JPH0380107A - Lipophilic modified basic calcium carbonate and production thereof - Google Patents
Lipophilic modified basic calcium carbonate and production thereofInfo
- Publication number
- JPH0380107A JPH0380107A JP21488089A JP21488089A JPH0380107A JP H0380107 A JPH0380107 A JP H0380107A JP 21488089 A JP21488089 A JP 21488089A JP 21488089 A JP21488089 A JP 21488089A JP H0380107 A JPH0380107 A JP H0380107A
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- fatty acid
- basic calcium
- higher fatty
- coating layer
- 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.)
- Granted
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 98
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000002245 particle Substances 0.000 claims abstract description 44
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 29
- 239000000194 fatty acid Substances 0.000 claims abstract description 29
- 229930195729 fatty acid Natural products 0.000 claims abstract description 29
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 28
- 239000011247 coating layer Substances 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 238000004438 BET method Methods 0.000 claims abstract 2
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 150000001447 alkali salts Chemical class 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 13
- 229920003023 plastic Polymers 0.000 abstract description 13
- 239000004033 plastic Substances 0.000 abstract description 13
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 abstract description 10
- 239000005639 Lauric acid Substances 0.000 abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 abstract description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 abstract description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005642 Oleic acid Substances 0.000 abstract description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 abstract description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 abstract description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 2
- 241000276425 Xiphophorus maculatus Species 0.000 abstract 2
- 229930195733 hydrocarbon Natural products 0.000 abstract 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 description 38
- 238000012360 testing method Methods 0.000 description 10
- 239000000725 suspension Substances 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000454 talc Substances 0.000 description 6
- 229910052623 talc Inorganic materials 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- 229910021532 Calcite Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009778 extrusion testing Methods 0.000 description 2
- -1 fatty acid anion Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、塩基性炭酸カルシウムに関し、更に詳しくは
、プラスチックスｍ汎用白色先位剤として好ましい平板
状ザブミクロン粒子からなり、かつ永久的な親油性表面
に変性された塩基性炭酸カルシウムとその製造方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to basic calcium carbonate, and more particularly, the present invention is made of tabular Zabumicron particles suitable as a general-purpose white leading agent for plastics, and has a permanent parent This invention relates to basic calcium carbonate modified to have an oily surface and a method for producing the same.
従来からプラスチックス・コンポジットに望ましい物理
性質を付与すると共に経済効果を得る１」的で、各種の
無機化合物や鉱物の粉体が汎用充填剤として用いられて
来ている。その代表的なものは、軽質炭酸カルシウム、
重質炭酸カルシウム、タルク、カオリンクレーなどであ
る。これらの無機化合物や鉱物粉体のポリマーマトリッ
クスに対する親和性を向上させる目的で各種の有機化合
物で表面改質を行うことも実施されて来た。しかしなが
ら、これら従来の無機フィラーは、いくつかの利用上の
欠点を有している。たとえば、軽質炭酸カルシウムのう
ち、普通品は粒子径が１〜２μｍあるいはそれ以上であ
って、粒子径が相対的に大きいため、これを充填したコ
ンポジットは、引張りや折曲げによって非可逆的な応力
白化を発生し、コンポジットの色調を損ねてしまう欠点
がある。サブミクロン以下の粒子から成る膠質炭酸カル
シウムは、０．０３μｍないし０．３μｍの間で各種粒
子径グレードのものが提供されているが、これら膠質炭
酸カルシウムは、普通にはその粒子形状が立方体に近い
菱面体カルサイト結晶であって、これらを充填したプラ
スチックス・コンパウンドの加工成形における寸法安定
性が十分てない。重質炭酸カルシウムは結晶質石灰石（
カルザイト）の機械的粉砕物であって、その製造工程で
粉砕物を分級して各種粒度分布をもったグレード品が提
供されているが、粒子径が粗く、粒子形状は不規則なブ
ロック状であって、軽質炭酸カルシウム普通品に類似し
た欠点を有する。また、これらはプラスチックス充填剤
として理想粒子形状とされている平板状からは程遠いも
のであった。タルクおよびカオリンは層状構造の粘土鉱
物であって、粒子形および粒子形状が理想的なサブミク
ロン級の平板状粒子からなる製品が供給されているが、
天然の土壌着色物たとえば腐植質、鉄やチタン酸化物な
どによって大なり小なり汚染されており、炭酸カルシウ
ムのような純白に近い高白色度原鉱の産出が地域上限定
されており、また、一般にこれら着色汚染物質を十分に
除去する経済的プロセスが無いのが現状である。高い白
色度を有し、タルク、カリオンのようなサブミクロン粒
度と平板状粒子形状からなる理想的な汎用充填剤の供給
が強く要望されている。たとえば、石膏石灰学会発行「
石膏と石灰」誌Ｎｏ、１９８（１９８５年９月）無機フ
ィラー特集号第６６ページないし７４ページ、鶴田康生
著「無機フィラーの特性とその複合効果」において、今
後の課題として、薄板状炭酸カルシウムの出現の要望が
述べられている。さらに、プラスチックス用無機充填剤
として一般的にコンポジットの軽量化や容積コスト逓減
効果に寄与するための低比重充填剤に対する潜在的な要
求がある。Powders of various inorganic compounds and minerals have been used as general-purpose fillers in order to impart desirable physical properties to plastic composites and to obtain economic effects. The typical examples are light calcium carbonate,
These include heavy calcium carbonate, talc, and kaolin clay. In order to improve the affinity of these inorganic compounds and mineral powders for polymer matrices, surface modification with various organic compounds has also been carried out. However, these conventional inorganic fillers have some drawbacks in their use. For example, among light calcium carbonate, ordinary products have a particle size of 1 to 2 μm or more, and because the particle size is relatively large, a composite filled with this is subject to irreversible stress due to tension or bending. It has the disadvantage of causing whitening and impairing the color tone of the composite. Colloidal calcium carbonate, which consists of submicron particles, is available in various particle size grades between 0.03 μm and 0.3 μm, but the particle shape of these colloidal calcium carbonates is usually cubic. These are nearly rhombohedral calcite crystals, and the dimensional stability of plastic compounds filled with them is not sufficient during processing and molding. Heavy calcium carbonate is crystalline limestone (
This is a mechanically crushed product of calzite), and grades with various particle size distributions are provided by classifying the crushed product during the manufacturing process, but the particle size is coarse and the particle shape is irregular block-like. However, it has drawbacks similar to ordinary light calcium carbonate products. Furthermore, these particles were far from the flat plate shape that is considered to be the ideal particle shape for plastic fillers. Talc and kaolin are clay minerals with a layered structure, and products consisting of submicron-level tabular grains with ideal particle shapes and shapes are supplied.
It is contaminated to a greater or lesser extent by natural soil colorants such as humus, iron and titanium oxides, and the production of highly white raw minerals such as calcium carbonate, which is close to pure white, is limited in some areas. Currently, there is generally no economical process to adequately remove these colored contaminants. There is a strong need to supply an ideal general-purpose filler with high whiteness and consisting of submicron particle size and tabular particle shape, such as talc and carrion. For example, published by the Gypsum and Lime Society,
"Gypsum and Lime" Magazine No. 198 (September 1985) Special Issue on Inorganic Fillers, pages 66 to 74, Yasuo Tsuruta, "Characteristics of Inorganic Fillers and Their Combined Effects" A request for appearance is stated. Furthermore, there is a potential demand for low specific gravity fillers as inorganic fillers for plastics in general to contribute to the weight reduction and volumetric cost reduction effect of composites.
石灰乳を制御された条件で炭酸ガスを導入して炭酸化す
ることにより、サブミクロン級の平板状粒子から成る塩
基性炭酸カルシウムを生成する技術は既に開発されてい
る（山田英夫、原尚道、石膏と石灰、 Ｎｏ、１９８．
１３０〜１４０ページ。A technology has already been developed to produce basic calcium carbonate consisting of submicron-sized tabular particles by carbonating milk of lime by introducing carbon dioxide gas under controlled conditions (Hideo Yamada, Naomichi Hara, Gypsum and lime, No. 198.
Pages 130-140.
１９８５ 、山田英夫、原尚道、公開６０−７１５２３
）。本品は比重が２．３〜２，４で炭酸カルシウム（２
，７） 、タルク（２，８） 、カリオン（２，６）よ
りも小さく好ましいが、本品を生成反応系から濾過脱水
し、乾燥させたものは強固な粒子間凝結によって大きな
二次凝結粒子を形成し、ポリマーマトリックス中で分散
が極めて不良で充填剤として全く機能しなかった。すな
わち、塩基性炭酸カルシウムをプラスチックス用充填剤
として素材化するためには、その強い粒子間凝結力を弱
めるとともに、塩基性基である水酸基に帰因する粒子表
面の強い親水性を疎水化して親油性に変換し、有機マト
リックスに対する濡れと分散性を改善することが必要で
ある。1985, Hideo Yamada, Naomichi Hara, Published 60-71523
). This product has a specific gravity of 2.3 to 2.4 and calcium carbonate (2.
, 7), talc (2, 8), and carrion (2, 6) are preferable, but when this product is filtered and dehydrated from the production reaction system and dried, large secondary coagulated particles are formed due to strong interparticle coagulation. was formed and was extremely poorly dispersed in the polymer matrix and did not function as a filler at all. In other words, in order to turn basic calcium carbonate into a material as a filler for plastics, it is necessary to weaken its strong interparticle coagulation force and to hydrophobize the strong hydrophilicity of the particle surface due to the hydroxyl group, which is a basic group. It is necessary to convert it to lipophilicity and improve its wetting and dispersibility in organic matrices.
本発明は、前記従来技術における問題を解決したプラス
チックス用汎用白色充填剤として好ましい親油性変性塩
基性炭酸カルシウムを提供することを目的とする。An object of the present invention is to provide a lipophilic modified basic calcium carbonate which is preferable as a general-purpose white filler for plastics and solves the problems in the prior art.
〔問題点を解決するための手段〕
前述したとおり、本発明は、タルクやカオリンのような
、プラスチックス用汎用充填剤として好ましい平板状な
いし薄板状のサブミクロン（０，１μｍ〜１μｍ）粒子
からなり、その粒子表面は永久的に親油性に変性された
塩基性炭酸カルシウムを提供しようとするものである。[Means for Solving the Problems] As mentioned above, the present invention is based on flat or thin plate-like submicron (0.1 μm to 1 μm) particles such as talc and kaolin, which are preferable as general-purpose fillers for plastics. The particle surface is intended to provide basic calcium carbonate whose particle surface is permanently modified to be lipophilic.
石灰乳を制御された条件で、かつ水酸化カルシラムに対
して所定割合の炭酸ガスを導入することにより、０．１
μｍ以上１μｍ未満の範囲で設定した粒子径をもつ平板
状塩基性炭酸カルシウム−次粒子からなるカードハウス
形凝結体を含む懸濁液を得る。この懸濁液から、濾過、
脱水、乾燥、粉砕と正常なプロセスを経由して得た塩基
性炭酸カルシウム粉体は、ポリマーマトリックスとは親
和性の乏しい分散性の悪い凝結体二次粒子となって一次
粒子の微粒子性は全く発揮されない。水晶をプラスチッ
クス用汎用充填剤として有用化するためには、先ず第１
に一次粒子間の強い凝結力を弱めると共に、ポリマー、
可塑剤およびその他有機液体など有機マトリックスとの
親和性を高めるために、粒子表面親水性を永久的な粒子
表面親油性に変換することが達成されなければならない
。さらに、粒子表面物質とマトリックスとの界面におけ
る分子ディメンションでの相互作用による分子の絡みの
生成をもたらすことが粒子−マトリックス界面での空孔
発生を防ぐ上で望ましいことである。By introducing milk of lime under controlled conditions and a predetermined ratio of carbon dioxide gas to calcium hydroxide,
A suspension containing cardhouse-shaped aggregates consisting of tabular basic calcium carbonate secondary particles having a particle size set in the range of .mu.m or more and less than 1 .mu.m is obtained. From this suspension, filtration,
Basic calcium carbonate powder obtained through normal processes such as dehydration, drying, and pulverization becomes secondary particles of aggregates with poor affinity and poor dispersibility for the polymer matrix, and the fine particle nature of the primary particles is completely eliminated. Not demonstrated. In order to make crystal useful as a general-purpose filler for plastics, the first step is to
In addition to weakening the strong cohesive force between primary particles, polymers,
In order to increase compatibility with organic matrices such as plasticizers and other organic liquids, conversion of particle surface hydrophilicity to permanent particle surface lipophilicity must be achieved. Furthermore, it is desirable to generate molecular entanglements through interaction in the molecular dimension at the interface between the particle surface substance and the matrix in order to prevent the generation of pores at the particle-matrix interface.
さて、本発明者らは、塩基性炭酸カルシウム生成系中で
、該塩基性炭酸カルシウム粒子表面に、ある種の好まし
い有機化合物の被覆層を形成せしめることによって、上
述した問題を解決することに成功した。該有機化合物は
、その分子構造中に塩基性炭酸カルシウム粒子表面と永
久的に結合するような官能基を有し、他方、該有機化合
物が粒子表面で被覆層を形成した状態で、界面において
マトリックスポリマー分子と絡み生成の機会をつくり出
すようなディメンションを持つ親油性基を有する二元的
機能性のものであり、好ましい有機化合物の代表的なも
のは、高級脂肪酸、望ましくは不飽和度の小さい飽和炭
化水素鎖を有する脂肪酸であり、本発明達成のために一
般的に云えば、一つのカルボキシル基または炭素の二重
結合当り少なくとも８個の炭素数からなる炭化水素直鎖
を有する高級脂肪酸から選ぶことができる。Now, the present inventors succeeded in solving the above-mentioned problem by forming a coating layer of a certain kind of preferable organic compound on the surface of the basic calcium carbonate particles in a basic calcium carbonate production system. did. The organic compound has a functional group in its molecular structure that permanently bonds with the surface of the basic calcium carbonate particles, and on the other hand, the organic compound forms a coating layer on the particle surface and forms a matrix at the interface. Preferred organic compounds are typically dual-functional ones that have lipophilic groups with dimensions that create opportunities for entanglement with polymer molecules, such as higher fatty acids, preferably saturated fatty acids with a low degree of unsaturation. A fatty acid having a hydrocarbon chain, generally speaking for achieving the present invention, selected from higher fatty acids having a straight hydrocarbon chain consisting of at least 8 carbon atoms per carboxyl group or carbon double bond. be able to.
たとえば、
ラウリン酸 Ｃ１１Ｈ２３ＣＯＯＨ
ミリスチン酸 Ｃ１３Ｈ２７ＣＯＯＨ
バルミチン酸 Ｃ１５Ｈ３１ＣＯＯＨ
ステアリン酸 Ｃ１７Ｈ３５ＣＯＯＨ
アラキン酸 Ｃｔ ９ Ｈｓ ９ ＣＯＯＨベヘン酸Ｃ
２１■４３ＣＯＯＨ
オレイン酸 Ｃ３Ｈ１７ＣＨ−
ＣＨＣ７Ｈ１４ＣＯＯＨ
エルカ酸Ｃ３Ｈ１７ＣＨ−
ＣＨＣ１１Ｈ２２ＣＯＯＨ
の如き単独脂肪酸、またはこれら脂肪酸を主成分とする
天然油脂加水分解物ならびにそれらの水素添加物であっ
てよい。For example, Lauric acid C11H23COOH Myristic acid C13H27COOH Valmitic acid C15H31COOH Stearic acid C17H35COOH Arachic acid Ct 9 Hs 9 COOH Behenic acid C
21■43COOH Oleic acid C3H17CH- CHC7H14COOH Erucic acid C3H17CH- CHC11H22COOH It may be a single fatty acid such as C3H17CH- CHC11H22COOH, or a natural oil or fat hydrolyzate containing these fatty acids as a main component, or a hydrogenated product thereof.
塩基性炭酸カルシウム懸濁液に添加して、塩基性炭酸カ
ルシウム粒子表面に吸着層を形成せしめるためには、上
記から選んだ脂肪酸を中和当量の水酸化アルカリを含む
熱水溶液に溶解して陰イオン態となし、塩基性炭酸カル
シウム懸濁液に添加することによって達成できる。In order to form an adsorption layer on the surface of basic calcium carbonate particles by adding it to a basic calcium carbonate suspension, a fatty acid selected from the above is dissolved in a hot aqueous solution containing an amount of alkali hydroxide in an amount equivalent to neutralization. This can be achieved by converting it into an ionic state and adding it to a basic calcium carbonate suspension.
次に塩基性炭酸カルシウム粒子表面を十分な親油性に変
換するために必要な脂肪酸の添加量は、たとえば、ＢＥ
Ｔ窒素吸着法から求めた当該塩基性炭酸カルシウムの比
表面積と脂肪Ｍ１分子当りの単分子膜占有面積ならびに
分子量から、粒子異面積を当該脂肪酸のｔ１＋分子膜で
飽和するのに十分な邑として引算で求めることができる
。この引算の貝体例を次に示す。Next, the amount of fatty acid added necessary to convert the basic calcium carbonate particle surface to sufficient lipophilicity is, for example, BE
Based on the specific surface area of the basic calcium carbonate obtained from the T nitrogen adsorption method, the area occupied by a monolayer per molecule of fat M, and the molecular weight, the particle different area was determined as a sufficient area to be saturated with the t1+ molecular film of the fatty acid. It can be found by calculation. An example of this subtraction is shown below.
塩基性炭酸カルシウム比表面積 １４ＴＩｉ、／ ’ｊ
（Ｔ、 ）ラウリン酸１分子の占有面積 ２３Ａ２
” （１［）ラウリン酸の分子量 ２００
、（ＩＩＩ ）とすれば、塩基性炭酸カルシウム１００
ｇ当りに必要なラウリン酸の量は２．０５７である（計
算：
＊）稲葉恵−２平野二部編著「新版 脂肪酸化学」（昭
和５６年９月５日初版 発行；幸綱房）５８頁。Basic calcium carbonate specific surface area 14TIi, / 'j
(T, ) Occupied area of one molecule of lauric acid 23A2
” (1 [) Molecular weight of lauric acid 200
, (III), basic calcium carbonate 100
The amount of lauric acid required per gram is 2.057 (calculation: *) "New Edition Fatty Acid Chemistry" edited by Megumi Inaba-2 Hirano (first published on September 5, 1980; Yukitsunabo), p. 58.
表３４３による。According to Table 343.
さて、塩基性炭酸カルシウム懸濁液に脂肪酸ｊ′ルカリ
の熱水溶液を添加すると、陰イオン態となった該脂肪酸
アニオンが塩星性炭酸力ルシウム粒子表面の正電荷中心
に静電的結合によって強固に吸着され、新曲基である炭
化水素鎖を外側に配向して永久的新曲性化を達成づ−る
。この反応は短時間で進行するので脂肪酸アルカリの熱
水溶液を添加するに当って、塩基性炭酸カルシウム懸濁
液を高剪断ミキリーーで・激しい攪拌を継続しておくこ
とが望ましい。Now, when a hot aqueous solution of fatty acid j' lucali is added to a basic calcium carbonate suspension, the fatty acid anion, which has become an anion, is firmly fixed by electrostatic bonding to the positively charged center on the surface of the salt star lucium carbonate particle. The hydrocarbon chains, which are new bending groups, are oriented outward to achieve permanent new bending properties. Since this reaction proceeds in a short time, it is desirable to continue to vigorously stir the basic calcium carbonate suspension with a high-shear mixer before adding the hot aqueous solution of fatty acid alkali.
次いで懸濁液を濾過脱水して’ＩＪた／／−４−を乾燥
した後、ハンマーミルに通して粉砕して粉末化する。生
成物が親油性に変性されていること唸、このようにして
（りた粉末を水に加えて攪拌しても全く濡れず、水面に
浮遊リ−ることからＬ明らかである。The suspension is then filtered and dehydrated to dry the 'IJta//-4-, and then ground through a hammer mill to form a powder. It is clear that the product has been modified to be lipophilic because even when the powder is added to water and stirred, it does not get wet at all and floats on the water surface.
実施例 １ 親油性変性塩基性炭酸ノＪルシウムの製造
比表面積が１３．８′ｎ１．７ｇ、平均粒子径が０．３
ｏｍのほぼ均一な平板状塩基性炭酸カルシウムの１０％
水懸濁液１０Ｋｇを３０刃のポリ土ヂレン反応槽に仕込
み、ディスク型インペラミキリーーで２，０ＯＯｒｐＨ
＋で攪拌する。別にヤシ脂肪酸（中和価２６５．ヨー素
価８）２５ｇを４．６２５ｇの水酸化ナトリウムを含む
熱水溶液２５０ｇに加え完全に溶解する。このヤシ脂肪
酸ナトリウム熱水溶液を塩基性炭酸カルシウム懸濁液に
添加し、１５分間撹拌を行った後、フィルタープレスで
脱水した。得られたプレスケーキを６０℃の温風乾燥機
で乾燥したのち、ハンマーミルで粉砕した。Example 1 Production of lipophilic modified basic lucium carbonate Specific surface area is 13.8'n1.7g, average particle diameter is 0.3
10% of nearly uniform tabular basic calcium carbonate of om
Pour 10 kg of water suspension into a 30-blade polyethylene reaction tank, and use a disc-type impeller mill to adjust the pH to 2.0 O OrpH.
Stir with +. Separately, 25 g of coconut fatty acid (neutralization value 265, iodine value 8) was added to 250 g of a hot aqueous solution containing 4.625 g of sodium hydroxide and completely dissolved. This hot aqueous solution of sodium coconut fatty acid was added to the basic calcium carbonate suspension, stirred for 15 minutes, and then dehydrated using a filter press. The obtained press cake was dried in a hot air dryer at 60°C and then ground in a hammer mill.
上記で得た製品試料をデシケータ−で２４時間乾燥し、
そのｌＯｇを精秤して３００ｍ１分液ロートに入れ、試
料にエチルアルコールを滴下して湿らした後、１：１塩
酸を加えて分解し、炭酸ガスの発泡が終ってからエチル
エーテルを加えて遊離脂肪酸を抽出した。抽出操作を３
回くり返し、抽出酸を合してエーテルを蒸発させて脂肪
酸を定員した結果は２．２７％であった（本実施例にお
ける単分子膜形成所要量は２．０％である）。The product sample obtained above was dried in a desiccator for 24 hours,
Accurately weigh 10g of the sample, put it into a 300ml separatory funnel, add ethyl alcohol dropwise to the sample to moisten it, add 1:1 hydrochloric acid to decompose it, and after the carbon dioxide gas has stopped bubbling, add ethyl ether to liberate it. Fatty acids were extracted. Extract operation 3
The result of repeating this process several times was to combine the extracted acids and evaporate the ether to obtain a fatty acid concentration of 2.27% (the amount required to form a monomolecular film in this example was 2.0%).
実施例 ２ 軟質塩化ビニル樹脂配合物実施例１と同様
にして製造したヤシ脂肪酸による親油性変性塩基性炭酸
カルシウムを軟質塩化ビ↓ １
ニル樹脂に配合し、コンパウンディング性を評価した。Example 2 Soft vinyl chloride resin formulation Lipophilic modified basic calcium carbonate with coconut fatty acid produced in the same manner as in Example 1 was blended into a soft vinyl chloride resin, and the compounding properties were evaluated.
比較に脂肪酸無処理の塩基性炭酸カルシウムについても
同時に試験した。For comparison, basic calcium carbonate without fatty acid treatment was also tested at the same time.
配 合
塩化ビニル樹脂にポリッ）ＳＬ）
ジオクチルフタレート
ト リ ベ − スステアリン酸鉛
充填剤試料
コンパウンディング試験
試験条件
ドライアップ試験：
設定温度１００℃；プラネタリーミ
回転速度７０ｒｐｍ
混練試験：
設定温度１６０℃；ローラ
度２５ｒｐｍで５分後５０ｒｐｍ
込み６０ｇ
ミキサー回転速
コンパウンド仕
重量部
１００（４００ｇ）
５ｏ（２００ｇ）
５（２０ｇ）
１（４ｇ）
３１００（４００
キサ−の
３
押
出試験：
設定温度 人ロ１４０°Ｃ〜中間１５０℃〜１６０℃〜
出口１６０℃、スクリュー回転速度３０ｒｐｍｓダイヘ
ッド５０Ｘ０．５ ｍ川、リボン型４
得られた押出試験片は、何れも桃色に変色し、試料Ｉの
方が試料■より強く着色した。また試験片を６倍ルーペ
で観察したところ、塩基性炭酸カルシウムが粗い二次凝
結粒子となって梨地状に分散しているのが認められた。Compounded polyvinyl chloride resin (SL) dioctyl phthalate tri-based lead stearate filler sample Compounding test Test conditions Dry-up test: Set temperature 100°C; Planetary mill rotation speed 70 rpm Kneading test: Set temperature 160°C; Roller 5 minutes at 25 rpm, then 50 rpm including 60 g Mixer rotation speed Compound weight part 100 (400 g) 5 o (200 g) 5 (20 g) 1 (4 g) 3100 (400 Kisa-no 3 Extrusion test: Set temperature 140 ° C ~ Intermediate 150℃~160℃~
Exit: 160°C, screw rotation speed: 30 rpms, die head: 50 x 0.5 m, ribbon type 4. All of the obtained extruded test pieces turned pink, with Sample I being more strongly colored than Sample II. When the test piece was observed using a 6x magnifying glass, it was observed that basic calcium carbonate was dispersed as coarse secondary coagulated particles in a satin-like pattern.
配合および試験条件：実験１に同じ
５
７
６
上記試験１，２から明らかなとおり、十分な量の脂肪酸
で表面処理して得た親油性変性塩基性炭酸カルシウム（
試験■１本発明製品）は、ドライアップ時間が短かく、
優れた混練性、押出し性を示し、加工性に優れているこ
とが明らかである。Formulation and test conditions: Same as Experiment 1 5 7 6 As is clear from Tests 1 and 2 above, lipophilic modified basic calcium carbonate obtained by surface treatment with a sufficient amount of fatty acid (
Test ■1 The product of the present invention) has a short dry-up time,
It is clear that it shows excellent kneading properties and extrudability, and is excellent in processability.
本発明製品である試料■配合押出試験片は変色がなく、
良好な分散状態であり、試験片を折曲げても応力白化が
認められないことから、粒子界面におけるポリマーマト
リックスとの分子絡み形成性も良好であることは、試料
Ｖ配合試験片が折曲げによる応力白化が容易に発生する
ことと比較して明らかである。Sample ■ Compound extrusion test piece, which is a product of the present invention, has no discoloration.
Since the dispersion state is good and stress whitening is not observed even when the test piece is bent, the ability to form molecular entanglements with the polymer matrix at the particle interface is also good. This is clear compared to the fact that stress whitening occurs easily.
本発明は、上述のように構成したものである。 The present invention is configured as described above.
本発明を達成することによって得られた親油性変性塩基
性炭酸カルシウムは、軟質塩化ビニル樹脂の如きプラス
チックス・マトリックスに対して良好な分散性を示し、
分散粒子表面とマトリックスとの界面の親和性に優れ、
プラスチックス成形加工におけるコンパウンディング性
ならびに成形性８
に優れ、プラスチックス用汎用白色充埴剤として提供す
ることが可能である。また、塩基性炭酸カルシウムそれ
自体、炭酸カルシウム（カルサイト、アラゴナイト）、
タルク、カオリンなど従来の汎用白色系充填剤よりも比
重が小さいので、本発明製品を充填することにより軽い
プラスチックス・コンポジットを提供することが可能で
ある。The lipophilic modified basic calcium carbonate obtained by achieving the present invention exhibits good dispersibility in plastic matrices such as soft vinyl chloride resin,
Excellent compatibility between the surface of the dispersed particles and the matrix,
It has excellent compounding and moldability in plastic molding processes, and can be provided as a general-purpose white filler for plastics. In addition, basic calcium carbonate itself, calcium carbonate (calcite, aragonite),
Since the specific gravity is lower than that of conventional general-purpose white fillers such as talc and kaolin, it is possible to provide a light plastic composite by filling the product of the present invention.
代 理 人teenager Reason Man
Claims (1)
粒子から成る塩基性炭酸カルシウムの粒子表面が、飽和
炭化水素直鎖を有する１価の高級脂肪酸または炭素の二
重結合当り少なくとも８個の炭素数からなる飽和炭化水
素直鎖を有する１価の高級脂肪酸の吸着層で飽和された
被覆層を形成していることを特徴とする親油性変性塩基
性炭酸カルシウム。 ２、被覆層が、窒素吸着法（ＢＥＴ法）により測定した
塩基性炭酸カルシウムの表面積に対して、少なくとも等
量の占有面積を有する高級脂肪酸被覆層である特許請求
の範囲第１項記載の親油性変性塩基性炭酸カルシウム。 ３、粒子径が０．１μｍ以上、１．０μｍ以下の平板状
粒子から成る塩基性炭酸カルシウムの水懸濁液に、飽和
炭化水素直鎖を有する１価の高級脂肪酸または炭素の二
重結合当り少なくとも８個の炭素数からなる飽和炭化水
素直鎖を有する１価の高級脂肪酸のアルカリ塩水溶液を
、該塩基性炭酸カルシウムの表面積に対し該高級脂肪酸
の占有面積が少なくとも等量となる量の割合で添加して
粒子表面に該高級脂肪酸の被覆層を形成することにより
、粒子表面を永久的に親油性に変換したのち、濾過、脱
水、乾燥、粉砕することを特徴とする親油性変性塩基性
炭酸カルシウムの製造方法。[Scope of Claims] 1. The particle surface of basic calcium carbonate consisting of tabular particles with a particle size of 0.1 μm or more and 1.0 μm or less is a monovalent higher fatty acid having a saturated hydrocarbon linear chain or carbon A lipophilic modified basic calcium carbonate characterized by forming a coating layer saturated with an adsorption layer of a monovalent higher fatty acid having a straight saturated hydrocarbon chain having at least 8 carbon atoms per double bond. . 2. The parent according to claim 1, wherein the coating layer is a higher fatty acid coating layer having an occupied area at least equal to the surface area of basic calcium carbonate measured by a nitrogen adsorption method (BET method). Oil-based modified basic calcium carbonate. 3. To an aqueous suspension of basic calcium carbonate consisting of tabular particles with a particle size of 0.1 μm or more and 1.0 μm or less, add a monovalent higher fatty acid having a saturated hydrocarbon straight chain or per carbon double bond. An aqueous solution of an alkali salt of a monovalent higher fatty acid having a straight saturated hydrocarbon chain consisting of at least 8 carbon atoms is added in an amount such that the area occupied by the higher fatty acid is at least equal to the surface area of the basic calcium carbonate. The lipophilic modified base is characterized in that the particle surface is permanently converted to lipophilic by adding it to form a coating layer of the higher fatty acid on the particle surface, followed by filtration, dehydration, drying, and pulverization. Method for producing calcium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1214880A JPH0699151B2 (en) | 1989-08-23 | 1989-08-23 | Lipophilic modified basic calcium carbonate and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1214880A JPH0699151B2 (en) | 1989-08-23 | 1989-08-23 | Lipophilic modified basic calcium carbonate and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0380107A true JPH0380107A (en) | 1991-04-04 |
| JPH0699151B2 JPH0699151B2 (en) | 1994-12-07 |
Family
ID=16663099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1214880A Expired - Lifetime JPH0699151B2 (en) | 1989-08-23 | 1989-08-23 | Lipophilic modified basic calcium carbonate and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0699151B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11349846A (en) * | 1998-04-10 | 1999-12-21 | Maruo Calcium Co Ltd | Surface-treated calcium carbonate filler its production, and resin composition containing the filler |
| JP2002309112A (en) * | 2001-04-13 | 2002-10-23 | Shiraishi Kogyo Kaisha Ltd | Chlorinated polymer compound composition containing flaky calcium carbonate |
| WO2003048046A1 (en) * | 2001-12-03 | 2003-06-12 | Shiraishi Kogyo Kaisha, Ltd. | Material for imparting thixotropy and pasty resin composition |
| CN100435930C (en) * | 2004-10-29 | 2008-11-26 | 清华大学 | Modified calcium adsorbent for purifying incinerated smoke and preparation process thereof |
| US7798052B2 (en) | 2006-11-29 | 2010-09-21 | Smc Kabushiki Kaisha | Fluid pressure cylinder |
| CN113522931A (en) * | 2021-07-09 | 2021-10-22 | 浙江工业大学 | Mineral oxidation acid production inhibition method based on in-situ rapid film formation on surface of sulfurized mineral |
-
1989
- 1989-08-23 JP JP1214880A patent/JPH0699151B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11349846A (en) * | 1998-04-10 | 1999-12-21 | Maruo Calcium Co Ltd | Surface-treated calcium carbonate filler its production, and resin composition containing the filler |
| JP2002309112A (en) * | 2001-04-13 | 2002-10-23 | Shiraishi Kogyo Kaisha Ltd | Chlorinated polymer compound composition containing flaky calcium carbonate |
| WO2003048046A1 (en) * | 2001-12-03 | 2003-06-12 | Shiraishi Kogyo Kaisha, Ltd. | Material for imparting thixotropy and pasty resin composition |
| US7186763B2 (en) | 2001-12-03 | 2007-03-06 | Shiraishi Kogyo Kaisha, Ltd. | Material for imparting thixotropy and pasty resin composition |
| CN100435930C (en) * | 2004-10-29 | 2008-11-26 | 清华大学 | Modified calcium adsorbent for purifying incinerated smoke and preparation process thereof |
| US7798052B2 (en) | 2006-11-29 | 2010-09-21 | Smc Kabushiki Kaisha | Fluid pressure cylinder |
| CN113522931A (en) * | 2021-07-09 | 2021-10-22 | 浙江工业大学 | Mineral oxidation acid production inhibition method based on in-situ rapid film formation on surface of sulfurized mineral |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0699151B2 (en) | 1994-12-07 |
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|---|---|---|---|
| EXPY | Cancellation because of completion of term |