JP4099640B2 - Porous particles and method for producing the same - Google Patents
Porous particles and method for producing the same Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、低置換度セルロースエーテルからなる多孔質粒子の製造方法に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
従来から、セルロース、タンパク質等の天然高分子を材質とした多孔質粒子が抗菌剤、芳香剤、消臭剤等の吸着材、バイオリアクターの固定担体あるいは室内園芸用培土等に使用されている。このうちセルロースの多孔質粒子については、特開平９−１７６３２７号公報でビスコースに多糖類をアルカリ水溶液にて混合したものを酸性水溶液中で凝固・再生して製造される再生セルロースの多孔質粒子が報告されている。
【０００３】
また、特開平３−１７０５０１号公報には、ビスコースに炭酸カルシウムを混合させた溶液を酸性水溶液中で凝固・再生させることによって製造される多孔質粒子が報告されている。
【０００４】
しかし、これらの多孔質粒子は、セルロースを毒性の強い二硫化炭素で処理して作られるセルロースザンテートをアルカリ水溶液に溶かしたビスコースを原材料として使用するため、その製造段階で作業者が二硫化炭素に暴露される危険性があると指摘されている。また、精製を十分に行わないと、多孔質粒子に微量の硫黄分が残存し、製品自体の機能を低下させたり、臭気が出たりする可能性もある。
【０００５】
本発明は、上記事情を鑑みなされたもので、従来のビスコース由来の多孔質粒子に代替し得る性能を有し、かつその製造工程において毒性の強い二硫化炭素を使用することなく、硫黄臭を伴わない多孔質粒子の製造方法を提供することを目的とする。
【０００６】
【課題を解決するための手段及び発明の実施の形態】
発明者らは、上記目的を達成するため鋭意検討した結果、一定のモル置換度を有する低置換度セルロースエーテルからなる多孔質粒子が、従来のビスコース由来の多孔質粒子に代替し得る性能を有し、かつその製造工程において毒性の強い二硫化炭素を使用することなく、硫黄臭を伴わないで得られることを知見し、本発明をなすに至ったものである。
【０００７】
従って、本発明は、
［Ｉ］アルキル基及び／又はヒドロキシアルキル基によるモル置換度が０．０５〜１．０である水には溶解しないが、アルカリ水溶液に溶解する低置換度セルロースエーテルと水溶性高分子物質又は炭酸塩とをアルカリ水溶液に溶解した混合液を酸と接触させ、低置換度セルロースエーテルを凝固・再生することを特徴とする低置換度セルロースエーテルの多孔質粒子の製造方法、
［ＩＩ］上記混合液と酸との接触方法が、酸水溶液に上記混合液を滴下する方法であることを特徴とする［Ｉ］記載の低置換度セルロースエーテルの多孔質粒子の製造方法、
［ＩＩＩ］低置換度セルロースエーテルと炭酸塩とをアルカリ水溶液に溶解した混合液を酸と接触させ、低置換度セルロースエーテルを凝固・再生すると共に、炭酸塩と酸との反応で二酸化炭素を発生させて多孔質粒子を形成することを特徴とする［Ｉ］又は［ＩＩ］記載の低置換度セルロースエーテルの多孔質粒子の製造方法
を提供する。
【０００８】
以下、本発明につき更に詳しく説明すると、本発明に係る低置換度セルロースエーテルはセルロースを構成しているグルコース環の水酸基の水素原子をアルキル基及び／又はヒドロキシアルキル基で置換したセルロースエーテルのうち、モル置換度が０．０５〜１．０、好ましくは０．１〜０．７と低いもので、水には溶解しないが、アルカリ水溶液に溶解するものである。モル置換度が０．０５よりも低いとアルカリ水溶液に溶解しにくく、多孔質粒子の製造が困難になり、１．０を超えると水への溶解性が高くなり、多孔質粒子としての機能が失われるためである。
【０００９】
低置換度セルロースエーテルとしては、低置換度メチルセルロース、低置換度エチルセルロース等の低置換度アルキルセルロース、低置換度ヒドロキシエチルセルロース、低置換度ヒドロキシプロピルセルロース等の低置換度ヒドロキシアルキルセルロース、低置換度ヒドロキシプロピルメチルセルロース、低置換度ヒドロキシエチルメチルセルロース、低置換度ヒドロキシエチルエチルセルロース等の低置換度ヒドロキシアルキルアルキルセルロースが例示できる。
【００１０】
多孔質粒子は、粒子の中に一定量の空隙を含むものであり、空隙の多少、すなわち空隙率（粒子体積中に占める空隙の体積割合）は用途によって適宜選択すればよく、特に制限はないが、空隙率が３０〜９８％、特に５０〜９８％であることが好ましい。空隙率が３０％未満であると多孔質粒子としての機能を発揮することができず、また９８％を超えると粒子の機械的強度が弱くなり、実用に供することができない場合があるからである。
【００１１】
本発明の多孔質粒子は、第１の方法として、低置換度セルロースエーテルと水溶性高分子物質とをアルカリ水溶液に溶解した混合液を酸と接触させ、低置換度セルロースエーテルを凝固・再生することにより製造することができる。この場合、凝固・再生した低置換度セルロースエーテルから水溶性高分子物質が酸水溶液あるいはその後の水洗工程で除去されることにより、多孔質粒子が形成される。
【００１２】
ここで、アルカリ水溶液は、苛性ソーダ水溶液、苛性カリ水溶液等が挙げられ、そのアルカリ水溶液濃度は、使用する低置換度セルロースエーテルの置換基の種類やモル置換度によって異なるので適宜決定すればよいが、通常は苛性アルカリの量として、２〜２５重量％、特に３〜１５重量％が好ましい。典型的な例としては、モル置換度０．２の低置換度ヒドロキシプロピルセルロースは１０重量％濃度の苛性ソーダ水溶液に溶解する。
【００１３】
水溶性高分子物質は、アルカリ水溶液に溶解するものであれば特に制限はなく、デンプン、プルラン、グアーガム、アラビアガム、アルギン酸等の天然高分子、セルロース、デンプン等の天然高分子の誘導体であるメチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、ヒドロキシプロピルデンプン、デキストリン、酸化デンプン等の半合成高分子、あるいはポリビニルアルコール、ポリビニルピロリドン、ポリエチレンオキサイド、ポリアクリル酸ソーダ等の合成高分子が例示できる。
【００１４】
低置換度セルロースエーテルと水溶性高分子物質との混合比率及びアルカリ水溶液中におけるこれらの成分の合計濃度についても特に制限はなく、目的とする多孔質粒子の物性及び操作性を勘案して適宜選択すればよいが、通常は低置換度セルロースエーテルの濃度が２〜２０重量％、特に３〜１５重量％が好ましい。また、水溶性高分子物質は低置換度セルロース量１重量部に対して０．１〜５重量部添加することが好ましい。低置換度セルロースエーテルと水溶性高分子物質をアルカリ水溶液に混合する場合、最初に低置換度セルロースエーテルと水溶性高分子物質を別個にアルカリ水溶液に溶解したものを調製し、その後それぞれを混合してもよいし、予め低置換度セルロースエーテルをアルカリ水溶液に溶かし、その後水溶性高分子物質を添加してもかまわない。
【００１５】
酸としては塩酸、硫酸等の鉱酸、クエン酸、リンゴ酸、酢酸等の水溶液を使用することができる。この場合、酸の濃度は１〜２０重量％が好ましい。
【００１６】
上記低置換度セルロースエーテルと水溶性高分子物質とのアルカリ混合液を酸と接触する方法としては、特に制限されるものではないが、酸水溶液にアルカリ混合液を除々に滴下していく方法が好適に採用される。この場合、アルカリ混合液の滴下速度は１〜６０ｍｌ／分が好ましい。なお、この接触は０〜３０℃にて行うことが好ましい。
【００１７】
更に、本発明は、低置換度セルロースエーテルと炭酸塩とをアルカリ水溶液に溶解した液を液滴として酸に接触させ、低置換度セルロースエーテルを凝固・再生させて、低置換度セルロースエーテル多孔質粒子を製造する方法を提供するものである。この場合、低置換度セルロースエーテルが凝固・再生される際に炭酸塩が酸と反応して二酸化炭素を発生して多孔質粒子が形成される。ここで、アルカリ水溶液及び酸は上記したものと同じものが使用できる。
【００１８】
炭酸塩としては、炭酸ナトリウム、炭酸カルシウム、炭酸水素ナトリウム、炭酸マグネシウム等が例示できるが、特に水不溶性の炭酸カルシウム、炭酸マグネシウムが好ましい。低置換度セルロースエーテルと炭酸塩との混合比率及びアルカリ水溶液中におけるこれらの成分の合計濃度についても特に制限はなく、目的とする多孔質粒子の物性、及び操作性を勘案して適宜選択すればよいが、通常は低置換度セルロースエーテルの濃度が２〜２０重量％、特に３〜１５重量％が好ましい。また、炭酸塩は低置換度セルロース量１重量部に対して０．１〜１０重量部添加することが好ましい。低置換度セルロースエーテルと炭酸塩とを混合する場合、最初に低置換度セルロースエーテルをアルカリ水溶液に溶かし、その後炭酸塩を添加してもかまわない。
【００１９】
なお、酸水溶液の濃度、アルカリ混合液と酸水溶液との接触方法・条件は、上記と同様である。また、上記いずれの製造方法においても、凝固・再生された多孔質粒子は、ろ過や遠心分離機等で母液から分離した後、水洗、凍結真空乾燥等により乾燥される。
【００２０】
【実施例】
以下、実施例と比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記例で部は重量部を示す。
【００２１】
［実施例１〜６］
表１に示した低置換度セルロースエーテル６部を１０重量％の苛性ソーダ水溶液９５部に溶解して試料液を調製し、ヒドロキシプロピルスターチ６部を１０重量％の苛性ソーダ水溶液９５部に溶解した試料液と混合した。この混合液を攪拌下、３．６重量％の塩酸水溶液にノズル（口径：１ｍｍφ）から毎分２ｍｌの速度で滴下した。
【００２２】
凝固・再生した粒子はろ過法で分離した後、水洗し、その後、凍結真空乾燥した。得られた粒子について、空隙率及び硫黄臭の有無について調べた。結果を表２に示す。
【００２３】
空隙率の測定方法
粒子を真球と仮定し、レーザー散乱式粒径測定装置で求めた試料粒子１００個の平均粒径から粒子の平均体積（Ａ）を求めた。別に上記の試料粒子１００個の平均重量（Ｂ）を求め、かさ密度ｄ（Ｂ÷Ａ）を算出した。予め液体置換法によって求めた粒子原料の真比重（Ｄ）及びｄより下記の式から空隙率を求めた。
空隙率＝１−ｄ／Ｄ
【００２４】
【表１】
［比較例１］
低置換度セルロースエーテルを苛性ソーダ水溶液に溶解した試料液の代わりに、セルロース換算濃度６％、苛性ソーダ濃度１０重量％のビスコースを使用する以外は、実施例１〜６と同様に処理して、再生セルロースの多孔質粒子を調製し、空隙率及び硫黄臭の有無について調べた。結果を表２に示す。
【００２６】
［実施例７〜１２］
表１に示した低置換度セルロースエーテル６部を１０重量％の苛性ソーダ水溶液９５部に溶解し、これに１８部の炭酸カルシウムを加え攪拌して試料分散液を調製した。この分散液を攪拌下、１０重量％の塩酸水溶液にノズル（口径：１ｍｍφ）から毎分５ｍｌの速度で滴下した。凝固・再生した粒子はろ過法で分離した後、水洗し、その後、凍結乾燥した。得られた粒子についてその空隙率及び硫黄臭の有無について調べた。結果を表２に示す。
【００２７】
［比較例２］
低置換度セルロースエーテルを苛性ソーダ水溶液に溶解した試料液の代わりに、セルロース換算濃度６％、苛性ソーダ濃度１０重量％のビスコースを使用する以外は、実施例７〜１２と同様に処理して、再生セルロースの多孔質粒子を調製し、その空隙率及び硫黄臭の有無について調べた。結果を表２に示す。
【００２８】
【表２】
【発明の効果】
本発明によれば、製造段階において毒性の強い二硫化炭素を使用する必要がなく、硫黄の残存に伴う臭いの問題もないことから、抗菌剤、芳香剤、消臭剤等の吸着材、バイオリアクターの固定担体あるいは室内園芸用培土等、従来からビスコース由来の再生セルロース多孔質粒子が使用されていた分野での代替が可能な多孔質粒子を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for manufacturing a porous grain element consisting of low-substituted cellulose ether.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, porous particles made of natural polymers such as cellulose and protein have been used for adsorbents such as antibacterial agents, fragrances and deodorants, bioreactor stationary carriers, indoor horticulture soils, and the like. Among these, as for the porous particles of cellulose, the porous particles of regenerated cellulose produced by coagulating and regenerating a mixture of viscose and polysaccharides in an alkaline aqueous solution in an acidic aqueous solution in JP-A-9-176327. Has been reported.
[0003]
JP-A-3-170501 reports porous particles produced by coagulating and regenerating a solution in which calcium carbonate is mixed with viscose in an acidic aqueous solution.
[0004]
However, these porous particles use viscose made from cellulose xanthate, which is produced by treating cellulose with highly toxic carbon disulfide, in an alkaline aqueous solution. It has been pointed out that there is a risk of exposure to carbon. In addition, if the purification is not performed sufficiently, a minute amount of sulfur remains in the porous particles, and the function of the product itself may be deteriorated or an odor may be generated.
[0005]
The present invention has been made in view of the above circumstances, has a performance that can be substituted for conventional viscose-derived porous particles, and does not use toxic carbon disulfide in its production process. and to provide a porous grain terminal manufacturing method without.
[0006]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive studies to achieve the above object, the inventors have found that porous particles made of low-substituted cellulose ether having a certain degree of molar substitution can replace conventional porous particles derived from viscose. It has been found that it can be obtained without using a sulfur odor without using carbon disulfide which is highly toxic in the production process and has led to the present invention.
[0007]
Therefore, the present invention
[I] Low-substituted cellulose ether and water-soluble polymer or carbonic acid that does not dissolve in water having a molar substitution degree of 0.05 to 1.0 with an alkyl group and / or hydroxyalkyl group, but dissolves in an alkaline aqueous solution the salt is contacted with an acid mixture was dissolved in an aqueous alkali solution, a method of manufacturing the porous particles of low-substituted cellulose ether you characterized in that coagulation and reproducing low-substituted cellulose ether,
[II] The method for producing porous particles of low-substituted cellulose ether according to [I] , wherein the method of contacting the mixed solution and the acid is a method of dropping the mixed solution into an acid aqueous solution,
[III] A mixture of low-substituted cellulose ether and carbonate dissolved in an alkaline aqueous solution is brought into contact with an acid to coagulate and regenerate the low-substituted cellulose ether, and carbon dioxide is generated by the reaction between the carbonate and acid. A method for producing porous particles of low-substituted cellulose ether according to [I] or [II] , wherein the porous particles are formed by forming a porous particle.
[0008]
Hereinafter, the present invention will be described in more detail. The low-substituted cellulose ether according to the present invention is a cellulose ether in which the hydrogen atom of the hydroxyl group of the glucose ring constituting the cellulose is substituted with an alkyl group and / or a hydroxyalkyl group. The degree of molar substitution is as low as 0.05 to 1.0, preferably 0.1 to 0.7, and does not dissolve in water, but dissolves in an alkaline aqueous solution. If the degree of molar substitution is lower than 0.05, it is difficult to dissolve in an alkaline aqueous solution, making it difficult to produce porous particles. If it exceeds 1.0, the solubility in water is increased, and the function as porous particles is increased. Because it is lost.
[0009]
Low substituted cellulose ethers include low substituted alkyl celluloses such as low substituted methyl cellulose and low substituted ethyl cellulose, low substituted hydroxyalkyl celluloses such as low substituted hydroxyethyl cellulose and low substituted hydroxypropyl cellulose, low substituted hydroxy Examples include low-substituted hydroxyalkylalkylcelluloses such as propylmethylcellulose, low-substituted hydroxyethylmethylcellulose, and low-substituted hydroxyethylethylcellulose.
[0010]
The porous particles include a certain amount of voids in the particles, and the degree of voids, that is, the void ratio (volume ratio of voids in the particle volume) may be appropriately selected depending on the application, and is not particularly limited. However, the porosity is preferably 30 to 98%, particularly 50 to 98%. This is because if the porosity is less than 30%, the function as porous particles cannot be exhibited, and if it exceeds 98%, the mechanical strength of the particles becomes weak and may not be put to practical use. .
[0011]
The porous particles of the present invention, as a first method, coagulate and regenerate the low-substituted cellulose ether by contacting a mixed solution obtained by dissolving the low-substituted cellulose ether and the water-soluble polymer substance in an alkaline aqueous solution with an acid. Can be manufactured. In this case, porous particles are formed by removing the water-soluble polymer substance from the coagulated and regenerated low-substituted cellulose ether in an acid aqueous solution or a subsequent water washing step.
[0012]
Here, examples of the alkaline aqueous solution include a caustic soda aqueous solution and a caustic potassium aqueous solution, and the concentration of the alkaline aqueous solution may be appropriately determined because it varies depending on the type and molar substitution degree of the low-substituted cellulose ether used. Is preferably 2 to 25% by weight, particularly 3 to 15% by weight, as the amount of caustic. As a typical example, a low-substituted hydroxypropyl cellulose having a molar substitution degree of 0.2 is dissolved in a 10% strength by weight aqueous sodium hydroxide solution.
[0013]
The water-soluble polymer substance is not particularly limited as long as it is soluble in an alkaline aqueous solution, and is a natural polymer such as starch, pullulan, guar gum, gum arabic, or alginic acid, or a derivative of a natural polymer such as cellulose or starch. , Semi-synthetic polymers such as hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, hydroxypropyl starch, dextrin, oxidized starch, or synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, sodium polyacrylate It can be illustrated.
[0014]
The mixing ratio of the low-substituted cellulose ether and the water-soluble polymer substance and the total concentration of these components in the alkaline aqueous solution are not particularly limited, and are appropriately selected in consideration of the physical properties and operability of the target porous particles. Usually, the concentration of the low-substituted cellulose ether is preferably 2 to 20% by weight, particularly preferably 3 to 15% by weight. The water-soluble polymer substance is preferably added in an amount of 0.1 to 5 parts by weight with respect to 1 part by weight of the low-substituted cellulose. When mixing low-substituted cellulose ether and water-soluble polymer substance in alkaline aqueous solution, first prepare low-substituted cellulose ether and water-soluble polymer substance separately dissolved in alkaline aqueous solution, then mix each one Alternatively, the low-substituted cellulose ether may be previously dissolved in an alkaline aqueous solution, and then a water-soluble polymer substance may be added.
[0015]
As the acid, a mineral acid such as hydrochloric acid or sulfuric acid, or an aqueous solution such as citric acid, malic acid or acetic acid can be used. In this case, the acid concentration is preferably 1 to 20% by weight.
[0016]
The method for bringing the alkali mixture of the low-substituted cellulose ether and the water-soluble polymer substance into contact with the acid is not particularly limited, but there is a method in which the alkali mixture is gradually dropped into the acid aqueous solution. Preferably employed. In this case, the dropping rate of the alkali mixed solution is preferably 1 to 60 ml / min. In addition, it is preferable to perform this contact at 0-30 degreeC.
[0017]
Further, the present invention provides a low-substituted cellulose ether porous material in which a low-substituted cellulose ether and a carbonate dissolved in an alkaline aqueous solution are brought into contact with an acid as droplets to coagulate and regenerate the low-substituted cellulose ether. A method for producing particles is provided. In this case, when the low-substituted cellulose ether is solidified and regenerated, the carbonate reacts with the acid to generate carbon dioxide to form porous particles. Here, the same alkaline aqueous solution and acid as described above can be used.
[0018]
Examples of the carbonate include sodium carbonate, calcium carbonate, sodium hydrogen carbonate, magnesium carbonate and the like, but water-insoluble calcium carbonate and magnesium carbonate are particularly preferable. There is no particular limitation on the mixing ratio of the low-substituted cellulose ether and the carbonate and the total concentration of these components in the aqueous alkali solution, and may be appropriately selected in consideration of the physical properties and operability of the target porous particles. Usually, the concentration of the low-substituted cellulose ether is preferably 2 to 20% by weight, particularly preferably 3 to 15% by weight. The carbonate is preferably added in an amount of 0.1 to 10 parts by weight with respect to 1 part by weight of the low-substituted cellulose. When mixing the low-substituted cellulose ether and the carbonate, the low-substituted cellulose ether may be first dissolved in an alkaline aqueous solution, and then the carbonate may be added.
[0019]
The concentration of the acid aqueous solution and the contact method / condition between the alkali mixed solution and the acid aqueous solution are the same as described above. In any of the above production methods, the coagulated and regenerated porous particles are separated from the mother liquor by filtration or a centrifuge, and then dried by washing, freeze-drying, or the like.
[0020]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, parts indicate parts by weight.
[0021]
[Examples 1 to 6]
A sample solution was prepared by dissolving 6 parts of low-substituted cellulose ether shown in Table 1 in 95 parts of 10% by weight aqueous caustic soda solution, and sample liquid in which 6 parts of hydroxypropyl starch was dissolved in 95 parts of 10% by weight aqueous caustic soda solution. Mixed with. This mixed solution was added dropwise to a 3.6 wt% aqueous hydrochloric acid solution with stirring at a rate of 2 ml / min from a nozzle (caliber: 1 mmφ).
[0022]
The coagulated / regenerated particles were separated by filtration, washed with water, and then freeze-dried. The obtained particles were examined for porosity and presence of sulfur odor. The results are shown in Table 2.
[0023]
Method for measuring porosity The average volume (A) of the particles was determined from the average particle size of 100 sample particles obtained with a laser scattering particle size measurement device, assuming that the particles were true spheres. Separately, the average weight (B) of 100 sample particles described above was obtained, and the bulk density d (B ÷ A) was calculated. From the following formula, the porosity was determined from the true specific gravity (D) and d of the particle raw material previously determined by the liquid replacement method.
Porosity = 1-d / D
[0024]
[Table 1]
[Comparative Example 1]
Regenerated by treating in the same manner as in Examples 1 to 6 except that viscose having a cellulose equivalent concentration of 6% and a caustic soda concentration of 10% by weight was used instead of the sample solution obtained by dissolving the low-substituted cellulose ether in an aqueous caustic soda solution. Cellulose porous particles were prepared and examined for porosity and presence of sulfur odor. The results are shown in Table 2.
[0026]
[Examples 7 to 12]
6 parts of low-substituted cellulose ether shown in Table 1 was dissolved in 95 parts of a 10% by weight aqueous caustic soda solution, and 18 parts of calcium carbonate was added thereto and stirred to prepare a sample dispersion. This dispersion was added dropwise to a 10% by weight aqueous hydrochloric acid solution with stirring at a rate of 5 ml / min from a nozzle (caliber: 1 mmφ). The coagulated / regenerated particles were separated by filtration, washed with water, and then freeze-dried. The obtained particles were examined for porosity and sulfur odor. The results are shown in Table 2.
[0027]
[Comparative Example 2]
Regenerated by treating in the same manner as in Examples 7 to 12 except that viscose having a cellulose equivalent concentration of 6% and a caustic soda concentration of 10% by weight was used in place of the sample solution obtained by dissolving the low-substituted cellulose ether in an aqueous caustic soda solution. Cellulose porous particles were prepared, and the porosity and sulfur odor were examined. The results are shown in Table 2.
[0028]
[Table 2]
【The invention's effect】
According to the present invention, it is not necessary to use highly toxic carbon disulfide in the production stage, and there is no problem of odor due to residual sulfur, so that an adsorbent such as an antibacterial agent, fragrance, and deodorant, bio It is possible to obtain porous particles that can be replaced in fields where regenerated cellulose porous particles derived from viscose have been used, such as fixed carriers for reactors or indoor horticulture soils.
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| DE102004050562A1 (en) * | 2004-10-15 | 2006-05-04 | Henkel Kgaa | Absorbable particles |
| EP3369749A4 (en) * | 2015-10-30 | 2019-08-07 | Toray Industries, Inc. | Cellulose ether derivative fine particles |
| GB2560915A (en) * | 2017-03-27 | 2018-10-03 | Futamura Chemical Uk Ltd | Packaging material |
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