JP2007099613A - Method for producing inorganic particle agglomerate - Google Patents
Method for producing inorganic particle agglomerate Download PDFInfo
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- JP2007099613A JP2007099613A JP2006240844A JP2006240844A JP2007099613A JP 2007099613 A JP2007099613 A JP 2007099613A JP 2006240844 A JP2006240844 A JP 2006240844A JP 2006240844 A JP2006240844 A JP 2006240844A JP 2007099613 A JP2007099613 A JP 2007099613A
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- 239000010954 inorganic particle Substances 0.000 title claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 47
- 239000000049 pigment Substances 0.000 claims abstract description 40
- 241000628997 Flos Species 0.000 claims abstract description 29
- 239000000945 filler Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000002761 deinking Substances 0.000 claims abstract description 22
- 239000010893 paper waste Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims description 30
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- 239000010703 silicon Substances 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 4
- 239000010802 sludge Substances 0.000 abstract description 34
- 238000010304 firing Methods 0.000 abstract description 16
- 238000001035 drying Methods 0.000 abstract description 12
- 238000010298 pulverizing process Methods 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 17
- 239000000976 ink Substances 0.000 description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 16
- 238000007639 printing Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000011247 coating layer Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 238000007602 hot air drying Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910021532 Calcite Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000013055 pulp slurry Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- -1 it has fluidity Substances 0.000 description 1
- 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 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010947 wet-dispersion method Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Treatment Of Sludge (AREA)
- Silicon Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Paper (AREA)
Abstract
Description
本発明は、製紙工場の排水処理工程で排出される填料や顔料を含有する排水スラッジ、古紙処理工程の古紙溶解工程や異物除去工程で排出される製紙スラッジ、古紙脱墨工程で排出される脱墨フロス等の製紙スラッジ、原料調整工程で排出される製紙スラッジなどを焼成して得られた、製紙用の填料や顔料、あるいは充填剤、断熱材、防音材などとして利用することができる、好適には製紙スラッジ由来の無機粒子凝集体の製造方法に関するものである。 The present invention relates to wastewater sludge containing fillers and pigments discharged in the wastewater treatment process of a paper mill, papermaking sludge discharged in the wastepaper dissolution process and foreign matter removal process in the wastepaper treatment process, and dewatering discharged in the wastepaper deinking process. Can be used as a papermaking sludge such as black floss, papermaking sludge discharged in the raw material adjustment process, etc., and can be used as a filler or pigment for papermaking, or as a filler, heat insulating material, soundproofing material, etc. Relates to a method for producing an aggregate of inorganic particles derived from papermaking sludge.
無機粒子は農薬の展着剤・増量剤、塗料・印刷インクの体質顔料、ゴム類の補強剤、プラスチック類（成形品、フィルム、繊維など）の充填剤・改質剤などとして利用されている。ここでは、白色顔料としての使用量が最も多い製紙産業での利用形態を代表例として記載する。 Inorganic particles are used as spreaders and extenders for agricultural chemicals, extenders for paints and printing inks, reinforcing agents for rubbers, fillers and modifiers for plastics (molded articles, films, fibers, etc.) . Here, the usage form in the paper industry where the amount of white pigment used is the largest is described as a representative example.
製紙の技術分野においては、紙の白色度、不透明度、紙表面の平坦性、印刷時の網点再現性の向上などを目的として、近年、要求が高まっている紙の軽量化を進めるにあたっての不透明度、裏抜け対策を目的として、抄紙における湿紙の乾燥速度の向上・乾燥エネルギーコストの削減を目的として、増量材効果による原料コストの削減を目的として、あるいは紙表面の諸特性を改善するためにパルプを主とする基紙上に設ける塗工層用顔料として用いられている。 In the papermaking technical field, in order to improve paper whiteness, opacity, paper surface flatness, halftone dot reproducibility during printing, etc. For the purpose of countermeasures for opacity and back-through, to improve the drying speed of wet paper in papermaking and to reduce the drying energy cost, to reduce the raw material cost by the effect of the bulking material, or to improve various characteristics of the paper surface Therefore, it is used as a pigment for a coating layer provided on a base paper mainly composed of pulp.
このような製紙用の填料、顔料としては、白土（含水ケイ酸アルミニウム）、炭酸カルシウム、酸化亜鉛、水酸化アルミニウム、硫化亜鉛、二酸化チタン、硫酸カルシウム、亜硫酸カルシウム、硫酸バリウム、タルク、シリカなどが知られており、単独又はこれらを適宜組み合わせて用いられている。 Examples of such papermaking fillers and pigments include clay (hydrous aluminum silicate), calcium carbonate, zinc oxide, aluminum hydroxide, zinc sulfide, titanium dioxide, calcium sulfate, calcium sulfite, barium sulfate, talc, and silica. It is known and used alone or in combination.
以下、本明細書記載の「填料」とは、製紙において抄紙時の原料調整工程で添加するいわゆる内添填料をいう。また、本明細書記載の「顔料」とは、塗被紙製造時において塗被組成物中に添加する顔料をいう。 Hereinafter, the “filler” described in the present specification refers to a so-called internal filler that is added in the raw material adjustment step during papermaking in papermaking. In addition, the “pigment” described in the present specification refers to a pigment added to a coating composition at the time of producing coated paper.
製紙工程においては、製紙原料であるパルプなどの繊維分、澱粉や合成接着剤などの有機物、紙製品に歩留らずに排水中に含まれて処理される前記製紙用填料・顔料を主とする無機物、さらには、パルプ化工程で洗い出されたリグニンや古紙由来の製紙用顔料、それに付着した印刷インク、また生物排水処理工程で生じる余剰汚泥などからなる、いわゆる製紙スラッジが発生する。近年、古紙利用率が高まるにつれて、古紙の脱墨工程由来の製紙スラッジが増加の一途を辿っている。 In the papermaking process, the main ingredients are fiber content such as pulp as a raw material for papermaking, organic substances such as starch and synthetic adhesives, and the fillers and pigments for papermaking that are contained in wastewater without being produced in paper products. In addition, a so-called paper sludge is generated, which is composed of inorganic substances that are washed out, lignin washed out in the pulping process, papermaking pigments derived from waste paper, printing ink attached thereto, surplus sludge generated in the biological wastewater treatment process, and the like. In recent years, as the waste paper utilization rate increases, paper sludge derived from the waste paper deinking process continues to increase.
これらの製紙スラッジは、回収され、流動床炉やストーカー炉などの焼却炉で製紙スラッジ中の有機物を燃焼して製紙スラッジの減容化を図るとともに、エネルギーとして回収されている。しかしながら、製紙スラッジには、多量の無機物が含有されているため、燃焼しても多量の燃焼灰（無機物）が残り、減容化にも限度がある。そこで、この燃焼灰をセメント原料として活用することや、土壌改良剤として活用すること等の努力もなされている。しかし、これらは、セメント原料や土壌改良剤の助剤として焼却灰を利用する方法で、その使用量はわずかなものであり、結局、大部分の燃焼灰は埋立処分されているのが実情である。 These paper sludges are collected, and the organic sludge in the paper sludge is burned in an incinerator such as a fluidized bed furnace or a stalker furnace to reduce the volume of the paper sludge and is recovered as energy. However, since papermaking sludge contains a large amount of inorganic substances, a large amount of combustion ash (inorganic substances) remains even after combustion, and there is a limit to volume reduction. Therefore, efforts have been made to utilize the combustion ash as a raw material for cement and as a soil conditioner. However, these are methods that use incinerated ash as an auxiliary material for cement raw materials and soil conditioners, and the amount of use is very small. After all, most of the combustion ash is landfilled. is there.
このため、焼却によってエネルギーとして回収されている有機物だけでなく、焼却灰として残る無機物を製紙用填料、顔料として再利用することは、製紙業界において古紙利用率の向上とともに環境問題に関わる重要な改善課題である。しかしながら、単なる製紙スラッジの焼却灰には燃焼されずに残った有機物がカーボンとして含まれるため白色度が低く、あるいは、無機物の焼結が進んだりして、粒径が不揃いで大きくなっており、そのままの状態では紙の填料や塗工用顔料として使用するのに適さない。そこで、特許文献１は燃焼灰（焼却灰）を再燃焼し、白色度を向上させてから使用する方法を開示している。 For this reason, the reuse of not only organic materials recovered as energy by incineration but also inorganic materials remaining as incineration ash as fillers and pigments for papermaking is an important improvement related to environmental issues in the papermaking industry as well as to improve the wastepaper utilization rate. It is a problem. However, the incineration ash of simple papermaking sludge contains organic substances that remain without being burned as carbon, so the whiteness is low, or the sintering of inorganic substances progresses, and the particle size is uneven and large, As it is, it is not suitable for use as a paper filler or a coating pigment. Therefore, Patent Document 1 discloses a method of using combustion ash (incineration ash) after reburning and improving the whiteness.
しかしながら、焼却灰を再燃焼する方法による場合、再燃焼温度を５００〜９００℃に設定すると、焼却灰の白色度は５０％程度にまでしか向上せず、紙の填料や塗工用顔料として使用するに適するものとはならないことが知見された。また、再燃焼温度を９００℃超に設定すると、燃焼灰（無機物）が焼結、溶融し、極めて硬くなることが知見された。また、再燃焼灰を填料として使用すると、この再燃焼灰は非常に硬い性質をもつため、抄紙ワイヤーの磨耗進行が早く、抄紙ワイヤーの寿命が非常に短くなるため、実操業には使用できるものではなかった。また、この再燃焼灰を塗工用顔料として使用すると、再燃焼灰が非常に硬い性質であるため、カレンダー処理を行ってもその塗工層表面の平滑性が劣るという問題が生じる。 However, in the method of reburning incinerated ash, when the reburning temperature is set to 500 to 900 ° C., the whiteness of the incinerated ash is improved only to about 50%, and it is used as a paper filler or coating pigment. It has been found that it is not suitable to do. It has also been found that when the reburning temperature is set to over 900 ° C., the burning ash (inorganic material) is sintered and melted and becomes extremely hard. Also, when reburned ash is used as a filler, this reburned ash has very hard properties, so the papermaking wire wears out quickly and the life of the papermaking wire becomes very short, so it can be used in actual operations. It wasn't. Further, when the reburned ash is used as a coating pigment, the reburned ash has a very hard property, so that there arises a problem that the smoothness of the surface of the coating layer is inferior even when the calendar treatment is performed.
この点、再燃焼灰を粉砕し、その粒径を小さくして、磨耗の低減、平滑性の向上を図ることも考えられるが、内添填料として使用する場合には、抄紙時における歩留りが低いものであったり、燃焼灰自体が極めて硬いため、粉砕のためのエネルギーコストが極めて高いものとなったりする。 In this regard, it is conceivable to grind the reburned ash and reduce its particle size to reduce wear and improve smoothness, but when used as an internal filler, the yield during paper making is low. Or because the combustion ash itself is extremely hard, the energy cost for pulverization becomes extremely high.
また、特許文献２のように、スラッジを、酸素含有ガスを注入した反応器内に供給し、２５０〜３００℃、３０００ｐｓｉｇ程度の加温加圧下で０．２５〜５時間酸化して、製紙スラッジ中の無機物を製紙用の顔料として再生化する方法が提案されている。 In addition, as in Patent Document 2, sludge is supplied into a reactor into which an oxygen-containing gas has been injected, and oxidized at 250 to 300 ° C. under a heating and pressurization of about 3000 psig for 0.25 to 5 hours. A method for regenerating the inorganic material as a pigment for papermaking has been proposed.
しかし、この方法は、スラッジの湿式空気酸化処理によるものであるから、有機物除去が十分でなく、また、得られた顔料の白色度が低く、粒径も不揃いで、しかも反応操作が複雑でコストが高いという問題がある。 However, since this method is based on wet air oxidation treatment of sludge, organic matter removal is not sufficient, the whiteness of the obtained pigment is low, the particle size is not uniform, and the reaction operation is complicated and costly. There is a problem that is high.
一方、特許文献３には、製紙スラッジをいぶし焼きしてＰＳ炭とした後、さらにこれをキルンで焼却して製紙用原料となる白土を生成させる方法が提案されている。しかし、この方法は製紙スラッジをいぶし焼きするため、製紙スラッジからエネルギーを有効に取り出すことができないばかりか、逆に投入エネルギーが必要になるという大きなデメリットがある。さらに、生成した白土も粒径が不揃いで大きくなっており、製紙用顔料としては使用できないという問題がある。 On the other hand, Patent Document 3 proposes a method in which after making papermaking sludge into PS charcoal, it is further incinerated with a kiln to produce white clay as a papermaking raw material. However, this method has a great demerit that not only energy cannot be effectively extracted from the papermaking sludge but also input energy is required because the papermaking sludge is fried. Further, the generated white clay also has a large particle size and has a problem that it cannot be used as a papermaking pigment.
すなわち、従来公知の方法により得られた無機粒子を抄紙工程において内添する場合には歩留りの安定性が得られず、塗工紙用顔料を調整する際の分散状態が不安定となる場合が多く、塗工層の表面処理において所定の紙厚では平滑性が得られず、画線の明瞭性が低下するなど、品質として不安定なものであった。
本発明者らはこれらの問題を解決するため鋭意研究を重ねた結果、無機粒子を形成する成分構成とそれらの成分が粒子全体に占める割合によって解決できることを見出した。したがって、本発明が解決しようとする主たる課題は、原料として製紙スラッジ等の廃棄物を使用し、従来の再生無機粒子では得られなかった、製紙時における歩留性、嵩高性、表面平坦性、印刷適性、吸油性に優れた無機粒子凝集体の製造方法を提供することにある。 As a result of intensive studies to solve these problems, the present inventors have found that the composition can be solved by the component constitution forming inorganic particles and the ratio of these components to the whole particle. Therefore, the main problem to be solved by the present invention is to use waste such as papermaking sludge as a raw material, which was not obtained with conventional recycled inorganic particles, yield at the time of papermaking, bulkiness, surface flatness, An object of the present invention is to provide a method for producing an inorganic particle aggregate excellent in printability and oil absorption.
この課題を解決した本発明は、次のとおりである。
〔請求項１記載の発明〕
製紙用の填料又は顔料として使用できる無機粒子凝集体であって、
古紙脱墨処理工程で排出される脱墨フロスを主原料として、
脱水及び乾燥させ、焼成し、粉砕して得られ、下記組成となるように調整し、ＪＩＳ Ｋ ５１０１法による吸油度が、３０〜１００ｍｌ／１００ｇである無機粒子凝集体を得る、
ことを特徴とする無機粒子凝集体の製造方法。
（組成）
前記無機粒子凝集体は、無機粒子凝集体の粒子構成成分がカルシウム、ケイ素及びアルミニウムを、酸化物換算で３０〜８２：９〜３５：９〜３５の質量割合で含有し、かつ、前記無機粒子凝集体の粒子構成成分の内、前記カルシウム、前記ケイ素及び前記アルミニウムの合計含有割合が無機粒子構成成分中の９０質量％以上である無機粒子凝集体。
The present invention that has solved this problem is as follows.
[Invention of Claim 1]
An inorganic particle aggregate that can be used as a filler or pigment for papermaking,
Using the deinking floss discharged in the wastepaper deinking process as the main raw material,
Dehydrated and dried, calcined, pulverized, adjusted to the following composition, and obtained an inorganic particle aggregate having an oil absorption of 30 to 100 ml / 100 g according to JIS K 5101 method.
The manufacturing method of the inorganic particle aggregate characterized by the above-mentioned.
(composition)
The inorganic particle aggregate contains calcium, silicon, and aluminum as particle constituents of the inorganic particle aggregate in a mass ratio of 30 to 82: 9 to 35: 9 to 35 in terms of oxide, and the inorganic particle The inorganic particle aggregate whose total content rate of the said calcium, the said silicon, and the said aluminum is 90 mass% or more in an inorganic particle structural component among the particle structural components of an aggregate.
（作用効果）
・ 本発明の無機粒子凝集体は、脱墨フロスを主原料するものを焼成して得られたもの、つまり原料として脱墨フロスが使用されているので、廃棄物が増えるとの問題が生じず、また、原料が安価であることによって製造コストが削減される。
・ 本発明の脱墨フロスを主原料として、脱水及び乾燥させ、焼成し、粉砕して（粉砕後に粒子を凝集させる工程を経ることなくて）得られた無機粒子凝集体は、顔料として塗工液に添加した場合において、バインダーや分散剤との相性が良く、高濃度での分散特性に優れるため、塗工層の強度が向上する。
・ 本発明の無機粒子凝集体は、空隙を多く含むため吸油性が高く、顔料として塗工液に添加するとインク着肉性が良好になり印刷適性が向上する。
・ 本発明の無機粒子凝集体は、カルシウムが酸化物換算で３０質量割合以上とされているので、内添した紙の白色度が高くなる。
・ 炭酸カルシウムには、六方結晶系のカルサイト結晶（方解石）や、斜方結晶系のアラゴナイト結晶（あられ石）などの同質異像があり、天然に産する石灰石はそのほとんどがカルサイト系で、貝殻類にはカルサイト結晶のほかアラゴナイト結晶がある。また、炭酸カルシウムには、天然には存在しないがバテライト系がある。脱墨フロス中から得られるカルシウムは多種多様であるが、焼成凝集化することでほぼ均一の炭酸カルシウム性状となる。したがって、無機微粒子そのものの品質安定性に寄与し、異なる成分で構成される凝集体でありながら、殆ど性状が安定した無機微粒子が得られる。
・ 本発明の無機粒子凝集体は、ケイ素を含むところ、ケイ素の１次粒子は微細なので、光学的屈折率が高い。したがって、ケイ素が酸化物換算で９質量％割合以上とされている本発明の無機粒子凝集体を填料として内添した紙は、不透明度が高い。
・ また、ケイ素の１次粒子が微細であると、バインダー等の水溶性接着剤や水溶性助剤との親和性が高まる。したがって、ケイ素が酸化物換算で９質量割合以上とされている本発明の無機粒子凝集体を顔料として塗工液に含ませると、印刷インクの吸収性や乾燥性が向上する。
・ 他方、本発明の無機粒子凝集体は、ケイ素が酸化物換算で３５質量割合以下とされているので、顔料として使用した場合においても、流動性、固形分濃度の安定性、つまり分散性が高い。これは、無機粒子凝集体の形成により、ケイ素が持つ高い吸水能が制限されることによるためと考えられる。
・ 本発明の無機粒子凝集体は、アルミニウムを酸化物換算で９質量割合以上含む。このアルミニウムは、クレー中のアルミニウムや、抄紙工程における助剤として添加される３価の硫酸アルミニウム、１８水和物、不純物としてタルクに含有されるアルミニウムを、主たる由来源としている。アルミニウムが本来持つ極めて高いカチオン性を示し、アニオン性を示す従来の無機填料と比べ、アニオン性のパルプ繊維との結合力が向上し、歩留まり、薬品定着性が向上する。
・ 他方、本発明の無機粒子凝集体は、アルミニウムが酸化物換算で３５質量割合以下とされているので、過剰なカチオン性による塗料ショックを生じさせることがなく、パルプ懸濁液中（パルプスラリー中）や塗工液中における安定した分散性を得ることができる。
・ ＪＩＳ Ｋ ５１０１法による吸油度が、３０〜１００ｍｌ／１００ｇとされている。本発明に従う、カルシウム、ケイ素及びアルミニウムを、酸化物換算で３０〜８２：９〜３５：９〜３５の質量割合で含有し、かつ、前記カルシウム、前記ケイ素及び前記アルミニウムの合計含有割合が、９０質量％以上である無機粒子凝集体において、吸油度が３０ｍｌ／１００ｇ未満では、インク吸収効果が少なく裏層抜け防止効果が低い。１００ｍｌ／１００ｇ以上では、画線部のニジミや印刷品質が沈んだ状態になり印刷光沢が悪くなる。
(Function and effect)
The inorganic particle agglomerates of the present invention are obtained by calcining what is the main raw material for deinking floss, that is, since deinking floss is used as a raw material, there is no problem of increased waste. In addition, the manufacturing cost is reduced because the raw material is inexpensive.
The inorganic particle aggregate obtained by using the deinked floss of the present invention as a main raw material, dehydrated and dried, calcined, and pulverized (without going through the step of aggregating particles after pulverization) is applied as a pigment. When added to the liquid, the compatibility with the binder and the dispersant is good and the dispersion characteristics at a high concentration are excellent, so that the strength of the coating layer is improved.
The inorganic particle aggregate of the present invention has a high oil absorbency because it contains many voids, and when it is added as a pigment to the coating liquid, the ink setting property is improved and the printability is improved.
-In the inorganic particle aggregate of the present invention, calcium is 30% by mass or more in terms of oxide, so that the whiteness of the internally added paper is increased.
・ Calcium carbonate has homogeneities such as hexagonal calcite crystal (calcite) and orthorhombic aragonite crystal (aragonite), and most limestone produced in nature is calcite. Shellfish include aragonite crystals in addition to calcite crystals. Calcium carbonate has a vaterite system that does not exist in nature. Calcium obtained from the deinking floss is various, but it becomes an almost uniform calcium carbonate property by calcination and aggregation. Therefore, inorganic fine particles that contribute to the quality stability of the inorganic fine particles themselves and have almost stable properties while being aggregates composed of different components can be obtained.
-The inorganic particle aggregate of the present invention contains silicon, and since the primary particles of silicon are fine, the optical refractive index is high. Therefore, the paper in which the inorganic particle aggregate of the present invention in which silicon is 9% by mass or more in terms of oxide is internally added as a filler has high opacity.
In addition, when the primary particles of silicon are fine, the affinity with a water-soluble adhesive such as a binder or a water-soluble auxiliary agent is increased. Therefore, when the inorganic particle aggregate of the present invention in which silicon is in an oxide equivalent of 9% by mass or more is included as a pigment in the coating liquid, the absorbability and drying property of the printing ink are improved.
On the other hand, since the inorganic particle aggregate of the present invention has a silicon content of 35% by mass or less in terms of oxide, even when used as a pigment, it has fluidity, solid content concentration stability, that is, dispersibility. high. This is presumably because the formation of inorganic particle aggregates limits the high water absorption capability of silicon.
-The inorganic particle aggregate of this invention contains aluminum 9 mass% or more in conversion of an oxide. The main sources of aluminum are aluminum in clay, trivalent aluminum sulfate added as an auxiliary in the papermaking process, 18 hydrate, and aluminum contained in talc as impurities. Compared with the conventional inorganic filler which shows the extremely high cationic property which aluminum originally has, and anionic property, the bond strength with an anionic pulp fiber improves, and a yield and chemical fixability improve.
On the other hand, since the inorganic particle aggregate of the present invention has an aluminum content of 35% or less in terms of oxide, it does not cause paint shock due to excessive cationicity, and is not generated in the pulp suspension (pulp slurry). Middle) and a stable dispersibility in the coating liquid.
-Oil absorption by JIS K 5101 method is 30-100 ml / 100g. According to the present invention, calcium, silicon and aluminum are contained in a mass ratio of 30 to 82: 9 to 35: 9 to 35 in terms of oxides, and the total content of the calcium, silicon and aluminum is 90 When the oil absorption is less than 30 ml / 100 g in the inorganic particle aggregate having a mass% or more, the ink absorption effect is small and the back layer removal prevention effect is low. If it is 100 ml / 100 g or more, the blurring of the image area and the print quality will be sunk and the print gloss will deteriorate.
〔請求項２記載の発明〕
コールターカウンター法による平均粒子径が、０．１〜１０μｍである請求項１記載の無機粒子凝集体の製造方法。
[Invention of Claim 2]
The method for producing an inorganic particle aggregate according to claim 1, wherein an average particle size by a Coulter counter method is 0.1 to 10 µm.
（作用効果）
・ 本発明の無機粒子凝集体は、コールターカウンター法による平均粒子径が、０．１〜１０μｍである。平均粒子径を０．１〜１０μｍの範囲にした理由は、製紙用として内添用製紙顔料や塗工用製紙顔料に利用する場合に、その分散性、摩耗性、白色度、明度及び不透明度への影響を考慮して、この範囲が最適であると判断し設定したためである。
・ 本発明の無機粒子凝集体は、平均粒子径が０．１μｍ以上の凝集体とされているので、近年の１３００ｍ／分を越える高速抄紙において歩留まりがよく、顔料としては、紙層の被覆性に優れるという利点を有する。他方、本発明の無機粒子凝集体は、平均粒子径が１０μｍ以下とされているので、高速塗工におけるストリーク発生の問題を軽減するとともに、紙粉、粉落ちの発生が少ないという利点を有する。
さらに、無機粒子凝集体は、塗工紙の顔料として用いた場合、平均粒径が０．１μｍ以下の場合、コート液を調製する際に、水若しくはバインダー水溶液に填料を分散する時に分散液の粘度が上昇し、コート液の填料濃度を十分上げることが困難となる。また、インクジェット記録用紙の筆記性、表面強度も低下する。
一方、平均粒径が１０μｍよりも大きい場合、コート層表面に非晶質シリカ粉末に由来する凹凸が生じ紙面の手触りが悪くなり、インクドットの真円性も低下する。
特に好ましい無機粒子凝集体の平均粒子径は、４〜９μｍである。
・ 無機粒子凝集体は、分散剤を添加してスラリー化した後、分散機による湿式分散により平均粒径０．１〜１０μｍまで細かくするが、白色顔料の用途に応じて、例えば塗工用の製紙用顔料としては０．３〜５μｍ、内添用の製紙用顔料としては０．５〜１０μｍとするのが好ましい。
・ さらに、カルシウム、ケイ素及びアルミニウムを、酸化物換算で３０〜８２：９〜３５：９〜３５の質量割合で含有し、かつ、前記カルシウム、前記ケイ素及び前記アルミニウムの合計含有割合が、９０質量％以上からなる多孔質となっているので、比重が軽く、過度の水溶液吸収が抑えられるため、パルプ懸濁液中（パルプスラリー中）や塗工液中における分散性が高い。したがって、嵩高な塗工層、紙層を形成しやすく、かつ紙層に歩留まり易い。
(Function and effect)
-The average particle diameter of the inorganic particle aggregate of this invention by a Coulter counter method is 0.1-10 micrometers. The reason why the average particle size is in the range of 0.1 to 10 μm is that when used for papermaking pigment for internal use or papermaking pigment for coating, its dispersibility, abrasion, whiteness, brightness and opacity This is because this range is determined to be optimum in consideration of the influence on the environment.
Since the inorganic particle aggregate of the present invention is an aggregate having an average particle diameter of 0.1 μm or more, the yield is good in high-speed papermaking exceeding 1300 m / min in recent years. It has the advantage of being excellent. On the other hand, since the average particle diameter of the inorganic particle aggregate of the present invention is 10 μm or less, it has the advantages of reducing the problem of streak generation in high-speed coating and reducing the occurrence of paper dust and powder falling off.
Further, when the inorganic particle aggregate is used as a pigment for coated paper, the average particle size is 0.1 μm or less, and when the coating liquid is prepared, the dispersion liquid is dispersed when dispersed in water or an aqueous binder solution. The viscosity increases and it becomes difficult to sufficiently increase the filler concentration of the coating solution. Further, the writing property and surface strength of the ink jet recording paper are also lowered.
On the other hand, when the average particle size is larger than 10 μm, irregularities derived from the amorphous silica powder are generated on the surface of the coating layer, the feel of the paper surface is deteriorated, and the roundness of the ink dots is also lowered.
A particularly preferable average particle size of the inorganic particle aggregate is 4 to 9 μm.
The inorganic particle aggregate is slurried by adding a dispersant, and then finely divided to an average particle size of 0.1 to 10 μm by wet dispersion using a disperser. Depending on the application of the white pigment, for example, for coating It is preferable that the papermaking pigment is 0.3 to 5 μm, and the papermaking pigment for internal addition is 0.5 to 10 μm.
-Furthermore, calcium, silicon and aluminum are contained in a mass ratio of 30 to 82: 9 to 35: 9 to 35 in terms of oxide, and the total content ratio of the calcium, silicon and aluminum is 90 mass. Since the specific gravity is light and excessive aqueous solution absorption is suppressed, the dispersibility in the pulp suspension (pulp slurry) and in the coating liquid is high. Therefore, it is easy to form a bulky coating layer and paper layer, and it is easy to yield on the paper layer.
〔請求項３記載の発明〕
コールターカウンター法による粒度分布の微分曲線における平均粒子径のピーク高さが、３０％以上である、請求項１または２記載の無機粒子凝集体の製造方法。
[Invention of Claim 3]
The method for producing an inorganic particle aggregate according to claim 1 or 2, wherein a peak height of an average particle diameter in a differential curve of particle size distribution by a Coulter counter method is 30% or more.
（作用効果）
・ コールターカウンター法による粒度分布の微分曲線における平均粒子径のピーク高さが３０％以上である。本発明において、無機粒子凝集体の粒度分布としては、微分曲線におけるピーク高さが３０％以上好ましくは３５％以上、半値幅は５μｍ以下であることが好ましい。かかる微分曲線におけるピーク高さが３０％以上かつ好ましくは半値幅が５μｍ以下であることは、粒度分布が狭い（シャープである）ことを意味する。粒度分布の狭い無機粒子ほど、画線部の明瞭性や、高精細な画像を得るのに好適である。逆に、ピーク高さ及び半値幅が上記範囲から外れる（粒度分布がブロードである）場合、精細さが欠け、画像が不鮮明になる。
・ また、かかる微分曲線において、ピークは１つ存在するのが最も好ましいが、他に５％以下のピークであれば１つ以上存在しても良い。しかし、ピークが２つ以上存在する場合、部分的に精細が欠ける部分が混在することとなり、ピークが１つの場合と比べると画像は不鮮明となる。
(Function and effect)
-The average particle size peak height in the differential curve of the particle size distribution by the Coulter counter method is 30% or more. In the present invention, as the particle size distribution of the inorganic particle aggregate, the peak height in the differential curve is preferably 30% or more, preferably 35% or more, and the half width is preferably 5 μm or less. A peak height in such a differential curve of 30% or more and preferably a half width of 5 μm or less means that the particle size distribution is narrow (sharp). Inorganic particles with a narrow particle size distribution are more suitable for obtaining clarity of image areas and high-definition images. On the other hand, when the peak height and the half width are out of the above ranges (the particle size distribution is broad), the fineness is lost and the image becomes unclear.
-In such a differential curve, it is most preferable that one peak exists, but one or more peaks may exist if the peak is 5% or less. However, when two or more peaks are present, a portion lacking in detail is mixed, and the image is unclear compared to the case of one peak.
本発明によると、従来の再生無機粒子では得られなかった、製紙時における歩留性、嵩高性、表面平坦性、印刷適性、吸油性に優れた無機粒子凝集体を提供することが可能となり、アート紙、コート紙などの塗被組成物を構成する顔料として、あるいはＰＰＣ用紙、感熱紙、感圧紙、熱転写紙、インクジェット用紙、静電記録紙、磁気記録紙等の情報用紙に用いる填料、顔料として、あるいは上級、中級印刷用紙などの非塗工紙に用いる填料として、あるいはライスペーパー、工業用雑種紙などに用いる填料、顔料などとして広い範囲にわたり使用可能である。 According to the present invention, it has become possible to provide an inorganic particle aggregate excellent in yield, bulkiness, surface flatness, printability, and oil absorption during papermaking, which was not obtained with conventional regenerated inorganic particles. Fillers and pigments used as pigments for coating compositions such as art paper and coated paper, or for information paper such as PPC paper, thermal paper, pressure sensitive paper, thermal transfer paper, ink jet paper, electrostatic recording paper, magnetic recording paper, etc. As a filler used for non-coated paper such as high-grade and intermediate printing paper, or as filler or pigment used for rice paper, industrial hybrid paper, etc., it can be used over a wide range.
次に、本発明の実施の形態を、本発明に係る無機粒子凝集体を好適に使用できる製紙用填料、顔料用途の製造方法を主たる対象として説明する。以下の実施の形態は、本発明に基づく無機粒子凝集体を製造する好適な実施の形態を示し、この実施の形態に限定されるものではない。
〔用途〕
本形態の製紙用の無機粒子凝集体は、製紙用の填料又は顔料として使用できる。
Next, an embodiment of the present invention will be described mainly with respect to a paper filler and a manufacturing method for pigments that can suitably use the inorganic particle aggregate according to the present invention. The following embodiment shows a preferred embodiment for producing an inorganic particle aggregate based on the present invention, and is not limited to this embodiment.
[Use]
The inorganic particle aggregate for papermaking of this form can be used as a filler or pigment for papermaking.
〔無機粒子凝集体〕
本形態の無機粒子凝集体は、脱墨フロスを主原料するものを焼成して得られたものである。
[Inorganic particle aggregates]
The inorganic particle aggregate of the present embodiment is obtained by firing what is mainly made of deinked floss.
〔廃棄物〕
製紙工場からの廃棄物としては、例えば、製紙工場の排水処理工程で排出される填料や顔料を含有する排水スラッジ、古紙処理工程の古紙溶解工程や異物除去工程で排出される製紙スラッジ、古紙脱墨工程で排出される脱墨フロス等の製紙スラッジ、あるいは、原料調整工程で排出される製紙スラッジなどを例示することができる。
このうち、本発明は、脱墨フロスを主原料するものである。脱墨フロス以外の製紙スラッジなどは、構成成分が変動し易いため、製品の性状の変動要因になりやすい。これに対し、脱墨フロスは、構成成分がほとんど変動しないため、得られる無機粒子凝集体の白色度等の品質をコントロールすることが容易となり、製紙用とするに好適である。なお、脱墨フロスの構成成分がほぼ変動せずに安定しているのは、古紙パルプの性状の安定が再生紙の品質安定につながる観点から古紙パルプの原料たる古紙をほぼ同質にしている理由による。
構成成分の変動の抑制手法としては、前記脱墨フロスの利用以外に、性状が安定している、塗工工程スラッジや抄紙工程のスラッジなど出所が明確なスラッジを所定量混合することで調整可能になる。
ここで脱墨フロスとは、古紙処理工程において、脱インクし、パルプを取り出した後の残渣である。主として、カオリン、炭酸カルシウム、タルク、二酸化チタン等の無機粒子、残留インク粒子、繊維、コーティング剤等の有機系化合物、及び、水を含む。
脱墨フロスは、例えば、沈殿や加圧浮上等の方法で固液分離して固形分を回収し、所定の水分に乾燥した後、第１焼成工程で所定の未燃率となるように調整して焼成する。これにより、塊状に凝集した多孔質原料となる。
〔waste〕
Examples of waste from the paper mill include waste sludge containing fillers and pigments discharged in the waste water treatment process of the paper mill, paper sludge discharged in the waste paper dissolution process and foreign matter removal process in the waste paper treatment process, and waste paper removal. Examples include papermaking sludge such as deinking floss discharged in the blacking process, or papermaking sludge discharged in the raw material adjustment process.
Of these, the present invention mainly uses deinking floss. Paper sludges other than deinking floss are likely to cause fluctuations in product properties because their constituent components tend to fluctuate. On the other hand, since deinking floss has almost no change in constituent components, it is easy to control the quality such as whiteness of the resulting inorganic particle aggregate, and is suitable for papermaking. The components of the deinking floss are stable with almost no change because the stability of the properties of the used paper pulp leads to stable quality of the recycled paper, because the used paper used as the raw material of the used paper pulp is almost the same quality. by.
In addition to the use of the deinking floss, it can be adjusted by mixing a certain amount of sludge with a stable property, such as coating process sludge and papermaking process sludge. become.
Here, the deinking floss is a residue after deinking and taking out the pulp in the used paper processing step. It mainly contains inorganic particles such as kaolin, calcium carbonate, talc and titanium dioxide, residual ink particles, fibers, organic compounds such as coating agents, and water.
The deinking floss is, for example, solid-liquid separated by a method such as precipitation or pressurized flotation, collected solids, dried to a predetermined moisture, and adjusted to a predetermined unburned rate in the first firing step And fired. Thereby, it becomes the porous raw material aggregated in the lump shape.
以下は、脱墨フロスを例にとり、本発明に基づく微細無機粒子凝集体の製造方法例を詳述する。
〔フロック化・脱水〕
通常脱墨フロスは、水分率９５〜９８質量％程度であり、凝集剤を加えてフロックを形成させ、脱水処理を行う。脱水処理は、１段でも複数段でも実施可能ではあるが、フロックを固化させると、後工程の第２焼成工程において焼成ムラが生じる原因になるため、複数段で水分率を５０〜６０質量％程度まで脱水することが好ましい。
Hereinafter, taking deinking floss as an example, an example of a method for producing fine inorganic particle aggregates according to the present invention will be described in detail.
[Flocking and dehydration]
Usually, the deinking floss has a moisture content of about 95 to 98% by mass, and a floc is formed by adding a flocculant to perform dehydration. The dehydration process can be performed in one or more stages, but if the floc is solidified, it causes firing unevenness in the second firing step, which is a subsequent process. It is preferred to dehydrate to the extent.
〔乾燥・分級〕
脱水物は、予め乾燥される。乾燥手段は、熱風乾燥等公知の乾燥手段を使用可能であるが、脱墨フロスを乾燥させながらほぐす事が可能であり、更に比重分級をも可能な熱風乾燥手段が最も好適に使用できる。
好適に使用できる熱風乾燥手段を具体的に例示すると、脱水製紙フロスをインペラ等のほぐし設備にてほぐしながら、インペラ設備下方に設けた熱風吹きだし手段にて熱風を吹き込み熱風乾燥を行う。ほぐされ、乾燥された製紙フロスのうち、比重の軽い製紙フロスを熱風乾燥手段の上部に設けた取出し口から排出させることで、乾燥と分級とを行うことができる。
乾燥させた脱墨フロスの分級には、好適な手段として、サイクロンによる分級を採用することもできる。
[Drying / Classification]
The dehydrated product is dried in advance. As the drying means, known drying means such as hot air drying can be used, but it is possible to loosen the deinked floss while drying, and hot air drying means that can also perform specific gravity classification can be most preferably used.
Specific examples of the hot air drying means that can be suitably used include hot air drying by blowing hot air with hot air blowing means provided below the impeller equipment while loosening the dehydrated paper floss with an unwinding equipment such as an impeller. Drying and classification can be performed by discharging the papermaking floss having a low specific gravity out of the loosened and dried papermaking floss from a take-out port provided at the upper part of the hot air drying means.
As a suitable means for classification of the deinked floss that has been dried, classification by a cyclone can be employed.
〔焼成〕
乾燥・分級された脱墨フロスは、第１焼成工程に送られる、第１焼成工程においては、未燃率を１０質量％以上、１５質量％未満になるように調整することが肝要である。未燃率を１０質量％以上とすることで、次の第２焼成工程の焼成において粒子に多孔性を付与することができる。さらに、未燃率を１５質量％未満にすることで、次の第２焼成工程で自燃による過焼成で粒子が硬化することを防ぐことが可能になる。
焼成は、６５０℃以下で行うのが好ましく、特に、残カーボンによる白色度の低下を避けるために、４５０〜６５０℃の範囲で段階をつけて行うのが好ましい。６５０℃超の高温で焼成を行うと、炭酸カルシウムが分解して酸化カルシウムとなり、また、無機物の溶融が生じて極めて硬度が高く多孔性が低い無機粒子となるおそれがある。なお、酸化カルシウムは水溶性であるため、抄紙工程において添加した際に溶け出してしまい、例えば、サイズ剤等の薬品効果を妨げるおそれがある。
本形態の無機粒子凝集体は、以上の多孔質原料を、９０質量％以上含み、かつこの多孔質原料が、カルシウム、ケイ素及びアルミニウムを酸化物換算で３０〜８２：９〜３５：９〜３５の質量割合で含むことを特徴とする。好ましくは、４０〜８２：９〜３０：９〜３０の質量割合、より好ましくは、６０〜８２：９〜２０：９〜２０の割合である。
第１焼成工程及び第２焼成工程において、本発明の割合に調整するための方法としては、脱墨フロスにおける原料構成を調整することが本筋ではあるが、乾燥・分級工程、第１焼成工程及び第２焼成工程において、出所が明確な塗工フロスや調整工程フロスをスプレー等で工程内に含有させる手段や、焼却炉スクラバー石灰を含有させる手段にて調整することも可能である。
例えば、無機粒子凝集体中のカルシウムの調整には、中性抄紙系の排水スラッジや、塗工紙製造工程の排水スラッジを用い、ケイ素の調整には、不透明度向上剤として多量添加されている新聞用紙製造系の排水スラッジを、アルミニウムの調整には酸性抄紙系等の硫酸バンドの使用がある抄紙系の排水スラッジや、タルク使用の多い上質紙抄造工程における排水スラッジを適宜用いることができる。
カルシウム、ケイ素及びアルミニウムの合計含有割合を、９０質量％以上にする手法としては、排水スラッジの凝集処理に用いる凝集剤に鉄分を含まないものを使用する、製造設備工程を鉄以外素材で設計又はライニングし、摩滅等により鉄分が系内に混入することを防止する、更に、乾燥・分級設備内に磁石等の高い磁性体を設置し取り除くことで調整可能になる。
特に鉄分が、酸化により白色度低下の起因物質になるため、選択的に取り除くことが好ましい。
[Baking]
The deinked floss that has been dried and classified is sent to the first firing step. In the first firing step, it is important to adjust the unburnt rate to be 10 mass% or more and less than 15 mass%. By setting the unburned rate to 10% by mass or more, it is possible to impart porosity to the particles in the subsequent firing in the second firing step. Furthermore, by setting the unburned ratio to less than 15% by mass, it becomes possible to prevent the particles from being hardened by over-baking due to self-combustion in the next second baking step.
Firing is preferably performed at 650 ° C. or less, and in particular, in order to avoid a decrease in whiteness due to residual carbon, it is preferable to perform the steps in a range of 450 to 650 ° C. When calcination is performed at a high temperature exceeding 650 ° C., calcium carbonate is decomposed to become calcium oxide, and the inorganic substance may be melted to become inorganic particles having extremely high hardness and low porosity. In addition, since calcium oxide is water-soluble, it dissolves when added in the paper making process, and there is a possibility that, for example, chemical effects such as a sizing agent may be hindered.
The inorganic particle aggregate of this embodiment contains 90% by mass or more of the above porous raw material, and the porous raw material contains calcium, silicon and aluminum in terms of oxides of 30 to 82: 9 to 35: 9 to 35. It is characterized by including in the mass ratio. The mass ratio is preferably 40 to 82: 9 to 30: 9 to 30, more preferably 60 to 82: 9 to 20: 9 to 20.
In the first firing step and the second firing step, as a method for adjusting to the ratio of the present invention, the main point is to adjust the raw material composition in the deinking floss, but the drying / classifying step, the first firing step, In the second firing step, it is also possible to adjust the coating floss and the adjustment step floss, which have a clear origin, by means such as spraying or the like, or by means including the incinerator scrubber lime.
For example, neutral papermaking wastewater sludge and coated paper manufacturing process wastewater sludge are used to adjust calcium in inorganic particle aggregates, and silicon is added in large quantities as an opacity improver. Newspaper manufacturing wastewater sludge can be appropriately used for adjustment of aluminum. Papermaking wastewater sludge such as acidic papermaking system that uses sulfuric acid band and wastewater sludge in high quality papermaking process that uses a lot of talc can be used.
As a technique for making the total content ratio of calcium, silicon and aluminum 90% by mass or more, the manufacturing equipment process is designed with a material other than iron, using a coagulant which does not contain iron as a coagulant used for coagulation treatment of drainage sludge. It can be adjusted by lining and preventing iron from being mixed into the system due to wear and the like, and by installing and removing a high magnetic material such as a magnet in the drying / classifying equipment.
In particular, it is preferable to selectively remove iron, because it becomes a causative substance for decreasing whiteness due to oxidation.
〔溶解・粉砕〕
第１焼成工程及び第２焼成工程より焼成された無機物は、抄紙あるいは塗工工程で使用するには粒径が不揃いであるため、そのままでは填料、顔料への利用は問題がある。
填料、顔料用途への使用においては、粒径の均一化や微細化が必要であるが、本発明に基づく無機粒子凝集体における填料、顔料用途等への最適な粒径、顔料径について鋭意検討を重ねた結果、本形態の無機粒子凝集体は、平均粒子径０．１〜１０μｍであるのが好ましいことを知見した。
本形態の無機粒子凝集体は、例えば、吸油量が３０〜１００ｍｌ／１００ｇで、抄紙工程で内添用として用いる場合は、平均粒径が０．１〜１０μｍ、塗工工程で顔料として用いる場合には、平均粒径を０．３〜５μｍに調整することが好ましい。
本発明の無機粒子凝集体は前記の乾燥・分級・焼成方法により粉砕処理前に既に４０μｍ以下の粒子が９０％以上となるよう処理しておくことが好ましい。これにより、従来一般的に行われている乾式粉砕による大粒子の粉砕及び湿式粉砕による微粒子化といった複数段の粉砕処理を行うことなく、湿式による１段粉砕処理が可能となる。これによりコールターカウンター法による粒度分布の微分曲線における平均粒子径のピーク高さを３０％以上とすることができ、さらには原料スラッジ中のカルシウム、ケイ素及びアルミニウムを、酸化物換算で３０〜８２：９〜３５：９〜３５の質量割合に調整することで、無機粒子凝集体の細孔容積を０．１５〜０．６０ｃｃ／ｇ、細孔表面積を１０〜２５ｍ２／ｇ、細孔半径を３００〜１０００オングストロームとすることができる。
[Dissolution / Crushing]
Since the inorganic materials fired from the first firing step and the second firing step have irregular particle sizes for use in the papermaking or coating step, there is a problem in using them as fillers and pigments as they are.
For use in fillers and pigment applications, it is necessary to make the particle size uniform and finer, but we have intensively studied the optimum particle size and pigment diameter for fillers and pigment applications in the inorganic particle aggregates according to the present invention. As a result, it was found that the inorganic particle aggregate of this embodiment preferably has an average particle size of 0.1 to 10 μm.
The inorganic particle aggregate of this embodiment has, for example, an oil absorption of 30 to 100 ml / 100 g, and when used as an internal additive in a paper making process, an average particle size of 0.1 to 10 μm and used as a pigment in a coating process For this, it is preferable to adjust the average particle size to 0.3 to 5 μm.
The inorganic particle aggregate of the present invention is preferably treated by the above-mentioned drying / classification / calcination method so that particles of 40 μm or less are already 90% or more before pulverization. This makes it possible to perform a one-stage pulverization process by a wet process without performing a multi-stage pulverization process such as the pulverization of large particles by dry pulverization and the atomization by wet pulverization which are generally performed conventionally. Thereby, the peak height of the average particle diameter in the differential curve of the particle size distribution by the Coulter counter method can be set to 30% or more. Furthermore, calcium, silicon and aluminum in the raw material sludge can be converted into oxides in an amount of 30 to 82: By adjusting to a mass ratio of 9 to 35: 9 to 35, the pore volume of the inorganic particle aggregate is 0.15 to 0.60 cc / g, the pore surface area is 10 to 25 m 2 / g, and the pore radius is 300. It can be ˜1000 angstroms.
以下、本発明を更に具体的に説明するために実施例を示すが、本発明はこれらの実施例に限定されるものではない。
（１）原紙構成
坪量６４ｇ／ｍ2。ＢＰＧＷ（３０質量％）、ＮＢＫＰ（３０質量％）、ＬＢＫＰ（２５質量％）、ＤＩＰ（１５質量％）、本発明に基づく無機粒子凝集体を実施例表２に基づき添加した。評価法を次記に示す。
（２）ハンター白色度：ＪＩＳ Ｐ ８１４８
（３）ハンター不透明度：ＪＩＳ Ｐ ８１４９
（４）ベック平滑度：ＪＩＳ Ｐ ８１１９
（５）灰分：ＪＩＳ Ｐ ８２５１（温度５２５℃）
（６）白紙光沢度：村上色彩技術研究所製：光沢度計 ＪＩＳ Ｐ ８１４２
（７）印刷光沢度：ＲＩ印刷適性試験機（明製作所製）を使用し、オフセット印刷用インキ０．４ｍｌを使用しベタ印刷した面を村上色彩技術研究所製：光沢度計にて測定した。
（８）画線部の明瞭性：目視にて画線部の明瞭性を判断。◎：にじみ・かすれがない、○：にじみが見られるが使用に問題ない、△：にじみがはっきり分かる、×：にじみ・かすれとも多い。
（９）インク裏抜け：目視にて、印刷後の用紙裏面を判断。◎：裏面へのにじみがない、○：裏面へのにじみが見られるが使用に問題ない、△：裏面へのにじみがはっきり分かる、×：裏面へのにじみが多い。
（１０）粉落ち：黒色ビニール上で、Ｂ５寸法裁断試料を２０枚束ねて５回軽く振ったさいの、粉落ちを目視で判断。◎：粉落ちが見られない、〇：粉落ちは殆どない、△：粉落ちが見られる、×：粉落ちが多い。
（１１）平均粒子径、粒度分布測定：サンプル１０ｍｇをメタノール溶液８ｍｌに添加し、超音波分散機（出力８０ワット）で３分間分散させた。この溶液をコールターカウンター粒度分布測定装置（ＣＯＵＬＴＥＲ ＥＬＥＣＴＲＯＮＩＣＳ 社製ＴＡ−II型）にて、５０μｍのアパチャーを用いて測定を行った。ただし、５０μｍのアパチャーで測定不可能なものについては２００μｍのアパチャーを使用し測定した。また、電解液はＩＳＯＴＯＮ II（商品名；ＣＯＵＬＴＥＲ ＥＬＥＣＴＲＯＮＩＣＳ 社製、０．７％の高純度ＮａＣｌ水溶液）を用いた。
（１２）吸油量測定：ＪＩＳ−Ｋ５１０１に準じて測定を行った。
（１３）記録紙の作成：純水２００ｇに本発明に基づく無機粒子凝集体を実施例表３に基づき添加し、ホモディスパーＳＬ（商品名：特殊機化工業（株）社製）を用いて充分分散した後、ポリビニルアルコール（ＰＶＡ クラレＲ−１１３０）の１０％水溶液２００ｇを加え混合した。この塗工液を坪量８０ｇ／ｍ2の上質紙にバーコーター（Ｎｏ．６０）を用いて塗工し、パイロットスーパーカレンダーにて平坦化処理を行い、記録紙を得た。
（１４）記録画像評価：上記（１３）で得られた記録紙にＲＩ印刷適性試験機（明製作所製）を使用してオフセット印刷用インキでベタ印刷し印字濃度印字画像の濃度評価を行い、キヤノン社製のＰＩＸＵＳ９９００ｉプリンターを用いて印字し、ドットの真円性印字画像、インクの吸収性、筆記性評価を行い、セロハンテープにより表面強度評価を行った。
ａ．印字濃度印字画像の濃度をマクベスＲＤ９１８にて測定した。
ｂ．ドットの真円性印字画像についてドットをルーペで拡大観察。
Ａ：真円に近い形状の割合が９５％以上。
Ｂ：７０％以上９０％未満。
Ｃ：７０％未満。
ｃ．インクの吸収性キヤノン社製のＰＩＸＵＳ９９００ｉのインクカートリッジから抜き取ったマゼンダインク０．５μリットルを用いて、マイクロシリンジにより１ｃｍの高さから紙面に滴下し、完全に吸収されるまでの時間を測定した。
ｄ．筆記性ＨＢの鉛筆による筆記。
〇：コピー用紙と比較して同程度の筆記性のもの。
△：やや劣るが問題なく書けるものもの。
×：ほとんど書けないもの。
ｅ．表面強度をセロハンテープによる塗工層の剥がれ具合で評価した。
○：ほとんど剥がれない（表面強度強い）。
△：剥がれる。
×：かなり剥がれる（表面強度弱い）。
製造例を表１に、試験結果を表２及び表３に示した。
EXAMPLES Hereinafter, examples will be shown to describe the present invention more specifically, but the present invention is not limited to these examples.
(1) Base paper configuration Basis weight 64 g / m 2 . BPGW (30% by mass), NBKP (30% by mass), LBKP (25% by mass), DIP (15% by mass) and inorganic particle aggregates based on the present invention were added according to Example Table 2. The evaluation method is shown below.
(2) Hunter whiteness: JIS P 8148
(3) Hunter opacity: JIS P 8149
(4) Beck smoothness: JIS P 8119
(5) Ash content: JIS P 8251 (temperature 525 ° C.)
(6) Gloss on white paper: Murakami Color Research Laboratory: Gloss meter JIS P 8142
(7) Glossiness of printing: Using an RI printing aptitude tester (Meiji Seisakusho), the surface printed with 0.4 ml of offset printing ink was measured with a gloss meter by Murakami Color Research Laboratory. .
(8) Clarity of the image line portion: The clarity of the image line portion is visually determined. A: No blurring or blurring, B: Smearing is observed but no problem in use, △: Smearing is clearly evident, X: Many blurring / smearing.
(9) Ink back-through: Visually determine the back side of the paper after printing. A: There is no blur on the back surface, B: Smear on the back surface is observed but there is no problem in use, Δ: A blur on the back surface is clearly seen, X: There is a lot of blur on the back surface.
(10) Powder fall: On a black vinyl, 20 pieces of B5 size cut samples are bundled and shaken lightly 5 times, and the powder fall is judged visually. A: No powder fall is observed, O: Almost no powder fall, Δ: Powder fall is seen, X: Many powder fall off.
(11) Measurement of average particle diameter and particle size distribution: 10 mg of a sample was added to 8 ml of a methanol solution, and dispersed for 3 minutes with an ultrasonic disperser (output 80 watts). This solution was measured with a Coulter counter particle size distribution analyzer (TA-II type manufactured by COULTER ELECTRONICS) using an aperture of 50 μm. However, for those that could not be measured with a 50 μm aperture, measurements were made using a 200 μm aperture. The electrolyte used was ISOTON II (trade name; manufactured by COULTER ELECTRONICS, 0.7% high-purity NaCl aqueous solution).
(12) Oil absorption measurement: Measurement was performed according to JIS-K5101.
(13) Preparation of recording paper: An inorganic particle aggregate based on the present invention was added to 200 g of pure water based on Example Table 3, and a homodisper SL (trade name: manufactured by Tokushu Kika Kogyo Co., Ltd.) was used. After sufficiently dispersing, 200 g of a 10% aqueous solution of polyvinyl alcohol (PVA Kuraray R-1130) was added and mixed. This coating solution was coated on high-quality paper having a basis weight of 80 g / m 2 using a bar coater (No. 60), and flattened with a pilot super calendar to obtain a recording paper.
(14) Recorded image evaluation: The recording paper obtained in (13) above was solid printed with an offset printing ink using an RI printing aptitude tester (manufactured by Meisei Seisakusho), and the density evaluation of the print density print image was performed. Printing was performed using a PIXUS9900i printer manufactured by Canon Inc., dot round print images, ink absorbency, and writing properties were evaluated, and surface strength was evaluated using cellophane tape.
a. Print density The density of the printed image was measured with a Macbeth RD918.
b. Magnified observation of dots with a magnifying glass on the dot circular print image.
A: The ratio of the shape close to a perfect circle is 95% or more.
B: 70% or more and less than 90%.
C: Less than 70%.
c. Ink Absorption Using 0.5 μl of magenta ink extracted from an ink cartridge of PIXUS9900i manufactured by Canon, the ink was dropped from a height of 1 cm onto a paper surface by a microsyringe, and the time until complete absorption was measured.
d. Written with a pencil of writing HB.
◯: Writable on the same level as copy paper.
Δ: Slightly inferior but can be written without problems.
X: What can hardly be written.
e. The surface strength was evaluated by the degree of peeling of the coating layer using cellophane tape.
○: Almost no peeling (high surface strength).
Δ: Peel off.
X: It peels considerably (surface strength is weak).
Production examples are shown in Table 1, and test results are shown in Tables 2 and 3.
本発明による利点は、実施例から容易に把握することが可能である。
すなわち、歩留性は、実施例表２における灰分において、カルシウム、ケイ素及びアルミニウムを、酸化物換算で３０〜８２：９〜３５：９〜３５の質量割合で含有し、かつ、前記カルシウム、前記ケイ素及び前記アルミニウムの合計含有割合が、９０質量％以上であるものが高い灰分を示していることから、紙中への歩留性が高いことを示している。
嵩高性については、実施例表２から、無機粒子凝集体が同一添加量で、比較製造例無機粒子凝集体と比較し灰分が高いにも関わらず、低い密度を示していることから、嵩高性効果は明瞭である。
本発明に基づく無機粒子凝集体の効果をみるために、塗工層への顔料として使用した場合にて評価を行った実施例表３の結果からも明らかなように、本発明に基づく無機粒子凝集体は、比較製造例の無機粒子凝集体と比較し、表面平坦性、印刷適性、吸油性とも秀でていることが判る。
The advantages of the present invention can be easily understood from the embodiments.
That is, in the ash content in Example Table 2, the yield includes calcium, silicon, and aluminum in a mass ratio of 30 to 82: 9 to 35: 9 to 35 in terms of oxides, and the calcium, What has a total content of silicon and aluminum of 90% by mass or more indicates a high ash content, which indicates that the yield in paper is high.
Regarding the bulkiness, it is shown from Example Table 2 that the inorganic particle aggregates have the same added amount, and the ash content is higher than that of the comparative production example inorganic particle aggregates, but the density is low. The effect is clear.
In order to see the effect of the inorganic particle aggregates based on the present invention, as is apparent from the results of Example Table 3 evaluated when used as a pigment in the coating layer, the inorganic particles based on the present invention It can be seen that the aggregate is superior in surface flatness, printability, and oil absorption compared to the inorganic particle aggregate of the comparative production example.
Claims (3)
古紙脱墨処理工程で排出される脱墨フロスを主原料として、
脱水及び乾燥させ、焼成し、粉砕して得られ、下記組成となるように調整し、ＪＩＳ Ｋ ５１０１法による吸油度が、３０〜１００ｍｌ／１００ｇである無機粒子凝集体を得る、
ことを特徴とする無機粒子凝集体の製造方法。
（組成）
前記無機粒子凝集体は、無機粒子凝集体の粒子構成成分がカルシウム、ケイ素及びアルミニウムを、酸化物換算で３０〜８２：９〜３５：９〜３５の質量割合で含有し、かつ、前記無機粒子凝集体の粒子構成成分の内、前記カルシウム、前記ケイ素及び前記アルミニウムの合計含有割合が無機粒子構成成分中の９０質量％以上である無機粒子凝集体。 An inorganic particle aggregate that can be used as a filler or pigment for papermaking,
Using the deinking floss discharged in the wastepaper deinking process as the main raw material,
Dehydrated and dried, calcined, pulverized, adjusted to the following composition, and obtained an inorganic particle aggregate having an oil absorption of 30 to 100 ml / 100 g according to JIS K 5101 method.
The manufacturing method of the inorganic particle aggregate characterized by the above-mentioned.
(composition)
The inorganic particle aggregate contains calcium, silicon, and aluminum as particle constituents of the inorganic particle aggregate in a mass ratio of 30 to 82: 9 to 35: 9 to 35 in terms of oxide, and the inorganic particle The inorganic particle aggregate whose total content rate of the said calcium, the said silicon, and the said aluminum is 90 mass% or more in an inorganic particle structural component among the particle structural components of an aggregate.
請求項１記載の無機粒子凝集体の製造方法。 The average particle size by the Coulter counter method is 0.1 to 10 μm.
The manufacturing method of the inorganic particle aggregate of Claim 1.
請求項１または２記載の無機粒子凝集体の製造方法。 The peak height of the average particle diameter in the differential curve of the particle size distribution by the Coulter counter method is 0% or more.
The manufacturing method of the inorganic particle aggregate of Claim 1 or 2.
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