JP2009030111A - Silver fine particle colloid-dispersed liquid, and silver film - Google Patents
Silver fine particle colloid-dispersed liquid, and silver film Download PDFInfo
- Publication number
- JP2009030111A JP2009030111A JP2007195519A JP2007195519A JP2009030111A JP 2009030111 A JP2009030111 A JP 2009030111A JP 2007195519 A JP2007195519 A JP 2007195519A JP 2007195519 A JP2007195519 A JP 2007195519A JP 2009030111 A JP2009030111 A JP 2009030111A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- silver fine
- fine particle
- fine particles
- colloidal dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 184
- 239000004332 silver Substances 0.000 title claims abstract description 184
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 239000010419 fine particle Substances 0.000 title claims abstract description 130
- 239000007788 liquid Substances 0.000 title claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 47
- 239000011248 coating agent Substances 0.000 claims abstract description 45
- 239000002270 dispersing agent Substances 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 239000011976 maleic acid Substances 0.000 claims abstract description 14
- 238000001246 colloidal dispersion Methods 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 30
- 238000007641 inkjet printing Methods 0.000 claims description 19
- 239000002932 luster Substances 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 13
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000016615 flocculation Effects 0.000 abstract 1
- 238000005189 flocculation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 34
- 239000007864 aqueous solution Substances 0.000 description 26
- 239000006185 dispersion Substances 0.000 description 23
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 22
- 239000000084 colloidal system Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000010944 silver (metal) Substances 0.000 description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 238000007639 printing Methods 0.000 description 10
- -1 and in particular Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 6
- 239000001509 sodium citrate Substances 0.000 description 6
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- BJINVQNEBGOMCR-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl acetate Chemical compound COCCOCCOC(C)=O BJINVQNEBGOMCR-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 108010015046 cell aggregation factors Proteins 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
本発明は、銀微粒子を溶媒中に分散させた銀微粒子コロイド分散液に係り、特に、金属光沢を有する銀膜を形成するための塗布液（銀膜形成用塗布液）に適用可能な銀微粒子コロイド分散液と、上記塗布液により得られた金属光沢を有する銀膜に関するものである。 The present invention relates to a silver fine particle colloidal dispersion in which silver fine particles are dispersed in a solvent, and in particular, silver fine particles applicable to a coating solution (a coating solution for forming a silver film) for forming a silver film having a metallic luster. The present invention relates to a colloidal dispersion and a silver film having a metallic luster obtained by the coating solution.
従来から、銀微粒子を溶媒に分散させた銀微粒子コロイド分散液は、コンピュータディスプレイの漏洩電磁波防止に用いられる透明導電層形成塗布液（特開平１１−３２９０７１号公報、特開２０００−２６８６３９号公報）や、抗菌コーティング形成塗布液（特開平４−３２１６２８号公報）等として用いられている。また、銀微粒子コロイド分散液の他の用途としては、金属光沢を有する文字や図形等をインクジェット印刷等により紙面上に形成するための塗布液がある（特開２００５−１２０２２６号公報）。この用途では、銀の高い可視光線反射率を活かし、従来の黒、シアン、マゼンダ、イエローの混色による印刷物では実現できなかった金属光沢感に優れる印刷物を可能にしている。 Conventionally, a silver fine particle colloid dispersion liquid in which silver fine particles are dispersed in a solvent is a coating solution for forming a transparent conductive layer used for preventing leakage electromagnetic waves in computer displays (Japanese Patent Laid-Open Nos. 11-329071 and 2000-268639). And an antibacterial coating-forming coating solution (Japanese Patent Laid-Open No. 4-321628). Another application of the silver fine particle colloidal dispersion is a coating liquid for forming characters or figures having metallic luster on a paper surface by ink jet printing or the like (Japanese Patent Laid-Open No. 2005-120226). In this application, the high visible light reflectance of silver is utilized to enable a printed material with excellent metallic luster that could not be realized with a printed material using a conventional mixed color of black, cyan, magenta, and yellow.
ところで、銀微粒子コロイド分散液の製造方法には、（Ａ）銀を減圧下のガス中で蒸発・凝縮させ、分散剤を含んだ溶剤中に回収するガス中蒸発法等の乾式法、（Ｂ）銀塩の水溶液に分散剤等の存在下で還元剤を添加してコロイド状銀微粒子を得る湿式法、が用いられている。一般に、（Ａ）の乾式法は、生産性が悪く、得られる銀微粒子コロイド分散液も非常に高価になるため、（Ｂ）の湿式法が好んで用いられている。 By the way, a method for producing a silver fine particle colloidal dispersion includes (A) a dry method such as a gas evaporation method in which silver is evaporated and condensed in a gas under reduced pressure and recovered in a solvent containing a dispersant; ) A wet method is used in which colloidal silver fine particles are obtained by adding a reducing agent to an aqueous silver salt solution in the presence of a dispersant or the like. In general, the dry method (A) is poor in productivity, and the resulting silver fine particle colloidal dispersion is very expensive. Therefore, the wet method (B) is preferably used.
例えば、湿式法の代表的な銀微粒子コロイド分散液の製造方法として、カレー・リー（Ｃａｒｅｙ−Ｌｅａ）法［Ａｍ. Ｊ. Ｓｃｉ.，３７、３８、４７（１８８９）］がある。Ｃａｒｅｙ−Ｌｅａ法では、硫酸鉄（II）水溶液とクエン酸ナトリウム水溶液の混合液に、硝酸銀水溶液を混合して反応させ、得られた銀微粒子凝集体を濾過・洗浄した後、そのケーキ（cake）に純水を加えることにより、比較的高濃度な銀微粒子コロイド分散液（Ａｇ：０．１〜１０重量％）が得られる。 For example, a typical method for producing a colloidal dispersion of silver fine particles by a wet method is the Carey-Lea method [Am. J. Sci., 37, 38, 47 (1889)]. In the Carey-Lea method, an aqueous solution of iron nitrate (II) and an aqueous solution of sodium citrate is mixed and reacted with an aqueous solution of silver nitrate, and the resulting silver fine particle aggregate is filtered and washed, and then a cake. By adding pure water, a comparatively high concentration silver fine particle colloidal dispersion (Ag: 0.1 to 10% by weight) is obtained.
上記Ｃａｒｅｙ−Ｌｅａ法で得られる銀微粒子は、粒径２〜１５ｎｍの微細なナノコロイド粒子である。しかし、実際の製造過程において、一般に行なわれているバッチ方式では、片方の原料水溶液［例えば、硫酸鉄（II）水溶液とクエン酸ナトリウム水溶液の混合液］が入った容器に他方の原料水溶液［硝酸銀水溶液］を一気に加えるため、液の混合状態が不均一となりやすく、生成する銀微粒子の粒径制御が困難となり、例えば、通常の粒径５〜１５ｎｍ程度の銀微粒子に粒径３０ｎｍ程度の粗大粒子が混入してしまうことがあり、特に処理液量が多い場合に顕著であった。 Silver fine particles obtained by the Carey-Lea method are fine nanocolloid particles having a particle diameter of 2 to 15 nm. However, in an actual manufacturing process, in a batch system generally performed, one raw material aqueous solution [for example, a mixed solution of an iron (II) sulfate aqueous solution and a sodium citrate aqueous solution] is placed in a container containing the other raw aqueous solution [silver nitrate. Since the aqueous solution] is added all at once, the mixed state of the liquid tends to be non-uniform, and the particle size control of the generated silver fine particles becomes difficult. For example, coarse particles having a particle size of about 30 nm are added to the usual silver fine particles of about 5 to 15 nm. Was particularly noticeable when the amount of the treatment liquid was large.
そこで、製造過程での上記原料水溶液同士の混合・反応を均一にして、粒度分布の狭い銀微粒子コロイド液が効率良く得られるようにするため、スタティックミキサー等を用いて原料水溶液の混合・反応状態を一定に保ちながら連続的に銀微粒子を生成させる方法（特開２００４−１８８９１号公報）や、原料水溶液を別々のノズルからそれぞれ吐出させて混合する方法（特開２００４−６８０７２号公報）等が提案されている。 Therefore, the mixing / reaction state of the aqueous raw material solution using a static mixer or the like is performed so that the mixing / reaction of the aqueous raw material solutions can be made uniform and the silver fine particle colloid liquid with a narrow particle size distribution can be obtained efficiently. A method of continuously producing fine silver particles while maintaining the same (Japanese Patent Laid-Open No. 2004-18891), a method of discharging and mixing raw material aqueous solutions from separate nozzles (Japanese Patent Laid-Open No. 2004-68072), etc. Proposed.
そして、これら方法を採用することにより、例えば、小さい粒径では２〜７ｎｍの範囲で、大きい粒径では１０〜１５ｎｍの範囲で、それぞれ粒度分布の狭い銀微粒子コロイド液を得ることが可能になっている。 By adopting these methods, it is possible to obtain a silver fine particle colloidal solution having a narrow particle size distribution, for example, in the range of 2 to 7 nm for a small particle size and in the range of 10 to 15 nm for a large particle size. ing.
ところで、金属光沢を有する文字や図形等を形成するための上記塗布液に用いられる銀微粒子コロイド分散液には、インクジェット印刷時におけるノズル詰まりを防止でき、数ヶ月という長い期間保管された場合でも分散安定性を維持することができ、しかも、印刷後の自然乾燥により金属光沢を有する文字や図形等を形成できることが要請される。更に、特開２００５−１２０２２６号公報に記載されているように、金属光沢を有する印刷物の硫化等に起因した劣化（変色）が起らないようにするため、例えばメルカプトベンゾチアゾール等のメルカプト基含有化合物が銀微粒子コロイド分散液に加えられる必要もある。 By the way, the silver fine particle colloid dispersion used in the coating solution for forming characters and figures having metallic luster can prevent nozzle clogging during ink jet printing, and can be dispersed even when stored for a long period of several months. It is required that stability can be maintained and that characters, figures, and the like having metallic luster can be formed by natural drying after printing. Further, as described in JP-A-2005-120226, in order to prevent deterioration (discoloration) due to sulfurization or the like of a printed matter having a metallic luster, it contains a mercapto group such as mercaptobenzothiazole. It is also necessary that the compound be added to the silver particulate colloidal dispersion.
そして、従来のＣａｒｅｙ−Ｌｅａ法で得られる銀微粒子コロイド液はそれ自体である程度の分散安定性を有しているが、メルカプトベンゾチアゾール等のメルカプト基含有化合物が加えられた場合には、上記分散安定性を失って銀微粒子の凝集が起りやすく、インクジェット印刷用のインク（塗布液）に適用することが困難となる問題があった。 The silver fine particle colloidal solution obtained by the conventional Carey-Lea method itself has a certain degree of dispersion stability. However, when a mercapto group-containing compound such as mercaptobenzothiazole is added, the above dispersion Aggregation of silver fine particles is likely to occur due to loss of stability, and there is a problem that it is difficult to apply to ink for ink jet printing (coating liquid).
尚、特開２００５−１２０２２６号公報では、メルカプトベンゾチアゾール等のメルカプト基含有化合物をインク（塗布液）に加える場合、インク組成物の分散安定性を向上させるため、インク組成物を酸性に向かわせる傾向のある成分を加える前に塩基性物質を加えておいてインク組成物が常に塩基性に保たれる方法を例示しているが、その効果については明らかになっていない。 In JP-A-2005-120226, when a mercapto group-containing compound such as mercaptobenzothiazole is added to the ink (coating liquid), the ink composition is made acidic in order to improve the dispersion stability of the ink composition. An example is given of a method in which a basic substance is always added before adding a component having a tendency to keep the ink composition basic, but the effect is not clear.
このような分散安定性の問題に対して、銀微粒子コロイド分散液に多量の分散剤を添加する方法も考えられる。しかし、銀微粒子コロイド分散液に多量の分散剤が添加されると、分散剤の影響により、形成された文字や図形等の金属光沢感が著しく失われてしまう別の弊害を生ずる問題があった。
本発明はこのような問題点に着目してなされたもので、その課題とするところは、例えメルカプトベンゾチアゾール等のメルカプト基含有化合物が加えられた場合でも銀微粒子の凝集が起り難い銀微粒子コロイド分散液を提供し、合わせてこの銀微粒子コロイド分散液が適用された銀膜形成用塗布液により形成される銀膜を提供することにある。 The present invention has been made paying attention to such problems, and the problem is that, for example, a silver fine particle colloid in which aggregation of silver fine particles hardly occurs even when a mercapto group-containing compound such as mercaptobenzothiazole is added. The object of the present invention is to provide a dispersion and to provide a silver film formed by a coating solution for forming a silver film to which the colloidal dispersion of silver fine particles is applied.
すなわち、請求項１に係る発明は、
溶媒と、この溶媒中に分散した銀微粒子とを主成分とする銀微粒子コロイド分散液を前提とし、
上記銀微粒子の平均粒径が５〜１００ｎｍで、かつ、銀微粒子表面が下記構造式（１）で表されるオレフィン・マレイン酸共重合物系の高分子分散剤で保護されていることを特徴とする。
That is, the invention according to claim 1
Assuming a silver fine particle colloidal dispersion mainly composed of a solvent and silver fine particles dispersed in the solvent,
The average particle diameter of the silver fine particles is 5 to 100 nm, and the surface of the silver fine particles is protected with an olefin / maleic acid copolymer-based polymer dispersant represented by the following structural formula (1). And
請求項１に記載の銀微粒子コロイド分散液を前提とし、
上記高分子分散剤中のカルボン酸基において、総カルボン酸基の内３３〜８０％がアルカリ金属で中和されていることを特徴とし、
請求項３に係る発明は、
請求項１または２に記載の銀微粒子コロイド分散液を前提とし、
上記銀微粒子が、カレー・リー（Ｃａｒｅｙ−Ｌｅａ）法で製造された銀微粒子であることを特徴とする。
Based on the silver fine particle colloidal dispersion according to claim 1,
In the carboxylic acid group in the polymer dispersant, 33 to 80% of the total carboxylic acid group is neutralized with an alkali metal,
The invention according to claim 3
Based on the silver fine particle colloidal dispersion according to claim 1 or 2,
The silver fine particles are silver fine particles produced by the Curry-Lea method.
次に、請求項４に係る発明は、
銀膜形成用塗布液を用いて形成される銀膜を前提とし、
請求項１、２または３に記載の銀微粒子コロイド分散液が適用された銀膜形成用塗布液を塗布・乾燥して形成されたことを特徴とし、
請求項５に係る発明は、
請求項４に記載の銀膜を前提とし、
上記銀膜形成用塗布液の塗布方法が、液滴を吐出させて行うインクジェット印刷法であることを特徴とし、
請求項６に係る発明は、
請求項４または５に記載の銀膜を前提とし、
金属光沢を有することを特徴とする。
Next, the invention according to claim 4 is:
Assuming a silver film formed using a silver film forming coating solution,
The silver fine particle colloid dispersion according to claim 1, 2, or 3 is formed by applying and drying a coating solution for forming a silver film,
The invention according to claim 5
Based on the silver film according to claim 4,
The method for applying the silver film forming coating liquid is an ink jet printing method in which droplets are discharged,
The invention according to claim 6
Based on the silver film according to claim 4 or 5,
It has a metallic luster.
請求項１に記載の発明に係る銀微粒子コロイド分散液によれば、
銀微粒子表面が上記構造式（１）で表されるオレフィン・マレイン酸共重合物系の高分子分散剤で保護されており、上記高分子分散剤を多量に添加しなくても銀微粒子コロイド分散液における分散安定性が大幅に高められている。
According to the silver fine particle colloid dispersion according to the invention of claim 1,
The silver fine particle surface is protected with an olefin / maleic acid copolymer based polymer dispersant represented by the above structural formula (1), and the silver fine particle colloidal dispersion is carried out without adding a large amount of the polymer dispersant. The dispersion stability in the liquid is greatly enhanced.
従って、上記銀微粒子コロイド分散液が適用された銀膜形成用塗布液（インキ）をインクジェット印刷した場合でもノズル詰まりが起こり難く、長期間に亘って保管された場合にも塗布液（インキ）の分散安定性が保持され、更に、銀膜形成用塗布液（インキ）の分散安定性を損なうことなくメルカプト基含有化合物を添加することができるため、形成された銀膜の金属光沢を長期に亘って維持することが可能となる。 Therefore, even when the silver film-forming coating liquid (ink) to which the above-mentioned silver fine particle colloidal dispersion is applied is subjected to inkjet printing, nozzle clogging is unlikely to occur, and the coating liquid (ink) of the coating liquid (ink) can be stored even when stored for a long period of time. Dispersion stability is maintained, and furthermore, since a mercapto group-containing compound can be added without impairing the dispersion stability of the coating liquid (ink) for forming a silver film, the metallic luster of the formed silver film can be maintained over a long period of time. Can be maintained.
以下、本発明の実施の形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
まず、本発明に係る銀微粒子コロイド分散液は、溶媒と、この溶媒中に分散した銀微粒子とを主成分とする銀微粒子コロイド分散液を前提とし、
上記銀微粒子の平均粒径が５〜１００ｎｍで、かつ、銀微粒子表面が下記構造式（１）で表されるオレフィン・マレイン酸共重合物系の高分子分散剤で保護されていることを特徴とする。
First, the silver fine particle colloid dispersion according to the present invention is premised on a silver fine particle colloid dispersion mainly composed of a solvent and silver fine particles dispersed in the solvent.
The silver fine particles have an average particle diameter of 5 to 100 nm, and the surface of the silver fine particles is protected with an olefin / maleic acid copolymer-based polymer dispersant represented by the following structural formula (1). And
このような平均粒径の小さな銀微粒子は、例えば、Ｃａｒｅｙ−Ｌｅａ法で安価に製造することができる。 Such silver fine particles having a small average particle diameter can be produced at low cost by the Carey-Lea method, for example.
まず、Ｃａｒｅｙ−Ｌｅａ法［Ａｍ. Ｊ. Ｓｃｉ.，３７、３８、４７（１８８９）参照］を用いて、粒径の小さい銀微粒子の凝集体が比較的高濃度に含む反応液を調製する。 First, using the Carey-Lea method [Am. J. Sci., 37, 38, 47 (1889)], a reaction liquid containing a relatively high concentration of silver fine particle aggregates having a small particle diameter is prepared.
すなわち、硫酸鉄（II）水溶液とクエン酸ナトリウム水溶液の混合液に、硝酸銀水溶液を混合して銀微粒子を生成させる。 That is, a silver nitrate aqueous solution is mixed with a mixed solution of an iron (II) sulfate aqueous solution and a sodium citrate aqueous solution to form silver fine particles.
この銀微粒子の生成反応は下記化学式（２）のように表される。
Ａｇ＋ ＋Ｆｅ２＋ →Ａｇ＋Ｆｅ３＋ （２）
上記化学式（２）を含む一連の反応は、各原料水溶液の混合後１〜２秒以内に起きる。また、生成した銀微粒子は、共存するクエン酸イオンの保護作用を受けると同時に、高濃度の鉄イオン、ナトリウムイオン等により急速に凝集するため、クエン酸イオンで保護された銀微粒子の凝集体が形成される。
The formation reaction of the silver fine particles is represented by the following chemical formula (2).
Ag + + Fe 2+ → Ag + Fe 3+ (2)
A series of reactions including the above chemical formula (2) occurs within 1 to 2 seconds after the mixing of each raw material aqueous solution. In addition, the produced silver fine particles are protected by the coexisting citrate ions, and at the same time, rapidly aggregate due to high concentrations of iron ions, sodium ions, etc., so the aggregates of silver fine particles protected with citrate ions It is formed.
尚、硫酸鉄（II）水溶液とクエン酸ナトリウム水溶液の混合液に、硝酸銀水溶液を混合する方法としては、バッチ式であっても連続式であってもよく任意である。例えば、スタティックミキサー（機械的可動部分が存在しない混合装置）等を用いて、混合・反応状態を一定に保ちながら、連続的に銀微粒子を生成させることも可能である。 In addition, as a method of mixing a silver nitrate aqueous solution into a mixed solution of an iron (II) sulfate aqueous solution and a sodium citrate aqueous solution, a batch method or a continuous method may be used. For example, using a static mixer (mixing device having no mechanically movable part) or the like, it is possible to continuously generate silver fine particles while keeping the mixing / reaction state constant.
上記反応で得られた銀微粒子の凝集体は、濾過され、銀微粒子凝集体のケーキ（cake）とされる。銀微粒子凝集体の濾過には、メンブレンフィルター濾過、遠心分離、フィルタープレス等の常用の方法を用いることができる。また、銀微粒子が洗い出されない程度の少量の純水でケーキの洗浄を行うことも可能である。 Aggregates of silver fine particles obtained by the above reaction are filtered to obtain a cake of silver fine particle aggregates. Conventional methods such as membrane filter filtration, centrifugation, and filter press can be used for filtration of the silver fine particle aggregates. It is also possible to wash the cake with a small amount of pure water that does not wash out silver particles.
その後、上記銀微粒子凝集体のケーキに純水を加えることにより、銀微粒子コロイド分散液が得られる。銀微粒子凝集体のケーキに純水を加えると、液中の鉄イオンとナトリウムイオンの濃度が大幅に低下するため、凝集要因がなくなり、クエン酸イオンで保護された銀微粒子は液中に再分散して、銀微粒子のコロイド分散液となるのである。このようなコロイド分散液の製造方法は、一般的に洗い出し法と呼ばれている。 Thereafter, pure water is added to the cake of the silver fine particle aggregate to obtain a silver fine particle colloidal dispersion. When pure water is added to the silver fine particle agglomerated cake, the concentration of iron ions and sodium ions in the liquid is greatly reduced, so there is no aggregation factor, and silver fine particles protected with citrate ions are redispersed in the liquid. Thus, a colloidal dispersion of silver fine particles is obtained. Such a method for producing a colloidal dispersion is generally called a washing-out method.
このようにして本発明に適した平均粒径が５〜１００ｎｍである銀微粒子のコロイド分散液が得られる。尚、本発明における粒径とは、透過電子顕微鏡（ＴＥＭ）で観察される銀微粒子の粒径を意味する。 In this way, a colloidal dispersion of silver fine particles having an average particle diameter of 5 to 100 nm suitable for the present invention is obtained. The particle size in the present invention means the particle size of silver fine particles observed with a transmission electron microscope (TEM).
次に、銀微粒子が分散された上記コロイド分散液を用いて、本発明に係る銀微粒子コロイド分散液を製造する方法について説明する。 Next, a method for producing a silver fine particle colloidal dispersion according to the present invention using the colloidal dispersion in which silver fine particles are dispersed will be described.
まず、銀微粒子が分散されたコロイド分散液（銀微粒子濃度：０．１〜１０重量％）を濃縮、洗浄することにより、水の溶媒中に銀微粒子が高濃度に分散した銀微粒子コロイド洗浄濃縮液が得られる。銀微粒子が分散された上記コロイド分散液の濃縮処理は、減圧エバポレーター、限外濾過等の常用の方法で行うことができる。また、洗浄処理としては、透析、電気透析、イオン交換、限外濾過等の方法を用いて行うことができるが、中でも限外濾過法は濃縮処理と洗浄処理を同時に行うことが可能であるため好ましい方法である。 First, a colloidal dispersion liquid (silver fine particle concentration: 0.1 to 10% by weight) in which silver fine particles are dispersed is concentrated and washed, whereby silver fine particle colloid washing and concentration in which silver fine particles are dispersed in a high concentration in a water solvent. A liquid is obtained. The concentration treatment of the colloidal dispersion in which silver fine particles are dispersed can be performed by a common method such as a vacuum evaporator or ultrafiltration. The washing treatment can be performed using methods such as dialysis, electrodialysis, ion exchange, and ultrafiltration. Among them, the ultrafiltration method can perform concentration treatment and washing treatment at the same time. This is the preferred method.
得られた銀微粒子コロイド洗浄濃縮液は、洗浄処理により溶媒中の電解質濃度が低下しているため銀濃度が高い割には比較的安定である。電解質濃度が高い場合には一般にコロイドは電解質で凝集してしまうが、電解質濃度が低い場合には凝集が妨げられるからである。そして、銀微粒子の分散安定性を実用レベルまで高めるため、上記濃縮処理と洗浄処理により、銀微粒子コロイド洗浄濃縮液から銀微粒子を除去した溶媒部分の電気伝導度が５００μＳ（ジーメンス）／ｃｍ以下、好ましくは２００μＳ／ｃｍ以下となるまで、電解質濃度を低下させることが好ましい。 The obtained silver fine particle colloid washing concentrated liquid is relatively stable for a high silver concentration because the electrolyte concentration in the solvent is lowered by the washing treatment. This is because when the electrolyte concentration is high, colloids generally aggregate in the electrolyte, but when the electrolyte concentration is low, aggregation is hindered. In order to increase the dispersion stability of the silver fine particles to a practical level, the electric conductivity of the solvent portion from which the silver fine particles are removed from the silver fine particle colloid washing concentrated liquid by the concentration treatment and the washing treatment is 500 μS (Siemens) / cm or less, It is preferable to reduce the electrolyte concentration until it becomes 200 μS / cm or less.
次に、メルカプト基に対する安定性を上げるため（すなわち、上述したメルカプトベンゾチアゾール等のメルカプト基含有化合物が添加された場合における銀微粒子の分散安定性を維持するため）に高分子分散剤を添加して銀微粒子コロイド分散液を調製する。添加する高分子分散剤は、前記構造式（１）で表されるオレフィン・マレイン酸共重合物系の高分子分散剤が最適で、分子中のカルボン酸が一部アルカリ金属で中和されたものがよい。好ましくは、２０〜９０％、更に好ましくは３０〜８０％がアルカリ金属で中和されていることが望ましい。２０〜９０％の範囲外であると、銀微粒子コロイド分散液が適用された銀膜形成用塗布液において、銀微粒子の安定性が低下し銀微粒子の凝集を生じ易くなる場合がある。 Next, a polymer dispersant is added to increase the stability to mercapto groups (that is, to maintain the dispersion stability of silver fine particles when a mercapto group-containing compound such as mercaptobenzothiazole described above is added). To prepare a silver fine particle colloidal dispersion. As the polymer dispersant to be added, the olefin / maleic acid copolymer polymer dispersant represented by the structural formula (1) is optimal, and the carboxylic acid in the molecule is partially neutralized with an alkali metal. Things are good. Preferably, 20 to 90%, more preferably 30 to 80%, is neutralized with an alkali metal. If the content is outside the range of 20 to 90%, the silver fine particle colloid dispersion may be applied to a silver film forming coating solution, which may reduce the stability of the silver fine particles and easily cause aggregation of the silver fine particles.
オレフィン・マレイン酸共重合物系の上記高分子分散剤としては、花王（株）社製の商品名デモールＥＰや、日本油脂（株）社製の商品名ポリスターＯＭ等が市販されている。添加する分散剤溶液のアルカリ金属量（ｐＨ）を調整するために分散剤溶液のイオン交換を行うことも可能である。 As the above olefin / maleic acid copolymer-based polymer dispersant, a trade name “Demol EP” manufactured by Kao Corporation and a trade name “Polystar OM” manufactured by Nippon Oil & Fats Co., Ltd. are commercially available. In order to adjust the alkali metal amount (pH) of the dispersant solution to be added, it is also possible to perform ion exchange of the dispersant solution.
前記構造式（１）で表されるオレフィン・マレイン酸共重合物系高分子分散剤の添加量は、上記分散剤の分子量にもよるが、銀微粒子に対する重量換算で１／５から１／５０、より好ましくは１／１０〜１／２０がよい。上記高分子分散剤が１／５より多いと、銀微粒子コロイド分散液が適用された銀膜形成用塗布液を用いて形成される塗膜（銀膜）の金属光沢が出にくく、また、上記高分子分散剤が１／５０より少ないと高分子分散剤による分散安定化の効果が少なくなる。 The addition amount of the olefin / maleic acid copolymer polymer dispersant represented by the structural formula (1) depends on the molecular weight of the dispersant, but is 1/5 to 1/50 in terms of weight with respect to silver fine particles. More preferably, it is 1/10 to 1/20. When the amount of the polymer dispersant is more than 1/5, the coating film (silver film) formed using the silver film forming coating liquid to which the silver fine particle colloidal dispersion is applied is less likely to have a metallic luster, When the amount of the polymer dispersant is less than 1/50, the effect of stabilizing the dispersion by the polymer dispersant is reduced.
このようにして得られた銀微粒子コロイド分散液は、そのままでも印刷または塗布は可能であるが、分散液の溶媒が水系であるため、プラスチック等の基材の種類によっては成膜工程においてハジキ等の塗布欠陥を生じる場合がある。このような場合、上記銀微粒子コロイド分散液に有機溶媒を加えてもよい。銀微粒子コロイド分散液の塗布性は、有機溶媒の添加により大幅に改善される。 The silver fine particle colloidal dispersion obtained in this way can be printed or applied as it is, but since the solvent of the dispersion is aqueous, repelling or the like may occur in the film forming process depending on the type of substrate such as plastic. Application defects may occur. In such a case, an organic solvent may be added to the silver fine particle colloidal dispersion. The applicability of the silver fine particle colloidal dispersion is greatly improved by the addition of an organic solvent.
適用される有機溶媒としては、上記銀微粒子コロイド分散液との相溶性、基材に対する溶解性、成膜条件等を考慮して、適宜選定することができる。例えば、メタノール（ＭＡ）、エタノール（ＥＡ）、１−プロパノール（ＮＰＡ）、イソプロパノール（ＩＰＡ）、ブタノール、ペンタノール、ベンジルアルコール、ジアセトンアルコール（ＤＡＡ）等のアルコール系溶媒、アセトン、メチルエチルケトン（ＭＥＫ）、メチルプロピルケトン、メチルイソブチルケトン（ＭＩＢＫ）、シクロヘキサノン、イソホロン等のケトン系溶媒、酢酸エチル、酢酸ブチル、乳酸メチル等のエステル系溶媒、エチレングリコールモノメチルエーテル（ＭＣＳ）、エチレングリコールモノエチルエーテル（ＥＣＳ）、エチレングリコールイソプロピルエーテル（ＩＰＣ）、エチレングリコールモノブチルエーテル（ＢＣＳ）、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、プロピレングリコールメチルエーテル（ＰＧＭ）、プロピレングリコールエチルエーテル（ＰＥ）、プロピレングリコールメチルエーテルアセテート（ＰＧＭ−ＡＣ）、プロピレングリコールエチルエーテルアセテート（ＰＥ−ＡＣ）、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノブチルエーテル等のグリコール誘導体、トルエン、キシレン、メシチレン、ドデシルベンゼン等のベンゼン誘導体、ホルムアミド（ＦＡ）、Ｎ−メチルホルムアミド、ジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミド、ジメチルスルフォキシド(ＤＭＳＯ)、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、γ−ブチロラクトン、エチレングリコール、ジエチレングリコール、テトラヒドロフラン（ＴＨＦ）、クロロホルム等が挙げられるが、これらに限定されるものではない。 The organic solvent to be applied can be appropriately selected in consideration of compatibility with the above-mentioned silver fine particle colloidal dispersion, solubility in the substrate, film forming conditions, and the like. For example, alcohol solvents such as methanol (MA), ethanol (EA), 1-propanol (NPA), isopropanol (IPA), butanol, pentanol, benzyl alcohol, diacetone alcohol (DAA), acetone, methyl ethyl ketone (MEK) , Ketone solvents such as methyl propyl ketone, methyl isobutyl ketone (MIBK), cyclohexanone and isophorone, ester solvents such as ethyl acetate, butyl acetate and methyl lactate, ethylene glycol monomethyl ether (MCS), ethylene glycol monoethyl ether (ECS) ), Ethylene glycol isopropyl ether (IPC), ethylene glycol monobutyl ether (BCS), ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl Ether acetate, propylene glycol methyl ether (PGM), propylene glycol ethyl ether (PE), propylene glycol methyl ether acetate (PGM-AC), propylene glycol ethyl ether acetate (PE-AC), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dip Glycol derivatives such as pyrene glycol monoethyl ether and dipropylene glycol monobutyl ether, benzene derivatives such as toluene, xylene, mesitylene and dodecylbenzene, formamide (FA), N-methylformamide, dimethylformamide (DMF), dimethylacetamide, dimethylsulfate Examples include, but are not limited to, foxoxide (DMSO), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, ethylene glycol, diethylene glycol, tetrahydrofuran (THF), chloroform, and the like.
前記構造式（１）で表されるオレフィン・マレイン酸共重合物系の高分子分散剤が添加された上記銀微粒子コロイド分散液を、水、グリセリン、ジエチレングリコールモノブチルエーテル等の溶剤で更に希釈し、変色防止剤としてメルカプトベンゾチアゾールやそのＮａ塩を添加することにより銀膜形成用塗布液（インクジェット印刷等の印刷または塗布ができるように、銀微粒子の濃度が調整されかつ各種添加剤や溶剤が調合された組成を有する銀微粒子コロイド分散液を、以後、「銀膜形成用塗布液」と称する場合がある）を調製することができる。 The silver fine particle colloidal dispersion added with the olefin / maleic acid copolymer based polymer dispersant represented by the structural formula (1) is further diluted with a solvent such as water, glycerin, diethylene glycol monobutyl ether, Addition of mercaptobenzothiazole or its Na salt as an anti-discoloring agent coating solution for forming a silver film (the concentration of silver fine particles is adjusted and various additives and solvents are prepared so that printing or coating such as inkjet printing can be performed. The silver fine particle colloidal dispersion having the composition described above may be hereinafter referred to as “a silver film forming coating solution”).
そして、上記銀膜形成用塗布液中における銀微粒子の平均粒径は５〜１００ｎｍであることを要する。平均粒子径が１００ｎｍを超えると銀膜形成用塗布液に沈降が起こり易くインクジェット印刷時のノズル詰まりの原因となり、また、粒径が大きいと印刷面の凹凸原因となり良好な金属光沢が得られないことがある。他方、平均粒径が５ｎｍ以下の銀微粒子は商業ベースでの入手が困難である。 And the average particle diameter of the silver fine particle in the said coating liquid for silver film formation needs to be 5-100 nm. If the average particle diameter exceeds 100 nm, the silver film-forming coating solution tends to settle, causing nozzle clogging during ink jet printing, and if the particle diameter is large, it causes unevenness on the printed surface and a good metallic luster cannot be obtained. Sometimes. On the other hand, silver fine particles having an average particle diameter of 5 nm or less are difficult to obtain on a commercial basis.
また、上記銀膜形成用塗布液が塗布される基材は、用途に応じて適宜選択することができる。例えば、紙の表面にアルミナをコートした光沢紙、アクリル（ＰＭＭＡ）、ポリカーボネート（ＰＣ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリエーテルサルフォン（ＰＥＳ）、ポリイミド（ＰＩ）等のプラスチックからなるフィルムまたは板、あるいはガラス板等を用いることができる。また、銀膜形成用塗布液を基材上に印刷または塗布する方法としては、インクジェット印刷以外にも、例えば、スクリーン印刷、グラビア印刷、ワイヤーバーコーティング法、ドクターブレードコーティング法、ロールコーティング法、スピンコーティング法等の各種方式が適用可能である。 Moreover, the base material with which the said coating liquid for silver film formation is apply | coated can be suitably selected according to a use. For example, glossy paper whose surface is coated with alumina, acrylic (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyimide (PI), etc. A plastic film or plate, a glass plate, or the like can be used. In addition to inkjet printing, for example, screen printing, gravure printing, wire bar coating, doctor blade coating, roll coating, spin coating, and other methods for printing or coating a silver film-forming coating solution on a substrate. Various methods such as a coating method can be applied.
以下、本発明の実施例を具体的に説明するが、本発明はこれ等の実施例に限定されるものではない。また、本文中の「％」は「重量％」を示し、「部」は「重量部」を示している。 Examples of the present invention will be specifically described below, but the present invention is not limited to these examples. Further, “%” in the text indicates “% by weight”, and “part” indicates “part by weight”.
２３．１％硫酸鉄（ＦｅＳＯ４・７Ｈ２Ｏ）水溶液２０８ｇと３７．５％クエン酸ナトリウム［Ｃ３Ｈ４(ＯＨ)(ＣＯＯＮａ)３・２Ｈ２Ｏ］水溶液２５６ｇの混合液に、９．１％硝酸銀（ＡｇＮＯ３）水溶液１７６ｇを混合かつ反応させ、銀微粒子の凝集体を含む反応液を得た。尚、硫酸鉄水溶液とクエン酸ナトリウム水溶液の混合液、および、硝酸銀水溶液の液温は、それぞれ２０℃と１０℃に設定した。 23.1% iron sulfate (FeSO 4 · 7H 2 O) aqueous solution 208g and 37.5% sodium citrate [C 3 H 4 (OH) (COONa) 3 · 2H 2 O] a mixture of aqueous 256 g, 9. 176 g of 1% silver nitrate (AgNO 3 ) aqueous solution was mixed and reacted to obtain a reaction solution containing an aggregate of silver fine particles. The liquid temperature of the iron sulfate aqueous solution and sodium citrate aqueous solution and the silver nitrate aqueous solution were set to 20 ° C. and 10 ° C., respectively.
上記反応液から銀微粒子の凝集体を遠心分離機で濾別して銀微粒子凝集体のケーキを得ると共に、このケーキに純水を加えて洗い出しを行い、銀微粒子が分散されたコロイド分散液（Ａｇ：０．８５％）を得た。 A silver fine particle aggregate cake is obtained by filtering the silver fine particle agglomerate from the reaction solution with a centrifugal separator, and the cake is washed by adding pure water to the colloidal dispersion liquid (Ag: Ag: 0.85%).
このようにして得られたコロイド分散液中の銀微粒子は、その平均粒径が７．５ｎｍであり、粒径５〜１０ｎｍの粒状の銀微粒子が全体の９０％以上を占める粒度分布のものであった。尚、銀微粒子の粒径測定は、銀微粒子コロイド液の透過電子顕微鏡（ＴＥＭ）観察によって行った。 The silver fine particles in the colloidal dispersion thus obtained have an average particle size of 7.5 nm and a particle size distribution in which granular silver fine particles having a particle size of 5 to 10 nm account for 90% or more of the total. there were. The particle size of the silver fine particles was measured by observing the silver fine particle colloid liquid with a transmission electron microscope (TEM).
次に、銀微粒子が分散された上記コロイド分散液を、限外濾過により濃縮、洗浄することによって銀微粒子コロイド洗浄濃縮液（Ａｇ：２５％、残部：水）を得た。 Next, the colloidal dispersion liquid in which silver fine particles were dispersed was concentrated and washed by ultrafiltration to obtain a silver fine particle colloid washing concentrated liquid (Ag: 25%, balance: water).
他方、マレイン酸とイソブチレンの共重合体のナトリウム塩の１０％水溶液を、カチオンイオン交換樹脂で処理することによって、カルボキシル基（ＣＯＯＨ）の水素の一部がナトリウムで置換（ＣＯＯＮａ；水を含む溶液中ではＣＯＯ−＋Ｎａ＋）された高分子分散剤（重量平均分子量[Ｍｗ]＝６５００、ＣＯＯＨ／ＣＯＯＮａ＝２０／８０）の水溶液を調製した。尚、ナトリウムの置換量は液のナトリウム分析値から求めた。 On the other hand, a 10% aqueous solution of a sodium salt of a copolymer of maleic acid and isobutylene is treated with a cation ion exchange resin so that part of the hydrogen of the carboxyl group (COOH) is replaced with sodium (COONa; water-containing solution) Among them, an aqueous solution of a polymer dispersant (weight average molecular weight [Mw] = 6500, COOH / COONa = 20/80) formed as COO − + Na + was prepared. The amount of sodium substitution was determined from the sodium analysis value of the solution.
そして、上述した銀微粒子コロイド洗浄濃縮液（Ａｇ：２５％、残部：水）に、上記高分子分散剤の水溶液と水を加えて、高分子分散剤で保護された実施例１に係る銀微粒子コロイド分散液（Ａｇ：２０％、高分子分散剤：２％、残部：水）を製造した。 Then, the silver fine particles according to Example 1 protected by the polymer dispersant by adding the aqueous solution of the polymer dispersant and water to the above-described silver fine particle colloid washing concentrate (Ag: 25%, balance: water). A colloidal dispersion (Ag: 20%, polymer dispersant: 2%, balance: water) was produced.
次に、製造された上記銀微粒子コロイド分散液に、グリセリン、エチレングリコールモノブチルエーテル、水、メルカプトベンゾチアゾールのＮａ塩をそれぞれ加え、銀膜形成用塗布液（Ａｇ：３％、高分子分散剤：０．３％、グリセリン：２３．２％、エチレングリコールモノブチルエーテル：１０％、メルカプトベンゾチアゾールのＮａ塩：０．３７５％、Ｈ２Ｏ：残部）を調製した。 Next, glycerin, ethylene glycol monobutyl ether, water, and Na salt of mercaptobenzothiazole are added to the produced silver fine particle colloidal dispersion, respectively, and a silver film forming coating solution (Ag: 3%, polymer dispersant: 0.3%, glycerin: 23.2%, ethylene glycol monobutyl ether: 10%, mercaptobenzothiazole Na salt: 0.375%, H 2 O: balance).
この銀膜形成用塗布液をインクカートリッジに詰め、家庭用インクジェットプリンター（キャノン社製、ＰＩＸＵＳ５６０ｉ）を用いてインクジェット印刷用光沢紙に印字し、銀色の金属光沢を有する実施例１に係る銀膜（印字）が得られた。 This silver film-forming coating solution is packed in an ink cartridge, printed on glossy paper for inkjet printing using a household inkjet printer (PIXUS560i, manufactured by Canon Inc.), and the silver film according to Example 1 having a silver metallic gloss ( Print).
そして、インクジェット印刷による印字はノズルが詰まることはなく、３ヶ月以上たっても問題なく印字を行うことができた。尚、銀膜形成用塗布液の粘度（２３℃）は、３ｍＰａ・ｓであった。また、銀膜形成用塗布液の粘度は、山一電機（株）社製の振動式粘度計ＶＭ−１００−Ｌを用いて測定した。 In addition, printing by ink jet printing did not clog the nozzles, and printing could be performed without problems even after 3 months or more. In addition, the viscosity (23 degreeC) of the coating liquid for silver film formation was 3 mPa * s. Moreover, the viscosity of the coating solution for forming a silver film was measured using a vibration viscometer VM-100-L manufactured by Yamaichi Electronics Co., Ltd.
次に、インクジェット印刷により印字された光沢紙を大気中に２週間放置したが、大きな変色はなく金属光沢感が維持されていた。また、得られた銀膜（印字）を指先で軽く擦って膜の傷を目視観察し、密着力評価を行ったところ良好であった。 Next, glossy paper printed by ink jet printing was left in the atmosphere for 2 weeks, but there was no significant discoloration and the metallic gloss was maintained. Further, the obtained silver film (printing) was lightly rubbed with a fingertip and the film scratches were visually observed to evaluate the adhesion, which was satisfactory.
上記マレイン酸とイソブチレンの共重合体のナトリウム塩に対するカチオンイオン交換樹脂の処理条件を変えて、カルボキシル基（ＣＯＯＨ）の水素の一部がナトリウムで置換（ＣＯＯＮａ；水を含む溶液中ではＣＯＯ−＋Ｎａ＋）された高分子分散剤（重量平均分子量[Ｍｗ]＝６５００、ＣＯＯＨ／ＣＯＯＮａ＝６７／３３）の水溶液を調製した。 By changing the treatment conditions of the cation ion exchange resin for the sodium salt of the maleic acid and isobutylene copolymer, a part of the hydrogen of the carboxyl group (COOH) is replaced with sodium (COONa; in a solution containing water, COO − + Na + ) An aqueous solution of a polymer dispersant (weight average molecular weight [Mw] = 6500, COOH / COONa = 67/33) was prepared.
そして、実施例１の銀微粒子コロイド洗浄濃縮液（Ａｇ：２５％、残部：水）に、上記高分子分散剤の水溶液と水を加えて、高分子分散剤で保護された実施例２に係る銀微粒子コロイド分散液（Ａｇ：２０％、高分子分散剤：２％、残部：水）を製造した。 Then, the aqueous solution of the above polymer dispersant and water were added to the silver fine particle colloid washing concentrated liquid of Example 1 (Ag: 25%, balance: water), and Example 2 was protected with the polymer dispersant. A silver fine particle colloidal dispersion (Ag: 20%, polymer dispersant: 2%, balance: water) was produced.
次に、製造された銀微粒子コロイド分散液を用いて実施例１と同様にして銀膜形成用塗布液を調製し、かつ、この銀膜形成用塗布液をインクカートリッジに詰め、上記家庭用インクジェットプリンターを用いてインクジェット印刷用光沢紙に印字し、銀色の金属光沢を有する実施例２に係る銀膜（印字）が得られた。 Next, a silver film-forming coating solution is prepared using the produced silver fine particle colloidal dispersion in the same manner as in Example 1, and this silver film-forming coating solution is filled in an ink cartridge, and the above-mentioned household inkjet Printing on glossy paper for inkjet printing using a printer gave a silver film (printing) according to Example 2 having a silver metallic luster.
そして、インクジェット印刷による印字はノズルが詰まることはなく、３ヶ月以上たっても問題なく印字を行うことができた。尚、銀膜形成用塗布液の粘度（２３℃）は、３ｍＰａ・ｓであった。 In addition, printing by ink jet printing did not clog the nozzles, and printing could be performed without problems even after 3 months or more. In addition, the viscosity (23 degreeC) of the coating liquid for silver film formation was 3 mPa * s.
次に、インクジェット印刷により印字された光沢紙を大気中に２週間放置したが、大きな変色はなく金属光沢感が維持されていた。 Next, glossy paper printed by ink jet printing was left in the atmosphere for 2 weeks, but there was no significant discoloration and the metallic gloss was maintained.
［比較例１］
実施例１の銀微粒子コロイド洗浄濃縮液（Ａｇ：２５％、残部：水）に、直接、グリセリン、エチレングリコールモノブチルエーテル、水、メルカプトベンゾチアゾールのＮａ塩を加えて、銀膜形成用塗布液（Ａｇ：３％、グリセリン：２３．２％、エチレングリコールモノブチルエーテル：１０％、メルカプトベンゾチアゾールのＮａ塩：０．３７５％、Ｈ２Ｏ：残部）を調製した。すなわち、オレフィン・マレイン酸共重合物系の高分子分散剤で保護されていない銀微粒子のコロイド分散液を用いて、銀膜形成用塗布液を調製した。
[Comparative Example 1]
To the silver fine particle colloid washing concentrated liquid of Example 1 (Ag: 25%, balance: water), glycerin, ethylene glycol monobutyl ether, water, and Na salt of mercaptobenzothiazole were directly added to form a silver film-forming coating liquid ( Ag: 3% glycerin: 23.2%, ethylene glycol monobutyl ether: 10% Na salt of mercaptobenzothiazole: 0.375% H 2 O: balance) was prepared. That is, a silver film-forming coating solution was prepared using a colloidal dispersion of silver fine particles not protected with an olefin / maleic acid copolymer polymer dispersant.
しかし、メルカプトベンゾチアゾールのＮａ塩の添加により銀微粒子コロイド分散液内の銀微粒子が凝集したため、安定した銀膜形成用塗布液を調製することができず、インクジェット印刷による印字を行えなかった。 However, the addition of the Na salt of mercaptobenzothiazole aggregated the silver fine particles in the silver fine particle colloidal dispersion, so that a stable coating solution for forming a silver film could not be prepared, and printing by ink jet printing could not be performed.
そして、実施例１〜２と比較例１の結果から、銀微粒子の表面をオレフィン・マレイン酸共重合物系の高分子分散剤で保護しない場合、調製される銀膜形成用塗布液の安定性が非常に悪く、インクジェット印刷を行えないことが確認された。 From the results of Examples 1 and 2 and Comparative Example 1, the stability of the coating solution for forming a silver film is prepared when the surface of the silver fine particles is not protected with an olefin / maleic acid copolymer polymer dispersant. It was confirmed that ink jet printing cannot be performed.
本発明の銀微粒子コロイド分散液によれば、銀微粒子表面が前記構造式（１）で表されるオレフィン・マレイン酸共重合物系の高分子分散剤で保護されており、上記高分子分散剤を多量に添加しなくても銀微粒子コロイド分散液における分散安定性が大幅に高められている。従って、金属光沢を有する銀膜を形成するための銀膜形成用塗布液に適用される産業上の利用可能性を有している。 According to the silver fine particle colloid dispersion of the present invention, the surface of the silver fine particles is protected with the olefin / maleic acid copolymer-based polymer dispersant represented by the structural formula (1). Even if a large amount of is not added, the dispersion stability in the colloidal dispersion of silver fine particles is greatly improved. Therefore, it has industrial applicability applied to a silver film forming coating solution for forming a silver film having a metallic luster.
Claims (6)
上記銀微粒子の平均粒径が５〜１００ｎｍで、かつ、銀微粒子表面が下記構造式（１）で表されるオレフィン・マレイン酸共重合物系の高分子分散剤で保護されていることを特徴とする銀微粒子コロイド分散液。
The silver fine particles have an average particle diameter of 5 to 100 nm, and the surface of the silver fine particles is protected with an olefin / maleic acid copolymer-based polymer dispersant represented by the following structural formula (1). A silver fine particle colloidal dispersion.
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