JP2016160554A - Production method of fine cellulose fiber madreporic body - Google Patents
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- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010298 pulverizing process Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 229920002678 cellulose Polymers 0.000 description 16
- 239000001913 cellulose Substances 0.000 description 16
- 239000000123 paper Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- -1 fatty acid esters Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000010009 beating Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- IVNPXOUPZCTJAK-UHFFFAOYSA-N 4-methylmorpholin-4-ium;hydroxide Chemical compound O.CN1CCOCC1 IVNPXOUPZCTJAK-UHFFFAOYSA-N 0.000 description 2
- 229920000433 Lyocell Polymers 0.000 description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- SNAQINZKMQFYFV-UHFFFAOYSA-N 1-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]butane Chemical compound CCCCOCCOCCOCCOC SNAQINZKMQFYFV-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Paper (AREA)
Abstract
Description
本発明は、微細セルロース繊維多孔体の製造方法及び微細セルロース繊維多孔体に関するものである。 The present invention relates to a method for producing a fine cellulose fiber porous body and a fine cellulose fiber porous body.
植物の細胞壁を支えるセルロースは、リグニンやヘミセルロースと共存しており、蒸解によってリグニン部分を除くと繊維状となり、パルプとして紙の原料となる。紙を作製する場合、パルプの表面を機械的に叩くことにより、表面のセルロース結晶が僅かに崩れて微細化し、パルプ間の相互作用をコントロールすることができる。これを叩解と言い、叩解を弱めにして、繊維間の相互作用を抑制すると、低密度紙が得られ、パルプを細かくしながら叩解を進めると、グラシン紙やトレーシング紙などの高密度紙が得られる。 Cellulose that supports plant cell walls coexists with lignin and hemicellulose. When the lignin portion is removed by cooking, it becomes fibrous and becomes a raw material for paper as pulp. When producing paper, mechanically hitting the surface of the pulp, the cellulose crystals on the surface are slightly broken and refined, and the interaction between the pulps can be controlled. This is called beating, and weakening the beating and suppressing the interaction between the fibers results in a low-density paper.When the beating is advanced while making fine pulp, high-density paper such as glassine paper or tracing paper is used. can get.
一方、パルプを一度溶解させて利用する方法が知られていて、アルカリ／二硫化炭素で溶解させるもの（レーヨン）、銅アンモニア錯体で溶解させるもの（キュプラ）、Ｎ−メチルモルホリンＮ−オキシド／水で溶解させるもの（リヨセル（登録商標）、テンセル（登録商標））などが知られており、再生セルロースとして、繊維化されるなどして利用されている。 On the other hand, there are known methods for dissolving and using the pulp once, those dissolved with alkali / carbon disulfide (rayon), those dissolved with a copper ammonia complex (cupra), N-methylmorpholine N-oxide / water (Lyocell (registered trademark), Tencel (registered trademark)) and the like are known, and are used as regenerated cellulose by being fiberized.
セルロース分子は化学的に変性することができる。例えば、アルカリ条件下でクロル酢酸を付加させると、カルボキシメチル化し、このナトリウム塩では水溶性化して増粘剤などに利用されている。エチレンオキサイドを付加させると、ヒドロキシエチル化して水溶性化することも知られている。また、無水酢酸を用いてアセチル化すると熱可塑性樹脂となり、繊維、フィルム、テープなどに利用されている。 Cellulose molecules can be chemically modified. For example, when chloroacetic acid is added under alkaline conditions, it is carboxymethylated, and this sodium salt is water-solubilized and used as a thickener. It is also known that when ethylene oxide is added, it becomes hydroxyethylated and water-solubilized. Further, when acetylated with acetic anhydride, it becomes a thermoplastic resin and is used for fibers, films, tapes and the like.
また、別なセルロースの利用方法の一つとして、パルプを酸やアルカリで処理して、非結晶部分を化学的に溶解して、ミクロンサイズの微細セルロース繊維を作り出す方法（例えば、特許文献１参照）が知られており、これらは食品添加剤や薬剤などの医療用などに利用されている。さらに、この高純度パルプを機械的に粉砕すると、高度に表面がフィブリル化された微細セルロース繊維が得られることも知られており（例えば、特許文献２参照）、これらは、食品添加剤や濾過用凝集剤などとして用いられている。 As another method of utilizing cellulose, a method of producing micron-sized fine cellulose fibers by treating pulp with acid or alkali and chemically dissolving the non-crystalline portion (see, for example, Patent Document 1) These are used for medical purposes such as food additives and drugs. Furthermore, it is also known that when this high-purity pulp is mechanically pulverized, fine cellulose fibers having a highly fibrillated surface can be obtained (see, for example, Patent Document 2). It is used as an aggregating agent.
近年、化学的に変性して微細セルロース繊維を取り出す方法（例えば、非特許文献１参照）や、各種の機械的粉砕された微細セルロース繊維（例えば、特許文献３参照）などが知られるに至って、この微細セルロース繊維を通じて、セルロースの特異的な物性（例えば高い弾性率や低い熱膨張係数）が知られるようになり、樹脂との複合化や電池用セパレータなど、各種の利用方法が提案されるに至っている。 In recent years, a method of chemically modifying and taking out fine cellulose fibers (for example, see Non-Patent Document 1), various mechanically pulverized fine cellulose fibers (for example, see Patent Document 3), etc. have been known, Through this fine cellulose fiber, the specific physical properties of cellulose (for example, high elastic modulus and low thermal expansion coefficient) become known, and various utilization methods such as composite with resin and battery separator are proposed. Has reached.
汎用性が高いと考えられる機械的粉砕によって得られる微細セルロース繊維は、叩解が過度に進んだセルロース繊維であるために、水中から取り出すと、微細化されたセルロース繊維間の強い相互作用のために、高密度化してフィルムとなり、内部での高い空隙率と表裏間での連続孔を有する多孔体とすることは難しかった。また、微細セルロース部分での保水性が非常に高く、紙を製造する際に用いられる抄紙機では、濾過工程によって水を除去して繊維を取り出すことが難しいために、微細セルロース繊維を用いた多孔体を製造するには、特殊な方法を用いる必要があった。 The fine cellulose fiber obtained by mechanical crushing, which is considered to be highly versatile, is a cellulose fiber that has been excessively beaten. Therefore, when it is taken out from the water, it is because of strong interaction between the refined cellulose fibers. It was difficult to obtain a porous body having a high density inside and a high porosity inside and continuous pores between the front and back surfaces. In addition, since the water retention in the fine cellulose part is very high and it is difficult to remove the fiber by removing water through the filtration process in the paper machine used for producing paper, it is difficult to remove the fiber. In order to manufacture the body, it was necessary to use a special method.
特許文献４には、微細セルロース繊維の水分散液に有機溶媒であるジエチレングリコールジメチルエーテルを混合して濾過する方法が記載されている。しかし、この方法では、多量の有機溶媒と水の混合した廃液が発生し、かつ、乾燥工程でも有機溶媒が蒸散するので、濾過・乾燥工程とも外界と隔離する必要があり、設備費用が嵩むという問題があった。 Patent Document 4 describes a method in which diethylene glycol dimethyl ether, which is an organic solvent, is mixed with an aqueous dispersion of fine cellulose fibers and then filtered. However, in this method, a waste liquid in which a large amount of organic solvent and water are mixed is generated, and the organic solvent evaporates even in the drying process. Therefore, it is necessary to isolate the filtration and drying process from the outside world, which increases the equipment cost. There was a problem.
一方、特許文献５では、水と有機溶媒の複合溶媒を用いているものの、濾過工程を経ずに乾燥工程のみで成膜するために、特許文献４記載の方法よりも工程が簡素化されているが、トリエチレングリコールブチルメチルエーテルや炭酸プロピレンなどの高沸点溶媒を用いるために、乾燥ゾーンでの負荷が大きく、問題となっていた。 On the other hand, in Patent Document 5, although a composite solvent of water and an organic solvent is used, since the film is formed only by the drying process without passing through the filtration process, the process is simplified compared to the method described in Patent Document 4. However, since a high boiling point solvent such as triethylene glycol butyl methyl ether or propylene carbonate is used, the load in the drying zone is large, which is a problem.
本発明の課題は、微細セルロース繊維多孔体を簡便に製造することができる微細セルロース繊維多孔体の製造方法を提供することである。 The subject of this invention is providing the manufacturing method of the fine cellulose fiber porous body which can manufacture a fine cellulose fiber porous body simply.
下記に示した本発明によって、上記課題は解決された。 The above-described problems have been solved by the present invention described below.
（Ａ）高純度αセルロースよりなるパルプを、疎水化剤を共存させながら、機械的粉砕方法によって処理し、微細セルロース繊維を得る工程、（Ｂ）微細セルロース繊維の分散液が支持体上に塗工される工程、（Ｃ）乾燥成膜する工程、を含む微細セルロース繊維多孔体の製造方法。 (A) The process which processes the pulp which consists of high purity alpha cellulose by the mechanical grinding | pulverization method coexisting a hydrophobizing agent, and obtains a fine cellulose fiber, (B) The dispersion liquid of a fine cellulose fiber is coated on a support body. The manufacturing method of the fine cellulose fiber porous body including the process processed (C) the process of carrying out dry film-forming.
本発明では、微細セルロース繊維多孔体を簡便に製造することができる微細セルロース繊維多孔体の製造方法を提供することができる。 In this invention, the manufacturing method of the fine cellulose fiber porous body which can manufacture a fine cellulose fiber porous body easily can be provided.
本発明に係わる微細セルロース繊維とは、原料である高純度αセルロースを機械粉砕して得られる繊維である。高純度αセルロースとしては、結晶形がＩ型のセルロース（セルロースＩ型）である木材パルプの中で、リグニン及びヘミセルロースが充分に除去された溶解パルプ又は溶解クラフトパルプ；コットン、リンター、麻、柔細胞繊維などの非木系パルプで同様にリグニン及びヘミセルロースが除去されているもの；結晶形がII型のセルロース（セルロースII型）である、溶解剤としてＮ−メチルモルホリンＮ−オキシド／水溶媒、銅アンモニア錯体、水酸化ナトリウム／二硫化炭素を用いた再生セルロース繊維などが用いられる。セルロースII型は、分子量及び結晶化度が低下していて、セルロースＩ型よりも繊維が切れやすく、また、耐熱性も低いので、特に好ましい材料としてはセルロースＩ型である。 The fine cellulose fiber according to the present invention is a fiber obtained by mechanically pulverizing high-purity α-cellulose as a raw material. As high-purity α-cellulose, dissolved pulp or dissolved kraft pulp from which lignin and hemicellulose have been sufficiently removed in wood pulp having a crystal form of type I cellulose (cellulose type I); cotton, linter, hemp, soft Non-woody pulp such as cell fiber from which lignin and hemicellulose are similarly removed; N-methylmorpholine N-oxide / water solvent as a solubilizer, wherein the crystal form is cellulose of type II (cellulose type II), Copper ammonia complex, regenerated cellulose fiber using sodium hydroxide / carbon disulfide, and the like are used. Cellulose type II is a cellulose I type as a particularly preferred material because it has a reduced molecular weight and crystallinity, is more easily cut than cellulose type I, and has low heat resistance.
本発明の微細セルロース繊維多孔体の製造方法は、（Ａ）高純度αセルロースよりなるパルプを、疎水化剤を共存させながら、機械的粉砕方法によって処理し、微細セルロース繊維を得る工程、（Ｂ）微細セルロース繊維の分散液が支持体上に塗工される工程、（Ｃ）乾燥成膜する工程、を含む。 The method for producing a fine cellulose fiber porous body of the present invention comprises (A) a step of treating a pulp comprising high-purity α-cellulose by a mechanical pulverization method in the presence of a hydrophobizing agent to obtain fine cellulose fibers (B ) A step of applying a dispersion of fine cellulose fibers on a support, and (C) a step of forming a dry film.
工程（Ａ）において、高純度αセルロースは、疎水化剤を共存させた状態で、機械的に粉砕される。疎水化剤とは、粉砕工程で液化している、炭素数が８から４０の飽和又は不飽和炭化水素系の溶剤であって、官能基として、カルボン酸、水酸基、エステル構造を有していても構わない。特に、炭素数が１６以上であることが好ましい。このような疎水化剤としては、液状αオレフィン、（不飽和）脂肪酸、（不飽和）脂肪酸エステル、（不飽和）高級アルコールなどが挙げられる。 In the step (A), the high-purity α-cellulose is mechanically pulverized in a state where a hydrophobizing agent coexists. The hydrophobizing agent is a saturated or unsaturated hydrocarbon solvent having 8 to 40 carbon atoms that is liquefied in the pulverization step, and has a carboxylic acid, a hydroxyl group, or an ester structure as a functional group. It doesn't matter. In particular, the carbon number is preferably 16 or more. Such hydrophobizing agents include liquid α-olefins, (unsaturated) fatty acids, (unsaturated) fatty acid esters, (unsaturated) higher alcohols, and the like.
疎水化剤は、高純度αセルロースが、機械的に粉砕され、微細化する際に生成する新たなセルロース表面に吸着して、微細セルロース繊維が（Ｃ）乾燥成膜工程で相互に凝集するプロセスを阻害して、多孔体を形成させる役割を果たす。本発明では、多孔体の「多孔性」を、「好ましくは３０％以上、より好ましくは５０％以上の内部空隙率を有し、表裏間で連続孔を有する」と定義する。 Hydrophobizing agent is a process in which high-purity α-cellulose is mechanically pulverized and adsorbed on the new cellulose surface that is produced when it is refined, and the fine cellulose fibers are agglomerated with each other in the (C) dry film formation step. Inhibits the formation of a porous body. In the present invention, the “porosity” of the porous body is defined as “preferably having an internal porosity of 30% or more, more preferably 50% or more and having continuous pores between the front and back surfaces”.
疎水化剤は、高純度αセルロース１００質量部に対して、好ましくは０．５〜５０質量部、より好ましくは２〜３０質量部含有される。疎水化剤の含有量が少ないと、多孔性が充分に発現せず、微細セルロース繊維は密着し過ぎてしまう場合がある。疎水化剤の含有量が５０質量部を超えると、余剰疎水化剤によって多孔が埋められてしまう場合がある。 The hydrophobizing agent is preferably contained in an amount of 0.5 to 50 parts by mass, more preferably 2 to 30 parts by mass with respect to 100 parts by mass of high-purity α-cellulose. When the content of the hydrophobizing agent is small, the porosity is not sufficiently developed, and the fine cellulose fibers may be adhered too much. If the content of the hydrophobizing agent exceeds 50 parts by mass, the excess hydrophobizing agent may fill the pores.
機械的粉砕方法としては、パルプを、ビーターやリファイナーで所定の長さとして、高圧ホモジナイザー、グラインダー、衝撃粉砕機、ビーズミルなどを用いて、フィブリル化又は微細化して粉砕する方法が挙げられる。 Examples of the mechanical pulverization method include a method in which the pulp is pulverized by fibrillation or refinement using a high-pressure homogenizer, a grinder, an impact pulverizer, a bead mill, or the like with a predetermined length using a beater or refiner.
工程（Ｂ）において、微細セルロース繊維の分散液の濃度は０．２〜４．０質量％が好ましく、より好ましくは０．５〜２．０質量％である。微細セルロース繊維濃度が低いと、成膜時に微細セルロース繊維が水を保持しきれず、水が分離して、成膜に悪影響が出る場合がある。セルロース濃度が高すぎると、流動性が低下して、工程（Ｂ）における作業性が低下する場合がある。水中に分散された微細セルロース繊維は、工程（Ｂ）において、支持体上に塗工される。支持体としては、ポリエチレン、ポリプロピレン、ポリエステル、フッ素樹脂などのプラスチック製のフィルム；金属箔；紙；不織布などが挙げられる。支持体上に塗工された後、工程（Ｃ）において、乾燥成膜され、微細セルロース繊維多孔体となる。 In the step (B), the concentration of the fine cellulose fiber dispersion is preferably 0.2 to 4.0% by mass, more preferably 0.5 to 2.0% by mass. If the concentration of fine cellulose fibers is low, the fine cellulose fibers cannot hold water at the time of film formation, and water may be separated to adversely affect the film formation. If the cellulose concentration is too high, the fluidity is lowered, and the workability in the step (B) may be lowered. The fine cellulose fibers dispersed in water are coated on the support in the step (B). Examples of the support include films made of plastic such as polyethylene, polypropylene, polyester, and fluororesin; metal foil; paper; non-woven fabric. After coating on the support, in step (C), a dry film is formed to form a fine cellulose fiber porous body.
分散液を塗工して成膜する際に、各種添加剤が利用できる。添加剤は分散液に添加すれば良い。添加剤としては、カルボキシメチルセルロースナトリウム、ポリアクリルアミドなどの紙力増強剤；サイズ剤；微細セルロース繊維の凝集性をコントロールするカチオン系界面活性剤、アンモニア、水酸化アルミニウムなどのカチオン剤も利用することができる。特にアンモニアは、工程（Ｃ）における乾燥処理によって、微細セルロース繊維多孔体から除去できるので、優れた材料である。さらに、内部に残存する空気による泡を除去するために、消泡剤などを併用することもできる。 Various additives can be used when the dispersion is applied to form a film. The additive may be added to the dispersion. As additives, paper strength enhancers such as sodium carboxymethyl cellulose and polyacrylamide; sizing agents; cationic surfactants that control the cohesiveness of fine cellulose fibers, and cationic agents such as ammonia and aluminum hydroxide can also be used. it can. In particular, ammonia is an excellent material because it can be removed from the fine cellulose fiber porous body by the drying treatment in the step (C). Further, an antifoaming agent or the like can be used in combination to remove bubbles caused by air remaining inside.
塗工方法としては、エアドクターコーター、ブレードコーター、ナイフコーター、ロッドコーター、スクイズコーター、含浸コーター、グラビアコーター、キスロールコーター、ダイコーター、リバースロールコーター、トランスファーロールコーター、スプレーコーターなどを用いた方法を使用することができる。微細セルロース繊維多孔体の塗工量は、乾燥質量で０．５〜２０ｇ／ｍ２であることが好ましく、より好ましくは１〜１０ｇ／ｍ２である。セルロースの密度を１．５ｇ／ｃｍ３とした場合に得られる微細セルロース繊維多孔体の内部空隙率は、好ましくは３０％以上であり、より好ましくは５０％以上であり、更に好ましくは５５％以上である。また、内部空隙率は、好ましくは８０％以下であり、より好ましくは７５％以下である。内部空隙率が３０％よりも小さい場合、微細セルロース繊維多孔体内の細孔が埋まり易くなり、連続孔が形成し難くなる場合がある。また、内部空隙率が８０％を超えると、微細セルロース繊維多孔体の強度が低下して、ピンホールなどが形成し易くなるという問題が発生する場合がある。 As a coating method, a method using an air doctor coater, blade coater, knife coater, rod coater, squeeze coater, impregnation coater, gravure coater, kiss roll coater, die coater, reverse roll coater, transfer roll coater, spray coater, etc. Can be used. The coating amount of the fine cellulose fiber porous body is preferably 0.5 to 20 g / m 2 by dry mass, and more preferably 1 to 10 g / m 2 . The internal porosity of the fine cellulose fiber porous material obtained when the density of cellulose is 1.5 g / cm 3 is preferably 30% or more, more preferably 50% or more, and further preferably 55% or more. It is. Further, the internal porosity is preferably 80% or less, and more preferably 75% or less. When the internal porosity is less than 30%, the pores in the fine cellulose fiber porous body are likely to be filled, and it may be difficult to form continuous pores. On the other hand, if the internal porosity exceeds 80%, the strength of the fine cellulose fiber porous body may be reduced, which may cause a problem that pinholes are easily formed.
工程（Ｃ）において、支持体上に塗工された微細セルロース繊維を含有する分散液は、好ましくは４０〜１８０℃、より好ましくは６０〜１３０℃の温度で乾燥され、セットされて成膜される。この時点で、多孔体は支持体面から剥離できる。工程（Ｃ）の後に、更に加熱工程（Ｄ）を行っても良い。特に、アンモニアを添加した場合、工程（Ｄ）で、多孔体中に残存する水溶性アンモニウム塩を除去する。水溶性アンモニウム塩を除去する方法としては、有機溶媒洗浄によって除去する方法、熱的に除去する方法などが挙げられるが、有機溶媒を使用することなく、簡便に水溶性アンモニウム塩が除去できることから、熱的に除去する方法である加熱工程（Ｄ）が好ましい。工程（Ｄ）における加熱温度としては、好ましくは６０〜２５０℃であり、より好ましくは８０〜２００℃である。加熱温度が２５０℃を超えると、微細セルロース繊維の非結晶部分に熱的なダメージが発生して、着色や強度劣化の原因となる場合がある。６０℃より低い温度では、乾燥時間が長くなり、作業性が低下する場合がある。 In the step (C), the dispersion containing fine cellulose fibers coated on the support is preferably dried at a temperature of 40 to 180 ° C., more preferably 60 to 130 ° C., and set to form a film. The At this point, the porous body can be peeled off from the support surface. You may perform a heating process (D) after a process (C). In particular, when ammonia is added, the water-soluble ammonium salt remaining in the porous body is removed in step (D). Examples of the method for removing the water-soluble ammonium salt include a method for removing it by washing with an organic solvent, a method for removing it thermally, and the like, but since the water-soluble ammonium salt can be easily removed without using an organic solvent, The heating step (D) which is a method of removing thermally is preferable. As heating temperature in a process (D), Preferably it is 60-250 degreeC, More preferably, it is 80-200 degreeC. When the heating temperature exceeds 250 ° C., thermal damage may occur in the non-crystalline portion of the fine cellulose fiber, which may cause coloring or strength deterioration. When the temperature is lower than 60 ° C., the drying time becomes long and workability may be lowered.
本発明を実施例によって更に詳細に説明するが、本発明はこれらに何ら限定されるものではない。 The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
＜実施例１＞
工程（Ａ）
高純度αセルロースよりなるリンターパルプ１００質量部に対して、疎水化剤として７．５質量部のオレイン酸を添加し、パルプ濃度２．５質量％として、石臼型磨砕機（増幸産業製、マスコロイダー（登録商標）１２インチ型）を用いて、微細セルロース繊維を分散液の状態で得た。用いた砥石は８０メッシュタイプ、砥石の回転数は１５００ｒｐｍとした。
<Example 1>
Process (A)
7.5 parts by mass of oleic acid as a hydrophobizing agent is added to 100 parts by mass of linter pulp made of high-purity α-cellulose, and the pulp concentration is 2.5% by mass. Using a Royder (registered trademark) 12-inch type), fine cellulose fibers were obtained in a dispersion state. The grindstone used was 80 mesh type, and the rotational speed of the grindstone was 1500 rpm.
工程（Ｂ）及び（Ｃ）
微細セルロース繊維の分散液を、支持体であるポリエチレンテレフタレート（ＰＥＴ）フィルム上に湿潤状態０．７ｍｍ厚で塗工して、８０℃で乾燥させて成膜し、乾燥状態２３μｍ厚の、白濁した、シート状の微細セルロース繊維多孔体を得た。この微細セルロース繊維多孔性体の表面をＳＥＭで観察した。得られたＳＥＭ写真を図１に示した。得られた微細セルロース繊維多孔体のガーレー透気度を東洋精機製ガーレー式デンソメーターで測定したところ、４００ｓｅｃ／１００ｍｌであった。平均細孔径をＰｏｒｏｕｓ Ｍａｔｅｒｉａｌｓ Ｉｎｃ．製Ｃａｐｉｌｌａｒｙ Ｆｌｏｗ Ｐｏｒｏｍｅｔｅｒ ＣＥＰ−１５００Ａで測定したところ、２．２μｍであり、内部空隙率は５５％であり、多孔性を有していた。
Steps (B) and (C)
A fine cellulose fiber dispersion was applied to a polyethylene terephthalate (PET) film as a support in a wet state of 0.7 mm thickness, dried at 80 ° C. to form a film, and a dry state of 23 μm thickness and white turbidity. A sheet-like fine cellulose fiber porous body was obtained. The surface of this fine cellulose fiber porous body was observed by SEM. The obtained SEM photograph is shown in FIG. It was 400 sec / 100 ml when the Gurley air permeability of the obtained fine cellulose fiber porous body was measured with a Toyo Seiki Gurley type densometer. The average pore diameter was measured using Porous Materials Inc. When measured with Capillary Flow Porometer CEP-1500A manufactured by the manufacturer, it was 2.2 μm, the internal porosity was 55%, and it was porous.
＜比較例１＞
実施例１の工程（Ａ）で、疎水化剤を使用しなかった以外は、同様な方法で微細セルロース繊維の分散液を得た。この微細セルロース繊維の分散液を、ＰＥＴフィルム上に湿潤状態１．０ｍｍ厚で塗工して、８０℃で乾燥させて成膜し、乾燥状態１２μｍ厚の、半透明な微細セルロース繊維のシートを得た。このシートのガーレー透気度は１万ｓｅｃ／１００ｍｌを超えていて、測定限界を超えており、このシートは多孔性を有していないことが確認された。
<Comparative Example 1>
A fine cellulose fiber dispersion was obtained in the same manner except that the hydrophobizing agent was not used in step (A) of Example 1. This fine cellulose fiber dispersion was coated on a PET film in a wet state of 1.0 mm thickness, dried at 80 ° C. to form a film, and a dry state of 12 μm thick translucent fine cellulose fiber sheet. Obtained. The Gurley air permeability of this sheet exceeded 10,000 sec / 100 ml, exceeding the measurement limit, and it was confirmed that this sheet has no porosity.
本発明の微細セルロース繊維多孔体の製造方法によって得られた微細セルロース繊維多孔体は、樹脂との複合体や、電池用・キャパシター用セパレータとして利用できる。 The fine cellulose fiber porous body obtained by the method for producing a fine cellulose fiber porous body of the present invention can be used as a composite with a resin, a battery separator, or a capacitor separator.
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