロキサン粒子）を調製する方法としては、水を含む溶媒中で加水分解して縮重合させる方法が挙げられる。また、ポリシロキサン骨格とビニル重合体とを複合化させる場合には、シラン化合物として、ラジカル重合性基を有するシラン系架橋性モノマーを使用し、重合性ポリシロキサン粒子（すなわち、ラジカル重合性基を有するポリシロキサン骨格を有する粒子）を調製すればよい。加水分解と縮重合は、一括、分割、連続等、任意の方法を採用できる。加水分解し、縮重合させるにあたっては、触媒としてアンモニア、尿素、エタノールアミン、テトラメチルアンモニウムハイドロオキサイド、アルカリ金属水酸化物、アルカリ土類金属水酸化物等の塩基性触媒を好ましく用いることができる。 Examples of the method of preparing seed particles (that is, polysiloxane particles) from a silane compound include a method of hydrolyzing in a solvent containing water to cause polycondensation. When the polysiloxane skeleton and the vinyl polymer are combined, a silane-based crosslinkable monomer having a radically polymerizable group is used as the silane compound, and the polymerizable polysiloxane particles (that is, the radically polymerizable group is Particles having a polysiloxane skeleton) may be prepared. For hydrolysis and polycondensation, any method such as batch, division, continuous, etc. can be adopted. For hydrolysis and polycondensation, a basic catalyst such as ammonia, urea, ethanolamine, tetramethylammonium hydroxide, alkali metal hydroxide or alkaline earth metal hydroxide can be preferably used as a catalyst.
前記水を含む溶媒中には、水や触媒以外に有機溶剤を含めることができる。有機溶剤としては、例えば、メタノール、エタノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ｓｅｃ−ブタノール、ｔ−ブタノール、ペンタノール、エチレングリコール、プロピレングリコール、１，４−ブタンジオール等のアルコール類；アセトン、メチルエチルケトン等のケトン類；酢酸エチル等のエステル類；イソオクタン、シクロへキサン等の（シクロ）パラフィン類；ベンゼン、トルエン等の芳香族炭化水素類等を挙げることができる。これらは単独で用いても２種以上を併用してもよい。 The solvent containing water may contain an organic solvent in addition to water and a catalyst. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol and 1,4-butanediol; acetone, Examples thereof include ketones such as methyl ethyl ketone; esters such as ethyl acetate; (cyclo) paraffins such as isooctane and cyclohexane; and aromatic hydrocarbons such as benzene and toluene. These may be used alone or in combination of two or more.
加水分解縮合ではまた、アニオン性、カチオン性、非イオン性の界面活性剤や、ポリビニルアルコール、ポリビニルピロリドン等の高分子分散剤を併用することもできる。これらは単独で用いても２種以上を併用してもよい。加水分解縮合は、原料となるシラン系モノマーと、触媒や水および有機溶剤を含む溶媒を混合した後、温度０℃以上１００℃以下、好ましくは０℃以上７０℃以下で、３０分以上１００時間以下撹拌することにより行うことができる。 In the hydrolytic condensation, anionic, cationic or nonionic surfactants and polymeric dispersants such as polyvinyl alcohol and polyvinylpyrrolidone can also be used in combination. These may be used alone or in combination of two or more. The hydrolysis condensation is carried out at a temperature of 0 ° C. or higher and 100 ° C. or lower, preferably 0 ° C. or higher and 70 ° C. or lower for 30 minutes or longer and 100 hours after mixing a silane-based monomer as a raw material and a solvent containing a catalyst, water and an organic solvent It can be performed by stirring below.
前記吸収工程では、親水性単量体等のビニル系単量体をシード粒子に吸収させる。吸収させる方法は、シード粒子の存在下に、ビニル系単量体を存在させた状態で進行するものであれば特に限定されない。したがって、シード粒子を分散させた溶媒中にビニル系単量体を加えてもよいし、ビニル系単量体を含む溶媒中にシード粒子を加えてもよい。なかでも、前者のように、予めシード粒子を分散させた溶媒中に、ビニル系単量体を加えるのが好ましい。特に、加水分解、縮合工程で得られたシード粒子を反応液（シード粒子分散液）から取り出すことなく、この反応液にビニル系単量体を加える方法は、工程が複雑にならず、生産性に優れるため好ましい。 In the absorbing step, the seed particles absorb a vinyl monomer such as a hydrophilic monomer. The absorption method is not particularly limited as long as it proceeds in the presence of the vinyl monomer in the presence of seed particles. Therefore, the vinyl-based monomer may be added to the solvent in which the seed particles are dispersed, or the seed particles may be added to the solvent containing the vinyl-based monomer. Among them, like the former, it is preferable to add the vinyl-based monomer to the solvent in which the seed particles are dispersed in advance. In particular, the method of adding a vinyl-based monomer to the reaction liquid without removing the seed particles obtained in the hydrolysis and condensation steps from the reaction liquid (seed particle dispersion liquid) does not complicate the process and improves productivity. It is excellent because it is preferable.
前記吸収工程において、ビニル系単量体の添加のタイミングは特に限定されず、一括で加えてもよいし、数回に分けて加えてもよいし、任意の速度でフィードしてもよい。また、ビニル系単量体を加えるにあたっては、ビニル系単量体のみを添加してもビニル系単量体の溶液を添加してもいずれでもよいが、ビニル系単量体を予め乳化剤で水または水性媒体に乳化分散させた乳化液をシード粒子に混合することが、シード粒子への吸収がより効率よく行われるため好ましい。 In the absorbing step, the timing of addition of the vinyl-based monomer is not particularly limited, and the vinyl-based monomer may be added all at once, may be added several times, or may be fed at an arbitrary rate. In addition, when adding the vinyl-based monomer, either the vinyl-based monomer alone or a solution of the vinyl-based monomer may be added. Alternatively, it is preferable to mix the seed particles with an emulsion that is emulsified and dispersed in an aqueous medium, because the seed particles can be more efficiently absorbed.
前記乳化剤は特に限定されないが、例えば、アニオン性界面活性剤や、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、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシソルビタン脂肪酸エステル、ポリオキシエチレンアルキルアミン、グリセリン脂肪酸エステル、オキシエチレン−オキシプロピレンブロックポリマー等のノニオン性界面活性剤が、シード粒子、ビニル系単量体を吸収した後のシード粒子の分散状態を安定化させることもできるので好ましい。これらの乳化剤は、１種のみを使用しても２種以上を併用してもよい。 The emulsifier is not particularly limited, but for example, an anionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkyl. Nonionic surfactants such as amine, glycerin fatty acid ester, and oxyethylene-oxypropylene block polymer are preferable because they can stabilize the dispersion state of the seed particles and the seed particles after absorbing the vinyl monomer. These emulsifiers may be used alone or in combination of two or more.
また、ビニル系単量体を乳化剤で乳化分散させる際には、ビニル系単量体の質量に対して０．３倍以上１０倍以下の水や水溶性有機溶剤を使用するのが好ましい。前記水溶性有機溶剤としては、メタノール、エタノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ｓｅｃ−ブタノール、ｔ−ブタノール、ペンタノール、エチレングリコール、プロピレングリコール、１，４−ブタンジオール等のアルコール類；アセトン、メチルエチルケトン等のケトン類；酢酸エチル等のエステル類等が挙げられる。 When the vinyl-based monomer is emulsified and dispersed with an emulsifier, it is preferable to use water or a water-soluble organic solvent in an amount of 0.3 to 10 times the mass of the vinyl-based monomer. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol and 1,4-butanediol; acetone. Ketones such as methyl ethyl ketone; esters such as ethyl acetate.
吸収工程は、０℃以上６０℃以下の温度範囲で、５分間以上７２０分間以下、撹拌しながら行うのが好ましい。これらの条件は、用いるシード粒子やモノマーの種類等によって、適宜設定すればよく、これらの条件は１種のみ、あるいは２種以上を合わせて採用してもよい。吸収工程において、ビニル系単量体がシード粒子に吸収されたかどうかの判断については、例えば、ビニル系単量体を加える前および吸収段階終了後に、顕微鏡により粒子を観察し、ビニル系単量体の吸収により粒子径が大きくなっていることを確認することで容易に判断できる。 The absorption step is preferably performed in a temperature range of 0 ° C. or higher and 60 ° C. or lower for 5 minutes or more and 720 minutes or less while stirring. These conditions may be appropriately set depending on the type of seed particles and monomers used, and these conditions may be used alone or in combination of two or more. In the absorption step, for determining whether or not the vinyl-based monomer has been absorbed by the seed particles, for example, before adding the vinyl-based monomer and after the end of the absorption step, the particles are observed with a microscope and the vinyl-based monomer is used. This can be easily determined by confirming that the particle size has increased due to the absorption of.
重合工程では、シード粒子に吸収されたビニル系単量体を重合反応させる。ここで、シード粒子が重合性ポリシロキサンである場合には、吸収させたビニル系単量体と重合性ポリシロキサン骨格が有するラジカル重合性基とが重合して、ポリシロキサン骨格とビニル重合体とが複合化する。重合方法は特に限定されないが、例えば、ラジカル重合開始剤を用いる方法が挙げられ、前記ラジカル重合開始剤としては、特に限定されないが、例えば、過酸化物系開始剤や、アゾ系開始剤等が使用可能である。これらラジカル重合開始剤は、単独で用いても２種以上を併用してもよい。 In the polymerization step, the vinyl-based monomer absorbed by the seed particles is polymerized. Here, when the seed particles are a polymerizable polysiloxane, the absorbed vinyl-based monomer and the radically polymerizable group of the polymerizable polysiloxane skeleton are polymerized to form a polysiloxane skeleton and a vinyl polymer. Becomes complex. Although the polymerization method is not particularly limited, examples thereof include a method using a radical polymerization initiator, and the radical polymerization initiator is not particularly limited, and examples thereof include a peroxide-based initiator and an azo-based initiator. It can be used. These radical polymerization initiators may be used alone or in combination of two or more kinds.
ラジカル重合を行う際の反応温度は４０℃以上が好ましく、より好ましくは５０℃以上であり、１００℃以下が好ましく、より好ましくは８０℃以下である。反応温度が低すぎる場合には、重合度が十分に上がらず複合粒子の機械的特性が不充分となる傾向があり、一方、反応温度が高すぎる場合には、重合中に粒子間の凝集が起こりやすくなる傾向がある。なお、ラジカル重合を行う際の反応時間は、用いる重合開始剤の種類に応じて適宜変更すればよいが、通常、５分以上が好ましく、より好ましくは１０分以上であり、６００分以下が好ましく、より好ましくは３００分以下である。反応時間が短すぎる場合には、重合度が十分に上がらない場合があり、反応時間が長すぎる場合には、粒子間で凝集が起こり易くなる傾向がある。 The reaction temperature when performing radical polymerization is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, preferably 100 ° C. or lower, and more preferably 80 ° C. or lower. If the reaction temperature is too low, the degree of polymerization does not sufficiently increase and the mechanical properties of the composite particles tend to be insufficient, while if the reaction temperature is too high, agglomeration between particles during polymerization may occur. It tends to happen easily. The reaction time when performing radical polymerization may be appropriately changed depending on the type of the polymerization initiator used, but is usually preferably 5 minutes or longer, more preferably 10 minutes or longer, and preferably 600 minutes or shorter. , And more preferably 300 minutes or less. If the reaction time is too short, the degree of polymerization may not be sufficiently increased, and if the reaction time is too long, aggregation tends to occur between particles.
合成後の導電粒子用基材粒子の個数基準の平均分散粒子径は１．１μｍ以上が好ましく、より好ましくは１．２μｍ以上、さらに好ましくは１．３μｍ以上であり、３．０μｍ以下が好ましく、より好ましくは２．８μｍ以下、さらに好ましくは２．７μｍ以下である。また、分散粒子径の個数基準の変動係数は１０％以下が好ましく、より好ましくは９％以下、さらに好ましくは７％以下である。 The number-based average dispersed particle size of the base particles for conductive particles after synthesis is preferably 1.1 μm or more, more preferably 1.2 μm or more, further preferably 1.3 μm or more, and 3.0 μm or less, It is more preferably 2.8 μm or less, still more preferably 2.7 μm or less. The number-based coefficient of variation of the dispersed particle size is preferably 10% or less, more preferably 9% or less, and further preferably 7% or less.
上記のようにして合成した導電粒子用基材粒子は、必要に応じて、所定の粒子径となるように分級に供することが好ましい。分級方法は特に限定されず、例えば、電成ふるい等によるふるい分け；メンブランフィルター、プリーツフィルター、セラミック膜フィルター等のフィルターを使用した濾過；質量差および流体抵抗差の相互作用によって分級する公知の装置（粒子の落下速度等の重力差が原理である重力分級機、自由渦または半自由渦による遠心力と空気抗力の釣り合いを原理とする（半）自由渦遠心分級、回転する分級羽根（ローター）によってつくられる回転流によって生じる遠心力と空気による抗力の釣り合いを原理とする回転羽根付き遠心分級）を用いた分級；等が挙げられる。これらの中でも、分級精度と生産性の観点から電成ふるいを用いた分級が好ましい。 The base particles for conductive particles synthesized as described above are preferably subjected to classification so as to have a predetermined particle size, if necessary. The classification method is not particularly limited and includes, for example, sieving with an electro-sieve, filtration using a filter such as a membrane filter, a pleated filter, and a ceramic membrane filter; a known device for classification by the interaction of mass difference and fluid resistance difference ( Gravity classifier whose principle is gravity difference such as particle falling velocity, and (semi) free vortex centrifugal classification, which is a principle of balancing centrifugal force and air drag due to free vortex or semi-free vortex, rotating classifying blade (rotor) Classification using a centrifugal impeller with a rotating blade on the principle of balancing the centrifugal force generated by the rotating flow created and the drag force by air). Among these, classification using an electro-sieve is preferable from the viewpoint of classification accuracy and productivity.
電成ふるいを用いて分級する場合、導電粒子用基材粒子を液状媒体に分散させた分散体を電成ふるいに通過させることが好ましい。前記液状媒体としては、例えば、水；メタノール、エタノール、プロパノール、ブタノール等のアルコール類；ヘキサン、オクタン等の炭化水素類；ベンゼン、トルエン、キシレン等の芳香族炭化水素類；等が挙げられる。これらは単独で使用してもよいし、２種以上を併用してもよい。これらの中でも、アルコール類、炭化水素類が好ましく、メタノール、ヘキサンがより好ましい。なお、導電粒子用基材粒子の分散性を高めるために、液状媒体に各種分散剤を添加してもよい。 In the case of classification using an electro-sieve, it is preferable to pass a dispersion obtained by dispersing base particles for conductive particles in a liquid medium through the electro-sieve. Examples of the liquid medium include water; alcohols such as methanol, ethanol, propanol and butanol; hydrocarbons such as hexane and octane; aromatic hydrocarbons such as benzene, toluene and xylene. These may be used alone or in combination of two or more. Among these, alcohols and hydrocarbons are preferable, and methanol and hexane are more preferable. In addition, various dispersants may be added to the liquid medium in order to enhance the dispersibility of the base particles for conductive particles.
前記液状媒体の使用量は、導電粒子用基材粒子１００質量部に対して、１００質量部以上が好ましく、より好ましくは２００質量部以上、さらに好ましくは５００質量部以上であり、１００００質量部以下が好ましく、より好ましくは５０００質量部以下、さらに好ましくは２０００質量部以下である。導電粒子用基材粒子を液状媒体に分散させる方法は特に限定されず、例えば、超音波を照射させて分散させる方法；通常攪拌装置、高速攪拌装置、コロイドミルまたはホモジナイザーのような剪断分散装置等により分散させる方法；等が挙げられる。 The amount of the liquid medium used is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, still more preferably 500 parts by mass or more and 10000 parts by mass or less, relative to 100 parts by mass of the base particles for conductive particles. Is preferable, more preferably 5000 parts by mass or less, and further preferably 2000 parts by mass or less. The method of dispersing the base particles for conductive particles in a liquid medium is not particularly limited, and examples thereof include a method of irradiating with ultrasonic waves to disperse; a normal stirring device, a high-speed stirring device, a shear dispersing device such as a colloid mill or a homogenizer, and the like. And the like; and the like.
電成ふるいを通過させる際の分散体液温は、特に限定されず、使用する液状媒体に応じて適宜調整すればよいが、通常は０℃以上１００℃以下である。なお、分散体の液温は、当然、液状媒体の沸点未満である。電成ふるいのふるい孔の寸法は、所望とする平均粒子径、変動係数に応じて変更すればよい。電成ふるいによる分級を行うことにより、粗大粒子を除去することができ、導電粒子用基材粒子の粒子径の変動係数を小さくすることができる。 The dispersion liquid temperature at the time of passing through the electro-sieve is not particularly limited and may be appropriately adjusted according to the liquid medium used, but is usually 0 ° C. or higher and 100 ° C. or lower. The liquid temperature of the dispersion is naturally lower than the boiling point of the liquid medium. The size of the sieving holes of the electroformed sieve may be changed according to the desired average particle diameter and coefficient of variation. Coarse particles can be removed and the coefficient of variation of the particle diameter of the base particles for conductive particles can be reduced by performing classification with an electro-sieve.
合成後、必要に応じて分級された導電粒子用基材粒子は、通常、乾燥され、場合によっては上述した焼成（加熱処理）に付される。乾燥や焼成などの加熱処理については、公知の方法に従って行えばよいが、上述したように、導電粒子用基材粒子を形成するための親水性単量体成分中のシラン系非架橋性モノマーの含有割合が所定の量を超える場合には、このような加熱処理における温度を２００℃未満に制限することが重要である。 After the synthesis, the base particles for conductive particles, which have been classified according to need, are usually dried, and optionally subjected to the above-mentioned firing (heat treatment). The heat treatment such as drying and baking may be performed according to a known method, but as described above, the silane-based non-crosslinking monomer in the hydrophilic monomer component for forming the base particles for the conductive particles is used. When the content ratio exceeds a predetermined amount, it is important to limit the temperature in such heat treatment to less than 200 ° C.
以上のようにして得られた導電粒子用基材粒子（基材）の形状は、特に限定されるものではなく、例えば、球状、回転楕円体状、金平糖状、薄板状、針状、まゆ状等のいずれでも良いが、球状が好ましく、特に真球状が好ましい。 The shape of the base particles (base material) for conductive particles obtained as described above is not particularly limited, and examples thereof include spherical shape, spheroidal shape, spinach-like shape, thin plate shape, needle shape, and eyebrow shape. Any of the above may be used, but a spherical shape is preferable, and a true spherical shape is particularly preferable.
以下に本発明の実施例を説明するが、本発明の趣旨を逸脱しない限り、本発明はこれら実施例に限定されるものではない。なお、以下においては、特に断りのない限り、「部」は「質量部」を意味する。 Examples of the present invention will be described below, but the present invention is not limited to these examples without departing from the spirit of the present invention. In the following, "parts" means "parts by mass" unless otherwise specified.
１．物性測定方法および評価方法
各種物性の測定は以下の方法で行った。
1. Physical property measuring method and evaluation method Various physical properties were measured by the following methods.
＜シード粒子および導電粒子用基材粒子の平均分散粒子および変動係数（ＣＶ値）＞
シード粒子または導電粒子用基材粒子０．００５部に、乳化剤であるポリオキシエチレンアルキルエーテル硫酸エステルアンモニウム塩（第一工業製薬株式会社製「ハイテノール（登録商標）Ｎ−０８」）の１％水溶液２０部を加え、超音波で１０分間分散させた後、粒度分布測定装置（ベックマンコールター社製「コールターマルチサイザーＩＩＩ型」）を用いて、３００００個の粒子の粒子径（μｍ）を測定し、個数基準の平均分散粒子径を求めた。また、個数基準の平均分散粒子径、分散粒子径の標準偏差を求めるとともに、下記式に従って分散粒子径の個数基準のＣＶ値（変動係数）を算出した。
粒子の変動係数（％）＝１００×（粒子径の標準偏差／個数基準平均分散粒子径）
＜導電粒子用基材粒子の１０％Ｋ値＞
微小圧縮試験機（島津製作所社製「ＭＣＴ−Ｗ５００」）を用いて、室温（２５℃）において、試料台（材質：ＳＫＳ材平板）上に散布した粒子１個について、直径５０μｍの円形平板圧子（材質：ダイヤモンド）を用いて、「軟質表面検出」モードで、粒子の中心方向へ一定の負荷速度（０．３８７ｍＮ／秒）で荷重をかけた。そして、圧縮荷重（Ｆ）として、圧縮変位が粒子径の１０％となったときの荷重（ｍＮ）を、ならびに、圧縮変位（Ｓ）として、粒子が変形により破壊したときの変位量（μｍ）を測定した。得られた圧縮荷重（Ｆ）、粒子の圧縮変位（Ｓ）および粒子半径（Ｒ）を下記式（１）にあてはめ、１０％Ｋ値（Ｅ）を算出した。なお、測定は各試料について、異なる１０個の粒子に対して行い、平均した値を測定値とした。
１０％Ｋ値（Ｅ）＝３×Ｆ／（２２／１×Ｓ３／２×Ｒ１／２）・・・式（１）
＜分散性の評価＞
サンプル管に導電粒子用基材粒子０．１ｇ、１％乳化水を４ｇおよびメタノール１．２ｇを加え、１５分間スターラーで撹拌した。撹拌後、導電粒子用基材粒子の分散状態をマイクロスコープにて観察した。その結果を以下の条件で評価した。
○：単粒子に分散。
△１：単粒子が存在するが、２〜５個未満の粒子が凝集している。
△２：５個以上の粒子が凝集する凝集塊が２つ以上存在する。
×：１０個以上の粒子が凝集する凝集塊が存在する。
<Average dispersed particles and coefficient of variation (CV value) of seed particles and base particles for conductive particles>
To 0.005 parts of seed particles or base particles for conductive particles, 1% of polyoxyethylene alkyl ether sulfate ammonium salt (“Hitenol (registered trademark) N-08” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) which is an emulsifier. After 20 parts of an aqueous solution was added and dispersed by ultrasonic waves for 10 minutes, the particle size (μm) of 30,000 particles was measured using a particle size distribution analyzer (“Beckman Coulter's“ Coulter Multisizer III ”)”. The number-based average dispersed particle diameter was determined. Further, the number-based average dispersed particle diameter and the standard deviation of the dispersed particle diameter were obtained, and the number-based CV value (variation coefficient) of the dispersed particle diameter was calculated according to the following formula.
Coefficient of variation of particles (%) = 100 × (standard deviation of particle size / number-based average dispersed particle size)
<10% K value of base particles for conductive particles>
Using a micro compression tester (“MCT-W500” manufactured by Shimadzu Corporation), at room temperature (25 ° C.), a circular plate indenter having a diameter of 50 μm was used for one particle dispersed on a sample table (material: SKS plate). Using (material: diamond), a load was applied at a constant load speed (0.387 mN / sec) toward the center of the particle in the “soft surface detection” mode. Then, as the compressive load (F), the load (mN) when the compressive displacement becomes 10% of the particle diameter, and as the compressive displacement (S), the displacement amount (μm) when the particles are broken by deformation. Was measured. The obtained compressive load (F), particle compressive displacement (S) and particle radius (R) were applied to the following formula (1) to calculate a 10% K value (E). The measurement was performed on 10 different particles for each sample, and the averaged value was used as the measured value.
10% K value (E) = 3 × F / (2 2/1 × S 3/2 × R 1/2 ) ... Formula (1)
<Evaluation of dispersibility>
To the sample tube, 0.1 g of base particles for conductive particles, 4 g of 1% emulsified water and 1.2 g of methanol were added and stirred with a stirrer for 15 minutes. After stirring, the dispersed state of the base particles for conductive particles was observed with a microscope. The results were evaluated under the following conditions.
◯: Dispersed in single particles.
Δ1: Single particles are present, but 2 to less than 5 particles are aggregated.
Δ2: There are two or more aggregates in which 5 or more particles are aggregated.
X: There is an agglomerate in which 10 or more particles agglomerate.
＜初期抵抗値の評価＞
接続構造体について電極間の初期抵抗値Ａを測定し、以下の条件で評価した。
◎：初期抵抗値Ａが３Ω未満の場合。
○：初期抵抗値Ａが３Ω以上５Ω以下の場合。
×：初期抵抗値Ａが５Ωを超える場合。
<Evaluation of initial resistance value>
The initial resistance value A between the electrodes of the connection structure was measured and evaluated under the following conditions.
⊚: When the initial resistance value A is less than 3Ω.
◯: When the initial resistance value A is 3Ω or more and 5Ω or less.
X: When the initial resistance value A exceeds 5Ω.
＜抵抗値上昇率の評価＞
低圧接続構造体を８５℃、８５％ＲＨの雰囲気下に５００時間放置した後、上記初期抵抗値Ａと同様に抵抗値Ｂを測定し、下記式（４）に基づき抵抗値上昇率（％）を求めた。
抵抗値上昇率（％）＝［（Ｂ−Ａ）／Ａ］×１００・・・式（４）
求めた抵抗値上昇率を以下の条件で評価した。
◎：抵抗値上昇率（％）が１％未満の場合。
○：抵抗値上昇率（％）が１％以上３％以下の場合。
×：抵抗値上昇率（％）が３％を超える場合。
<Evaluation of rate of increase in resistance>
After the low-voltage connection structure was left in an atmosphere of 85 ° C. and 85% RH for 500 hours, the resistance value B was measured in the same manner as the initial resistance value A, and the resistance value increase rate (%) was calculated based on the following formula (4). I asked.
Resistance increase rate (%) = [(B−A) / A] × 100 ... Equation (4)
The obtained rate of increase in resistance was evaluated under the following conditions.
⊚: When the resistance value increase rate (%) is less than 1%.
◯: When the resistance increase rate (%) is 1% or more and 3% or less.
X: When the resistance value increase rate (%) exceeds 3%.
２．導電粒子用基材粒子の作製
［実施例１］
＜導電粒子用基材粒子の作製＞
冷却管、温度計、滴下口を備えた四つ口フラスコに、イオン交換水１６００部と、２５％アンモニア水２０部、メタノール４００部を入れ、攪拌下、滴下口から、重合性シラン化合物（無機質成分）として３−メタクリロキシプロピルトリメトキシシラン（ＭＰＴＭＳ）４０部を添加し、３−メタクリロキシプロピルトリメトキシシランの加水分解、縮合反応を行って、メタクリロイル基を有するポリシロキサン粒子(シード粒子)の乳濁液を調製した。このポリシロキサン粒子の個数基準の平均分散粒子径は１．１６μｍであった。
2. Preparation of base particles for conductive particles [Example 1]
<Preparation of base material particles for conductive particles>
In a four-necked flask equipped with a cooling tube, a thermometer, and a dropping port, 1600 parts of ion-exchanged water, 20 parts of 25% ammonia water, and 400 parts of methanol were put, and the polymerizable silane compound (inorganic As a component), 40 parts of 3-methacryloxypropyltrimethoxysilane (MPTMS) is added, and hydrolysis and condensation reaction of 3-methacryloxypropyltrimethoxysilane are performed to obtain polysiloxane particles (seed particles) having methacryloyl groups. An emulsion was prepared. The number-based average dispersed particle diameter of the polysiloxane particles was 1.16 μm.
次いで、乳化剤としてポリオキシエチレンスチレン化フェニルエーテル硫酸エステルアンモニウム塩（第一工業製薬社製「ハイテノール（登録商標）ＮＦ−０８」）の２０％水溶液３．０部をイオン交換水１２０部に溶解した溶液に、吸収モノマー（単量体成分）としてスチレン（Ｓｔ）９０部および２−ヒドロキシエチルメタクリレート（ＨＥＭＡ）３０部と、２，２’−アゾビス（２，４−ジメチルバレロニトリル）（和光純薬工業社製「Ｖ−６５」）２．４部とを溶解した溶液を加え、乳化分散させて吸収モノマーの乳化液を調製した。乳化分散の開始から１時間後、得られた乳化液を、ポリシロキサン粒子（シード粒子）の乳濁液中に添加して、さらに攪拌を行った。乳化液の添加から１時間後、混合液をサンプリングして顕微鏡で観察を行ったところ、ポリシロキサン粒子が吸収モノマーを吸収して肥大化していることが確認された。 Then, 3.0 parts of a 20% aqueous solution of polyoxyethylene styrenated phenyl ether sulfate ammonium salt (“Hitenol (registered trademark) NF-08” manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) as an emulsifier is dissolved in 120 parts of ion-exchanged water. 90 parts of styrene (St) and 30 parts of 2-hydroxyethyl methacrylate (HEMA) as an absorbing monomer (monomer component), 2,2′-azobis (2,4-dimethylvaleronitrile) (Wako Pure) 2.4 parts of "V-65" manufactured by Yakuhin Kogyo Co., Ltd.) was added and emulsified and dispersed to prepare an emulsion of an absorbing monomer. One hour after the start of emulsification and dispersion, the obtained emulsion was added to the emulsion of polysiloxane particles (seed particles) and further stirred. One hour after the addition of the emulsified liquid, the mixed liquid was sampled and observed with a microscope. As a result, it was confirmed that the polysiloxane particles had absorbed the absorbed monomer and were enlarged.
次いで、ポリオキシエチレンスチレン化フェニルエーテル硫酸エステルアンモニウム塩の２０％水溶液３．０部を加え、窒素雰囲気下で反応液を６５℃まで昇温させて、６５℃で２時間保持し、単量体成分のラジカル重合を行った。ラジカル重合後の乳濁液を固液分離し、得られたケーキをイオン交換水、メタノールで洗浄した後、窒素雰囲気下８０℃で４時間真空乾燥し、導電粒子用基材粒子（１）を得た。得られた導電粒子用基材粒子の平均分散粒子径、１０％Ｋ値、変動係数および分散性の評価は表１に示すとおりであった。 Then, 3.0 parts of a 20% aqueous solution of polyoxyethylene styrenated phenyl ether sulfate ammonium salt was added, and the reaction solution was heated to 65 ° C. under a nitrogen atmosphere and kept at 65 ° C. for 2 hours to obtain the monomer Radical polymerization of the components was performed. The emulsion after radical polymerization is subjected to solid-liquid separation, the obtained cake is washed with ion-exchanged water and methanol, and then vacuum-dried at 80 ° C. for 4 hours in a nitrogen atmosphere to obtain base particles (1) for conductive particles. Obtained. Table 1 shows the average dispersed particle diameter, 10% K value, coefficient of variation, and evaluation of dispersibility of the obtained base particles for conductive particles.
＜導電粒子の作製＞
基材とする導電粒子用基材粒子（１）に、水酸化ナトリウムによるエッチング処理を施した後、二塩化スズ溶液に接触させることによりセンシタイジングし、次いで二塩化パラジウム溶液に浸漬させることによりアクチベーティングする方法（センシタイジング−アクチベーション法）によって、パラジウム核を形成させた。次に、パラジウム核を形成させた導電粒子用基材粒子２部をイオン交換水４００部に添加し、超音波分散処理を行った後、得られた導電粒子用基材粒子懸濁液を７０℃の温浴で加温した。このように懸濁液を加温した状態で、別途７０℃に加温した無電解めっき液（日本カニゼン（株）製「シューマーＳ６８０」）６００部を加えることにより、無電解ニッケルめっき反応を生じさせた。水素ガスの発生が終了したことを確認した後、固液分離を行い、イオン交換水、メタノールの順で洗浄し、１００℃で２時間真空乾燥して、ニッケルめっきを施した粒子を得た。次いで、得られたニッケルめっき粒子を、シアン化金カリウムを含有する置換金めっき液に加え、ニッケル層表面にさらに金めっきを施すことにより、導電粒子（１）を得た。
<Production of conductive particles>
By subjecting the base particles (1) for conductive particles as a base material to etching treatment with sodium hydroxide, sensitizing by contact with a tin dichloride solution, and then immersing in a palladium dichloride solution Palladium nuclei were formed by the activating method (sensitizing-activating method). Next, 2 parts of the base particle for conductive particles on which palladium nuclei were formed was added to 400 parts of ion-exchanged water and subjected to ultrasonic dispersion treatment, and then the obtained base particle suspension for conductive particles was added to 70 parts. It was heated in a warm bath at ℃. By adding 600 parts of the electroless plating solution (“Sumer S680” manufactured by Nippon Kanigen Co., Ltd.) separately heated to 70 ° C. in the state where the suspension is heated, an electroless nickel plating reaction is caused. Let After confirming that the generation of hydrogen gas was completed, solid-liquid separation was performed, followed by washing with ion-exchanged water and methanol in that order, and vacuum drying at 100 ° C. for 2 hours to obtain nickel-plated particles. Next, the obtained nickel-plated particles were added to a displacement gold plating solution containing potassium gold cyanide, and the surface of the nickel layer was further gold-plated to obtain conductive particles (1).
＜異方性導電材料（異方性導電フィルム）の作製＞ 導電粒子（１）１部に、バインダー樹脂としてのエポキシ樹脂（三菱化学製「ＪＥＲ８２８」）１００部と、硬化剤（三新化学社製「サンエイド（登録商標）ＳＩ−１５０」）２部と、トルエン１００部とを加え、さらにφ１ｍｍのジルコニアビーズ５０部を加えて、ステンレス製の２枚撹拌羽根を用いて３００ｒｐｍで１０分間撹拌して分散させた。そして、得られたペースト状組成物をバーコーターにて剥離処理を施したＰＥＴフィルム状に塗布し乾燥させることにより異方性導電フィルム（１）を得た。 <Production of Anisotropic Conductive Material (Anisotropic Conductive Film)> 100 parts of an epoxy resin (“JER828” manufactured by Mitsubishi Chemical) as a binder resin and a curing agent (Sanshin Chemical Co., Ltd.) per 1 part of conductive particles (1) 2 parts of "San-Aid (registered trademark) SI-150") and 100 parts of toluene are added, and further 50 parts of zirconia beads having a diameter of 1 mm is added, and the mixture is stirred at 300 rpm for 10 minutes using a stainless steel two-stage stirring blade. Dispersed. And the anisotropic conductive film (1) was obtained by apply | coating the obtained paste composition on the PET film which carried out the peeling process with a bar coater, and making it dry.
＜異方性導電材料を用いた接続構造体の作製＞
得られた異方性導電フィルム（１）を、抵抗測定用の線を有した全面アルミ蒸着ガラス基板と２０μｍ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に挟みこみ、１ＭＰａ、１９０℃で圧着することにより、接続構造体（１）（高圧接続構造体および低圧接続構造体）を作製した。作製した接続構造体（１）における初期抵抗値および抵抗値上昇率の評価を表１に示す。
<Fabrication of connection structure using anisotropic conductive material>
The anisotropic conductive film (1) thus obtained was sandwiched between a full-scale aluminum vapor-deposited glass substrate having lines for resistance measurement and a polyimide film substrate having a copper pattern formed on a pitch of 20 μm, at 1 MPa and 190 ° C. The connection structure (1) (high-voltage connection structure and low-voltage connection structure) was produced by pressure bonding. Table 1 shows the evaluation of the initial resistance value and the resistance value increase rate in the manufactured connection structure (1).
［実施例２］
実施例１の＜導電粒子用基材粒子の作製＞におけるスチレン（Ｓｔ）の代わりに、ジベニルベンゼン「ＤＶＢ９６０」（新日鐵化学社製：ジビニルベンゼン９６％、エチルビニルベンゼン４％含有）を用いた以外は、同様の手順で導電粒子用基材粒子（２）を得た。得られた導電粒子用基材粒子の平均分散粒子径、１０％Ｋ値、変動係数および分散性の評価は表１に示すとおりであった。
[Example 2]
In place of styrene (St) in <Preparation of base material particles for conductive particles> of Example 1, divenylbenzene “DVB960” (manufactured by Nippon Steel Chemical Co., Ltd .: containing 96% divinylbenzene and 4% ethylvinylbenzene) was used. Substrate particles for conductive particles (2) were obtained by the same procedure except for the above. Table 1 shows the average dispersed particle diameter, 10% K value, coefficient of variation, and evaluation of dispersibility of the obtained base particles for conductive particles.
また、導電粒子用基材粒子（２）を用いて、実施例１と同様の手順で、導電粒子（２）、異方性導電フィルム（２）、接続構造体（２）を得た。得られた導電粒子（２）の分散性の評価、ならびに作製した接続構造体（２）における初期抵抗値および抵抗値上昇率の評価を表１に示す。 Further, using the base particles for conductive particles (2), the conductive particles (2), the anisotropic conductive film (2), and the connection structure (2) were obtained in the same procedure as in Example 1. Table 1 shows the evaluation of the dispersibility of the obtained conductive particles (2) and the evaluation of the initial resistance value and the resistance value increase rate in the produced connection structure (2).
［実施例３］
実施例１の＜導電粒子用基材粒子の作製＞における親水性単量体である２−ヒドロキシエチルメタクリレート（ＨＥＭＡ）の代わりに、メトキシポリエチレングリコールモノメタクリレート「ＰＭＥ−４００」（日油社製ブレンマー（登録商標）、表１中、「ＰＭＥ４００」と記載。）を用いた以外は、同様の手順で導電粒子用基材粒子（３）を得た。得られた導電粒子用基材粒子の平均分散粒子径、１０％Ｋ値、変動係数および分散性の評価は表１に示すとおりであった。
[Example 3]
Instead of 2-hydroxyethyl methacrylate (HEMA) which is a hydrophilic monomer in <Preparation of base material particles for conductive particles> of Example 1, methoxypolyethylene glycol monomethacrylate "PME-400" (Blemmer manufactured by NOF CORPORATION). (Registered trademark), described in Table 1 as “PME400”), the base particles for conductive particles (3) were obtained by the same procedure. Table 1 shows the average dispersed particle diameter, 10% K value, coefficient of variation, and evaluation of dispersibility of the obtained base particles for conductive particles.
また、導電粒子用基材粒子（３）を用いて、実施例１と同様の手順で、導電粒子（３）、異方性導電フィルム（３）、接続構造体（３）を得た。得られた導電粒子（３）の分散性の評価、ならびに作製した接続構造体（３）における初期抵抗値および抵抗値上昇率の評価を表１に示す。 Further, using the base particles for conductive particles (3), the conductive particles (3), the anisotropic conductive film (3), and the connection structure (3) were obtained in the same procedure as in Example 1. Table 1 shows the evaluation of the dispersibility of the obtained conductive particles (3) and the evaluation of the initial resistance value and the resistance value increase rate in the produced connection structure (3).
［実施例４］
実施例１の＜導電粒子用基材粒子の作製＞における親水性単量体である２−ヒドロキシエチルメタクリレート（ＨＥＭＡ）の代わりに、４−ヒドロキシブチルアクリレート（４ＨＢＡ）を用いた以外は、同様の手順で導電粒子用基材粒子（４）を得た。得られた導電粒子用基材粒子の平均分散粒子径、１０％Ｋ値、変動係数および分散性の評価は表１に示すとおりであった。
[Example 4]
The same as in Example 1 except that 4-hydroxybutyl acrylate (4HBA) was used in place of 2-hydroxyethyl methacrylate (HEMA) which is a hydrophilic monomer in <Preparation of base material particles for conductive particles>. Base material particles (4) for conductive particles were obtained by the procedure. Table 1 shows the average dispersed particle diameter, 10% K value, coefficient of variation, and evaluation of dispersibility of the obtained base particles for conductive particles.
また、導電粒子用基材粒子（４）を用いて、実施例１と同様の手順で、導電粒子（４）、異方性導電フィルム（４）、接続構造体（４）を得た。得られた導電粒子（４）の分散性の評価、ならびに作製した接続構造体（４）における初期抵抗値および抵抗値上昇率の評価を表１に示す。 Further, using the base particles for conductive particles (4), the conductive particles (4), the anisotropic conductive film (4), and the connection structure (4) were obtained in the same procedure as in Example 1. Table 1 shows the evaluation of the dispersibility of the obtained conductive particles (4) and the evaluation of the initial resistance value and the increase rate of the resistance value in the produced connection structure (4).
［実施例５］
実施例１の＜導電粒子用基材粒子の作製＞における親水性単量体である２−ヒドロキシエチルメタクリレート（ＨＥＭＡ）の代わりに、メタクリル酸（ＭＡＡ）を用いた以外は、同様の手順で導電粒子用基材粒子（５）を得た。得られた導電粒子用基材粒子の平均分散粒子径、１０％Ｋ値、変動係数および分散性の評価は表１に示すとおりであった。
[Example 5]
Conducting in the same procedure except that methacrylic acid (MAA) was used in place of 2-hydroxyethyl methacrylate (HEMA) which is the hydrophilic monomer in <Preparation of base material particles for conductive particles> of Example 1. Base particles for particles (5) were obtained. Table 1 shows the average dispersed particle diameter, 10% K value, coefficient of variation, and evaluation of dispersibility of the obtained base particles for conductive particles.
また、導電粒子用基材粒子（５）を用いて、実施例１と同様の手順で、導電粒子（５）、異方性導電フィルム（５）、接続構造体（５）を得た。得られた導電粒子（５）の分散性の評価、ならびに作製した接続構造体（５）における初期抵抗値および抵抗値上昇率の評価を表１に示す。 Further, using the base particles for conductive particles (5), the conductive particles (5), the anisotropic conductive film (5), and the connection structure (5) were obtained in the same procedure as in Example 1. Table 1 shows the evaluation of the dispersibility of the obtained conductive particles (5) and the evaluation of the initial resistance value and the increase rate of the resistance value in the produced connection structure (5).
［実施例６］
実施例１の＜導電粒子用基材粒子の作製＞における親水性単量体である２−ヒドロキシエチルメタクリレート（ＨＥＭＡ）の代わりに、ジメチルアミノエチルメタクリレート（ＤＡＭ）「ライトエステルＤＭ」（共栄社化学社製）を用いた以外は、同様の手順で導電粒子用基材粒子（６）を得た。得られた導電粒子用基材粒子の平均分散粒子径、１０％Ｋ値、変動係数および分散性の評価は表１に示すとおりであった。
[Example 6]
Instead of 2-hydroxyethyl methacrylate (HEMA) which is a hydrophilic monomer in <Preparation of base material particles for conductive particles> of Example 1, dimethylaminoethyl methacrylate (DAM) “light ester DM” (Kyoeisha Chemical Co., Ltd.) Substrate particles for conductive particles (6) were obtained by the same procedure except that the product (1) was used. Table 1 shows the average dispersed particle diameter, 10% K value, coefficient of variation, and evaluation of dispersibility of the obtained base particles for conductive particles.
また、導電粒子用基材粒子（６）を用いて、実施例１と同様の手順で、導電粒子（６）、異方性導電フィルム（６）、接続構造体（６）を得た。得られた導電粒子（６）の分散性の評価、ならびに作製した接続構造体（６）における初期抵抗値および抵抗値上昇率の評価を表１に示す。 Further, using the base particles for conductive particles (6), the conductive particles (6), the anisotropic conductive film (6), and the connection structure (6) were obtained in the same procedure as in Example 1. Table 1 shows the evaluation of the dispersibility of the obtained conductive particles (6) and the evaluation of the initial resistance value and the increase rate of the resistance value in the manufactured connection structure (6).
［比較例１］
実施例の＜導電粒子用基材粒子の作製＞において親水性単量体である２−ヒドロキシエチルメタクリレート（ＨＥＭＡ）を用いず、Ｓｔの量を１２０部に増やした。それ以外は、実施例１と同様の手順で導電粒子用基材粒子（１’）を得た。得られた導電粒子用基材粒子の平均分散粒子径、１０％Ｋ値、変動係数および分散性の評価は表１に示すとおりであった。
[Comparative Example 1]
In <Production of base material particles for conductive particles> of the example, the amount of St was increased to 120 parts without using 2-hydroxyethyl methacrylate (HEMA) which is a hydrophilic monomer. Other than that, the base particle for conductive particles (1 ′) was obtained by the same procedure as in Example 1. Table 1 shows the average dispersed particle diameter, 10% K value, coefficient of variation, and evaluation of dispersibility of the obtained base particles for conductive particles.
また、導電粒子用基材粒子（１’）を用いて、実施例１と同様の手順で、導電粒子（１’）、異方性導電フィルム（１’）、接続構造体（１’）を得た。得られた導電粒子（１’）の分散性の評価、ならびに作製した接続構造体（１’）における初期抵抗値および抵抗値上昇率の評価を表１に示す。 In addition, the conductive particles (1 ′), the anisotropic conductive film (1 ′), and the connection structure (1 ′) were prepared using the conductive particle base material particles (1 ′) in the same procedure as in Example 1. Obtained. Table 1 shows the evaluation of the dispersibility of the obtained conductive particles (1 ') and the evaluation of the initial resistance value and the increase rate of the resistance value in the produced connection structure (1').
［比較例２］
冷却管、温度計、滴下口を備えた四つ口フラスコに、イオン交換水１４００部と、２５％アンモニア水２０部、メタノール６００部を入れ、攪拌下、滴下口から、重合性シラン化合物（単量体成分）として３−メタクリロキシプロピルトリメトキシシラン（ＭＰＴＭＳ）４０部を添加し、３−メタクリロキシプロピルトリメトキシシランの加水分解、縮合反応を行って、メタクリロイル基を有するポリシロキサン粒子(シード粒子)の乳濁液を調製した。このポリシロキサン粒子の個数基準の平均分散粒子径は１．５０μｍであった。
[Comparative Example 2]
In a four-necked flask equipped with a cooling tube, a thermometer, and a dropping port, 1400 parts of ion-exchanged water, 20 parts of 25% ammonia water, and 600 parts of methanol were put, and the polymerizable silane compound (single As a monomer component), 40 parts of 3-methacryloxypropyltrimethoxysilane (MPTMS) is added, hydrolysis and condensation reaction of 3-methacryloxypropyltrimethoxysilane are performed, and polysiloxane particles having a methacryloyl group (seed particles )) Was prepared. The number-based average dispersed particle diameter of the polysiloxane particles was 1.50 μm.
続くモノマー吸収工程以降は、吸収モノマーとしてスチレン（Ｓｔ）４０部のみを用いた以外は、実施例１と同様にして、導電粒子用基材粒子（２’）を得た。得られた導電粒子用基材粒子の平均分散粒子径、１０％Ｋ値、変動係数および分散性の評価は表１に示すとおりであった。 Subsequent to the subsequent monomer absorption step, conductive particle base particles (2 ') were obtained in the same manner as in Example 1 except that only 40 parts of styrene (St) was used as an absorption monomer. Table 1 shows the average dispersed particle diameter, 10% K value, coefficient of variation, and evaluation of dispersibility of the obtained base particles for conductive particles.
また、導電粒子用基材粒子（２’）を用いて、実施例１と同様の手順で、導電粒子（２’）、異方性導電フィルム（２’）、接続構造体（２’）を得た。得られた導電粒子（２’）の分散性の評価、ならびに作製した接続構造体（２’）における初期抵抗値および抵抗値上昇率の評価を表１に示す。 In addition, the conductive particles (2 ′), the anisotropic conductive film (2 ′), and the connection structure (2 ′) were prepared using the conductive particle base material particles (2 ′) in the same procedure as in Example 1. Obtained. Table 1 shows the evaluation of the dispersibility of the obtained conductive particles (2 ') and the evaluation of the initial resistance value and the resistance value increase rate in the produced connection structure (2').
各実施例および比較例において得られた導電粒子用基材粒子の組成および各種物性、並びに接続構造体における物理測定結果を表１に示す。 Table 1 shows the composition and various physical properties of the base particles for conductive particles obtained in each of the examples and comparative examples, and the physical measurement results of the connection structure.
親水性単量体に由来する構造単位を有する実施例と、親水性単量体に由来する構造単位を有さない比較例とを比べると、親水性単量体に由来する構造単位を有する実施例は、分散性、初期抵抗値、および抵抗値上昇率のいずれも優れていた。 Comparing an example having a structural unit derived from a hydrophilic monomer and a comparative example not having a structural unit derived from a hydrophilic monomer, an example having a structural unit derived from a hydrophilic monomer The examples were excellent in dispersibility, initial resistance, and rate of increase in resistance.
また、水酸基含有単官能モノマーに由来する構造単位を有する実施例１および２と、それ以外の親水性単量体に由来する構造単位を有する実施例３〜６とを比べると、水酸基含有単官能モノマーに由来する構造単位を有する実施例１および２は、初期抵抗値および抵抗値上昇率において、より優れた結果を示した。 Further, comparing Examples 1 and 2 having a structural unit derived from a hydroxyl group-containing monofunctional monomer with Examples 3 to 6 having a structural unit derived from a hydrophilic monomer other than that, a hydroxyl group-containing monofunctional monomer was compared. Examples 1 and 2 having a structural unit derived from a monomer showed better results in terms of initial resistance value and rate of increase in resistance value.
本発明は、導電材料を使用する分野において利用することができる。 INDUSTRIAL APPLICABILITY The present invention can be utilized in the field of using conductive materials.
Claims (6)
親水性単量体に由来する構造単位を有する、導電粒子用基材粒子。 The average particle size is 1.0 μm to 2.5 μm,
Substrate particles for conductive particles having a structural unit derived from a hydrophilic monomer.
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| JP2010083954A (en) * | 2008-09-30 | 2010-04-15 | Nippon Shokubai Co Ltd | Polymer microparticle, method for manufacturing the same, and electroconductive microparticle |
| JP2012216530A (en) * | 2011-03-30 | 2012-11-08 | Nippon Shokubai Co Ltd | Conductive particulate and anisotropic conductive material using the same |
| JP2013258138A (en) * | 2012-05-16 | 2013-12-26 | Hitachi Chemical Co Ltd | Conductive particle, anisotropic conductive adhesive film, and connection structure |
| JP2014192051A (en) * | 2013-03-27 | 2014-10-06 | Nippon Shokubai Co Ltd | Electroconductive particulates and anisotropic electroconductive material using the same |
| WO2018061374A1 (en) * | 2016-09-30 | 2018-04-05 | 積水化成品工業株式会社 | Conductive resin particles and use of same |
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| JP2012216530A (en) * | 2011-03-30 | 2012-11-08 | Nippon Shokubai Co Ltd | Conductive particulate and anisotropic conductive material using the same |
| JP2013258138A (en) * | 2012-05-16 | 2013-12-26 | Hitachi Chemical Co Ltd | Conductive particle, anisotropic conductive adhesive film, and connection structure |
| JP2014192051A (en) * | 2013-03-27 | 2014-10-06 | Nippon Shokubai Co Ltd | Electroconductive particulates and anisotropic electroconductive material using the same |
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