JP2751264B2 - Hollow fiber membrane for water purification - Google Patents
Hollow fiber membrane for water purificationInfo
- Publication number
- JP2751264B2 JP2751264B2 JP29602188A JP29602188A JP2751264B2 JP 2751264 B2 JP2751264 B2 JP 2751264B2 JP 29602188 A JP29602188 A JP 29602188A JP 29602188 A JP29602188 A JP 29602188A JP 2751264 B2 JP2751264 B2 JP 2751264B2
- Authority
- JP
- Japan
- Prior art keywords
- hollow fiber
- fiber membrane
- water purification
- added
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、浄水用中空糸膜に関する。更に詳しくは、
乾湿式紡糸法により得られた中空糸膜よりなる浄水用中
空糸膜に関する。Description: TECHNICAL FIELD The present invention relates to a hollow fiber membrane for water purification. More specifically,
The present invention relates to a hollow fiber membrane for water purification comprising a hollow fiber membrane obtained by a dry-wet spinning method.
〔従来の技術〕および〔発明が解決しようとする課題〕 現在浄水器などに用いられている浄水用中空糸膜は、
水道水中のカルキ臭などの原因となっている塩素分を減
少乃至除去することを目的としており、それに伴って中
空糸膜の表面に堆積した雑菌などが繁殖し易い状態とな
っており、不衛生に使用されることも多い。[Prior art] and [Problems to be solved by the invention] Currently, hollow fiber membranes for water purification used in water purifiers are:
The purpose is to reduce or remove chlorine, which is the cause of the smell of tap water in the tap water.Accordingly, various bacteria accumulated on the surface of the hollow fiber membrane are liable to propagate, and Often used for.
雑菌類が繁殖するとそこに異臭の発生がみられるよう
になり、それを防止するために、中空糸膜を洗浄したり
あるいは防菌剤や防黴剤を添加したりすることが行われ
るが、前者は持続性に欠けるのでくり返し定期的に洗浄
することが必要であり、また後者は有機化合物であるた
め溶出の危険性がある。When germs grow, an off-flavor starts to appear, and in order to prevent it, washing the hollow fiber membrane or adding a fungicide or fungicide is performed. The former lacks sustainability and requires repeated cleaning, and the latter is an organic compound and may be eluted.
本発明の目的は、中空糸膜に口過残渣となった黴、雑
菌、藻類などの繁殖または腐敗を有効に防止し、異臭発
生を抑制させる浄水用中空糸膜を提供することにある。An object of the present invention is to provide a hollow fiber membrane for water purification that effectively prevents the growth or decay of molds, germs, algae, etc., which have become a mouth residue on the hollow fiber membrane, and suppresses the generation of off-flavors.
かかる目的を達成せしめる本発明の浄水用中空糸膜
は、約0.1〜30重量％の抗菌セラミックス粉末を添加し
た高分子物質より形成され、膜の外面側層が密で内部側
が疎な構造を有する中空糸膜よりなる。The water purifying hollow fiber membrane of the present invention that achieves the above object is formed of a polymer material to which about 0.1 to 30% by weight of antibacterial ceramic powder is added, and has a structure in which the outer surface layer is dense and the inner side is sparse. It consists of a hollow fiber membrane.
膜の外面側層が密で内部側が疎な構造を有する中空糸
膜は、高分子物質の有機溶媒溶液を紡糸原液（ドープ
液）とする通常の乾湿式紡糸法により形成され、一般に
水などが用いられるゲル化浴と接触する外面側層は密な
構造となり、一方内部側は疎な構造となる。A hollow fiber membrane having a structure in which the outer layer is dense and the inner side is sparse is formed by a normal dry-wet spinning method using an organic solvent solution of a polymer substance as a spinning solution (dope solution). The outer layer in contact with the gelling bath used has a dense structure, while the inner layer has a sparse structure.
中空糸膜の主構成成分となる高分子物質としては、例
えばポリスルホン、ポリエーテルスルホン、ポリアクリ
ロニトリル、芳香族ポリアミド、ポリ塩化ビニル、ポリ
フッ化ビニリデン、ポリオレフィン、ポリスチレン、ポ
リカーボネート、ポリメチルメタクリレート、ポリビニ
ルアルコール、エチレン−酢酸ビニル共重合体、酢酸セ
ルロースなどが用いられる。Examples of the polymer substance serving as a main component of the hollow fiber membrane include polysulfone, polyether sulfone, polyacrylonitrile, aromatic polyamide, polyvinyl chloride, polyvinylidene fluoride, polyolefin, polystyrene, polycarbonate, polymethyl methacrylate, polyvinyl alcohol, Ethylene-vinyl acetate copolymer, cellulose acetate and the like are used.
これらの高分子物質には、約0.1〜30重量％の抗菌セ
ラミックス粉末が添加され、紡糸原液を調製した上で乾
湿式紡糸される。抗菌セラミックスの添加割合がこれよ
り少ないと、本発明の目的とする異臭発生の抑制効果が
発揮されず、一方これより多い割合で添加すると、例え
ば後記実施例においてポリフッ化ビニリデン15重量部に
対して抗菌セラミックスを７重量部（約32重量％）添加
すると、外面側層が密で内部側が疎な構造の中空糸膜が
得られなくなり、即ち雑菌が繁殖し易い膜の外面側層の
構造が密となることにより抗菌セラミックスもその層に
多く存在し、雑菌の繁殖を有効に防止するという本発明
の目的が達成されないようになる。About 0.1 to 30% by weight of an antibacterial ceramic powder is added to these polymer substances, and a spinning dope is prepared, followed by dry-wet spinning. When the addition ratio of the antibacterial ceramic is less than this, the effect of suppressing the generation of off-flavors aimed at by the present invention is not exhibited, while when added at a higher ratio, for example, in the Examples described later, for 15 parts by weight of polyvinylidene fluoride When 7 parts by weight (approximately 32% by weight) of antibacterial ceramic is added, a hollow fiber membrane having a dense outer layer and a sparse inner layer cannot be obtained. As a result, a large amount of antibacterial ceramics is also present in the layer, and the object of the present invention of effectively preventing the propagation of various bacteria cannot be achieved.
高分子物質の有機溶媒溶液中にセラミックス粉末を高
充填した紡糸原液を乾湿式紡糸することは、既に本出願
人によって提案されているが（特開昭62−52,185号公
報）、そこでは乾湿式紡糸して得られた複合膜を焼成し
て多孔質セラミックス膜を製造することを目的としてい
るため、当然セラミックス粉末の充填濃度は高く、その
実施例では約67％となっており、そこではセラミックス
粉末充填濃度と中空糸膜構造との関係については何な考
慮されていない。Dry-wet spinning of a spinning solution in which ceramic powder is highly filled in an organic solvent solution of a polymer substance has already been proposed by the present applicant (Japanese Patent Application Laid-Open No. 62-52,185). Since the purpose is to produce a porous ceramic film by firing the composite film obtained by spinning, the filling concentration of the ceramic powder is naturally high, and it is about 67% in the example. No consideration is given to the relationship between the powder filling concentration and the hollow fiber membrane structure.
抗菌セラミックス粉末は、イオン化した金属を骨格構
造内にイオン結合させたゼオライト系セラミックスであ
り、殺菌作用を有する金属としての銀、銅、亜鉛、錫な
どが各種合成ゼオライト、合成モルデナイト、ハイシリ
カゼオライトなどの合成品ゼオライトまたはモルデナイ
ト、クリノプチロライト、チャバサイトなどの天然品ゼ
オライトにイオン状態で保持された、一般に平均粒径約
10μｍ以下のものが用いられる。Antibacterial ceramic powders are zeolite-based ceramics in which ionized metals are ion-bonded in the skeletal structure. Silver, copper, zinc, tin, etc., as germicidal metals, are various synthetic zeolites, synthetic mordenites, high silica zeolites, etc. Synthetic zeolites or natural zeolites such as mordenite, clinoptilolite and chabazite, which are held in an ionic state, generally having an average particle size of about
Those having a size of 10 μm or less are used.
かかる抗菌セラミックス粉末を添加した紡糸原液の乾
湿式紡糸は、通常の方法に従って行われる。Dry-wet spinning of the spinning stock solution to which the antibacterial ceramic powder is added is performed according to a usual method.
本発明に係る浄水用中空糸膜は、膜の外面側層が密で
内部側が疎な構造を有しており、これを浄水に用いた場
合には水は中空糸膜の内部から外部にロ過され、その際
雑菌は外面側層に多く堆積するが、その部分の膜構造を
密にし、抗菌セラミックス粉末量を多く保持せしめるこ
とにより、雑菌の繁殖を有効に防止し、異臭の発生を持
続的かつ効果的に抑制することができる。The hollow fiber membrane for water purification according to the present invention has a structure in which the outer surface layer of the membrane is dense and the inner side is sparse, and when this is used for water purification, water flows from the inside of the hollow fiber membrane to the outside. At that time, many germs accumulate on the outer surface layer, but by making the membrane structure of that part dense and keeping a large amount of antibacterial ceramic powder, the propagation of germs is effectively prevented, and the generation of odor is maintained. Can be effectively and effectively suppressed.
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
実施例 ポリフッ化ビニリデン（三菱油化製品カイナー460）1
5重量部、ジメチルアセトアミド（関東化学製品）78重
量部およびポリエチレングリコール（関東化学製品＃60
00）10重量部よりなる紡糸原液中に、５重量部（25重量
％）抗菌セラミックス（シナネンニューセラミックス社
製品ゼオミックス）を添加し、この分散液を次の紡糸条
件下で乾湿式紡糸して中空糸を得た。また、比較のため
に、抗菌セラミックスを添加しない中空糸も紡糸した。Example Polyvinylidene fluoride (Mitsubishi Yuka Kainer 460) 1
5 parts by weight, 78 parts by weight of dimethylacetamide (Kanto Chemical) and polyethylene glycol (Kanto Chemical # 60)
00) 5 parts by weight (25% by weight) of antibacterial ceramic (Zeomix manufactured by Sinanen New Ceramics Co., Ltd.) was added to 10 parts by weight of the spinning dope, and this dispersion was dried and wet spun under the following spinning conditions to form a hollow. Yarn was obtained. For comparison, a hollow fiber to which no antibacterial ceramic was added was also spun.
紡糸ノズル：内径0.3mm、外径0.5mm 紡糸速度:25m/分 ゲル化浴：水（20℃） 得られた中空糸を10cmの長さに切断し、その５本づつ
を100mlの無菌水中で洗浄し、この洗浄液のロ過液中の
一般細菌を標準寒天培地法で培養（ペプトン5g、粉末酵
母エキス2.5g、ぶどう糖1gおよび粉末寒天15gを水１
中に加温溶解して滅菌し、シャーレを冷却して作った標
準寒天培地に展開し、37℃で24時間培養）した後、培地
上に生長したコロニー数を計測すると、抗菌セラミック
スを添加しない中空糸の洗浄水についてはコロニー数が
3000ケ/mlであるのに対し、５重量部の抗菌セラミック
スを添加した中空糸の洗浄水では50ケ/mlであった。Spinning nozzle: inner diameter 0.3 mm, outer diameter 0.5 mm Spinning speed: 25 m / min Gelation bath: water (20 ° C.) The obtained hollow fiber is cut into 10 cm lengths, and each of the five fibers is cut in 100 ml of sterile water. After washing, the general bacteria in the filtrate of this washing solution are cultured by a standard agar medium method (5 g of peptone, 2.5 g of powdered yeast extract, 1 g of glucose and 15 g of powdered agar and 1 g of water).
After heating and dissolving in a sterile medium, cooling the Petri dish to spread on a standard agar medium, and culturing at 37 ° C for 24 hours), counting the number of colonies that grew on the medium, no antimicrobial ceramic was added The number of colonies in the hollow fiber washing water
In contrast to 3000 pcs / ml, the washing water of the hollow fiber to which 5 parts by weight of the antibacterial ceramic was added was 50 pcs / ml.
また、これらの中空糸を用い、水道水中の一般細菌
（細菌数５〜10×105/ml）について、上記と同様にロ過
および培養を行った後、20℃の空気中に３日間放置して
腐敗臭の有無を調べたところ、抗菌セラミックスを添加
しない中空糸については腐敗臭が感じられたが、添加し
た中空糸については腐敗臭がなかった。Using these hollow fibers, filtration and cultivation of common bacteria (number of bacteria 5 to 10 × 10 5 / ml) in tap water in the same manner as described above, and then left in the air at 20 ° C. for 3 days When the presence or absence of putrefaction odor was examined, a putrefaction odor was felt for the hollow fiber to which the antibacterial ceramic was not added, but no putrefaction odor was found for the added hollow fiber.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｄ０１Ｆ 6/48 Ｄ０１Ｆ 6/48 Ｃ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 identification code FI D01F 6/48 D01F 6/48 C
Claims (1)
添加した高分子物質より形成され、膜の外面側層が密で
内部側が疎な構造を有する中空糸膜よりなる浄水用中空
糸膜。1. A hollow fiber membrane for water purification, comprising a hollow fiber membrane formed of a polymer material to which 0.1 to 30% by weight of an antibacterial ceramic powder is added and having a structure in which the outer surface layer is dense and the inner side is sparse.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29602188A JP2751264B2 (en) | 1988-11-25 | 1988-11-25 | Hollow fiber membrane for water purification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29602188A JP2751264B2 (en) | 1988-11-25 | 1988-11-25 | Hollow fiber membrane for water purification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02144133A JPH02144133A (en) | 1990-06-01 |
| JP2751264B2 true JP2751264B2 (en) | 1998-05-18 |
Family
ID=17828093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29602188A Expired - Fee Related JP2751264B2 (en) | 1988-11-25 | 1988-11-25 | Hollow fiber membrane for water purification |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2751264B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004525755A (en) * | 2001-01-23 | 2004-08-26 | アマシャム・バイオサイエンス・メムブレイン・セパレイションズ・コーポレイション | Asymmetric hollow fiber membrane |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2491532C (en) | 2002-06-28 | 2013-03-19 | Mosaic Systems Bv | Functional porous fibres |
-
1988
- 1988-11-25 JP JP29602188A patent/JP2751264B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004525755A (en) * | 2001-01-23 | 2004-08-26 | アマシャム・バイオサイエンス・メムブレイン・セパレイションズ・コーポレイション | Asymmetric hollow fiber membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02144133A (en) | 1990-06-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |