JP5506228B2 - Colloidal calcium carbonate filler, method for producing the same, and resin composition containing the filler - Google Patents
Colloidal calcium carbonate filler, method for producing the same, and resin composition containing the filler Download PDFInfo
- Publication number
- JP5506228B2 JP5506228B2 JP2009090793A JP2009090793A JP5506228B2 JP 5506228 B2 JP5506228 B2 JP 5506228B2 JP 2009090793 A JP2009090793 A JP 2009090793A JP 2009090793 A JP2009090793 A JP 2009090793A JP 5506228 B2 JP5506228 B2 JP 5506228B2
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- colloidal calcium
- colloidal
- filler
- oxidation inhibitor
- 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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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims description 285
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims description 140
- 239000000945 filler Substances 0.000 title claims description 65
- 239000011342 resin composition Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 230000003647 oxidation Effects 0.000 claims description 38
- 238000007254 oxidation reaction Methods 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 38
- 239000011347 resin Substances 0.000 claims description 38
- 239000003112 inhibitor Substances 0.000 claims description 34
- 239000007900 aqueous suspension Substances 0.000 claims description 20
- 239000012756 surface treatment agent Substances 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 5
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 230000001186 cumulative effect Effects 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 125000000101 thioether group Chemical group 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- -1 iron Chemical class 0.000 description 23
- 238000000034 method Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 230000000704 physical effect Effects 0.000 description 16
- 239000010410 layer Substances 0.000 description 13
- 229920001155 polypropylene Polymers 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 230000032683 aging Effects 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 235000019738 Limestone Nutrition 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000006028 limestone Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 238000004381 surface treatment Methods 0.000 description 7
- 235000011116 calcium hydroxide Nutrition 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000000691 measurement method Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 5
- 235000012255 calcium oxide Nutrition 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000003352 sequestering agent Substances 0.000 description 5
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- 229920003002 synthetic resin Polymers 0.000 description 5
- 239000000057 synthetic resin Substances 0.000 description 5
- AURFNYPOUVLIAV-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]-2-hydroxyacetic acid Chemical compound OC(=O)C(O)N(CC(O)=O)CCN(CC(O)=O)CC(O)=O AURFNYPOUVLIAV-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 150000003973 alkyl amines Chemical class 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001016 Ostwald ripening Methods 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229940114930 potassium stearate Drugs 0.000 description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 230000021148 sequestering of metal ion Effects 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 1
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 1
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- HVYJSOSGTDINLW-UHFFFAOYSA-N 2-[dimethyl(octadecyl)azaniumyl]acetate Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CC([O-])=O HVYJSOSGTDINLW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- KGMSWPSAVZAMKR-UHFFFAOYSA-N Me ester-3, 22-Dihydroxy-29-hopanoic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(=C(C)C)C=C1CC2 KGMSWPSAVZAMKR-UHFFFAOYSA-N 0.000 description 1
- 229920003354 Modic® Polymers 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-ONCXSQPRSA-N Neoabietic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CCC(=C(C)C)C=C2CC1 KGMSWPSAVZAMKR-ONCXSQPRSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- WVMHLYQJPRXKLC-UHFFFAOYSA-N borane;n,n-dimethylmethanamine Chemical compound B.CN(C)C WVMHLYQJPRXKLC-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
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- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000011981 development test Methods 0.000 description 1
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- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical class C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
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- 238000009998 heat setting Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
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- 229940094506 lauryl betaine Drugs 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- 150000003009 phosphonic acids Chemical class 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
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- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- CAAIULQYGCAMCD-UHFFFAOYSA-L zinc;hydroxymethanesulfinate Chemical compound [Zn+2].OCS([O-])=O.OCS([O-])=O CAAIULQYGCAMCD-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Description
本発明はコロイド炭酸カルシウム填剤及びその製造方法、並びに該填剤を配合してなる樹脂組成物に関し、さらに詳しくは、色相安定性に優れ、耐熱性、耐光性に優れることから、例えば合成樹脂シートに添加された場合に、高度の白色性を長期間保持することが可能で、例えば、ノート型パソコンや携帯電話等で使用されるサイドライト型バックライトの光反射シートや、液晶ＴＶで用いられる直下型バックライトの光反射シート、ポスターや地図等のポリオレフィン系白色合成紙用途において好適に使用することができるコロイド炭酸カルシウム填剤及びその製造方法、並びに該填剤を配合してなる樹脂組成物に関する。 The present invention relates to a colloidal calcium carbonate filler, a method for producing the same, and a resin composition formed by blending the filler. More specifically, the resin composition has excellent hue stability, heat resistance, and light resistance. When added to a sheet, it is possible to maintain a high degree of whiteness for a long period of time. For example, it is used in a light-reflecting sheet of a sidelight-type backlight used in a notebook computer or a mobile phone, or in a liquid crystal TV. Colloidal calcium carbonate filler that can be suitably used in polyolefin-based white synthetic paper applications such as light reflecting sheets, posters and maps for direct type backlights, a method for producing the same, and a resin composition comprising the filler Related to things.
従来より、白色系合成樹脂としては、地図、包装紙、書籍用紙、ポスター用紙等に使われるポリオレフィン系白色合成紙（例えば、特許文献１）や、ノート型パソコンや携帯電話等で使用されるサイドライト型バックライトの光反射シートや、液晶ＴＶで用いられる直下型バックライトの光反射シートとして、白色ＰＥＴシートや白色ＰＰシート（例えば特許文献２、３）が提案されている。これらの合成紙やＰＥＴシート、ＰＰシートの製造方法は、炭酸カルシウム等を樹脂に添加し、延伸法で空孔ボイドを形成させ、光の乱反射で白色性を付与する方法である。従って、このような白色系樹脂用途に用いる炭酸カルシウムもまた、高度の白色性を有し、その色相が長期に亘り安定していることが必要であり、バックライトの光反射シートに用いられる場合は、更に、バックライト光源に起因する耐熱性や耐光性にも優れていることが必要である。 Conventionally, as white synthetic resin, polyolefin white synthetic paper (for example, Patent Document 1) used for maps, wrapping paper, book paper, poster paper, etc., side used for notebook computers, mobile phones, etc. White PET sheets and white PP sheets (for example, Patent Documents 2 and 3) have been proposed as light-reflecting sheets for light-type backlights and light-reflecting sheets for direct-type backlights used in liquid crystal TVs. These synthetic papers, PET sheets, and PP sheets are produced by adding calcium carbonate or the like to a resin, forming voids by a stretching method, and imparting whiteness by irregular reflection of light. Therefore, the calcium carbonate used for such white resin application also needs to have a high degree of whiteness and its hue to be stable over a long period of time, and when used for a light reflecting sheet of a backlight. Furthermore, it is necessary to be excellent in heat resistance and light resistance caused by the backlight light source.
ところで、炭酸カルシウムは、一般的に天然の鉱物（糖晶質石灰石）を粉砕して粒度調整した重質炭酸カルシウムと、天然の鉱物（緻密質石灰石）を焼成して酸化カルシウムから炭酸カルシウムを得るコロイド炭酸カルシウムや軽質炭酸カルシウムで代表される沈降性炭酸カルシウムとに大別できる。色相の面では、重質炭酸カルシウムは乾式による粒度調整に対し、沈降性炭酸カルシウムは湿式であるため、篩工程等により比較的不純物が除去されやすい製法であるため、色相の良好な炭酸カルシウムを得ることができる。しかしながら、沈降性炭酸カルシウムも出発原料は天然の炭酸カルシウムであることに変わりはなく、従って、鉄、マンガン、クロム、銅、ニッケルなどの着色金属の不純物量が必ずしも一定ではないため、通常、炭酸カルシウムの色相も同様に一定ではない。特に鉄系の不純物は、炭酸カルシウムや該炭酸カルシウムを配合して得た樹脂組成物の黄変性に影響を与えるため、問題とされている。
従って、例えば、液晶用光反射樹脂シートに鉄などの着色金属を多く含有した炭酸カルシウムを配合した場合、樹脂シートが黄変しやすいばかりでなく、バックライト光源に起因する耐熱性や耐光性の経年劣化性においても劣化を促進させ、光反射率の低下を招きやすい問題がある。
なお、前述したコロイド炭酸カルシウムと軽質炭酸カルシウムとの違いは、同じ合成方法であるが、通常、コロイド形状か紡錘形状かとの形状における差や、例えば紙用に用いた場合、パルプから抜け落ちず該用途に使えるものを軽質、抜け落ちて使えないものをコロイドと呼ぶ。本発明の目的用途において、軽質炭酸カルシウムでは、凝集体粒子であるため光学用途では不適当であり、コロイド炭酸カルシウムであることが必要である。
By the way, calcium carbonate generally obtains calcium carbonate from calcium oxide by calcining natural mineral (sugar crystalline limestone) and calcining heavy calcium carbonate whose particle size is adjusted and natural mineral (dense limestone). It can be roughly classified into precipitated calcium carbonate represented by colloidal calcium carbonate and light calcium carbonate. In terms of hue, heavy calcium carbonate is a wet process, while precipitated calcium carbonate is wet, so that impurities are relatively easily removed by a sieving process, etc. Can be obtained. However, since precipitated calcium carbonate is still natural calcium carbonate as a starting material, and the amount of impurities of colored metals such as iron, manganese, chromium, copper, and nickel is not always constant, The hue of calcium is not constant as well. In particular, iron-based impurities are regarded as a problem because they affect the yellowing of calcium carbonate and a resin composition obtained by blending the calcium carbonate.
Therefore, for example, when calcium carbonate containing a large amount of colored metal such as iron is blended in the light reflecting resin sheet for liquid crystal, not only the resin sheet tends to yellow, but also the heat resistance and light resistance caused by the backlight light source. There is also a problem that the deterioration over time is also promoted, and the light reflectance is likely to decrease.
The difference between the colloidal calcium carbonate and light calcium carbonate described above is the same synthesis method, but usually the difference in shape between the colloidal shape and the spindle shape, for example, when used for paper, it does not fall off from the pulp. The one that can be used for the purpose is called light, and the one that falls off and cannot be used is called colloid. In the intended use of the present invention, light calcium carbonate is an agglomerated particle and is therefore unsuitable for optical use and needs to be colloidal calcium carbonate.
本発明は、かかる実情に鑑み、着色金属の含有量が増加しても色相の低下が抑制され、略均一な色相を長期間に亘って維持する色相安定性に優れ、例えば、樹脂に配合した場合、色相の安定的保持はもちろんのこと、耐熱性、耐光性に優れた樹脂組成物を与えることのできるコロイド炭酸カルシウム填剤を提供することにある。 In view of such circumstances, the present invention suppresses the decrease in hue even when the content of the colored metal is increased, and is excellent in hue stability for maintaining a substantially uniform hue over a long period of time. It is an object of the present invention to provide a colloidal calcium carbonate filler capable of providing a resin composition excellent in heat resistance and light resistance as well as maintaining stable hue.
本発明者らは、上記課題の解決のため鋭意検討した結果、コロイド炭酸カルシウム填剤を製造する過程において、金属の酸化を抑制する薬剤を含有させたコロイド炭酸カルシウム填剤が、例えば白色系合成樹脂に配合された場合においても、前記した課題を解決できること見出し本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the present inventors have found that a colloidal calcium carbonate filler containing an agent that suppresses metal oxidation in the process of producing a colloidal calcium carbonate filler is, for example, a white compound. Even when blended with a resin, the inventors have found that the above-mentioned problems can be solved and have completed the present invention.
即ち、本発明の第１の特徴は、コロイド炭酸カルシウム中に、酸化抑制剤が含有されてなり、下記の（ａ）平均粒子径Ｄ50及び（ｂ）最大粒子径Ｄａを満足するコロイド炭酸カルシウム填剤である。
（ａ）０．３≦Ｄ50≦１．５ （μｍ）
（ｂ）Ｄａ≦２０ （μｍ）
Ｄ50：レーザー回折式粒度分布測定装置（マイクロトラックＦＲＡ：日機装社製）で測定した篩上積算平均粒子径 [μｍ]
Ｄａ：レーザー回折式粒度分布測定装置（マイクロトラックＦＲＡ：日機装社製）で測定した時に示す最大粒子径 [μｍ]
That is, the first feature of the present invention is that the colloidal calcium carbonate contains an oxidation inhibitor, and the colloidal calcium carbonate filler satisfies the following (a) average particle diameter D50 and (b) maximum particle diameter Da. It is an agent.
(A) 0.3 ≦ D50 ≦ 1.5 (μm)
(B) Da ≦ 20 (μm)
D50: Cumulative average particle diameter on a sieve [μm] measured with a laser diffraction particle size distribution analyzer (Microtrac FRA: manufactured by Nikkiso Co., Ltd.)
Da: Maximum particle size [μm] indicated when measured with a laser diffraction particle size distribution analyzer (Microtrac FRA: Nikkiso Co., Ltd.)
本発明の第２の特徴は、コロイド炭酸カルシウムが、飽和脂肪酸、縮合リン酸、ホスホン酸、及びそれらの塩からなる群より選択される少なくとも１種の表面処理剤で処理されている。 In the second feature of the present invention, the colloidal calcium carbonate is treated with at least one surface treatment agent selected from the group consisting of saturated fatty acids, condensed phosphoric acid, phosphonic acid, and salts thereof.
本発明の第３の特徴は、上記酸化抑制剤が還元剤である。 A third feature of the present invention is that the oxidation inhibitor is a reducing agent.
本発明の第４の特徴は、上記酸化抑制剤が硫化物系還元剤である。 According to a fourth feature of the present invention, the oxidation inhibitor is a sulfide-based reducing agent.
本発明の第５の特徴は、上記酸化抑制剤の含有量が、コロイド炭酸カルシウムに対し０．００１〜１０重量％である。 A fifth feature of the present invention is that the content of the oxidation inhibitor is 0.001 to 10% by weight with respect to colloidal calcium carbonate.
本発明の第６の特徴は、水酸化カルシウム水懸濁液に炭酸ガスを導通して炭酸化反応により得たコロイド炭酸カルシウム水懸濁液に、酸化抑制剤をコロイド炭酸カルシウム固形分に対し０．００１〜１０重量％添加した後熟成し、乾燥、解砕した乾粉を分級する請求項１記載のコロイド炭酸カルシウム填剤の製造方法である。 The sixth feature of the present invention is that a colloidal calcium carbonate aqueous suspension obtained by conducting carbonation gas through a calcium hydroxide aqueous suspension and conducting a carbonation reaction has an oxidation inhibitor added to the solid content of the colloidal calcium carbonate. 2. The method for producing a colloidal calcium carbonate filler according to claim 1, wherein the dry powder which has been ripened after being added in an amount of 0.001 to 10% by weight, dried and crushed is classified.
本発明の第７の特徴は、樹脂中に、上記コロイド炭酸カルシウム填剤を配合してなる樹脂組成物である。 The seventh feature of the present invention is a resin composition obtained by blending the colloidal calcium carbonate filler in a resin.
本発明のコロイド炭酸カルシウム填剤は、白色度が高く、耐熱性や耐光性に優れているので、特に、光反射シートや合成紙等の白色系合成樹脂用の填剤として好適である。 Since the colloidal calcium carbonate filler of the present invention has high whiteness and excellent heat resistance and light resistance, it is particularly suitable as a filler for white synthetic resins such as light reflecting sheets and synthetic paper.
上記したように、沈降性炭酸カルシウムは、石灰石を焼成して得た生石灰に水を加えて得た石灰乳と、焼成時に出る炭酸ガスとを反応させて得られる。コロイド炭酸カルシウムの一般的用途は、塗料やゴムなどの白色系体質顔料であるため、鉄、マンガン、クロム、銅、ニッケル等の合成樹脂の黄変に影響を与える着色金属が多く含有されているのは好ましくない。 As described above, precipitated calcium carbonate is obtained by reacting lime milk obtained by adding water to quick lime obtained by firing limestone and carbon dioxide gas produced during firing. The general use of colloidal calcium carbonate is white extender pigments such as paint and rubber, so it contains a lot of colored metals that affect the yellowing of synthetic resins such as iron, manganese, chromium, copper, and nickel. Is not preferred.
着色金属の中でも、特に鉄は他の着色金属より石灰石中での含有量が多いため、例えば、特開平１０−７２２１５号公報の従来技術で記載されているように、コロイド炭酸カルシウムの一次粒子を分散および成長させる目的で熟成させる場合、該炭酸カルシウムの色相の低下（黄変）が起こりやすく、また、熟成時間と該炭酸カルシウムの色相低下とは、比例する傾向を示す。
前記したコロイド炭酸カルシウムの熟成と色相低下とが比例する傾向を示すことのメカニズムについては必ずしも明確ではないが、熟成が進む程、鉄化合物である無色又は無色に近い水酸化第一鉄（２価）から、不溶性で赤褐色の水酸化第二鉄（３価）への酸化が進む、もしくは熟成によるコロイド炭酸カルシウムの成長に合わせ、水酸化第二鉄も同様に成長し、色相低下することが考えられる。
Among colored metals, particularly iron has a higher content in limestone than other colored metals. For example, as described in the prior art of JP-A-10-72215, primary particles of colloidal calcium carbonate are used. In the case of aging for the purpose of dispersing and growing, the hue (yellowing) of the calcium carbonate tends to decrease, and the aging time and the hue decrease of the calcium carbonate tend to be proportional.
The mechanism of the proportionality between the aging of the colloidal calcium carbonate and the decrease in hue is not necessarily clear, but as the aging progresses, the iron compound is colorless or nearly colorless ferrous hydroxide (divalent). ) To insoluble and reddish brown ferric hydroxide (trivalent), or ferric hydroxide grows in the same way with the growth of colloidal calcium carbonate by aging, and it is considered that the hue decreases. It is done.
従って、コロイド炭酸カルシウムの色相低下を抑制する方法としては、イオン交換法等の対応は該炭酸カルシウムが存在する水懸濁液系では困難であることから、着色金属の酸化を抑制する酸化抑制剤を添加することが好適である。このような酸化抑制剤としては、着色金属イオンを補足して酸化を抑制する金属イオン封鎖剤や、着色金属イオンを還元させる還元剤などが挙げられる。 Therefore, as a method for suppressing the decrease in the hue of colloidal calcium carbonate, it is difficult to cope with ion exchange and the like in an aqueous suspension system in which the calcium carbonate is present. Is preferably added. Examples of such an oxidation inhibitor include a metal ion sequestering agent that captures colored metal ions and suppresses oxidation, and a reducing agent that reduces colored metal ions.
金属イオン封鎖剤としては、ヒドロキシエチレンジアミン四酢酸（HEDTA ）等のＥＤＴＡ系有機系封鎖剤が例示できるが、一般に有機系の場合は、耐熱性や耐光性が低いアミノカルボン酸系が多いため耐熱性や耐光性の要求される用途では適当ではない場合が多い。 Examples of the metal ion sequestering agent include EDTA organic sequestering agents such as hydroxyethylenediaminetetraacetic acid (HEDTA). Generally, in the case of an organic sequestering agent, since there are many aminocarboxylic acid systems having low heat resistance and light resistance, heat resistance is high. It is often not suitable for applications that require light resistance.
一方、還元剤の場合は、鉄等の着色金属の酸化防止作用や漂白作用があり、また無機系のものが多く、耐熱性や耐光性に優れている。
従って、耐熱性や耐光性が要求される用途においては、酸化抑制剤として還元剤が好適である。還元剤としては、二酸化硫黄（ＳＯ2 ）、亜硫酸ソーダ（Ｎａ2 ＳＯ3 ）、硫酸ソーダ（Ｎａ2 ＳＯ4 ）、チオ硫酸ソーダ（Ｎａ2 Ｓ2 Ｏ3 ）、亜二チオン酸ソーダ（Ｎａ2 Ｓ2 Ｏ4 ）、ホルムアミジンスルフィン酸（（ＮＨ2 ）（ＮＨ）ＣＳＯ2 Ｈ）、ホルムアルデヒドスルホキシル酸ソーダ（ＮａＨＳＯ2 ・ＣＨ2 Ｏ・Ｈ2 Ｏ）、ホルムアルデヒドスルホキシル酸亜鉛（Ｚｎ（ＨＳＯ2 ・ＣＨ2 Ｏ）2 ）、重亜硫酸ソーダ（Ｎａ2 Ｓ2 Ｏ3 ）などの硫化物系；塩化第一スズ（ＳｎＣｌ2 ）などのスズ(II)イオン系；ギ酸（ＣＨ2 Ｏ2 ）、シュウ酸（Ｃ2 Ｈ2 Ｏ4 ）などの有機物系；ソーダボロハイドライド（ＮａＢＨ4 ）、ジメチルアミンボラン（（ＣＨ3 ）3 ＨＮＢＨ3 ）、トリメチルアミンボラン（（ＣＨ3 ）3 ＨＮＢＨ4 ）、水素化シアノホウ素ソーダ（ＮａＣＮＢＨ3 ) などのホウ素系などが挙げられる。
これらの中では、チオ硫酸ソーダや亜二チオン酸ソーダ、ホルムアミジンスルフィン酸、硫酸ソーダ、重亜硫酸ソーダ等の硫化物系は、環境面やコスト面、安定性の面で好ましく、特にチオ硫酸ソーダや亜二チオン酸ソーダは、食品添加物としても認められているため、ポリオレフィン等衛生協議会での自主基準（ポジティブリスト）に適合する面で好ましい。
On the other hand, in the case of a reducing agent, it has an antioxidant action and a bleaching action of colored metals such as iron, and many inorganic ones are excellent in heat resistance and light resistance.
Therefore, in applications that require heat resistance and light resistance, a reducing agent is suitable as an oxidation inhibitor. Examples of the reducing agent include sulfur dioxide (SO 2 ), sodium sulfite (Na 2 SO 3 ), sodium sulfate (Na 2 SO 4 ), sodium thiosulfate (Na 2 S 2 O 3 ), sodium dithionite (Na 2). S 2 O 4 ), formamidine sulfinic acid ((NH 2 ) (NH) CSO 2 H), sodium formaldehyde sulfoxylate (NaHSO 2 · CH 2 O · H 2 O), zinc formaldehyde sulfoxylate (Zn (HSO 2 · CH 2 O) 2 ), sulfide systems such as sodium bisulfite (Na 2 S 2 O 3 ); tin (II) ion systems such as stannous chloride (SnCl 2 ); formic acid (CH 2 O 2 ) Organic materials such as oxalic acid (C 2 H 2 O 4 ); sodaborohydride (NaBH 4 ), dimethylamine borane ((CH 3 ) 3 HNBH 3 ), trimethylamine borane ((CH 3 ) 3 HNBH 4 ), hydrogen Conversion Like boron such Anohou containing soda (NaCNBH 3).
Among these, sulfide systems such as sodium thiosulfate, sodium dithionite, formamidine sulfinic acid, sodium sulfate, sodium bisulfite and the like are preferable in terms of environment, cost, and stability, especially sodium thiosulfate. Since sodium dithionite is also recognized as a food additive, it is preferable in terms of meeting the voluntary standards (positive list) of the Sanitation Council for Polyolefins.
本発明で用いる酸化抑制剤の含有量は特に限定されるものでないが、コロイド炭酸カルシウムの白色度を積極的に高めるのではなく、色相低下の抑制を目的としているため、通常、コロイド炭酸カルシウムに対し、０．００１〜１０重量％が適当である。０．００１重量％未満では十分な酸化抑制効果が得られ難く、一方、１０重量％を超えてもそれ以上の酸化抑制効果が得られ難くいばかりか、例えば、樹脂とのコンパウンドの際、他の添加剤と併用された場合，その添加剤に悪影響を及ぼす可能性がある。従って、好ましくは０．００３〜１重量％、さらに好ましくは０．００５〜０．１重量％である。 Although the content of the oxidation inhibitor used in the present invention is not particularly limited, it is not intended to positively increase the whiteness of the colloidal calcium carbonate but to suppress a decrease in hue. On the other hand, 0.001 to 10% by weight is appropriate. If it is less than 0.001% by weight, it is difficult to obtain a sufficient oxidation-inhibiting effect. On the other hand, if it exceeds 10% by weight, it is difficult to obtain a further oxidation-inhibiting effect. When used in combination with other additives, the additive may be adversely affected. Therefore, it is preferably 0.003 to 1% by weight, and more preferably 0.005 to 0.1% by weight.
本発明のコロイド炭酸カルシウム填剤は、水酸化カルシウム水懸濁液に炭酸ガスを導通して炭酸化反応により得たコロイド炭酸カルシウム水懸濁液に、酸化抑制剤をコロイド炭酸カルシウム固形分に対し０．００１〜１０重量％添加することにより製造することができる。
コロイド炭酸カルシウム水懸濁液の製造方法は特に限定されないが、例えば、特開２００６−２６５４７２号公報の製造方法を例示することができる。
該公報に記載の製造方法は、炭酸ガス化合法で、石灰石を焼成して得た生石灰に水を加えて得た石灰乳と、焼成時に出る炭酸ガスを導通して反応させる方法であり、得られる粒子が微細で一次粒子の粒径・形状も均一である。また反応時の条件や反応後の工程によって粒度調整、粗大粒子除去も可能であり、得られる粒子の物性に対する経済性や環境への負荷の点でも優れており、本発明の目的の一つである白色系合成樹脂シートに用いるのに好適である。
The colloidal calcium carbonate filler of the present invention is a colloidal calcium carbonate aqueous suspension obtained by conducting a carbonation reaction by passing carbon dioxide through a calcium hydroxide aqueous suspension. It can manufacture by adding 0.001 to 10 weight%.
Although the manufacturing method of colloidal calcium carbonate aqueous suspension is not specifically limited, For example, the manufacturing method of Unexamined-Japanese-Patent No. 2006-265472 can be illustrated.
The production method described in the publication is a method in which lime milk obtained by adding water to quick lime obtained by calcining limestone and carbon dioxide gas emitted at the time of conduction are reacted with each other by carbon dioxide gas compound method. The resulting particles are fine and the primary particles have a uniform particle size and shape. The particle size can be adjusted and coarse particles can be removed depending on the reaction conditions and the post-reaction process, which is excellent in terms of economics and physical load on the physical properties of the resulting particles, and is one of the objects of the present invention. It is suitable for use in a certain white type synthetic resin sheet.
原料として用いられる石灰石は不純物に留意して選択することが好ましく、着色金属の総量（鉄＋マンガン＋クロム＋銅＋ニッケル）が1000ppm 以下、好ましくは100ppm以下、さらに好ましくは50ppm 以下である石灰石を用いることが好ましい。なお、着色金属の含有量の測定は、ＩＣＰ（シーケンシャル高周波プラズマ発光分析装置）や原子吸光分光光度計などで測定することができる。焼成時の燃料は一般にコークスや灯油、ガス等が直接添加されているが、コスト的に許される限り、不純物の少ない軽油や灯油、（天然）ガスで焼成を行うことが色相の点でより好ましい。 Limestone used as a raw material is preferably selected in consideration of impurities, and limestone having a total amount of colored metals (iron + manganese + chromium + copper + nickel) of 1000 ppm or less, preferably 100 ppm or less, more preferably 50 ppm or less. It is preferable to use it. The content of the colored metal can be measured with an ICP (sequential high frequency plasma emission analyzer), an atomic absorption spectrophotometer, or the like. Generally, coke, kerosene, gas, etc. are added directly to the fuel during firing, but it is more preferable in terms of hue to fire with light oil, kerosene, or (natural) gas with less impurities as far as the cost is allowed. .
酸化抑制剤の添加時期は、コロイド炭酸カルシウムの黄変化が顕著になる熟成工程前に添加するのが好ましい。従って、炭酸化前の水酸化カルシウム水懸濁液または炭酸化後のコロイド炭酸カルシウムの水懸濁液系で、よく混合される工程において、酸化抑制剤を溶かし込んだ水溶液を適量添加することが好ましい。また、水酸化カルシウム水懸濁液中に酸化抑制剤を適量添加する場合は、コロイド炭酸カルシウム換算で行うことにし、コロイド炭酸カルシウム水懸濁液に添加する場合は、熟成工程で、好ましくは熟成工程の早い段階で添加することが好ましい。 It is preferable to add the oxidation inhibitor before the aging step in which yellowing of the colloidal calcium carbonate becomes remarkable. Therefore, an appropriate amount of an aqueous solution in which an oxidation inhibitor is dissolved can be added in a well-mixed process in a calcium hydroxide aqueous suspension before carbonation or an aqueous suspension of colloidal calcium carbonate after carbonation. preferable. In addition, when an appropriate amount of an oxidation inhibitor is added to the calcium hydroxide aqueous suspension, it is calculated in terms of colloidal calcium carbonate. When added to the colloidal calcium carbonate aqueous suspension, it is an aging step, preferably an aging step. It is preferable to add at an early stage of the process.
熟成工程で粒度調整を行って得られたコロイド炭酸カルシウム水懸濁液は、脱水され乾燥され解砕された後、本発明の色相が安定したコロイド炭酸カルシウム填剤が得られる。 After the colloidal calcium carbonate aqueous suspension obtained by adjusting the particle size in the aging step is dehydrated, dried and crushed, the colloidal calcium carbonate filler having a stable hue of the present invention is obtained.
なお、解砕後、必要に応じて空気分級等の分級操作を行い、乾燥によって生じた凝集体や不純物を除去することは効果的であり、特に、コロイド炭酸カルシウム粒子の均一性や分散性を要求される白色系樹脂シート用においては、下記の式を満足することがより好ましい。
（ａ）０．３≦Ｄ50≦１．５ （μｍ）
（ｂ）Ｄａ≦２０ （μｍ）
但し、
Ｄ50 ：レーザー回折式粒度分布測定装置（マイクロトラックＦＲＡ：日機装社製）で測定した篩上積算平均粒子径 [μｍ]
Ｄａ ：レーザー回折式粒度分布測定装置（マイクロトラックＦＲＡ：日機装社製）で測定した時に示す最大粒子径 [μｍ]
After crushing, it is effective to perform classification operations such as air classification as necessary to remove aggregates and impurities generated by drying. In particular, the uniformity and dispersibility of colloidal calcium carbonate particles are improved. For the required white resin sheet, it is more preferable to satisfy the following formula.
(A) 0.3 ≦ D50 ≦ 1.5 (μm)
(B) Da ≦ 20 (μm)
However,
D50: Cumulative average particle diameter on a sieve [μm] measured with a laser diffraction particle size distribution analyzer (Microtrac FRA: manufactured by Nikkiso Co., Ltd.)
Da: Maximum particle diameter [μm] indicated when measured with a laser diffraction particle size distribution analyzer (Microtrac FRA: Nikkiso Co., Ltd.)
上記（ａ）式は、本発明のコロイド炭酸カルシウム填剤を、下記のレーザー回折式粒度分布測定装置で測定した篩上積算平均粒子径D50 で、０．３〜１．５（μm ）の範囲内にあることが好ましく、０．３〜１．０μm であることがより好ましい。平均粒子径D50 を０．３μm 未満にすることは技術上可能であるがコストの点で好ましくなく、一方、１．５μm を越えると、フィルムシート一次粒子の凝集体で構成する２次粒子の凝集力が強く、樹脂中でも二次粒子のままで存在するため、例えば、光反射用白色樹脂シートに用いた場合、延伸法で空孔ボイドを形成させる際に、目的とする孔径以上の大きな空孔ができ、反射率が低下するなど適さない場合がある。 The above formula (a) is the range of 0.3 to 1.5 (μm) in terms of the cumulative average particle diameter D50 on the sieve when the colloidal calcium carbonate filler of the present invention is measured by the following laser diffraction particle size distribution measuring device. It is preferably within the range, and more preferably 0.3 to 1.0 μm. Although it is technically possible to make the average particle diameter D50 less than 0.3 μm, it is not preferable in terms of cost. On the other hand, if it exceeds 1.5 μm, the aggregation of secondary particles composed of aggregates of primary particles of the film sheet Because it is strong and exists as a secondary particle even in the resin, for example, when used in a white resin sheet for light reflection, when forming void voids by the stretching method, large pores larger than the target pore diameter May be unsuitable, such as a decrease in reflectivity.
＜測定方法＞
下記の配合材（Ｉ）と（II）をビーカに秤量し、超音波分散機にて予備分散させたものを試料として、粒度測定を行う。
（Ｉ）炭酸カルシウム試料 ０．１〜０．５ｇ
（II）メタノール ５０ｇ
予備分散として用いる超音波分散は、一定条件下で行う方が好ましく、本発明では超音波分散機としてＵＳ−３００Ｔ（日本精機製作所社製）を用い、電流値３００μＡの下で、６０秒間の一定条件で予備分散させた。また、レーザー回折式粒度分布測定装置は、前記のマイクロトラックＦＲＡを使用した。
<Measurement method>
The following compounding materials (I) and (II) are weighed in a beaker, and a particle size measurement is performed using a sample preliminarily dispersed by an ultrasonic disperser.
(I) Calcium carbonate sample 0.1-0.5g
(II) Methanol 50g
The ultrasonic dispersion used as the preliminary dispersion is preferably performed under a certain condition. In the present invention, US-300T (manufactured by Nippon Seiki Seisakusho) is used as the ultrasonic dispersion machine, and the current dispersion is constant for 60 seconds under a current value of 300 μA. Pre-dispersed under conditions. The laser diffraction particle size distribution analyzer used the microtrack FRA.
上記（ｂ）式は、レーザー回折式粒度分布装置で測定した時の最大粒径（Ｄａ）であり、（ａ）式と同様の理由から、Ｄａ≦２０（μｍ）の範囲内にあることが好ましく、Ｄａ≦１５（μｍ）の範囲内であることがより好ましく、Ｄａ≦１０（μｍ）の範囲内であることが更に好ましい。 The above equation (b) is the maximum particle size (Da) when measured with a laser diffraction particle size distribution device, and for the same reason as equation (a), it may be within the range of Da ≦ 20 (μm). Preferably, it is more preferably within a range of Da ≦ 15 (μm), and further preferably within a range of Da ≦ 10 (μm).
本発明のコロイド炭酸カルシウム填剤は、例えば光反射用樹脂等に配合される場合、該樹脂への安定性や分散性を付与するために各種表面処理剤で処理（被覆処理）することはさらに有効である。 When the colloidal calcium carbonate filler of the present invention is blended in, for example, a light reflecting resin, it is further treated with various surface treatment agents (coating treatment) in order to impart stability and dispersibility to the resin. It is valid.
表面処理剤は特に限定されるものでなく、例えば、飽和脂肪酸、不飽和脂肪酸、脂環族カルボン酸、樹脂酸、それらの塩やエステル、アルコール系界面活性剤、ソルビタン脂肪酸エステル類、アミド系やアミン系界面活性剤、ポリオキシアルキレンアルキルエーテル類、ポリオキシエチレンノニルフェニルエーテル、アルファオレフィンスルフォン酸ナトリウム、長鎖アルキルアミノ酸、アミンオキサイド、アルキルアミン、第四級アンモニウム塩、アミノカルボン酸、ホスホン酸、多価カルボン酸、縮合リン酸等が例示され、これらは、単独で又は必要に応じ２種以上組み合わせて用いることができる。 The surface treatment agent is not particularly limited, and examples thereof include saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids, resin acids, salts and esters thereof, alcohol surfactants, sorbitan fatty acid esters, amides, Amine surfactants, polyoxyalkylene alkyl ethers, polyoxyethylene nonyl phenyl ether, alpha olefin sodium sulfonate, long chain alkyl amino acids, amine oxides, alkyl amines, quaternary ammonium salts, aminocarboxylic acids, phosphonic acids, Examples thereof include polyvalent carboxylic acids and condensed phosphoric acids, and these can be used alone or in combination of two or more as required.
飽和脂肪酸としては、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸等が挙げられ、不飽和脂肪酸としては、オレイン酸、リノール酸、リノレン酸等が挙げられ、脂環族カルボン酸としては、シクロペンタン環やシクロヘキサン環の末端にカルボキシル基を持つナフテン酸等が挙げられ、樹脂酸としてアビエチン酸、ピマル酸、ネオアビエチン酸等が挙げられる。 Examples of saturated fatty acids include capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid. Examples of unsaturated fatty acids include oleic acid, linoleic acid, and linolenic acid. Examples of alicyclic carboxylic acids include And naphthenic acid having a carboxyl group at the end of the cyclopentane ring or cyclohexane ring, and examples of the resin acid include abietic acid, pimaric acid, and neoabietic acid.
アルコール系界面活性剤としては、アルキル硫酸エステルナトリウム、アルキルエーテル硫酸エステルナトリウム等が挙げられ、ソルビタン脂肪酸エステル類としては、ソルビタンモノラウレートやポリオキシエチレンソルビタンモノステアレート等が挙げられ、アミド系やアミン系界面活性剤としては、脂肪酸アルカノールアミド、アルキルアミンオキシド等が挙げられ、ポリオキシアルキレンアルキルエーテル類としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンノニルフェニルエーテル等が挙げられ、長鎖アルキルアミノ酸としては、ラウリルベタイン、ステアリルベタイン等が挙げられる。 Examples of alcohol surfactants include sodium alkyl sulfates and sodium alkyl ether sulfates. Examples of sorbitan fatty acid esters include sorbitan monolaurate and polyoxyethylene sorbitan monostearate. Examples of amine surfactants include fatty acid alkanolamides and alkylamine oxides, and examples of polyoxyalkylene alkyl ethers include polyoxyethylene alkyl ethers, polyoxyethylene lauryl ethers, polyoxyethylene nonylphenyl ethers, and the like. Examples of long-chain alkyl amino acids include lauryl betaine and stearyl betaine.
アミンオキサイドとしては、ポリオキシエチレン脂肪酸アミド、アルキルアミンオキサイド等が挙げられ、アルキルアミンとしては、ステアリルアミンアセテート等が挙げられ、第四級アンモニウム塩としては、ステアリルトリメチルアンモニウムクロライドや第四級アンモニウムサルフェート等が挙げられる。 Examples of amine oxides include polyoxyethylene fatty acid amides and alkylamine oxides. Examples of alkylamines include stearylamine acetate. Examples of quaternary ammonium salts include stearyltrimethylammonium chloride and quaternary ammonium sulfate. Etc.
アミノカルボン酸としては、エチレンジアミン四酢酸やニトリロ三酢酸、ヒドロキシエチルエチレンジアミン三酢酸、ジエチレントリアミン五酢酸、トリエチレンテトラアミン六酢酸等が挙げられる。
ホスホン酸としては、１−ヒドロキシエチリデン−１，１−ジホスホン酸（ＨＥＤＰ）、アミノトリメチレンホスホン酸（ＡＴＭＰ）等が挙げられる。
多価カルボン酸系としては、ポリアクリル酸やポリマレイン酸等のポリカルボン酸や、その共重合物等が挙げられる。
縮合リン酸としては、ポリリン酸ナトリウム、ピロリン酸ナトリウム、ヘキサメタリン酸ナトリウム等が挙げられる。
Examples of the aminocarboxylic acid include ethylenediaminetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, and the like.
Examples of the phosphonic acid include 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), aminotrimethylenephosphonic acid (ATMP), and the like.
Examples of the polyvalent carboxylic acid include polycarboxylic acids such as polyacrylic acid and polymaleic acid, and copolymers thereof.
Examples of the condensed phosphoric acid include sodium polyphosphate, sodium pyrophosphate, sodium hexametaphosphate and the like.
上記各種酸は、例えば、カリウムやナトリウムのアルカリ金属塩や、アンモニウム塩としても使うことができる。 The above-mentioned various acids can be used, for example, as alkali metal salts or ammonium salts of potassium or sodium.
これらの中でも、樹脂への相溶性や粉体白色度、耐光性の観点から、ステアリン酸等で代表される飽和系脂肪酸及びその塩、縮合リン酸及びその塩、ホスホン酸及びその塩が好適に使用できる。 Among these, from the viewpoint of compatibility with the resin, powder whiteness, and light resistance, saturated fatty acids represented by stearic acid and the like, salts thereof, condensed phosphoric acid and salts thereof, phosphonic acid and salts thereof are preferable. Can be used.
上記表面処理剤の使用量は、コロイド炭酸カルシウムの比表面積や、コンパウンド条件等に応じて変わるので一概には規定しにくいが、通常、コロイド炭酸カルシウムに対して０．０５〜１０重量％が好ましい。使用量が０．０５重量％未満では充分な表面処理効果が得られ難く、一方、１０重量％を越えて添加しても効果の更なる向上が認められ難かったり、表面処理剤がブリードし易い傾向がある。 The amount of the surface treatment agent used varies depending on the specific surface area of the colloidal calcium carbonate, compounding conditions, etc., and thus is generally difficult to define, but is usually preferably 0.05 to 10% by weight with respect to the colloidal calcium carbonate. . When the amount used is less than 0.05% by weight, it is difficult to obtain a sufficient surface treatment effect. On the other hand, even if added over 10% by weight, further improvement of the effect is difficult to be recognized, and the surface treatment agent tends to bleed. Tend.
表面処理方法としては、例えば、スーパーミキサーやヘンシェルミキサー等のミキサーを用い、粉体に直接表面処理剤を混合し、必要に応じて加熱して表面処理する一般に乾式処理と呼ばれる方法や、表面処理剤を水溶媒等で溶解し、炭酸カルシウム水懸濁液中に添加して表面処理した後、脱水、乾燥する一般に湿式処理と呼ばれる方法でも、その両者の複合でもよいが、炭酸カルシウム粒子表面への処理の度合いと経済的な観点から、主として湿式法単独が好ましく用いられる。 As the surface treatment method, for example, using a mixer such as a super mixer or a Henschel mixer, a surface treatment agent is directly mixed with the powder, and if necessary, the surface treatment is performed by heating and surface treatment is generally performed. The agent is dissolved in an aqueous solvent, etc., added to the calcium carbonate aqueous suspension, surface-treated, then dehydrated and dried, generally called a wet process, or a combination of both. In view of the degree of treatment and economic viewpoint, the wet method alone is preferably used mainly.
表面処理剤量は、コロイド炭酸カルシウムの比表面積や表面処理剤の種類、配合される樹脂、コンパウンド条件等に応じて異なるため一概に規定されないが、通常、表面処理剤率（Ａｓ）として、０．１〜４ｍｇ／ｍ2 であることが好ましい。Ａｓが０．１ｍｇ／ｍ2 未満では十分な分散効果が得られにくく、一方、４ｍｇ／ｍ2 未満を超えても、更なる効果の向上が得られにくいばかりでなく、処理剤過多による表面処理剤成分あるいは樹脂成分への遊離の原因になりやすい。
なお、表面処理率（Ａｓ）は下記の測定方法により求められる。
＜表面処理率（Ａｓ）の測定方法＞
熱天秤（リガク社製ＴＧ−８１１０型）にて、直径１０ｍｍで０．５ｍｌの白金製容器に表面処理したコロイド炭酸カルシウム粒子１５０ｍｇを入れ、１５℃／分の昇温速度で昇温して２００℃から５００℃までの熱減量を測定し、表面処理した炭酸カルシウム粒子１ｇ当りの熱減量率（ｍｇ／ｇ）を求め、この値をＢＥＴ比表面積で除して求める。
The amount of the surface treatment agent is not generally defined because it varies depending on the specific surface area of colloidal calcium carbonate, the type of the surface treatment agent, the resin to be blended, the compounding conditions, etc. Usually, the surface treatment agent ratio (As) is 0 It is preferable that it is 1-4 mg / m < 2 >. If As is less than 0.1 mg / m 2, it is difficult to obtain a sufficient dispersion effect. On the other hand, if it exceeds 4 mg / m 2 , not only is it difficult to improve the effect, but also surface treatment due to excessive treatment agent. It tends to cause release to the agent component or resin component.
The surface treatment rate (As) is determined by the following measurement method.
<Method for measuring surface treatment rate (As)>
Using a thermobalance (TG-8110 type manufactured by Rigaku Corporation), 150 mg of colloidal calcium carbonate particles surface-treated in a platinum container having a diameter of 10 mm and a volume of 0.5 ml was added, and the temperature was raised at a rate of 15 ° C./min. The heat loss from 500C to 500 ° C is measured, the heat loss rate (mg / g) per gram of the surface-treated calcium carbonate particles is determined, and this value is divided by the BET specific surface area.
上記の如くして得られる本発明の色相が安定したコロイド炭酸カルシウム填剤の白色度は、下記の方法で測定することができる。
＜白色度の測定方法＞
色相測定方法は、コロイド炭酸カルシウム填剤と可塑剤（ＤＯＰ）を脱泡機にて１：１に混合した後、分光式色差計（ZE-2000 ，日本電色社製）を用い、標準白色板（Ｐ６００４）との比較で明度（Ｌ値）（色相）と黄変度（ｂ値）を出力した。コロイド炭酸カルシウム填剤の白色度が高いほどＬ値は高く、ｂ値はゼロに近づく。また、ｂ値が高いほど黄変度が高い。
本発明のコロイド炭酸カルシウム填剤を光反射シートや合成紙に使用する場合、Ｌ値とｂ値の両者が、特定の範囲にあることが好ましい。具体的に例示すると、Ｌ値は、通常８１以上であることが好ましく、より好ましくは８３以上である。一方、ｂ値は、通常５以下であることが好ましく、より好ましくは４以下である。
The whiteness of the colloidal calcium carbonate filler having a stable hue according to the present invention obtained as described above can be measured by the following method.
<Measurement method of whiteness>
The hue is measured by mixing a colloidal calcium carbonate filler and a plasticizer (DOP) 1: 1 with a defoaming machine, and then using a spectroscopic color difference meter (ZE-2000, manufactured by Nippon Denshoku). Lightness (L value) (hue) and yellowing degree (b value) were output in comparison with the plate (P6004). The higher the whiteness of the colloidal calcium carbonate filler, the higher the L value and the b value approaches zero. Moreover, yellowing degree is so high that b value is high.
When the colloidal calcium carbonate filler of the present invention is used for a light reflecting sheet or synthetic paper, it is preferable that both the L value and the b value are in a specific range. Specifically, it is preferable that the L value is usually 81 or more, more preferably 83 or more. On the other hand, the b value is usually preferably 5 or less, more preferably 4 or less.
本発明のコロイド炭酸カルシウム填剤が配合とされる樹脂としては特に限定されないが、例えば、ポリエステル、ポリカーボネート、ポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、エチレン又はプロピレンと他のモノマーの共重合体等が挙げられる。なかでも、白色合成紙や光反射用白色樹脂シートとして用いる場合は、前記した如く、耐熱性や耐光性等で経時劣化が少なく経済的な点で、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂が好ましい。 Although it does not specifically limit as resin with which the colloidal calcium carbonate filler of this invention is mix | blended, For example, a polyester, a polycarbonate, polyethylene, a polypropylene, an ethylene propylene copolymer, a copolymer of ethylene or a propylene, and another monomer, etc. Is mentioned. Among them, when used as white synthetic paper or a white resin sheet for light reflection, polyolefin resins such as polyethylene and polypropylene are preferable from the viewpoint of heat resistance, light resistance and the like with little deterioration over time.
本発明のコロイド炭酸カルシウム填剤と樹脂との配合割合は、特に限定されるものでなく、樹脂の種類や用途、所望する物性やコストによって大きく異なるので、それらに応じて適宜決定すればよいが、前記した白色系樹脂へ配合される場合は、樹脂１００重量部に対して６０〜１５０重量部が適当であり、好ましくは８０〜１２０重量部である。 The blending ratio of the colloidal calcium carbonate filler and the resin of the present invention is not particularly limited, and varies greatly depending on the type and use of the resin, desired physical properties and cost, and may be appropriately determined according to them. When blended into the above-described white resin, 60 to 150 parts by weight is suitable for 100 parts by weight of resin, and preferably 80 to 120 parts by weight.
また、本発明のコロイド炭酸カルシウム填剤の効能を阻害しない範囲で、シート特性の向上を目的として、脂肪酸、脂肪酸アミド、エチレンビスステアリン酸アミド、ソルビタン脂肪酸エステル等の滑剤、可塑剤及び安定剤、酸化防止剤等を添加してもよく、更に、一般に樹脂組成物に用いられる添加物、例えば滑剤、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、中和剤、防曇剤、アンチブロッキング剤、帯電防止剤、スリップ剤、着色剤等を配合してもよい。 Further, for the purpose of improving sheet properties within the range not inhibiting the efficacy of the colloidal calcium carbonate filler of the present invention, lubricants such as fatty acids, fatty acid amides, ethylene bis stearic acid amides, sorbitan fatty acid esters, plasticizers and stabilizers, Antioxidants and the like may be added, and additives generally used in resin compositions such as lubricants, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, You may mix | blend an antiblocking agent, an antistatic agent, a slip agent, a coloring agent, etc.
本発明のコロイド炭酸カルシウム填剤と前記した各種添加剤を樹脂に配合する場合、通常、一軸あるいは二軸押出機、ニーダー、バンバリーミキサー等で加熱混練し、Ｔダイ等でシートを作成後に一軸または二軸で延伸して微細な孔を有する多孔質フィルム製品とされる。
また、混練後にＴダイ押出、あるいはインフレーション成形等の公知の成形機を用いて製膜し、それらを酸処理して本発明のコロイド炭酸カルシウム填剤を溶解して微細な孔を有するシート製品としてもよい。
When the colloidal calcium carbonate filler of the present invention and the various additives described above are blended in a resin, the mixture is usually heated and kneaded with a single screw or twin screw extruder, kneader, Banbury mixer, etc. A biaxially stretched porous film product having fine pores.
Further, after kneading, a film product is formed using a known molding machine such as T-die extrusion or inflation molding, and these are acid-treated to dissolve the colloidal calcium carbonate filler of the present invention, thereby producing a sheet product having fine pores. Also good.
樹脂の形状にはペレット状及び任意の粒径に調整されたパウダー（グラニュー）状があり、分散性の面からはパウダー状の樹脂を用い、ヘンシェルミキサー、タンブラー型ミキサー、リボンブレンダー等の公知のミキサーと称される混練機を用いて混合することが好ましい。
本発明のコロイド炭酸カルシウム填剤は、ペレット状樹脂とともに用いられた場合でも、本発明以外の填剤に比べて、樹脂中での分散性等で良好な物性を示すが、パウダー状の樹脂と混合して使用すると特に良好である。例えばヘンシェルミキサーで混合した場合、混合が速やかに行えるメリットの他に、ミキサーの内壁面や攪拌・混合用の羽根への付着が少なく、ミキサー内部での付着が誘引する変質樹脂や凝集物の発生も少なくなり、混合の作業性が良好で、更に、後工程での混練押出機でのストレーナーの目詰まり等の発生も少ない等の特徴を有している。
The shape of the resin includes pellets and powders (granulated) adjusted to an arbitrary particle size. From the viewpoint of dispersibility, powdered resins are used, and known resins such as Henschel mixers, tumbler mixers, and ribbon blenders are used. It is preferable to mix using a kneader called a mixer.
Even when the colloidal calcium carbonate filler of the present invention is used together with a pellet-like resin, it exhibits good physical properties such as dispersibility in the resin, compared to fillers other than the present invention. It is particularly good when mixed and used. For example, when mixing with a Henschel mixer, in addition to the advantage of being able to mix quickly, there is little adhesion to the inner wall surface of the mixer and the blades for stirring and mixing, and generation of modified resins and aggregates that induce adhesion inside the mixer In addition, the mixing workability is good, and further, the occurrence of clogging of the strainer in the kneading extruder in the subsequent process is reduced.
上記の混練機も様々な機種や設定条件があり、原料の投入方法も、樹脂中での粒子の分散性の他にも樹脂自体のＭＩ値等への影響やコストを勘案して適宜決定される。
本発明のコロイド炭酸カルシウム填剤を樹脂に配合する場合も、それらを考慮して選択されるが、ヘンシェルミキサー等で適度な粒度範囲の樹脂パウダーと混合した混合物を、二軸混練機等の混練機のホッパーに定量的に投入する方法が好ましい。
混練機と製膜の間において、一旦、マスターバッチと称される本発明の炭酸カルシウム填剤と樹脂、更には必要に応じ、各種添加物を含有するペレットを作成し、該ペレットを樹脂と混合して溶融・製膜しても良い。更に必要に応じ、上記工程中のＴダイ押出機を複数個重ねたり、あるいは延伸時に張り合わせるような工程を導入してもよい。
There are various models and setting conditions for the above-mentioned kneaders, and the raw material charging method is appropriately determined in consideration of the influence on the MI value of the resin itself and the cost in addition to the dispersibility of the particles in the resin. The
When the colloidal calcium carbonate filler of the present invention is blended into the resin, it is selected in consideration of them, but the mixture mixed with the resin powder having an appropriate particle size range with a Henschel mixer or the like is kneaded with a biaxial kneader or the like. A method of quantitatively charging the hopper of the machine is preferable.
Between the kneader and the film forming, the calcium carbonate filler and resin of the present invention, which is referred to as a master batch, and further, if necessary, pellets containing various additives are prepared, and the pellets are mixed with the resin Then, it may be melted and formed into a film. Furthermore, if necessary, a plurality of T-die extruders in the above process may be stacked or a process of bonding at the time of stretching may be introduced.
以下、本発明を更に実施例に基づいて具体的に説明するが、本発明の範囲はこれら実施例により何ら制限されるものではない。
なお、実施例及び比較例で作製したコロイド炭酸カルシウム填剤のＢＥＴ比表面積は、下記の測定方法に従った。
Hereinafter, the present invention will be described in more detail based on examples, but the scope of the present invention is not limited by these examples.
In addition, the BET specific surface area of the colloidal calcium carbonate filler produced by the Example and the comparative example followed the following measuring method.
＜ＢＥＴ比表面積（Ｓｗ）の測定方法＞
全自動BET 比表面積測定装置（NOVA2000，ユアサアイオニクス社製）を用い測定した。
<Measurement method of BET specific surface area (Sw)>
Measurement was performed using a fully automatic BET specific surface area measuring device (NOVA2000, manufactured by Yuasa Ionics).
実施例１
灯油を熱源に灰色緻密質石灰石を流動槽式キルンで焼成して得られた生石灰を溶解して消石灰水懸濁液とし、炭酸ガスと反応させコロイド炭酸カルシウムを合成した。該炭酸カルシウムの着色金属含有量を表１に示したが、着色金属含有量（鉄＋マンガン＋クロム＋銅＋ニケッル）は８０ｐｐｍであった。次に、２００メッシュ篩で異物や粗大粒子の除去を行った後、コロイド炭酸カルシウム固形分に対し、酸化抑制剤として０．００５重量％の亜二チオン酸ソーダ（還元剤）を添加したコロイド炭酸カルシウム水懸濁液をオストワルド熟成により粒子成長を行わせ、ＢＥＴ比表面積５ｍ2 ／g のコロイド炭酸カルシウムを１０重量％含有する水懸濁液を得た。
次に、表面処理剤として、ステアリン酸カリウムとヘキサメタリン酸ナトリウムを用い、炭酸カルシウム固形分に対して各々１．５重量％と０．５重量％を表面処理し、その後、脱水・乾燥・解砕し、更に得られた乾粉を精密空気分級機で分級を行い、炭酸カルシウムを得た。得られたコロイド炭酸カルシウム填剤の各物性値を表２に示す。
Example 1
The quick lime obtained by baking gray dense limestone with kerosene as a heat source in a fluidized tank kiln was dissolved into a slaked lime water suspension and reacted with carbon dioxide to synthesize colloidal calcium carbonate. The colored metal content of the calcium carbonate is shown in Table 1, and the colored metal content (iron + manganese + chromium + copper + nickel) was 80 ppm. Next, after removing foreign matters and coarse particles with a 200 mesh sieve, colloidal carbonate in which 0.005 wt% sodium dithionite (reducing agent) is added as an oxidation inhibitor to the solid content of colloidal calcium carbonate. Particle growth of the calcium water suspension was carried out by Ostwald ripening to obtain an aqueous suspension containing 10% by weight of colloidal calcium carbonate having a BET specific surface area of 5 m 2 / g.
Next, potassium stearate and sodium hexametaphosphate are used as surface treatment agents, and 1.5 wt% and 0.5 wt% are surface-treated with respect to the solid content of calcium carbonate, respectively, followed by dehydration, drying and crushing Further, the obtained dry powder was classified with a precision air classifier to obtain calcium carbonate. Table 2 shows the physical property values of the obtained colloidal calcium carbonate filler.
実施例２
酸化抑制剤をチオ硫酸ソーダに変更した以外は、実施例１と同様の操作を行いコロイド炭酸カルシウムを得た。得られたコロイド炭酸カルシウム填剤の各物性値を表２に示す。
Example 2
A colloidal calcium carbonate was obtained in the same manner as in Example 1 except that the oxidation inhibitor was changed to sodium thiosulfate. Table 2 shows the physical property values of the obtained colloidal calcium carbonate filler.
実施例３
酸化抑制剤をホルムアミジンスルフィン酸に変更した以外は、実施例１と同様の操作を行いコロイド炭酸カルシウムを得た。得られたコロイド炭酸カルシウム填剤の各物性値を表２に示す。
Example 3
Colloidal calcium carbonate was obtained in the same manner as in Example 1 except that the oxidation inhibitor was changed to formamidinesulfinic acid. Table 2 shows the physical property values of the obtained colloidal calcium carbonate filler.
実施例４
酸化抑制剤をソーダボロハイドライドに変更した以外は、実施例１と同様の操作を行いコロイド炭酸カルシウムを得た。得られたコロイド炭酸カルシウム填剤の各物性値を表２に示す。
Example 4
A colloidal calcium carbonate was obtained in the same manner as in Example 1 except that the oxidation inhibitor was changed to sodaborohydride. Table 2 shows the physical property values of the obtained colloidal calcium carbonate filler.
実施例５
酸化抑制剤を鉄の封鎖剤であるヒドロキシエチレンジアミン四酢酸（ＨＥＤＴＡ）に変更した以外は、実施例１と同様の操作を行いコロイド炭酸カルシウムを得た。得られたコロイド炭酸カルシウム填剤の各物性値を表２に示す。
Example 5
A colloidal calcium carbonate was obtained in the same manner as in Example 1 except that the oxidation inhibitor was changed to hydroxyethylenediaminetetraacetic acid (HEDTA) which is an iron sequestering agent. Table 2 shows the physical property values of the obtained colloidal calcium carbonate filler.
実施例６〜１０
実施例１〜５の酸化抑制剤の含有量を、コロイド炭酸カルシウム固形分に対し、それぞれ０．０５重量％に変更した以外は、実施例１と同様の操作を行いコロイド炭酸カルシウムを得た。得られたコロイド炭酸カルシウム填剤の各物性値を表２に示す。
Examples 6-10
Colloidal calcium carbonate was obtained in the same manner as in Example 1 except that the content of the oxidation inhibitor in Examples 1 to 5 was changed to 0.05% by weight with respect to the solid content of colloidal calcium carbonate. Table 2 shows the physical property values of the obtained colloidal calcium carbonate filler.
実施例１１〜１５
実施例１〜５の酸化抑制剤の含有量を、コロイド炭酸カルシウム固形分に対し、それぞれ１．０重量％に変更した以外は、実施例１と同様の操作を行いコロイド炭酸カルシウムを得た。得られたコロイド炭酸カルシウム填剤の各物性値を表３に示す。
Examples 11-15
A colloidal calcium carbonate was obtained by performing the same operation as in Example 1 except that the content of the oxidation inhibitor of Examples 1 to 5 was changed to 1.0% by weight with respect to the solid content of the colloidal calcium carbonate. Table 3 shows each physical property value of the obtained colloidal calcium carbonate filler.
実施例１６〜２０
実施例１〜５の酸化抑制剤の含有量を、コロイド炭酸カルシウム固形分に対し、それぞれ１０重量％に変更した以外は、実施例１と同様の操作を行いコロイド炭酸カルシウムを得た。得られたコロイド炭酸カルシウム填剤の各物性値を表３に示す。
Examples 16-20
Colloidal calcium carbonate was obtained in the same manner as in Example 1 except that the content of the oxidation inhibitor in Examples 1 to 5 was changed to 10% by weight with respect to the solid content of colloidal calcium carbonate. Table 3 shows each physical property value of the obtained colloidal calcium carbonate filler.
実施例２１
酸化抑制剤を添加するタイミングを、オストワルド熟成の終了後に変更した以外は、実施例２と同様の操作を行いコロイド炭酸カルシウムを得た。得られたコロイド炭酸カルシウム填剤の各物性値を表３に示す。
Example 21
Colloidal calcium carbonate was obtained by performing the same operation as in Example 2 except that the timing of adding the oxidation inhibitor was changed after the Ostwald ripening was completed. Table 3 shows each physical property value of the obtained colloidal calcium carbonate filler.
実施例２２
実施例１と同様の操作で、コロイド炭酸カルシウムを合成後、酸化抑制剤としてチオ硫酸ソーダを0.01重量％添加し、オストワルド熟成により粒子成長を行わせ、ＢＥＴ比表面積５ｍ2 ／g のコロイド炭酸カルシウムを得た。その後、脱水・乾燥・解砕し、更に得られた乾粉を精密空気分級機で分級を行い、コロイド炭酸カルシウム填剤を得た。得られたコロイド炭酸カルシウム填剤の各物性値を表３に示す。
Example 22
In the same manner as in Example 1, after synthesizing colloidal calcium carbonate, 0.01% by weight of sodium thiosulfate was added as an oxidation inhibitor, and particle growth was performed by Ostwald ripening. Colloidal calcium carbonate having a BET specific surface area of 5 m 2 / g Got. Thereafter, dehydration, drying and pulverization were performed, and the obtained dry powder was classified with a precision air classifier to obtain a colloidal calcium carbonate filler. Table 3 shows each physical property value of the obtained colloidal calcium carbonate filler.
比較例１
酸化抑制剤を添加しない以外は、実施例１と同様の操作を行い、コロイド炭酸カルシウムを得た。得られたコロイド炭酸カルシウム填剤の各物性値を表３に示す。
Comparative Example 1
A colloidal calcium carbonate was obtained in the same manner as in Example 1 except that the oxidation inhibitor was not added. Table 3 shows each physical property value of the obtained colloidal calcium carbonate filler.
比較例２
一般的な軽質炭酸カルシウムの調整として、実施例１で得た生石灰を溶解して消石灰水懸濁液とし、特開平６−７３６９０の比較例１の如く炭酸化反応を行い、軽質炭酸カルシウムを合成した。次に、実施例１と同様に２００メッシュ篩で異物や粗大粒子の除去を行った後、軽質炭酸カルシウムを１０重量％含有する水懸濁液を調整した。尚、ＢＥＴ比表面積は４ｍ2 ／g であった。
次に、表面処理剤として、ステアリン酸カリウムとヘキサメタリン酸ナトリウムを用い、それぞれの軽質炭酸カルシウム固形分に対して各々１．３重量％と０．４重量％を表面処理し、その後、脱水・乾燥・解砕し、更に得られた乾粉を精密空気分級機で分級を行い軽質炭酸カルシウムを得た。得られた軽質炭酸カルシウム填剤の各物性値を表３に示す。
Comparative Example 2
As a general adjustment of light calcium carbonate, quick lime obtained in Example 1 is dissolved to obtain a slaked lime water suspension and subjected to a carbonation reaction as in Comparative Example 1 of JP-A-6-73690 to synthesize light calcium carbonate. did. Next, after removing foreign substances and coarse particles with a 200 mesh sieve in the same manner as in Example 1, a water suspension containing 10% by weight of light calcium carbonate was prepared. The BET specific surface area was 4 m 2 / g.
Next, as the surface treatment agent, potassium stearate and sodium hexametaphosphate are used, and 1.3% by weight and 0.4% by weight, respectively, of the light calcium carbonate solids are surface-treated, and then dehydrated and dried. -After pulverization, the obtained dry powder was classified with a precision air classifier to obtain light calcium carbonate. Table 3 shows each physical property value of the obtained light calcium carbonate filler.
比較例３
比較例２で調整した軽質炭酸カルシウム水懸濁液に対し、酸化抑制剤として軽質炭酸カルシウム固形分に対し０．００５重量％の亜二チオン酸ソーダを添加した以外は、比較例２と同様の操作を行い軽質炭酸カルシウムを得た。得られた軽質炭酸カルシウム填剤の各物性値を表３に示す。
Comparative Example 3
Comparative Example 2 was the same as Comparative Example 2 except that 0.005% by weight of sodium dithionite was added to the light calcium carbonate solids as an oxidation inhibitor to the light calcium carbonate aqueous suspension prepared in Comparative Example 2. Operation was performed to obtain light calcium carbonate. Table 3 shows each physical property value of the obtained light calcium carbonate filler.
得られたコロイド又は軽質炭酸カルシウム填剤の白色度を上記［００４０］に記載した測定方法で測定した。測定結果を表２、表３に示す。 The whiteness of the obtained colloid or light calcium carbonate filler was measured by the measurement method described in the above [0040]. The measurement results are shown in Tables 2 and 3.
実施例２３〜４４、比較例４〜６
ポリプロピレン樹脂（住友化学（株）社製FS2011DG2 、ＭＩ＝2.0 ｇ／10ｍｉｎ）１００重量部、実施例１〜２２及び比較例１〜３で得られたコロイド又は軽質炭酸カルシウム填剤１１０重量部、ステアリン酸カルシウム１重量部、ヒンダードアミンン系光安定剤１重量部をヘンシェルミキサーに仕込み５分間混合して樹脂組成物を得た。
得られた樹脂組成物をベント型二軸押出機によりペレット状に加工した。このペレットを、Ｔダイを装着した押出機を用いて未延伸シートを得た。得られた未延伸シートをテンターオーブン中で１４０℃の温度下で約７倍に延伸し厚さ１８０μｍの光反射シートを作製した。
このように得られた光反射シートについて下記の方法で耐光性試験を行い、耐光性試験前後の拡散反射率を評価した。評価結果を表４、表５に示す。
Examples 23 to 44, Comparative Examples 4 to 6
100 parts by weight of polypropylene resin (FS2011DG2 manufactured by Sumitomo Chemical Co., Ltd., MI = 2.0 g / 10 min), 110 parts by weight of colloid or light calcium carbonate filler obtained in Examples 1 to 22 and Comparative Examples 1 to 3, and steer 1 part by weight of calcium phosphate and 1 part by weight of a hindered amine light stabilizer were charged into a Henschel mixer and mixed for 5 minutes to obtain a resin composition.
The obtained resin composition was processed into a pellet form by a vent type twin screw extruder. An unstretched sheet was obtained from the pellets using an extruder equipped with a T die. The obtained unstretched sheet was stretched about 7 times in a tenter oven at a temperature of 140 ° C. to prepare a light reflecting sheet having a thickness of 180 μm.
The light reflection sheet thus obtained was subjected to a light resistance test by the following method, and the diffuse reflectance before and after the light resistance test was evaluated. The evaluation results are shown in Tables 4 and 5.
「評価・測定方法」
１）拡散反射率
拡散反射率の測定は、紫外可視分光光度計（UV3101PC，島津製作所社製) を用い、４００〜１０００ｎｍの波長領域を測定し、５５０ｎｍの拡散反射率を代表値とした。拡散反射率が高い程、光反射シートの色相が良好である。
"Evaluation and measurement methods"
1) Diffuse reflectance The diffuse reflectance was measured by using a UV-visible spectrophotometer (UV3101PC, manufactured by Shimadzu Corporation), measuring a wavelength region of 400 to 1000 nm, and taking a diffuse reflectance of 550 nm as a representative value. The higher the diffuse reflectance, the better the hue of the light reflecting sheet.
２）耐光性試験
耐光性試験はJIS K7350-2 に準拠し、キセノンウェザーメーター（ＳＸ７５，スガ試験機社製）を用い、波長＝３００〜４００ｎｍ、放射照度＝１８０Ｗ／ｍ2 、ブラックパネル温度＝８３℃、湿度＝５０％ＲＨの条件で、１４４ｈｒ照射した。
2) Light resistance test The light resistance test is based on JIS K7350-2, using a xenon weather meter (SX75, manufactured by Suga Test Instruments Co., Ltd.), wavelength = 300 to 400 nm, irradiance = 180 W / m 2 , black panel temperature = Irradiation was performed for 144 hr under the conditions of 83 ° C. and humidity = 50% RH.
上記表４、表５の評価結果より、本発明の酸化抑制剤を含有したコロイド炭酸カルシウム填剤を配合してなる光反射シートの拡散反射率は、酸化抑制剤を含有していないコロイド炭酸カルシウム填剤を配合した比較例４と比べ、反射率が高く、耐光性も良く維持されていることが確認できる。また比較例５と比較例６は、配合した軽質炭酸カルシウム填剤が軽質炭酸カルシウムに酸化抑制剤を添加していないか、しているかの違いであるが、軽質炭酸カルシウムは熟成工程がない製法であるため、反射率において両者の差は殆どなく、また、アルカリを多く含む凝集体であるため、反射率も低いことが確認できる。 From the evaluation results in Tables 4 and 5 above, the diffuse reflectance of the light reflecting sheet obtained by blending the colloidal calcium carbonate filler containing the oxidation inhibitor of the present invention is the colloidal calcium carbonate containing no oxidation inhibitor. It can be confirmed that the reflectance is high and the light resistance is well maintained as compared with Comparative Example 4 in which a filler is blended. Moreover, the comparative example 5 and the comparative example 6 are the difference in whether the compounded light calcium carbonate filler does not add the oxidation inhibitor to the light calcium carbonate, but light calcium carbonate has a aging process. Therefore, there is almost no difference between the two in the reflectance, and it can be confirmed that the reflectance is low because of the aggregate containing a large amount of alkali.
実施例４５〜６６、比較例７〜９
（１）下記に示す配合からなる、基材層用の樹脂組成物（Ｉ）を、押出機を用いて溶融混練後、ダイより２００℃の温度でシート状に押し出し、該シートを約５０℃の温度まで冷却した後、１４０℃に加熱して、縦方向に５倍延伸した。
＜基材層用樹脂組成物（Ｉ）の配合＞
ポリプロピレン（日本ポリプロ社製、ＭＡ−６）：７５重量部
実施例１〜２２、比較例１〜３で得られたコロイド又は軽質炭酸カルシウム填剤：１５重量部
高密度ポリエチレン（日本ポリプロ社製、ＥＹ−４０）：１０重量部
Examples 45-66, Comparative Examples 7-9
(1) The resin composition (I) for the base material layer, which has the following composition, is melt-kneaded using an extruder, and then extruded from a die at a temperature of 200 ° C., and the sheet is about 50 ° C. Then, it was heated to 140 ° C. and stretched 5 times in the machine direction.
<Formulation of resin composition (I) for substrate layer>
Polypropylene (manufactured by Nippon Polypro, MA-6): 75 parts by weight Colloid or light calcium carbonate filler obtained in Examples 1-22 and Comparative Examples 1-3: 15 parts by weight High-density polyethylene (manufactured by Nippon Polypro, EY-40): 10 parts by weight
（２）下記に示す配合からなる、中間層用の樹脂組成物（II）と、表面層用の樹脂組成物（III)を、別々の押出機を用い溶融混練し、ダイより２００℃の温度でシート状に押し出しラミネート化し、５層構造「表面層（III)／中間層（II）／基材層（Ｉ）／中間層（II）／表面層（III)」からなる積層シートを得た。
＜中間層用樹脂組成物（II）の配合＞
ポリプロピレン（日本ポリプロ社製、ＭＡ−３）：４５重量部
実施例１〜２２、比較例１〜３で得られたコロイド又は軽質炭酸カルシウム填剤：４５重量部
高密度ポリエチレン樹脂（日本ポリプロ、ＥＹ−４０）：５重量部
グラフトポリプロピレン（三菱化学社製，モディック）：５重量部
＜表面層用樹脂組成物（III)の配合＞
ポリプロピレン（日本ポリプロ社製、ＭＡ−３）：５０重量部
高密度ポリエチレン樹脂（日本ポリプロ、ＥＹ−４０）：５０重量部
(2) The resin composition (II) for the intermediate layer and the resin composition (III) for the surface layer, which have the following composition, are melt-kneaded using separate extruders, and the temperature is 200 ° C. from the die. And laminated into a sheet shape to obtain a laminated sheet having a five-layer structure “surface layer (III) / intermediate layer (II) / base material layer (I) / intermediate layer (II) / surface layer (III)” .
<Mixture of resin composition (II) for intermediate layer>
Polypropylene (manufactured by Nippon Polypro, MA-3): 45 parts by weight Colloid or light calcium carbonate filler obtained in Examples 1-22 and Comparative Examples 1-3: 45 parts by weight High-density polyethylene resin (Nippon Polypro, EY) -40): 5 parts by weight Graft polypropylene (Mitsubishi Chemical Co., Modic): 5 parts by weight <Formulation of resin composition (III) for surface layer>
Polypropylene (Nippon Polypro, MA-3): 50 parts by weight High-density polyethylene resin (Nippon Polypro, EY-40): 50 parts by weight
（３）得られた積層シートを４０℃まで冷却した後、再度１５５℃まで加熱し、テンターを用いて横方向に８倍延伸し、次いで１６２℃の温度に設定されたオーブン中を通過させて熱セットし、更にコロナ放電処理して、基材層（Ｉ）の２軸延伸フィルムの肉厚が５０μm 、中間層（II）の一軸延伸フィルム肉厚が２０μm 、表面層の一軸延伸フィルム（III)の肉厚が５μm の５層構造の合成紙（膜圧１００μm ）を得た。 (3) After cooling the obtained laminated sheet to 40 ° C., it is heated again to 155 ° C., stretched 8 times in the transverse direction using a tenter, and then passed through an oven set at a temperature of 162 ° C. After heat setting and further corona discharge treatment, the thickness of the biaxially stretched film of the substrate layer (I) is 50 μm, the uniaxially stretched film thickness of the intermediate layer (II) is 20 μm, and the uniaxially stretched film (III ) Was obtained as a 5-layer synthetic paper (film pressure 100 μm).
（４）積層シートの表面層（III)に下記の配合からなる塗工剤を厚さ１５μm の塗工膜が得られるように塗工し、７０℃の温度で１分間乾燥させて、塗工層（IV）を形成させ、７層構造「（IV）／（III)／（II）／（Ｉ）／（II）／（III)／（IV）」からなる記録材料を調製した。
＜塗工剤の配合＞
クレー「ウルトラコート、ＥＭＣ製」 ７０重量部
重質炭酸カルシウム「スーパー１７００、丸尾カルシウム社製」 ３０重量部
カルボキシル化ＳＢラテックス「Ｌ１６０８、旭化成工業社製」 １１重量部
スターチ「王子エースＡ、王子コンスターチ社製」 ３重量部
分散剤：ポリアクリル酸ソーダ「アロンＴ−４０、東亜合成社製」 ０．２重量部
中和剤：苛性ソーダ ０．１重量部
(4) A coating agent having the following composition is applied to the surface layer (III) of the laminated sheet so as to obtain a coating film having a thickness of 15 μm, and dried at a temperature of 70 ° C. for 1 minute. Layer (IV) was formed to prepare a recording material having a seven-layer structure “(IV) / (III) / (II) / (I) / (II) / (III) / (IV)”.
<Composition of coating agent>
Clay "Ultracoat, made by EMC" 70 parts by weight Heavy calcium carbonate "Super 1700, made by Maruo Calcium Co., Ltd." 30 parts by weight Carboxylated SB latex "L1608, made by Asahi Kasei Corporation" 11 parts by weight Starch "Oji Ace A, Oji Constarch 3 parts by weight Dispersant: Polyacrylic acid soda “Aron T-40, manufactured by Toa Gosei Co., Ltd.” 0.2 parts by weight Neutralizing agent: 0.1 parts by weight of caustic soda
（５）得られた記録材料の表面にオフセット印刷機（４Ｅ−４，三菱重工業社製）でオフセット印刷し、下記の方法で耐光性試験を行い、耐光性試験前後の発色濃度の評価を行った。評価結果を表６、表７に示す。
１）発色濃度
得られた発色画像部と未印字の地肌部の発色濃度を光学濃度計マクベスＲＤ９１８を用いてそれぞれ測定した。発色画像部については数値が大きいほど画像保存性に優れ、未印字の地肌部については数値が小さいほど変色が少なく優れていることを示す。
２）耐光性試験
発色試験において得た発色画像部と未印字の地肌部を、JIS K7350-2 に準拠し、キセノンウェザーメーター（ＳＸ７５，スガ試験機社製）を用い、波長＝３００〜４００ｎｍ、放射照度＝１８０Ｗ／ｍ2 、ブラックパネル温度＝６３℃、湿度＝６５％ＲＨの条件で、２４ｈｒ照射した。
(5) Offset printing is performed on the surface of the obtained recording material with an offset printer (4E-4, manufactured by Mitsubishi Heavy Industries, Ltd.), a light resistance test is performed by the following method, and a color density before and after the light resistance test is evaluated. It was. The evaluation results are shown in Tables 6 and 7.
1) Color density The color density of the obtained color image portion and the unprinted background portion was measured using an optical densitometer Macbeth RD918. As for the color image portion, the larger the numerical value, the better the image storability. As for the unprinted background portion, the smaller the value, the smaller the color change and the better.
2) Light resistance test The color image portion obtained in the color development test and the unprinted background portion are based on JIS K7350-2, using a xenon weather meter (SX75, manufactured by Suga Test Instruments Co., Ltd.), wavelength = 300 to 400 nm, Irradiation was performed for 24 hours under the conditions of irradiance = 180 W / m @ 2, black panel temperature = 63 DEG C., and humidity = 65% RH.
上記表６、表７の評価結果より、本発明の酸化抑制剤を含有したコロイド炭酸カルシウム填剤を配合してなる合成紙は、酸化抑制剤を含有していないコロイド炭酸カルシウム填剤を配合した比較例７と比べ、変色が少なく耐光性も良く維持されていることがわかる。また比較例８と比較例９は、配合した軽質炭酸カルシウム填剤が軽質炭酸カルシウムに酸化抑制剤を添加していないか、しているかの違いであるが、軽質炭酸カルシウムは熟成工程がない製法であるため、耐光性において両者の差は殆どなく、また、アルカリを多く含む凝集体であるため、変色していることが確認できる。 From the evaluation results in Tables 6 and 7 above, the synthetic paper obtained by blending the colloidal calcium carbonate filler containing the oxidation inhibitor of the present invention was blended with the colloidal calcium carbonate filler not containing the oxidation inhibitor. Compared to Comparative Example 7, it can be seen that there is little discoloration and the light resistance is well maintained. Moreover, the comparative example 8 and the comparative example 9 are the difference in whether the compounded light calcium carbonate filler does not add the oxidation inhibitor to the light calcium carbonate, but light calcium carbonate has a aging process. Therefore, there is almost no difference between the two in terms of light resistance, and since it is an aggregate containing a large amount of alkali, it can be confirmed that it is discolored.
叙上のとおり、本発明のコロイド炭酸カルシウム填剤は、白色度が高く、耐熱性や耐光性に優れているので、特に、光反射シートや合成紙等の白色系合成樹脂用の填剤として好適である。 As described above, the colloidal calcium carbonate filler of the present invention has a high whiteness and is excellent in heat resistance and light resistance. Therefore, as a filler for white synthetic resins such as light reflecting sheets and synthetic papers. Is preferred.
Claims (7)
（ａ）０．３≦Ｄ50≦１．５ （μｍ）
（ｂ）Ｄａ≦２０ （μｍ）
Ｄ50：レーザー回折式粒度分布測定装置（マイクロトラックＦＲＡ：日機装社製）で測定した篩上積算平均粒子径 [μｍ]
Ｄａ：レーザー回折式粒度分布測定装置（マイクロトラックＦＲＡ：日機装社製）で測定した時に示す最大粒子径 [μｍ] A colloidal calcium carbonate filler comprising an oxidation inhibitor in colloidal calcium carbonate and satisfying the following (a) average particle diameter D50 and (b) maximum particle diameter Da.
(A) 0.3 ≦ D50 ≦ 1.5 (μm)
(B) Da ≦ 20 (μm)
D50: Cumulative average particle diameter on a sieve [μm] measured with a laser diffraction particle size distribution analyzer (Microtrac FRA: manufactured by Nikkiso Co., Ltd.)
Da: Maximum particle size [μm] indicated when measured with a laser diffraction particle size distribution analyzer (Microtrac FRA: Nikkiso Co., Ltd.)
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| US11441008B2 (en) * | 2016-09-08 | 2022-09-13 | Schaefer Kalk Gmbh & Co. Kg | Composite powder containing calcium carbonate and having microstructured particles |
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| JPS5435897A (en) * | 1977-08-26 | 1979-03-16 | Shiraishi Chuo Kenkiyuushiyo K | Method of improving surface property of calicium carbonate |
| JPH0689160B2 (en) * | 1986-12-25 | 1994-11-09 | 東レ株式会社 | White polyethylene terephthalate film |
| JPH0822910B2 (en) * | 1990-01-08 | 1996-03-06 | 四国化成工業株式会社 | Method for producing polymer composition containing calcium carbonate composition |
| JP3067856B2 (en) * | 1991-08-09 | 2000-07-24 | 丸尾カルシウム株式会社 | Surface-treated calcium carbonate and method for producing the same |
| JP3223589B2 (en) * | 1992-07-20 | 2001-10-29 | 王子製紙株式会社 | Method for producing light calcium carbonate |
| ATE193346T1 (en) * | 1994-12-28 | 2000-06-15 | Minerals Tech Inc | BLEACHING PAPER CONTAINING FILLERS |
| JP3058255B2 (en) * | 1996-08-29 | 2000-07-04 | 丸尾カルシウム株式会社 | Method for producing precipitated calcium carbonate |
| JP2001089505A (en) * | 1999-09-21 | 2001-04-03 | Maruo Calcium Co Ltd | Inorganic dispersant, stabilizer for suspension polymerization, polymer particle and unsaturated polyester resin composition |
| JP4263838B2 (en) * | 2000-03-31 | 2009-05-13 | 株式会社ユポ・コーポレーション | Multilayer resin stretched film |
| US6623555B1 (en) * | 2000-06-01 | 2003-09-23 | Jukka P. Haverinen | Composite precipitated calcium carbonate/silicon compound pigment and method of making same |
| TWI283235B (en) * | 2001-11-16 | 2007-07-01 | Maruo Calcium | Surface-treated calcium carbonate, production method thereof, and resin composition containing the calcium carbonate |
| KR101009601B1 (en) * | 2002-10-03 | 2011-01-20 | 마루오 칼슘 가부시키가이샤 | Surface-treated calcium carbonate and resin composition comprising the same |
| JP4866075B2 (en) * | 2004-12-17 | 2012-02-01 | 株式会社ユポ・コーポレーション | Light reflector and surface light source device using the same |
| JP5100972B2 (en) * | 2005-03-25 | 2012-12-19 | 丸尾カルシウム株式会社 | Light reflecting porous film filler and light reflecting porous film containing the filler |
| FR2885900B1 (en) * | 2005-05-20 | 2009-02-13 | Omya Development Ag | MINERAL MATERIALS CONTAINING CARBONATE WITH REDUCED FOSSIL FUEL CELL CARBONIC GAS EMISSION AT THE TIME OF THEIR DECOMPOSITIONS AND THEIR SYNTHESIS PROCESS AND USES THEREOF. |
| JP4850522B2 (en) * | 2006-01-27 | 2012-01-11 | 丸尾カルシウム株式会社 | Surface-treated calcium carbonate filler for curable resin composition, and curable resin composition containing the filler |
| JP2008127408A (en) * | 2006-11-17 | 2008-06-05 | Toyo Ink Mfg Co Ltd | Resin composition containing inorganic filler and its molded article |
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2009
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