JPWO2020004625A1 - Manufacturing method of finely pulverized cellulose - Google Patents
Manufacturing method of finely pulverized cellulose Download PDFInfo
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- JPWO2020004625A1 JPWO2020004625A1 JP2020527684A JP2020527684A JPWO2020004625A1 JP WO2020004625 A1 JPWO2020004625 A1 JP WO2020004625A1 JP 2020527684 A JP2020527684 A JP 2020527684A JP 2020527684 A JP2020527684 A JP 2020527684A JP WO2020004625 A1 JPWO2020004625 A1 JP WO2020004625A1
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 121
- 239000001913 cellulose Substances 0.000 title claims abstract description 121
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 43
- 238000010298 pulverizing process Methods 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 52
- 239000006185 dispersion Substances 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 239000011324 bead Substances 0.000 claims description 26
- 238000006460 hydrolysis reaction Methods 0.000 claims description 21
- 230000007062 hydrolysis Effects 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 239000006228 supernatant Substances 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002609 medium Substances 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002612 dispersion medium Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 43
- 235000010980 cellulose Nutrition 0.000 description 107
- 238000005303 weighing Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241000251555 Tunicata Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 229920002749 Bacterial cellulose Polymers 0.000 description 1
- 229910000669 Chrome steel Inorganic materials 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000005016 bacterial cellulose Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011176 biofiber Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- -1 filters Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/16—Mills in which a fixed container houses stirring means tumbling the charge
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
Landscapes
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Crushing And Grinding (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
水への分散性に優れたセルロース微粉砕物の提供。セルロース含有原料を加水分解すること、及び、得られた加水分解物を、湿式の衝撃式の粉砕機を用いて低導電率有機溶媒中で湿式粉砕し、セルロース微粉砕物を調製することを含む、セルロース微粉砕物の製造方法。Provision of finely pulverized cellulose with excellent dispersibility in water. This includes hydrolyzing a cellulose-containing raw material and wet-pulverizing the obtained hydrolyzate in a low-conductivity organic solvent using a wet impact pulverizer to prepare a finely pulverized cellulose product. , A method for producing finely pulverized cellulose.
Description
本発明は、セルロース微粉砕物の製造方法に関する。 The present invention relates to a method for producing a finely pulverized cellulose product.
近年、持続可能な社会の構築の観点から、再生可能な循環型資源であるバイオマスが注目されている。また、バイオマスを加工して得られたバイオマス材料が工業的に利用されている。バイオマス材料の例としては、木材等の植物資源由来のセルロースを機械的処理又は化学的処理により微細化して得られた微細化セルロースが知られている。微細化セルロースは、軽量、高強度、低熱膨張性、及び再生型資源であるといった優れた特徴を持つことから、食品、医療、家電部材、自動車等の幅広い分野で機能性材料として注目されている。例えば、微細化セルロースを含むフィルム、不織布、樹脂材料の複合材などの開発が行われている。 In recent years, biomass, which is a renewable recycling resource, has been attracting attention from the viewpoint of building a sustainable society. In addition, biomass materials obtained by processing biomass are used industrially. As an example of the biomass material, micronized cellulose obtained by micronizing cellulose derived from a plant resource such as wood by mechanical treatment or chemical treatment is known. Since micronized cellulose has excellent characteristics such as light weight, high strength, low thermal expansion, and a regenerative resource, it is attracting attention as a functional material in a wide range of fields such as food, medical treatment, home appliance parts, and automobiles. .. For example, films containing finely divided cellulose, non-woven fabrics, composite materials of resin materials, and the like are being developed.
一般に、セルロースの微細化は、水を分散媒とする分散液中で行われる。ところが、微細化セルロースを含む水分散液を乾燥させると、乾燥過程でセルロース粒子間に水素結合が形成されることにより粒子同士が結合して固化するため、乾燥後のセルロースの分散性は低下する。そのため、従来の微細化されたセルロースは水分散液の形態で流通しており、輸送コストがかかっていた。さらに、微細化セルロースの水分散液を充填剤として樹脂材料の製造に用いる場合、予め微細化セルロースの分散媒を水から有機溶媒に置換する工程が必要となるため、製造工程が煩雑であった。 Generally, the miniaturization of cellulose is carried out in a dispersion liquid using water as a dispersion medium. However, when the aqueous dispersion containing the finely divided cellulose is dried, hydrogen bonds are formed between the cellulose particles in the drying process, so that the particles are bonded to each other and solidified, so that the dispersibility of the cellulose after drying is lowered. .. Therefore, the conventional finely divided cellulose is distributed in the form of an aqueous dispersion, which requires a transportation cost. Further, when the aqueous dispersion of finely divided cellulose is used as a filler in the production of a resin material, the production process is complicated because a step of replacing the dispersion medium of the finely divided cellulose with an organic solvent in advance is required. ..
特許文献１には、有機溶媒中でセルロースを微細化することを含むセルロースの微細化方法により、水を使用せずに微細化セルロースが得られることが記載されている。該有機溶媒は極性の大きいものが好ましく、氷酢酸、アセトニトリル、Ｎ，Ｎ−ジメチルアセトアミドなどが用いられる。特許文献２には、粉、粒又は短繊維状のセルロース系素材をジメチルホルムアミド、トルエン等の溶剤中で湿式粉砕することにより得られた微細化セルロース系素材が、粒径が均一で凝集しにくく、樹脂や塗料中に均一に分散することが記載されている。 Patent Document 1 describes that a finely divided cellulose can be obtained without using water by a method for refining cellulose, which comprises refining cellulose in an organic solvent. The organic solvent preferably has a large polarity, and glacial acetic acid, acetonitrile, N, N-dimethylacetamide and the like are used. In Patent Document 2, the finely divided cellulosic material obtained by wet pulverizing a powder, granules or short fibrous cellulosic material in a solvent such as dimethylformamide or toluene has a uniform particle size and is difficult to aggregate. , It is described that it is uniformly dispersed in a resin or a paint.
一方、微細化セルロースの水への再分散性を向上させる方法が提案されている。特許文献３には、微細化セルロースの分散液と、再分散剤と、再分散促進剤とを混合し、得られた混合液を乾燥させることにより、水への再分散性に優れた微細化セルロース含有乾燥体を製造する方法が開示されている。特許文献４には、低誘電率有機溶媒中で結晶性バイオファイバーを回転二枚刃ホモジナイザーなどで粉砕し、その後、該有機溶媒を乾燥除去することにより、水への再分散性に優れたバイオナノウィスカー含有粉末を製造する方法が開示されている。 On the other hand, a method for improving the redispersibility of the finely divided cellulose in water has been proposed. In Patent Document 3, a dispersion of finely divided cellulose, a redispersant, and a redispersion accelerator are mixed, and the obtained mixed solution is dried to make it finer with excellent redispersibility in water. A method for producing a cellulose-containing dried product is disclosed. According to Patent Document 4, crystalline biofibers are pulverized in a low dielectric constant organic solvent with a rotary double-edged homogenizer or the like, and then the organic solvent is dried and removed to obtain bio-nano having excellent redispersibility in water. A method for producing a whisker-containing powder is disclosed.
微細化セルロースの水中での分散性の向上が求められている。また、特許文献３に記載されるような再分散剤を含む微細化セルロース材料は、材料等へ添加した際に再分散剤由来の不具合が生じることがある。本発明は、再分散剤を含有していなくとも水への分散性に優れた微細化セルロースの製造方法を提供する。 Improving the dispersibility of finely divided cellulose in water is required. Further, the finely divided cellulose material containing the redispersant as described in Patent Document 3 may have problems derived from the redispersant when added to the material or the like. The present invention provides a method for producing finely divided cellulose having excellent dispersibility in water even if it does not contain a redispersant.
本発明者らは、セルロース含有原料を加水分解し、得られた加水分解物を、湿式の衝撃式の粉砕機を用いた所定の条件にて、低導電率有機溶媒中で湿式粉砕することによって、水への分散性に優れたセルロース微粉砕物が得られることを見出した。 The present inventors hydrolyze a cellulose-containing raw material, and wet-pulverize the obtained hydrolyzate in a low-conductivity organic solvent under predetermined conditions using a wet impact pulverizer. , It was found that a finely pulverized cellulose product having excellent dispersibility in water can be obtained.
したがって、本発明は、以下を提供する。
〔１〕セルロース微粉砕物の製造方法であって、
セルロース含有原料を加水分解すること、及び、
得られた加水分解物を、湿式の衝撃式の粉砕機を用いて低導電率有機溶媒中で湿式粉砕し、セルロース微粉砕物を調製すること、
を含む、方法。
〔２〕前記湿式の衝撃式の粉砕機が媒体式粉砕機である、〔１〕記載の方法。
〔３〕前記媒体式粉砕機がビーズミルである、〔２〕記載の方法。
〔４〕前記ビーズミルに用いられるビーズが直径０．０３〜３ｍｍである、〔３〕記載の方法。
〔５〕前記湿式粉砕において、前記ビーズミルでの撹拌速度が５００ｒｐｍ以上、かつ該ビーズミルでの撹拌時間が、粉砕処理にかけられる対象物１Ｌあたり０．０１分間以上である、〔３〕又は〔４〕記載の方法。
〔６〕前記低導電率有機溶媒中における前記加水分解物の含有量が、固形物量換算で１質量％以上である、〔１〕〜〔５〕のいずれか１項記載の方法。
〔７〕前記低導電率有機溶媒がトルエン、シクロヘキサン、ヘキサン及び酢酸エチルからなる群より選択される少なくとも１種である、〔１〕〜〔６〕のいずれか１項記載の方法。
〔８〕前記加水分解が、前記セルロース含有原料を酸又はアルカリの溶液に浸漬させることを含み、
前記酸又はアルカリの濃度が１〜２５規定であり、
前記セルロース含有原料と該酸又はアルカリの溶液との質量比が１：３〜４０であり、
前記加水分解の処理時間が１〜１２０分間である、
〔１〕〜〔７〕のいずれか１項記載の方法。
〔９〕前記加水分解が酸加水分解である、〔８〕記載の方法。
〔１０〕前記加水分解で得られた加水分解物を中和及び／又は洗浄することをさらに含む、〔８〕又は〔９〕記載の方法。
〔１１〕前記加水分解で得られた加水分解物の分散媒を前記低導電率有機溶媒に置換することをさらに含む、〔１〕〜〔１０〕のいずれか１項記載の方法。
〔１２〕前記湿式粉砕で得られた前記セルロース微粉砕物を含む分散液から前記低導電率有機溶媒を除去することをさらに含む、〔１〕〜〔１１〕のいずれか１項記載の方法。
〔１３〕前記セルロース微粉砕物の水分散液の上清中に含まれる該セルロース微粉砕物の画分の量が０．４０％以上である、〔１〕〜〔１２〕のいずれか１項記載の方法。
〔１４〕前記セルロース微粉砕物の平均粒度が２０μｍ以下である、〔１〕〜〔１３〕のいずれか１項記載の方法。Therefore, the present invention provides the following.
[1] A method for producing a finely pulverized cellulose product.
Hydrolyzing cellulose-containing raw materials and
The obtained hydrolyzate is wet-pulverized in a low-conductivity organic solvent using a wet impact-type pulverizer to prepare a finely pulverized cellulose product.
Including methods.
[2] The method according to [1], wherein the wet impact type crusher is a medium type crusher.
[3] The method according to [2], wherein the medium-type crusher is a bead mill.
[4] The method according to [3], wherein the beads used in the bead mill have a diameter of 0.03 to 3 mm.
[5] In the wet pulverization, the stirring speed in the bead mill is 500 rpm or more, and the stirring time in the bead mill is 0.01 minute or more per 1 L of the object to be pulverized, [3] or [4]. The method described.
[6] The method according to any one of [1] to [5], wherein the content of the hydrolyzate in the low conductivity organic solvent is 1% by mass or more in terms of the amount of solid matter.
[7] The method according to any one of [1] to [6], wherein the low conductivity organic solvent is at least one selected from the group consisting of toluene, cyclohexane, hexane and ethyl acetate.
[8] The hydrolysis comprises immersing the cellulose-containing raw material in a solution of an acid or an alkali.
The concentration of the acid or alkali is 1 to 25, and
The mass ratio of the cellulose-containing raw material to the acid or alkali solution is 1: 3 to 40.
The hydrolysis treatment time is 1-120 minutes.
The method according to any one of [1] to [7].
[9] The method according to [8], wherein the hydrolysis is acid hydrolysis.
[10] The method according to [8] or [9], further comprising neutralizing and / or washing the hydrolyzate obtained by the hydrolysis.
[11] The method according to any one of [1] to [10], further comprising substituting the dispersion medium of the hydrolyzate obtained by the hydrolysis with the low conductivity organic solvent.
[12] The method according to any one of [1] to [11], further comprising removing the low conductivity organic solvent from the dispersion liquid containing the finely pulverized cellulose obtained by the wet pulverization.
[13] Any one of [1] to [12], wherein the fraction of the finely pulverized cellulose contained in the supernatant of the aqueous dispersion of the finely pulverized cellulose is 0.40% or more. The method described.
[14] The method according to any one of [1] to [13], wherein the average particle size of the finely pulverized cellulose product is 20 μm or less.
本発明により提供されるセルロース微粉砕物は、従来の微細化セルロースと比べて優れた水への分散性を有する。本発明のセルロース微粉砕物は、乾燥粉末の状態で水に添加した場合でも、水中に良好に分散する。本発明により提供されるセルロース微粉砕物は、水分散液の形態で保存又は輸送する必要がなく、そのため分散媒を有機溶媒に置換する操作を省略できる。本発明によれば、微細化セルロースを利用した工業製品の製造におけるコストと手間を低減することができる。 The finely divided cellulose product provided by the present invention has excellent dispersibility in water as compared with conventional finely divided cellulose. The finely pulverized cellulose product of the present invention disperses well in water even when it is added to water in the form of a dry powder. The finely pulverized cellulose product provided by the present invention does not need to be stored or transported in the form of an aqueous dispersion, so that the operation of replacing the dispersion medium with an organic solvent can be omitted. According to the present invention, it is possible to reduce the cost and labor in manufacturing an industrial product using finely divided cellulose.
本発明のセルロース微粉砕物の製造方法は、セルロース含有原料を加水分解すること、及び、得られた加水分解物を、湿式の衝撃式の粉砕機を用いて低導電率有機溶媒中で湿式粉砕し、セルロース微粉砕物を調製すること、を含む。 The method for producing a finely pulverized cellulose product of the present invention is to hydrolyze a cellulose-containing raw material, and to wet-pulverize the obtained hydrolyzate in a low conductivity organic solvent using a wet impact pulverizer. And to prepare a finely ground cellulose product.
本発明の方法で用いられる該セルロース含有原料としては、セルロースを含有する植物又は動物由来材料、例えば、木材チップ、パルプ、紙粉、綿、リンター、籾殻、バガス、微結晶セルロース、バクテリアセルロース、ホヤの被嚢などが挙げられ、これらのいずれか１種又は２種以上を組み合わせて用いることができる。これらのセルロース含有原料中のセルロース量は、好ましくは５〜１００質量％程度であり得る。該セルロース含有原料は、必要に応じて、後述する加水分解処理の前に切断又は粉砕してもよい。 The cellulose-containing raw materials used in the method of the present invention include cellulose-containing plant or animal-derived materials such as wood chips, pulp, paper powder, cotton, linters, rice husks, bagasse, microcrystalline cellulose, bacterial cellulose, and sea squirts. The capsule of the sea squirt and the like can be mentioned, and any one or a combination of two or more of these can be used. The amount of cellulose in these cellulose-containing raw materials can be preferably about 5 to 100% by mass. If necessary, the cellulose-containing raw material may be cut or pulverized before the hydrolysis treatment described later.
該セルロース含有原料の加水分解は、加熱、酸又はアルカリ、酵素などの公知の手段を用いて行うことができるが、好ましくは、酸又はアルカリによる加水分解である。好適に用いられる酸としては、塩酸、硫酸、硝酸などが挙げられる。好適に用いられるアルカリとしては、水酸化ナトリウム、水酸化カリウムなどが挙げられる。当該酸又はアルカリによる加水分解処理においては、該セルロース含有原料を酸又はアルカリ溶液に浸漬させる。酸加水分解処理の場合は反応液を加熱することが好ましい。必要に応じて反応液を撹拌してもよい。当該酸又はアルカリ溶液の溶媒は、特に限定されないが、好ましくは水である。当該酸又はアルカリ溶液における酸又はアルカリの濃度は、好ましくは１〜２５規定、より好ましくは１〜５規定である。該加水分解反応液における該セルロース含有原料と酸又はアルカリ溶液との質量比は、好ましくは１：３〜４０程度、より好ましくは１：５〜２０である。該加水分解の処理時間は、好ましくは１〜１２０分間、より好ましくは３０〜９０分間である。 The hydrolysis of the cellulose-containing raw material can be carried out by heating, acid or alkali, known means such as an enzyme, but is preferably hydrolysis by acid or alkali. Preferred examples of the acid include hydrochloric acid, sulfuric acid, nitric acid and the like. Examples of the alkali preferably used include sodium hydroxide and potassium hydroxide. In the hydrolysis treatment with the acid or alkali, the cellulose-containing raw material is immersed in an acid or alkali solution. In the case of acid hydrolysis treatment, it is preferable to heat the reaction solution. The reaction solution may be stirred if necessary. The solvent of the acid or alkaline solution is not particularly limited, but is preferably water. The concentration of acid or alkali in the acid or alkali solution is preferably 1 to 25, more preferably 1 to 5. The mass ratio of the cellulose-containing raw material to the acid or alkaline solution in the hydrolysis reaction solution is preferably about 1: 3 to 40, more preferably 1: 5 to 20. The treatment time for the hydrolysis is preferably 1 to 120 minutes, more preferably 30 to 90 minutes.
当該酸又はアルカリによる加水分解で得られた加水分解物は、好ましくは、後述する湿式粉砕の前に、中和及び／又は洗浄される。中和により、酸又はアルカリに由来する塩が生じるため、中和に続いて、洗浄及び／又は脱塩を行うことが好ましい。加水分解又は中和後の洗浄には、上述の酸又はアルカリ処理で用いた酸又はアルカリ溶液の溶媒、好ましくは水を用いる。洗浄は１〜５回程度、又は洗浄した液が中性付近になるまで行うことが好ましい。脱塩は、通常行い得る方法、例えばろ過や膜処理などによって行うことができる。 The hydrolyzate obtained by hydrolysis with the acid or alkali is preferably neutralized and / or washed prior to wet grinding described below. Since the neutralization produces a salt derived from an acid or an alkali, it is preferable to perform washing and / or desalting after the neutralization. For washing after hydrolysis or neutralization, the solvent of the acid or alkaline solution used in the above-mentioned acid or alkaline treatment, preferably water, is used. It is preferable to perform the washing about 1 to 5 times or until the washed liquid becomes near neutral. Desalination can be carried out by a method that can be usually carried out, such as filtration or membrane treatment.
後述する湿式粉砕処理の効率化のため、さらに必要に応じて、該湿式粉砕の前に、該加水分解物に対してセルロース以外の成分を除去する精製処理を行うことができる。該精製処理は、篩分け、洗浄、比重差による分配等の公知の方法で行うことができる。該湿式粉砕に供される該加水分解物のセルロース含有量は、セルロース含有原料におけるセルロース含有量によって変わり得るが、固形物換算で、好ましくは３０質量％以上、より好ましくは５０質量％以上、さらに好ましくは７０質量％以上、さらに好ましくは８５質量％以上、さらに好ましくは９５質量％以上である。 In order to improve the efficiency of the wet pulverization treatment described later, if necessary, a purification treatment for removing components other than cellulose can be performed on the hydrolyzate before the wet pulverization. The purification treatment can be carried out by a known method such as sieving, washing, and distribution by difference in specific gravity. The cellulose content of the hydrolyzate subjected to the wet pulverization may vary depending on the cellulose content in the cellulose-containing raw material, but in terms of solid matter, it is preferably 30% by mass or more, more preferably 50% by mass or more, and further. It is preferably 70% by mass or more, more preferably 85% by mass or more, still more preferably 95% by mass or more.
上述した加水分解、及び必要に応じて上述した中和、洗浄又は精製に続いて、得られた加水分解物を湿式粉砕する。好ましくは、該湿式粉砕の前に、該加水分解、中和、洗浄又は精製で得られた加水分解物を含む分散液の分散媒を除去し、該湿式粉砕に用いる低導電率有機溶媒へと置換する。分散媒の置換は、減圧ろ過、遠心、脱水、乾燥等の通常の手順を用いて行うことができる。より好ましくは、該加水分解、中和、洗浄又は精製で得られた加水分解物を含む水分散液から水を分離除去した後、アセトン等の有機溶媒を加えて１〜５回程度遠心することで水分をさらに除去し、その後、低導電率有機溶媒を加えてさらに１〜５回程度遠心することで、該加水分解物の分散媒を低導電率有機溶媒へと置換する。得られた分散液には、後述の湿式粉砕で得られるセルロース微粉砕物が所望の水分散性を達成できる限りにおいて、低導電率有機溶媒以外の液分（他の有機溶媒や水など）が少量（例えば５質量％以下）混在していてもよい。 Following the above-mentioned hydrolysis and, if necessary, the above-mentioned neutralization, washing or purification, the obtained hydrolyzate is wet-milled. Preferably, prior to the wet pulverization, the dispersion medium of the dispersion containing the hydrolyzate obtained by the hydrolysis, neutralization, washing or purification is removed to obtain a low conductivity organic solvent used for the wet pulverization. Replace. The dispersion medium can be replaced by using ordinary procedures such as vacuum filtration, centrifugation, dehydration, and drying. More preferably, after separating and removing water from the aqueous dispersion containing the hydrolyzate obtained by the hydrolysis, neutralization, washing or purification, an organic solvent such as acetone is added and the mixture is centrifuged about 1 to 5 times. After that, a low conductivity organic solvent is added and the mixture is centrifuged about 1 to 5 times to replace the dispersion medium of the hydrolyzate with the low conductivity organic solvent. The obtained dispersion contains a liquid other than the low conductivity organic solvent (other organic solvent, water, etc.) as long as the finely pulverized cellulose obtained by the wet pulverization described later can achieve the desired water dispersibility. A small amount (for example, 5% by mass or less) may be mixed.
本発明の方法で用いられる低導電率有機溶媒とは、比較的低い導電率を有する有機溶媒をいい、より詳細には、常温（２０℃）、常圧（１気圧）における導電率の値が１．０×１０−７（Ｓ／ｍ）以下のものをいう。低導電率有機溶媒の例としては、トルエン、シクロヘキサン、ベンゼン、キシレン、酢酸エチル、クロロホルム、四塩化炭素、１，２−ジクロロエタン、ジエチルエーテル、ジイソプロピルエーテル、ペンタン、ヘキサン、ヘプタン、ニトロベンゼン、ピリジン等が挙げられ、これらのうちのいずれか１種を単独で、又はいずれか２種以上を組み合わせて用いることができる。このうち、乾燥除去の容易性の観点からは、トルエン、シクロヘキサン、ヘキサン及び酢酸エチルからなる群より選択される少なくとも１種が好ましく、トルエン又はシクロヘキサンがより好ましい。湿式粉砕の液媒として該低導電率有機溶媒を用いることにより、粉砕したセルロースの凝集を抑制し、水への再分散性に優れたセルロース微粉砕物を得ることができる。The low conductivity organic solvent used in the method of the present invention means an organic solvent having a relatively low conductivity, and more specifically, the value of conductivity at normal temperature (20 ° C.) and normal pressure (1 atm) is used. 1.0 × 10-7 (S / m) or less. Examples of low conductivity organic solvents include toluene, cyclohexane, benzene, xylene, ethyl acetate, chloroform, carbon tetrachloride, 1,2-dichloroethane, diethyl ether, diisopropyl ether, pentane, hexane, heptane, nitrobenzene, pyridine and the like. Any one of these can be used alone or in combination of two or more. Of these, from the viewpoint of ease of drying and removal, at least one selected from the group consisting of toluene, cyclohexane, hexane and ethyl acetate is preferable, and toluene or cyclohexane is more preferable. By using the low conductivity organic solvent as the liquid medium for wet pulverization, it is possible to suppress the aggregation of pulverized cellulose and obtain a finely pulverized cellulose product having excellent redispersibility in water.
本発明の方法では、該加水分解物を、該低導電率有機溶媒中で湿式粉砕する。該湿式粉砕には、湿式の衝撃式の粉砕機が用いられる。本発明の方法で用いることができる湿式の衝撃式の粉砕機としては、湿式にて媒体（ビーズなど）による衝撃を与えることによって試料を粉砕する粉砕機（例えば、媒体式粉砕機）が挙げられる。本発明の方法で用いられる湿式の衝撃式の粉砕機は、連続式のものであってもバッチ式のものであってもよい。 In the method of the present invention, the hydrolyzate is wet-milled in the low conductivity organic solvent. A wet impact type crusher is used for the wet pulverization. Examples of the wet impact type crusher that can be used in the method of the present invention include a crusher (for example, a medium type crusher) that crushes a sample by applying an impact with a medium (beads or the like) in a wet manner. .. The wet impact type crusher used in the method of the present invention may be a continuous type or a batch type.
媒体式粉砕機には、容器駆動型の粉砕機のように、粉砕室を運動させることによって媒体にエネルギーを伝達して媒体を試料に衝突させるタイプと、媒体撹拌型の粉砕機のように、撹拌棒などを介して媒体にエネルギーを伝達して媒体を試料に衝突させるタイプがある。本発明の方法ではいずれのタイプの媒体式粉砕機も使用することができるが、好ましくは、後者の媒体撹拌型の粉砕機が利用され、さらに好ましくは、媒体としてビーズを用いるビーズミル（ボールミルとも呼ばれる）が用いられる。 The medium-type crusher includes a type such as a container-driven crusher that transfers energy to the medium by moving a crushing chamber to cause the medium to collide with a sample, and a medium-stirring type crusher. There is a type in which energy is transferred to the medium via a stirring rod or the like to cause the medium to collide with the sample. Any type of medium-type crusher can be used in the method of the present invention, but preferably the latter medium-stirring type crusher is used, and more preferably, a bead mill (also called a ball mill) using beads as a medium. ) Is used.
該ビーズミルによる粉砕は、ビーズとともに該加水分解物を撹拌することによって行われ得る。該ビーズミルに用いられるビーズの材質としては、通常使用されるもの、例えば、ガラス、高クロム鋼やステンレス等の合金類、アルミナやジルコニア等のセラミクス、及びこれらの組み合わせなどが挙げられる。好ましくはジルコニア製のビーズが用いられる。 Grinding with the bead mill can be performed by stirring the hydrolyzate with the beads. Examples of the material of the beads used in the bead mill include those usually used, for example, glass, alloys such as high chrome steel and stainless steel, ceramics such as alumina and zirconia, and combinations thereof. Beads made of zirconia are preferably used.
粉砕の条件は、セルロース含有原料の種類、粉砕される加水分解物の量などに応じて適宜選択すればよい。例えば、ビーズミルによる粉砕の場合、粉砕に用いるビーズのサイズは、直径０．０３〜３ｍｍであればよく、好ましくは直径０．３〜２ｍｍ、より好ましくは直径１〜２ｍｍである。また得られるセルロース微粉砕物の粒子径を制御する観点からは、撹拌速度は、５００ｒｐｍ以上であればよく、好ましくは５００〜５０００ｒｐｍ、より好ましくは１０００〜４０００ｒｐｍ、さらに好ましくは２０００〜３５００ｒｐｍであり、さらに好ましくは２０００〜３０００ｒｐｍである。一方、撹拌の時間は、粉砕処理にかけられる対象物（該低導電率有機溶媒と該加水分解物との混合物、例えば上述した溶媒置換で得られた該加水分解物の低導電率有機溶媒分散液）１Ｌあたり、０．０１分間以上であればよい。該撹拌の時間の上限は特に限定されないが、時間当たりのセルロース微粉砕物の製造効率の観点からは、該対象物１Ｌあたり７０分間以下が好ましい。例えば、該攪拌の時間は、該対象物１Ｌあたり、好ましくは０．０１〜６０分間、より好ましくは０．３６〜５５分間、さらに好ましくは２〜６０分間、さらに好ましくは２〜５５分間、さらに好ましくは２〜５０分間、さらに好ましくは５〜６０分間、さらに好ましくは５〜５５分間、さらに好ましくは５〜５０分間である。該撹拌処理の際の温度や圧力は特に限定されず、例えば常温、常圧下で実行すればよい。必要に応じて、試料の過度の温度上昇が生じないように、短時間ずつ複数回の粉砕を行ってもよい。このような粉砕条件の制御により、水中に長期間保存しても凝集や沈殿しにくい、水分散性のよいセルロース微粉砕物を効率よく調製することができる。 The pulverization conditions may be appropriately selected according to the type of the cellulose-containing raw material, the amount of the hydrolyzate to be pulverized, and the like. For example, in the case of crushing with a bead mill, the size of the beads used for crushing may be 0.03 to 3 mm in diameter, preferably 0.3 to 2 mm in diameter, and more preferably 1 to 2 mm in diameter. From the viewpoint of controlling the particle size of the obtained finely pulverized cellulose, the stirring speed may be 500 rpm or more, preferably 500 to 5000 rpm, more preferably 1000 to 4000 rpm, still more preferably 2000 to 3500 rpm. More preferably, it is 2000 to 3000 rpm. On the other hand, the stirring time is such that the object to be subjected to the pulverization treatment (a mixture of the low conductivity organic solvent and the hydrolyzate, for example, a low conductivity organic solvent dispersion of the hydrolyzate obtained by the above-mentioned solvent substitution). ) It may be 0.01 minutes or more per 1L. The upper limit of the stirring time is not particularly limited, but from the viewpoint of the production efficiency of the finely pulverized cellulose product per hour, it is preferably 70 minutes or less per 1 L of the object. For example, the stirring time is preferably 0.01 to 60 minutes, more preferably 0.36 to 55 minutes, still more preferably 2 to 60 minutes, still more preferably 2 to 55 minutes, and further, per 1 L of the object. It is preferably 2 to 50 minutes, more preferably 5 to 60 minutes, still more preferably 5 to 55 minutes, still more preferably 5 to 50 minutes. The temperature and pressure during the stirring treatment are not particularly limited, and may be carried out at room temperature or normal pressure, for example. If necessary, the sample may be pulverized a plurality of times for a short period of time so as not to cause an excessive temperature rise of the sample. By controlling such pulverization conditions, it is possible to efficiently prepare a finely pulverized cellulose product having good water dispersibility, which is less likely to aggregate or precipitate even when stored in water for a long period of time.
上記のような粉砕条件を達成することができるビーズミルとしては、例えば、「アクアターボＴＺ」（フロイント・ターボ株式会社）；「スターミルＬＭＺ」（アシザワ・ファインテック株式会社）；「イージーナノＲＭＢ型」、「レディーミルＲＭＨ型」、「バッチ式サンドグラインダーＢＳＧ型」、「ビスコミルＮＶＭ型」及び「ビスコミルＵＶＭ型」（アイメックス株式会社）；ＤＹＮＯ−ＭＩＬＬ ＫＤシリーズ（株式会社シンマルエンタープライゼス）；「アペックスミル／ＡＭ」（広島メタル＆マシナリーケムテックカンパニー）などが挙げられる。ただし本発明の方法で用いることができるビーズミルはこれらに限定されない。 Examples of the bead mill capable of achieving the above crushing conditions include "Aqua Turbo TZ" (Freund Turbo Co., Ltd.); "Star Mill LMZ" (Ashizawa Finetech Co., Ltd.); "Easy Nano RMB type". , "Lady Mill RMH Type", "Batch Type Sand Grinder BSG Type", "Visco Mill NVM Type" and "Visco Mill UVM Type" (IMEX Co., Ltd.); DYNO-MILL KD Series (Symmal Enterprises Co., Ltd.); "Apex" Mill / AM ”(Hiroshima Metal & Machinery Chemtech Company) and others. However, the bead mill that can be used by the method of the present invention is not limited to these.
該湿式粉砕において、該低導電率有機溶媒中の該加水分解物の含有量は、該低導電率有機溶媒と該加水分解物との混合物（例えば、該加水分解物の低導電率有機溶媒分散液）の全量に対する該加水分解物の固形物量換算で、１質量％以上であればよく、好ましくは１〜３０質量％、より好ましくは３〜２０質量％である。粉砕処理される混合物中での該加水分解物の量を１質量％以上に調整することで、水中に長期間保存しても凝集や沈殿しにくい水分散性のよいセルロース微粉砕物を効率よく調製することができる。ただし、該混合物中の該加水分解物の含有量が３０質量％を超えると、粉砕処理のときに粉砕機への負荷が高くなる。 In the wet grinding, the content of the hydrolyzate in the low conductivity organic solvent is a mixture of the low conductivity organic solvent and the hydrolyzate (for example, low conductivity organic solvent dispersion of the hydrolyzate). In terms of the solid content of the hydrolyzate with respect to the total amount of the liquid), it may be 1% by mass or more, preferably 1 to 30% by mass, and more preferably 3 to 20% by mass. By adjusting the amount of the hydrolyzate in the mixture to be pulverized to 1% by mass or more, a finely pulverized cellulose product having good water dispersibility that does not easily aggregate or precipitate even when stored in water for a long period of time can be efficiently produced. Can be prepared. However, if the content of the hydrolyzate in the mixture exceeds 30% by mass, the load on the crusher becomes high during the pulverization treatment.
上記の湿式粉砕により、セルロース微粉砕物の低導電率有機溶媒分散液が調製される。該分散液中に含まれるセルロース微粉砕物は、その粒度が、好ましくは２０μｍ以下、より好ましくは１７μｍ以下、さらに好ましくは１０μｍ以下であり、一方で、好ましくは０．１μｍ以上、より好ましくは１μｍ以上、さらに好ましくは３μｍ以上である。セルロース微粉砕物の粒度を小さくすると、水への分散性が高まるため好ましい。一方、セルロース微粉砕物の粒度が小さくなり過ぎると、該分散液からのセルロース微粉砕物の回収率が低下することがある。なお本明細書において、セルロース微粉砕物の粒度とは、湿式の粒度分布計を用いてレーザー回折・散乱法により算出された累積中位径（Ｄ５０）をいう。 By the above wet pulverization, a low conductivity organic solvent dispersion of finely pulverized cellulose is prepared. The particle size of the finely pulverized cellulose contained in the dispersion is preferably 20 μm or less, more preferably 17 μm or less, still more preferably 10 μm or less, while preferably 0.1 μm or more, more preferably 1 μm. Above, more preferably 3 μm or more. It is preferable to reduce the particle size of the finely divided cellulose product because the dispersibility in water is improved. On the other hand, if the particle size of the finely pulverized cellulose product becomes too small, the recovery rate of the finely pulverized cellulose product from the dispersion may decrease. In the present specification, the particle size of the finely pulverized cellulose material means the cumulative medium diameter (D50) calculated by the laser diffraction / scattering method using a wet particle size distribution meter.
上記湿式粉砕で得られた、セルロース微粉砕物を含む分散液から低導電率有機溶媒を除去することで、セルロース微粉砕物を回収することができる。低導電率有機溶媒の除去は、分散液の濾過、遠心分離、乾燥、又はそれらの組み合わせなどによって行うことができる。 By removing the low conductivity organic solvent from the dispersion liquid containing the finely pulverized cellulose obtained by the above wet pulverization, the finely pulverized cellulose can be recovered. The removal of the low conductivity organic solvent can be performed by filtering the dispersion, centrifuging, drying, or a combination thereof.
本発明の方法で得られたセルロース微粉砕物は、水に分散させても相分離（セルロース微粉砕物を含む沈降相と、上清液相との分離）を起こしにくい。また該セルロース微粉砕物は、水中で凝集や相分離を起こした場合でも、軽く振盪するだけで水に再分散する。セルロース微粉砕物の水分散性は、該セルロース微粉砕物の水分散液の上清中に含まれる該セルロース微粉砕物の画分の量（本明細書において、セルロース微粉砕物の「上清中含量」という）を基準に評価することができる。本明細書におけるセルロース微粉砕物の「上清中含量」の量は、下記の手順で測定された値である。 The finely pulverized cellulose obtained by the method of the present invention is unlikely to undergo phase separation (separation between the precipitated phase containing the finely pulverized cellulose and the supernatant liquid phase) even when dispersed in water. Further, even when the finely pulverized cellulose product aggregates or undergoes phase separation in water, it is redispersed in water by simply shaking it lightly. The water dispersibility of the finely pulverized cellulose is defined as the amount of the fraction of the finely pulverized cellulose contained in the supernatant of the aqueous dispersion of the finely pulverized cellulose (in the present specification, the "supernatant" of the finely pulverized cellulose. It can be evaluated on the basis of "content"). The amount of the "content in the supernatant" of the finely divided cellulose in the present specification is a value measured by the following procedure.
（セルロース微粉砕物の上清中含量の測定）
１）容器にセルロース微粉砕物と水を入れて十分に混和し、セルロース微粉砕物の水分散液を調製する。このとき、該分散液中のセルロース微粉砕物の量は１質量％に調整する。該分散液は１０分間静置する。
２）静置後の該分散液を最上部から１２．５容量％取り、秤量瓶に入れて重量を測定する。秤量瓶自体の重量は予め測定しておく。次いで、分散液を入れた秤量瓶を１０５℃で１２時間以上乾燥させ、乾燥後の秤量瓶の重量を測定する。
３）以下の式に従って、セルロース微粉砕物の上清中含量を算出する。
上清中含量（％）＝（Ｂ−Ｃ）／（Ａ−Ｃ）×１００
Ａ：分散液を入れた秤量瓶の乾燥前重量
Ｂ：分散液を入れた秤量瓶の乾燥後重量
Ｃ：秤量瓶重量(Measurement of the content in the supernatant of finely pulverized cellulose)
1) Put the finely pulverized cellulose product and water in a container and mix them well to prepare an aqueous dispersion of the finely pulverized cellulose product. At this time, the amount of the finely pulverized cellulose in the dispersion is adjusted to 1% by mass. The dispersion is allowed to stand for 10 minutes.
2) Take 12.5% by volume of the dispersion after standing and put it in a weighing bottle to measure the weight. The weight of the weighing bottle itself is measured in advance. Next, the weighing bottle containing the dispersion liquid is dried at 105 ° C. for 12 hours or more, and the weight of the dried weighing bottle is measured.
3) The content of the finely pulverized cellulose supernatant in the supernatant is calculated according to the following formula.
Content in supernatant (%) = (BC) / (AC) x 100
A: Weight of the weighing bottle containing the dispersion before drying B: Weight of the weighing bottle containing the dispersion after drying C: Weight of the weighing bottle
該上清中含量が高い該セルロース微粉砕物ほど、より水分散性が高い。本発明の方法で得られたセルロース微粉砕物は、その上清中含量が、０．４０％以上であればよく、好ましくは０．４２％以上、より好ましくは０．４５％以上、さらに好ましくは０．５０％以上、さらに好ましくは０．５５％以上、さらに好ましくは０．６０％以上、さらに好ましくは０．７０％以上である。一方、以下の実施例に示すとおり、湿式の衝撃式の粉砕機を用いた低導電率有機溶媒中での湿式粉砕を行わずに得られたセルロース微粉砕物は、上清中含量が低く、最大でも０．３２％程度であった。 The higher the content of the supernatant in the finely divided cellulose, the higher the water dispersibility. The finely pulverized cellulose obtained by the method of the present invention may have a content in the supernatant of 0.40% or more, preferably 0.42% or more, more preferably 0.45% or more, still more preferably. Is 0.50% or more, more preferably 0.55% or more, still more preferably 0.60% or more, still more preferably 0.70% or more. On the other hand, as shown in the following examples, the finely pulverized cellulose obtained without wet pulverization in a low conductivity organic solvent using a wet impact pulverizer has a low content in the supernatant. The maximum was about 0.32%.
本発明の方法で得られたセルロース微粉砕物は、セルロース材料として、樹脂材料、フィルター、フィルム、繊維品、医療材料、食品又は化粧品材料、自動車部品材料などの各種工業製品の製造に使用することができる。該セルロース微粉砕物は、乾燥物として輸送、保存及び使用することができる。あるいは、上記本発明の方法における湿式粉砕で得られたセルロース微粉砕物の低導電率有機溶媒分散液を、分散媒を除去せずに、そのまま工業材料、例えば樹脂材料の充填材等として用いることができる。あるいは、該湿式粉砕で得られたセルロース微粉砕物の分散液は、低導電率有機溶媒を他の有機溶媒や水に置換して、該他の有機溶媒の分散液や水分散液の形態で使用してもよい。 The finely pulverized cellulose obtained by the method of the present invention shall be used as a cellulose material in the production of various industrial products such as resin materials, filters, films, textiles, medical materials, food or cosmetic materials, and automobile parts materials. Can be done. The finely pulverized cellulose product can be transported, stored and used as a dried product. Alternatively, the low-conductivity organic solvent dispersion of the finely pulverized cellulose obtained by the wet pulverization in the method of the present invention can be used as it is as a filler for an industrial material, for example, a resin material without removing the dispersion medium. Can be done. Alternatively, the dispersion liquid of the finely pulverized cellulose obtained by the wet pulverization is in the form of a dispersion liquid or an aqueous dispersion liquid of the other organic solvent by substituting the low conductivity organic solvent with another organic solvent or water. You may use it.
次に実施例を示して本発明をさらに詳細に説明するが、本発明は以下の実施例に限定されるものではない。 Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
（参考例１）粒度の測定
セルロース微粉砕物粉末を１質量％となるように精製水に分散させた液を５分間超音波処理した後、分散液中のセルロース微粉砕物の粒度分布を湿式粒度分布計（Ｍｉｃｒｏｔｒａｃ ＭＴ３０００、マイクロトラックベル株式会社製）を用いてレーザー回折・散乱法により測定し、累積中位径（Ｄ５０）を求めた。(Reference Example 1) Measurement of particle size After ultrasonically treating a solution of finely pulverized cellulose powder in purified water so as to be 1% by mass for 5 minutes, the particle size distribution of the finely pulverized cellulose in the dispersion is wet. The cumulative medium diameter (D50) was determined by measurement by a laser diffraction / scattering method using a particle size distribution meter (Microtrac MT3000, manufactured by Microtrac Bell Co., Ltd.).
（参考例２）水分散性の測定
容積５０ｍＬの規格瓶に、セルロース微粉砕物粉末０．４ｇを精密に量り取り、合計重量が４０ｇになるように精製水を加えた分散液を５分間超音波処理し、次いで転倒混和してセルロース微粉砕物の水分散液を調製した。該水分散液を１０分間静置した。静置後の分散液の最上部から５ｍＬを予め重量を測定しておいた秤量瓶に入れ、重量を測定した。この分散液５ｍＬが入った秤量瓶を１０５℃、１２時間以上乾燥した後、乾燥後の秤量瓶の重量を測定した。以下の式に従って、セルロース微粉砕物の上清中含量を算出した。
上清中含量（％）＝（Ｂ−Ｃ）／（Ａ−Ｃ）×１００
Ａ：分散液を入れた秤量瓶の乾燥前重量
Ｂ：分散液を入れた秤量瓶の乾燥後重量
Ｃ：秤量瓶重量(Reference Example 2) Measurement of water dispersibility In a standard bottle with a volume of 50 mL, 0.4 g of finely pulverized cellulose powder was precisely weighed, and purified water was added so that the total weight was 40 g. After sonication, the mixture was overturned and mixed to prepare an aqueous dispersion of finely pulverized cellulose. The aqueous dispersion was allowed to stand for 10 minutes. 5 mL from the top of the dispersion after standing was placed in a weighing bottle whose weight had been measured in advance, and the weight was measured. The weighing bottle containing 5 mL of this dispersion was dried at 105 ° C. for 12 hours or more, and then the weight of the dried weighing bottle was measured. The content of the finely pulverized cellulose supernatant in the supernatant was calculated according to the following formula.
Content in supernatant (%) = (BC) / (AC) x 100
A: Weight of the weighing bottle containing the dispersion before drying B: Weight of the weighing bottle containing the dispersion after drying C: Weight of the weighing bottle
（製造例１）セルロース微粉砕物の調製
１）加水分解物の調製
脱脂綿（オオサキメディカル株式会社製）３００ｇを四ツ口フラスコに入れ、２．５規定塩酸水溶液３０００ｍＬを加えて、１時間煮沸還流した。反応液に２０００ｍＬの精製水を加えて４０℃以下になるまで氷冷した後、減圧ろ過した。その後、ろ液が中性付近になるまで約３０００ｍＬの精製水で洗浄を行い、残渣として加水分解物を得た。得られた加水分解物を、３０００ｍＬのアセトンを加えて減圧ろ過した。ろ物を回収して３０００ｍＬのトルエンを加え、加水分解物のスラリーを得た。得られたスラリーの分散媒は、トルエンが主体であり、残存アセトン及び水を若干量含んでいた。(Production Example 1) Preparation of finely pulverized cellulose product 1) Preparation of hydrolyzate 300 g of cotton wool (manufactured by Osaki Medical Co., Ltd.) is placed in a four-necked flask, 3000 mL of a 2.5 specified hydrochloric acid aqueous solution is added, and the mixture is boiled at reflux for 1 hour. did. 2000 mL of purified water was added to the reaction mixture, the mixture was ice-cooled to 40 ° C. or lower, and then filtered under reduced pressure. Then, it was washed with about 3000 mL of purified water until the filtrate became near neutral, and a hydrolyzate was obtained as a residue. The obtained hydrolyzate was filtered under reduced pressure with the addition of 3000 mL of acetone. The filter was collected and 3000 mL of toluene was added to obtain a slurry of the hydrolyzate. The dispersion medium of the obtained slurry was mainly toluene and contained a small amount of residual acetone and water.
２）セルロース微粉砕物の調製
上記１）で作製した加水分解物のスラリー（スラリー濃度１０質量％）を、連続式の湿式ビーズミル（レディーミルＲＭＨ、アイメックス株式会社製）を用いて表１記載の条件で湿式粉砕して懸濁液を得た。得られた懸濁液を減圧ろ過してろ物を回収し、５０℃、２４時間減圧乾燥して、粉末状のセルロース微粉砕物を製造した。2) Preparation of finely pulverized cellulose The hydrolyzate slurry (slurry concentration 10% by mass) prepared in 1) above is shown in Table 1 using a continuous wet bead mill (Lady Mill RMH, manufactured by IMEX Co., Ltd.). Wet pulverization under the conditions to obtain a suspension. The obtained suspension was filtered under reduced pressure to collect a filtrate, and dried under reduced pressure at 50 ° C. for 24 hours to produce a powdered finely pulverized cellulose product.
（製造例２〜４）
製造例１と同様の手順で、ただし湿式粉砕の条件を表１のとおりに変更して、製造２〜４のセルロース微粉砕物を製造した。(Manufacturing Examples 2 to 4)
In the same procedure as in Production Example 1, however, the conditions for wet pulverization were changed as shown in Table 1, and the finely pulverized cellulose products of Productions 2 to 4 were produced.
（製造例５〜６）
製造例１と同様の手順でセルロース微粉砕物を製造した。ただし加水分解物スラリーの湿式粉砕は、バッチ式の湿式ビーズミル（イージーナノＲＭＢ、アイメックス株式会社製）を用いて、表１記載の条件で行った。(Manufacturing Examples 5 to 6)
A finely pulverized cellulose product was produced in the same procedure as in Production Example 1. However, the wet pulverization of the hydrolyzate slurry was carried out under the conditions shown in Table 1 using a batch type wet bead mill (Easy Nano RMB, manufactured by IMEX Co., Ltd.).
（比較例１〜１０）
製造例１と同様の手順で加水分解物スラリーを調製し、これを湿式の衝撃式の粉砕機以外の粉砕機で粉砕してセルロース微粉砕物を得た。粉砕は表２、３に示す条件で行った。(Comparative Examples 1 to 10)
A hydrolyzate slurry was prepared in the same procedure as in Production Example 1, and this was pulverized with a pulverizer other than a wet impact pulverizer to obtain a finely pulverized cellulose product. The pulverization was carried out under the conditions shown in Tables 2 and 3.
（試験例１）
参考例１、２の手順で、製造例１〜６及び比較例１〜１０のセルロース微粉砕物の粒度（Ｄ５０）及び水分散性（上清中含量）を測定した。結果を表１〜３に示す。製造例１〜６のセルロース微粉砕物は、粒度（Ｄ５０）がいずれも２０μｍ以下であり、比較例１〜１０と比較して微細化されていた。また、製造例１〜６のセルロース微粉砕物の上清中含量はいずれも０．４％以上であり、比較例１〜１０と比較して水分散性に優れていた。(Test Example 1)
In the procedure of Reference Examples 1 and 2, the particle size (D50) and water dispersibility (content in supernatant) of the finely pulverized cellulose of Production Examples 1 to 6 and Comparative Examples 1 to 10 were measured. The results are shown in Tables 1-3. The finely divided cellulose products of Production Examples 1 to 6 had a particle size (D50) of 20 μm or less, and were made finer as compared with Comparative Examples 1 to 10. In addition, the content of the finely pulverized cellulose products of Production Examples 1 to 6 in the supernatant was 0.4% or more, which was excellent in water dispersibility as compared with Comparative Examples 1 to 10.
（試験例２）
加水分解物のスラリーの分散媒をトルエンから、シクロヘキサン（製造例７）、アセトン（比較例１１）、又は水（比較例１２）に変更した以外は、製造例５と同様の手順で粉末状のセルロース微粉砕物を調製した。試験例１と同様の手順で、得られたセルロース微粉砕物の粒度及び水分散性を測定した。結果を表４に示す。なお、表４には製造例５の結果を再掲する。シクロヘキサン中の粉砕で得られたセルロース微粉砕物は優れた水分散性を有していたが、アセトン又は水中での粉砕で得られたセルロース微粉砕物は、粒度は小さいが、水分散性が著しく低下していた。(Test Example 2)
The dispersion medium of the hydrolyzate slurry was changed from toluene to cyclohexane (Production Example 7), acetone (Comparative Example 11), or water (Comparative Example 12). A finely pulverized cellulose product was prepared. The particle size and water dispersibility of the obtained finely pulverized cellulose were measured in the same procedure as in Test Example 1. The results are shown in Table 4. The results of Production Example 5 are shown again in Table 4. The finely pulverized cellulose obtained by pulverization in cyclohexane had excellent water dispersibility, whereas the finely pulverized cellulose obtained by pulverization in acetone or water had a small particle size but was water-dispersible. It was significantly reduced.
（試験例３）
製造例５と同様の手順で、ただし、加水分解物のスラリーの粉砕に用いた湿式ビーズミルのビーズ径、粉砕時の回転数、もしくは撹拌時間、又は該スラリーの濃度を表５〜８に示すように様々に変えて、セルロース微粉砕物を調製した。試験例１と同様の手順で、得られたセルロース微粉砕物の粒度及び水分散性を測定した。結果を表５〜８に示す。(Test Example 3)
The procedure is the same as in Production Example 5, except that the bead diameter of the wet bead mill used for pulverizing the slurry of the hydrolyzate, the rotation speed at the time of pulverization, or the stirring time, or the concentration of the slurry is shown in Tables 5 to 8. To prepare a finely pulverized cellulose product. The particle size and water dispersibility of the obtained finely pulverized cellulose were measured in the same procedure as in Test Example 1. The results are shown in Tables 5-8.
Claims (14)
セルロース含有原料を加水分解すること、及び、
得られた加水分解物を、湿式の衝撃式の粉砕機を用いて低導電率有機溶媒中で湿式粉砕し、セルロース微粉砕物を調製すること、
を含む、方法。It is a method for producing finely pulverized cellulose.
Hydrolyzing cellulose-containing raw materials and
The obtained hydrolyzate is wet-pulverized in a low-conductivity organic solvent using a wet impact-type pulverizer to prepare a finely pulverized cellulose product.
Including methods.
前記酸又はアルカリの濃度が１〜２５規定であり、
前記セルロース含有原料と該酸又はアルカリの溶液との質量比が１：３〜４０であり、
前記加水分解の処理時間が１〜１２０分間である、
請求項１〜７のいずれか１項記載の方法。The hydrolysis comprises immersing the cellulose-containing material in an acid or alkaline solution.
The concentration of the acid or alkali is 1 to 25, and
The mass ratio of the cellulose-containing raw material to the acid or alkali solution is 1: 3 to 40.
The hydrolysis treatment time is 1-120 minutes.
The method according to any one of claims 1 to 7.
The method according to any one of claims 1 to 13, wherein the average particle size of the finely pulverized cellulose product is 20 μm or less.
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