JP7420762B2 - インク組成物 - Google Patents
インク組成物 Download PDFInfo
- Publication number
- JP7420762B2 JP7420762B2 JP2021085609A JP2021085609A JP7420762B2 JP 7420762 B2 JP7420762 B2 JP 7420762B2 JP 2021085609 A JP2021085609 A JP 2021085609A JP 2021085609 A JP2021085609 A JP 2021085609A JP 7420762 B2 JP7420762 B2 JP 7420762B2
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- JP
- Japan
- Prior art keywords
- silver
- resin
- acid
- group
- meth
- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 40
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 197
- 239000004332 silver Substances 0.000 claims description 197
- 229910052709 silver Inorganic materials 0.000 claims description 190
- 229920002050 silicone resin Polymers 0.000 claims description 110
- 239000002105 nanoparticle Substances 0.000 claims description 78
- 229920005989 resin Polymers 0.000 claims description 76
- 239000011347 resin Substances 0.000 claims description 76
- -1 alkylene glycol monoalkyl ethers Chemical class 0.000 claims description 67
- 229910052751 metal Inorganic materials 0.000 claims description 65
- 239000002184 metal Substances 0.000 claims description 65
- 239000002131 composite material Substances 0.000 claims description 63
- 239000002270 dispersing agent Substances 0.000 claims description 53
- 229920000178 Acrylic resin Polymers 0.000 claims description 51
- 239000004925 Acrylic resin Substances 0.000 claims description 51
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 41
- 229920000642 polymer Polymers 0.000 claims description 41
- 229920002554 vinyl polymer Polymers 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- 239000000084 colloidal system Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 30
- 239000011354 acetal resin Substances 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 29
- 229920006324 polyoxymethylene Polymers 0.000 claims description 29
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 28
- 230000001681 protective effect Effects 0.000 claims description 28
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 26
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 13
- 229920001225 polyester resin Polymers 0.000 claims description 11
- 239000004645 polyester resin Substances 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000010408 film Substances 0.000 description 83
- 239000002932 luster Substances 0.000 description 62
- 239000000178 monomer Substances 0.000 description 55
- 239000000976 ink Substances 0.000 description 43
- 238000003917 TEM image Methods 0.000 description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 40
- 238000000034 method Methods 0.000 description 40
- 239000002253 acid Substances 0.000 description 39
- 239000010410 layer Substances 0.000 description 39
- 239000002082 metal nanoparticle Substances 0.000 description 34
- 229920005906 polyester polyol Polymers 0.000 description 31
- 229920005862 polyol Polymers 0.000 description 31
- 239000000463 material Substances 0.000 description 29
- 229920000180 alkyd Polymers 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 26
- 150000003077 polyols Chemical class 0.000 description 25
- 239000003795 chemical substances by application Substances 0.000 description 23
- 239000006185 dispersion Substances 0.000 description 21
- 239000003921 oil Substances 0.000 description 21
- 235000019198 oils Nutrition 0.000 description 21
- 235000014113 dietary fatty acids Nutrition 0.000 description 20
- 239000000194 fatty acid Substances 0.000 description 20
- 229930195729 fatty acid Natural products 0.000 description 20
- 239000005056 polyisocyanate Substances 0.000 description 20
- 229920001228 polyisocyanate Polymers 0.000 description 20
- 150000004665 fatty acids Chemical class 0.000 description 19
- 229920001577 copolymer Polymers 0.000 description 17
- 238000005191 phase separation Methods 0.000 description 17
- 238000000576 coating method Methods 0.000 description 14
- 230000002209 hydrophobic effect Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 12
- 230000007423 decrease Effects 0.000 description 12
- 239000012528 membrane Substances 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 11
- 150000007513 acids Chemical class 0.000 description 11
- 239000000049 pigment Substances 0.000 description 11
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 239000002344 surface layer Substances 0.000 description 9
- 229910001316 Ag alloy Inorganic materials 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 238000006359 acetalization reaction Methods 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 229910000881 Cu alloy Inorganic materials 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 239000004359 castor oil Substances 0.000 description 7
- 235000019438 castor oil Nutrition 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 239000003760 tallow Substances 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000000737 periodic effect Effects 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 150000005215 alkyl ethers Chemical class 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- 239000000944 linseed oil Substances 0.000 description 5
- 235000021388 linseed oil Nutrition 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 239000003495 polar organic solvent Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 235000019485 Safflower oil Nutrition 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000005713 safflower oil Nutrition 0.000 description 4
- 239000003813 safflower oil Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 235000012424 soybean oil Nutrition 0.000 description 4
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- 239000006228 supernatant Substances 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
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- 229920001567 vinyl ester resin Polymers 0.000 description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
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- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
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- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate trihydrate Substances [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- 239000010685 fatty oil Substances 0.000 description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
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- 238000007127 saponification reaction Methods 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- ZFYIQPIHXRFFCZ-QMMMGPOBSA-N (2s)-2-(cyclohexylamino)butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NC1CCCCC1 ZFYIQPIHXRFFCZ-QMMMGPOBSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- YWWVWXASSLXJHU-AATRIKPKSA-N (9E)-tetradecenoic acid Chemical compound CCCC\C=C\CCCCCCCC(O)=O YWWVWXASSLXJHU-AATRIKPKSA-N 0.000 description 2
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 2
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Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明のインク(またはインキ)組成物(またはコーティング組成物)において、樹脂成分として、非シリコーン系樹脂と、シリコーン系樹脂とを組み合わせることにより、金属光沢性(銀光沢性)と密着性および耐擦過性とを両立できるメカニズムは、以下のように推定できる。
本発明のインク組成物(メタリックインク組成物)は、銀を含む金属と保護コロイドとの複合体ナノ粒子(A)を含む。
銀含有金属ナノ粒子はナノメーターサイズである。銀含有金属ナノ粒子の数平均粒径(数平均一次粒径)は、例えば1~100nm(例えば2~80nm)、好ましくは3~70nm(例えば4~50nm)、さらに好ましくは5~40nm(特に10~30nm)である。
銀を含む金属(銀含有金属)は、銀単体であってもよく、銀と他の金属との合金であってもよい。他の金属としては、銀と合金化できれば特に限定されないが、例えば、Cr、Mo、W、Ni、Pd、Pt、Cu、Au、Zn、In、Sn、Pbなどが挙げられる。これら他の金属は、単独でまたは二種以上組み合わせて使用できる。これら他の金属のうち、Cuが好ましい。
保護コロイドは、分散剤であってもよく、非揮発性分散剤である場合が多い。特に、保護コロイドは、カルボキシル基またはその誘導体基を有する高分子分散剤を含むのが好ましい。なお、本願において、カルボキシル基には、酸無水物基の形態であるカルボキシル基も含まれる。
本発明のインク組成物は、複合体ナノ粒子(A)に加えて、非シリコーン系樹脂(B)をさらに含む。非シリコーン系樹脂は、前記銀含有金属ナノ粒子(特に、複合体ナノ粒子(A))に対して親和性が高いため、後述する親和性が低いシリコーン系樹脂(C)との組み合わせにおいて、膜中に相分離構造を形成できる。
(メタ)アクリル系樹脂(B1)は、特に限定されないが、例えば(メタ)アクリル系単量体の単独または共重合体、(メタ)アクリルポリオール、変性(メタ)アクリル系樹脂であってもよい。
ポリビニルアセタール系樹脂(B2)は、ポリ酢酸ビニルをケン化したポリビニルアルコールと、アルデヒド(特に、n-ブチルアルデヒド)とを反応(アセタール化反応)させて得られる。アセタール化反応において、ポリビニルアルコールを完全にアセタール化(特に、ブチラール化)することはできないため、水酸基が残存し、またケン化の際にも少量のアセチル基が残存するため、ポリビニルアセタール系樹脂(B2)は、構成単位中にアセタール基、水酸基、アセチル基を有している。
ポリエステル系樹脂(B3)は、単量体としてポリカルボン酸とポリオールとを脱水縮合してエステル結合を形成させることによって合成される重合体である。本開示におけるポリエステル系樹脂(B3)(またはポリエステル樹脂)としては、特に限定されないが、ポリエステルポリオール類(B3a)、アルキド樹脂(B3b)などが挙げられる。
アルキド樹脂(B3b)は、塗料分野などで利用される慣用のアルキド樹脂であり、例えば、短油アルキド樹脂、長油アルキド樹脂、変性アルキド樹脂、イソシアネート硬化型アルキド樹脂、エポキシエステル樹脂(エポキシ変性アルキド樹脂)、アルキドポリオール、オイルフリーアルキド樹脂などであってもよい。
本発明のインク組成物は、前記複合体ナノ粒子(A)および非シリコーン系樹脂(B)に加えて、シリコーン系樹脂(C)をさらに含む。シリコーン系樹脂(C)は、前記銀含有金属ナノ粒子(特に、複合体ナノ粒子(A))に対する親和性が非シリコーン系樹脂(B)よりも低いため、前記非シリコーン系樹脂(B)との組み合わせにおいて、膜中に相分離構造を形成できる。
本発明のインク組成物は、前記複合体ナノ粒子(A)、非シリコーン系樹脂(B)およびシリコーン系樹脂(C)に加えて、溶剤(D)をさらに含む。非シリコーン系樹脂(B)およびシリコーン系樹脂(C)に対して溶剤(D)を配合することにより、スピノーダル分解による相分離を促進できるとともに、製膜性も向上できる。
本発明のインク組成物は、前記複合体ナノ粒子(A)、非シリコーン系樹脂(B)、シリコーン系樹脂(C)および溶剤(D)に加えて、硬化剤(E)をさらに含んでいてもよい。硬化剤(E)としては、慣用の硬化剤、例えば、イソシアネート系硬化剤、アミン系硬化剤、酸無水物系硬化剤、イミダゾール系硬化剤などが挙げられる。これらのうち、イソシアネート系硬化剤が好ましく、ポリイソシアネートが特に好ましい。ポリイソシアネートなどのイソシアネート系硬化剤は、非シリコーン系樹脂が官能基(特に、水酸基)を有する場合に特に有効である。
本発明のインク組成物は、前記複合体ナノ粒子(A)、非シリコーン系樹脂(B)、シリコーン系樹脂(C)および溶剤(D)に加えて、他の金属ナノ粒子(F)をさらに含んでいてもよい。他の金属ナノ粒子(F)としては、例えば、周期表第8族金属(鉄、ニッケル、コバルト、ルテニウム、ロジウム、パラジウム、レニウム、イリジウム、白金など)、周期表第1B族金属(銅、金など)、周期表第3B族金属(アルミニウム、ガリウム、インジウムなど)および周期表第4B族金属(ゲルマニウム、スズ、鉛など)などであってもよい。なお、金属(金属原子)は、保護コロイドに対する配位性の高い金属、例えば、周期表第8族金属、周期表第1B族金属などである場合が多い。他の金属ナノ粒子(F)の割合は、前記複合体ナノ粒子(A)の銀含有金属100質量部に対して100質量部以下であり、好ましくは50質量部以下、さらに好ましくは10質量部以下である。
本発明のインク組成物は、本発明の効果を損なわない範囲で、他の成分(G)として、慣用の添加剤、例えば、可塑剤(または造膜助剤)、光沢付与剤、金属腐食防止剤(防錆剤)、安定剤(酸化防止剤、紫外線吸収剤、光安定剤など)、界面活性剤(アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤、特に、アニオン性界面活性剤および/またはノニオン性界面活性剤)、分散安定化剤、増粘剤または粘度調整剤、保湿剤、チクソトロピー性賦与剤、レベリング剤、浸透剤、消泡剤、pH調整剤、キレート剤、表面張力調整剤、着色剤(染顔料など)、色相改良剤、染料定着剤、殺菌剤、防カビ剤、防腐剤、酸素吸収剤などをさらに含んでいてもよい。なお、界面活性剤は、アセチレングリコール系界面活性剤、ポリシロキサン系界面活性剤、フッ素系界面活性剤などであってもよい。これらの添加剤は、単独でまたは二種以上組み合わせて使用できる。他の成分(G)の割合は、前記複合体ナノ粒子(A)の銀含有金属100質量部に対して50質量部以下であり、好ましくは30質量部以下、さらに好ましくは10質量部以下である。
本発明のインク組成物は、前記複合体ナノ粒子(A)、非シリコーン系樹脂(B)、シリコーン系樹脂(C)および溶剤(D)を慣用の方法で混合することにより調製できる。混合方法としては、慣用の攪拌装置を利用でき、例えば、攪拌脱泡装置を利用してもよい。前記複合体ナノ粒子(A)は、ジアルキレングリコールモノアルキルエーテルに分散させた分散液の形態で、非シリコーン系樹脂(B)、シリコーン系樹脂(C)およびアルキレングリコールモノアルキルエーテルと混合してもよい。
銀光沢膜は、被加飾体(基材)の上に前記インク組成物を塗布して塗膜を形成する塗布工程、塗膜を乾燥させてスピノーダル分解による相分離を形成して銀光沢膜を形成する相分離工程を経て得られる。
前記方法で得られた銀光沢膜は、基材(被加飾体)の上に形成されており、前記基材の上に積層され、かつ前記基材の上に積層され、かつ銀を含む金属と保護コロイドとの複合体ナノ粒子(A)で形成された界面層と、この界面層の上に積層され、銀を含む金属と保護コロイドとの複合体ナノ粒子(A)および非シリコーン系樹脂(B)を含む第1相と、銀を含む金属と保護コロイドとの複合体ナノ粒子(A)およびシリコーン系樹脂(C)を含み、銀を含む金属(銀含有金属)の含有割合が前記第1相よりも少ない第2相とに相分離した中間層と、この中間層の上に積層され、かつ銀を含む金属と保護コロイドとの複合体ナノ粒子(A)で形成された表面層とで形成されている。
アクリル樹脂A:東亞合成(株)製「ARUFON UH2170」、スチレンアクリル系樹脂(水酸基含有タイプのアクリル系ポリマー)、不揮発分98%以上、水酸基価88mgKOH/g、ガラス転移温度60℃、重量平均分子量Mw14,000
アクリル樹脂B:DIC(株)製「WVU-120」、イソシアネート硬化型アクリル樹脂(アクリルポリオール)、不揮発分29.5%、水酸基価10.2mgKOH/g
ポリビニルブチラール樹脂:積水化学工業(株)製「エスレックKS-10」、アセタール化度70モル%以上、アセチル基3モル%以下、水酸基25モル%、10質量%溶液粘度(温度20℃、回転粘度型(BM型)、溶媒=トルエン/エタノール=50/50(質量比))10~30mPa・s、ガラス転移温度106℃、重量平均分子量17,000
ポリエステル樹脂:DIC(株)製「ODX-2420」、ポリエステルポリオール、粘度5,600mPa・s(25℃)、平均分子量2,000、酸価0.4mgKOH/g、水酸基価56mgKOH/g
アルキド樹脂:DIC(株)製「D-128-65BA」、イソシアネート硬化型アルキド樹脂、不揮発分65%、水酸基価90mgKOH/g、酸価5.0mgKOH/g
シリコーン樹脂A:信越化学工業(株)製「KR211」、メチルフェニル系シリコーンレジン
シリコーン樹脂B:DOW東レ(株)製「RSN6018」、プロピルフェニル系シリコーンレジン
シリコーン樹脂C:DOW東レ(株)製「RSN0233」、メチルフェニル系シリコーンレジン
エポキシ樹脂:三菱ケミカル(株)製「jER1055」、ビスフェノールF型エポキシ樹脂
硬化剤:DIC(株)製「バーノックDN902S」、イソシアネート化合物
3-メトキシ-3-メチルブタノール:東京化成工業(株)製、沸点174℃
エチルカルビトール:富士フイルム和光純薬(株)製、沸点202℃
酢酸ブチル:富士フイルム和光純薬(株)製、沸点126℃。
アピアランスアナライザー(コニカミノルタジャパン(株)製「Rhopoint IQ-S」)を用い、20°光沢度を測定し、以下の基準に従いランク付け(A、B、C)した。なお、光沢度の値が400以上であると目視で金属光沢(鏡面)を確認することができるため、ランクA、Bを合格とした。
ランクB:光沢度が400以上600未満(合格)
ランクC:光沢度が400未満(不合格)。
紫外可視近赤外分光光度計((株)島津製作所製「UV-3100PC」)、積分球ISR-3100を用い、380~780nmの波長域の可視光透過率を測定した。ブランク測定(大気)の積分値に対する透過率の積分値を、380~780nmの波長域における透過率を積分して求め、以下の基準に従い評価した。ブランク測定に対する透過率の積分値は、小さい方が膜の透過性が低く、優れている。
△:透過率の積分値が1.0%より大きく5.0%以下(合格)
×:透過率の積分値が5.0%より大きい(不合格)。
硬化膜に対し、セロテープ(登録商標)を貼り、勢いよく剥離し、以下の基準で評価した。
×:膜に剥離がある(不合格)。
硬化膜に対し、摩擦摩耗試験機を用い、乾いた木綿で、荷重500gおよび10往復する摩擦試験を行った。摩擦試験後の硬化膜の20°光沢度を測定し、摩擦試験前後での光沢度の低下率を求め、以下の基準に従い耐擦過性を評価した。
△:光沢度の低下率が20%以上50%未満(合格)
×:光沢度の低下率が50%以上(不合格)。
光沢度、光非透過性、密着性、耐擦過性の結果から、優劣判定を行い、A、B判定を合格とした。
B判定:光沢度がランクB、光非透過性、密着性、耐擦過性が合格
C判定:光沢度がランクC、または光非透過性、密着性、耐擦過性のいずれかが不合格。
得られた銀光沢膜から試料を切り出し、汎用の包埋樹脂であるエポキシ樹脂で試料を包埋し、ミクロトームにて切削断面を露出させてSEM観察を行った。さらに、微細な構造観察を行うため、ミクロトームにて切削断面を露出した後、100nm以下程度の厚みで超薄切片を作製し、TEM観察を行なって、以下の方法により、分散相のサイズ(平均径および平均ピッチ)を測定した。
銀ナノ粒子が凝集している分散相(島)について長径と短径を測定し、その平均値を分散相(島)の径とした。そして、任意の10個の分散相(島)について算出した径の平均値を分散相の平均径とした。
分散相の長径と短径との交点を分散相の中心とし、隣接する分散相の中心間の距離を測定した。任意の10カ所について測定した中心間の距離の平均値を、分散相の平均ピッチとした。
(銀ナノ粒子分散液1の調製方法)
硝酸銀66.8g、カルボキシル基を有する高分子分散剤(ビックケミー社製「ディスパービック190」、顔料親和性基を有する高分子量ブロック共重合物の溶液、溶媒:水、不揮発成分40%、酸価10mgKOH/g、アミン価0)7.2gを、イオン交換水100gに投入し、激しく攪拌し、懸濁液を得た。この懸濁液に対して、ジメチルアミノエタノール(和光純薬工業(株)製)100gを水温が50℃を超えないように徐々に加えた後、水温50℃のウォーターバス中で4時間加熱攪拌した。
カルボキシル基を有する高分子分散剤(ビックケミー社製「ディスパービック2015」、顔料親和性基を有するアクリルコポリマーの溶液、溶媒:水、不揮発成分40%、酸価10mgKOH/g、アミン価0)を用いたこと以外は、銀ナノ粒子分散液1と同様に銀ナノ粒子(複合体ナノ粒子)分散液2を調製した。得られた銀ナノ粒子分散液2について、透過型電子顕微鏡(日本電子(株)製)で銀ナノ粒子の粒径を確認したところ、一次粒子の個数平均粒子径は約30nmであった。
硝酸銀65.58g、カルボキシル基を有する高分子分散剤(ビックケミー社製「ディスパービック190」、顔料親和性基を有する高分子量ブロック共重合物の溶液、溶媒:水、不揮発成分40%、酸価10mgKOH/g、アミン価0)7.2gを、イオン交換水100gに投入し、激しく攪拌し、懸濁液Aを得た。
表1~5に示す割合で、得られた複合体ナノ粒子分散液、樹脂、溶剤を、攪拌脱泡装置(クラボウ(株)製「マゼルスター」)を用いて攪拌混合し、メタリックインク組成物を調製した。なお、表のアクリル樹脂および硬化剤の量は、固形分換算の含有量である。メタリックインク組成物をガラス基板に20μmのアプリケーターで塗布した。その後、50℃のホットプレートで10分間加熱後、80℃のホットプレートで120分間加熱した。得られた銀光沢膜の厚み(前記塗膜の乾燥厚み)は約2μmであった。
Claims (7)
- 銀を含む金属と保護コロイドとの複合体ナノ粒子(A)、非シリコーン系樹脂(B)、C 1-4 アルキルC 6-10 アリール系シリコーンレジンを含むシリコーン系樹脂(C)および溶剤(D)を含むインク組成物。
- 前記非シリコーン系樹脂(B)と前記シリコーン系樹脂(C)との質量比が、前者/後者=95/5~5/95である請求項1記載のインク組成物。
- 前記非シリコーン系樹脂(B)および前記シリコーン系樹脂(C)の合計割合が、前記複合体ナノ粒子(A)の銀を含む金属100質量部に対して10~300質量部である請求項1または2記載のインク組成物。
- 前記非シリコーン系樹脂(B)が、水酸基を有する樹脂である請求項1~3のいずれか一項に記載のインク組成物。
- 前記非シリコーン系樹脂(B)が、(メタ)アクリル系樹脂、ポリビニルアセタール系樹脂およびポリエステル系樹脂からなる群より選択された少なくとも1種である請求項1~4のいずれか一項に記載のインク組成物。
- 前記溶剤(D)が、エステル類、アルキレングリコールモノアルキルエーテルおよびジアルキレングリコールモノアルキルエーテルからなる群より選択された少なくとも1種を含む請求項1~5のいずれか一項に記載のインク組成物。
- 前記複合体ナノ粒子(A)が、銀ナノ粒子の表面に保護コロイドが付着または配位した粒子であり、前記銀ナノ粒子の平均粒径が1~100nmであり、かつ前記保護コロイドが、カルボキシル基またはその塩を有する高分子分散剤を含む請求項1~6のいずれか一項に記載のインク組成物。
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WO2016052036A1 (ja) | 2014-10-02 | 2016-04-07 | 株式会社ダイセル | 銀粒子塗料組成物 |
JP2019172955A (ja) | 2018-03-29 | 2019-10-10 | 株式会社リコー | インク、画像形成方法、画像形成装置、及び画像形成物 |
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