CN118120032A - Paste for electronic component - Google Patents
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- Publication number
- CN118120032A CN118120032A CN202280070299.0A CN202280070299A CN118120032A CN 118120032 A CN118120032 A CN 118120032A CN 202280070299 A CN202280070299 A CN 202280070299A CN 118120032 A CN118120032 A CN 118120032A
- Authority
- CN
- China
- Prior art keywords
- binder
- paste
- cellulose
- dispersant
- terminal
- 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
- 239000011230 binding agent Substances 0.000 claims abstract description 119
- 239000002270 dispersing agent Substances 0.000 claims abstract description 78
- 229920002678 cellulose Polymers 0.000 claims abstract description 73
- 239000001913 cellulose Substances 0.000 claims abstract description 73
- 239000000919 ceramic Substances 0.000 claims abstract description 61
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 60
- 239000010954 inorganic particle Substances 0.000 claims abstract description 58
- 239000002245 particle Substances 0.000 claims abstract description 42
- 150000007942 carboxylates Chemical group 0.000 claims abstract description 31
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 92
- 239000001856 Ethyl cellulose Substances 0.000 claims description 91
- 229920001249 ethyl cellulose Polymers 0.000 claims description 91
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 91
- 229920001577 copolymer Polymers 0.000 claims description 46
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 11
- 239000002923 metal particle Substances 0.000 claims description 10
- 229920003086 cellulose ether Polymers 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- 229920000896 Ethulose Polymers 0.000 claims description 2
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 48
- 229910052759 nickel Inorganic materials 0.000 abstract description 16
- 238000001179 sorption measurement Methods 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 23
- 239000000843 powder Substances 0.000 description 23
- 238000005481 NMR spectroscopy Methods 0.000 description 21
- 239000000853 adhesive Substances 0.000 description 21
- 230000001070 adhesive effect Effects 0.000 description 21
- 230000007847 structural defect Effects 0.000 description 20
- HBNHCGDYYBMKJN-UHFFFAOYSA-N 2-(4-methylcyclohexyl)propan-2-yl acetate Chemical compound CC1CCC(C(C)(C)OC(C)=O)CC1 HBNHCGDYYBMKJN-UHFFFAOYSA-N 0.000 description 18
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 17
- 239000011354 acetal resin Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 229920006324 polyoxymethylene Polymers 0.000 description 17
- 229920002554 vinyl polymer Polymers 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 15
- 238000005227 gel permeation chromatography Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000004793 Polystyrene Substances 0.000 description 11
- -1 Trimethylsilyl (TMS) Chemical class 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 229920002223 polystyrene Polymers 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 9
- 229910002113 barium titanate Inorganic materials 0.000 description 8
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 8
- 238000007046 ethoxylation reaction Methods 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 239000003985 ceramic capacitor Substances 0.000 description 7
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 7
- 238000001212 derivatisation Methods 0.000 description 7
- 229960003750 ethyl chloride Drugs 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003522 acrylic cement Substances 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 6
- 125000004185 ester group Chemical group 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 6
- 230000007717 exclusion Effects 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 229920005822 acrylic binder Polymers 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000008034 disappearance Effects 0.000 description 5
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000006266 etherification reaction Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical group CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- FRQDZJMEHSJOPU-UHFFFAOYSA-N Triethylene glycol bis(2-ethylhexanoate) Chemical compound CCCCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CCCC FRQDZJMEHSJOPU-UHFFFAOYSA-N 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 238000006200 ethylation reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-M sodium 2-anthraquinonesulfonate Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)[O-])=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-M 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010947 wet-dispersion method Methods 0.000 description 2
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical class ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XCOBLONWWXQEBS-KPKJPENVSA-N N,O-bis(trimethylsilyl)trifluoroacetamide Chemical compound C[Si](C)(C)O\C(C(F)(F)F)=N\[Si](C)(C)C XCOBLONWWXQEBS-KPKJPENVSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000205 poly(isobutyl methacrylate) Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- PDKSBUDYYWLQGH-UHFFFAOYSA-N propan-2-yl 2-[benzyl-[2-[benzyl-(2-oxo-2-propan-2-yloxyethyl)amino]ethyl]amino]acetate Chemical group C=1C=CC=CC=1CN(CC(=O)OC(C)C)CCN(CC(=O)OC(C)C)CC1=CC=CC=C1 PDKSBUDYYWLQGH-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000009681 x-ray fluorescence measurement Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Conductive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Ceramic Capacitors (AREA)
Abstract
The present invention provides a paste for electronic components, which contains a dispersant and a binder capable of improving the adhesion between inorganic particles such as nickel particles and ceramic particles without increasing the amount of the binder. The paste for electronic components of the present invention comprises inorganic particles (1), a dispersant (2), binders (4, 5) and an organic solvent, wherein the binder comprises a1 st binder (5) adsorbed on the surface of the inorganic particles (1), and a2 nd binder (4) not adsorbed on the surface of the inorganic particles (1), and at least the 1 st binder (5) is a cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate.
Description
Technical Field
The present invention relates to a paste for electronic components, which contains inorganic particles, a dispersant, a binder and an organic solvent, and is used for manufacturing electronic components, and more particularly, to an improvement of the binder.
Background
For example, japanese patent application laid-open No. 2018-168838 (patent document 1) describes a conductive paste, which is a paste for electronic components, that is, a paste for electronic components that can be used to form internal electrodes in a laminated ceramic capacitor as electronic components. The conductive paste contains a conductive powder, an organic resin (hereinafter referred to as a "binder"), an organic solvent, an additive, and a dielectric powder, the binder is composed of ethyl cellulose alone, the organic solvent is composed of terpineol alone, and the additive contains a composition containing an unsaturated carboxylic acid-based dispersant and an oleylamine-based dispersant. In patent document 1, a nickel powder is exemplified as the conductive powder, and a ceramic powder is exemplified as the dielectric powder.
In the conductive paste, the content of the unsaturated carboxylic acid-based dispersant in the additive is 0.2 mass% or more and 1.2 mass% or less relative to the total amount of the conductive paste, and the content of the oleylamine-based dispersant in the same additive is 0.3 mass% or more and 2.0 mass% or less relative to the total amount of the conductive paste.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2018-168838
Disclosure of Invention
Problems to be solved by the invention
In general, cellulose is known to have hydroxyl groups on one non-reducing terminal side and hydroxyl groups tautomeric with formyl groups on the other reducing terminal side. The ethylcellulose as the binder can be easily estimated that the terminal hydroxyl groups are mostly ethoxylated by the known production process. Therefore, it is considered that one end (corresponding to the non-reducing end side of cellulose) of a general ethylcellulose is ethoxy, and the other end (corresponding to the reducing end side of cellulose) is ethoxy or formyl.
Since a general dispersant has an alkyl chain, an ether chain or an ester chain, the dispersant has a weak adhesion to ethylcellulose. In addition, in the conductive paste, not all of the ethylcellulose as the binder is adsorbed to inorganic particles such as nickel particles and ceramic particles, and ethylcellulose that is not adsorbed to any inorganic particles is also present.
Therefore, the adhesion force at the interface between the dispersant adsorbed on the surface of the inorganic particles and the ethylcellulose not adsorbed on the surface of the inorganic particles is reduced, and as a result, the adhesion force between the inorganic particles, more specifically, between the nickel particles, between the ceramic particles, or between the nickel particles and the ceramic particles in the conductive paste is reduced. In this case, in the production process of the multilayer ceramic capacitor, there is a tendency that the nickel particles in the internal electrode are broken by aggregation (separation in the internal electrode layer) between each other, between ceramic particles, or between nickel particles and ceramic particles. Since the internal electrode is likely to be broken by aggregation, peeling of the internal electrode layer occurs during press-cutting of the laminate before firing, delamination of the laminated ceramic capacitor after firing, and deterioration of moisture resistance of the laminated ceramic capacitor after baking of the external electrode, etc., it is required that the internal electrode is as free of aggregation as possible.
There is also a method of increasing the amount of ethylcellulose as a binder in order to improve the inter-particle adhesion. However, if the binder amount is increased, the filling rate of nickel particles in the internal electrode coating film decreases, and after firing, the internal electrode coverage decreases.
On the other hand, if the conductive paste does not contain a dispersant, the interface with weak adhesion can be eliminated. However, without a dispersant, it is difficult to ensure dispersibility of the conductive paste.
Therefore, it is required to contain a dispersant and to improve the adhesion between inorganic particles such as nickel particles and ceramic particles without increasing the amount of binder.
Accordingly, an object of the present invention is to provide a paste for electronic components which satisfies the above-mentioned requirements.
Means for solving the problems
The invention is characterized in that: the present invention relates to a paste for electronic components, which comprises inorganic particles, a dispersant, a binder and an organic solvent, wherein the binder comprises a1 st binder adsorbed on the surfaces of the inorganic particles and a2 nd binder not adsorbed on the surfaces of the inorganic particles, and at least the 1 st binder is a cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the paste for electronic parts of the present invention, even if the adhesive force at the interface between the dispersant adsorbed on the surface of the inorganic particles and the 2 nd binder not adsorbed on the inorganic particles is low, the adhesive force at the interface between the cellulose derivative having a single terminal carboxyl group or a single terminal carboxylate as the 1 st binder adsorbed on the surface of the inorganic particles and the 2 nd binder not adsorbed on the surface of the inorganic particles is high. As a result, the adhesion between the inorganic particles is improved by the higher adhesion at the interface of the 1 st adhesive and the 2 nd adhesive as described above as a whole. Therefore, when the present invention is applied to a conductive paste for internal electrodes used in the production of a laminated ceramic capacitor, for example, it is possible to prevent the occurrence of aggregation failure (peeling in the internal electrode layer) between metal particles, between ceramic particles, or between metal particles and ceramic particles.
Drawings
Fig. 1 is a diagram schematically showing the effects of the paste for electronic parts of the present invention, in the case where the paste for electronic parts contains the comb-shaped polymer dispersant 2, (a) the inorganic particles 1 are adsorbed with the dispersant 2 alone, and (B) the inorganic particles 1 are adsorbed with the dispersant 2 and the 1 st binder 5.
Fig. 2 is a diagram schematically showing the effects of the paste for electronic parts of the present invention, in the case where the low-molecular dispersant 3 is contained, (a) the inorganic particles 1 are adsorbed with only the dispersant 3, and (B) the inorganic particles 1 are adsorbed with the dispersant 3 and the 1 st binder 5.
FIG. 3 is a chart showing 1 H-NMR spectra of ethylcellulose derivative products.
Fig. 4 is a graph showing the correlation between the molecular weight of ethylcellulose obtained by NMR and the molecular weight of ethylcellulose obtained by GPC.
Detailed Description
The paste for electronic components of the present invention comprises inorganic particles, a dispersant, a binder and an organic solvent. The binder includes a1 st binder adsorbed on the surfaces of the inorganic particles and a2 nd binder not adsorbed on the surfaces of the inorganic particles. At least the 1 st binder is a cellulose derivative having a single terminal carboxyl group or a single terminal carboxylate.
Here, it is noted that the cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate as the 1 st binder has a size of several tens to several hundreds nm longer than the steric exclusion portion (side chain in the case of a comb-shaped dispersant, main chain in the case of a single-terminal adsorption dispersant) of the dispersant. The molecular weight Mn of the cellulose derivative in terms of polystyrene is generally about 10000 to 90000, and the size thereof is about 25 to 225 nm.
At the time of paste, the dispersant is generally adsorbed on the particle surface to form a layer of molecular chains of several nm (corresponding to the length of the side chains in the case of a high molecular dispersant and the length of the main chain in the case of a low molecular dispersant), thereby achieving dispersion stabilization by wetting with a solvent or steric repulsion. However, at the time point of drying the film, the compatibility between the three-dimensional repulsive portion (side chain in the case of comb-shaped dispersant, main chain in the case of single-terminal adsorption dispersant) of several nm in the dispersant and the interface of the adhesive is poor, and thus, there is a problem that the adhesion is lowered. The reason for this is presumed to be: since the dispersing agent forms steric exclusion portions by disposing molecular chains at narrow intervals on the particle surface, it is difficult to exhibit adhesion between the binder and the molecular chains of the dispersing agent due to steric constraints.
The above state will be described with reference to fig. 1 and 2. In fig. 1a, a comb-shaped polymer dispersant (hereinafter referred to as "polymer dispersant") 2 is adsorbed on the surface of an inorganic particle 1. In fig. 2a, a low-molecular one-terminal adsorption dispersant (hereinafter referred to as "low-molecular dispersant") 3 is adsorbed on the surface of an inorganic particle 1. Since the polymer dispersant 2 and the low-molecular dispersant 3 form steric exclusion portions by disposing molecular chains at narrow intervals on the surface of the inorganic particles 1, for example, the 2 nd binder 4 containing a cellulose derivative is difficult to exhibit adhesion (poor compatibility) between the binder and the molecular chains of the dispersant 2 or 3.
Here, as shown in fig. 1 (B) and 2 (B), it is considered that, when a gap of the dispersant 2 or 3 is not adsorbed on the surface of the inorganic particle 1, a cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate having a size of several tens to several hundreds nm longer than a steric exclusion portion of the dispersant 2 or 3 (a side chain in the case of the comb-shaped polymer dispersant 2, or a main chain in the case of the single-terminal adsorption dispersant such as the low-molecular dispersant 3) is adsorbed as the 1 st binder 5, since the molecular chains are arranged at a wide interval, the steric restriction is less likely to occur, and the 2 nd binder 4 and the 1 st binder 5 are oriented to easily exhibit the adhesion.
As a result, the contact between the 1 st binder 5 and the 2 nd binder 4 increases, and therefore, the adhesion between the inorganic particles 1 can be improved.
In the present invention, the binder adsorbed on the surface of the inorganic particles is defined as "1 st binder", and the binder not adsorbed on the surface of the inorganic particles is defined as "2 nd binder". Thus, the 2 nd binder may be a binder of the same composition as the 1 st binder, i.e. both may be cellulose derivatives having a single terminal carboxyl group or a single terminal carboxylate. Of course, the 2 nd binder may also be a cellulose derivative having no single terminal carboxyl group or single terminal carboxylate.
The 2 nd binder is particularly preferably a copolymer having a portion of a cellulose derivative (the terminal may be arbitrary) or a polymer mixture containing a cellulose derivative, and if this is the case, a high intermolecular force acts between the cellulose derivative and the cellulose derivative portion of the 2 nd binder adsorbed at one terminal of the 1 st binder on the surface of the inorganic particles, and a high adhesion improving effect can be obtained.
The surface adsorption rate of the inorganic particles of the cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate does not reach 100%. The reason for this is that: the adsorption phenomenon is not completely irreversible because of single-point adsorption. The surface adsorption rate of the inorganic particles is changed by the chemical state of the surfaces of the inorganic particles, the surface area, the kind of the solvent contained in the paste for electronic parts, the amount and concentration of the binder added to the paste for electronic parts, and the like. In the non-excessive region, about 30 to 90% of the amount added is adsorbed.
In summary, in the case where a cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate is not contained as a binder, as shown in fig. 1 (a) and 2 (a), only the interface having a low adhesion force between the dispersant 2 or 3 and the 2 nd binder 4 is dominant, the dispersant 2 or 3 is adsorbed to the surface of the inorganic particles 1, and the 2 nd binder 4 is not adsorbed to the inorganic particles 1 and contains, for example, a cellulose derivative.
In contrast, when the 1 st binder 5 containing a cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate is contained as a binder, as shown in fig. 1 (B) and 2 (B), the 1 st binder 5 contains not only an interface having a relatively low adhesion force between the 1 st binder 5 and the 2 nd binder 4 but also an interface having a relatively high adhesion force between the 1 st binder 5 and the 2 nd binder 4, the dispersant 2 or 3 is adsorbed on the surface of the inorganic particles 1, the 2 nd binder 4 is not adsorbed on the surface of the inorganic particles 1 and contains, for example, a cellulose derivative, and the 1 st binder 5 is adsorbed on the surface of the inorganic particles 1 and contains a cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate. As a result, the adhesion between the inorganic particles 1 as a whole is improved.
More specifically, the metal particles, the ceramic particles, or the metal particles and ceramic particles are less likely to be broken by aggregation, and when the paste for electronic components is applied to, for example, a conductive paste for internal electrodes used in the production of a laminated ceramic capacitor, the internal electrode layer is less likely to be peeled off, particularly in the press-cutting of the laminate before firing.
In the paste for electronic parts, the cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate as the 1 st binder preferably contains 1.0mg/m 2～5.0mg/m2 relative to the total surface area of the inorganic particles. In other words, as the cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate of the 1 st binder, 1.0mg/m 2～5.0mg/m2 is preferably adsorbed to the total surface area of the inorganic particles. The reason for this is that: the adsorption amount reaches more than 1.0mg/m 2, and the obvious effect is shown. On the other hand, there is almost no case where the adsorption exceeds 5.0mg/m 2.
The cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate is preferably a cellulose ether having a single-terminal carboxyl group or a single-terminal carboxylate. The reason for this is that: if the following synthetic reaction scheme is considered, it is more practical to obtain cellulose ether having a single-terminal carboxyl group or a single-terminal carboxylate as a cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate.
The cellulose ether having a single-terminal carboxyl group or a single-terminal carboxylate is more preferably at least one selected from the group consisting of methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose and hydroxypropyl methyl cellulose.
As the dispersant contained in the paste for electronic parts, a comb-type polymer dispersant and a low-molecular one-terminal adsorption dispersant are preferably used as described above. As the comb-type polymer dispersant, for example, a polycarboxylic acid-based dispersant is used. Since comb-type polymer dispersants such as polycarboxylic acid dispersants and low-molecular single-end adsorption dispersants have a structure in which molecular chains are arranged at narrow intervals on the surface of inorganic particles to form steric exclusion portions, there is a problem in that it is difficult to exhibit adhesion (poor compatibility) between a binder and the molecular chains of the dispersant due to steric constraints. However, this problem is advantageously solved as described above by the cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate as a binder contained in the paste for electronic parts of the present invention.
The inorganic particles contained in the paste for electronic components of the present invention preferably contain at least one of ceramic particles and metal particles. For example, the paste for forming the dielectric layer in the laminated ceramic capacitor contains at least ceramic particles, and the paste for forming the internal electrode layer contains at least metal particles. The ceramic particles contain at least one element selected from Ba, ti, ca, zr and Sr, for example. The metal particles include, for example, at least one metal selected from Cu, ni, au, and Ag.
Experimental example 1
[ Synthesis of cellulose derivative ]
In this experimental example, various synthesis methods are shown below in order to understand the single-end carboxylated cellulose derivative and the single-end esterified cellulose derivative to be used as binders contained in the paste for electronic parts. The synthesis method shown below is a synthesis method of ethylcellulose which is one of cellulose derivatives and is widely used in pastes for electronic parts and the like. These synthetic methods are merely examples, and are not limited thereto.
< Method for synthesizing Single-terminal carboxylated cellulose derivative >
(1) Production of single-end carboxylated cellulose by oxidation of the reduced ends of cellulose
To the aqueous slurry of cellulose (solid content 1440 g), 50% aqueous sodium hydroxide solution (1680 g) was added. Thereafter, anthraquinone-2-sodium sulfonate (24 g) dissolved in 30% hydrogen peroxide was added, and stirring was performed, whereby the reduced end of cellulose was oxidized, and then filtration and water washing were performed, whereby single-end carboxylated cellulose was obtained. This reaction is a reaction in which a formyl group in a state of having a formyl group is oxidized to a carboxyl group by ring-opening in tautomerization of a reducing end of cellulose.
Various methods for oxidizing the formyl group of a sugar having a reducing end or a ring opening of cellulose have been known.
(2) Deprotonation reactions using sodium hydroxide
To the aqueous solution of the single-end carboxylated cellulose was added a 50% aqueous solution of sodium hydroxide, and the mixture was stirred at 60℃for 20 minutes to obtain an alkali cellulose having a hydroxyl group of-ONa and a single end of-COONa.
(3) Ethoxylation (etherification) and ethylation reactions with ethyl chloride
In a 0.5MPa autoclave, alkali cellulose and ethyl chloride were stirred at 110℃for 12 hours to obtain ethylcellulose having hydroxyl groups of-OEt and one terminal groups of-COONa or-COOH or-COOEt. The amount of sodium hydroxide and the amount of ethyl chloride to be added were adjusted so that the Degree of Substitution (DS) of ethoxylation of 3 OH groups with respect to the monomer unit of the cellulose obtained at this time was in the range of 2.46 to 2.58 (degree of ethoxylation of 48.0 to 49.5 mass%). In this synthesis, since the etherification reaction proceeds more than the esterification reaction, the esterification to-COOEt is less.
(4) Hydrolysis of esters
The reaction of hydrolyzing the ethyl cellulose having one end of-COOEt to form-COOEt, ethylcellulose with hydroxyl groups of-OEt (degree of substitution 2.5) and with one end of-COONa (carboxylate) or-COOH (carboxyl) is obtained.
The hydrolysis reaction conditions are various, and the reaction proceeds by adding water to an alcohol solvent and heating the mixture. In order to efficiently perform the reaction, a catalyst may be added. In the etherification reaction using ethyl chloride, esterification is not easily performed, and thus, ethyl cellulose having most of one terminal-COONa (carboxylate) or-COOH (carboxyl) groups can be obtained without performing the above step.
(5) Washing and drying
After removing salts and byproducts by washing with hot water, drying under reduced pressure, a solid of ethylcellulose having a degree of substitution of 2.5 of ethoxylation of-COONa (carboxylate) or-COOH (carboxyl) at one end and-OEt (ether) at the other end was obtained. By adjusting the number average molecular weight of the cellulose to be used initially within a range of 1 to 10 tens of thousands, 4 kinds of ethylcellulose having a number average molecular weight of 1.3×10 4、2.0×104、5.4×104 and 8.8×10 4 can be produced. The number average molecular weight was obtained by converting polystyrene by GPC (Gel Permeation Chromatography ) in THF (tetrahydrofuran) solvent.
< Method for synthesizing Single-terminal esterified cellulose derivative >
(1) Production of single-end carboxylated cellulose by oxidation of the reduced ends of cellulose
To the aqueous slurry of cellulose (solid component 1440 g) was added 50% aqueous sodium hydroxide solution (1680 g) in the same manner as in the synthesis of the above-mentioned single-end carboxylated cellulose derivative. Thereafter, anthraquinone-2-sodium sulfonate (24 g) dissolved in 30% hydrogen peroxide was added, and stirring was performed, whereby the reduced end of cellulose was oxidized, and then filtration and water washing were performed, whereby single-end carboxylated cellulose was obtained.
(2) Deprotonation reactions using sodium hydroxide
As in the case of the synthesis of the above-mentioned single-end carboxylated cellulose derivative, a 50% aqueous solution of sodium hydroxide was added to the aqueous solution of single-end carboxylated cellulose, and the mixture was stirred at 60℃for 20 minutes to obtain alkali cellulose having a hydroxyl group of-ONa and a single end of-COONa.
(3) Ethoxylation (etherification) and ethylation reactions with ethyl chloride
As in the case of the synthesis of the above-mentioned single-end carboxylated cellulose derivative, the alkali cellulose and ethyl chloride were stirred at 110℃for 12 hours in a 0.5MPa autoclave to obtain ethylcellulose having a hydroxyl group of-OEt and a single end of-COONa or-COOH or-COOEt. The amount of sodium hydroxide and the amount of ethyl chloride to be added were adjusted so that the Degree of Substitution (DS) of ethoxylation of OH groups of the cellulose obtained in this case was in the range of 2.46 to 2.58 (degree of ethoxylation of 48.0 to 49.5 mass%).
Then, after removing salts and byproducts by washing with hot water, drying under reduced pressure was performed to obtain a solid of ethylcellulose.
(4) Esterification reaction
After dissolving the solid of ethylcellulose obtained in the above (3) in ethanol, concentrated sulfuric acid is added dropwise as an acid catalyst, whereby the carboxyl group at one end is esterified.
(5) Washing and drying
After removing salts and byproducts by washing with hot water, drying under reduced pressure was performed to obtain a solid of ethylcellulose having a substitution degree of 2.5 of one-terminal-COOEt (ethyl ester group) and the other-terminal-OEt (ether) ethoxylation. By adjusting the number average molecular weight of the cellulose to be used initially within a range of 1 to 10 ten thousand, 4 kinds of ethylcellulose having number average molecular weights Mn of 1.4×10 4、2.0×104、5.2×104 and 8.9×10 4, respectively, can be produced. In the same manner as in the above case, the number average molecular weight was obtained by converting the GPC in the THF solvent into polystyrene.
< Quantification of carboxyl groups in Single-terminal carboxylated Ethyl cellulose >
The amount of carboxyl groups in the single-end carboxylated ethylcellulose synthesized in the above manner was quantified by 1 H-NMR (Nuclear Magnetic Resonance ) measurement. Since the conventional NMR measurement is expected to have insufficient sensitivity in quantitative determination of a trace amount of terminal carboxyl groups, a Trimethylsilyl (TMS) derivatization method was used.
The TMS derivatization method is a method in which H of a hydroxyl group contained in a carboxyl group of ethylcellulose is substituted with a trimethylsilyl group (Si (CH 3)3). By this derivatization, the number of hydrogen in the carboxyl group is changed from 1H to 9H, and thus the detection sensitivity in 1 H-NMR is 9 times.
The derivatization product was obtained by adding ethylcellulose and a derivatizing reagent (BSTFA) to the dehydrated chloroform solvent and heating at 70℃for 1 hour. The derivatizing reagent acts on both the hydroxyl groups and carboxyl groups of the ethylcellulose, and therefore the amount of reagent added is set to about 1.5 times the molar amount of the hydroxyl groups and terminal carboxyl groups of the ethylcellulose. It was confirmed that the quantitative values of the hydroxyl group and the carboxyl group by TMS were not changed even if the amount of the reagent added exceeded 1.5 times the molar amount. The reacted solution was returned to room temperature, dried under vacuum, and subjected to GPC separation, whereby a dried cured product of the derivatization product from which the solvent and unreacted derivatization reagent were removed was obtained. The dried cured product was redissolved in deuterated chloroform as a solvent for NMR measurement, and 1 H-NMR measurement was performed. The 1 H-NMR spectrum of the ethylcellulose-derived product is shown in FIG. 3.
In 1 H-NMR spectra of ethylcellulose-derived products, the peak from the derivatization of the carboxyl group was detected at 0.3ppm indicated by the arrow in FIG. 3. The concentration of carboxyl groups in ethylcellulose was determined by calculating the molar ratios of the cellulose backbone, ethoxy groups, carboxyl groups and hydroxyl groups, based on the peak area ratios observed in 1 H-NMR. The results of the quantification of carboxyl groups and the average molecular weights of the corresponding samples are shown in Table 1. GPC was performed in a THF solvent, and the number average molecular weight was obtained by conversion to polystyrene.
TABLE 1
TABLE 1
The larger the molecular weight, the fewer carboxyl groups in the ethylcellulose, suggesting that carboxyl groups are present at a site dependent on the molecular weight. The higher the molecular weight of 1 chain, the lower the concentration of the polymer ends, and therefore, it is considered that a predetermined amount of carboxyl groups are present at the ends. Further, from the aspect of the synthetic reaction scheme of the sample, it was judged that the carboxyl group analyzed by NMR was present at one end.
Further, assuming that carboxyl groups were present at one end of the ethylcellulose by NMR, the number of repetitions of ethylcellulose was calculated, thereby calculating the molecular weight of ethylcellulose. The average molecular weight obtained by NMR and the average molecular weight obtained by GPC are shown in table 2.
TABLE 2
TABLE 2
Since the average molecular weight obtained by GPC is converted to polystyrene, the average molecular weight obtained by NMR does not match the absolute value of the average molecular weight obtained by GPC. On the other hand, as shown in fig. 4, when the values of the molecular weights obtained by two methods for the samples having different molecular weights are compared, a higher correlation is exhibited. This is a result indicating that carboxyl groups are present at one end of ethylcellulose, and it can be considered that NMR quantifies carboxyl groups present at one end.
[ Production of conductive paste ]
1.1 Parts by mass of single-end esterified ethylcellulose (number average molecular weight=2.0×10 4) or single-end carboxylated ethylcellulose (number average molecular weight=2.0×10 4) shown in the column of "1 st binder" of tables 3 and 4 (2.9 mg/m 2 relative to the total surface area of nickel powder and ceramic powder), and 39.7 parts by mass of dihydroterpineol acetate as an organic solvent were mixed to obtain 1 st organic carrier.
45.5 Parts by mass of the 1 st organic support, 45.0 parts by mass of a nickel powder having a BET (Brunauer-Emmett-Teller) diameter of 177nm (SSA (specific surface area) =3.8 m 2/g), 3.70 parts by mass of a ceramic powder containing barium titanate as a main component having a BET diameter of 13nm (SSA=77 m 2/g), and 0.70 parts by mass of a polycarboxylic acid polymer dispersant were mixed and dispersed by a three-roll mill to obtain an intermediate conductive paste.
Thereafter, the intermediate conductive paste was added with the materials shown in the column containing "binder 2" in tables 3 and 4
Shan Moduan esterified ethylcellulose,
Cellulose acetate butyrate,
Acrylic adhesive A (adhesive comprising poly (isobutyl methacrylate)),
A polyvinyl butyral resin,
Shan Moduan mixing of esterified ethyl cellulose with a polyvinyl butyral resin,
Mixing of cellulose acetate butyrate with a polyvinyl butyral resin,
Mixing of cellulose acetate butyrate with acrylic adhesive A,
Copolymer A (see below for details),
Copolymer B (see below for details),
Copolymer C (see below for details),
Copolymer D (see below for details),
Copolymer E (see further below), and
1.1 Parts by mass of any one of the copolymers F (see below), and
8.9 Parts by mass of dihydroterpineol acetate
The 2 nd organic vehicle of (2) was subjected to roll dispersion treatment to complete the conductive paste.
The dispersion method is not limited to the above method, and various methods such as a roll mill, a ball mill, a bead mill, and high-pressure dispersion may be applied. This is not limited to the operations herein for obtaining a conductive paste, but may be considered as such for other operations.
The details of each of the above copolymers a to F, and experimental operations for obtaining the organic vehicle (binder solution) containing each of the copolymers a to F are as follows.
< Copolymer A >
The copolymer A is a copolymer of single-end carboxylated ethylcellulose and an acrylic binder B (the main monomer is isobutyl methacrylate, comprising 5mol% of 2-hydroxyethyl methacrylate).
5.5 Parts by mass of a single-end carboxylated ethylcellulose having a number average molecular weight mn=2.0×10 4 and 5.5 parts by mass of the acrylic binder B having a number average molecular weight mn=2.1×10 4 were dried under reduced pressure, 89 parts by mass of dihydroterpineol acetate was added, and dissolved at 50 ℃ under a nitrogen atmosphere. To the obtained solution, (1 mole of the sum of the Mn equivalent moles of the single-end carboxylated ethylcellulose and the acrylic binder B) was added 1.5 mole of methacrylic acid, 2.0 mole of diisopropylcarbodiimide as a condensing agent, and 0.01 times mole of dimethylaminopyridine as a reaction accelerator as the molar numbers of the condensing agent, and the mixture was stirred at a temperature of 50 ℃ for 24 hours to allow the reaction to proceed. Thus, introduction of the methacrylate into the single-end carboxylated ethyl cellulose and the acrylic binder B, and esterification of the hydroxyl groups of the acrylic binder B and the single-end carboxylated ethyl cellulose with the carboxyl groups of the single-end carboxylated ethyl cellulose were performed.
Then, 0.1 mol of Azoisobutyronitrile (AIBN) as a polymerization initiator for the introduced methacrylate ester (the total of the Mn conversion mole number of the single-end carboxylated ethyl cellulose and the acrylic adhesive B was 1 mol) was mixed and reacted at 70 ℃ for 5 hours to obtain an adhesive solution containing the copolymer a.
From 1 H-NMR of the obtained copolymer A, it was confirmed that the formation of ester groups and the disappearance of vinyl groups were observed, and the number average molecular weight Mn was 2.3X10- 4 or the like, which was increased from the number average molecular weight before the reaction, and therefore, it was found that the polymerization reaction was performed. The number average molecular weight was obtained by converting polystyrene by GPC in THF solvent.
< Copolymer B >
The copolymer B is a copolymer of a single-terminal esterified ethyl cellulose and a polyvinyl butyral resin.
5.5 Parts by mass of single-end esterified ethylcellulose having a number average molecular weight mn=2.0×10 4 and 5.5 parts by mass of polyvinyl acetal resin having a number average molecular weight mn=2.2×10 4 (BL-S manufactured by the water chemical industry) having hydroxyl groups are dried under reduced pressure, 89 parts by mass of dihydroterpineol acetate is added, and dissolved at 50 ℃ under a nitrogen atmosphere. To the obtained solution, (1 mole of the total of the Mn equivalent mole numbers of the single-end esterified ethylcellulose and the polyvinyl acetal resin) was added 1.5 mole amount of methacrylic acid, 1.5 mole amount of diisopropylcarbodiimide as a condensing agent, and 0.01 times mole amount of dimethylaminopyridine as a reaction accelerator as the molar numbers of the condensing agent, and the mixture was stirred at a temperature of 50 ℃ for 24 hours to allow the reaction to proceed. Thus, introduction of the methacrylate ester into the hydroxyl group of the single-end esterified ethyl cellulose and the polyvinyl acetal resin was performed.
Then, 0.1 mol of Azoisobutyronitrile (AIBN) as a polymerization initiator for the introduced methacrylate ester (the total of the Mn conversion mole number of the single-end esterified ethyl cellulose and the polyvinyl acetal resin was 1 mol) was mixed and reacted at 70 ℃ for 5 hours to obtain a binder solution containing the copolymer B.
From 1 H-NMR of the obtained copolymer B, it was confirmed that the formation of ester groups and the disappearance of vinyl groups were observed, and the number average molecular weight Mn was 2.5X10- 4 or the like, which was increased from the number average molecular weight before the reaction, and therefore, it was found that the polymerization reaction was performed. The number average molecular weight was obtained by converting polystyrene by GPC in THF solvent.
< Copolymer C >
The copolymer C is a copolymer of a single-terminal carboxylated ethyl cellulose and a polyvinyl butyral resin.
5.5 Parts by mass of a single-end carboxylated ethylcellulose having a number average molecular weight mn=2.0×10 4 and 5.5 parts by mass of a polyvinyl acetal resin having a number average molecular weight mn=2.2×10 4 (BL-S manufactured by the water chemical industry) having a hydroxyl group were dried under reduced pressure, 89 parts by mass of dihydroterpineol acetate was added, and dissolved at 50 ℃ under a nitrogen atmosphere. To the obtained solution, (1 mole of the sum of the Mn equivalent moles of the single-end carboxylated ethylcellulose and the polyvinyl acetal resin) was added 1.5 mole of methacrylic acid, 2.0 mole of diisopropylcarbodiimide as a condensing agent, and 0.01 times mole of dimethylaminopyridine as a reaction accelerator as the molar numbers of the condensing agent, and the mixture was stirred at 50 ℃ for 24 hours to allow the reaction to proceed. Thus, introduction of the methacrylate into the hydroxyl groups of the single-end carboxylated ethyl cellulose and the polyvinyl acetal resin, and esterification of the hydroxyl groups of the polyvinyl acetal resin and the single-end carboxylated ethyl cellulose with the carboxyl groups of the single-end carboxylated ethyl cellulose were performed.
Then, 0.1 mol of Azoisobutyronitrile (AIBN) as a polymerization initiator for the introduced methacrylate ester (the total of the Mn conversion mole number of the single-end carboxylated ethyl cellulose and the polyvinyl acetal resin was 1 mol) was mixed and reacted at 70 ℃ for 5 hours to obtain a binder solution containing copolymer C.
From 1 H-NMR of the obtained copolymer C, it was confirmed that the formation of ester groups and the disappearance of vinyl groups were observed, and the number average molecular weight Mn was 2.6X10- 4 or the like, which was increased from the number average molecular weight before the reaction, and therefore, it was found that the polymerization reaction was performed. The number average molecular weight was obtained by converting polystyrene by GPC in THF solvent.
< Copolymer D >
The copolymer D is a copolymer of a single-terminal carboxylated ethyl cellulose and a polyvinyl butyral resin.
5.5 Parts by mass of a single-end carboxylated ethylcellulose having a number average molecular weight mn=2.0×10 4 and 5.5 parts by mass of a polyvinyl acetal resin having a number average molecular weight mn=2.2×10 4 (BL-S manufactured by the water chemical industry) having a hydroxyl group were dried under reduced pressure, 89 parts by mass of dihydroterpineol acetate was added, and dissolved at 50 ℃ under a nitrogen atmosphere. To the obtained solution, (1 mole in terms of Mn of the single-end carboxylated ethylcellulose) was added 1.1 mole of diisopropylcarbodiimide as a condensing agent and 0.01 mole of dimethylaminopyridine as a reaction accelerator in terms of mole of condensing agent, and the mixture was stirred at a temperature of 50 ℃ for 24 hours to effect a reaction. Thus, a binder solution containing a polyvinyl acetal resin and a copolymer D obtained by esterifying a hydroxyl group of a single-end carboxylated ethyl cellulose with a carboxyl group of a single-end carboxylated ethyl cellulose was obtained.
From 1 H-NMR of the obtained copolymer, it was confirmed that the formation of ester groups and the number average molecular weight Mn of 2.4X10- 4 were increased from those before the reaction, and therefore, it was confirmed that the polymerization reaction was performed. The number average molecular weight was obtained by converting polystyrene by GPC in THF solvent.
< Copolymer E >
The copolymer E is a copolymer of cellulose acetate butyrate and a polyvinyl butyral resin.
5.5 Parts by mass of cellulose acetate butyrate having a number average molecular weight mn=2.0×10 4 ("CAB 381-0.1" manufactured by Eastman) and 5.5 parts by mass of a polyvinyl acetal resin having a number average molecular weight mn=2.2×10 4 ("BL-S" manufactured by water chemistry industry) were dried under reduced pressure, 89 parts by mass of dihydroterpineol acetate was added, and dissolved at 50 ℃ under a nitrogen atmosphere. To the obtained solution, (the total of the molar amounts of cellulose acetate butyrate and the polyvinyl acetal resin in terms of Mn was 1 mol) was added 2 mol of methacrylic acid, 2 mol of diisopropylcarbodiimide as a condensing agent, and 0.01 times the molar amount of dimethylaminopyridine as a reaction accelerator as the condensing agent, and the mixture was stirred at 50 ℃ for 24 hours to effect a reaction. Thus, introduction of the methacrylate ester into the cellulose acetate butyrate and the polyvinyl acetal resin was performed.
Then, 0.1 mol of Azoisobutyronitrile (AIBN) as a polymerization initiator for the introduced methacrylate ester (the total of the number of moles of cellulose acetate butyrate and the number of moles of Mn converted to the number of moles of polyvinyl acetal resin was 1 mol) was mixed and reacted at 70 ℃ for 5 hours to obtain a binder solution containing copolymer E.
From 1 H-NMR of the obtained copolymer, it was confirmed that the formation of ester groups and the disappearance of vinyl groups were observed, and the number average molecular weight Mn was 2.3X10: 10 4 or the like, which was increased from the number average molecular weight before the reaction, and therefore, it was found that the polymerization reaction was performed. The number average molecular weight was obtained by converting polystyrene by GPC in THF solvent.
< Copolymer F >
The copolymer F is a copolymer of cellulose acetate butyrate and an acrylic adhesive B (the main monomer is isobutyl methacrylate, and 5mol% of 2-hydroxyethyl methacrylate is contained).
5.5 Parts by mass of cellulose acetate butyrate having a number average molecular weight mn=2.0×10 4 ("CAB 381-0.1" manufactured by Eastman) and 5.5 parts by mass of the above-mentioned acrylic adhesive B having a number average molecular weight mn=2.1×10 4 were dried under reduced pressure, 89 parts by mass of dihydroterpineol acetate was added thereto, and dissolved at 50 ℃ under a nitrogen atmosphere. To the obtained solution, (the total of the molar amounts of cellulose acetate butyrate and the polyvinyl acetal resin in terms of Mn was 1 mol) was added 2 mol of methacrylic acid, 2 mol of diisopropylcarbodiimide as a condensing agent, and 0.01 times the molar amount of dimethylaminopyridine as a reaction accelerator as the condensing agent, and the mixture was stirred at 50 ℃ for 24 hours to effect a reaction. Thus, the introduction of the methacrylate ester into the cellulose acetate butyrate and the acrylic adhesive B was performed.
Then, 0.1 mol of Azoisobutyronitrile (AIBN) as a polymerization initiator for the introduced methacrylate ester (the total of the number of moles of cellulose acetate butyrate and the number of moles of Mn converted to the number of moles of polyvinyl acetal resin was 1 mol) was mixed and reacted at 70 ℃ for 5 hours to obtain a binder solution containing copolymer F.
From 1 H-NMR of the obtained copolymer, it was confirmed that the formation of ester groups and the disappearance of vinyl groups were observed, and the number average molecular weight Mn was 2.4X10: 10 4 or the like, which was increased from the number average molecular weight before the reaction, and therefore, it was found that the polymerization reaction was performed. The number average molecular weight was obtained by converting polystyrene by GPC in THF solvent.
[ Evaluation of adhesive adsorption amount of conductive paste ]
The following operations were performed on the prepared conductive paste to evaluate the adsorption amount of the binder.
400Cc of acetone was added to 200cc of the conductive paste, stirred for 30 minutes by a planetary mixer, and then treated by a centrifuge (himac, "CS100 FNX") at 29000rpm for 15 minutes to precipitate nickel powder and ceramic powder, and the supernatant was separated. Since the separated supernatant contains an unadsorbed binder, the concentration of the organic solid component in the whole supernatant is calculated from the weight change during drying. The total organic solid content in the conductive paste was calculated from the weight change when the paste dry matter was heated to 1000 ℃ by TG-DTA (thermogravimetric differential thermal analysis apparatus) in an N 2 atmosphere.
The binder adsorption amount with respect to the total surface area of the nickel powder and the ceramic powder was determined by applying the values obtained above to the following formula.
Binder adsorption amount= (total organic solid component amount-total organic solid component amount in total supernatant-total additive dispersion amount)/total surface area of nickel powder and ceramic powder
Since the polycarboxylic acid-based dispersant was used as the conductive paste of the sample, the sample was in a substantially irreversible adsorption state, and the sample was calculated so that the supernatant liquid contained no dispersant.
The obtained binder adsorption amount is shown in the column of "binder adsorption amount with respect to total surface area of nickel powder and ceramic powder" in tables 3 and 4.
[ Evaluation of adhesive adsorption amount and adsorbate of conductive paste ]
For comparative example 1-1 and example 1-1, the following evaluations (1) and (2) were additionally performed to evaluate the adsorption amount and adsorbate of the adhesive.
< Evaluation (1) >
400Cc of acetone was added to 200cc of the conductive paste, stirred for 30 minutes by a planetary mixer, and then treated by a centrifuge (himac, "CS100 FNX") at 33000rpm for 15 minutes to precipitate nickel powder and ceramic powder, and the supernatant was separated. The separated supernatant was dried, and the solid content (i.e., the unadsorbed binder) of the obtained supernatant was dried to TMS, and then subjected to NMR measurement to identify the unadsorbed binder. In the case where a plurality of binders or a dispersant is contained in the supernatant, separation by HPLC (high performance liquid chromatography) is required.
< Evaluation (2) >
To the solid component precipitated by centrifugal separation in the evaluation (1), 400cc of acetone was added, and stirring treatment was performed at 12000rpm for 30 minutes using a homogenizer "MARK II" manufactured by PRIMIX, whereby a part of the binder adsorbed on the particle surface was desorbed.
Next, the mixture was treated with a centrifuge (himac "CS100 FNX") at 29000rpm for 15 minutes to precipitate nickel powder and ceramic powder, and the supernatant was separated. The separated supernatant was dried, and the obtained supernatant dried solid content was subjected to TMS and NMR measurement to identify the adsorption binder. In the case where a plurality of binders are contained or a dispersant is contained, separation by HPLC is required.
As a result, with comparative example 1-1, single-ended esterified ethylcellulose was detected in both of the evaluation (1) and the evaluation (2); on the other hand, with respect to example 1-1, in evaluation (1), ethyl cellulose was esterified at (one terminal): (single-terminal carboxylated ethylcellulose) =3: 1 and single-end esterified ethylcellulose were detected in a ratio around 1, and in evaluation (2), the ratio of (single-end esterified ethylcellulose): (single-terminal carboxylated ethylcellulose) =1: the ratio of about 7 detected single-terminal esterified ethylcellulose and single-terminal carboxylated ethylcellulose. Therefore, it was confirmed that a paste in which single-end carboxylated ethylcellulose was adsorbed to each surface of nickel particles and ceramic particles was produced.
[ Production of unfired laminate chip ]
A ceramic material containing barium titanate as a main component having a BET diameter of 150nm, a polyvinyl butyral resin, toluene and EKINEN: 5 and triethylene glycol di (2-ethylhexanoate) as a plasticizer in a predetermined ratio, and wet dispersion treatment is performed using a bead mill, thereby obtaining a ceramic slurry.
Next, the ceramic slurry was molded on a PET (polyethylene terephthalate ) film using a doctor blade method so that the thickness after drying was 1.0 μm, thereby obtaining a ceramic green sheet.
Next, the conductive paste of the above sample was printed on a ceramic green sheet by a screen printer to form a conductive paste coating film to be an internal electrode, which was patterned to have a planar size of 1.0mm×0.5mm of the chip-shaped laminate after cutting and firing obtained later, and a nickel thickness after drying was 0.30 μm on average (measured by fluorescence X-ray analysis (XRF)) and a physical thickness was 0.60 μm on average (observed by a Focused Ion Beam (FIB) processed section Scanning Electron Microscope (SEM)).
Next, after each ceramic green sheet was peeled off from the PET film, first, 50 ceramic green sheets without a conductive paste coating film were stacked, then 350 ceramic green sheets with a conductive paste coating film printed thereon were stacked, further 30 ceramic green sheets without a conductive paste coating film printed thereon were stacked, and the obtained laminated structure was placed in a predetermined mold. Next, the laminate structure in the mold is pressurized to obtain an unfired laminate. The obtained unfired laminate was heated to 90 ℃, and cut into a predetermined size by press cutting, to obtain an unfired laminate chip.
[ Evaluation of production of structural defects ]
For each of 100 unfired laminate chips randomly selected from the unfired laminate chips, the cut surface of the press-cut was observed by an optical microscope, and the presence or absence of cohesive failure (peeling in the internal electrode layer) in the conductive coating film as a structural defect was confirmed.
In the column of "structural defect count" in tables 3 and 4, the number of laminate chips in which structural defects were observed among 100 laminate chips is shown. The occurrence of structural defects was evaluated based on the number of stacked chips in which structural defects were observed, according to the following criteria.
And (3) the following materials: the number of stacked bodies in which structural defects were observed was 0 or 1.
O: the number of stacked bodies in which structural defects were observed was 2 or more and 5 or less.
X: the number of stacked bodies in which structural defects were observed was 6 or more.
TABLE 3
TABLE 3 Table 3
TABLE 4
TABLE 4 Table 4
From a comparison of comparative examples 1-1 to 1-13 shown in Table 3 with examples 1-1 to 1-13 shown in Table 4, it is understood that by adsorbing the single-terminal carboxylated ethylcellulose as the 1 st binder to the nickel particles and the ceramic particles, the number of structural defects can be greatly reduced without particularly selecting the kind of binder added as the 2 nd binder.
A polymeric comb-type dispersant such as a polycarboxylic acid dispersant and a low-molecular single-end adsorption dispersant have a problem in that it is difficult to exhibit the adhesion force (poor compatibility) between the binder and the dispersant molecular chain because of steric constraints because the molecular chain is arranged at a narrow interval on the surface of the inorganic particles to form a steric exclusion portion. In contrast, it is considered that when the single-end carboxylated ethylcellulose having a high molecular weight is adsorbed on the surface of the inorganic particle, the molecular chains are arranged at wide intervals, and therefore, the steric restriction is not easily caused, and the adhesion between the binder and the single-end carboxylated ethylcellulose is easily exhibited (compatibility is easily achieved).
Further, as is clear from a comparison between examples 1-5 to 1-7 and examples 1-8 to 1-13, the use of the copolymer having a cellulose derivative portion as in examples 1-8 to 1-13 for the adhesive is more effective in suppressing structural defects than the use of the mixture containing a cellulose derivative as in examples 1-5 to 1-7. The reason for this is presumed to be: in the heterogeneous adhesive mixed systems of examples 1-5 to 1-7, the adhesion of the interface of the heterogeneous adhesive was weak, and the cohesive failure (peeling in the internal electrode layer) was generated from this as a starting point.
Furthermore, as is clear from comparison of examples 1-1 to 1-2 with examples 1-8 to 1-13, the copolymer of the cellulose derivative having a high Tg with the heterogeneous binder having a low Tg is softer and is less likely to crack than the composition of the cellulose derivative alone having a high Tg (glass transition point).
Experimental example 2
In experimental example 2, the amount of adhesive adsorption and the occurrence of structural defects were evaluated for a sample having a composition of the organic vehicle in the conductive paste in the same manner as in the case of experimental example 1.
[ Production of conductive paste ]
To obtain examples 2-1 to 2-4 shown in Table 5, 45.5 parts by mass of nickel powder having a BET diameter of 177nm (SSA=3.8 m 2/g), 3.0 parts by mass of ceramic powder having a BET diameter of 13nm (SSA=77 m 2/g) and containing barium titanate as a main component, 0.70 parts by mass of a polycarboxylic acid-based polymer dispersant, parts by mass of single-end carboxylated ethylcellulose having a number average molecular weight of 2.0X10 4 as the 1 st binder shown in column "1 st binder" of Table 5, and 39.7 parts by mass of dihydroterpineol acetate as an organic solvent were mixed, and roll dispersion treatment was performed to obtain an intermediate conductive paste.
Thereafter, to this intermediate conductive paste, the copolymer C as the 2 nd binder and 8.9 parts by mass of dihydroterpineol acetate as shown in the column of "2 nd binder" in table 5 were added, and dispersion treatment was performed by a three-roll mill to obtain conductive pastes of examples 2-1 to 2-4 shown in table 5.
On the other hand, in order to obtain examples 2 to 5 shown in table 5, 45.5 parts by mass of nickel powder having a BET diameter of 177nm (ssa=3.8 m 2/g), 3.0 parts by mass of ceramic powder having a BET diameter of 13nm (ssa=77 m 2/g) containing barium titanate as a main component, 0.70 parts by mass of a polycarboxylic acid-based polymer dispersant, 1.6 parts by mass of single-end carboxylated ethylcellulose having a number average molecular weight of 2.0×10 4 as the 1 st binder, and 39.2 parts by mass of dihydroterpineol acetate were mixed, and roll dispersion treatment was performed to obtain an intermediate conductive paste.
Thereafter, 1.1 parts by mass of single-end carboxylated ethylcellulose having a number average molecular weight of 2.0X10 4 as the 2 nd binder and 8.9 parts by mass of dihydroterpineol acetate were added to the intermediate conductive paste, and dispersion treatment was performed by a three-roll mill to obtain conductive pastes of examples 2 to 5 shown in Table 5.
TABLE 5
TABLE 5
[ Evaluation of adhesive adsorption amount and Structure Defect Generation ]
The adhesive adsorption amount to the total surface area of the nickel powder and the ceramic powder and the number of structural defects in the green laminate were evaluated by the same method as in the case of experimental example 1. The results are shown in Table 6.
TABLE 6
TABLE 6
As is clear from Table 6, the adsorption amount of the single-end carboxylated ethylcellulose with respect to the total surface area of the nickel powder and the ceramic powder is particularly preferably 1.0mg/m 2 or more and 5.0mg/m 2 or less.
Experimental example 3
In experimental example 3, samples having different molecular weights of cellulose derivatives contained in the conductive paste were prepared in the same manner as in the case of experimental example 1.
[ Production of conductive paste ]
45.5 Parts by mass of nickel powder having a BET diameter of 177nm (SSA=3.8 m 2/g), 3.0 parts by mass of ceramic powder having a BET diameter of 13nm (SSA=77 m 2/g) and containing barium titanate as a main component, 0.70 parts by mass of a polycarboxylic acid-based polymer dispersant, 1.1 parts by mass of single-end carboxylated ethylcellulose having a number average molecular weight shown in column "1 st binder" of Table 7 as 1 st binder, and 39.7 parts by mass of dihydroterpineol acetate were mixed and subjected to roll dispersion treatment to obtain an intermediate conductive paste.
Thereafter, 1.1 parts by mass of the copolymer C as the binder 2 and 8.9 parts by mass of dihydroterpineol acetate were added to the intermediate conductive paste, and dispersion treatment was performed by a three-roll mill to obtain conductive pastes of examples 3-1 to 3-3 shown in Table 7.
[ Evaluation of adhesive adsorption amount and Structure Defect Generation ]
The adhesive adsorption amount to the total surface area of the nickel powder and the ceramic powder and the number of structural defects in the green laminate were evaluated by the same method as in the case of experimental example 1. The results are shown in Table 7. Table 7 also shows the evaluation results of examples 1 to 10 produced in experimental example 1.
TABLE 7
TABLE 7
From table 7, even if the molecular weight of the single-end carboxylated ethylcellulose adsorbed to the nickel particles and the ceramic particles was changed, the adsorption amount was not changed greatly, and no structural defect was confirmed. From this, it is understood that the molecular weight of the single-terminal carboxylated ethylcellulose is not particularly limited in order to obtain the effect of the present invention.
The reason why the adsorption amount does not change greatly even when the molecular weight is changed is assumed to be the following equilibrium relationship: the shorter the molecular chain of the single-end carboxylated ethylcellulose, the smaller the repulsion of the molecular chains to each other adsorbed on the surfaces of the nickel particles and the ceramic particles, the greater the adsorption number of the single-end carboxylated ethylcellulose, and on the other hand, the longer the molecular chain of the single-end carboxylated ethylcellulose, the greater the repulsion of the molecular chains to each other adsorbed on the surfaces of the nickel particles and the ceramic particles, and the smaller the adsorption number of the single-end carboxylated ethylcellulose.
Experimental example 4
In experimental example 4, samples having different types of inorganic particles contained in the paste were prepared by the same method as in the case of experimental example 1.
[ Production of conductive paste ]
45.5 Parts by mass of a decanoic acid coated Cu powder having a BET diameter of 204nm (SSA=3.4 m 2/g), 3.0 parts by mass of a ceramic powder having a BET diameter of 13nm (SSA=77 m 2/g) and containing barium titanate as a main component, 0.35 parts by mass of a polycarboxylic acid-based polymer dispersant, 0.8 parts by mass of a single-end carboxylated ethylcellulose having a number average molecular weight of 2.0X10 4 as the 1 st binder, and 40.05 parts by mass of dihydroterpineol acetate were mixed and subjected to roll dispersion treatment to obtain an intermediate conductive paste.
Thereafter, 1.4 parts by mass of the copolymer C as the binder 2 and 8.9 parts by mass of dihydroterpineol acetate were added to the intermediate conductive paste, and dispersion treatment was performed by a three-roll mill to obtain the conductive paste of example 4-1 shown in Table 8.
[ Production of ceramic paste ]
33.6 Parts by mass of a powder containing barium titanate as a main component having a BET diameter of 149nm (SSA=6.7 m 2/g), 0.45 parts by mass of a polycarboxylic acid-based polymer dispersant, 0.4 parts by mass of a single-end carboxylated ethylcellulose having a number average molecular weight of 2.0X10: 10 4 as a1 st binder, and 40.05 parts by mass of dihydroterpineol acetate were mixed and subjected to roll dispersion treatment to obtain an intermediate ceramic paste.
Thereafter, 3.0 parts by mass of the copolymer C as the binder 2 and 22.5 parts by mass of dihydroterpineol acetate were added to the intermediate ceramic paste, and dispersion treatment was performed by a three-roll mill to obtain ceramic pastes of example 4-2 shown in Table 8.
[ Production of unfired laminate chip ]
An unfired laminate chip was obtained for the conductive paste of example 4-1 by the same method as in the case of experimental example 1.
For the ceramic paste of example 4-2, an unfired laminate chip was obtained by the method shown below.
A ceramic material containing barium titanate as a main component having a BET diameter of 150nm, a polyvinyl butyral resin, toluene and EKINEN: 5 and triethylene glycol di (2-ethylhexanoate) as a plasticizer in a predetermined ratio, and wet dispersion treatment using a bead mill to obtain a ceramic slurry.
Next, the ceramic slurry was formed on a PET (polyethylene terephthalate) film using a doctor blade method so that the thickness after drying was 1.0 μm, thereby obtaining a ceramic green sheet.
Next, the conductive pastes of examples 1 to 10 were printed on the ceramic green sheets by a screen printer to form conductive paste coating films to be internal electrodes, which had a pattern of 1.0mm×0.5mm in planar dimensions of the chip-shaped laminate after cutting and firing, and a nickel thickness after drying of 0.30 μm (XRF measurement) and a physical thickness of 0.60 μm on average (FIB milling cross-sectional SEM observation).
Thereafter, the ceramic pastes of example 4-2 shown in Table 8 were further printed by a screen printer at the portions where the conductive paste coating films were not formed so that the physical thickness was 0.30 μm on average (as observed by the FIB-processed cross-section SEM), to form coating films for compensating for the step difference generated in the thickness of the conductive paste coating films as the internal electrodes.
Next, after each ceramic green sheet was peeled off from the PET film, first, 50 ceramic green sheets without a conductive paste coating film were stacked, then 350 ceramic green sheets with a conductive paste coating film printed thereon were stacked, further 30 ceramic green sheets without a conductive paste coating film printed thereon were stacked, and the obtained laminated structure was placed in a predetermined mold. Next, the laminate structure in the mold is pressurized to obtain an unfired laminate. The obtained unfired laminate was heated to 90℃and cut into a predetermined size by press cutting to obtain an unfired laminate chip of example 4-2.
[ Evaluation of production of structural defects ]
For example 4-1, the adhesive adsorption amount to the total surface area of the nickel powder and the ceramic powder and the number of structural defects in the green laminate were evaluated by the same method as in example 1.
On the other hand, in example 4-2, the existence of aggregation failure (peeling in the internal electrode layer or in the step-difference compensating coating film) in the conductive paste coating film or in the step-difference compensating coating film, which is a structural defect, was confirmed by observing the cut-off surface of the press-cut by an optical microscope for each of 100 unfired laminate chips randomly selected from the unfired laminate chips.
In the column of "structural defect count" in table 8, the number of laminate chips in which structural defects were observed among 100 laminate chips is shown. The "determination" in table 8 is based on the same criteria as the "determination" in tables 3 and 4.
TABLE 8
TABLE 8
As can be seen from the observation of table 8, the same effect can be obtained regardless of the combination of the binder with other metal particles such as copper particles or the combination of the binder with ceramic particles such as BaTiO 3 particles, as long as the adsorption effect can be confirmed by the combination with nickel particles. From this, it is understood that the inorganic particles contained in the paste for electronic parts may be any inorganic particles as long as they can be adsorbed by the cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate.
Description of the reference numerals
1: Inorganic particles
2: Comb-type high polymer dispersing agent
3: Low molecular weight dispersants
4: 2 Nd adhesive
5: 1 St adhesive.
Claims (12)
1. A paste for electronic parts, which comprises inorganic particles, a dispersant, a binder and an organic solvent,
The binder comprises a1 st binder adsorbed on the surface of the inorganic particles and a 2 nd binder not adsorbed on the surface of the inorganic particles,
At least the 1 st binder is a cellulose derivative having a single terminal carboxyl group or a single terminal carboxylate.
2. The paste for electronic parts according to claim 1, wherein the 2 nd binder is a cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate.
3. The paste for electronic parts according to claim 1, wherein the 2 nd binder is a cellulose derivative having no single-terminal carboxyl group or single-terminal carboxylate.
4. The paste for electronic components according to claim 1, wherein the 2 nd binder is a copolymer having a cellulose derivative portion or a mixture of a plurality of polymers containing a cellulose derivative.
5. The paste for electronic parts according to any one of claims 1 to 4, wherein the cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate as the 1 st binder is contained in an amount of 1.0mg/m 2 to 5.0mg/m 2 inclusive relative to the total surface area of the inorganic particles.
6. The paste for electronic components according to any one of claims 1 to 5, wherein the inorganic particles comprise at least one of ceramic particles and metal particles.
7. The paste for electronic components according to claim 6, wherein the ceramic particles contain at least one element selected from Ba, ti, ca, zr and Sr.
8. The paste for electronic components according to claim 6, wherein the metal particles comprise at least one metal selected from the group consisting of Cu, ni, au, and Ag.
9. The paste for electronic parts according to any one of claims 1 to 8, wherein the cellulose derivative having a single-terminal carboxyl group or a single-terminal carboxylate is a cellulose ether having a single-terminal carboxyl group or a single-terminal carboxylate.
10. The paste for electronic components according to claim 9, wherein the cellulose ether having a single-terminal carboxyl group or a single-terminal carboxylate is at least one selected from the group consisting of methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethylhydroxyethyl cellulose, and hydroxypropyl methyl cellulose.
11. The paste for electronic components according to any one of claims 1 to 10, wherein the dispersant is a polymeric dispersant.
12. The paste for electronic components according to claim 11, wherein the polymer dispersant is a polycarboxylic acid dispersant.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-195053 | 2021-12-01 | ||
| JP2021195053 | 2021-12-01 | ||
| PCT/JP2022/038492 WO2023100503A1 (en) | 2021-12-01 | 2022-10-15 | Paste for electronic components |
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| Publication Number | Publication Date |
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| CN118120032A true CN118120032A (en) | 2024-05-31 |
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|---|---|---|---|
| CN202280070299.0A Pending CN118120032A (en) | 2021-12-01 | 2022-10-15 | Paste for electronic component |
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|---|---|
| JP (1) | JPWO2023100503A1 (en) |
| KR (1) | KR20240100390A (en) |
| CN (1) | CN118120032A (en) |
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| JP2018131681A (en) * | 2017-02-14 | 2018-08-23 | 住友金属鉱山株式会社 | Nickel paste and method for producing the same, and nickel organic slurry and method for producing the same |
| JP6939015B2 (en) | 2017-03-29 | 2021-09-22 | 住友金属鉱山株式会社 | Conductive paste for gravure printing for internal electrodes of multilayer ceramic capacitors |
| JP6810778B1 (en) * | 2019-09-25 | 2021-01-06 | 株式会社ノリタケカンパニーリミテド | Conductive paste and manufacturing method of electronic parts using it |
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- 2022-10-15 CN CN202280070299.0A patent/CN118120032A/en active Pending
- 2022-10-15 WO PCT/JP2022/038492 patent/WO2023100503A1/en active Application Filing
- 2022-10-15 JP JP2023564783A patent/JPWO2023100503A1/ja active Pending
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| TW202336121A (en) | 2023-09-16 |
| WO2023100503A1 (en) | 2023-06-08 |
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| KR20240100390A (en) | 2024-07-01 |
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