JP6557556B2 - Conductive particles and conductive composition containing the same - Google Patents
Conductive particles and conductive composition containing the same Download PDFInfo
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- JP6557556B2 JP6557556B2 JP2015173009A JP2015173009A JP6557556B2 JP 6557556 B2 JP6557556 B2 JP 6557556B2 JP 2015173009 A JP2015173009 A JP 2015173009A JP 2015173009 A JP2015173009 A JP 2015173009A JP 6557556 B2 JP6557556 B2 JP 6557556B2
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- 239000002245 particle Substances 0.000 title claims description 108
- 239000000203 mixture Substances 0.000 title claims description 17
- 239000011162 core material Substances 0.000 claims description 53
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 43
- 229910001887 tin oxide Inorganic materials 0.000 claims description 43
- 239000011247 coating layer Substances 0.000 claims description 35
- 239000011164 primary particle Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 239000008119 colloidal silica Substances 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 5
- 238000002441 X-ray diffraction Methods 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 29
- 239000004020 conductor Substances 0.000 description 29
- 239000002002 slurry Substances 0.000 description 26
- 238000010304 firing Methods 0.000 description 23
- 239000012298 atmosphere Substances 0.000 description 13
- 150000003606 tin compounds Chemical class 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000002019 doping agent Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910052787 antimony Inorganic materials 0.000 description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 229940079864 sodium stannate Drugs 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000001419 dependent effect Effects 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910001432 tin ion Inorganic materials 0.000 description 5
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007771 core particle Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 239000012811 non-conductive material Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- -1 etc. Substances 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 229910052752 metalloid Inorganic materials 0.000 description 3
- 150000002738 metalloids Chemical class 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical class C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000009125 cardiac resynchronization therapy Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002737 metalloid compounds Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 229920003196 poly(1,3-dioxolane) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
本発明は、酸化スズの導電層を有する導電性粒子及びそれを含む導電性組成物に関する。 The present invention relates to conductive particles having a conductive layer of tin oxide and a conductive composition including the same.
ポリマー等の非導電材料に導電性を付与する導電性材料として、界面活性剤、金属粉末、カーボンブラック、アンチモン等をドープした酸化スズ粉末、アンチモン等をドープした酸化スズ皮膜を有する粉末、酸化スズ粉末、酸化亜鉛粉末、酸化スズ皮膜を有する二酸化チタン粉末や硫酸バリウム粉末等が知られている。これらの導電性材料のうち、酸化スズ皮膜を有する二酸化チタン粉末や硫酸バリウム粉末に関する従来の技術としては、特許文献１及び２に記載のものが知られている。特許文献１には、Ｘ線回折測定によりシェラー法を使用して算出された前記酸化スズの結晶子径と、ＢＥＴ法による比表面積測定から真球近似をして算出された平均一次粒径との比率が１：０．８〜１：２．５である粒子が記載されている。同文献では、この粒子を研磨材として用いている。特許文献２には、酸化チタン粒子と、その表面を被覆する酸化スズの被覆層を有する導電性粒子において、酸化スズ粒子の平均粒子径が１ｎｍ以上５０ｎｍ以下であることが記載されている。 As conductive materials for imparting conductivity to non-conductive materials such as polymers, surfactant, metal powder, tin oxide powder doped with carbon black, antimony, etc., powder with tin oxide film doped with antimony, tin oxide Known are powder, zinc oxide powder, titanium dioxide powder having a tin oxide film, barium sulfate powder, and the like. Among these conductive materials, those described in Patent Documents 1 and 2 are known as conventional techniques related to titanium dioxide powder having a tin oxide film and barium sulfate powder. In Patent Document 1, the crystallite diameter of the tin oxide calculated using the Scherrer method by X-ray diffraction measurement, and the average primary particle diameter calculated by approximating the sphere from the specific surface area measurement by the BET method, Particles with a ratio of 1: 0.8 to 1: 2.5 are described. In this document, this particle is used as an abrasive. Patent Document 2 describes that in conductive particles having titanium oxide particles and a tin oxide coating layer covering the surface thereof, the average particle diameter of the tin oxide particles is 1 nm or more and 50 nm or less.
ところで、上述した導電性材料によって導電性が付与されたポリマーは、その電気的特性を活かして画像形成装置の転写ベルトなどの構成材料として使用される。そのような構成材料は、トナーの紙への転写性を考慮して、ある程度高抵抗であること、及び転写時の画像乱れを抑制する観点から塗膜抵抗の電圧依存性が小さいことが求められる。例えば特許文献３は、導電ポリマー層の表面抵抗率をある範囲に設定することでこれらの課題を解決できることを示している。しかし、使用する導電性材料によって抵抗の電圧依存性がどのように変化するかについては、全く検討が行われていない。特許文献１及び２に関しても同様である。 By the way, the polymer imparted with conductivity by the above-described conductive material is used as a constituent material for a transfer belt of an image forming apparatus, taking advantage of its electrical characteristics. Such a constituent material is required to have a certain degree of high resistance in consideration of transferability of toner to paper and to have low voltage dependency of coating film resistance from the viewpoint of suppressing image disturbance during transfer. . For example, Patent Document 3 shows that these problems can be solved by setting the surface resistivity of the conductive polymer layer within a certain range. However, no consideration has been given to how the voltage dependency of the resistance changes depending on the conductive material used. The same applies to Patent Documents 1 and 2.
したがって本発明の課題は、前述した従来技術が有する種々の欠点を解消し得る導電性粒子を提供することにある。 Therefore, the subject of this invention is providing the electroconductive particle which can eliminate the various fault which the prior art mentioned above has.
本発明は、無機物を有する芯材と、該芯材の表面に配置された導電性酸化スズを有する被覆層とを有する導電性粒子であって、
Ｘ線回折測定によりＨａｌｄｅｒ−Ｗａｇｎｅｒ法を使用して算出された前記酸化スズの結晶子径をＤ１とし、透過型電子顕微鏡観察で測定された前記酸化スズの一次粒子径をＤ２としたとき、Ｄ１／Ｄ２の値が０．２以上１．０以下である導電性粒子を提供するものである。
The present invention is a conductive particle having a core material having an inorganic substance and a coating layer having a conductive tin oxide disposed on the surface of the core material,
When the crystallite diameter of the tin oxide calculated using the Halder-Wagner method by X-ray diffraction measurement is D1, and the primary particle diameter of the tin oxide measured by transmission electron microscope observation is D2, D1 The conductive particles having a value of / D2 of 0.2 or more and 1.0 or less are provided.
また本発明は、前記の導電性粒子と、バインダ樹脂とを含む導電性組成物を提供するものである。 Moreover, this invention provides the electroconductive composition containing the said electroconductive particle and binder resin.
更に本発明は、導電性粒子と、酸化スズ粒子とを含む導電性混合粉、及び該導電性混合粉とバインダ樹脂とを含む導電性組成物を提供するものである。 Furthermore, the present invention provides a conductive mixed powder containing conductive particles and tin oxide particles, and a conductive composition containing the conductive mixed powder and a binder resin.
本発明の導電性粒子を用いて導電体を製造すると、該導電体の電気抵抗が、印加電圧に依存しにくいものとなる。 When a conductor is produced using the conductive particles of the present invention, the electrical resistance of the conductor becomes less dependent on the applied voltage.
以下本発明を、その好ましい実施形態に基づき説明する。なお以下の説明において、導電性粒子とは、文脈に応じて個々の粒子を指す場合と、粒子の集合体としての粉体を指す場合とがある。本発明の導電性粒子は、芯材と、導電性の酸化スズ（ＳｎＯ２）を有する被覆層とを備えたものである。被覆層は好適には酸化スズ（ＳｎＯ２）から実質的になる。芯材は粒子状の形態をしている。芯材は、本発明の導電性粒子における容積の大部分を占める部位であり、導電性粒子の中心域に位置する。一方、被覆層は、本発明の導電性粒子の最表面に位置する。被覆層と芯材とは直接に接していてもよく、あるいは両者間に他の層が介在していてもよい。好ましくは、被覆層と芯材とは直接に接している。 Hereinafter, the present invention will be described based on preferred embodiments thereof. In the following description, the conductive particles may refer to individual particles depending on the context, or may refer to powder as an aggregate of particles. Conductive particles of the present invention are those having a core material and a coating layer having a conductive tin oxide (SnO 2). The coating layer preferably consists essentially of tin oxide (SnO 2 ). The core material has a particulate form. A core material is a site | part which occupies most volume in the electroconductive particle of this invention, and is located in the center area | region of electroconductive particle. On the other hand, a coating layer is located in the outermost surface of the electroconductive particle of this invention. The coating layer and the core material may be in direct contact with each other, or another layer may be interposed therebetween. Preferably, the coating layer and the core material are in direct contact.
芯材は一般に非導電性材料を有するものであり、非導電性材料からなるものでもよい。この非導電性材料は、金属又は半金属の化合物であり得る。金属又は半金属の例としては、例えばアルミニウム、チタン及びジルコニウムなどの金属や、ケイ素などの半金属が挙げられる。本明細書でいう非導電性とは、体積抵抗率が例えば１０５Ω・ｃｍ以上であることをいう。 The core material generally has a non-conductive material, and may be made of a non-conductive material. The non-conductive material can be a metal or metalloid compound. Examples of the metal or metalloid include metals such as aluminum, titanium and zirconium, and metalloids such as silicon. The term “non-conductive” as used herein means that the volume resistivity is, for example, 10 5 Ω · cm or more.
芯材を構成する材料としては、例えば、無機酸化物、無機水酸化物、無機窒化物、及び無機炭化物などを用いることができる。また、硫酸塩などの無機塩を用いることもでき、又はこれらの材料の混合物を用いることができる。これらの各種無機物は水不溶性であることが好ましい。特に好ましい無機物としては、金属酸化物である酸化チタン（ＴｉＯ２）、酸化アルミニウム（Ａｌ２Ｏ３）及び酸化ジルコニウム（ＺｒＯ２）、半金属の酸化物である二酸化ケイ素（ＳｉＯ２）、並びに金属塩である硫酸バリウム（ＢａＳＯ４）、チタン酸カリウム（Ｋ２Ｏ・ｎＴｉＯ２）、ホウ酸アルミニウム（９Ａｌ２Ｏ３・２Ｂ２Ｏ３）等が挙げられる。 As a material constituting the core material, for example, an inorganic oxide, an inorganic hydroxide, an inorganic nitride, an inorganic carbide, or the like can be used. In addition, inorganic salts such as sulfates can be used, or a mixture of these materials can be used. These various inorganic materials are preferably water-insoluble. Particularly preferable inorganic substances include titanium oxide (TiO 2 ), aluminum oxide (Al 2 O 3 ) and zirconium oxide (ZrO 2 ), which are metal oxides, silicon dioxide (SiO 2 ), which is a metalloid oxide, and metals. Examples thereof include barium sulfate (BaSO 4 ), potassium titanate (K 2 O.nTiO 2 ), and aluminum borate (9Al 2 O 3 .2B 2 O 3 ).
芯材の形状は、その表面に導電性酸化スズの被覆層を形成することが可能な形状であればよく、導電性粒子の用途に応じて、球状、多面体状、フレーク状、針状等の種々の形状のものが用いられる。本発明において、被覆層の厚みは芯材の大きさに比べて非常に小さいので、通常、芯材と導電性粒子の形状は概ね同じであるとみなすことができる。芯材の一次粒子径は０．００１μｍ以上０．５μｍ以下であることが好ましく、０．００１μｍ以上０．４μｍ以下であることが更に好ましく、０．０５μｍ以上０．４μｍ以下であることが一層好ましい。特に、コロイダルシリカやコロイダルアルミナなど、一次粒子径が０．００１μｍ以上０．１３μｍ以下の微粒の芯材を用いると、導電性酸化スズから得られる導電膜の透明性が一層向上し、且つ導電性も一層向上するので好ましい。なお、透明性及び導電性の更に一層の向上の観点からは芯材の一次粒子径は０．１１μｍ以下であることが更に好ましい。コロイダルシリカやコロイダルアルミナは、これらを単独で用いることもできるし、あるいは両者を組み合わせて用いることもできる。なお、製造容易性の観点からは芯材の一次粒子径は０．０１μｍ以上であることが好ましい。芯材の一次粒子径は、芯材を透過型電子顕微鏡（以下、「ＴＥＭ」ともいう。）で５千倍以上５０万倍以下程度に拡大し、３００個以上の芯材を対象として、該芯材の拡大像を例えばソフトウェアマックビューで画像解析し、Ｆｅｒｅｔ径を算出する。その相加平均を算出し、その値を一次粒子径とする。 The shape of the core material only needs to be a shape capable of forming a coating layer of conductive tin oxide on the surface, and may be spherical, polyhedral, flaky, needle-like, etc., depending on the use of the conductive particles. Various shapes are used. In the present invention, since the thickness of the coating layer is very small compared to the size of the core material, it can be generally regarded that the shape of the core material and the conductive particles are substantially the same. The primary particle diameter of the core material is preferably 0.001 μm or more and 0.5 μm or less, more preferably 0.001 μm or more and 0.4 μm or less, and further preferably 0.05 μm or more and 0.4 μm or less. . In particular, when a fine core material having a primary particle diameter of 0.001 μm or more and 0.13 μm or less, such as colloidal silica or colloidal alumina, is used, the transparency of the conductive film obtained from conductive tin oxide is further improved and the conductivity is improved. Is also preferable because it improves further. From the viewpoint of further improving the transparency and conductivity, the primary particle diameter of the core material is more preferably 0.11 μm or less. These colloidal silica and colloidal alumina can be used alone or in combination. From the viewpoint of ease of manufacture, the primary particle diameter of the core material is preferably 0.01 μm or more. The primary particle diameter of the core material is increased from 5,000 to 500,000 times with a transmission electron microscope (hereinafter also referred to as “TEM”). An enlarged image of the core material is subjected to image analysis, for example, with a software Mac view, and a Feret diameter is calculated. The arithmetic average is calculated, and the value is defined as the primary particle diameter.
導電性粒子の最外層をなす被覆層は、芯材の表面が全く露出しないように該表面を満遍なく連続して被覆していることが、導電性粒子の導電性を高める点から好ましい。しかし被覆層は、本発明の効果を損なわない範囲において、芯材の表面が一部露出するように該表面を不連続に被覆していてもよい。 The coating layer that forms the outermost layer of the conductive particles preferably covers the surface uniformly and continuously so that the surface of the core material is not exposed at all, from the viewpoint of increasing the conductivity of the conductive particles. However, the coating layer may cover the surface discontinuously so that the surface of the core material is partially exposed as long as the effects of the present invention are not impaired.
被覆層の厚みは、本発明の導電性粒子の導電性が充分に発現する程度であれば、過度に厚くする必要はない。被覆層の厚みを酸化スズ（ＳｎＯ２）の量に換算して表すと、本発明の導電性粒子に占める酸化スズの割合が２０質量％以上７５質量％以下、特に２５質量％以上７５質量％以下、とりわけ４０質量％以上７５質量％以下となるような厚みであることが好ましい。導電性粒子中のスズの量は、導電性粒子の被覆層をアルカリで溶解させて得られる溶液について、ＩＣＰ発光分光測定器で測定することによって求めることができる。 The coating layer need not be excessively thick as long as the conductivity of the conductive particles of the present invention is sufficiently developed. When the thickness of the coating layer is expressed in terms of the amount of tin oxide (SnO 2 ), the proportion of tin oxide in the conductive particles of the present invention is 20% by mass to 75% by mass, particularly 25% by mass to 75% by mass. In particular, the thickness is preferably 40% by mass to 75% by mass. The amount of tin in the conductive particles can be determined by measuring the solution obtained by dissolving the coating layer of the conductive particles with an alkali with an ICP emission spectrometer.
被覆層の導電性を高める観点から、該被覆層を構成する酸化スズには、必要に応じてドーパント元素を含有させることができる。ドーパント元素は、それを添加した後の酸化スズの導電性を、添加前の酸化スズに比べて変化させることができる元素である。具体的にはドーパント元素としては、アンチモン（Ｓｂ）、ニオブ（Ｎｂ）、タンタル（Ｔａ）、タングステン（Ｗ）、リン（Ｐ）、フッ素（Ｆ）、塩素（Ｃｌ）、ビスマス（Ｂｉ）、アルミニウム（Ａｌ）、ホウ素（Ｂ）、モリブデン（Ｍｏ）、窒素（Ｎ）、亜鉛（Ｚｎ）などを挙げることができる。ドーパント元素は、これらのうちの１種又は２種以上を用いることができる。特に、ドーパント元素がアンチモン（Ｓｂ）、ニオブ（Ｎｂ）、タンタル（Ｔａ）、リン（Ｐ）、フッ素（Ｆ）及びタングステン（Ｗ）のうちの少なくとも１種以上であり、とりわけアンチモン（Ｓｂ）であることが、導電性粒子の導電性が周囲環境に依存しにくくなる点から好ましい。被覆層に含まれるドーパント元素の総和の割合は、該被覆層に含まれる酸化スズにおけるスズの全量に対して１．０質量％以上２０．０質量％以下であることが好ましく、１．５質量％以上１７．０質量％以下であることが一層好ましい。また被覆層に、本発明の効果を損なわない範囲において、不可避不純物が少量含まれることは許容される。 From the viewpoint of increasing the conductivity of the coating layer, the tin oxide constituting the coating layer can contain a dopant element as necessary. A dopant element is an element which can change the electroconductivity of the tin oxide after adding it compared with the tin oxide before addition. Specifically, as the dopant element, antimony (Sb), niobium (Nb), tantalum (Ta), tungsten (W), phosphorus (P), fluorine (F), chlorine (Cl), bismuth (Bi), aluminum (Al), boron (B), molybdenum (Mo), nitrogen (N), zinc (Zn), and the like can be given. One or more of these dopant elements can be used. In particular, the dopant element is at least one of antimony (Sb), niobium (Nb), tantalum (Ta), phosphorus (P), fluorine (F), and tungsten (W), particularly antimony (Sb). It is preferable that the conductivity of the conductive particles is less dependent on the surrounding environment. The ratio of the sum of the dopant elements contained in the coating layer is preferably 1.0% by mass or more and 20.0% by mass or less, based on the total amount of tin in the tin oxide contained in the coating layer, and 1.5% by mass. % To 17.0% by mass is even more preferable. In addition, the coating layer is allowed to contain a small amount of inevitable impurities as long as the effects of the present invention are not impaired.
本発明の導電性粒子は被覆層の構造に特徴の一つを有する。詳細には被覆層を構成する酸化スズは、Ｘ線回折測定によりＨａｌｄｅｒ−Ｗａｇｎｅｒ法を使用して算出された結晶子径をＤ１とし、ＴＥＭ観察で測定された一次粒子径をＤ２としたとき、Ｄ１／Ｄ２の値が０．２以上１．０以下であることを特徴の一つとするものである。Ｄ１／Ｄ２の値をこの範囲内に設定することによって、本発明の導電性粒子は、これを用いて導電体を製造すると、該導電体の電気抵抗が、印加電圧に依存しにくくなるという特異な効果を奏するようになる。この効果を一層顕著なものとする観点から、Ｄ１／Ｄ２の値は０．３以上１．０以下であることが好ましく、０．４以上１．０以下であることが更に好ましい。 The electroconductive particle of this invention has one of the characteristics in the structure of a coating layer. Specifically, the tin oxide constituting the coating layer has a crystallite diameter calculated using the Halder-Wagner method by X-ray diffraction measurement as D1, and a primary particle diameter measured by TEM observation as D2. One of the characteristics is that the value of D1 / D2 is 0.2 or more and 1.0 or less. By setting the value of D1 / D2 within this range, the conductive particles of the present invention have a unique characteristic that when a conductor is produced using this, the electrical resistance of the conductor becomes less dependent on the applied voltage. The effect will come out. From the viewpoint of making this effect even more prominent, the value of D1 / D2 is preferably 0.3 or more and 1.0 or less, and more preferably 0.4 or more and 1.0 or less.
Ｄ１／Ｄ２の値は、被覆層を構成する酸化スズにおける結晶性の高さを表す尺度であり、その上限値は１である。Ｄ１／Ｄ２の値が１に近いほど、酸化スズは単結晶の構造に近くなる。酸化スズが単結晶の構造に近くなるということは、被覆層中に存在する結晶粒界の数が少なくなることにつながる。酸化スズの結晶粒界の数は、酸化スズの導電性に影響する要因の一つと考えられることから、結晶粒界の数が少なくなることによって、本発明の導電性粒子を用いて導電体を製造すると、該導電体の電気抵抗が、印加電圧に依存しにくくなると考えられる。Ｄ１／Ｄ２の値を上述の範囲内とするためには、例えば後述する製造方法に従い被覆層を形成すればよい。 The value of D1 / D2 is a scale representing the high crystallinity of tin oxide constituting the coating layer, and the upper limit is 1. The closer the value of D1 / D2 is to 1, the closer the tin oxide is to a single crystal structure. The fact that tin oxide has a single crystal structure leads to a reduction in the number of crystal grain boundaries present in the coating layer. Since the number of crystal grain boundaries of tin oxide is considered to be one of the factors affecting the conductivity of tin oxide, the number of crystal grain boundaries is reduced, so that the conductors can be formed using the conductive particles of the present invention. When manufactured, the electrical resistance of the conductor is considered to be less dependent on the applied voltage. In order to set the value of D1 / D2 within the above-mentioned range, for example, a coating layer may be formed according to the manufacturing method described later.
上述の結晶子径Ｄ１は、次の方法で測定される。すなわち、Ｘ線回折装置Ｕｌｔｉｍａ
ＩＶ（株式会社リガク製）を用いてＸＲＤ測定を行う（条件：Ｘ−ｒａｙ ＣｕＫα、４０ｋＶ、５０ｍＡ、測定範囲２０°≦２θ≦１００°、線源：ＣｕＫα、走査軸：２θ／θ、測定方法：ＦＴ、係数単位：Ｃｏｕｎｔｓ、ステップ幅：０．０１°、係数時間：３秒、発散スリット：２／３°、発散縦制限スリット：１０ｍｍ、散乱スリット：２／３°、受光スリット：０．３ｍｍ、モノクロ受光スリット：０．８ｍｍ）。続いて、リガク製の解析ソフトウェアＰＤＸＬを用いて測定データを読み込み（ＳｎＯ２のＩＣＤＤカード：００−０４６−１０８８を使用）、精密化した後にＨａｌｄｅｒ−Ｗａｇｎｅｒ法により結晶子径の算出を行った（外部標準試料による幅補正を行い、解析対象は結晶子径と格子歪とした）。一次粒子径Ｄ２は、導電性粒子をＴＥＭで１０万倍以上５０万倍以下程度に拡大し、３００個以上の導電性粒子を対象として、該導電性粒子中の被覆層の拡大像を例えばソフトウェアマックビューで画像解析し、Ｆｅｒｅｔ径を算出する。その相加平均を算出し、その値をＤ２とする。
The crystallite diameter D1 is measured by the following method. That is, the X-ray diffractometer Ultima
XRD measurement is performed using IV (manufactured by Rigaku Corporation) (conditions: X-ray CuKα, 40 kV, 50 mA, measurement range 20 ° ≦ 2θ ≦ 100 °, radiation source: CuKα, scanning axis: 2θ / θ, measurement method) : FT, coefficient unit: Counts, step width: 0.01 °, coefficient time: 3 seconds, divergence slit: 2/3 °, divergence longitudinal limit slit: 10 mm, scattering slit: 2/3 °, light receiving slit: 0. 3 mm, monochrome light receiving slit: 0.8 mm). Subsequently, the measurement data was read using Rigaku's analysis software PDXL (SnO 2 ICDD card: 00-046-1088 was used), and after refinement, the crystallite diameter was calculated by the Halder-Wagner method ( The width was corrected using an external standard sample, and the analysis target was the crystallite diameter and lattice strain). The primary particle diameter D2 is obtained by enlarging the conductive particles to about 100,000 to 500,000 times by TEM, and using 300 or more conductive particles as an object, an enlarged image of the coating layer in the conductive particles is, for example, software. Image analysis is performed with a Mac view, and the Feret diameter is calculated. The arithmetic average is calculated and the value is set to D2.
Ｄ１／Ｄ２の値は上述のとおりであるところ、Ｄ１の値そのものは、Ｄ１／Ｄ２の値が上述の範囲であることを条件として、４ｎｍ以上２０ｎｍ以下であることが好ましく、５ｎｍ以上２０ｎｍ以下であることが更に好ましく、６ｎｍ以上２０ｎｍ以下であることが一層好ましい。Ｄ２の値に関しては、Ｄ１／Ｄ２の値が上述の範囲であることを条件として、４ｎｍ以上５０ｎｍ以下であることが好ましく、４ｎｍ以上４０ｎｍ以下であることが更に好ましく、４ｎｍ以上３０ｎｍ以下であることが一層好ましい。 The value of D1 / D2 is as described above, and the value of D1 itself is preferably 4 nm or more and 20 nm or less, provided that the value of D1 / D2 is in the above range, and is 5 nm or more and 20 nm or less. More preferably, it is 6 nm or more and 20 nm or less. The value of D2 is preferably 4 nm or more and 50 nm or less, more preferably 4 nm or more and 40 nm or less, and more preferably 4 nm or more and 30 nm or less, provided that the value of D1 / D2 is in the above range. Is more preferable.
本発明の導電性粒子は、結晶子径Ｄ１及び一次粒子径Ｄ２が上述の範囲内であることのほか、レーザー回折散乱式粒度分布測定法による累積体積５０容量％における体積累積粒径Ｄ５０が好ましくは０．０５μｍ以上１．０μｍ以下であり、更に好ましくは０．１μｍ以上０．８μｍ以下であり、一層好ましくは０．２μｍ以上０．７μｍ以下である。粒径Ｄ５０がこの範囲内であることによって、本発明の導電性粒子を配合してなる導電性組成物は、その塗布性が良好になったり、塗膜の導電性が良好になったりする。 Conductive particles of the present invention, in addition to the crystallite diameter D1 and a primary particle diameter D2 is within the above range, the volume cumulative particle diameter D 50 in the cumulative volume 50% by volume by laser diffraction scattering particle size distribution measurement method Preferably they are 0.05 micrometer or more and 1.0 micrometer or less, More preferably, they are 0.1 micrometer or more and 0.8 micrometers or less, More preferably, they are 0.2 micrometer or more and 0.7 micrometers or less. By the particle diameter D 50 is within this range, the conductive composition obtained by blending the conductive particles of the present invention, or become better its coatability, the conductivity of the coated film or become better .
上述のＤ５０の測定は、例えば以下の方法で行うことができる。０．１ｇの測定試料を、ヘキサメタリン酸ナトリウムの２０ｍｇ／Ｌ水溶液１００ｍＬと混合し、超音波ホモジナイザ（日本精機製作所製 ＵＳ−３００Ｔ）で１０分間分散させる。その後、レーザー回折散乱式粒度分布測定装置、例えば日機装社製マイクロトラックＸ−１００を用いて粒度分布を測定する。 Measurements of the above D 50 can be carried out, for example, by the following method. 0.1 g of a measurement sample is mixed with 100 mL of a 20 mg / L aqueous solution of sodium hexametaphosphate, and dispersed with an ultrasonic homogenizer (US-300T, manufactured by Nippon Seiki Seisakusho) for 10 minutes. Thereafter, the particle size distribution is measured using a laser diffraction scattering type particle size distribution measuring apparatus, for example, Microtrack X-100 manufactured by Nikkiso Co., Ltd.
本発明の導電性粒子は、バインダ樹脂への分散性の観点の点から、そのＢＥＴ比表面積が、１０ｍ２／ｇ以上１３０ｍ２／ｇ以下であることが好ましく、１０ｍ２／ｇ以上１１０ｍ２／ｇ以下であることが更に好ましく、１２ｍ２／ｇ以上９０ｍ２／ｇ以下であることが一層好ましい。導電性粒子の比表面積を前記の範囲内とするためには、後述する導電性粒子の製造方法において、焼成温度及び焼成雰囲気を適切に制御すればよい。ＢＥＴ比表面積は、例えばユアサアイオニクス（株）製のモノソーブ（商品名）を用い、ＢＥＴ１点法（Ｈｅ／Ｎ2混合ガス）に従い測定することができる。後述する実施例においては、粉末の量を０．３gとし、予備脱気条件は大気圧下、１０５℃で１０分間として測定を行った。 Conductive particles of the present invention, from the viewpoint of dispersibility in the perspective of the binder resin, the BET specific surface area is preferably not more than 10 m 2 / g or more 130m 2 / g, 10m 2 / g or more 110m 2 / more preferably g or less, and more preferably 12m 2 / g or more 90m 2 / g or less. In order to set the specific surface area of the conductive particles within the above range, the firing temperature and firing atmosphere may be appropriately controlled in the method for producing conductive particles described later. The BET specific surface area can be measured, for example, using a monosorb (trade name) manufactured by Yuasa Ionics Co., Ltd. according to the BET one-point method (He / N 2 mixed gas). In Examples described later, the amount of powder was 0.3 g, and the preliminary degassing conditions were measured under atmospheric pressure at 105 ° C. for 10 minutes.
本発明の導電性粒子は導電性を有するものである。導電性の程度は、圧粉抵抗値で表して好ましくは１．０×１０１Ω・ｃｍ以上１．０×１０８Ω・ｃｍ以下、更に好ましくは１．０×１０１Ω・ｃｍ以上１．０×１０７Ω・ｃｍ以下である。この範囲の圧粉抵抗値は、導電性粒子から導電膜を形成するのに充分に低い値である。圧粉抵抗値の測定方法は次のとおりである。導電性粒子５ｇを５００ｋｇｆの荷重で０．５分間プレスし、直径２５ｍｍの円筒状ペレットを作製する。得られたペレットの抵抗値を、三菱化学製のＭＣＰ―Ｔ６００（商品名）を用い、四探針法により測定する。 The electroconductive particle of this invention has electroconductivity. The degree of conductivity, preferably represents a dust resistance 1.0 × 10 1 Ω · cm or more 1.0 × 10 8 Ω · cm or less, more preferably 1.0 × 10 1 Ω · cm or more 1 0.0 × 10 7 Ω · cm or less. The dust resistance value in this range is sufficiently low to form a conductive film from conductive particles. The measuring method of the dust resistance value is as follows. 5 g of conductive particles are pressed with a load of 500 kgf for 0.5 minutes to produce cylindrical pellets with a diameter of 25 mm. The resistance value of the obtained pellet is measured by a four-point probe method using MCP-T600 (trade name) manufactured by Mitsubishi Chemical.
上述したとおり、本発明の導電性粒子は、これを用いて導電体を製造すると、該導電体の電気抵抗が、印加電圧に依存しにくいものとなるという特異な効果を奏するものである。例えば、本発明の導電性粒子７．４１質量部と、バインダ樹脂６．４１質量部とを含む導電性組成物から形成された導電膜について、１００Ｖの印加電圧下で測定された表面抵抗率Ｒ１００に対する、１０Ｖの印加電圧下で測定された表面抵抗率Ｒ１０の変化率であるＲ１０／Ｒ１００の値が好ましくは１００以下、更に好ましくは８０以下という、印加電圧依存性の低い導電体が得られる。 As described above, when the conductive particles of the present invention are used to produce a conductor, the electrical resistance of the conductor is less dependent on the applied voltage, and has a unique effect. For example, for a conductive film formed from a conductive composition containing 7.41 parts by mass of the conductive particles of the present invention and 6.41 parts by mass of a binder resin, the surface resistivity R measured under an applied voltage of 100V. Conductor having a low applied voltage dependency, wherein the value of R 10 / R 100 , which is the rate of change of surface resistivity R 10 measured with respect to 100 under an applied voltage of 10 V, is preferably 100 or less, more preferably 80 or less Is obtained.
上述の導電体の表面抵抗率の測定は次のように行う。バインダ樹脂として三菱レイヨン製のアクリル系コーティング樹脂であるダイヤナールＬＲ-１６７を用いる。このバインダ樹脂と本発明の導電性粒子とを、上述の比率でもって混合する。混合を充分に行う目的で、有機溶媒であるトルエンとｎ−ブタノールの混合溶媒（容積比７：３）を９．６４質量部添加する。次いでペイントシェーカー（浅田鉄鋼製）を用い、１時間分散を行う。ペイントシェーカーの運転条件は、６０Ｈｚ環境下の運転条件とする。このようにして得られた導電性組成物を、ポリエチレンテレフタレート製のＯＨＰフィルム（株式会社内田洋行製のトランスペアレンシー ＯＨＰ用フィルム）に塗工する。塗工にはバーコーター＃１０（テスター産業株式会社製のＲＯＤ Ｎｏ．１０）を用い、使用液量約１ｍＬで塗膜を形成する。塗膜形成後、大気下に８０℃で１５分間にわたり乾燥を行い、導電体を得る。この導電体について、三菱アナリテック製のハイレスタを用いて表面抵抗率を測定する。測定にはＵＰプローブを用いる。印加電圧は、上述のとおり１０Ｖ及び１００Ｖ（いずれも直流）とする。測定は、一つの導電体中の異なる測定位置１０箇所について行う。それらの平均値をもって表面抵抗率の値とする。 The measurement of the surface resistivity of the conductor is performed as follows. As a binder resin, Dainar LR-167, which is an acrylic coating resin manufactured by Mitsubishi Rayon, is used. The binder resin and the conductive particles of the present invention are mixed at the above ratio. For the purpose of sufficiently mixing, 9.64 parts by mass of a mixed solvent of toluene and n-butanol (volume ratio 7: 3) as an organic solvent is added. Next, dispersion is performed for 1 hour using a paint shaker (manufactured by Asada Steel). The operating condition of the paint shaker is an operating condition under a 60 Hz environment. The conductive composition thus obtained is applied to an OHP film made of polyethylene terephthalate (transparency OHP film made by Uchida Yoko Co., Ltd.). For coating, a bar coater # 10 (ROD No. 10 manufactured by Tester Sangyo Co., Ltd.) is used, and a coating film is formed with a use liquid amount of about 1 mL. After forming the coating film, drying is performed in the air at 80 ° C. for 15 minutes to obtain a conductor. About this conductor, surface resistivity is measured using Mitsubishi Analitec Hiresta. An UP probe is used for the measurement. The applied voltage is 10 V and 100 V (both DC) as described above. The measurement is performed at 10 different measurement positions in one conductor. The average value thereof is used as the surface resistivity value.
本発明の導電性粒子は、これを用いて製造された導電体のヘイズが低いことが好ましい。具体的には、導電体のヘイズは７０％以下であることが好ましく、６０％以下であることが更に好ましく、３０％以下であることが一層好ましく、１７％以下であることが更に一層好ましい。特に、上述したコロイダルシリカやコロイダルアルミナなど、一次粒子径が０．０１μｍ以上０．１１μｍ以下の微粒の芯材を用いると、導電体のヘイズを１０％以下という低い値にすることができる。ヘイズの測定に供される導電体は前記の方法で形成される。導電体のヘイズは例えば、日本電色工業（株）製のヘイズメーターＮＤＨ４０００（商品名）によって測定する。測定はＪＩＳ Ｋ７１３６に準拠し、積分球式測定法により行う。 It is preferable that the electroconductive particle of this invention has the low haze of the conductor manufactured using this. Specifically, the haze of the conductor is preferably 70% or less, more preferably 60% or less, still more preferably 30% or less, and even more preferably 17% or less. In particular, when a fine core material having a primary particle diameter of 0.01 μm or more and 0.11 μm or less, such as the above-described colloidal silica or colloidal alumina, the haze of the conductor can be reduced to a low value of 10% or less. The conductor used for the measurement of haze is formed by the method described above. The haze of the conductor is measured by, for example, a haze meter NDH4000 (trade name) manufactured by Nippon Denshoku Industries Co., Ltd. The measurement is performed in accordance with JIS K7136 by an integrating sphere measurement method.
なお、導電性組成物の調製時に、上述のペイントシェーカーを用いて各成分の分散を行うと、場合によっては、外力によって本発明の導電性粒子が一部破壊され、被覆層と芯材とが分離した状態になることがある。そのような状態の導電性組成物は、本発明の導電性粒子と、酸化スズ粒子とを含む導電性混合粉、及びバインダ樹脂を含有したものになる。酸化スズ粒子は、導電性粒子の被覆層由来のものであるから、Ｄ１／Ｄ２の値が０．２以上１．０以下であるという前記の特徴を満たすものである。このような形態の導電性組成物を用いて導電体を製造した場合にも、該導電体は、その体積抵抗率が印加電圧に依存しにくくなる。 In addition, when each component is dispersed using the above-described paint shaker during the preparation of the conductive composition, in some cases, the conductive particles of the present invention are partially destroyed by an external force, and the coating layer and the core material are separated. May become separated. The conductive composition in such a state contains a conductive mixed powder containing the conductive particles of the present invention and tin oxide particles, and a binder resin. Since the tin oxide particles are derived from the conductive particle coating layer, the tin oxide particles satisfy the above feature that the value of D1 / D2 is 0.2 or more and 1.0 or less. Even when a conductor is manufactured using the conductive composition having such a form, the volume resistivity of the conductor is less likely to depend on the applied voltage.
次に、本発明の導電性粒子の好適な製造方法について説明する。導電性粒子は、芯材の表面に酸化スズの被覆層を形成することによって製造される。 Next, the suitable manufacturing method of the electroconductive particle of this invention is demonstrated. The conductive particles are produced by forming a tin oxide coating layer on the surface of the core material.
被覆層の形成においては、スズ源を含有し、且つ芯材を分散させたスラリーを中和することによって、該芯材の表面にスズ化合物を被覆させる。スラリーの分散媒としては、芯材の種類や、中和反応の条件等に応じて適切な液体が選択される。一般的には水が用いられる。 In forming the coating layer, the surface of the core material is coated with a tin compound by neutralizing the slurry containing the tin source and in which the core material is dispersed. As the slurry dispersion medium, an appropriate liquid is selected according to the type of the core material, the conditions for the neutralization reaction, and the like. In general, water is used.
スズ源の添加前のスラリーにおいて、分散媒と芯材との配合比率は、分散媒１リットルに対して芯材が５０ｇ以上２４０ｇ以下、特に６０ｇ以上２００ｇ以下であることが好ましい。両者の配合比率がこの範囲内にあると、芯材の表面にスズ化合物の均一な被覆層が容易に形成されるからである。 In the slurry before the addition of the tin source, the mixing ratio of the dispersion medium and the core material is preferably 50 g or more and 240 g or less, particularly 60 g or more and 200 g or less with respect to 1 liter of the dispersion medium. This is because a uniform coating layer of a tin compound is easily formed on the surface of the core material when the blending ratio of both is within this range.
スズ源は、芯材を被覆するスズ化合物の層を形成するために用いられる。スズ源としては、芯材の表面にスズ化合物の層を形成し得るものが用いられる。スズ源は水溶性化合物であることが好ましい。スズ源は１種を単独で又は２種以上を組み合わせて用いることができる。上述したドーパント元素を被覆層中に含有させるためには、該ドーパント元素源をスズ源と併用すればよい。ドーパント元素源は、ドーパント元素を含む水溶性化合物であることが好ましい。 The tin source is used to form a layer of a tin compound that covers the core material. As the tin source, one capable of forming a tin compound layer on the surface of the core material is used. The tin source is preferably a water-soluble compound. A tin source can be used individually by 1 type or in combination of 2 or more types. In order to contain the dopant element described above in the coating layer, the dopant element source may be used in combination with the tin source. The dopant element source is preferably a water-soluble compound containing a dopant element.
スラリーにおけるスズ源と芯材との配合比率は、該芯材１００質量部に対するスズ源中のＳｎ量が１０質量部以上９０質量部以下、特に１５質量部以上８５質量部以下であることが好ましい。両者の配合比率がこの範囲内にあると、芯材の表面にスズ化合物の均一な層を形成しやすい。 The mixing ratio of the tin source and the core material in the slurry is such that the Sn amount in the tin source with respect to 100 parts by mass of the core material is 10 parts by mass or more and 90 parts by mass or less, particularly 15 parts by mass or more and 85 parts by mass or less. . When the blending ratio of the two is within this range, a uniform layer of a tin compound is easily formed on the surface of the core material.
スラリーの中和には通常、酸又はアルカリを用いる。酸としては、例えば硫酸、硝酸、酢酸などの水溶液が用いられる。硫酸を用いる場合、希硫酸、特に濃度が１０容量％以上５０容量％以下の希硫酸を用いると、スズ化合物の均一な層が得られやすいため好ましい。アルカリとしては、例えば水酸化ナトリウム水溶液などを用いることができる。スズ源の添加と、酸又はアルカリの添加とは、どちらが先でもよく、同時でもよい。 An acid or alkali is usually used for neutralization of the slurry. As the acid, for example, an aqueous solution of sulfuric acid, nitric acid, acetic acid or the like is used. When sulfuric acid is used, it is preferable to use dilute sulfuric acid, particularly dilute sulfuric acid having a concentration of 10% by volume or more and 50% by volume or less because a uniform layer of a tin compound is easily obtained. As the alkali, for example, an aqueous sodium hydroxide solution can be used. Either the addition of the tin source and the addition of the acid or alkali may be performed first or simultaneously.
中和を行う際のスラリーのｐＨは、好ましくは０．５以上６．０以下、更に好ましくは１．５以上４．０以下とする。中和の際のｐＨをこの範囲内とすることにより、芯材の表面にスズ化合物の層を容易に形成することができる。中和を行った後、スラリーの撹拌を継続させてエージングを行うことが好ましい。熟成は３０分以上１８０分以下、特に６０分以上１２０分以下行うことが好ましい。熟成によってスズ化合物の均一な層が形成されやすくなる。熟成は、一般に７０℃以上８０℃以下で行うことができる。 The pH of the slurry at the time of neutralization is preferably 0.5 or more and 6.0 or less, more preferably 1.5 or more and 4.0 or less. By setting the pH during neutralization within this range, a tin compound layer can be easily formed on the surface of the core material. After neutralization, it is preferable to perform aging by continuing stirring of the slurry. The aging is preferably performed for 30 minutes to 180 minutes, particularly 60 minutes to 120 minutes. A uniform layer of tin compound is easily formed by aging. Aging can be generally performed at 70 ° C. or higher and 80 ° C. or lower.
このようにしてスズ化合物の層が表面に形成された芯材は、反応系から分離され、好ましくは洗浄及び乾燥工程を経て、次工程である焼成工程に付される。それによって酸化スズで被覆された導電性粒子が得られる。その後、必要に応じて解砕工程に付され、所望の粒径に調整される。 The core material having the tin compound layer formed on the surface in this way is separated from the reaction system, and is preferably subjected to a subsequent baking process, which is a washing and drying process. Thereby, conductive particles coated with tin oxide are obtained. Thereafter, it is subjected to a crushing step as necessary, and adjusted to a desired particle size.
本発明においては前記の製造方法において、（ｉ）スズ源として用いる化合物の種類や、（ii）焼成工程の条件を適切に選択することで、上述したＤ１／Ｄ２の値を満たす導電性粒子を容易に製造することができる。以下、これら（ｉ）及び（ii）の条件について説明する。これら（ｉ）及び（ｉｉ）の条件は択一的に用いてもよく、二つを併用してもよい。 In the present invention, in the production method described above, (i) the type of compound used as a tin source, and (ii) the conductive particles satisfying the value of D1 / D2 described above by appropriately selecting the conditions of the firing step. It can be manufactured easily. Hereinafter, the conditions (i) and (ii) will be described. These conditions (i) and (ii) may be used alternatively or in combination.
（ｉ）の条件においては、スズ源として用いるスズ化合物として少なくとも２種類の化合物を用い、各スズ化合物を順次用いて、芯材の表面に各化合物を層状に積層する。少なくとも２種類のスズ化合物としては、例えばスズ酸ナトリウム及び四塩化スズを用いることができる。特に、第一段階目の化合物としてスズ酸ナトリウムを用い、且つ第二段階目の化合物として四塩化スズを用いることが、目的とする酸化スズの被覆層を首尾よく形成し得る点から好ましい。例えば、第一段階目の操作として、芯材を含むスラリーにスズ酸ナトリウムを添加し、該スラリーのｐＨを調整することで中和を行い、スズを含む沈殿物を芯材の表面に付着させ、次いで第二段階目の操作として、スラリー中に四塩化スズを添加し、該スラリーのｐＨを調整することで二度目の中和を行い、既にスズの沈殿物が付着している芯材の表面に、別のスズの沈殿物を積層付着させる操作を行う。その後は上述した焼成工程を行い、目的とする導電性粒子を得る。この場合、第一段階目の操作の完了時には、スラリー中にスズイオンは存在していてもよく、あるいは存在していなくてもよい。特に、第一段階目の操作の完了時に、スラリー中にスズイオンが実質的に存在していないことが好ましい。スズイオンが実質的に存在していないとは、スラリー中のスズイオンの濃度が１．５×１０-3ｍｏｌ／Ｌ以下であることを言う。 Under the condition (i), at least two types of compounds are used as the tin compound used as the tin source, and each compound is sequentially used, and each compound is layered on the surface of the core material. As at least two types of tin compounds, for example, sodium stannate and tin tetrachloride can be used. In particular, it is preferable to use sodium stannate as the first-stage compound and use tin tetrachloride as the second-stage compound from the viewpoint that the target tin oxide coating layer can be successfully formed. For example, as the first stage operation, sodium stannate is added to the slurry containing the core material, neutralization is performed by adjusting the pH of the slurry, and the precipitate containing tin is adhered to the surface of the core material. Then, as a second stage operation, tin tetrachloride is added to the slurry, and the slurry is neutralized a second time by adjusting the pH of the slurry. An operation of depositing another tin deposit on the surface is performed. Thereafter, the firing step described above is performed to obtain the desired conductive particles. In this case, at the completion of the first stage operation, tin ions may or may not be present in the slurry. In particular, it is preferable that tin ions are not substantially present in the slurry when the first stage operation is completed. The fact that tin ions are substantially absent means that the concentration of tin ions in the slurry is 1.5 × 10 −3 mol / L or less.
（ii）の条件においては、焼成は、大気等の酸化性雰囲気中で行うこともできるが、非酸化性雰囲気中で行うことが好ましい。非酸化性雰囲気としては、例えば窒素雰囲気やアルゴン雰囲気などの非酸化性且つ非還元性雰囲気、少量の水素を含有した窒素雰囲気等の弱還元性雰囲気等が挙げられる。これらのうち、弱還元性雰囲気を用いると、酸化スズ中に酸素欠損が適度に形成されるので好ましい。特に、弱還元性雰囲気として水素を含有した窒素雰囲気を用いる場合、焼成を二段階の異なる条件で行うことが好ましい。具体的には第一段階目の焼成を、相対的に水素の濃度が低い還元性雰囲気下で行い、第二段階目の焼成を、相対的に水素の濃度が高い還元性雰囲気下で行うことが好ましい。この場合、第一段階目の焼成における雰囲気の水素濃度は、好ましくは０．１体積％以上１．０体積％以下、更に好ましくは０．１体積％以上０．５体積％以下である。一方、第二段階目の焼成における雰囲気の水素濃度は、第一段階目の焼成における雰囲気の水素濃度よりも高いことを条件として、好ましくは２．０体積％以上３．５体積％以下、更に好ましくは２．０体積％以上３．０体積％以下である。このような焼成条件を採用することで、スズを金属に還元させることなく、目的とする酸化スズの被覆層を首尾よく形成することができる。 Under the condition (ii), the calcination can be performed in an oxidizing atmosphere such as air, but is preferably performed in a non-oxidizing atmosphere. Examples of the non-oxidizing atmosphere include a non-oxidizing and non-reducing atmosphere such as a nitrogen atmosphere and an argon atmosphere, and a weak reducing atmosphere such as a nitrogen atmosphere containing a small amount of hydrogen. Among these, it is preferable to use a weakly reducing atmosphere because oxygen vacancies are appropriately formed in tin oxide. In particular, when a nitrogen atmosphere containing hydrogen is used as the weakly reducing atmosphere, the firing is preferably performed under two different conditions. Specifically, the first stage firing is performed in a reducing atmosphere with a relatively low hydrogen concentration, and the second stage firing is performed in a reducing atmosphere with a relatively high hydrogen concentration. Is preferred. In this case, the hydrogen concentration in the atmosphere in the first stage firing is preferably 0.1% by volume or more and 1.0% by volume or less, more preferably 0.1% by volume or more and 0.5% by volume or less. On the other hand, preferably, the hydrogen concentration in the atmosphere in the second stage firing is higher than the hydrogen concentration in the atmosphere in the first stage firing, preferably 2.0% by volume to 3.5% by volume, Preferably they are 2.0 volume% or more and 3.0 volume% or less. By adopting such firing conditions, the target tin oxide coating layer can be successfully formed without reducing tin to metal.
焼成温度は、第一段階目か、第二段階目かによらず、好ましくは４００℃以上９００℃以下、更に好ましくは５００℃以上８００℃以下である。焼成時間も、第一段階目か、第二段階目かによらず、好ましくは２０分以上１２０分以下、更に好ましくは４０分以上１００分以下である。焼成温度及び時間がこれらの範囲内にあると、焼成によって得られる導電性粒子が凝集を起こしにくい。 The firing temperature is preferably 400 ° C. or higher and 900 ° C. or lower, more preferably 500 ° C. or higher and 800 ° C. or lower, regardless of whether it is the first stage or the second stage. The firing time is preferably 20 minutes or longer and 120 minutes or shorter, more preferably 40 minutes or longer and 100 minutes or shorter, regardless of whether it is the first stage or the second stage. When the firing temperature and time are within these ranges, the conductive particles obtained by firing are less likely to aggregate.
このようにして得られた導電性粒子は例えば、プリンタや複写機関連の帯電ローラー、定着ローラー、用紙搬送用ローラー、感光体、トナー、静電ブラシ等の分野、フラットパネルディスプレイ、ＣＲＴ、ブラウン管等の分野、塗料、インク、エマルジョンの分野、静電防止袋・キャリアテープ・カバーテープ等の分野等など、幅広い用途に適用できる。 The conductive particles thus obtained include, for example, fields such as printers and copier-related charging rollers, fixing rollers, paper transport rollers, photoreceptors, toners, electrostatic brushes, flat panel displays, CRTs, cathode ray tubes, etc. It can be applied to a wide range of applications such as coatings, inks, emulsions, antistatic bags, carrier tapes and cover tapes.
また、得られた導電性粒子は、これを含む導電性組成物の状態で好適に用いられる。例えば導電性粒子をバインダ樹脂及び有機溶媒と混合して導電性ペーストとなすことができる。この導電性ペーストには、必要に応じガラスフリット等の他の成分も混合することができる。あるいは、導電性粒子を有機溶媒等と混合してインクとなすことができる。このようにして得られた導電性ペーストやインクを適用対象物の表面に施すことで、所望のパターンを有する導電体を得ることができる。 Moreover, the obtained electroconductive particle is used suitably in the state of the electroconductive composition containing this. For example, conductive particles can be mixed with a binder resin and an organic solvent to form a conductive paste. If necessary, other components such as glass frit can be mixed in the conductive paste. Alternatively, the conductive particles can be mixed with an organic solvent or the like to form an ink. A conductive material having a desired pattern can be obtained by applying the conductive paste and ink thus obtained to the surface of the object to be applied.
以下、実施例により本発明を更に詳細に説明する。しかしながら本発明の範囲は、かかる実施例に制限されない。特に断らない限り、「％」は「質量％」を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to such examples. Unless otherwise specified, “%” means “mass%”.
〔実施例１〕
ＴｉＯ２粒子を芯材として用いた。この芯材はＢＥＴ比表面積が１０ｍ２／ｇであり、透過型電子顕微鏡観察画像をソフトウェアマックビューで画像解析して測定された一次粒子径（Ｆｅｒｅｔ径）が０．２μｍであった。この芯材１５０ｇを水１．５Ｌに分散させてスラリーを得た。このスラリーを７５℃まで加熱した後、２５％水酸化ナトリウム水溶液を滴下して、スラリーのｐＨを１２程度に調整した。次いでスズ酸ナトリウム（Ｎａ２ＳｎＯ３、純度９１％）２００ｇを水４００ｍＬに溶解してなるスズ酸ナトリウム水溶液を全量スラリーに添加した。引き続きスラリーを３０分間撹拌した。次いで、２０％硫酸水溶液を９０分かけて添加してｐＨ２．５まで中和した。この時点で、スラリー中にスズイオンは実質的に存在していなかった。その後、四塩化スズ五水和物（ＳｎＣｌ４・５Ｈ２Ｏ、純度９７％）５０ｇを水１００ｍＬに溶解してなる四塩化スズ水溶液を３０分かけて添加した。この添加中に、２５％水酸化ナトリウム水溶液を滴下し、スラリーのｐＨを２．５に維持した。中和後のスラリーを、ｐＨ２．５及び温度７５℃に保持しながら３時間熟成した。熟成後のスラリーを濾過し、固形分を水で洗浄した。洗浄は水の導電度が２００μＳ／ｃｍまで低下するまで行った後、濾過・乾燥した。得られた乾燥物を、横型チューブ炉で第一還元焼成した。焼成条件は、０．２体積％Ｈ２／Ｎ２雰囲気下で、５００℃、０．５時間とした。引き続き第二還元焼成を行った。焼成条件は、２．０体積％Ｈ２／Ｎ２雰囲気下に、５００℃、１．５時間とした。このようにして目的とする導電性粒子を得た。
[Example 1]
TiO 2 particles were used as the core material. The core material had a BET specific surface area of 10 m 2 / g, and the primary particle diameter (Feret diameter) measured by analyzing the transmission electron microscope observation image with a software Mac view was 0.2 μm. 150 g of this core material was dispersed in 1.5 L of water to obtain a slurry. After heating this slurry to 75 ° C., a 25% aqueous sodium hydroxide solution was added dropwise to adjust the pH of the slurry to about 12. Next, an aqueous sodium stannate solution obtained by dissolving 200 g of sodium stannate (Na 2 SnO 3 , purity 91%) in 400 mL of water was added to the slurry. The slurry was subsequently stirred for 30 minutes. Subsequently, 20% sulfuric acid aqueous solution was added over 90 minutes to neutralize to pH 2.5. At this point, tin ions were not substantially present in the slurry. Was then added over tin tetrachloride pentahydrate (SnCl 4 · 5H 2 O, 97% purity) composed of a 50g dissolved in water 100mL stannic chloride solution for 30 minutes. During this addition, a 25% aqueous sodium hydroxide solution was added dropwise to maintain the pH of the slurry at 2.5. The neutralized slurry was aged for 3 hours while maintaining the pH at 2.5 and the temperature of 75 ° C. The slurry after aging was filtered, and the solid content was washed with water. Washing was performed until the water conductivity decreased to 200 μS / cm, and then filtered and dried. The obtained dried product was subjected to first reduction firing in a horizontal tube furnace. The firing conditions were 500 ° C. and 0.5 hour in a 0.2 vol% H 2 / N 2 atmosphere. Subsequently, second reduction firing was performed. The firing conditions were 500 ° C. and 1.5 hours in a 2.0 volume% H 2 / N 2 atmosphere. In this way, desired conductive particles were obtained.
〔実施例２〕
実施例１において、芯材粒子をＢａＳＯ４とし、二段階の焼成を行わず、それに代えて２．０体積％Ｈ２／Ｎ２雰囲気下で、５００℃、２．０時間の焼成を行った。これ以外は実施例１と同様にして導電性粒子を得た。
[Example 2]
In Example 1, the core particle was BaSO 4 , and the two-stage firing was not performed, but instead, the firing was performed at 500 ° C. for 2.0 hours in a 2.0 volume% H 2 / N 2 atmosphere. . Except this, it carried out similarly to Example 1, and obtained electroconductive particle.
〔実施例３〕
実施例１において、芯材粒子をＢａＳＯ４とし、スズ化合物の添加を二段階で行わず、それに代えてスズ源として四塩化スズ五水和物のみを用いた。このスズ源２９０ｇを５００ｍＬの水に溶解して水溶液を調製し、この水溶液全量をスラリーに添加した。これ以外は実施例１と同様にして導電性粒子を得た。
Example 3
In Example 1, the core particle was BaSO 4 , the tin compound was not added in two steps, and instead only tin tetrachloride pentahydrate was used as the tin source. An aqueous solution was prepared by dissolving 290 g of this tin source in 500 mL of water, and the entire amount of this aqueous solution was added to the slurry. Except this, it carried out similarly to Example 1, and obtained electroconductive particle.
〔実施例４〕
実施例１において、芯材粒子をＳｉＯ２とし、二段焼成を行わず、それに代えて２．０体積％Ｈ２／Ｎ２雰囲気下で、５００℃、２．０時間の焼成を行った。これ以外は実施例１と同様にして導電性粒子を得た。
Example 4
In Example 1, the core material particles were made of SiO 2 , and the two-stage firing was not performed. Instead, firing was performed at 500 ° C. for 2.0 hours in a 2.0 volume% H 2 / N 2 atmosphere. Except this, it carried out similarly to Example 1, and obtained electroconductive particle.
〔実施例５〕
実施例１において芯材粒子をＡｌ２Ｏ３とした。これ以外は実施例１と同様にして導電性粒子を得た。
Example 5
In Example 1, the core particles were Al 2 O 3 . Except this, it carried out similarly to Example 1, and obtained electroconductive particle.
〔実施例６〕
実施例１において芯材粒子をＺｒＯ２とした。これ以外は実施例１と同様にして導電性粒子を得た。
Example 6
In Example 1, the core particles were ZrO 2 . Except this, it carried out similarly to Example 1, and obtained electroconductive particle.
〔実施例７〕
実施例１において、芯材粒子として、一次粒子径が０．０２μｍであるコロイダルシリカを用いた。また、スズ源の第一段階及び第二段階の仕込み量を、表１に示すとおりとした。更に、スズ源の第一段階での仕込み時に、全スズ量（第一段階の仕込み量と第二段階の仕込み量の総和）に対して６.３％のアンチモンを、三塩化アンチモン水溶液の形態で添加した。これら以外は実施例１と同様にして導電性粒子を得た。
Example 7
In Example 1, colloidal silica having a primary particle diameter of 0.02 μm was used as the core material particles. In addition, the amounts charged in the first stage and the second stage of the tin source were as shown in Table 1. Furthermore, when charging the tin source in the first stage, 6.3% of antimony was added to the total amount of tin (total of the first stage charge and the second stage charge) in the form of an antimony trichloride aqueous solution. Added at. Except these, it carried out similarly to Example 1, and obtained electroconductive particle.
〔実施例８〕
実施例１において、芯材粒子として、一次粒子径が０．０５μｍであるコロイダルシリカを用いた。また、スズ源の第一段階及び第二段階の仕込み量を、表１に示すとおりとした。更に、スズ源の第一段階での仕込み時に、全スズ量（第一段階の仕込み量と第二段階の仕込み量の総和）に対して１．９％のリンを、リン酸水溶液の形態で添加した。これら以外は実施例１と同様にして導電性粒子を得た。
Example 8
In Example 1, colloidal silica having a primary particle diameter of 0.05 μm was used as the core material particles. In addition, the amounts charged in the first stage and the second stage of the tin source were as shown in Table 1. Furthermore, when the tin source is charged in the first stage, 1.9% of phosphorus in the form of an aqueous phosphoric acid solution is added to the total tin amount (sum of the first stage charge and the second stage charge). Added. Except these, it carried out similarly to Example 1, and obtained electroconductive particle.
〔実施例９〕
実施例１において、芯材粒子として、一次粒子径が０．０５μｍであるコロイダルシリカを用いた。また、スズ源の第一段階及び第二段階の仕込み量を、表１に示すとおりとした。これら以外は実施例１と同様にして導電性粒子を得た。
Example 9
In Example 1, colloidal silica having a primary particle diameter of 0.05 μm was used as the core material particles. In addition, the amounts charged in the first stage and the second stage of the tin source were as shown in Table 1. Except these, it carried out similarly to Example 1, and obtained electroconductive particle.
〔実施例１０〕
実施例１において、芯材粒子として、一次粒子径が０．０５μｍであるコロイダルアルミナを用いた。また、スズ源の第一段階及び第二段階の仕込み量を、表１に示すとおりとした。これら以外は実施例１と同様にして導電性粒子を得た。
Example 10
In Example 1, colloidal alumina having a primary particle diameter of 0.05 μm was used as the core material particles. In addition, the amounts charged in the first stage and the second stage of the tin source were as shown in Table 1. Except these, it carried out similarly to Example 1, and obtained electroconductive particle.
〔比較例１〕
実施例１において、スズ化合物の添加を二段階で行わず、それに代えてスズ源としてスズ酸ナトリウムのみを用いた。このスズ源１５０ｇを５００ｍＬの水に溶解して水溶液を調製し、この水溶液全量をスラリーに添加した。
また、実施例１において、二段階の焼成を行わず、それに代えて２．０体積％Ｈ２／Ｎ２雰囲気下で、５００℃、２．０時間の焼成を行った。これ以外は実施例１と同様にして導電性粒子を得た。
[Comparative Example 1]
In Example 1, the addition of the tin compound was not performed in two steps, but instead only sodium stannate was used as the tin source. An aqueous solution was prepared by dissolving 150 g of this tin source in 500 mL of water, and the entire amount of this aqueous solution was added to the slurry.
Further, in Example 1, two-stage baking was not performed, and instead, baking was performed at 500 ° C. for 2.0 hours in a 2.0 volume% H 2 / N 2 atmosphere. Except this, it carried out similarly to Example 1, and obtained electroconductive particle.
〔評価〕
実施例及び比較例で得られた導電性粒子について、上述の方法で、被覆層中の酸化スズの結晶子径Ｄ１及び一次粒子径Ｄ２を測定した。また導電性粒子のＢＥＴ比表面積及び粒径Ｄ５０を測定した。更に、以下の方法で導電性粒子の圧粉抵抗を測定した。更に上述の方法で、導電性組成物を調製し、該導電性組成物から形成された導電体の表面抵抗率及びヘイズを、上述の方法で測定した。それらの結果を以下の表２に示す。
[Evaluation]
About the electroconductive particle obtained by the Example and the comparative example, the crystallite diameter D1 and primary particle diameter D2 of the tin oxide in a coating layer were measured with the above-mentioned method. The measured BET specific surface area and particle size D 50 of the conductive particles. Further, the dust resistance of the conductive particles was measured by the following method. Furthermore, the conductive composition was prepared by the above-described method, and the surface resistivity and haze of the conductor formed from the conductive composition were measured by the above-described method. The results are shown in Table 2 below.
〔導電性粒子の圧粉抵抗〕
上述したとおり、圧粉抵抗測定システム（三菱化学ＰＤ−４１）と抵抗率測定器（三菱化学ＭＣＰ−Ｔ６００）を用いて測定した。試料５ｇをプローブシリンダへ投入し、プローブユニットをＰＤ−４１へセットする。油圧ジャッキによって５００ｋｇｆの荷重を印加したときの抵抗値（ペレット直径２５ｍｍ）を、ＭＣＰ−Ｔ６００を用いて測定した。測定した抵抗値と試料厚みから、体積抵抗を算出した。
[Crush resistance of conductive particles]
As above-mentioned, it measured using the dust resistance measuring system (Mitsubishi Chemical PD-41) and the resistivity measuring device (Mitsubishi Chemical MCP-T600). 5 g of the sample is put into the probe cylinder, and the probe unit is set on the PD-41. The resistance value (pellet diameter 25 mm) when a load of 500 kgf was applied by a hydraulic jack was measured using MCP-T600. The volume resistance was calculated from the measured resistance value and sample thickness.
表１及び表２に示す結果から明らかなとおり、実施例１〜１０で得られた導電性粒子を用いて形成された導電体は、比較例１に比べて、電気抵抗が印加電圧に依存しにくいことが判る。また、実施例１〜１０で得られた導電性粒子を用いて形成された導電体は、そのヘイズの値が、比較例１と同程度であるか、又はそれに比べて低いことが判る。特に、微粒の芯材であるコロイダルシリカを用いた実施例７〜１０では、導電体の抵抗が低く、且つヘイズも低いことが判る。 As is clear from the results shown in Tables 1 and 2, the conductor formed using the conductive particles obtained in Examples 1 to 10 has an electric resistance that depends on the applied voltage as compared with Comparative Example 1. It turns out to be difficult. Moreover, it turns out that the conductor formed using the electroconductive particle obtained in Examples 1-10 has the value of the haze which is comparable as the comparative example 1, or is low compared with it. In particular, in Examples 7 to 10 using colloidal silica which is a fine core material, it can be seen that the resistance of the conductor is low and the haze is also low.
Claims (10)
Ｘ線回折測定によりＨａｌｄｅｒ−Ｗａｇｎｅｒ法を使用して算出された前記導電性酸化スズの結晶子径をＤ１とし、透過型電子顕微鏡観察で測定された前記導電性酸化スズの一次粒子径をＤ２としたとき、Ｄ１／Ｄ２の値が０．２以上１．０以下である導電性粒子。 Conductive particles having a core material having an inorganic substance and a coating layer having conductive tin oxide disposed on the surface of the core material,
The crystallite diameter of the conductive tin oxide calculated using the Halder-Wagner method by X-ray diffraction measurement is D1, and the primary particle diameter of the conductive tin oxide measured by transmission electron microscope observation is D2. Conductive particles having a D1 / D2 value of 0.2 or more and 1.0 or less.
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