TW202337552A - In-liquid substance separation membrane using octosilicate material and production method for same - Google Patents

In-liquid substance separation membrane using octosilicate material and production method for same Download PDF

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TW202337552A
TW202337552A TW111117911A TW111117911A TW202337552A TW 202337552 A TW202337552 A TW 202337552A TW 111117911 A TW111117911 A TW 111117911A TW 111117911 A TW111117911 A TW 111117911A TW 202337552 A TW202337552 A TW 202337552A
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separation membrane
liquid substance
substance separation
plate
liquid
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TW111117911A
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中川敬三
新谷卓司
吉岡朋久
北川裕丈
高熊紀之
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國立大學法人神戶大學
日商日產化學股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/08—Polysaccharides
    • B01D71/10—Cellulose; Modified cellulose
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material

Abstract

To provide: an in-liquid substance separation membrane molded body that is made of highly chemical-resistant components, has a high membrane solvent permeation speed, and efficiently separates the substances (e.g., the ionic organic substances) in a liquid; and a production method for the in-liquid substance separation membrane molded body. According to the present invention, an in-liquid substance separation membrane molded body includes: lamellar particles (A) that include a quaternary ammonium ion (a) that has a total of 15-45 carbon atoms and has one or two alkyl groups that have 10-20 carbon atoms and an anion surfactant (b) that has an ammonium ion, have an average thickness of 0.7-100 nm, an average length of 50-10,000 nm, and a (maximum length/width orthogonal to maximum length) ratio of 1.0-10.0, and are a separated layer substance formed by separating the layers of a layered compound; and a base material (B). The lamellar particles (A) are an aqueous dispersion of the lamellar particles (A) that includes (a) and (b) for the separation of the layers of the layered compound. The 90% cumulative particle size value for a laser diffraction particle size distribution of the lamellar particles (A) of the aqueous dispersion is 1.5-10 times the average value for the particle size distribution.

Description

使用八矽酸鹽材料之液中物質分離膜及其製造方法Substance separation membrane in liquid using octa-silicate material and manufacturing method thereof

本發明關於使用層狀化合物之層間剝離所造成的剝離層物質之板狀粒子的液中物質分離膜成形體及彼等之製造方法。The present invention relates to liquid substance separation membrane formed bodies using plate-shaped particles of exfoliated layer substances caused by interlayer delamination of layered compounds, and their manufacturing methods.

以選擇地去除溶液中的物質(例如離子成分)為目的，嘗試利用膜技術。從環境技術或資源再利用之觀點來看被注目。 例如揭示有使用含有金屬離子輸送性配位子的金屬離子分離膜，從水性溶液去除重金屬離子(參照專利文獻1)。記載有高分子膜為纖維素衍生物，使用坎普(Kempic)酸癸基醯胺或坎普酸十二基醯胺等之坎普酸衍生物作為配位子，具有經由膜輸送銅離子、鉛離子、水銀離子、鎂離子、鈣離子等之能力。 又，揭示有由層狀化合物之層間剝離所造成的剝離層物質所形成之板狀物質的分散液與使用該分散液之氣體分離膜(參照專利文獻2)。 [先前技術文獻] [專利文獻] Membrane technology is attempted to be used for the purpose of selectively removing substances (such as ionic components) from solutions. Attention is drawn from the viewpoint of environmental technology or resource recycling. For example, it is disclosed that a metal ion separation membrane containing a metal ion transporting ligand is used to remove heavy metal ions from an aqueous solution (see Patent Document 1). It is reported that the polymer membrane is a cellulose derivative and uses Kempic acid derivatives such as Kempic acid decylamide or Kempic acid dodecylamide as ligands, and has the ability to transport copper ions through the membrane. The ability of lead ions, mercury ions, magnesium ions, calcium ions, etc. Furthermore, a dispersion of a plate-shaped substance formed by a delamination layer material caused by delamination of a layered compound and a gas separation membrane using the dispersion are disclosed (see Patent Document 2). [Prior technical literature] [Patent Document]

[專利文獻1] 日本特開平10-290927號 [專利文獻2] 國際公開第2020/153352號小冊 [Patent Document 1] Japanese Patent Application Laid-Open No. 10-290927 [Patent Document 2] International Publication No. 2020/153352 Pamphlet

[發明所欲解決的課題][Problem to be solved by the invention]

本發明關於八矽酸鹽材料而得的分離膜，其可效率良好地去除液體中的物質(例如離子性物質)。又，本發明之目的在於提供液中物質分離膜成形體及其製造方法，該液中物質分離膜成形體係依分離膜成分而耐化學性高，膜中之包含被分離物質的溶液之溶劑穿透速度高，效率良好地分離液中的物質(例如離子性有機物)。 [解決課題的手段] The present invention relates to a separation membrane made of octa-silicate materials, which can efficiently remove substances (such as ionic substances) in liquids. Furthermore, an object of the present invention is to provide a liquid substance separation membrane molded body and a manufacturing method thereof. The liquid substance separation membrane molding system has high chemical resistance depending on the components of the separation membrane, and the solvent of the solution containing the substance to be separated in the membrane passes through. The penetration rate is high and substances in the liquid (such as ionic organic matter) can be separated efficiently. [Means to solve the problem]

本發明係作為第1觀點，為一種液中物質分離膜成形體，其包含液中物質分離膜與支撐該液中物質分離膜的基材(B)，該液中物質分離膜包含總碳原子數15~45且具有1~2個碳原子數10~20的烷基之四級銨離子(a)與具有銨離子的陰離子界面活性劑(b)，且包含具有平均厚度0.7~100nm、平均長徑50~10,000nm及(最大長徑/正交於最大長徑的寬度)=1.0~10.0，且為層狀化合物之層間剝離所造成的剝離層物質之板狀粒子(A)。 作為第2觀點，如第1觀點記載之液中物質分離膜成形體，其中上述層狀化合物為艾萊石(ilerite)。 作為第3觀點，如第1觀點或第2觀點記載之液中物質分離膜成形體，其中上述液中物質分離膜為艾萊石與氧化石墨烯之複合膜。 作為第4觀點，如第1觀點至第3觀點中任一觀點記載之液中物質分離膜成形體，其中上述液中物質分離膜係由包含用於上述層狀化合物之層間剝離的上述(a)與(b)之板狀粒子(A)的水性分散液所形成而成，該水性分散液中的板狀粒子(A)之雷射繞射式粒徑分布中90%累計粒徑值為該粒徑分布的平均值之1.5~10倍。 作為第5觀點，如第1觀點至第4觀點中任一觀點記載之液中物質分離膜成形體，其中上述液中物質分離膜係由包含用於上述層狀化合物之層間剝離的上述(a)與(b)之板狀粒子(A)的水性分散液所形成而成，該水性分散液之動態光散射法所測得的平均粒徑為10~10,000nm，上述(a)與(b)一起係相對於(A)而言在0.01~50.0質量%之範圍的板狀粒子(A)。 作為第6觀點，如第1觀點至第5觀點中任一觀點記載之液中物質分離膜成形體，其中上述基材(B)係選自由纖維素、合成高分子及陶瓷所成之群組的至少1種多孔質基材。 作為第7觀點，如第6觀點記載之液中物質分離膜成形體，其中上述纖維素為硝基纖維素、羧甲基纖維素或羥乙基纖維素。 作為第8觀點，如第6觀點記載之液中物質分離膜成形體，其中上述合成高分子為聚醚碸、聚碸、聚偏二氟乙烯、聚偏二氯乙烯、聚乙烯乙烯醇、聚乙烯醇、聚丙烯酸或聚甲基丙烯酸。 作為第9觀點，如第6觀點記載之液中物質分離膜成形體，其中上述陶瓷為二氧化矽、氧化鋁或莫來石。 作為第10觀點，如第1觀點至第9觀點中任一觀點記載之液中物質分離膜成形體，其中上述液中物質分離膜係形成在基材(B)表面上而成，上述液中物質分離膜具有1.5nm~10μm的膜厚。 作為第11觀點，如第1觀點至第10觀點中任一觀點記載之液中物質分離膜成形體，其中包含被分離物質的溶液之溶劑的穿透速度為0.1~100L・m -2・hr -1・bar -1。 作為第12觀點，如第1觀點至第11觀點中任一觀點記載之液中物質分離膜成形體，其中包含被分離物質的溶液之物質去除率為15~99%。 作為第13觀點，如第1觀點至第12觀點中任一觀點記載之液中物質分離膜成形體，其中被分離物質為離子性化合物。 作為第13觀點，如第12觀點記載之液中物質分離膜成形體，其中上述離子性化合物為至少具有磺酸離子或羧酸離子的有機化合物。 作為第15觀點，如第1觀點至第14觀點中任一觀點記載之液中物質分離膜成形體，其中包含被分離物質的溶液為包含被分離物質及與該被分離物質不同分子量的至少1種以上之溶質分子之溶液，液中物質分離膜成形體用於濃縮該溶液中的被分離物質。 作為第16觀點，一種如第1觀點至第15觀點中任一觀點記載之液中物質分離膜成形體之製造方法，其包含下述(i)步驟~(vi)步驟： (i)步驟：將矽酸化合物水溶液在90~150℃之溫度下水熱處理後，將靜置所得之層狀化合物進行分離並水洗，將所得之濕式凝膠添加至水中，製造層狀化合物的水性分散液之步驟； (ii)步驟：於(i)步驟所得之水性分散液中，添加四級銨離子(a)，在40~100℃下加熱12~48小時之步驟，該四級銨離子(a)成為層狀化合物的離子交換容量之等倍~三倍量，總碳原子數15~45，且具有1~2個碳原子數10~20的烷基； (iii)步驟：於(ii)步驟所得之液中添加純水，以液中的鈉離子濃度成為100ppm以下之方式，將鈉離子含有液去除到系外之步驟； (iv)步驟：使(iii)步驟所含有的濕式凝膠分散於濃度為0.01~1質量%的具有銨離子的陰離子界面活性劑(b)水溶液中後，進一步添加氨而將液中的pH調至9.0~12.0之步驟； (v)步驟：對於(iv)步驟所得之液在40~90℃下進行加熱12~48小時，得到板狀粒子(A)的分散液之步驟； (vi)步驟：在基材(B)表面上，使用(v)步驟所得之板狀粒子(A)的分散液來製造液中物質分離膜之步驟。 作為第17觀點，如第16觀點記載之液中物質分離膜成形體之製造方法，其中前述(vi)步驟係將液中物質分離膜製膜之步驟，包含在基材(B)表面上，使用(v)步驟所得之板狀粒子(A)的分散液來形成板狀粒子(A)層之步驟，及在該層之上使用氧化石墨烯的分散液來積層氧化石墨烯層之步驟。 作為第18觀點，如第16觀點或第17觀點記載之液中物質分離膜成形體之製造方法，其中在基材(B)表面上，使用(v)步驟所得之板狀粒子(A)的分散液進行製膜之步驟(vi)，係以抽吸過濾或加壓過濾進行。 作為第19觀點，如第16觀點或第17觀點記載之液中物質分離膜成形體之製造方法，其中於(v)步驟與(vi)步驟之間，進一步追加(v-0)步驟； (v-0)步驟：將(v)步驟所得之包含板狀粒子(A)的分散液，使總碳原子數15~45且具有1~2個碳原子數10~20的烷基之四級銨離子(a)與具有銨離子的陰離子界面活性劑(b)之含量一起相對於板狀粒子(A)而言減低至0.01~15.0質量%之範圍，得到包含板狀粒子(A)的分散液之步驟。 作為第20觀點，如第19觀點記載之液中物質分離膜成形體之製造方法，其中(v-0)步驟為下述(v-1)步驟； (v-1)步驟：對於(v)步驟所得之包含板狀粒子(A)的分散液，以20000~60000G進行超離心處理，得到使總碳原子數15~45且具有1~2個碳原子數10~20的烷基之四級銨離子(a)與具有銨離子的陰離子界面活性劑(b)之含量一起相對於(A)而言減低至0.01~15.0質量%之範圍，得到包含板狀粒子(A)的分散液之步驟。 [發明的效果] As a first aspect, the present invention provides a liquid substance separation membrane formed body, which includes a liquid substance separation membrane and a base material (B) supporting the liquid substance separation membrane, and the liquid substance separation membrane contains total carbon atoms. A quaternary ammonium ion (a) with a number of 15 to 45 and having 1 to 2 alkyl groups with a carbon number of 10 to 20, and an anionic surfactant (b) having an ammonium ion, and includes an average thickness of 0.7 to 100 nm and an average thickness of 0.7 to 100 nm. The long diameter is 50~10,000nm and (maximum long diameter/width orthogonal to the maximum long diameter) = 1.0~10.0, and it is a plate-shaped particle (A) of a peeling layer material caused by interlayer peeling of a layered compound. As a second aspect, in the liquid substance separation membrane formed body according to the first aspect, the layered compound is ilerite. As a third aspect, there is provided the liquid substance separation membrane molded body according to the first aspect or the second aspect, wherein the liquid substance separation membrane is a composite membrane of islaite and graphene oxide. As a fourth aspect, the liquid substance separation membrane formed body according to any one of the first to third aspects, wherein the liquid substance separation membrane is made of the above-mentioned (a) for interlayer delamination of the above-mentioned layered compound. ) and the aqueous dispersion of the plate-shaped particles (A) in (b). The 90% cumulative particle diameter value of the plate-shaped particles (A) in the aqueous dispersion is 1.5 to 10 times the average value of this particle size distribution. As a fifth aspect, the liquid substance separation membrane molded article according to any one of the first to fourth aspects, wherein the liquid substance separation membrane is made of the above-mentioned (a) for interlayer exfoliation of the above-mentioned layered compound. ) and (b) are formed from an aqueous dispersion of plate-shaped particles (A). The average particle diameter of the aqueous dispersion measured by the dynamic light scattering method is 10~10,000nm. The above (a) and (b) ) is a plate-shaped particle (A) in the range of 0.01 to 50.0% by mass relative to (A). As a sixth aspect, the liquid substance separation membrane formed body according to any one of the first to fifth aspects, wherein the base material (B) is selected from the group consisting of cellulose, synthetic polymers, and ceramics. At least one porous substrate. As a seventh aspect, in the liquid substance separation membrane molded article according to the sixth aspect, the cellulose is nitrocellulose, carboxymethyl cellulose or hydroxyethyl cellulose. As an eighth aspect, the liquid substance separation membrane molded article according to the sixth aspect, wherein the synthetic polymer is polyether ether, polyethylene, polyvinylidene fluoride, polyvinylidene chloride, polyethylene vinyl alcohol, poly Vinyl alcohol, polyacrylic acid or polymethacrylic acid. As a ninth aspect, in the liquid substance separation membrane formed body according to the sixth aspect, the ceramic is silica, alumina or mullite. As a tenth aspect, in the liquid substance separation membrane formed body according to any one of the first to ninth aspects, the liquid substance separation membrane is formed on the surface of the base material (B), and the liquid substance separation membrane is formed on the surface of the base material (B), and the liquid substance separation membrane is The material separation membrane has a film thickness of 1.5nm~10μm. As an eleventh aspect, the liquid substance separation membrane formed body according to any one of the first to tenth aspects, wherein the penetration rate of the solvent of the solution containing the substance to be separated is 0.1 to 100L·m -2 ·hr -1・bar -1 . As a twelfth aspect, in the liquid substance separation membrane formed body according to any one of the first to eleventh aspects, the substance removal rate of the solution containing the substance to be separated is 15 to 99%. As a thirteenth aspect, there is provided the liquid substance separation membrane formed body according to any one of the first to twelfth aspects, wherein the substance to be separated is an ionic compound. As a thirteenth aspect, in the liquid substance separation membrane formed body according to the twelfth aspect, the ionic compound is an organic compound having at least a sulfonate ion or a carboxylate ion. As a fifteenth aspect, the liquid substance separation membrane formed body according to any one of the first to fourteenth aspects, wherein the solution containing the substance to be separated contains the substance to be separated and at least 1 of the molecular weight different from the substance to be separated. A solution of more than one kind of solute molecules, and the material separation membrane formed body in the liquid is used to concentrate the separated substances in the solution. As a 16th aspect, a method for manufacturing a liquid substance separation membrane molded body according to any one of the 1st to 15th aspects, including the following steps (i) to (vi): (i) Step: The step of hydrothermal treatment of a silicic acid compound aqueous solution at a temperature of 90 to 150°C, separating the obtained layered compound and washing it with water, and adding the obtained wet gel to water to produce an aqueous dispersion of the layered compound. ; (ii) Step: Add quaternary ammonium ions (a) to the aqueous dispersion obtained in step (i), and heat at 40 to 100°C for 12 to 48 hours. The quaternary ammonium ions (a) become The ion exchange capacity of the layered compound is equal to three times the amount, the total number of carbon atoms is 15 to 45, and it has 1 to 2 alkyl groups with 10 to 20 carbon atoms; (iii) Step: obtained in step (ii) The step of adding pure water to the liquid and removing the sodium ion-containing liquid out of the system so that the sodium ion concentration in the liquid becomes 100 ppm or less; (iv) step: dispersing the wet gel contained in step (iii) After adding ammonia to an aqueous solution of the anionic surfactant (b) containing ammonium ions at a concentration of 0.01 to 1 mass %, further adding ammonia to adjust the pH in the solution to 9.0 to 12.0; (v) step: for (iv) The step of heating the liquid obtained in step 40 to 90°C for 12 to 48 hours to obtain a dispersion of plate-shaped particles (A); (vi) step: using the solution obtained in step (v) on the surface of substrate (B) A step of producing a separation membrane for substances in the liquid from a dispersion of plate-shaped particles (A). As a seventeenth aspect, there is a method for manufacturing a liquid substance separation membrane molded article as described in the sixteenth aspect, wherein the step (vi) is a step of forming a liquid substance separation membrane on the surface of the base material (B), The step of forming a layer of the plate-shaped particles (A) using the dispersion of the plate-shaped particles (A) obtained in step (v), and the step of laminating a graphene oxide layer on the layer using the dispersion of graphene oxide. As an eighteenth aspect, there is provided a method for producing a liquid substance separation membrane molded article as described in the sixteenth aspect or the seventeenth aspect, wherein the plate-shaped particles (A) obtained in the step (v) are used on the surface of the base material (B). The step (vi) of forming a membrane from the dispersion is carried out by suction filtration or pressure filtration. As a 19th aspect, the method for manufacturing a liquid substance separation membrane molded body as described in the 16th aspect or the 17th aspect, wherein a step (v-0) is further added between the (v) step and the (vi) step; ( v-0) step: convert the dispersion containing plate-shaped particles (A) obtained in step (v) into a quaternary liquid with a total carbon number of 15 to 45 and 1 to 2 alkyl groups with 10 to 20 carbon atoms. The contents of ammonium ions (a) and the anionic surfactant (b) containing ammonium ions are reduced to the range of 0.01 to 15.0 mass % relative to the plate-shaped particles (A), and a dispersion containing the plate-shaped particles (A) is obtained. liquid steps. As a 20th aspect, the method for manufacturing a liquid substance separation membrane molded body as described in the 19th aspect, wherein the step (v-0) is the following step (v-1); (v-1) step: (v) The dispersion containing plate-shaped particles (A) obtained in the step is subjected to ultracentrifugation at 20000~60000G to obtain a quaternary alkyl group with a total carbon number of 15~45 and 1~2 alkyl groups with 10~20 carbon atoms. The step of reducing the contents of ammonium ions (a) and the anionic surfactant (b) containing ammonium ions to the range of 0.01 to 15.0 mass % relative to (A) to obtain a dispersion containing plate-shaped particles (A) . [Effects of the invention]

目前，廣泛利用超過濾膜，超過濾膜係利用膜中之細孔，篩分具有某程度的分子量之分子，使溶劑通過到系外，藉此分離液中的物質之系統。然而，超過濾膜係基於此原理在通過細孔的液體量有限制，過濾的通液量有限。 另一方面，亦廣泛進行以過濾器從液體去除物質一事。然而，過濾器雖然通液量高，但是孔徑粗，液中溶解的離子性物質無法去除。 Currently, ultrafiltration membranes are widely used. Ultrafiltration membranes use pores in the membrane to screen molecules with a certain molecular weight, allowing the solvent to pass out of the system, thereby separating substances in the liquid. However, based on this principle, the ultrafiltration membrane system has a limit on the amount of liquid that can pass through the pores, and the amount of liquid that can be filtered is limited. On the other hand, the use of filters to remove substances from liquids is also widely practiced. However, although the filter has a high liquid flow rate, its pore size is large, and ionic substances dissolved in the liquid cannot be removed.

本發明為液中物質分離膜成形體，為能從溶液中去除物質(例如離子性成分)之分離膜成形體。 本發明之液中物質分離膜成形體具有液中物質分離膜，該分離膜係在成為網眼粗的支撐體之基材上，具有分離作用的物質以遍及一層至多層來積層的構造含有。液中物質分離膜係要求防止溶液中含有的物質(例如離子性成分)穿過分離物質之間而到達基材之情形的作用，作為其中之一，為使到達路徑迷路化藉此降低往基材之到達，及分子篩效果，當被分離物質為離子性物質例如具有負離子的離子性物質時，使用具有負離子的分離膜物質，藉由其電性的排斥力而防止通過分離膜物質之間的情形，藉此僅使不含被分離物質的溶液(或溶劑)通過，去除被分離物質(例如離子性物質)者。 The present invention is a separation membrane formed body for substances in a liquid, and is a separation membrane formed body capable of removing substances (eg, ionic components) from a solution. The liquid substance separation membrane molded article of the present invention has a liquid substance separation membrane attached to a base material that is a coarse-meshed support, and contains a substance having a separation effect in a structure in which it is laminated in one to a plurality of layers. The liquid substance separation membrane is required to prevent substances (such as ionic components) contained in the solution from passing between the separation substances and reaching the base material. As one of the functions, it is necessary to make the arrival path maze and thereby reduce the flow to the base material. The arrival of materials, and the molecular sieve effect, when the substance to be separated is an ionic substance, such as an ionic substance with negative ions, a separation membrane substance with negative ions is used to prevent the separation between substances passing through the separation membrane through its electrical repulsion. In this case, only the solution (or solvent) that does not contain the separated substance is passed through, and the separated substance (such as ionic substance) is removed.

本發明中具有分離功能的物質(分離膜物質)為層狀化合物(例如八矽酸鹽材料)之層間剝離所造成的剝離層物質之板狀粒子，故於基材上製膜為容易，藉由控制膜的厚度而層間的控制為容易。因此，不僅電性地排除物質(例如離子性物質)而已，而且亦可依照層間的尺寸，依照分子直徑的大小，排除(分離)分子直徑不同的物質(例如離子性物質)。In the present invention, the substance with the separation function (separation membrane substance) is the plate-shaped particle of the exfoliation layer substance caused by the interlayer exfoliation of the layered compound (such as octa-silicate material), so it is easy to form a film on the substrate by It is easy to control the thickness of the film and control between layers. Therefore, not only substances (such as ionic substances) are electrically excluded, but substances with different molecular diameters (such as ionic substances) can also be excluded (separated) according to the size of the layers and the size of the molecular diameter.

層狀化合物為板狀物質的積層體，於板狀物質之層間***鹼金屬離子，電性結合板狀物質間。藉由以大體積的化合物例如四級銨離子擴大該板狀物質之層間，而電性的結合力急劇降低，再者，添加陰離子界面活性劑等及進行加熱處理，藉此進行板狀物質之層間剝離，成為1片的薄片狀之板狀物質。此板狀物質可稱為板狀粒子，為分散於媒體中，直接進行層間剝離，或藉由分散於媒體中，形成板狀粒子的分散液者。此處，層間剝離時的陰離子界面活性劑亦用於在分散於媒體中時，提高分散性。此係因為板狀粒子(例如八矽酸鹽材料)中含有矽醇基時，藉由矽醇基所造成的負電荷與陰離子界面活性劑的負電荷之排斥力，在做成分散液時得到充分的分散性之故。The layered compound is a laminate of plate-like substances. Alkali metal ions are inserted between the layers of the plate-like substances to electrically bond the plate-like substances. By using large-volume compounds such as quaternary ammonium ions to expand the layers of the plate-like material, the electrical bonding force is sharply reduced. In addition, anionic surfactants are added and heat treatment is performed to proceed with the plate-like material. The layers peel off and become a flaky plate-like substance. This plate-shaped substance can be called plate-shaped particles, which are dispersed in the medium and directly peeled off, or dispersed in the medium to form a dispersion of plate-shaped particles. Here, the anionic surfactant used during interlayer delamination is also used to improve dispersibility when dispersed in the medium. This is because when the plate-like particles (such as octa-silicate materials) contain silyl groups, the repulsive force between the negative charges caused by the silyl groups and the negative charges of the anionic surfactant is obtained when the dispersion is made. Due to sufficient dispersion.

經剝離的板狀物質之板狀粒子亦被稱為奈米片，單層的厚度為數nm。層狀矽酸鹽，例如剝離艾萊石而得之奈米片為薄狀矽酸鹽，矽醇基具有負電荷且具有高的親水性，為電性排斥通過膜的溶液中之負離子性物質並排除，主要僅通過溶液的溶劑而可分離物質(例如離子性物質)者。The plate-like particles of the exfoliated plate-like material are also called nanosheets, and the thickness of a single layer is several nm. Layered silicate, for example, the nanosheets obtained by peeling off Islayite are thin silicate. The silyl alcohol group has a negative charge and is highly hydrophilic. It is an anionic substance in the solution that electrically repels through the membrane. And exclude those substances (such as ionic substances) that can be separated mainly only by the solvent of the solution.

本發明中藉由四級銨化合物剝離層間後，以濕式凝膠狀態分散於陰離子界面活性劑水溶液中，藉此得到粒徑分布窄，整齊的粒徑之板狀粒子，而將彼等在基板上製膜，藉此得到具有高的分離性能與高的溶液通過性能之液中物質分離膜成形體。In the present invention, after the quaternary ammonium compound is peeled off between layers, it is dispersed in a wet gel state in an anionic surfactant aqueous solution, thereby obtaining plate-shaped particles with a narrow particle size distribution and regular particle sizes, and they are By forming a membrane on the substrate, a liquid substance separation membrane molded body having high separation performance and high solution passing performance is obtained.

[實施發明的形態][Form of carrying out the invention]

本發明為一種液中物質分離膜成形體，其包含液中物質分離膜與支撐該液中物質分離膜的基材(B)，該液中物質分離膜包含總碳原子數15~45且具有1~2個碳原子數10~20的烷基之四級銨離子(a)與具有銨離子的陰離子界面活性劑(b)，且包含具有平均厚度0.7~100nm、平均長徑50~10,000nm及(最大長徑/正交於最大長徑的寬度) =1.0~10.0，且為層狀化合物之層間剝離所造成的剝離層物質之板狀粒子(A)。 本發明之液中物質分離膜成形體係用於從包含被分離物質的溶液，分離被分離物質，或得到被分離物質經濃縮或稀釋的溶液之液中物質分離膜成形體。 The present invention is a liquid substance separation membrane formed body, which includes a liquid substance separation membrane and a base material (B) supporting the liquid substance separation membrane. The liquid substance separation membrane contains a total carbon number of 15 to 45 and has 1 to 2 quaternary ammonium ions (a) with an alkyl group of 10 to 20 carbon atoms and an anionic surfactant (b) with ammonium ions, and contains an average thickness of 0.7 to 100 nm and an average long diameter of 50 to 10,000 nm. and (maximum long diameter/width orthogonal to the maximum long diameter) =1.0~10.0, and are plate-shaped particles (A) of exfoliated layer substances caused by interlayer delamination of layered compounds. The liquid substance separation membrane forming system of the present invention is used to separate the substance to be separated from a solution containing the substance to be separated, or to obtain a substance in liquid separation membrane formed body from a solution in which the substance to be separated is concentrated or diluted.

本發明中，液中物質分離膜成形體係意指一種成形體，其具備能將溶劑(極性溶劑或無極性溶劑，例如水性溶劑或有機溶劑)中溶解的物質分離成溶劑與物質之膜，為藉由使其分離而進行溶液中的物質之分離或濃縮或稀釋者。本發明中包含從包含被分離物質的溶液完全地分離成被分離物質與溶劑者，但典型上意指從溶解自被分離物質的溶液得到被分離物質濃度降低之溶液與被分離物質濃度上升之溶液的2種類溶液。又，於分離濃縮步驟中使包含被分離物質的溶液之膜穿透速度任意地變化，藉此亦可得到溶劑中之被分離物質濃度階段地變化之複數溶液。In the present invention, the liquid substance separation membrane forming system refers to a formed body, which has a membrane capable of separating substances dissolved in a solvent (polar solvent or non-polar solvent, such as an aqueous solvent or an organic solvent) into a solvent and a substance, and is A substance in a solution is separated, concentrated or diluted by separating it. The present invention includes complete separation of a solution containing a separated substance into a separated substance and a solvent, but typically means a solution obtained by dissolving the separated substance into a solution in which the concentration of the separated substance is reduced and a solution in which the concentration of the separated substance is increased. Two types of solutions. Furthermore, by arbitrarily changing the membrane penetration speed of the solution containing the separated substance in the separation and concentration step, it is also possible to obtain a plurality of solutions in which the concentration of the separated substance in the solvent changes stepwise.

本發明所用的(A)成分之板狀粒子(A)可以分散液之形態使用。板狀粒子(A)可為：分散於含有液狀媒體與四級銨離子(a)與具有銨離子的陰離子界面活性劑(b)之分散介質的狀態，藉由前述(a)及(b)之一者或兩者被覆至少其一部分或吸附而成之狀態，前述(a)及(b)之一者或兩者中介存在於板狀粒子(A)彼此之間而成之狀態的任一狀態。The plate-shaped particles (A) of the component (A) used in the present invention can be used in the form of a dispersion liquid. The plate-shaped particles (A) may be in a state of being dispersed in a dispersion medium containing a liquid medium, quaternary ammonium ions (a), and an anionic surfactant having ammonium ions (b). Through the above (a) and (b) ) is in a state where at least part of it is covered or adsorbed, and one or both of the aforementioned (a) and (b) are interposed between the plate-shaped particles (A). One state.

包含前述板狀粒子(A)的液中物質分離膜或形成其的水分散液，較佳為具有0.1質量%(1000ppm)以下或0.01質量%(100ppm)以下的Na離子濃度之膜或水分散液。 又，前述分散液中的板狀粒子(A)之濃度可設為30質量%以下、或0.01~30質量%、或0.1~30質量%。 The liquid substance separation membrane or the aqueous dispersion forming the same is preferably a membrane or water dispersion having a Na ion concentration of 0.1 mass % (1000 ppm) or less or 0.01 mass % (100 ppm) or less. liquid. Moreover, the concentration of the plate-shaped particles (A) in the dispersion liquid can be 30 mass% or less, or 0.01 to 30 mass%, or 0.1 to 30 mass%.

前述板狀粒子(A)之平均長徑及正交於最大長徑的寬度，可藉由穿透型電子顯微鏡觀察進行測定。板狀粒子(A)的[最大長徑(nm)/正交於最大長徑的寬度(nm)]之值亦可稱為縱橫比，在1.0~10.0之範圍。而且，板狀粒子(A)之正交於最大長徑的寬度(nm)可平均設為50~10000 nm、50~5000nm或50~3000nm。The average major diameter and the width orthogonal to the maximum major diameter of the plate-shaped particles (A) can be measured by observation with a transmission electron microscope. The value of [maximum major diameter (nm)/width orthogonal to the maximum major diameter (nm)] of the plate-shaped particle (A) can also be called the aspect ratio, and is in the range of 1.0 to 10.0. Furthermore, the width (nm) of the plate-shaped particles (A) perpendicular to the maximum major diameter can be set to an average of 50 to 10000 nm, 50 to 5000 nm, or 50 to 3000 nm.

又，前述板狀粒子(A)之平均厚度，可藉由AFM(原子力顯微鏡)觀察將分散液塗佈於基板上的塗佈面而測定。前述板狀粒子(A)之平均厚度為0.7~100nm或0.7~40nm。於AFM之觀察中，可使用將板狀粒子的濃度為1質量%以下的分散液滴下至雲母基板上並使其乾燥而得到的試料。試料的乾燥較佳為自然乾燥，但亦可進行加熱。此外，使用朗謬-布洛傑(Langmuir-Blodgett)法塗佈於基板上而得到的試料，亦可用於AFM之測定。 再者，板狀粒子(A)之平均粒徑，可作為分散液中的板狀粒子(A)之動態光散射法所測得的平均粒徑測定。此時，測定時的分散液之濃度(板狀粒子之濃度)可設為30質量%以下。 In addition, the average thickness of the plate-shaped particles (A) can be measured by observing the coating surface on which the dispersion liquid is applied on the substrate using an AFM (atomic force microscope). The average thickness of the aforementioned plate-shaped particles (A) is 0.7~100nm or 0.7~40nm. For AFM observation, a sample obtained by dropping a dispersion liquid having a plate-shaped particle concentration of 1 mass % or less onto a mica substrate and drying it can be used. The drying of the sample is preferably natural drying, but heating may also be used. In addition, the sample coated on the substrate using the Langmuir-Blodgett method can also be used for AFM measurement. In addition, the average particle diameter of the plate-shaped particle (A) can be measured as the average particle diameter measured by the dynamic light scattering method of the plate-shaped particle (A) in a dispersion liquid. At this time, the concentration of the dispersion liquid (concentration of the plate-shaped particles) during measurement can be set to 30 mass% or less.

上述板狀粒子(A)係可使用層狀化合物之層間剝離所造成的剝離層物質。層狀化合物可舉出例如層狀聚矽酸鹽、黏土礦物、錳酸鹽、鈦酸鹽、鈮酸、鈮酸鹽、GO(氧化石墨烯)等。作為黏土礦物，可舉出膨潤石、蛭石等。作為層狀聚矽酸鹽，可舉出水矽鈉石、多水矽鈉石、斜水矽鈉石、艾萊石(Ilerite亦被稱為ilerite、ilite、illite)等。As the plate-shaped particles (A), a substance with a peeling layer caused by interlayer peeling of a layered compound can be used. Examples of the layered compound include layered polysilicate, clay mineral, manganate, titanate, niobic acid, niobate, GO (graphene oxide), and the like. Examples of clay minerals include bentonite, vermiculite, and the like. Examples of the layered polysilicate include sodalite, sodalite, sodalite, and isleite (Ilerite is also called ilerite, ilite, illite), and the like.

於此等層狀化合物之中，較佳可使用艾萊石等之八矽酸鹽材料。艾萊石具有化學式Na 2O・8SiO 2・nH 2O，平面上具有矽酸骨架、層間具有矽醇基。艾萊石不存在於天然界，故進行人工合成。艾萊石可藉由例如下述般地合成：將混合有膠體二氧化矽與氫氧化鈉的水溶液(SiO 2/Na 2O莫耳比例如為4.0)或水玻璃置入密封容器內，進行90~150℃左右的水熱反應來合成。 Among these layered compounds, octa-silicate materials such as islaite are preferably used. Islay stone has the chemical formula Na 2 O・8SiO 2・nH 2 O. It has a silicic acid skeleton on the plane and silanol groups between the layers. Islay stone does not exist in nature, so it is synthesized artificially. Allite can be synthesized, for example, as follows: placing an aqueous solution of colloidal silica and sodium hydroxide (SiO 2 /Na 2 O molar ratio, for example, 4.0) or water glass into a sealed container. It is synthesized by hydrothermal reaction at about 90~150℃.

上述分散液中的Na離子，係以四級銨離子(a)將存在於層狀矽酸鹽之層間的Na離子進行離子交換時，從層狀化合物(層間)釋放出的Na離子，於那樣的狀態下，會在分散液中大量存在，但以後述說明之方法排出至系外。於分散液中，為了防止剝離層物質的再層化，宜將Na離子設為低濃度。例如，可將分散液中的Na離子濃度設為1000ppm以下或100ppm以下，例如0.1~1000ppm、1~1000ppm、0.1~100ppm或1~100ppm。The Na ions in the above dispersion liquid are Na ions released from the layered compound (between the layers) when the Na ions existing between the layers of the layered silicate are ion-exchanged with quaternary ammonium ions (a). In this state, it will exist in large amounts in the dispersion liquid, but it will be discharged out of the system by the method explained below. In the dispersion liquid, in order to prevent the peeling layer material from re-stratifying, it is appropriate to set the concentration of Na ions to a low level. For example, the Na ion concentration in the dispersion liquid can be set to 1000 ppm or less or 100 ppm or less, such as 0.1 to 1000 ppm, 1 to 1000 ppm, 0.1 to 100 ppm, or 1 to 100 ppm.

上述四級銨離子從具有作為擴大層狀化合物的層間之剝離劑的角色來看，較佳具有大體積的有機基，另一方面，較佳為溶解性高。因此，本發明中，使用總碳原子數13~45、或13~23、或15~45、或15~25，且具有1~2個碳原子數10~20的烷基之四級銨離子(a)。The above-mentioned quaternary ammonium ion preferably has a large-volume organic group in view of its role as a release agent that expands the interlayers of the layered compound. On the other hand, it is preferred that the quaternary ammonium ion has high solubility. Therefore, in the present invention, a quaternary ammonium ion having a total carbon number of 13 to 45, or 13 to 23, or 15 to 45, or 15 to 25, and having 1 to 2 alkyl groups of 10 to 20 carbon atoms is used. (a).

作為如此的四級銨離子(a)，可舉出例如十六基三甲基銨離子、二癸基二甲基銨離子、二甲基雙十八基銨、月桂基三甲基銨離子等。特別適合可使用月桂基三甲基銨離子。作為該銨離子的相對離子，可舉出氯離子或溴離子。Examples of such quaternary ammonium ions (a) include hexadecyltrimethylammonium ion, didecyldimethylammonium ion, dimethyldisoctadecylammonium ion, lauryltrimethylammonium ion, etc. . Particularly suitable are lauryltrimethylammonium ions. Examples of counter ions to this ammonium ion include chloride ions and bromide ions.

上述四級銨離子(a)在分散液中的濃度為30質量%以下或10質量%以下，可設為0.001~30質量%、0.001~20質量%或0.001~10質量%。The concentration of the above-mentioned quaternary ammonium ions (a) in the dispersion liquid is 30 mass% or less or 10 mass% or less, and can be set to 0.001 to 30 mass%, 0.001 to 20 mass%, or 0.001 to 10 mass%.

在由疏水基與親水基所構成的界面活性劑之中，上述具有銨離子的陰離子界面活性劑(b)係親水基部分為以陰離子與銨離子之成對所構成的化合物，基本上宜使用不含鈉離子或鉀離子的化合物。又，上述具有銨離子的陰離子界面活性劑(b)例如較佳為包含碳原子數為8至12左右的之比較長鏈的烷基作為疏水基之化合物，又較佳為不含芳香環的化合物。Among the surfactants composed of a hydrophobic group and a hydrophilic group, the above-mentioned anionic surfactant having ammonium ions (b) is a compound in which the hydrophilic group part is composed of a pair of anion and ammonium ion. Basically, it is preferable to use Compounds that do not contain sodium or potassium ions. In addition, the above-mentioned anionic surfactant (b) having ammonium ions is preferably a compound containing a relatively long-chain alkyl group with about 8 to 12 carbon atoms as a hydrophobic group, and it is also preferably a compound that does not contain an aromatic ring. compound.

作為上述具有銨離子的陰離子界面活性劑(b)，可舉出例如辛酸銨、癸酸銨、月桂酸銨、硬脂酸銨、己烷磺酸銨、辛烷磺酸銨、癸烷磺酸銨、十二烷磺酸銨、月桂基硫酸銨(十二基硫酸銨)、肉荳蔻基硫酸銨、月桂基磷酸銨、三聚磷酸銨等。其中，較佳可使用月桂基硫酸銨(十二基硫酸銨)。Examples of the anionic surfactant (b) having ammonium ions include ammonium octanoate, ammonium caprate, ammonium laurate, ammonium stearate, ammonium hexane sulfonate, ammonium octane sulfonate, and decane sulfonic acid. Ammonium, ammonium lauryl sulfonate, ammonium lauryl sulfate (ammonium dodecyl sulfate), ammonium myristyl sulfate, ammonium lauryl phosphate, ammonium tripolyphosphate, etc. Among them, ammonium lauryl sulfate (ammonium dodecyl sulfate) is preferably used.

上述具有銨離子的陰離子界面活性劑(b)在分散液中的濃度可設為0.01~20質量%。The concentration of the above-mentioned anionic surfactant (b) having ammonium ions in the dispersion liquid can be set to 0.01 to 20 mass%.

本發明中，必須使用具有1~2個碳原子數10~20的烷基之四級銨離子(a)與具有銨離子的陰離子界面活性劑(b)。不添加具有銨離子的陰離子界面活性劑(b)時，使用具有鈉離子代替銨離子的陰離子界面活性劑或具有鉀離子的陰離子界面活性劑時，層間剝離不進行，或者由於已層間剝離的剝離層物質容易再度形成層狀構造，故可能發生分散液的透明性降低(即，分散液的吸光度不降低)之事態。又，於層間剝離不進行之情況，液中物質(例如液中離子)分離用的迷路化變不充分，亦可能發生充分的液中物質(例如液中離子)分離性不展現之事態。In the present invention, it is necessary to use a quaternary ammonium ion (a) having 1 to 2 alkyl groups with 10 to 20 carbon atoms and an anionic surfactant (b) having ammonium ions. When the anionic surfactant (b) containing ammonium ions is not added, when an anionic surfactant containing sodium ions is used instead of ammonium ions or an anionic surfactant containing potassium ions is used, interlayer delamination does not proceed, or delamination occurs due to interlayer delamination. Since the layered substance easily forms a layered structure again, the transparency of the dispersion may decrease (that is, the absorbance of the dispersion may not decrease). Furthermore, when interlayer peeling does not proceed, the labyrinth transformation for separating substances in the liquid (eg, ions in the liquid) becomes insufficient, and a situation may arise in which sufficient separability of substances in the liquid (eg, ions in the liquid) is not demonstrated.

本發明之分散液係以透明性高作為特徵，例如於板狀粒子的濃度為0.1質量%的分散液、光徑長度1cm、波長620nm之條件下，其吸光度為0.1以下，尤其可設為0.015以下。 層狀化合物通常可以板狀粒子(A)的濃度為30質量%以下之濃度範圍的分散液進行製造。 The dispersion liquid of the present invention is characterized by high transparency. For example, under the conditions of a dispersion liquid with a plate-shaped particle concentration of 0.1% by mass, an optical path length of 1 cm, and a wavelength of 620 nm, the absorbance is 0.1 or less, especially 0.015. the following. The layered compound can usually be produced from a dispersion in which the concentration of the plate-shaped particles (A) is in a concentration range of 30% by mass or less.

又，本發明之分散液可將水等之水性媒體作為板狀粒子(A)的分散介質(液狀媒體)，可設為有機溶劑，亦可設為水與有機溶劑的混合系統。於製造本發明的分散液之際，可將水性媒體予以溶劑置換成為有機溶劑。溶劑置換可藉由蒸發法或超過濾法進行。In addition, the dispersion of the present invention may use an aqueous medium such as water as the dispersion medium (liquid medium) of the plate-shaped particles (A), may be an organic solvent, or may be a mixed system of water and an organic solvent. When producing the dispersion of the present invention, the aqueous medium can be replaced with an organic solvent by the solvent. Solvent replacement can be performed by evaporation or ultrafiltration.

作為上述有機溶劑，可舉出甲醇、乙醇、正丙醇、異丙醇、丁醇、二丙酮醇、丙二醇、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丁基醚、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、丙二醇單丁基醚乙酸酯、甲苯、二甲苯、甲基乙基酮、環戊酮、環己酮、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲酯、丙酮酸甲酯、丙酮酸乙酯、乙二醇、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丙基醚乙酸酯、乙二醇單丁基醚乙酸酯、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丙基醚、二乙二醇二丁基醚、丙二醇二甲基醚、丙二醇二乙基醚、丙二醇二丙基醚、丙二醇二丁基醚、乳酸乙酯、乳酸丙酯、乳酸異丙酯、乳酸丁酯、乳酸異丁酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸異丙酯、甲酸丁酯、甲酸異丁酯、甲酸戊酯、甲酸異戊酯、乙酸甲酯、乙酸乙酯、乙酸戊酯、乙酸異戊酯、乙酸己酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸異丙酯、丙酸丁酯、丙酸異丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸異丙酯、丁酸丁酯、丁酸異丁酯、3-甲氧基-2-甲基丙酸甲酯、2-羥基-3-甲基丁酸甲酯、甲氧基乙酸乙酯、3-甲氧基丁基乙酸酯、3-甲氧基丙基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、3-甲基-3-甲氧基丁基丁酸酯、乙醯乙酸甲酯、甲基丙基酮、甲基丁基酮、2-庚酮、3-庚酮、4-庚酮、N,N-二甲基甲醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、4-甲基-2-戊醇及γ-丁內酯等。此等溶劑可單獨或以二種以上之組合使用。Examples of the organic solvent include methanol, ethanol, n-propanol, isopropyl alcohol, butanol, diacetone alcohol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and propylene glycol monomethyl ether. ethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexane Ketone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxyethyl acetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol Alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate , butyl lactate, isobutyl formate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, acetic acid Ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, butyric acid Methyl ester, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, methyl 3-methoxy-2-methylpropionate, 2-hydroxy-3 -Methyl methylbutyrate, ethyl methoxyacetate, 3-methoxybutylacetate, 3-methoxypropylacetate, 3-methyl-3-methoxybutylacetate acid ester, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, methyl acetoacetate, methylpropyl ketone, methylbutyl base ketone, 2-heptanone, 3-heptanone, 4-heptanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N- Methyl-2-pyrrolidone, 4-methyl-2-pentanol and γ-butyrolactone, etc. These solvents can be used alone or in combination of two or more.

本發明之液中物質分離膜可為包含使層狀化合物之層間剝離所造成的剝離層物質(板狀粒子(A))之層複數積層而成的複層體之複合膜的形狀。所積層的層可為相同的剝離層物質之層，也可為其他的剝離層物質之層。 例如，可舉出一種複合膜，其包含於艾萊石等之八矽酸鹽材料的剝離層物質的層，積層有氧化石墨烯的層之積層體。 於包含複層體的複合膜之形狀的情況，各層所含有的層狀化合物(或剝離層物質)之含量，將最下層所含有的板狀粒子(A)作為1時，以質量比表示為1：0.01至1：10，較佳為1：0.05至1：5，更佳為1：0.1至1：1。 The liquid substance separation membrane of the present invention may be in the shape of a composite membrane including a multilayer body in which a plurality of layers of exfoliated layer substances (plate-shaped particles (A)) are laminated by exfoliation of layered compounds. The laminated layer may be a layer of the same peeling layer material, or may be a layer of another peeling layer material. For example, there is a composite film including a laminate in which a layer of a peeling material of an octa-silicate material such as islaite and a layer of graphene oxide are laminated. In the case of the shape of a composite film including a multi-layered body, the content of the layered compound (or peeling layer substance) contained in each layer is expressed as a mass ratio when the plate-shaped particles (A) contained in the lowermost layer are taken as 1 1:0.01 to 1:10, preferably 1:0.05 to 1:5, more preferably 1:0.1 to 1:1.

本發明包含下述(i)步驟~(vi)步驟： (i)步驟：將矽酸化合物水溶液在90~150℃之溫度下水熱處理後，將靜置所得之層狀化合物進行分離並水洗，將所得之濕式凝膠添加至水中，製造層狀化合物的水性分散液之步驟； (ii)步驟：於(i)步驟所得之水性分散液中，添加四級銨離子(a)，在40~100℃下進行加熱12~48小時之步驟，該四級銨離子(a)成為層狀化合物的離子交換容量之等倍~三倍量，總碳原子數15~45，且具有1~2個碳原子數10~20的烷基； (iii)步驟：於(ii)步驟所得之液中添加純水，以液中的鈉離子濃度成為100ppm以下之方式，將鈉離子含有液去除到系外之步驟； (iv)步驟：使(iii)步驟所含有的濕式凝膠分散於濃度為0.01~1質量%的具有銨離子的陰離子界面活性劑(b)水溶液中後，進一步添加氨而將液中的pH調至9.0~12.0之步驟； (v)步驟：將(iv)步驟所得之液在40~90℃下進行加熱12~48小時，得到板狀粒子(A)的分散液之步驟； (vi)步驟：在基材(B)表面上，使用(v)步驟所得之板狀粒子(A)的分散液來製造液中物質分離膜之步驟。 The present invention includes the following steps (i) to (vi): (i) Step: After hydrothermal treatment of the silicic acid compound aqueous solution at a temperature of 90 to 150°C, the layered compound obtained by standing is separated and washed with water, and the obtained wet gel is added to water to produce a layered compound. Aqueous dispersion steps; Step (ii): Add quaternary ammonium ions (a) to the aqueous dispersion obtained in step (i), and heat at 40 to 100°C for 12 to 48 hours. The quaternary ammonium ions (a) become The layered compound has equal to three times the ion exchange capacity, has a total carbon number of 15 to 45, and has 1 to 2 alkyl groups with 10 to 20 carbon atoms; (iii) Step: Add pure water to the liquid obtained in step (ii), and remove the sodium ion-containing liquid out of the system so that the sodium ion concentration in the liquid becomes 100 ppm or less; Step (iv): After dispersing the wet gel contained in step (iii) in an aqueous solution of the anionic surfactant (b) containing ammonium ions at a concentration of 0.01 to 1% by mass, ammonia is further added to remove the ammonia in the solution. Steps to adjust pH to 9.0~12.0; (v) step: heating the liquid obtained in step (iv) at 40 to 90°C for 12 to 48 hours to obtain a dispersion of plate-shaped particles (A); (vi) Step: A step of producing a liquid substance separation membrane on the surface of the base material (B) using the dispersion of the plate-shaped particles (A) obtained in the (v) step.

關於上述(i)步驟，於此例示艾萊石作為所用的層狀化合物進行說明。艾萊石為不存在於天然界的層狀化合物，可藉由例如將矽酸化合物水溶液進行90~150℃的水熱反應而合成。作為矽酸化合物，可舉出矽酸鈉、矽酸鉀等之矽酸鹽。作為上述矽酸化合物水溶液，較佳是SiO 2/M 2O莫耳比為3.5~4.0(其中，M表示Na、K)、矽酸化合物的濃度為10~30質量%左右的矽酸鈉水溶液。水熱條件為90~150℃，特佳為90~130℃，藉由1日~24日或1日~12日的靜置加熱，可合成艾萊石。 Regarding the above-mentioned step (i), allite is exemplified as the layered compound used and explained. Islay is a layered compound that does not exist in nature and can be synthesized by, for example, subjecting an aqueous solution of a silicic acid compound to a hydrothermal reaction at 90 to 150°C. Examples of silicic acid compounds include silicates such as sodium silicate and potassium silicate. As the silicic acid compound aqueous solution, a sodium silicate aqueous solution with a SiO 2 /M 2 O molar ratio of 3.5 to 4.0 (where M represents Na and K) and a silicic acid compound concentration of about 10 to 30% by mass is preferred. . The hydrothermal conditions are 90~150℃, and the optimal temperature is 90~130℃. Islay stone can be synthesized by standing and heating for 1 to 24 days or 1 to 12 days.

將藉由水熱反應而得的固體物質予以分離，水洗、乾燥後可回收艾萊石。為了使層間剝離或分散成為容易，於將經由水熱反應所得的固體物質進行分離、水洗後，亦可不經過乾燥，作為懸浮在水中的水性漿體而回收。水熱反應中為了使反應系統成為均勻，亦可在反應初期進行攪拌，但為了使艾萊石的粒子成長，較佳為靜置加熱。 微細的艾萊石係可藉由將艾萊石本身作為微細的種晶(種子粒子)，添加至矽酸鈉水溶液中而合成。 The solid material obtained by the hydrothermal reaction is separated, washed with water and dried, and the islaite can be recovered. In order to facilitate interlayer delamination or dispersion, the solid material obtained through the hydrothermal reaction may be separated and washed with water, and may be recovered as an aqueous slurry suspended in water without drying. In the hydrothermal reaction, in order to make the reaction system uniform, stirring may be carried out in the early stage of the reaction. However, in order to grow the particles of islayite, it is preferable to stand and heat. Fine islaite can be synthesized by adding islaite itself as fine seed crystals (seed particles) to an aqueous sodium silicate solution.

(i)步驟之層狀化合物係為了上述微細的艾萊石之合成，作為較佳的態樣，可將作為原材料的層狀物質進行粉碎，將此經粉碎的層狀物質作為種子粒子添加至矽酸鹽水溶液，在90~130℃下進行6~72小時的水熱處理，使用所生成的層狀化合物。此等層狀化合物係與層狀物質不同，成為微細的層狀化合物。再者，藉由將此微細的層狀化合物之濃度調整至30質量%以下，可製造層狀化合物的水性分散液。The layered compound in step (i) is for the synthesis of the above-mentioned fine islaite. As a preferred embodiment, the layered material as the raw material can be pulverized, and the pulverized layered material can be added as seed particles. The silicate aqueous solution is hydrothermally treated at 90 to 130°C for 6 to 72 hours, and the resulting layered compound is used. These layered compounds are different from layered substances and become fine layered compounds. Furthermore, by adjusting the concentration of the fine layered compound to 30% by mass or less, an aqueous dispersion of the layered compound can be produced.

又，於上述水熱處理之後，從水熱反應的媒體去除未反應的矽酸鈉，將靜置而得的層狀化合物進行分離、水洗，將所得之濕式凝膠添加至水中，使分散成為30質量%以下之濃度，亦可得到(i)步驟之層狀化合物的水性分散液。In addition, after the above hydrothermal treatment, unreacted sodium silicate is removed from the hydrothermal reaction medium, the layered compound obtained by standing is separated and washed with water, and the obtained wet gel is added to water to disperse it into At a concentration of 30% by mass or less, an aqueous dispersion of the layered compound in step (i) can also be obtained.

微細的層狀化合物(尤其艾萊石)，具體而言可藉由將上述矽酸鹽水溶液，或於上述矽酸鹽水溶液中，添加有未粉碎或粉碎的層狀物質作為種晶(種子粒子)之懸浮液，於90~150℃，尤其90~130℃下，1日~24日，尤其110℃下1日~12日右的靜置狀態之水熱反應而獲得。於製作微細的層狀化合物時添加於矽酸鹽水溶液中種晶(種子粒子)，係在粒徑並無限制，相對於矽酸鹽的質量，較佳為以0.1~10質量%、或0.1~5質量%、或0.1~2質量%之範圍添加。Fine layered compounds (especially islaite) can be produced by adding the above-mentioned silicate aqueous solution, or adding unpulverized or pulverized layered substances as seed crystals (seed particles) to the above-mentioned silicate aqueous solution. ) suspension is obtained by hydrothermal reaction in a standing state at 90~150°C, especially 90~130°C, for 1 to 24 days, especially 110°C for 1 to 12 days. When producing fine layered compounds, seed crystals (seed particles) are added to the silicate aqueous solution. The particle size is not limited, but it is preferably 0.1 to 10 mass %, or 0.1, relative to the mass of the silicate. ~5% by mass, or 0.1~2% by mass.

作為種晶(種子粒子)添加的經粉碎之層狀物質，較佳其動態光散射法所測得的粒徑為30~60nm，其以[(2θ=6.9~8.4°的繞射峰之積分強度的總和)/(2θ=5~40°的繞射峰之積分強度的總和)]×100表示的藉由粉末X射線繞射所測得的結晶化度為5~15%。 添加種晶(種子粒子)，藉由水熱反應而得的(微細的)層狀化合物(尤其艾萊石)之粒徑為平均長徑100nm~100000 nm、(最大長徑/正交於最大長徑的寬度)=1.0~10.0、正交於最大長徑(nm)的寬度(nm)為平均50nm~10000nm、50nm~ 5000nm、或50nm~3000nm。上述平均長徑(nm)、正交於最大長徑(nm)的寬度(nm)可藉由穿透型電子顯微鏡觀察進行測定。 又，上述微細的層狀化合物之動態光散射法所測得的平均粒徑可設為10nm~500000nm、20nm~300000nm、100nm~10000nm、或200nm~5000nm。 The pulverized layered material added as seed crystals (seed particles) preferably has a particle size of 30 to 60 nm as measured by dynamic light scattering, and the integrated intensity of the diffraction peak of [(2θ=6.9 to 8.4° The degree of crystallization measured by powder X-ray diffraction expressed by ×100 is 5 to 15%. The particle diameter of the (fine) layered compound (especially isletite) obtained by adding seed crystals (seed particles) through hydrothermal reaction is an average long diameter of 100 nm ~ 100000 nm, (maximum long diameter/orthogonal to the maximum Width of the major axis) = 1.0~10.0, and the width (nm) orthogonal to the maximum major axis (nm) is an average of 50nm~10000nm, 50nm~5000nm, or 50nm~3000nm. The above-mentioned average major diameter (nm) and the width (nm) orthogonal to the maximum major diameter (nm) can be measured by observation with a transmission electron microscope. In addition, the average particle size measured by the dynamic light scattering method of the above-mentioned fine layered compound can be 10 nm to 500000 nm, 20 nm to 300000 nm, 100 nm to 10000 nm, or 200 nm to 5000 nm.

種晶(種子粒子)(此處為艾萊石)係可藉由將作為原材料的層狀物質(此處為艾萊石)之粉碎而獲得。粉碎可藉由例如球磨粉碎進行。 粉碎可使用例如行星型球磨粉碎裝置進行。行星球磨係可藉由將裝有硬質球(例如氧化鋯球)與艾萊石的容器，使其自轉及公轉而進行粉碎。該行星球磨粉碎係可進行二階段的粉碎，先進行預備粉碎，然後進一步進行微粉碎，而可得到作為種晶(種子粒子)的艾萊石。粉碎可為濕式，也可為乾式，較佳為使用乾式粉碎。 用於上述種晶(種子粒子)的艾萊石亦可使用另外取得的艾萊石，可添加前批次的一部分，或使用反應容器中殘存者，連續地進行批次製造。 Seed crystals (seed particles) (herein, islaite) can be obtained by pulverizing a layered material (herein, islaite) as a raw material. Grinding can be performed by, for example, ball milling. Grinding can be performed using, for example, a planetary ball mill grinding device. The planetary ball mill system can grind a container filled with hard balls (such as zirconia balls) and islaite, causing it to rotate and revolve. This planetary ball mill pulverizing system can carry out two-stage pulverization. First, preliminary pulverization is performed, and then further fine pulverization is performed to obtain islet as seed crystals (seed particles). Grinding may be wet or dry, and dry grinding is preferred. The islaite used for the above-mentioned seed crystals (seed particles) can also be obtained separately, and a part of the previous batch can be added, or what remains in the reaction vessel can be used, and batch production can be performed continuously.

上述(ii)步驟係於(i)步驟所得之層狀化合物的水性分散液中，以成為層狀化合物的離子交換容量的等倍~20倍量之量的比例，添加總碳原子數為15~45且具有1~2個碳原子數10~20的烷基之四級銨離子(a)，在40~100℃下進行1~100小時的加熱之步驟。The above-mentioned step (ii) is to add a total carbon number of 15 to the aqueous dispersion of the layered compound obtained in step (i) in an amount equal to 20 times the ion exchange capacity of the layered compound. The quaternary ammonium ion (a) of ~45 and having 1 to 2 alkyl groups with 10 to 20 carbon atoms is heated at 40 to 100°C for 1 to 100 hours.

上述(iii)步驟係於(ii)步驟所得之液中添加純水，以該液中的鈉離子濃度成為1000ppm以下之方式，將鈉離子含有液去除到系外之步驟。於前述(ii)步驟中，存在於層狀化合物之層間的鈉離子係被置換成四級銨離子，藉由將游離至液中的鈉離子去除到系外，可防止鈉離子所造成的再置換，層間被四級銨離子擴張，而將層狀化合物層間剝離。將鈉離子去除之方法可舉出超過濾法或傾析法、過濾器的固液分離法。The above step (iii) is a step in which pure water is added to the liquid obtained in step (ii) and the sodium ion-containing liquid is removed from the system so that the sodium ion concentration in the liquid becomes 1000 ppm or less. In the aforementioned step (ii), the sodium ions existing between the layers of the layered compound are replaced with quaternary ammonium ions. By removing the sodium ions freed into the liquid out of the system, the regeneration caused by the sodium ions can be prevented. Replacement, the layers are expanded by quaternary ammonium ions, and the layered compounds are peeled off. Examples of methods for removing sodium ions include ultrafiltration, decantation, and filter solid-liquid separation.

上述(iv)步驟係使(iii)步驟所得者含有的濕式凝膠分散於濃度為0.01~20質量%的具有銨離子的陰離子界面活性劑(b)水溶液中，然後進一步添加氨而將液中的pH調至9.0~12.0之步驟。藉由具有銨離子的陰離子界面活性劑(b)之添加，被覆因層間剝離所產生剝離層物質，或陰離子界面活性劑(b)中介存在於該剝離層物質彼此，可抑制因後續(v)步驟發生的因層間剝離而產生的剝離層物質再度回到層狀化合物之形態。 此(iv)步驟係為了充分進行具有銨離子的陰離子界面活性劑(b)向剝離層物質(此處為艾萊石)表面之被覆，可在超音波照射下或攪拌下進行。 The above-mentioned step (iv) is to disperse the wet gel contained in the resultant of the step (iii) in an aqueous solution of the anionic surfactant (b) containing ammonium ions at a concentration of 0.01 to 20% by mass, and then further add ammonia to dissolve the solution. Steps to adjust the pH in the solution to 9.0~12.0. By adding the anionic surfactant (b) containing ammonium ions, the peeling layer substances produced due to interlayer peeling are covered, or the anionic surfactant (b) is interposed between the peeling layer substances, and the subsequent (v) can be suppressed. The peeling layer material produced by interlayer peeling in the step returns to the form of a layered compound again. This step (iv) is to fully coat the surface of the exfoliation layer material (herein, islaite) with the anionic surfactant (b) containing ammonium ions, and can be performed under ultrasonic irradiation or stirring.

上述(v)步驟係將(iv)步驟所得之液在40~100℃下進行1~100小時加熱之步驟。 此處所得之板狀粒子(A)具有平均厚度0.7~100nm、平均長徑50~10,000nm及(最大長徑/正交於最大長徑的寬度)=1.0~10.0，為層狀化合物之層間剝離所造成的剝離層物質之板狀粒子(A)，於水性分散液的板狀粒子(A)之雷射繞射式粒徑分布中，90%累計粒徑值為該粒徑分布的平均值之1.5~10倍、或1.5~6.0倍、或1.5~5.0倍、或1.5~3.0倍。板狀粒子(A)之雷射繞射法所測得的粒徑範圍為0.1μm~10μm，粒徑分布之廣度窄，凝聚體不存在。 又，水性分散液之動態光散射法所測得的平均粒徑為10~10,000nm，上述(a)與(b)一起係相對於(A)而言在0.01~3.0質量%之範圍的板狀粒子(A)或其分散液。 The above-mentioned step (v) is a step of heating the liquid obtained in step (iv) at 40-100°C for 1-100 hours. The plate-shaped particles (A) obtained here have an average thickness of 0.7~100nm, an average long diameter of 50~10,000nm, and (maximum long diameter/width orthogonal to the maximum long diameter) = 1.0~10.0, and are between layers of a layered compound. In the laser diffraction particle size distribution of the plate-shaped particles (A) of the peeling layer material caused by peeling in the aqueous dispersion, the 90% cumulative particle size value is the average of the particle size distribution The value is 1.5~10 times, or 1.5~6.0 times, or 1.5~5.0 times, or 1.5~3.0 times. The particle size range of the plate-shaped particles (A) measured by the laser diffraction method is 0.1 μm ~ 10 μm, the breadth of the particle size distribution is narrow, and there is no agglomerate. In addition, the average particle diameter measured by the dynamic light scattering method of the aqueous dispersion is 10 to 10,000 nm, and the above (a) and (b) are in the range of 0.01 to 3.0 mass % with respect to (A) shaped particles (A) or its dispersion.

於本發明之液中物質分離膜成形體之製造方法中，可在(v)步驟與下述(vi)步驟之間，進一步追加(v-0)步驟，亦即將(v)步驟所得之包含板狀粒子(A)的分散液，使總碳原子數15~45且具有1~2個碳原子數10~20的烷基之四級銨離子(a)與具有銨離子的陰離子界面活性劑(b)之含量一起相對於(A)而言減低至0.01~15.0質量%之範圍而得之板狀粒子(A)，在基材(B)上製膜之步驟。In the manufacturing method of the liquid substance separation membrane molded body of the present invention, a step (v-0) can be further added between the step (v) and the following step (vi), that is, the step obtained in the step (v) includes A dispersion of plate-like particles (A) containing quaternary ammonium ions (a) having a total carbon number of 15 to 45 and having 1 to 2 alkyl groups of 10 to 20 carbon atoms, and an anionic surfactant having ammonium ions. The step of forming a film on the base material (B) using plate-like particles (A) obtained by reducing the content of (b) to a range of 0.01 to 15.0% by mass relative to (A).

作為使上述(a)與(b)之含量一起相對於(A)而言減低至0.01~15.0質量%之範圍之方法，可舉出離心處理或超過濾處理。As a method of reducing the contents of the above-mentioned (a) and (b) together to the range of 0.01 to 15.0 mass % with respect to (A), centrifugation or ultrafiltration can be cited.

於本發明之液中物質分離膜成形體之製造方法中，可在(v)步驟與下述(vi)步驟之間，進一步追加(v-1)步驟； (v-1)步驟：對於板狀粒子(A)的分散液，以20000~ 60000G進行超離心處理，得到使總碳原子數15~45且具有1~2個碳原子數10~20的烷基之四級銨離子(a)與具有銨離子的陰離子界面活性劑(b)之含量一起相對於(A)而言減低至0.01~15.0質量%之範圍的板狀粒子(A)的分散液之步驟。 In the manufacturing method of the liquid substance separation membrane molded article of the present invention, a step (v-1) may be further added between the step (v) and the following step (vi); (v-1) Step: The dispersion of the plate-shaped particles (A) is subjected to ultracentrifugation at 20,000 to 60,000G to obtain an alkane having a total carbon number of 15 to 45 and 1 to 2 carbon atoms of 10 to 20. A dispersion of plate-like particles (A) in which the content of quaternary ammonium ions (a) and the anionic surfactant (b) containing ammonium ions is reduced to the range of 0.01 to 15.0 mass % relative to (A) steps.

使用藉由超離心處理減低界面活性劑後之板狀粒子(A)的分散液與基材(B)，可成為一種包含液中物質分離膜與支撐該液中物質分離膜的基材(B)之液中物質分離膜成形體，其中液中物質分離膜包含總碳原子數15~45且具有1~2個碳原子數10~20的烷基之四級銨離子(a)與具有銨離子的陰離子界面活性劑(b)之含量一起相對於(A)而言在0.01~15.0質量%或0.01~5.0質量%之範圍的板狀粒子(A)。Using a dispersion of plate-shaped particles (A) in which the surfactant has been reduced by ultracentrifugation and a base material (B), a base material (B) including a liquid substance separation membrane and a liquid substance separation membrane supporting the liquid substance separation membrane can be used. ) is a liquid substance separation membrane formed body, wherein the liquid substance separation membrane contains a quaternary ammonium ion (a) with a total carbon number of 15 to 45 and 1 to 2 alkyl groups with 10 to 20 carbon atoms and an ammonium ion. Plate-shaped particles (A) in which the content of the ionic anionic surfactant (b) is in the range of 0.01 to 15.0 mass % or 0.01 to 5.0 mass % relative to (A).

(vi)步驟為在基材(B)表面上，使用(v)步驟所得之板狀粒子(A)的分散液進行製膜之步驟。在(v)步驟與(vi)步驟之間，含有(v-0)或(v-1)步驟時，於(vi)步驟中代替(v)步驟所得之板狀粒子(A)的分散液，使用(v-0)或(v-1)步驟所得之板狀粒子(A)的分散液。The step (vi) is a step of forming a film on the surface of the base material (B) using the dispersion of the plate-shaped particles (A) obtained in the step (v). When the (v-0) or (v-1) step is included between the (v) step and the (vi) step, the dispersion of the plate-shaped particles (A) obtained in the (v) step is replaced in the (vi) step. , using the dispersion of the plate-shaped particles (A) obtained in the step (v-0) or (v-1).

在基材(B)表面上，將包含積層體的液中物質分離膜進行成膜時，製造上述(vi)步驟的液中物質分離膜之步驟包含：在基材(B)表面上，使用(v)步驟所得之板狀粒子(A)的分散液，形成板狀粒子(A)層之步驟，及在該層之上，使用層狀化合物之層間剝離所造成的剝離層物質之分散液，積剝離層層物質的層之步驟。 在(v)步驟與(vi)步驟之間包含(v-0)或(v-1)步驟時，於(vi)步驟中代替(v)步驟所得之板狀粒子(A)的分散液，使用(v-0)或(v-1)步驟所得之板狀粒子(A)的分散液。 作為層狀化合物之層間剝離所造成的剝離層物質的分散液，可使用上述(v)步驟、(v-0)或(v-1)所得之板狀粒子(A)的分散液，可使用市售的或以眾所周知的方法製造的包含上述層狀化合物之層間剝離所造成的剝離層物質的分散液。 作為積層的層，較佳可舉出使用氧化石墨烯的分散液之氧化石墨烯層。 When forming a liquid substance separation membrane including a laminate on the surface of the base material (B), the step of manufacturing the liquid substance separation membrane in the above step (vi) includes: on the surface of the base material (B), using (v) The dispersion of the plate-shaped particles (A) obtained in the step, the step of forming the layer of the plate-shaped particles (A), and the dispersion of a peeling layer substance on the layer using a layered compound. , the step of peeling off layers of substances. When the (v-0) or (v-1) step is included between the (v) step and the (vi) step, the dispersion of the plate-shaped particles (A) obtained in the (v) step is replaced in the (vi) step, The dispersion of the plate-shaped particles (A) obtained in the step (v-0) or (v-1) is used. As the dispersion of the exfoliated layer material caused by the interlayer delamination of the layered compound, the dispersion of the plate-shaped particles (A) obtained in the above (v) step, (v-0) or (v-1) can be used. A dispersion liquid containing a peeling layer substance caused by interlayer peeling of the above layered compound is commercially available or produced by a well-known method. Preferred layers to be laminated include a graphene oxide layer using a dispersion of graphene oxide.

將由積層體所成的膜進行成膜時，各層所含有的剝離層物質之含量為：將最下層所含有的板狀粒子(A)作為1時，以質量比表示為1：0.01至1：10，較佳為1：0.05至1：5，更佳為1：0.1至1：1。When forming a film from a laminated body, the content of the peeling layer substance contained in each layer is: When the plate-shaped particle (A) contained in the lowermost layer is taken as 1, the mass ratio is 1:0.01 to 1: 10, preferably 1:0.05 to 1:5, more preferably 1:0.1 to 1:1.

基材(B)可使用選自由纖維素、合成高分子及陶瓷所成之群組的至少1種多孔質基材。 作為纖維素，可舉出硝基纖維素、羧甲基纖維素或羥乙基纖維素等。 作為合成高分子，可舉出聚醚碸、聚碸、聚偏二氟乙烯、聚偏二氯乙烯、聚乙烯乙烯醇、聚乙烯醇、聚丙烯酸或聚甲基丙烯酸等。 作為陶瓷，可舉出二氧化矽、氧化鋁或莫來石等。 As the base material (B), at least one porous base material selected from the group consisting of cellulose, synthetic polymers, and ceramics can be used. Examples of cellulose include nitrocellulose, carboxymethylcellulose, hydroxyethylcellulose, and the like. Examples of synthetic polymers include polyether ether, polyethylene, polyvinylidene fluoride, polyvinylidene chloride, polyethylene vinyl alcohol, polyvinyl alcohol, polyacrylic acid or polymethacrylic acid. Examples of ceramics include silica, alumina, mullite, and the like.

使用包含板狀粒子(A)的分散液，將液中物質分離膜在基材(B)表面上製膜時，較佳為藉由抽吸過濾或加壓過濾進行。 基材(B)係成為支撐膜(支撐體)的材料，將基材(B)設置於過濾裝置，從其上部注入(v)步驟所得之板狀粒子(A)的分散液，進行抽吸過濾或加壓過濾。板狀粒子(A)的分散液較佳為在注入過濾裝置之前提高分散性，可進行例如0.1~1小時左右的超音波照射或攪拌等。亦可使用(v-0)或(v-1)步驟所得之板狀粒子(A)的分散液，同樣地製造液中物質分離膜。 液中物質分離膜包含複合膜時，使用(v)、(v-0)或(v-1)步驟所得之板狀粒子(A)的分散液，在基材(B)表面上形成板狀粒子(A)層後，若需要的話使其乾燥，從其上方注入包含剝離層物質的分散液，進行抽吸過濾或加壓過濾，可積剝離層層物質。剝離層物質的分散液較佳為在注入過濾裝置之前提高分散性，例如可進行0.1~1小時左右的超音波照射或攪拌等。 When a dispersion liquid containing plate-shaped particles (A) is used to form a separation membrane for substances in the liquid on the surface of the base material (B), it is preferably performed by suction filtration or pressure filtration. The base material (B) is a material that becomes a support film (support body). The base material (B) is placed in a filtration device, and the dispersion of the plate-shaped particles (A) obtained in step (v) is injected from the upper part and sucked. Filtration or pressure filtration. The dispersion of the plate-shaped particles (A) is preferably subjected to ultrasonic irradiation or stirring for about 0.1 to 1 hour to improve the dispersibility before being injected into the filter device. The dispersion of the plate-shaped particles (A) obtained in the step (v-0) or (v-1) can also be used to produce a substance separation membrane in the liquid in the same manner. When the liquid substance separation membrane includes a composite membrane, the dispersion of the plate-shaped particles (A) obtained in the step (v), (v-0) or (v-1) is used to form a plate-like shape on the surface of the base material (B) After the particles (A) are layered, they are dried if necessary, a dispersion containing the exfoliating layer material is injected from above, and suction filtration or pressure filtration is performed to accumulate the exfoliating layer material. The dispersion of the peeling layer substance is preferably irradiated with ultrasonic waves or stirred for about 0.1 to 1 hour before being injected into the filtration device to improve the dispersibility.

又，基材(B)為纖維素、聚醚碸、合成高分子等之有機系材料時，較佳為在純水中進行0.1~12小時左右的浸水而賦予親水性，設置於過濾裝置。 基材(B)係可在單面或兩面上製造包含板狀粒子(A)的液中物質(例如離子)分離膜。基材(B)為支撐體，基材(B)本身的膜厚可在數μm~數mm的膜厚任意地設定。可設定為例如1μm~10mm、10μm~1mm左右。 Moreover, when the base material (B) is an organic material such as cellulose, polyether ester, synthetic polymer, etc., it is preferably immersed in pure water for about 0.1 to 12 hours to impart hydrophilicity, and then installed in a filtering device. The base material (B) can be used to produce a liquid substance (for example, ion) separation membrane containing plate-shaped particles (A) on one side or both sides. The base material (B) is a support, and the film thickness of the base material (B) itself can be arbitrarily set to a film thickness of several μm to several mm. It can be set to approximately 1 μm to 10 mm, or 10 μm to 1 mm, for example.

在基材(B)表面上形成的發揮分離層之功能的液中物質分離膜，係該液中物質分離膜本身的膜厚可設定在以下之值。基材(B)表面上的液中物質(例如離子)分離膜的膜厚係在單面上，可設定在以下之值。液中物質分離膜中藉由積層板狀粒子(A)而產生的分子篩效果，為了有效地發揮功能，較佳為構成液中物質分離膜的板狀粒子(A)被複數層(例如2層以上)形成，可將膜厚設為例如1.5nm以上。液中物質分離膜的膜厚之下限值可設為例如1.5nm、40nm、50nm，另外膜厚之上限值可設為100nm、500nm、1μm、10μm。因此，膜厚可設定為例如1.5nm~ 10μm、40nm~1μm、50nm~500nm、1.5nm~100nm、1.5nm~500nm、50nm~10μm、50nm~1μm、50nm~100nm等。The film thickness of the liquid substance separation membrane that functions as a separation layer formed on the surface of the base material (B) can be set to the following values. The film thickness of the liquid substance (for example, ion) separation membrane on the surface of the base material (B) is on one side and can be set to the following value. In order to effectively exert the molecular sieve effect produced by stacking the plate-shaped particles (A) in the liquid substance separation membrane, it is preferable that the plate-shaped particles (A) constituting the liquid substance separation membrane are covered with a plurality of layers (for example, two layers). (above), the film thickness can be, for example, 1.5 nm or more. The lower limit of the film thickness of the liquid substance separation membrane can be set to, for example, 1.5 nm, 40 nm, or 50 nm, and the upper limit of the film thickness can be set to 100 nm, 500 nm, 1 μm, or 10 μm. Therefore, the film thickness can be set to, for example, 1.5 nm to 10 μm, 40 nm to 1 μm, 50 nm to 500 nm, 1.5 nm to 100 nm, 1.5 nm to 500 nm, 50 nm to 10 μm, 50 nm to 1 μm, 50 nm to 100 nm, and the like.

本發明中溶解物質(去除的物質或濃縮的物質)之溶劑為極性溶劑或無極性溶劑，可設為水性溶劑或有機溶劑。In the present invention, the solvent for dissolving substances (removed substances or concentrated substances) is a polar solvent or a non-polar solvent, and can be an aqueous solvent or an organic solvent.

本發明中包含物質的溶劑(水性溶劑或有機溶劑)之穿透速度可設為0.1~100L・m -2・hr -1・bar -1或5~25L・m -2・hr -1・bar -1。 本發明中包含被分離物質的溶劑(水性溶劑或有機溶劑)之物質去除率可設為15~99%、15~99%或80~99%。 The penetration speed of the solvent (aqueous solvent or organic solvent) containing substances in the present invention can be set to 0.1~100L・m -2・hr -1・bar -1 or 5~25L・m -2・hr -1・bar -1 . In the present invention, the substance removal rate of the solvent (aqueous solvent or organic solvent) containing the substance to be separated can be set to 15~99%, 15~99% or 80~99%.

又，被分離物質可設為溶劑(水性溶劑或有機溶劑)中的離子性化合物。 以下說明被分離物質為水性溶劑中的離子性化合物之情況。作為離子性化合物，可舉出至少具有磺酸離子或羧酸離子的有機化合物。 In addition, the substance to be separated may be an ionic compound in a solvent (aqueous solvent or organic solvent). The following explains the case where the substance to be separated is an ionic compound in an aqueous solvent. Examples of ionic compounds include organic compounds having at least sulfonate ions or carboxylate ions.

液中物質之分離，例如離子性物質之情況，從裝有包含水溶性離子性有機化合物的水性溶液之桶槽，使用泵注液到裝填有包括含有板狀粒子(A)的液中物質分離膜與支撐它的基材(B)之液中物質(離子)分離膜成形體之單元(cell)，而可分別分液成：通過液中物質(離子)分離膜而言減低水溶性離子性有機化合物的水性溶液，與不通過液中物質(離子)分離膜而將水溶性離子性有機化合物濃縮的水性溶液。因此，既是水性溶液中的水溶性離子性有機化合物之去除方法，也是水溶性離子性有機化合物之濃縮方法。Separation of substances in a liquid, such as the case of ionic substances, from a tank containing an aqueous solution containing a water-soluble ionic organic compound, using a pump to inject the liquid into a tank containing plate-shaped particles (A) The membrane and the base material (B) that supports it are the units (cells) of the liquid substance (ion) separation membrane formed body, and can be separated into liquids: reducing the water-soluble ionicity through the liquid substance (ion) separation membrane An aqueous solution of an organic compound, and an aqueous solution in which a water-soluble ionic organic compound is concentrated without passing through a separation membrane for substances (ions) in the liquid. Therefore, it is not only a method for removing water-soluble ionic organic compounds in an aqueous solution, but also a method for concentrating water-soluble ionic organic compounds.

雖然為典型例，但有效膜面積為2.54×10 -4m 2、泵壓為1.0~5.0大氣壓時，於液體之流量為1.0ml/分鐘之條件下，可將水溶性離子性有機化合物濃縮10ppm。即使上述泵壓力為5~15大氣壓，也水性溶劑穿透速度為6~8L・m -2・hr -1・bar -1，可經歷13小時實施穩定的透水。膜面積為9.6×10 -4m 2時，膜厚為100nm，當時的板狀粒子(A)係在基材(B)上為1mg的積層量。 Although this is a typical example, when the effective membrane area is 2.54×10 -4 m 2 , the pump pressure is 1.0~5.0 atmospheres, and the liquid flow rate is 1.0ml/minute, water-soluble ionic organic compounds can be concentrated to 10ppm. . Even if the above-mentioned pump pressure is 5 to 15 atmospheres, the aqueous solvent penetration rate is 6 to 8L·m -2 ·hr -1 ·bar -1 , and stable water permeability can be achieved for 13 hours. When the film area is 9.6×10 -4 m 2 , the film thickness is 100 nm, and the plate-shaped particles (A) at that time are laminated on the base material (B) in an amount of 1 mg.

作為上述水溶性離子性有機化合物，可舉出至少具有磺酸離子或羧酸離子的有機化合物，此等可具有染料結構。 作為具有磺酸鹽結構的化合物，可舉出伊凡氏藍、酸性紅265，此等表示以下之結構。 Examples of the water-soluble ionic organic compound include organic compounds having at least a sulfonate ion or a carboxylate ion, and these may have a dye structure. Examples of compounds having a sulfonate structure include Evans blue and Acid Red 265, which represent the following structures.

於上述條件下伊凡氏藍得到96%的阻止率，酸性紅265得到15~40%的阻止率。Under the above conditions, Evan's Blue obtained a blocking rate of 96%, and Acid Red 265 obtained a blocking rate of 15~40%.

本發明中可得到一種液中物質分離膜成形體，其能從包含分子量不同的2種以上之溶質分子的溶液中濃縮出1種溶質分子。例如於2種類的分子量不同的分子作為溶質溶存之溶液中，藉由阻止分子量大的分子通過膜，使分子量小的分子通過膜，可得到能濃縮分子量大的分子之液中物質分離膜成形體。例如使用具有1.3倍以上或1.5倍以上的分子量差之2種類以上的溶質分子，可將彼等之中最大分子量的溶質分子進行濃縮。 典型上，一種液中物質分離膜成形體，其係包含液中物質分離膜與支撐該液中物質分離膜的基材(B)之液中物質分離膜成形體，該液中物質分離膜包含總碳原子數15~45且具有1~2個碳原子數10~20的烷基之四級銨離子(a)與具有銨離子的陰離子界面活性劑(b)，且包含具有平均厚度0.7~100nm、平均長徑50~10,000nm及(最大長徑/正交於最大長徑的寬度)=1.0~10.0，且為層狀化合物之層間剝離所造成的剝離層物質之板狀粒子(A)，其中 板狀粒子(A)為包含上述層狀化合物之層間剝離用的上述(a)與(b)之板狀粒子(A)的水性分散液之形態，該水性分散液的板狀粒子(A)之雷射繞射式粒徑分布中90%累計粒徑值為該粒徑分布的平均值之1.5~10倍， 板狀粒子(A)為包含上述層狀化合物之層間剝離用的上述(a)與(b)之板狀粒子(A)的水性分散液之形態，該水性分散液之動態光散射法所測得的平均粒徑為10~10000 nm，使用上述(a)與(b)一起相對於(A)而言在0.01~15.0質量%之範圍的包含板狀粒子(A)的上述液中物質分離膜成形體，從液中的2種以上的溶質分子中濃縮1種溶質分子。 [實施例] According to the present invention, a liquid substance separation membrane formed body can be obtained, which can concentrate one solute molecule from a solution containing two or more solute molecules with different molecular weights. For example, in a solution in which two types of molecules with different molecular weights are dissolved as solutes, by preventing molecules with a large molecular weight from passing through the membrane and allowing molecules with a small molecular weight to pass through the membrane, a substance separation membrane molded body in the liquid that can concentrate the molecules with a large molecular weight can be obtained. . For example, by using two or more types of solute molecules having a molecular weight difference of 1.3 times or more or 1.5 times or more, the solute molecule with the largest molecular weight among them can be concentrated. Typically, a liquid substance separation membrane formed body is a liquid substance separation membrane formed body including a liquid substance separation membrane and a substrate (B) supporting the liquid substance separation membrane, and the liquid substance separation membrane includes Quaternary ammonium ions (a) with a total carbon number of 15 to 45 and 1 to 2 alkyl groups with 10 to 20 carbon atoms and an anionic surfactant (b) with ammonium ions, and include an average thickness of 0.7~ 100nm, average long diameter 50~10,000nm and (maximum long diameter/width orthogonal to the maximum long diameter) = 1.0~10.0, and are plate-shaped particles of exfoliation layer material caused by interlayer peeling of layered compounds (A) ,in The plate-shaped particles (A) are in the form of an aqueous dispersion containing the plate-shaped particles (A) of the above-mentioned (a) and (b) for interlayer peeling of the above-mentioned layered compound. The plate-shaped particles (A) of the aqueous dispersion The 90% cumulative particle size value in the laser diffraction particle size distribution is 1.5 to 10 times the average value of the particle size distribution. The plate-shaped particles (A) are in the form of an aqueous dispersion of the plate-shaped particles (A) containing the above-mentioned (a) and (b) for interlayer peeling of the above-mentioned layered compound, and the aqueous dispersion is measured by the dynamic light scattering method. The obtained average particle diameter is 10 to 10000 nm, and the above-mentioned liquid substances containing the plate-shaped particles (A) are separated using the above-mentioned (a) and (b) in the range of 0.01 to 15.0 mass % with respect to (A). The membrane formed body concentrates one solute molecule from two or more solute molecules in a liquid. [Example]

(評價方法) 動態光散射法：以SPECTRIS股份有限公司製商品名Zetasizer Nano S進行測定。 雷射繞射式粒度分布測定：以島津製作所製SALD-7500進行測定。 穿透型電子顯微鏡：使用日本電子股份有限公司製商品名JEM-1010。 平均長徑：從使用穿透型電子顯微鏡日本電子股份有限公司製JEM-1010拍攝的粒子影像200個，算出平均長徑與最大長徑/正交於最大長徑的寬度。 紫外可見近紅外分光光度計：使用日本分光股份有限公司製V630。 X射線繞射：使用Buruker製D2 PHASER。 (分離膜之透水性評價方法) 依循S. Kawada et al., Colloids and Surfaces A: Physicochem. Eng. Aspects, 2014, vol.451, p.33-37所記載之方法，藉由交叉流(cross-flow)式的透水裝置進行評價。以超純水製造裝置(「milli-Q(註冊商標)Direct Merck公司製)純化，將所得之超純水在一次側(供給側)壓力0.1~0.5 MPa之條件下供給至透水裝置，將每單位時間的透水量除以有效膜面積及壓力，藉此求出透水速度。 (溶質之阻止性能試驗) 於溶質之阻止性試驗中，使用以10ppm之比例溶解伊凡氏藍(EB)或酸性紅265(AR)之水溶液。以示於(分離膜之透水性評價方法)的試驗裝置，使上述水溶液(40mL)透過，藉由紫外可見近紅外分光光度計測定透過液中的溶質之濃度，算出溶質之阻止率。 (鹽之阻止性能試驗) 於鹽之阻止性試驗中，使用以500ppm之比例溶解硫酸鈉或氯化鈉之水溶液。以示於(分離膜之透水性評價方法)的試驗裝置，使上述水溶液(40mL)透過，藉由小型鈉離子計LAQUAtwin-Na-11(HORIBA)測定透過液中的鹽之濃度，算出鹽之阻止率。 (evaluation method) Dynamic light scattering method: Measured with Zetasizer Nano S, a product of SPECTRIS Co., Ltd. Laser diffraction particle size distribution measurement: Measured with SALD-7500 manufactured by Shimadzu Corporation. Transmission electron microscope: JEM-1010, a product of Japan Electronics Co., Ltd., was used. Average major diameter: From 200 particle images captured using a transmission electron microscope JEM-1010 manufactured by JEOL Ltd., the average major diameter and the maximum major diameter/the width orthogonal to the maximum major axis were calculated. Ultraviolet visible and near infrared spectrophotometer: V630 manufactured by JASCO Corporation was used. X-ray diffraction: Use Buruker D2 PHASER. (Method for evaluating water permeability of separation membranes) Following the method described in S. Kawada et al., Colloids and Surfaces A: Physicochem. Eng. Aspects, 2014, vol.451, p.33-37, evaluation was carried out using a cross-flow water permeable device. . Purify with an ultrapure water production device ("milli-Q (registered trademark) Direct Merck Co., Ltd."), and supply the ultrapure water obtained to the water permeable device at a primary side (supply side) pressure of 0.1 to 0.5 MPa. The water permeability per unit time is divided by the effective membrane area and pressure to calculate the water permeability rate. (Solute blocking performance test) In the solute repellency test, an aqueous solution in which Evans Blue (EB) or Acid Red 265 (AR) is dissolved at a ratio of 10 ppm is used. The above-mentioned aqueous solution (40 mL) was permeated using the test device shown in (Method for Evaluating Water Permeability of Separation Membranes), the concentration of the solute in the permeated liquid was measured with a UV-visible-near-infrared spectrophotometer, and the rejection rate of the solute was calculated. (Salt blocking performance test) In the salt barrier test, an aqueous solution in which sodium sulfate or sodium chloride is dissolved at a ratio of 500 ppm is used. The above aqueous solution (40 mL) was permeated using the test device shown in (Evaluation Method of Water Permeability of Separation Membranes), and the salt concentration in the permeate liquid was measured with a small sodium ion meter LAQUAtwin-Na-11 (HORIBA), and the salt concentration was calculated. Block rate.

(實施例1) (艾萊石之合成) 於市售的3號矽酸鈉中，添加日產化學(股)製的商品名ST-O，將經莫耳比調整的水玻璃(SiO 2：Na 2O：H 2O莫耳比為3.8：1：39.0，SiO 2濃度為23.05質量%，Na 2O濃度為6.25質量%)封入3L不鏽鋼(SUS316)製密閉容器內，在110℃下靜置加熱12日而水熱合成艾萊石。又，以XRD確認生成物為艾萊石(PDF card No.00-048-0655)。 將所得之艾萊石22.2g與直徑5mm的氧化鋯製粉碎球811.1g一起裝入行星球磨機(Verder Scientific製，PM100)的氮化矽製容器(容量500ml)中，在空氣環境下，以旋轉速度160rpm進行1小時的乾式粉碎。接著，將直徑5mm的粉碎球與直徑3mm的氧化鋯製粉碎球811.1g交換後，將旋轉速度變更為220rpm，在空氣環境下進行1小時的乾式粉碎。 將所得之艾萊石的粉碎粒子24.0g作為種晶(種子粒子)，於市售的3號矽酸鈉中，添加日產化學(股)製的商品名ST-O，添加至經莫耳比調整的水玻璃(SiO 2：Na 2O：H 2O莫耳比為4.0：1：39.0，SiO 2濃度為23.85質量%，Na 2O濃度為6.12質量%)2376.0g，將此封入SUS316製的密閉容器內，在120℃下加熱24小時，藉此得到動態光散射徑的個數基準中位徑為832.8nm的艾萊石之奈米粒子。所得之艾萊石為長徑845.0nm，正交於最大長徑的寬度為686.6nm，平均厚度38.1nm，(最大長徑/正交於最大長徑的寬度)之比為1.2。又，以XRD確認生成物為艾萊石(PDF card No.00-048-0655)。 (Example 1) (Synthesis of islaite) To commercially available No. 3 sodium silicate, ST-O, a trade name manufactured by Nissan Chemical Co., Ltd., was added, and the molar ratio-adjusted water glass (SiO 2 ) was: Na 2 O: H 2 O molar ratio is 3.8: 1: 39.0, SiO 2 concentration is 23.05 mass%, Na 2 O concentration is 6.25 mass%), sealed in a 3L stainless steel (SUS316) sealed container, and statically maintained at 110°C It is heated for 12 days to hydrothermally synthesize islaite. Furthermore, it was confirmed by XRD that the product was allite (PDF card No. 00-048-0655). 22.2 g of the obtained islaite and 811.1 g of zirconia crushed balls with a diameter of 5 mm were put into a silicon nitride container (capacity 500 ml) of a planetary ball mill (PM100 manufactured by Verder Scientific), and rotated in an air environment. Dry grinding was performed at a speed of 160 rpm for 1 hour. Next, after replacing the 5 mm diameter grinding ball with 811.1 g of zirconia grinding balls having a 3 mm diameter, the rotation speed was changed to 220 rpm, and dry grinding was performed in an air environment for 1 hour. 24.0 g of the obtained pulverized particles of islaite were used as seed crystals (seed particles), and commercially available No. 3 sodium silicate was added with a trade name of ST-O manufactured by Nissan Chemical Co., Ltd. 2376.0 g of adjusted water glass (SiO 2 : Na 2 O : H 2 O molar ratio is 4.0: 1: 39.0, SiO 2 concentration is 23.85 mass%, Na 2 O concentration is 6.12 mass%), and this is sealed in SUS316 In a sealed container, it was heated at 120°C for 24 hours to obtain islayite nanoparticles with a number-based median diameter of dynamic light scattering diameter of 832.8 nm. The obtained islay stone had a long diameter of 845.0 nm, a width perpendicular to the maximum long diameter of 686.6 nm, an average thickness of 38.1 nm, and a ratio of (maximum long diameter/width perpendicular to the maximum long diameter) of 1.2. Furthermore, it was confirmed by XRD that the product was allite (PDF card No. 00-048-0655).

(艾萊石奈米片水分散液之製造) 將包含上述艾萊石奈米粒子0.8g的分散液與月桂基三甲基銨氯化物0.96g添加至水78.2g，在100℃下進行24小時的靜置加熱，藉此以月桂基三甲基銨離子置換艾萊石的矽酸鹽層間之鈉離子。藉由膜濾器所致之過濾將經游離的鈉離子去除到系外後，回收濕粉，使其再度分散於水中藉此得到經離子交換的艾萊石水分散液。此時的艾萊石水分散液中之月桂基三甲基銨氯化物的濃度為1.2wt%，水分散液的固體成分濃度(1000℃燒成殘留份)為1.6wt%。 於經離子交換的艾萊石水分散液37g中添加10wt%十二基硫酸銨水溶液30g後，以艾萊石的固體成分濃度成為0.1wt%，十二基硫酸銨濃度成為1.5wt%之方式，以521g的純水稀釋。於此中添加氨水而將pH調整至10.1。在60℃、24小時的攪拌器之攪拌下加熱此處所得之溶液，藉此得到艾萊石的奈米粒子進行層剝離而成的奈米片(板狀粒子A)之膠體溶液(艾萊石奈米片水分散液)。 所得之艾萊石奈米片水分散液之動態光散射法所測得的平均粒徑為760nm。又，所得之艾萊石奈米片水分散液之雷射繞射式粒徑分布中90%累計粒徑值為3.3μm，雷射繞射式粒徑分布中平均粒徑值為1.3μm，因此(90%累計粒徑值)/(平均粒徑值)=2.5。 在基板上塗佈所得之水分散液，乾燥後藉由以AFM(原子力顯微鏡)觀察之方法進行測定，經剝離的奈米片(板狀粒子A)之平均厚度為1.5nm。 將把所得之水分散液在室溫下乾燥而成的試料，在100℃、60分鐘乾燥後進行TG測定(熱重量測定)，測定100℃至800℃的重量變化。220℃~500℃質量減少在2階段，認為為首先界面活性劑的分解(20質量%的減少)，接為四級銨的分解(14質量%的減少)。以重量比計為，奈米片(板狀粒子A)：四級銨離子(a)：陰離子界面活性劑(b)=66：14：20，四級銨離子(a)係相對於奈米片(板狀粒子A)而言為21.2質量%，陰離子界面活性劑(b)係相對於奈米片(板狀粒子A)而言為30.3質量%。 (Preparation of aqueous dispersion of islaite nanosheets) A dispersion liquid containing 0.8 g of the islaite nanoparticles and 0.96 g of lauryltrimethylammonium chloride was added to 78.2g of water, and left to be heated at 100° C. for 24 hours to use lauryltrimethylammonium chloride. Ammonium ions replace the sodium ions between the silicate layers of islaite. After the free sodium ions are removed from the system through filtration by a membrane filter, the wet powder is recovered and redispersed in water to obtain an ion-exchanged aqueous dispersion of allite. At this time, the concentration of lauryltrimethylammonium chloride in the allite aqueous dispersion was 1.2 wt%, and the solid content concentration of the aqueous dispersion (residue after firing at 1000° C.) was 1.6 wt%. After adding 30 g of 10 wt% ammonium dodecyl sulfate aqueous solution to 37 g of ion-exchanged allite aqueous dispersion, the solid content concentration of allite became 0.1 wt% and the ammonium dodecyl sulfate concentration became 1.5 wt%. , dilute with 521g of pure water. Aqueous ammonia was added thereto to adjust the pH to 10.1. The solution obtained here was heated at 60° C. with a stirrer for 24 hours, thereby obtaining a colloidal solution (Islay) of nanosheets (plate-shaped particles A) in which the nanoparticles of islay were exfoliated. aqueous dispersion of stone nanosheets). The average particle size of the obtained aqueous dispersion of islaite nanosheets measured by the dynamic light scattering method was 760 nm. In addition, the 90% cumulative particle size value in the laser diffraction particle size distribution of the obtained islaite nanosheet aqueous dispersion is 3.3 μm, and the average particle size value in the laser diffraction particle size distribution is 1.3 μm. Therefore (90% cumulative particle size value)/(average particle size value) = 2.5. The obtained aqueous dispersion was coated on the substrate, dried and measured by observing with an AFM (atomic force microscope). The average thickness of the exfoliated nanosheets (plate-shaped particles A) was 1.5 nm. A sample obtained by drying the obtained aqueous dispersion at room temperature was dried at 100°C for 60 minutes and then subjected to TG measurement (thermogravimetry) to measure the weight change from 100°C to 800°C. The mass decrease at 220°C to 500°C is in two stages, which is considered to be the decomposition of the surfactant first (a decrease of 20% by mass), followed by the decomposition of the quaternary ammonium (a decrease of 14% by mass). In terms of weight ratio, nanosheets (plate-shaped particles A): quaternary ammonium ions (a): anionic surfactants (b) = 66:14:20, quaternary ammonium ions (a) are relative to nanometer The amount of the anionic surfactant (b) was 21.2% by mass relative to the nanosheets (plate-like particles A) and 30.3% by mass relative to the nanosheets (plate-like particles A).

(艾萊石奈米片分離膜之製作) 於聚醚碸(PES)製支撐基材上，供給所得之艾萊石奈米片水分散液，進行抽吸過濾，而在支撐基材上形成艾萊石奈米片積層體。又，艾萊石奈米片水分散液之過濾結束後亦繼續抽吸過濾(減壓過濾)，去除艾萊石奈米片積層體所含有的水分，提高層間的密著性。供給至支撐基材上的艾萊石奈米片水分散液之濃度與量，係按照所形成的艾萊石奈米片積層體之厚度來適宜調整，例如當形成100nm的厚度之艾萊石奈米片積層體時，以艾萊石奈米片的固體成分成為1mg之方式，供給在超純水50mL中混合上述艾萊石奈米片水分散液1.25mL之溶液。另外，亦製作以積層體中的艾萊石奈米片之固體成分成為0.5mg或2mg之方式所調整的分離膜。 從藉由SEM(掃描型電子顯微鏡)拍攝艾萊石奈米片固體成分為1mg的分離膜之剖面構造的影像，觀察到由PES(聚醚碸，截留分子量100kDa，膜面積17.3×10 -4m 2)製的支撐基材與約100nm之厚度的奈米片(NS)積層體(液中物質分離膜)所構成之積層構造。 圖1中顯示以抽吸過濾，在基材(聚醚碸支撐膜)上製造包含由板狀粒子(A)所成的艾萊石奈米片之液中物質分離膜之步驟。 由所得之分離膜的X射線繞射測定結果，於所製作的分離膜中在2θ=9.6°觀測到繞射峰，此表示艾萊石奈米片積層體的層間距離為0.92nm。又，將同分離膜浸漬於超純水中72小時後，測定X射線繞射，結果在2θ=9.1°觀測到繞射峰，此表示濕潤狀態之艾萊石奈米片積層體的層間距離為0.97nm。從以乾燥狀態與濕潤狀態所測定的各自之層間距離為相同程度來看，本發明之分離膜可說是在水中的構造安定性高之膜。 (Preparation of islay nanosheet separation membrane) The obtained islay nanosheet aqueous dispersion is supplied on a support base made of polyether styrene (PES), followed by suction filtration to form a Islay nanosheet laminate. In addition, after the filtration of the islay nanosheet aqueous dispersion is completed, suction filtration (reduced pressure filtration) is continued to remove the moisture contained in the islay nanosheet laminate and improve the adhesion between layers. The concentration and amount of the islay nanosheet aqueous dispersion supplied to the supporting substrate are appropriately adjusted according to the thickness of the islay nanosheet laminate to be formed. For example, when forming islayite with a thickness of 100 nm In the case of a nanosheet laminate, a solution of 1.25 mL of the above-described aqueous dispersion of allite nanosheets mixed with 50 mL of ultrapure water is supplied so that the solid content of the allite nanosheets becomes 1 mg. Separation membranes adjusted so that the solid content of the allite nanosheets in the laminate became 0.5 mg or 2 mg were also produced. From the SEM (scanning electron microscope) image of the cross-sectional structure of a separation membrane with a solid content of 1 mg of allite nanosheets, it was observed that it is composed of PES (polyether styrene, molecular weight cutoff 100 kDa, membrane area 17.3×10 -4 A laminated structure consisting of a support substrate made of m 2 ) and a nanosheet (NS) laminate (substance separation membrane in liquid) with a thickness of approximately 100 nm. Figure 1 shows the steps of producing a substance separation membrane in a liquid containing allite nanosheets made of plate-shaped particles (A) on a substrate (polyetherseal support membrane) by suction filtration. According to the X-ray diffraction measurement results of the obtained separation film, a diffraction peak was observed at 2θ=9.6° in the produced separation film, which indicates that the interlayer distance of the islaite nanosheet laminate is 0.92 nm. Furthermore, after the separation membrane was immersed in ultrapure water for 72 hours, X-ray diffraction was measured. As a result, a diffraction peak was observed at 2θ = 9.1°, which indicates the interlayer distance of the islaite nanosheet laminate in a wet state. is 0.97nm. Since the interlayer distances measured in the dry state and the wet state are approximately the same, the separation membrane of the present invention can be said to be a membrane with high structural stability in water.

(實施例2) 於上述實施例1所得之艾萊石奈米片積層體上，供給氧化石墨烯(GO)的水分散液(Sigma Aldrich公司製，製品名Graphene oxide，4mg/mL)，進行抽吸過濾，而在艾萊石奈米片上積層氧化石墨烯(GO)層，在基材(B)上製作艾萊石奈米片與氧化石墨烯(GO)的複合膜之液中物質分離膜。又，氧化石墨烯(GO)的水分散液之過濾結束後亦繼續抽吸過濾(減壓過濾)，去除包含氧化石墨烯(GO)的積層體所含有的水分，提高層間的密著性。分別做成氧化石墨烯(GO)(將艾萊石作為1時)以質量比1：1所積層之液中物質分離膜成形體，與以1：0.1所積層之液中物質分離膜成形體。 (Example 2) An aqueous dispersion of graphene oxide (GO) (manufactured by Sigma Aldrich, product name: Graphene oxide, 4 mg/mL) was supplied to the allite nanosheet laminate obtained in the above Example 1, and suction filtration was performed. A graphene oxide (GO) layer is laminated on the allite nanosheets, and a substance separation membrane in the liquid is produced as a composite membrane of the allite nanosheets and graphene oxide (GO) on the substrate (B). In addition, after the filtration of the aqueous dispersion of graphene oxide (GO) is completed, suction filtration (reduced pressure filtration) is continued to remove moisture contained in the laminate containing graphene oxide (GO) and improve the adhesion between layers. A molded body of a substance separation membrane for liquids laminated with graphene oxide (GO) (taking allite as 1) at a mass ratio of 1:1, and a molded body of a substance separation membrane for liquids laminated with a mass ratio of 1:0.1 were produced. .

(比較例1) 於實施例1中的艾萊石奈米片水分散液之製造過程中，藉由膜濾器過濾經游離的鈉離子而去除到系外後，使濕粉在40℃下乾燥而得到艾萊石粉末。除了使用所得之粉末12g，與月桂基三甲基銨氯化物14g一起添加至水1174g中以外，與實施例1同樣地進行而得到艾萊石奈米片水分散液。 所得之水性分散液的雷射繞射式粒徑分布中90%累計粒徑值為45.8μm，雷射繞射式粒徑分布中平均粒徑值為3.6μm，因此(90%累計粒徑值)/(平均粒徑值)=12.7。 除了設為積層體中含有之經剝離之艾萊石的奈米粒子之固體成分成為5mg、7.5mg、10mg以外，與實施例1同樣地進行而得到分離膜。 (Comparative example 1) In the manufacturing process of the aqueous dispersion of islaite nanosheets in Example 1, free sodium ions are filtered through a membrane filter and removed from the system, and then the wet powder is dried at 40°C to obtain islaite. powder. Except using 12 g of the obtained powder and adding 14 g of lauryltrimethylammonium chloride to 1174 g of water, the same procedure as in Example 1 was performed to obtain an aqueous dispersion of islaite nanosheets. The 90% cumulative particle size value in the laser diffraction particle size distribution of the obtained aqueous dispersion is 45.8 μm, and the average particle size value in the laser diffraction particle size distribution is 3.6 μm. Therefore (90% cumulative particle size value )/(average particle size value)=12.7. A separation membrane was obtained in the same manner as in Example 1 except that the solid content of the exfoliated islaite nanoparticles contained in the laminate was set to 5 mg, 7.5 mg, or 10 mg.

(分離膜之性能評價) 圖2中顯示表示分離膜的透水試驗與分離性能之評價試驗方法的模型圖。將溶解有被分離物質(實施例1中伊凡氏藍或酸性紅265)的含被分離物質的水溶液從供給液槽通過泵，供給至分離膜成形體單元，分別於物質濃縮液槽中儲存未通過液中物質分離膜的被分離物質(實施例1中為伊凡氏藍或酸性紅265)經濃縮之液(為比被分離對象液更深色的溶液，根據紫外可見吸收光譜，被分離物質的吸光度高之溶液)，於分離水槽中儲存通過液中物質分離膜後的分離水(為無色或比被分離對象液更淺色的溶液，藉由紫外可見吸收光譜無法檢測出被分離物質的吸光度或低之溶液)。結果，從含被分離物質的水溶液分離被分離物質，另一方面，可將被分離物質濃縮。 又，代替分離膜成形體單元，使用實施例1所用的聚醚碸(PES)製支撐基材，進行同樣的試驗。僅支撐基材時，雖然被分離物質的阻止率為0%(零%，含被分離物質的水溶液與分離水槽中儲存的分離水相同顏色)，但是積層有艾萊石奈米片水分散液的分離膜成形體時，皆展現色素阻止性(物質去除性)。 (Performance evaluation of separation membrane) FIG. 2 shows a model diagram showing a water permeability test and separation performance evaluation test method of a separation membrane. The aqueous solution containing the separated substance (Evan's Blue or Acid Red 265 in Example 1) dissolved in it is supplied from the supply tank to the separation membrane molded body unit through a pump, and is stored in the substance concentration tank respectively. The concentrated liquid that has not passed through the liquid substance separation membrane (Evan's Blue or Acid Red 265 in Example 1) is a darker solution than the liquid to be separated. According to the ultraviolet-visible absorption spectrum, it is A solution with high absorbance of the separated substance), store the separated water after passing through the separation membrane of the substance in the liquid in the separation tank (a colorless or lighter-colored solution than the liquid to be separated, and the separation cannot be detected by ultraviolet-visible absorption spectrum The absorbance of the substance or solution is low). As a result, the separated substance is separated from the aqueous solution containing the separated substance, and on the other hand, the separated substance can be concentrated. In addition, the same test was performed using the support base material made of polyethersene (PES) used in Example 1 instead of the separation membrane molded unit. When only the base material is supported, the rejection rate of the substance to be separated is 0% (0%, the aqueous solution containing the substance to be separated is the same color as the separated water stored in the separation tank), but the aqueous dispersion of islaite nanosheets is laminated All separation membrane molded products exhibit pigment blocking properties (substance removal properties).

將依照實施例1及比較例1之分離膜的上述透水性評價方法算出透水速度的結果及依照上述溶質的阻止性能試驗算出EB(伊凡氏藍)及AR(酸性紅265、AR為僅實施例1的分離膜之試驗)之阻止率(%)的結果顯示於表1及圖6。圖6中為左軸表示透水性(L・m -2・hr -1・bar -1)，於圖表中以縱棒表示，右軸表示色素阻止率，於圖表中以＊△記號表示，橫軸表示支撐膜面積每9.6×10 -4m 2的奈米片之裝載量者。 於左側所示的實施例1之圖表中，＊表示伊凡氏藍的阻止率，△表示酸性紅265的阻止率。 又，於右側所示的比較例1之圖表中，＊表示伊凡氏藍的阻止率。 於比較例1所製作之膜中，奈米片裝載量為10mg時，透水性為0.32L・m -2・h -1・bar -1，此外EB(伊凡氏藍)阻止性為72%。相對於此，於本發明之分離膜中，儘管以較比較例1淡10倍的濃度，以奈米片裝載量為1mg製作，透水性為13L・m -2・h -1・bar -1，EB(伊凡氏藍)阻止性為95%。又，比EB(伊凡氏藍)更小分子量的AR(酸性紅265)阻止性係在本發明中為30%。根據圖6，實施例1之分離膜成形體係從相較於比較例1之分離膜成形體顯示高的透水性、色素阻止性(色素分離性)來看，本發明之分離膜成形體為具有優異的分離性與高的溶劑透過性者。 The results of calculating the water permeability rate according to the above-mentioned water permeability evaluation method of the separation membrane of Example 1 and Comparative Example 1 and calculating the results of EB (Evan's Blue) and AR (Acid Red 265, AR) based on the above-mentioned solute blocking performance test, AR are only implemented The results of the rejection rate (%) of the separation membrane test of Example 1 are shown in Table 1 and Figure 6. In Figure 6, the left axis represents the water permeability (L·m -2 ·hr -1 ·bar -1 ), which is represented by the vertical bar in the graph. The right axis represents the pigment rejection rate, which is represented by the *△ mark in the graph. The horizontal bar The axis represents the loading amount of nanosheets per 9.6×10 -4 m 2 of supporting film area. In the graph of Example 1 shown on the left, * represents the rejection rate of Evans blue, and Δ represents the rejection rate of Acid Red 265. In addition, in the graph of Comparative Example 1 shown on the right, * represents the rejection rate of Evans blue. In the membrane produced in Comparative Example 1, when the loading amount of nanosheets was 10 mg, the water permeability was 0.32L·m -2 ·h -1 ·bar -1 , and the EB (Evan's Blue) barrier property was 72%. . On the other hand, in the separation membrane of the present invention, although the concentration was 10 times lighter than that of Comparative Example 1 and the nanosheet loading amount was 1 mg, the water permeability was 13L·m -2 ·h -1 ·bar -1 , EB (Evan's Blue) blocking property is 95%. In addition, the inhibitory effect of AR (Acid Red 265), which has a smaller molecular weight than EB (Evan's Blue), is 30% in the present invention. According to FIG. 6 , the separation membrane molding system of Example 1 shows higher water permeability and pigment blocking properties (pigment separation properties) than the separation membrane molding of Comparative Example 1. It can be seen that the separation membrane molding of the present invention has Excellent separation properties and high solvent permeability.

圖3中顯示實施例1所得之基材上的分離膜之表面的掃描型電子顯微鏡照片。觀測到膜表面光滑且波狀的圖樣。 圖4中顯示實施例1所得之基材上的分離膜(裝載量1mg)之剖面的掃描型電子顯微鏡照片。確認於由板狀粒子(A)所成的包含奈米片之積層量1mg的膜中，膜厚大致為100nm。 FIG. 3 shows a scanning electron microscope photograph of the surface of the separation membrane on the substrate obtained in Example 1. A smooth and wavy pattern on the film surface was observed. FIG. 4 shows a scanning electron microscope photograph of the cross section of the separation membrane (loading amount: 1 mg) on the substrate obtained in Example 1. It was confirmed that the film thickness was approximately 100 nm in a film composed of plate-shaped particles (A) and containing nanosheets with a lamination amount of 1 mg.

圖5中顯示以40000G超離心處理實施例1所得之艾萊石奈米片水分散液，將四級銨與界面活性劑量相對於艾萊石而言減低至15質量%以下後，所形成的分離膜之X射線繞射測定結果。於乾燥狀態的分離膜之測定結果(dry)中，觀察到源自膜中的奈米片之積層的波峰(▼記號)。又，從與於分離膜中添加水而測定之結果(wet)比較，源自積層的波峰位置不位移來看，表示所得之分離膜係即使在水中構造安定性亦高。圖5係從上依序表示本件之原料的層間剝離前之艾萊石的X射線繞射圖、本件之使經層間剝離的艾萊石之奈米片積層而成的分離膜為濕潤狀態時的X射線繞射圖、本件之使經層間剝離的艾萊石之奈米片積層而成的分離膜為乾燥狀態時的X射線繞射圖、濕潤狀態的基材(聚醚碸)的X射線繞射圖、乾燥狀態的基材(聚醚碸)的X射線繞射圖。可知藉由超離心處理去除層狀化合物的剝離劑成分，源自經層間剝離的艾萊石的波峰變明確，同時包含艾萊石奈米片的分離膜係即使為濕潤狀態(水中)，構造亦安定。Figure 5 shows the aqueous dispersion of islay nanosheets obtained by ultracentrifugation at 40000G in Example 1, and the amount of quaternary ammonium and surfactant is reduced to less than 15 mass % relative to islay stone. X-ray diffraction measurement results of the separation membrane. In the measurement results of the separation membrane in a dry state (dry), a peak (▼ mark) originating from the stacking of nanosheets in the membrane was observed. Furthermore, compared with the result measured by adding water to the separation membrane (wet), the position of the wave peak derived from the lamination did not shift, indicating that the obtained separation membrane system has high structural stability even in water. Figure 5 shows, from top to bottom, the X-ray diffraction pattern of the islayite material before delamination, and when the separation membrane of the present invention, which is formed by laminating the delaminated islaye nanosheets, is in a wet state. The X-ray diffraction pattern of this product, the X-ray diffraction pattern of this product when the separation membrane made of laminated exfoliated Islay nanosheets is in a dry state, and the X-ray diffraction pattern, X-ray diffraction pattern of dry state substrate (polyether styrene). It can be seen that by removing the exfoliating agent component of the layered compound through ultracentrifugation, the peaks derived from the islayite exfoliated between the layers become clear, and the separation membrane system containing the islayite nanosheets has a structure even in a wet state (water). Also stable.

圖7中顯示使用實施例1所得之艾萊石奈米片水分散液所製造之分散膜成形體的透水性能與色素阻止率之結果。圖表右縱軸表示色素阻止率(%)，左縱軸表示透水性能(L・m -2・hr -1・bar -1)，橫軸表示支撐膜面積每9.6×10 -4m 2的奈米片之裝載量(mg)。虛線的圖表左側為使用利用未進行超離心處理的艾萊石奈米片水分散液，在支撐膜(聚醚碸)上製膜的分離膜成形體之試驗結果，虛線的圖表右側為使用利用以40000G經超離心處理的艾萊石奈米片水分散液，在指示膜(聚醚碸)上製膜的分子膜成形體之試驗結果。圖表之(＊)表示伊凡氏藍的阻止率，圖表之(△)表示酸性紅265的阻止率，棒圖為表示透水性能者。圖表左端表示作為空白組，僅使用支撐膜(聚醚碸)之試驗結果，伊凡氏藍與酸性紅265的阻止率皆為零，透水率為95(L・m -2・hr -1・bar -1)。 由圖7所示的結果，使用超離心處理前或超離心處理後的艾萊石奈米片水分散液所製造之液中物質分離膜成形體，皆可分離BE及AR，且為具有透水性者，因此可作為液中物質分離膜使用。 又，由圖7所示的結果，雖然使用超離心處理前的艾萊石奈米片水分散液所製膜之分離膜，奈米片之裝載量上升，且分離2種類物質的性能增大，但是透水性能(即處理量)降低。另一方面，可知使用超離心處理後的艾萊石奈米片水分散液所製膜之分離膜，儘管為低裝載量，分離2種類物質的性能高，可知透水性能(即處理量)亦比高裝載量時高。亦即可理解，藉由使用進行超離心處理，將四級銨與界面活性劑量相對於艾萊石而言設為15質量%以下(例如0.01~15.0質量%)的艾萊石奈米片水分散液，即使降低奈米片含量，亦效率良好地分離分子量不同的2種類物質，而且得到彼等溶質溶存的溶劑之透水性高的液中物質分離膜。即，可從包含被分離物質的處理液體中，更效率良好地分離濃縮液中物質。 Figure 7 shows the results of the water permeability and pigment rejection rate of the dispersion film formed body produced using the aqueous dispersion of allite nanosheets obtained in Example 1. The right vertical axis of the graph represents the pigment rejection rate (%), the left vertical axis represents the water permeability (L·m -2 ·hr -1 ·bar -1 ), and the horizontal axis represents the nanometers per 9.6 × 10 -4 m 2 of the support film area. Loading capacity of rice flakes (mg). The left side of the dotted line graph shows the test results of a separation membrane molded body formed on a support membrane (polyether sulfide) using an aqueous dispersion of islaite nanosheets that was not subjected to ultracentrifugation. The right side of the dotted line graph shows the test results using The test results of the molecular membrane molding formed by using 40000G ultracentrifugal aqueous dispersion of islaite nanosheets on the indicator film (polyether styrene). The graph (*) represents the rejection rate of Evans Blue, the graph (△) represents the rejection rate of Acid Red 265, and the bar graph represents the water permeability. The left end of the chart shows the test results of using only the support film (polyether turret) as a blank group. The rejection rates of Evans Blue and Acid Red 265 are both zero, and the water permeability is 95 (L・m -2・hr -1・bar -1 ). From the results shown in Figure 7, the liquid substance separation membrane molded body produced by using the aqueous dispersion of islaite nanosheets before ultracentrifugation or after ultracentrifugation can separate BE and AR and is water-permeable. properties, so it can be used as a separation membrane for substances in liquids. Furthermore, from the results shown in Figure 7, although a separation membrane made of an aqueous dispersion of allite nanosheets before ultracentrifugation was used, the loading capacity of the nanosheets increased and the performance of separating two types of substances increased. , but the water permeability (i.e. treatment capacity) is reduced. On the other hand, it was found that a separation membrane made of an aqueous dispersion of allite nanosheets treated by ultracentrifugation has high performance in separating two types of substances despite a low loading capacity. It is also known that the water permeability (ie, the throughput) is also Higher than at high loading. That is to say, it can be understood that by using islayite nanosheet water that is subjected to ultracentrifugation and has a quaternary ammonium and surfactant dosage of 15% by mass or less (for example, 0.01 to 15.0% by mass) relative to islaystone. Even if the content of nanosheets is reduced in the dispersion, two types of substances with different molecular weights can be efficiently separated, and a substance separation membrane in the liquid with high water permeability to the solvent in which the solutes are dissolved can be obtained. That is, the substance in the concentrated liquid can be separated more efficiently from the treatment liquid containing the substance to be separated.

圖8中顯示具有使用實施例1所用之艾萊石奈米片、其他板狀粒子的鈮酸(HNb 3O 8)奈米片與GO(氧化石墨烯)奈米片所得之分離膜的分離膜成形體之透水性能與色素阻止率之結果。圖表右縱軸表示色素阻止率(%)，左縱軸表示透水性能(L・m -2・hr -1・bar -1)，橫軸表示每支撐膜面積以同一裝載量所裝載的各奈米片之種類。圖表之(＊)表示伊凡氏藍(EB)的阻止率，圖表之(△)表示酸性紅265(AR)的阻止率，棒圖為表示透水性能者。 可知相較於包含鈮酸(HNb 3O 8)奈米片的分離為膜成形體或包含GO(氧化石墨烯)奈米片的分離膜成形體，包含艾萊石奈米片的分離膜成形體係效率良好地分離分子量不同的2種類物質(EB及AR)，而且可知彼等溶質溶存的液體之透水性能(即處理量)高。即，可從包含被分離物質的處理液體，效率良好地分離濃縮液中物質。 Figure 8 shows the separation of a separation membrane obtained by using the allite nanosheets used in Example 1, niobic acid (HNb 3 O 8 ) nanosheets and GO (graphene oxide) nanosheets using other plate-shaped particles. The result of the water permeability and pigment rejection rate of the membrane formed body. The right vertical axis of the graph represents the pigment rejection rate (%), the left vertical axis represents the water permeability (L·m -2 ·hr -1 ·bar -1 ), and the horizontal axis represents the nanoparticles loaded with the same loading amount per support membrane area. Types of rice flakes. The graph (*) represents the blocking rate of Evans Blue (EB), the graph (△) represents the blocking rate of Acid Red 265 (AR), and the bar graph represents the water permeability. It can be seen that compared to the separation membrane molded body containing niobate (HNb 3 O 8 ) nanosheets or the separation membrane molding body containing GO (graphene oxide) nanosheets, the separation membrane molding containing allite nanosheets is The system efficiently separates two types of substances (EB and AR) with different molecular weights, and it is known that the water permeability (ie, throughput) of the liquid in which these solutes are dissolved is high. That is, the substance in the concentrated liquid can be efficiently separated from the processing liquid containing the substance to be separated.

圖9中顯示將實施例1所得之分離膜成形體，於以鹽酸調整至pH3的水溶液中，或以氫氧化鈉調整至pH11的水溶液中，分別浸漬2星期後的艾萊石奈米片積層體的X射線繞射測定結果。了解到X射線的繞射圖型係在上述水溶液中浸漬前後無構造變化，對於pH3~11的水溶液為安定。圖9中從上依序為乾燥狀態、在pH7下保存狀態、在pH3下保存狀態、在pH11下保存狀態的艾萊石奈米片之X射線繞射圖型，源自各自的艾萊石奈米片之特徵波峰為2θ(degree)=9.3°、9.2°、9.4°、9.3°，d(晶面間距)分別為0.95nm、0.96nm、0.94nm、0.95nm，確認無構造變化。Figure 9 shows the lamination of islaite nanosheets after the separation membrane formed body obtained in Example 1 was immersed for 2 weeks in an aqueous solution adjusted to pH 3 with hydrochloric acid or in an aqueous solution adjusted to pH 11 with sodium hydroxide. X-ray diffraction measurement results of the body. It was found that the X-ray diffraction pattern has no structural change before and after immersion in the above-mentioned aqueous solution, and is stable for aqueous solutions with pH 3~11. Figure 9 shows the X-ray diffraction patterns of islay nanosheets in a dry state, a state stored at pH 7, a state stored at pH 3, and a state stored at pH 11, in order from top, derived from the respective islay stones. The characteristic wave peaks of the nanosheets are 2θ (degree) = 9.3°, 9.2°, 9.4°, and 9.3°, and d (crystal spacing) are 0.95nm, 0.96nm, 0.94nm, and 0.95nm respectively. It is confirmed that there is no structural change.

圖10中顯示測定實施例1所得之分離膜成形體的陰離子性色素阻止性能之結果。作為陰離子性色素，使用甲基橙(Methyl Orange，分子量327)、酸性紅265(Acid Red265，分子量636)、亮藍FCF(Brilliant Blue FCF，分子量793)、伊凡氏藍(Evans Blue，分子量961)、玫瑰紅(Rose Bengal，分子量974)。支撐膜面積每9.6×10 -4m 2的艾萊石奈米片之裝載量係黑■為0.1mg，黑●為05mg，黑▲為1.0mg之結果。甲基橙之去除率為0~10%，酸性紅265之去除率為0~18%，亮藍FCF之去除率為0~30%，伊凡氏藍之去除率為75~99%，玫瑰紅之去除率為90~99%。將艾萊石奈米片之裝載量在上述範圍內變化的成形體係於各自中，由陰離子性色素所成的被分離物水溶液係在分子量800附近進行分離或通過。因此，於實施例1所得之分離膜成形體中的陰離子性物質之分離中，期待在分子量800附近的高分離選擇性。 Figure 10 shows the results of measuring the anionic dye blocking performance of the separation membrane formed body obtained in Example 1. As anionic dyes, Methyl Orange (molecular weight 327), Acid Red 265 (molecular weight 636), Brilliant Blue FCF (molecular weight 793), and Evans Blue (molecular weight 961) are used. ), Rose Bengal (molecular weight 974). The loading amount of islay nanosheets per 9.6×10 -4 m 2 of support film area is the result of black ■ being 0.1 mg, black ● being 05 mg, and black ▲ being 1.0 mg. The removal rate of Methyl Orange is 0~10%, the removal rate of Acid Red 265 is 0~18%, the removal rate of Brilliant Blue FCF is 0~30%, the removal rate of Evans Blue is 75~99%, and the removal rate of Rose The removal rate of red is 90~99%. In each of the molding systems in which the loading amount of islaite nanosheets is changed within the above range, the aqueous solution of the separated product composed of anionic dyes is separated or passed around a molecular weight of 800. Therefore, in the separation of anionic substances in the separation membrane formed body obtained in Example 1, high separation selectivity in the vicinity of molecular weight 800 is expected.

圖11中顯示使用實施例1所得之分離膜成形體的聚乙二醇水溶液之截留分子量測定結果。為使用聚乙二醇水溶液進行非離子性物質之分離者。支撐膜面積每9.6×10 -4m 2的艾萊石奈米片之裝載量係黑■為0.1mg，黑●為05mg，黑▲為1.0mg之結果。使具有不同分子量(200、1000、6000、12000、20000、35000)的聚乙二醇水溶液各自通過裝載量不同的分離膜成形體，測定各自的去除率。裝載量0.1mg時分子量差所致的分離為不充分。裝載量為0.5mg時與1.0mg時，分子量在10000附近，去除率成為90%以上，表示被分離。因此，認為實施例1所得之分離膜成形體的非離子性物質之分離中的該膜之截留分子量係存在於10000附近。 Figure 11 shows the measurement results of the molecular weight cutoff of the polyethylene glycol aqueous solution using the separation membrane formed body obtained in Example 1. It is used to separate non-ionic substances using polyethylene glycol aqueous solution. The loading amount of islay nanosheets per 9.6×10 -4 m 2 of support film area is the result of black ■ being 0.1 mg, black ● being 05 mg, and black ▲ being 1.0 mg. Polyethylene glycol aqueous solutions with different molecular weights (200, 1000, 6000, 12000, 20000, 35000) were passed through separation membrane molded bodies with different loading amounts, and their respective removal rates were measured. When the loading amount is 0.1 mg, the separation due to the difference in molecular weight is insufficient. When the loading amount is 0.5 mg and 1.0 mg, the molecular weight is around 10,000, and the removal rate is more than 90%, indicating separation. Therefore, it is considered that the molecular weight cutoff of the separation membrane formed body obtained in Example 1 exists in the vicinity of 10,000 in the separation of nonionic substances.

圖12中顯示使用在實施例2所得之艾萊石奈米片上具有氧化石墨烯之層以1：1之質量比積層的液中物質分離膜之液中物質分離膜成形體之含鹽水溶液的透水性評價及鹽成分的分離試驗之結果。表12中，棒圖表示透水性能，黑◆表示硫酸鈉，黑×表示氯化鈉的鹽阻止率。Figure 12 shows the results of using an aqueous solution of a liquid substance separation membrane molded body of a liquid substance separation membrane formed by laminating a layer of graphene oxide on the islaite nanosheets obtained in Example 2 at a mass ratio of 1:1. Results of water permeability evaluation and salt component separation test. In Table 12, the bar graph represents the water permeability, black ◆ represents sodium sulfate, and black × represents the salt rejection rate of sodium chloride.

圖13中顯示使用在實施例2所得之艾萊石奈米片奈米片上含有氧化石墨烯層以1：0.1之質量比積層的液中物質分離膜之液中物質分離膜成形體之含鹽水溶液的透水性評價及鹽成分的分離試驗之結果。表13中，棒圖表示透水性能，黑◆表示硫酸鈉，黑×表示氯化鈉的鹽阻止率。Figure 13 shows the salt content of a liquid substance separation membrane formed body using a liquid substance separation membrane laminated with a graphene oxide layer on the islaite nanosheet nanosheets obtained in Example 2 at a mass ratio of 1:0.1. Results of water permeability evaluation of aqueous solutions and separation test of salt components. In Table 13, the bar graph represents the water permeability, black ◆ represents sodium sulfate, and black × represents the salt rejection rate of sodium chloride.

由圖12及圖13可知，相較於艾萊石單獨膜之情況、氧化石墨烯(GO)單獨膜之情況，藉由做成艾萊石與氧化石墨烯之複合膜，提高鹽類的阻止率。 [產業上的利用可能性] As can be seen from Figures 12 and 13, compared to the case of a single film of allite and a single film of graphene oxide (GO), by forming a composite film of allite and graphene oxide, the blocking of salts is improved. Rate. [Industrial utilization possibility]

提供可效率良好地去除液體中的被分離物質(例如離子性物質)之分離膜，分離膜成分為耐化學性高，膜中的溶劑穿透速度高，效率良好地分離液中的物質(例如離子性有機物或非離子性物質)之液中物質分離膜成形體與其製造方法。Provide a separation membrane that can efficiently remove substances to be separated (such as ionic substances) in liquids. The components of the separation membrane have high chemical resistance and a high penetration rate of solvents in the membrane, and can efficiently separate substances in liquids (such as ionic substances). Ionic organic matter or non-ionic substance) liquid substance separation membrane formed body and its manufacturing method.

[圖1]係顯示將包含板狀粒子(A)的液中物質分離膜在基材(支撐膜)上以抽吸過濾製膜的步驟之模型圖。 [圖2]係顯示分離膜成形體的透水試驗與分離性能的評價試驗方法之模型圖。 [圖3]為實施例1所得之分離膜成形體的表面之掃描型電子顯微鏡照片。倍率為1萬倍。 [圖4]為實施例1所得之分離膜成形體的剖面之掃描型電子顯微鏡照片。倍率為5萬倍。 [圖5]係顯示實施例1所得之分離膜成形體的X射線繞射測定結果者。 [圖6]係顯示實施例1與比較例1所得之分離膜成形體的EB(伊凡氏藍)與酸性紅265的透水性能與色素阻止率之圖表。 [圖7]係顯示使用將實施例1所得之艾萊石奈米片水分散液超離心處理前與後的水分散液所製膜的2種類之分離膜成形體的透水性能與色素阻止率之圖表。 [圖8]係顯示實施例1所得之包含艾萊石奈米片的分離膜成形體、包含鈮酸(HNb 3O 8)奈米片的分離膜成形體與包含GO(氧化石墨烯)奈米片的分離膜成形體之各透水性能與色素阻止率之圖表。 [圖9]係顯示將實施例1所得之分離膜成形體，於以鹽酸調整至pH3的水溶液中，或以氫氧化鈉調整至pH11的水溶液中，分別浸漬2星期後的艾萊石奈米片積層體的X射線繞射測定結果之圖。 [圖10]係顯示使用實施例1所得之分離膜成形體的陰離子性色素之阻止性能之圖。 [圖11]係顯示使用實施例1所得之分離膜成形體的無極性分子之聚乙二醇的截留分子量測定結果之圖。 [圖12]係顯示使用以1：1之質量比含有實施例2所得之艾萊石與氧化石墨烯的液中物質分離膜成形體之透水性評價及含鹽水溶液的鹽阻止率之圖表。 [圖13]係顯示使用以1：0.1之質量比含有實施例2所得之艾萊石與氧化石墨烯的液中物質分離膜成形體之透水性評價及含鹽水溶液的鹽阻止率之圖表。 [Fig. 1] is a model diagram showing the steps of forming a membrane by suction filtration on a substrate (support membrane) using a liquid substance separation membrane containing plate-shaped particles (A). [Fig. 2] is a model diagram showing the water permeability test and the separation performance evaluation test method of the separation membrane formed body. [Fig. 3] is a scanning electron microscope photograph of the surface of the separation membrane molded body obtained in Example 1. The magnification is 10,000 times. [Fig. 4] is a scanning electron microscope photograph of the cross section of the separation membrane molded body obtained in Example 1. The magnification is 50,000 times. [Fig. 5] shows the results of X-ray diffraction measurement of the separation membrane formed body obtained in Example 1. [Fig. 6] A graph showing the water permeability and dye rejection rate of EB (Evan's Blue) and Acid Red 265 of the separation membrane molded products obtained in Example 1 and Comparative Example 1. [Figure 7] shows the water permeability and pigment rejection rate of two types of separation membrane molded articles produced using the aqueous dispersion of allite nanosheets obtained in Example 1 before and after ultracentrifugation. chart. [Fig. 8] shows the separation membrane molded body containing allite nanosheets, the separation membrane molded body containing niobate ( HNb3O8 ) nanosheets, and the separation membrane molding body containing GO (graphene oxide) nanosheets obtained in Example 1. Chart showing the water permeability and pigment rejection rate of rice flakes separated membrane molded bodies. [Figure 9] shows the islaite nanoparticles after immersing the separation membrane molded body obtained in Example 1 for 2 weeks in an aqueous solution adjusted to pH 3 with hydrochloric acid or in an aqueous solution adjusted to pH 11 with sodium hydroxide. Figure showing the X-ray diffraction measurement results of the laminated body. [Fig. 10] A graph showing the blocking performance of the anionic dye using the separation membrane molded article obtained in Example 1. [Fig. 11] A graph showing the measurement results of the molecular weight cut-off of non-polar molecule polyethylene glycol using the separation membrane formed body obtained in Example 1. [Fig. 12] Fig. 12 is a graph showing the water permeability evaluation and the salt rejection rate of a salt-containing solution using a liquid substance separation membrane formed body containing allite and graphene oxide obtained in Example 2 at a mass ratio of 1:1. [Fig. 13] Fig. 13 is a graph showing the water permeability evaluation and the salt rejection rate of a salt-containing solution using a liquid substance separation membrane formed body containing the allite and graphene oxide obtained in Example 2 at a mass ratio of 1:0.1.

Claims (20)

一種液中物質分離膜成形體，其包含液中物質分離膜與支撐該液中物質分離膜的基材(B)，該液中物質分離膜包含總碳原子數15~45且具有1~2個碳原子數10~20的烷基之四級銨離子(a)與具有銨離子的陰離子界面活性劑(b)，且包含具有平均厚度0.7~100nm、平均長徑50~10,000nm及(最大長徑/正交於最大長徑的寬度)=1.0~ 10.0，且為層狀化合物之層間剝離所造成的剝離層物質之板狀粒子(A)。A liquid substance separation membrane formed body, which includes a liquid substance separation membrane and a base material (B) supporting the liquid substance separation membrane. The liquid substance separation membrane contains a total carbon number of 15 to 45 and has 1 to 2 A quaternary ammonium ion (a) of an alkyl group with 10 to 20 carbon atoms and an anionic surfactant (b) having an ammonium ion, and includes an average thickness of 0.7 to 100 nm, an average long diameter of 50 to 10,000 nm, and (maximum Long diameter/width perpendicular to the maximum long diameter) = 1.0~10.0, and are plate-shaped particles (A) of exfoliated layer materials caused by interlayer peeling of layered compounds. 如請求項1之液中物質分離膜成形體，其中上述層狀化合物為艾萊石(ilerite)。As claimed in claim 1, the liquid substance separation membrane formed body is characterized in that the layered compound is ilerite. 如請求項1或2之液中物質分離膜成形體，其中前述液中物質分離膜為艾萊石與氧化石墨烯之複合膜。As claimed in claim 1 or 2, the liquid substance separation membrane is a composite membrane of islaite and graphene oxide. 如請求項1~3中任一項之液中物質分離膜成形體，其中上述液中物質分離膜係由包含用於上述層狀化合物之層間剝離的上述(a)與(b)之板狀粒子(A)的水性分散液所形成而成，該水性分散液中的板狀粒子(A)之雷射繞射式粒徑分布中90%累計粒徑值為該粒徑分布的平均值之1.5~10倍。The liquid substance separation membrane molded article according to any one of claims 1 to 3, wherein the liquid substance separation membrane is composed of a plate-shaped plate containing the above-mentioned (a) and (b) for interlayer peeling of the above-mentioned layered compound. It is formed from an aqueous dispersion of particles (A). The 90% cumulative particle size value of the laser diffraction particle size distribution of the plate-shaped particles (A) in the aqueous dispersion is the average value of the particle size distribution. 1.5~10 times. 如請求項1~4中任一項之液中物質分離膜成形體，其中上述液中物質分離膜係由包含用於上述層狀化合物之層間剝離的上述(a)與(b)之板狀粒子(A)的水性分散液所形成而成，該水性分散液之動態光散射法所測得的平均粒徑為10~10,000nm，上述(a)與(b)一起係相對於(A)而言在0.01~50.0質量%之範圍的板狀粒子(A)。The liquid substance separation membrane molded article according to any one of claims 1 to 4, wherein the liquid substance separation membrane is composed of a plate-shaped plate containing the above-mentioned (a) and (b) for interlayer peeling of the above-mentioned layered compound. It is formed from an aqueous dispersion of particles (A). The average particle diameter measured by the dynamic light scattering method of the aqueous dispersion is 10~10,000nm. The above (a) and (b) are relative to (A) In terms of plate-shaped particles (A) in the range of 0.01 to 50.0% by mass. 如請求項1~5中任一項之液中物質分離膜成形體，其中上述基材(B)係選自由纖維素、合成高分子及陶瓷所成之群組的至少1種多孔質基材。The liquid substance separation membrane formed body according to any one of claims 1 to 5, wherein the substrate (B) is at least one porous substrate selected from the group consisting of cellulose, synthetic polymers, and ceramics. . 如請求項6之液中物質分離膜成形體，其中上述纖維素為硝基纖維素、羧甲基纖維素或羥乙基纖維素。As claimed in Claim 6, the liquid substance separation membrane formed body is wherein the cellulose is nitrocellulose, carboxymethyl cellulose or hydroxyethyl cellulose. 如請求項6之液中物質分離膜成形體，其中上述合成高分子為聚醚碸、聚碸、聚偏二氟乙烯、聚偏二氯乙烯、聚乙烯乙烯醇、聚乙烯醇、聚丙烯酸或聚甲基丙烯酸。Such as the liquid substance separation membrane formed body of claim 6, wherein the above-mentioned synthetic polymer is polyether styrene, polystyrene, polyvinylidene fluoride, polyvinylidene chloride, polyethylene vinyl alcohol, polyvinyl alcohol, polyacrylic acid or Polymethacrylic acid. 如請求項6之液中物質分離膜成形體，其中上述陶瓷為二氧化矽、氧化鋁或莫來石。As claimed in claim 6, the liquid substance separation membrane formed body is characterized in that the ceramic is silica, alumina or mullite. 如請求項1~9中任一項之液中物質分離膜成形體，其中上述液中物質分離膜係形成在基材(B)表面上而成，上述液中物質分離膜具有1.5nm~10μm的膜厚。The liquid substance separation membrane molded body according to any one of claims 1 to 9, wherein the liquid substance separation membrane is formed on the surface of the base material (B), and the liquid substance separation membrane has a diameter of 1.5 nm to 10 μm. film thickness. 如請求項1~10中任一項之液中物質分離膜成形體，其中包含被分離物質的溶液之溶劑的穿透速度為0.1~100L・m -2・hr -1・bar -1。 For example, in the liquid substance separation membrane formed body according to any one of claims 1 to 10, the penetration rate of the solvent of the solution containing the substance to be separated is 0.1 to 100L・m -2・hr -1・bar -1 . 如請求項1~11中任一項之液中物質分離膜成形體，其中包含被分離物質的溶液之物質去除率為15~99%。For example, the liquid substance separation membrane formed body according to any one of claims 1 to 11, wherein the substance removal rate of the solution containing the substance to be separated is 15 to 99%. 如請求項1~12中任一項之液中物質分離膜成形體，其中被分離物質為離子性化合物。The liquid substance separation membrane formed body according to any one of claims 1 to 12, wherein the substance to be separated is an ionic compound. 如請求項13之液中物質分離膜成形體，其中上述離子性化合物為至少具有磺酸離子或羧酸離子的有機化合物。The liquid substance separation membrane formed body according to claim 13, wherein the ionic compound is an organic compound having at least sulfonate ions or carboxylate ions. 如請求項1~14中任一項之液中物質分離膜成形體，其中包含被分離物質的溶液為包含被分離物質及與該被分離物質不同分子量的至少1種以上之溶質分子之溶液，液中物質分離膜成形體用於濃縮該溶液中的被分離物質。The liquid substance separation membrane formed body according to any one of claims 1 to 14, wherein the solution containing the substance to be separated is a solution containing the substance to be separated and at least one or more solute molecules having different molecular weights from the substance to be separated, The liquid substance separation membrane formed body is used to concentrate the substance to be separated in the solution. 一種如請求項1~15中任一項之液中物質分離膜成形體之製造方法，其包含下述(i)步驟~(vi)步驟： (i)步驟：將矽酸化合物水溶液在90~150℃之溫度下水熱處理後，將靜置所得之層狀化合物進行分離並水洗，將所得之濕式凝膠添加至水中，製造層狀化合物的水性分散液之步驟； (ii)步驟：於(i)步驟所得之水性分散液中，添加四級銨離子(a)，在40~100℃下加熱12~48小時之步驟，該四級銨離子(a)成為層狀化合物的離子交換容量之等倍~三倍量，總碳原子數15~45，且具有1~2個碳原子數10~20的烷基； (iii)步驟：於(ii)步驟所得之液中添加純水，以液中的鈉離子濃度成為100ppm以下之方式，將鈉離子含有液去除到系外之步驟； (iv)步驟：使(iii)步驟所含有的濕式凝膠分散於濃度為0.01~1質量%的具有銨離子的陰離子界面活性劑(b)水溶液中後，進一步添加氨而將液中的pH調至9.0~12.0之步驟； (v)步驟：將(iv)步驟所得之液在40~90℃下加熱12~48小時，得到板狀粒子(A)的分散液之步驟； (vi)步驟：在基材(B)表面上，使用(v)步驟所得之板狀粒子(A)的分散液來製造液中物質分離膜之步驟。 A method for manufacturing a liquid substance separation membrane formed body according to any one of claims 1 to 15, which includes the following steps (i) to (vi): (i) Step: After hydrothermal treatment of the silicic acid compound aqueous solution at a temperature of 90 to 150°C, the layered compound obtained by standing is separated and washed with water, and the obtained wet gel is added to water to produce a layered compound. Aqueous dispersion steps; Step (ii): Add quaternary ammonium ions (a) to the aqueous dispersion obtained in step (i), and heat at 40 to 100°C for 12 to 48 hours. The quaternary ammonium ions (a) form a layer It is equal to three times the ion exchange capacity of the compound, has a total carbon number of 15 to 45, and has 1 to 2 alkyl groups with 10 to 20 carbon atoms; (iii) Step: Add pure water to the liquid obtained in step (ii), and remove the sodium ion-containing liquid out of the system so that the sodium ion concentration in the liquid becomes 100 ppm or less; Step (iv): After dispersing the wet gel contained in step (iii) in an aqueous solution of the anionic surfactant (b) containing ammonium ions at a concentration of 0.01 to 1% by mass, ammonia is further added to remove the ammonia in the solution. Steps to adjust pH to 9.0~12.0; (v) step: heating the liquid obtained in step (iv) at 40 to 90°C for 12 to 48 hours to obtain a dispersion of plate-shaped particles (A); (vi) Step: A step of producing a liquid substance separation membrane on the surface of the base material (B) using the dispersion of the plate-shaped particles (A) obtained in the (v) step. 如請求項16之液中物質分離膜成形體之製造方法，其中前述(vi)步驟係將液中物質分離膜製膜之步驟，包含在基材(B)表面上，使用(v)步驟所得之板狀粒子(A)的分散液來形成板狀粒子(A)層之步驟，及在該層之上使用氧化石墨烯的分散液來積層氧化石墨烯層之步驟。As claimed in claim 16, the method for manufacturing a liquid substance separation membrane formed body, wherein the aforementioned step (vi) is a step of forming a liquid substance separation membrane on the surface of the substrate (B), obtained by using the step (v) A step of forming a layer of the plate-shaped particles (A) using a dispersion of the plate-shaped particles (A), and a step of laminating a graphene oxide layer on the layer using a dispersion of graphene oxide. 如請求項16或17之液中物質分離膜成形體之製造方法，其中在基材(B)表面上，使用(v)步驟所得之板狀粒子(A)的分散液進行製膜之步驟(vi)，係以抽吸過濾或加壓過濾進行。The method of claim 16 or 17, wherein the step of forming a membrane on the surface of the base material (B) is performed using the dispersion of the plate-shaped particles (A) obtained in the step (v) ( vi), which is carried out by suction filtration or pressure filtration. 如請求項16或17之液中物質分離膜成形體之製造方法，其中於(v)步驟與(vi)步驟之間，進一步追加(v-0)步驟； (v-0)步驟：將(v)步驟所得之包含板狀粒子(A)的分散液，使總碳原子數15~45且具有1~2個碳原子數10~20的烷基之四級銨離子(a)與具有銨離子的陰離子界面活性劑(b)之含量一起相對於板狀粒子(A)而言減低至0.01~15.0質量%之範圍，得到包含板狀粒子(A)的分散液之步驟。 The method for manufacturing a liquid substance separation membrane molded body according to claim 16 or 17, wherein a step (v-0) is further added between the (v) step and the (vi) step; Step (v-0): Divide the dispersion containing plate-shaped particles (A) obtained in step (v) into an alkyl group having a total carbon number of 15 to 45 and 1 to 2 alkyl groups of 10 to 20 carbon atoms. The contents of grade ammonium ions (a) and the anionic surfactant (b) containing ammonium ions are reduced to the range of 0.01 to 15.0 mass % relative to the plate-shaped particles (A), and a plate-shaped particle (A) is obtained. Dispersion steps. 如請求項19之液中物質分離膜成形體之製造方法，其中(v-0)步驟為下述(v-1)步驟； (v-1)步驟：對於(v)步驟所得之包含板狀粒子(A)的分散液，以20000~60000G進行超離心處理，得到使總碳原子數15~45且具有1~2個碳原子數10~20的烷基之四級銨離子(a)與具有銨離子的陰離子界面活性劑(b)之含量一起相對於(A)而言減低至0.01~15.0質量%之範圍之包含板狀粒子(A)的分散液之步驟。 As claimed in Claim 19, the method for manufacturing a liquid substance separation membrane formed body, wherein step (v-0) is the following step (v-1); Step (v-1): The dispersion containing plate-shaped particles (A) obtained in step (v) is subjected to ultracentrifugation at 20000~60000G to obtain a total carbon number of 15~45 and 1~2 carbon atoms. A plate containing a quaternary ammonium ion (a) with an alkyl group having an atom number of 10 to 20 and an anionic surfactant (b) having an ammonium ion that is reduced to a range of 0.01 to 15.0% by mass relative to (A) dispersion of particles (A).
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