WO2020213208A1 - Filter aid, and filter and hygiene product containing filter aid - Google Patents

Filter aid, and filter and hygiene product containing filter aid Download PDF

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Publication number
WO2020213208A1
WO2020213208A1 PCT/JP2019/048394 JP2019048394W WO2020213208A1 WO 2020213208 A1 WO2020213208 A1 WO 2020213208A1 JP 2019048394 W JP2019048394 W JP 2019048394W WO 2020213208 A1 WO2020213208 A1 WO 2020213208A1
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Prior art keywords
acrylonitrile
filter
filtration
based polymer
amino group
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PCT/JP2019/048394
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French (fr)
Japanese (ja)
Inventor
小見山拓三
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日本エクスラン工業株式会社
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Publication of WO2020213208A1 publication Critical patent/WO2020213208A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D37/00—Processes of filtration
    • B01D37/02—Precoating the filter medium; Addition of filter aids to the liquid being filtered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/42—Nitriles
    • C08F20/44—Acrylonitrile

Definitions

  • the present invention relates to a filtration aid made of an acrylonitrile-based polymer and a filter containing the filtration aid.
  • the filtration aid When separating the minute components contained in the liquid from the liquid, the filtration aid is capable of separating the fine components by physical filtration means by adsorbing and aggregating the fine components and coarsening them.
  • Such filtration aids are indispensable for removing unnecessary components in liquids in the food and medical industries, etc., and the efficiency of filtration performance has been actively improved, and various studies have been conducted.
  • Patent Document 1 discloses a filtration aid made of cellulose powder.
  • the filtration aid is not satisfactory because the clarity of the filtrate does not necessarily increase with respect to the treatment of a highly turbid liquid.
  • Non-Patent Document 1 raises a problem of a disposal method after use and the safety of diatomaceous earth itself.
  • Patent Documents 2 and 3 propose adsorbents using amino groups, but a large amount of amino groups are introduced in order to ensure adsorption performance, and there is a concern about amine elution.
  • the present invention has been devised in view of the current state of the art, and an object of the present invention is to provide a filtration aid having excellent performance as compared with conventional materials, and a filter and a sanitary product containing the filtration aid. To provide.
  • an acrylonitrile-based polymer containing an amino group or an ammonium group has excellent filtration aid performance, and has reached the present invention. ..
  • the present invention is achieved by the following means.
  • the filtration aid according to (1) or (2), wherein the acrylonitrile-based polymer is in the form of aggregated particles or pulp.
  • the filtration aid according to any one of (1) to (3) which is for manufacturing foods, cosmetics or pharmaceuticals.
  • the filtration aid of the present invention has an excellent filtration performance while having a smaller amount of amino groups or ammonium groups than before.
  • the filtration aid of the present invention includes various types such as electrolytic salt water, boiler water, industrial filtration such as metal recovery and refining, food filtration such as sake, wine, beer, juice, tea, and cooking oil, and filtration of pharmaceuticals and cosmetics. It can be used for filtration of organic and inorganic suspension components (proteins, lipids, microorganisms, insoluble salts, etc.) in various fields.
  • the filtration aid of the present invention comprises an acrylonitrile-based polymer.
  • an acrylonitrile-based polymer contains 70% by weight or more, preferably 80% by weight or more, and more preferably 85% by weight or more of acrylonitrile units as a polymerization composition.
  • the acrylonitrile unit is less than the above lower limit, the amphipathic property of the acrylonitrile-based polymer may not be sufficiently obtained, and the effect of removing the suspended component may not be sufficiently obtained. In addition, it tends to be in the form of an emulsion, which may make it unsuitable for use as a filtration aid.
  • the upper limit of the acrylonitrile unit is not particularly limited, but in the case of copolymerizing a vinyl-based monomer having an amino group or an ammonium group described later, it is preferably 99.5% by weight or less, more preferably 95. By weight or less, more preferably 92% by weight or less.
  • the acrylonitrile-based polymer used in the present invention contains an amino group or an ammonium group of 0.05 to 2.0 mmol / g, preferably 0.1 to 1.0 mmol / g. If the amount of amino group or ammonium group is less than the above lower limit, sufficient filtration performance may not be obtained, and if it exceeds the above upper limit, the hydrophilicity of the acrylonitrile polymer becomes too high and water It may swell or dissolve violently, making it difficult to handle.
  • a primary to tertiary amino group or a primary to quaternary ammonium group can be adopted, but from the viewpoint of filtration performance, a tertiary amino group or a quaternary ammonium group can be adopted. It is desirable to be a group.
  • the acrylonitrile-based polymer used in the present invention is preferably a copolymer containing acrylonitrile and a vinyl-based monomer having an amino group or an ammonium group as a constituent unit.
  • a method for introducing an amino group or an ammonium group into the acrylonitrile-based polymer a method of reacting the acrylonitrile-based polymer with an amino group or an ammonium group-containing compound can also be adopted, but the amino group or the ammonium group is added to the obtained polymer. Since there is a high possibility that the ammonium group-containing compound remains unreacted or that the reaction is insufficient and the bond with the polymer is unstable, the amino group is likely to be generated by copolymerization as described above. Alternatively, the method of introducing an ammonium group is preferable.
  • Examples of the vinyl-based monomer having an amino group or an ammonium group that can be used as a constituent unit of the acrylonitrile-based polymer used in the present invention include allylamine, dimethylaminomethylmethacrylate, ethylmethacrylatedimethylbenzylammonium chloride and the like. Be done.
  • the structural unit of the acrylonitrile-based polymer adopted in the present invention in addition to the above-mentioned acrylonitrile and the vinyl-based monomer having an amino group or an ammonium group, other monomers may be used if necessary.
  • other monomers include, but are not limited to, acrylic acid ester, methacrylic acid ester, acrylic acid, methacrylic acid, methacrylic sulfonic acid, p-styrene sulfonic acid, acrylamide, styrene, vinyl acetate and the like. ..
  • the acrylonitrile-based polymer used in the present invention has a specific surface area of 0.1 m 2 / g or more, preferably 4 m 2 / g or more.
  • the specific surface area is less than the above lower limit, the area that can come into contact with the object to be filtered is small, the proportion of amino groups or ammonium groups that cannot be effectively used increases, and the effect of removing suspended components can be sufficiently obtained. It may not be.
  • the upper limit of the specific surface area is not particularly limited, but if the specific surface area is too large, the structure of the polymer becomes brittle and may not be able to withstand actual use. When the specific surface area is 400 m 2 / g or less, the occurrence of such a problem can be suppressed.
  • the shape of the acrylonitrile-based polymer used in the present invention is not particularly limited, and a fibrous, particulate, film-like shape can be adopted. Further, in order to obtain a large specific surface area as described above, it is preferable to form agglomerated particles obtained by agglutinating fine particles or a pulp obtained by beating fibers.
  • the method for producing the acrylonitrile-based polymer adopted in the present invention described above is not particularly limited, and can be produced by a known polymerization method. Further, in order to obtain an acrylonitrile-based polymer in the form of aggregated particles, an aqueous precipitation polymerization method in which a monomer and a water-soluble polymerization initiator are added to water and polymerization is carried out can be adopted.
  • the water-based precipitation polymerization method referred to here uses a water-soluble polymerization initiator, does not add an emulsifier, a dispersion stabilizer, or the like, and as the polymerization progresses, the polymer aggregates and precipitates (suspends during stirring). It refers to the polymerization method.
  • a water-soluble polymerization initiator does not add an emulsifier, a dispersion stabilizer, or the like, and as the polymerization progresses, the polymer aggregates and precipitates (suspends during stirring). It refers to the polymerization method.
  • aqueous precipitation polymerization method precipitation of aggregates in which primary particles having an average particle diameter of 10 ⁇ m or less are aggregated occurs. The particle size of this aggregate is often 1000 ⁇ m or less.
  • the aggregate is not particularly specified, but in the present invention, it is an aggregate of particles having an average particle diameter of primary particles of 5 ⁇ m or less, and when the average particle diameter of the aggregate is 100 ⁇ m or less, the primary particles It is preferable because a large number of cavities are formed in the gaps between them and the specific surface area as an agglomerate increases.
  • a method for producing a fibrous acrylonitrile-based polymer a known method for producing an acrylonitrile fiber can be adopted.
  • a solvent such as nitrate, an aqueous solution of zinc chloride, an aqueous solution of sodium thiocyanate, N-methylpyrrolidone, DMF, DMAc, DMSO, etc.
  • the above-mentioned acrylonitrile polymer is dissolved in a solvent to prepare the product.
  • a fibrous acrylonitrile-based polymer can be obtained by undergoing each step of solidification, washing with water, stretching, heat treatment, and drying after spinning the spun stock solution from the nozzle.
  • the fibrous acrylonitrile-based polymer obtained as described above may be cut and beaten.
  • the method of beating is not limited, and a beating machine such as a beater or a refiner can be used.
  • a beating machine such as a beater or a refiner can be used.
  • the fibrous acrylonitrile-based polymer to be beaten not only the one after the drying step but also the undried fiber after stretching can be used.
  • the acrylonitrile-based polymer used in the present invention described above has excellent filtration performance is not clear, but in general, in addition to the acrylonitrile-based polymer having amyophilicity, the acrylonitrile-based polymer has in the present invention.
  • a nitrile group (anionic) and an amino group or an ammonium group (cationic) it becomes bipolar as a whole, and it seems that a wider range of suspended components can be removed.
  • the specific surface area it seems that the performance can be efficiently exhibited even if the amount of amino groups or ammonium groups is smaller than that of the conventional filtration aid.
  • the amount of amino groups or ammonium groups is smaller than that in the past. Therefore, there is little possibility that an amino group or ammonium group-containing component is eluted into the filtrate during filtration. Further, when the method of introducing an amino group or an ammonium group by the copolymerization as described above is adopted, the unreacted amino group or ammonium group-containing compound remains in the polymer or the bond with the polymer is formed. Since there is no possibility that an unstable amino group or ammonium group is generated, the elution of the amino group or ammonium group-containing component is further suppressed.
  • the filtration aid of the present invention that employs an acrylonitrile-based polymer having such properties also has applicability in the manufacturing process of products such as foods, cosmetics, and pharmaceuticals that need to be considered for their effects on the human body. ..
  • the filtration aid of the present invention is also effective for adsorption and aggregation of red blood cells in blood.
  • the filtration aid of the present invention contains an amino group or an ammonium group, and can also adsorb and aggregate proteins and lipids.
  • the surface of erythrocytes is composed of a lipid film, which contains a protein called glycophorin, and glycophorin has a sugar chain at which an anion-charged sugar called sialic acid is bound. .. Therefore, the filtration aid of the present invention can adsorb and aggregate red blood cells.
  • red blood cells can be applied to sanitary products such as sanitary napkins that absorb liquids containing blood. That is, in sanitary napkins and the like, super absorbent polymers are used, but such resins cannot absorb solid components. Therefore, in the absorption of blood, red blood cells accumulate on the surface of the superabsorbent polymer to form a film, and the absorption of the liquid is inhibited.
  • the filtration aid of the present invention when used, red blood cells in the blood are adsorbed and aggregated, so that the formation of a film on the surface of the superabsorbent polymer by the red blood cells is suppressed, and the liquid absorption is less likely to be inhibited. It is.
  • the filtration aid of the present invention can be used by a body feed method in which the liquid to be treated is directly mixed with the liquid to be treated, or a liquid to be treated after forming a layer of the filter aid on the surface of a filter medium such as a wire mesh prior to filtering the undiluted solution.
  • a precoat method or the like for filtering can be used.
  • the superabsorbent polymer and the filtration aid of the present invention are mixed to form a water-absorbent layer, or the filter aid of the present invention is contained on the skin side of the water-absorbent layer made of the superabsorbent polymer. Means such as providing a layer can be applied.
  • a non-woven fabric containing the fibrous filtration aid of the present invention as a constituent fiber a non-woven fabric containing the particulate filtration aid of the present invention as a constituent fiber, or the like is used as a binder.
  • a binder examples thereof include those attached by using and those filled inside a bag-shaped layer made of a blood-permeable material.
  • the filtration aid of the present invention described above can be used as a filter for removing impurities in many uses, for example, in the production of foods, cosmetics or pharmaceuticals, alone or in combination with other materials.
  • the content of the filtration aid of the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 20% by weight or more in terms of performance.
  • the other materials that can be combined are not particularly limited, and examples thereof include publicly used natural fibers, organic fibers, semi-synthetic fibers, synthetic fibers, inorganic fibers, and glass fibers.
  • it can be used as a member for improving absorption performance in sanitary products such as gauze, bandages, masks, gloves, adhesive plasters, sanitary products, and diapers.
  • the specific surface area is measured by the BET method.
  • ⁇ Measurement of filtration performance > 125 mg of the sample is added to 50 g of a suspension containing 2.5% of dry yeast (Nissin Super Camellia dry yeast), and the mixture is stirred for 10 minutes.
  • the filtrate after suction filtration with a Buchner funnel using filter paper (5A) is dried at 105 ° C. ⁇ 5 hours, and the amount of solids (W1 [g]) contained in the filtrate is measured.
  • Example 1 Ammonium persulfate and sodium metabisulfite were added in a liquid containing 29.1 parts by weight of acrylonitrile, 0.9 parts by weight of dimethylaminoethyl methacrylate and 70 parts by weight of pure water, respectively, at 0.5% and 0.3% based on the weight of the monomer. , Polymerized at 60 ° C. for 55 minutes, washed with water, dehydrated and dried to obtain an acrylonitrile-based polymer in the form of aggregated particles. The evaluation results of the obtained polymer are shown in Table 1.
  • Example 2 10 parts of the particles obtained in Example 1 were dissolved in 90 parts of a 48% sodium thiocyanate aqueous solution to prepare a spinning stock solution.
  • the spinning stock solution was spun into a coagulation bath at ⁇ 2.5 ° C. and subjected to each step of coagulation, washing with water, stretching, heat treatment, and drying to obtain a fibrous acrylonitrile-based polymer.
  • the evaluation results of the obtained polymer are shown in Table 1.
  • Example 3 The fibers obtained in Example 2 were beaten with a Niagara beater to obtain a pulp-like acrylonitrile-based polymer. The evaluation results of the obtained polymer are shown in Table 1.
  • Example 4 In Example 1, the same polymerization was carried out except that the ratio of the monomers was changed to 29.8 parts by weight of acrylonitrile and 0.2 parts by weight of dimethylaminoethyl methacrylate to obtain an acrylonitrile-based polymer in the form of aggregated particles. The evaluation results of the obtained polymer are shown in Table 1.
  • Example 5 In Example 1, polymerization was carried out in the same manner except that the ratio of the monomers was changed to 25.5 parts by weight of acrylonitrile and 4.5 parts by weight of dimethylaminoethyl methacrylate to obtain an acrylonitrile-based polymer in the form of aggregated particles. The evaluation results of the obtained polymer are shown in Table 1.
  • Example 1 ⁇ Comparative example 1>
  • the polymerization was carried out in the same manner except that the monomer was changed to only 30 parts of acrylonitrile to obtain an acrylonitrile-based polymer in the form of aggregated particles having no amino group.
  • the evaluation results of the obtained polymer are shown in Table 1.
  • Table 1 shows the evaluation results using commercially available powdered cellulose (powdered filter paper D manufactured by ADVANTEC).
  • Table 1 shows the evaluation results using a commercially available cellulosic cationic filtration filter (adsorption depth filter disk (Zeta Plus (TM))).
  • Example 1 Polymerization was carried out in the same manner except that the ratio of the monomers was changed to 19.5 parts by weight of acrylonitrile and 10.5 parts by weight of dimethylaminoethyl methacrylate.
  • the obtained acrylonitrile-based polymer has a small amount of acrylonitrile units, becomes a dispersed liquid (emulsion-like) of fine particles, and has redispersibility in water, so that it cannot be used as a filtration aid.
  • the acrylonitrile-based polymers of Examples 1 to 5 have a higher capture rate than the acrylonitrile-based polymers having no amino group of Comparative Example 1 and the cellulosic materials of Comparative Examples 2 to 4, and are filtered. It can be seen that it is highly effective as an auxiliary agent. Further, it can be understood that the acrylonitrile-based polymers of Examples 1 to 5 have a swelling degree of SAP higher than that of the blank (17.9) and have an effect of adsorbing and agglutinating erythrocytes.

Abstract

[Problem] Conventionally known filter aids include those made of a cellulose powder, those in which diatomaceous earth is used, and adsorbents in which an amino group is utilized. However, the filter aids were not necessarily satisfactory; for example, there was a lack of improvement in the filtrate clarity when treating liquids having a high turbidity, and there were concerns regarding safety and the disposal method after use. The present invention was developed in view of the current state of the prior art, and the purpose thereof is to provide a filter aid having a superior performance compared to conventional materials, and a filter containing the filter aid. [Solution] A filter aid comprising an acrylonitrile polymer containing at least 70 wt% of acrylonitrile units and 0.05-2.0 mmol/g of amino groups or ammonium groups, and having a specific surface area of 0.1-400 m2/g.

Description

濾過助剤並びに該濾過助剤を含むフィルター及び衛生用品Filtration aids and filters and hygiene products containing the filter aids
本発明は、アクリロニトリル系重合体からなる濾過助剤及び該濾過助剤を含むフィルターに関する。 The present invention relates to a filtration aid made of an acrylonitrile-based polymer and a filter containing the filtration aid.
濾過助剤は、液体中に含まれる微小成分を液体から分離するに際して、かかる微小成分を吸着凝集させて粗大化することにより、物理的な濾過手段で分離可能とするものである。かかる濾過助剤は食品や医療業界等で液体中の不要成分除去のため必要不可欠なものであり、濾過性能の効率化は盛んに行われており、様々な検討がなされている。例えば、特許文献１には、セルロース粉末からなる濾過助剤が開示されている。しかし、該濾過助剤は、濁質性の高い液体の処理に対して、必ずしも濾過液の清澄度が上がらず、満足できるものではなかった。 When separating the minute components contained in the liquid from the liquid, the filtration aid is capable of separating the fine components by physical filtration means by adsorbing and aggregating the fine components and coarsening them. Such filtration aids are indispensable for removing unnecessary components in liquids in the food and medical industries, etc., and the efficiency of filtration performance has been actively improved, and various studies have been conducted. For example, Patent Document 1 discloses a filtration aid made of cellulose powder. However, the filtration aid is not satisfactory because the clarity of the filtrate does not necessarily increase with respect to the treatment of a highly turbid liquid.
また、珪藻土を濾過助剤として使用する方法もよく知られているが、非特許文献１においては使用済み後の廃棄方法や珪藻土そのものの安全性の問題が提起されている。特許文献２や３においては、アミノ基を利用した吸着材が提案されているが、吸着性能を担保するために多量のアミノ基を導入しており、アミン溶出の懸念がある。 Further, a method of using diatomaceous earth as a filtration aid is well known, but Non-Patent Document 1 raises a problem of a disposal method after use and the safety of diatomaceous earth itself. Patent Documents 2 and 3 propose adsorbents using amino groups, but a large amount of amino groups are introduced in order to ensure adsorption performance, and there is a concern about amine elution.
特開平９－１７３７２８号公報Japanese Unexamined Patent Publication No. 9-173728 国際公開第２０１２／１４７９３７号International Publication No. 2012/147937 特開平７－１８５３３３号公報Japanese Unexamined Patent Publication No. 7-185333
上述したように、濾過助剤は様々な改良がおこなわれているが、性能面において必ずしも満足できるものではなかった。本発明は、かかる従来技術の現状に鑑みて創案されたものであり、その目的は、従来の素材と比較して優れた性能を有する濾過助剤及び該濾過助剤を含むフィルターおよび衛生用品を提供することにある。 As mentioned above, although various improvements have been made to the filtration aid, the performance is not always satisfactory. The present invention has been devised in view of the current state of the art, and an object of the present invention is to provide a filtration aid having excellent performance as compared with conventional materials, and a filter and a sanitary product containing the filtration aid. To provide.
本発明者は、上述の目的を達成するために鋭意検討を進めた結果、アミノ基またはアンモニウム基を含有するアクリロニトリル系重合体が優れた濾過助剤性能を有することを見出し、本発明に到達した。 As a result of diligent studies to achieve the above object, the present inventor has found that an acrylonitrile-based polymer containing an amino group or an ammonium group has excellent filtration aid performance, and has reached the present invention. ..
即ち、本発明は以下の手段により達成される。
（１）７０重量％以上のアクリロニトリル単位および０．０５～２．０ｍｍｏｌ／ｇのアミノ基またはアンモニウム基を含有しており、さらに０．１～４００ｍ２／ｇの比表面積を有しているアクリロニトリル系重合体からなる濾過助剤。
（２）アクリロニトリル系重合体が、アミノ基またはアンモニウム基を有するビニル系単量体を構成単位とするものであることを特徴とする（１）に記載の濾過助剤。
（３）アクリロニトリル系重合体の形状が凝集粒子状またはパルプ状であることを特徴とする（１）または（２）に記載の濾過助剤。
（４）食品、化粧品または医薬品製造用であることを特徴とする（１）～（３）のいずれかに記載の濾過助剤。
（５）（１）～（４）のいずれかに記載の濾過助剤を含むフィルター。
（６）（１）～（３）のいずれかに記載の濾過助剤を含む衛生用品。 That is, the present invention is achieved by the following means.
(1) Acrylonitrile containing 70% by weight or more of acrylonitrile units and 0.05 to 2.0 mmol / g of an amino group or an ammonium group, and further having a specific surface area of 0.1 to 400 m 2 / g. A filtering aid composed of a system polymer.
(2) The filtration aid according to (1), wherein the acrylonitrile-based polymer has a vinyl-based monomer having an amino group or an ammonium group as a constituent unit.
(3) The filtration aid according to (1) or (2), wherein the acrylonitrile-based polymer is in the form of aggregated particles or pulp.
(4) The filtration aid according to any one of (1) to (3), which is for manufacturing foods, cosmetics or pharmaceuticals.
(5) A filter containing the filtration aid according to any one of (1) to (4).
(6) A sanitary product containing the filtration aid according to any one of (1) to (3).
本発明の濾過助剤は、従来よりも少ないアミノ基量またはアンモニウム基量でありながら優れた濾過性能を有するものである。かかる本発明の濾過助剤は、電解塩水、ボイラー用水、金属の回収精錬等の工業濾過、清酒、ワイン、ビール、ジュース、お茶、食用油等の食品濾過、並びに医薬・化粧品等の濾過といった様々な分野の有機系、無機系の懸濁成分（タンパク質、脂質、微生物、不溶塩等）の濾過に利用することができる。とりわけ、従来の濾過助剤よりも含有されるアミノ基やアンモニウム基が少ないことから、アミンやアンモニウムの溶出が抑制されるため、食品、化粧品または医薬品などの人体に関わる製品の製造における濾過工程などに好適に利用することができる。 The filtration aid of the present invention has an excellent filtration performance while having a smaller amount of amino groups or ammonium groups than before. The filtration aid of the present invention includes various types such as electrolytic salt water, boiler water, industrial filtration such as metal recovery and refining, food filtration such as sake, wine, beer, juice, tea, and cooking oil, and filtration of pharmaceuticals and cosmetics. It can be used for filtration of organic and inorganic suspension components (proteins, lipids, microorganisms, insoluble salts, etc.) in various fields. In particular, since it contains less amino groups and ammonium groups than conventional filtration aids, the elution of amines and ammonium is suppressed, so that the filtration process in the manufacture of products related to the human body such as foods, cosmetics or pharmaceuticals, etc. Can be suitably used for.
本発明の濾過助剤はアクリロニトリル系重合体からなるものである。かかるアクリロニトリル系重合体は、重合組成としてアクリロニトリル単位を７０重量％以上、好ましくは８０重量％以上、より好ましくは８５重量％以上含有するものである。アクリロニトリル単位が上記下限に満たない場合には、アクリロニトリル系重合体の両親媒性が十分に得られず、懸濁成分の除去効果が十分に得られない場合がある。また、エマルジョン状となりやすく、濾過助剤としての利用に適さないものとなる場合がある。一方、アクリロニトリル単位の上限については特に限定は無いが、後述するアミノ基またはアンモニウム基を有するビニル系単量体を共重合する場合には、好ましくは９９．５重量％以下で、より好ましくは９５重量％以下、さらに好ましくは９２重量％以下である。 The filtration aid of the present invention comprises an acrylonitrile-based polymer. Such an acrylonitrile-based polymer contains 70% by weight or more, preferably 80% by weight or more, and more preferably 85% by weight or more of acrylonitrile units as a polymerization composition. When the acrylonitrile unit is less than the above lower limit, the amphipathic property of the acrylonitrile-based polymer may not be sufficiently obtained, and the effect of removing the suspended component may not be sufficiently obtained. In addition, it tends to be in the form of an emulsion, which may make it unsuitable for use as a filtration aid. On the other hand, the upper limit of the acrylonitrile unit is not particularly limited, but in the case of copolymerizing a vinyl-based monomer having an amino group or an ammonium group described later, it is preferably 99.5% by weight or less, more preferably 95. By weight or less, more preferably 92% by weight or less.
また、本発明に採用するアクリロニトリル系重合体は、アミノ基またはアンモニウム基を０．０５～２．０ｍｍｏｌ／ｇ、好ましくは０．１～１．０ｍｍｏｌ／ｇ含有するものである。アミノ基またはアンモニウム基の量が上記下限に満たない場合には、十分な濾過性能が得られないことがあり、上記上限を超える場合には、アクリロニトリル系重合体の親水性が高くなりすぎ、水に激しく膨潤したり、溶解したりして、取り扱いが困難となることがある。 The acrylonitrile-based polymer used in the present invention contains an amino group or an ammonium group of 0.05 to 2.0 mmol / g, preferably 0.1 to 1.0 mmol / g. If the amount of amino group or ammonium group is less than the above lower limit, sufficient filtration performance may not be obtained, and if it exceeds the above upper limit, the hydrophilicity of the acrylonitrile polymer becomes too high and water It may swell or dissolve violently, making it difficult to handle.
アミノ基およびアンモニウム基の種類としては、１級から３級のアミノ基、１級から４級のアンモニウム基のいずれでも採用しうるが、濾過性能の点からは、３級アミノ基または４級アンモニウム基であることが望ましい。 As the type of amino group and ammonium group, either a primary to tertiary amino group or a primary to quaternary ammonium group can be adopted, but from the viewpoint of filtration performance, a tertiary amino group or a quaternary ammonium group can be adopted. It is desirable to be a group.
さらに、本発明に採用するアクリロニトリル系重合体としては、アクリロニトリルとアミノ基またはアンモニウム基を有するビニル系単量体を構成単位として含有する共重合体であることが望ましい。なお、アクリロニトリル系重合体にアミノ基またはアンモニウム基を導入する方法として、アクリロニトリル系重合体にアミノ基またはアンモニウム基含有化合物を反応させる方法も採用しうるが、得られた重合体中にアミノ基またはアンモニウム基含有化合物が未反応のまま残留したり、反応が不十分で重合体と結合が不安定な状態のものが発生したりする可能性が高くなるため、上述のように共重合によりアミノ基またはアンモニウム基を導入する方法のほうが望ましい。 Further, the acrylonitrile-based polymer used in the present invention is preferably a copolymer containing acrylonitrile and a vinyl-based monomer having an amino group or an ammonium group as a constituent unit. As a method for introducing an amino group or an ammonium group into the acrylonitrile-based polymer, a method of reacting the acrylonitrile-based polymer with an amino group or an ammonium group-containing compound can also be adopted, but the amino group or the ammonium group is added to the obtained polymer. Since there is a high possibility that the ammonium group-containing compound remains unreacted or that the reaction is insufficient and the bond with the polymer is unstable, the amino group is likely to be generated by copolymerization as described above. Alternatively, the method of introducing an ammonium group is preferable.
本発明に採用するアクリロニトリル系重合体の構成単位として採用しうるアミノ基またはアンモニウム基を有するビニル系単量体としては、例えば、アリルアミン、ジメチルアミノメチルメタクリレート、メタクリル酸エチルジメチルベンジルアンモニウムクロライド等が挙げられる。 Examples of the vinyl-based monomer having an amino group or an ammonium group that can be used as a constituent unit of the acrylonitrile-based polymer used in the present invention include allylamine, dimethylaminomethylmethacrylate, ethylmethacrylatedimethylbenzylammonium chloride and the like. Be done.
本発明に採用するアクリロニトリル系重合体の構成単位としては、上述したアクリロニトリルおよびアミノ基またはアンモニウム基を有するビニル系単量体に加え、必要に応じてその他の単量体を使用してもよい。かかるその他の単量体としては、特に限定はないが、アクリル酸エステル、メタクリル酸エステル、アクリル酸、メタクリル酸、メタリルスルホン酸、ｐ－スチレンスルホン酸、アクリルアミド、スチレン、酢酸ビニル等が挙げられる。 As the structural unit of the acrylonitrile-based polymer adopted in the present invention, in addition to the above-mentioned acrylonitrile and the vinyl-based monomer having an amino group or an ammonium group, other monomers may be used if necessary. Examples of such other monomers include, but are not limited to, acrylic acid ester, methacrylic acid ester, acrylic acid, methacrylic acid, methacrylic sulfonic acid, p-styrene sulfonic acid, acrylamide, styrene, vinyl acetate and the like. ..
また、本発明に採用するアクリロニトリル系重合体は、比表面積として０．１ｍ２／ｇ以上、好ましくは４ｍ２／ｇ以上を有するものである。比表面積が上記下限未満である場合には、濾過対象物との接触できる面積が小さく、有効に利用できないアミノ基またはアンモニウム基の割合が多くなって、懸濁成分の除去効果が十分に得られない場合がある。一方、比表面積の上限については特に制限は無いが、あまりに比表面積が大きい場合には、重合体の構造が脆くなり、実使用に耐えられなくなる場合がある。比表面積が４００ｍ２／ｇ以下とするとこのような問題の発生を抑制することができる。 Further, the acrylonitrile-based polymer used in the present invention has a specific surface area of 0.1 m 2 / g or more, preferably 4 m 2 / g or more. When the specific surface area is less than the above lower limit, the area that can come into contact with the object to be filtered is small, the proportion of amino groups or ammonium groups that cannot be effectively used increases, and the effect of removing suspended components can be sufficiently obtained. It may not be. On the other hand, the upper limit of the specific surface area is not particularly limited, but if the specific surface area is too large, the structure of the polymer becomes brittle and may not be able to withstand actual use. When the specific surface area is 400 m 2 / g or less, the occurrence of such a problem can be suppressed.
本発明に採用するアクリロニトリル系重合体の形状としては、特に限定されず、繊維状、粒子状、フィルム状等の形状を採ることができる。また、上述したような大きな比表面積を得るには、微小粒子を凝集させて得られる凝集粒子状や繊維を叩解して得られるパルプ状とすることが好ましい。 The shape of the acrylonitrile-based polymer used in the present invention is not particularly limited, and a fibrous, particulate, film-like shape can be adopted. Further, in order to obtain a large specific surface area as described above, it is preferable to form agglomerated particles obtained by agglutinating fine particles or a pulp obtained by beating fibers.
上述してきた本発明に採用するアクリロニトリル系重合体を製造する方法としては特に制限はなく、公知の重合方法により製造することができる。また、凝集粒子状のアクリロニトリル系重合体を得るには、水中に単量体と水溶性重合開始剤を加えて重合を行う水系沈殿重合法を採用することができる。 The method for producing the acrylonitrile-based polymer adopted in the present invention described above is not particularly limited, and can be produced by a known polymerization method. Further, in order to obtain an acrylonitrile-based polymer in the form of aggregated particles, an aqueous precipitation polymerization method in which a monomer and a water-soluble polymerization initiator are added to water and polymerization is carried out can be adopted.
ここでいう水系沈殿重合法とは、水溶性重合開始剤を使用し、乳化剤、分散安定剤等の添加を行わず、重合が進むにつれ重合体が凝集、沈殿（攪拌時には懸濁）してくる重合方法のことを言う。アクリロニトリルを主成分とする重合の場合、この水系沈殿重合法を用いることにより、平均粒子径が１０μｍ以下の一次粒子が凝集した凝集体の沈殿が起こる。この凝集体の粒子径は、１０００μｍ以下である場合が多い。該凝集体については、特に規定はないが、本発明では、一次粒子の平均粒子径が５μｍ以下である粒子の凝集体であり、該凝集体の平均粒子径が１００μｍ以下である場合、一次粒子間の隙間に多数の空洞ができ、凝集体としての比表面積が大きくなるので好ましい。 The water-based precipitation polymerization method referred to here uses a water-soluble polymerization initiator, does not add an emulsifier, a dispersion stabilizer, or the like, and as the polymerization progresses, the polymer aggregates and precipitates (suspends during stirring). It refers to the polymerization method. In the case of polymerization containing acrylonitrile as a main component, by using this aqueous precipitation polymerization method, precipitation of aggregates in which primary particles having an average particle diameter of 10 μm or less are aggregated occurs. The particle size of this aggregate is often 1000 μm or less. The aggregate is not particularly specified, but in the present invention, it is an aggregate of particles having an average particle diameter of primary particles of 5 μm or less, and when the average particle diameter of the aggregate is 100 μm or less, the primary particles It is preferable because a large number of cavities are formed in the gaps between them and the specific surface area as an agglomerate increases.
また、繊維状のアクリロニトリル系重合体の製造方法としては、公知のアクリロニトリル繊維の製造方法を採用することができる。例えば、硝酸、塩化亜鉛水溶液、チオシアン酸ナトリウム水溶液、Ｎ－メチルピロリドン、ＤＭＦ、ＤＭＡｃ、ＤＭＳＯ等の溶剤を用いた湿式紡糸の場合であれば、上述のアクリロニトリル系重合体を溶剤に溶解して作製した紡糸原液をノズルから紡出後、凝固、水洗、延伸、熱処理、乾燥の各工程を経ることで、繊維状のアクリロニトリル系重合体を得ることができる。 Further, as a method for producing a fibrous acrylonitrile-based polymer, a known method for producing an acrylonitrile fiber can be adopted. For example, in the case of wet spinning using a solvent such as nitrate, an aqueous solution of zinc chloride, an aqueous solution of sodium thiocyanate, N-methylpyrrolidone, DMF, DMAc, DMSO, etc., the above-mentioned acrylonitrile polymer is dissolved in a solvent to prepare the product. A fibrous acrylonitrile-based polymer can be obtained by undergoing each step of solidification, washing with water, stretching, heat treatment, and drying after spinning the spun stock solution from the nozzle.
さらに、パルプ状のアクリロニトリル系重合体を得るには、たとえば、上述のようにして得られた繊維状のアクリロニトリル系重合体をカットし、叩解処理を行えばよい。この際、叩解の方法は限定されるものでなく、ビータやリファイナーなどの叩解機を用いることができる。また、叩解に供する繊維状のアクリロニトリル系重合体としても、乾燥工程後のものに限らず、延伸後の未乾燥繊維なども使用することができる。 Further, in order to obtain a pulp-like acrylonitrile-based polymer, for example, the fibrous acrylonitrile-based polymer obtained as described above may be cut and beaten. At this time, the method of beating is not limited, and a beating machine such as a beater or a refiner can be used. Further, as the fibrous acrylonitrile-based polymer to be beaten, not only the one after the drying step but also the undried fiber after stretching can be used.
上述してきた本発明に採用するアクリロニトリル系重合体が優れた濾過性能を有する理由に関しては明らかではないが、一般的にアクリロニトリル系重合体が両親媒性を有することに加え、本発明ではアクリロニトリルの有するニトリル基（アニオン性）とアミノ基またはアンモニウム基（カチオン性）を含有することで全体としては両極性となり、より広い懸濁成分の除去が可能となっているのではないかと思われる。さらに、比表面積を大きくすることより、アミノ基またはアンモニウム基量が従来の濾過助剤よりも少量であっても、性能が効率よく発現されるのではないかと思われる。 The reason why the acrylonitrile-based polymer used in the present invention described above has excellent filtration performance is not clear, but in general, in addition to the acrylonitrile-based polymer having amyophilicity, the acrylonitrile-based polymer has in the present invention. By containing a nitrile group (anionic) and an amino group or an ammonium group (cationic), it becomes bipolar as a whole, and it seems that a wider range of suspended components can be removed. Furthermore, by increasing the specific surface area, it seems that the performance can be efficiently exhibited even if the amount of amino groups or ammonium groups is smaller than that of the conventional filtration aid.
また、上述のように、本発明に採用するアクリロニトリル系重合体においては、アミノ基またはアンモニウム基量を従来よりも少量としている。このため、濾過の際に濾液中へアミノ基またはアンモニウム基含有成分が溶出する恐れが小さい。さらに、上述したような共重合によりアミノ基またはアンモニウム基を導入する方法を採用した場合には、未反応のアミノ基またはアンモニウム基含有化合物が重合体中に残留したり、重合体との結合が不安定なアミノ基またはアンモニウム基が発生したりする可能性もなくなるため、アミノ基またはアンモニウム基含有成分の溶出がより抑制されたものとなる。かかる特性を有するアクリロニトリル系重合体を採用する本発明の濾過助剤は、食品、化粧品または医薬品などの人体への影響を考慮する必要のある製品の製造工程への適用可能性も有するものである。 Further, as described above, in the acrylonitrile-based polymer used in the present invention, the amount of amino groups or ammonium groups is smaller than that in the past. Therefore, there is little possibility that an amino group or ammonium group-containing component is eluted into the filtrate during filtration. Further, when the method of introducing an amino group or an ammonium group by the copolymerization as described above is adopted, the unreacted amino group or ammonium group-containing compound remains in the polymer or the bond with the polymer is formed. Since there is no possibility that an unstable amino group or ammonium group is generated, the elution of the amino group or ammonium group-containing component is further suppressed. The filtration aid of the present invention that employs an acrylonitrile-based polymer having such properties also has applicability in the manufacturing process of products such as foods, cosmetics, and pharmaceuticals that need to be considered for their effects on the human body. ..
また、本発明の濾過助剤は、血液中の赤血球の吸着凝集にも有効である。上述したように本発明の濾過助剤はアミノ基またはアンモニウム基を含有するものであって、タンパク質や脂質も吸着凝集させることができるものである。この点、赤血球の表面は脂質皮膜で構成されており、グリコホリンと呼ばれるタンパク質が含まれており、グリコホリンはその末端にシアル酸と呼ばれるアニオン電荷を帯びた糖が結合した糖鎖を有している。このため、本発明の濾過助剤は赤血球を吸着凝集させることができる。 The filtration aid of the present invention is also effective for adsorption and aggregation of red blood cells in blood. As described above, the filtration aid of the present invention contains an amino group or an ammonium group, and can also adsorb and aggregate proteins and lipids. In this regard, the surface of erythrocytes is composed of a lipid film, which contains a protein called glycophorin, and glycophorin has a sugar chain at which an anion-charged sugar called sialic acid is bound. .. Therefore, the filtration aid of the present invention can adsorb and aggregate red blood cells.
この赤血球を吸着凝集できる特性は、生理用ナプキンなどの血液を含む液体を吸収する衛生用品などに応用することができる。すなわち、生理用ナプキンなどにおいては、高吸水性樹脂を使用しているが、かかる樹脂は固体成分を吸収することができない。このため、血液の吸収においては、吸収に伴い高吸水性樹脂の表面に赤血球が蓄積して被膜が形成され、液の吸収が阻害されるようになる。ここで、本発明の濾過助剤を用いると血液中の赤血球を吸着凝集させるため、赤血球による高吸水性樹脂の表面での被膜形成が抑制され、液吸収が阻害されにくくなるという効果が得られるのである。 This property of being able to adsorb and aggregate red blood cells can be applied to sanitary products such as sanitary napkins that absorb liquids containing blood. That is, in sanitary napkins and the like, super absorbent polymers are used, but such resins cannot absorb solid components. Therefore, in the absorption of blood, red blood cells accumulate on the surface of the superabsorbent polymer to form a film, and the absorption of the liquid is inhibited. Here, when the filtration aid of the present invention is used, red blood cells in the blood are adsorbed and aggregated, so that the formation of a film on the surface of the superabsorbent polymer by the red blood cells is suppressed, and the liquid absorption is less likely to be inhibited. It is.
本発明の濾過助剤の使用方法としては、処理したい液体に直接混ぜるボディーフィード法や、原液の濾過に先立ち、金網等の濾材表面に濾過助剤の層を形成させてから、処理したい液体を濾過するプレコート法等を用いることができる。また、衛生用品に用いる場合には、高吸水性樹脂と本発明の濾過助剤を混合して吸水層としたり、高吸水樹脂からなる吸水層よりも肌側に本発明の濾過助剤を含む層を設けたりするなどの手段を適用できる。後者の場合、本発明の濾過助剤を含む層としては、繊維状の本発明の濾過助剤を構成繊維として含む不織布や、粒子状の本発明の濾過助剤を不織布基材にバインダー等を用いて付着させたものや、血液透過性素材からなる袋状の層の内部に充填したものなどを挙げることができる。 The filtration aid of the present invention can be used by a body feed method in which the liquid to be treated is directly mixed with the liquid to be treated, or a liquid to be treated after forming a layer of the filter aid on the surface of a filter medium such as a wire mesh prior to filtering the undiluted solution. A precoat method or the like for filtering can be used. When used in sanitary products, the superabsorbent polymer and the filtration aid of the present invention are mixed to form a water-absorbent layer, or the filter aid of the present invention is contained on the skin side of the water-absorbent layer made of the superabsorbent polymer. Means such as providing a layer can be applied. In the latter case, as the layer containing the filtration aid of the present invention, a non-woven fabric containing the fibrous filtration aid of the present invention as a constituent fiber, a non-woven fabric containing the particulate filtration aid of the present invention as a constituent fiber, or the like is used as a binder. Examples thereof include those attached by using and those filled inside a bag-shaped layer made of a blood-permeable material.
以上に説明してきた本発明の濾過助剤は、単独で又は、他の素材と組み合わせることにより多くの用途、例えば食品、化粧品又は医薬品の製造において不純物を取り除くフィルターに利用できる。かかるフィルターにおいては、本発明の濾過助剤の含有率を好ましくは５重量％以上、より好ましくは１０重量％以上、さらに好ましくは２０重量％以上とすることが、性能の発現上望ましい。また、組み合わせることのできる他の素材としては特に制限はなく、公用されている天然繊維、有機繊維、半合成繊維、合成繊維、無機繊維、ガラス繊維等などを挙げることができる。また、別の用途として、ガーゼ、包帯、マスク、手袋、絆創膏、生理用品、おむつ等の衛生用品において吸収性能を向上させる部材として使用することができる。 The filtration aid of the present invention described above can be used as a filter for removing impurities in many uses, for example, in the production of foods, cosmetics or pharmaceuticals, alone or in combination with other materials. In such a filter, it is desirable that the content of the filtration aid of the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 20% by weight or more in terms of performance. The other materials that can be combined are not particularly limited, and examples thereof include publicly used natural fibers, organic fibers, semi-synthetic fibers, synthetic fibers, inorganic fibers, and glass fibers. As another application, it can be used as a member for improving absorption performance in sanitary products such as gauze, bandages, masks, gloves, adhesive plasters, sanitary products, and diapers.
以下に本発明の理解を容易にするために実施例を示すが、これらはあくまで例示的なものであり、本発明の要旨はこれらにより限定されるものではない。実施例中、部及び百分率は特に断りのない限り重量基準で示す。また、各特性の測定は以下の方法により実施した。 Examples are shown below to facilitate understanding of the present invention, but these are merely examples, and the gist of the present invention is not limited thereto. In the examples, parts and percentages are shown by weight unless otherwise specified. In addition, the measurement of each characteristic was carried out by the following method.
＜アミノ基量の測定＞
試料２ｇに１Ｎ－水酸化ナトリウム水溶液５０ｍｌを加えて１時間撹拌した後、濾過を行い、更に濾液が中性を示すまで脱塩水を通液する。濾別した試料に０．１Ｎ－塩酸水溶液を１００ｍｌ加え、８時間振盪する。振盪後、濾過を行い、濾液５０ｍｌをサンプリングし、これにフェノールフタレイン溶液を添加して０．１Ｎ－水酸化ナトリウム水溶液で滴定することにより中和点での滴定量（Ａ［ｍｌ］）を求め、次式によりアミノ基量を算出した。
アミノ基量［ｍｍｏｌ／ｇ］＝(５０－Ａ)×０．１ <Measurement of amino group amount>
50 ml of a 1N-sodium hydroxide aqueous solution is added to 2 g of the sample, and the mixture is stirred for 1 hour, filtered, and demineralized water is passed until the filtrate becomes neutral. Add 100 ml of a 0.1 N-hydrochloric acid aqueous solution to the filtered sample, and shake for 8 hours. After shaking, filtration is performed, 50 ml of the filtrate is sampled, a phenolphthalein solution is added thereto, and titration is performed with a 0.1 N-sodium hydroxide aqueous solution to perform titration (A [ml]) at the neutralization point. The amount of amino groups was calculated by the following formula.
Amino group amount [mmol / g] = (50-A) x 0.1
＜比表面積の測定＞
ＢＥＴ法にて比表面積測定を行う。 <Measurement of specific surface area>
The specific surface area is measured by the BET method.
＜濾過性能（捕捉率）の測定＞
ドライイースト（日清スーパーカメリアドライイースト）を２．５％含有する懸濁液５０ｇ中に試料１２５ｍｇを加えて１０分撹拌する。濾紙（５Ａ）を用いてブフナー漏斗で吸引濾過を行った後の濾液を１０５℃×５ｈ乾燥させて、濾液に中に含まれる固形分量（Ｗ１［ｇ］）を測定する。一方、別途、試料を加えない場合の濾液の固形分量（Ｗ２［ｇ］）を測定する。これらの測定値から下記式にてイーストの捕捉率を算出し、濾過性能の指標とする。
捕捉率［％］＝（Ｗ２－Ｗ１）／Ｗ２×１００ <Measurement of filtration performance (capture rate)>
125 mg of the sample is added to 50 g of a suspension containing 2.5% of dry yeast (Nissin Super Camellia dry yeast), and the mixture is stirred for 10 minutes. The filtrate after suction filtration with a Buchner funnel using filter paper (5A) is dried at 105 ° C. × 5 hours, and the amount of solids (W1 [g]) contained in the filtrate is measured. On the other hand, separately, the solid content (W2 [g]) of the filtrate when no sample is added is measured. From these measured values, the yeast capture rate is calculated by the following formula and used as an index of filtration performance.
Capture rate [%] = (W2-W1) / W2 × 100
＜赤血球の吸着凝集の評価（高吸水性樹脂（ＳＡＰ）の膨潤度測定）＞
評価サンプル０．２５ｇを詰めたカラム（内径１５ｍｍ）に馬血５ｍｌを加え、次いでカラム上部から手動ポンプにて空気を送り込んで馬血を押し出す。押し出された馬血から２ｍｌを採取してＳＡＰ（ポリアクリル酸系粒状高吸水性樹脂）５０ｍｇに加え、１０分間静置する。次いで、ろ紙を敷いたブフナー漏斗上で吸引ろ過を行い、ろ別したＳＡＰの重さ（Ｗ３［ｇ］）を測定する。得られた測定値から下記式にて膨潤度を計算する。
膨潤度（倍）＝Ｗ３／０．０５－１
なお、評価サンプルを加えずに評価した場合の膨潤度は１７．９倍であり、膨潤度がこの数値よりも大きいほど赤血球の吸着凝集効果が高いと評価できる。 <Evaluation of adsorption and aggregation of red blood cells (measurement of superabsorbent polymer (SAP) swelling degree)>
5 ml of horse blood is added to a column (inner diameter 15 mm) packed with 0.25 g of the evaluation sample, and then air is pumped from the upper part of the column with a manual pump to push out the horse blood. 2 ml is collected from the extruded horse blood, added to 50 mg of SAP (polyacrylic acid-based superabsorbent polymer), and allowed to stand for 10 minutes. Next, suction filtration is performed on a Büchner funnel lined with filter paper, and the weight (W3 [g]) of the filtered SAP is measured. The degree of swelling is calculated from the obtained measured values by the following formula.
Swelling degree (double) = W3 / 0.05-1
The degree of swelling when evaluated without adding the evaluation sample is 17.9 times, and it can be evaluated that the larger the degree of swelling is, the higher the adsorption / aggregation effect of erythrocytes.
＜実施例１＞
アクリロニトリル２９．１重量部及びジメチルアミノエチルメタクリレート０．９重量部と純水７０重量部含む液中に、過硫酸アンモニウムとピロ亜硫酸ナトリウムをモノマー重量に対してそれぞれ０．５％と０．３％加え、６０℃で５５分間重合させ、水洗、脱水、乾燥を行い、凝集粒子状のアクリロニトリル系重合体を得た。得られた重合体の評価結果を表１に示す。 <Example 1>
Ammonium persulfate and sodium metabisulfite were added in a liquid containing 29.1 parts by weight of acrylonitrile, 0.9 parts by weight of dimethylaminoethyl methacrylate and 70 parts by weight of pure water, respectively, at 0.5% and 0.3% based on the weight of the monomer. , Polymerized at 60 ° C. for 55 minutes, washed with water, dehydrated and dried to obtain an acrylonitrile-based polymer in the form of aggregated particles. The evaluation results of the obtained polymer are shown in Table 1.
＜実施例２＞
実施例１で得られた粒子１０部を４８％のチオシアン酸ナトリウム水溶液９０部に溶解し、紡糸原液を作成した。該紡糸原液を、－２．５℃の凝固浴に紡出し、凝固、水洗、延伸、熱処理、乾燥の各工程を行い、繊維状のアクリロニトリル系重合体を得た。得られた重合体の評価結果を表１に示す。 <Example 2>
10 parts of the particles obtained in Example 1 were dissolved in 90 parts of a 48% sodium thiocyanate aqueous solution to prepare a spinning stock solution. The spinning stock solution was spun into a coagulation bath at −2.5 ° C. and subjected to each step of coagulation, washing with water, stretching, heat treatment, and drying to obtain a fibrous acrylonitrile-based polymer. The evaluation results of the obtained polymer are shown in Table 1.
＜実施例３＞
実施例２で得られた繊維をナイアガラビーターにて叩解して、パルプ状のアクリロニトリル系重合体を得た。得られた重合体の評価結果を表１に示す。 <Example 3>
The fibers obtained in Example 2 were beaten with a Niagara beater to obtain a pulp-like acrylonitrile-based polymer. The evaluation results of the obtained polymer are shown in Table 1.
＜実施例４＞
実施例１において、モノマーの比率をアクリロニトリル２９．８重量部及びジメチルアミノエチルメタクリレート０．２重量部に変更したこと以外は同様に重合を行い、凝集粒子状のアクリロニトリル系重合体を得た。得られた重合体の評価結果を表１に示す。 <Example 4>
In Example 1, the same polymerization was carried out except that the ratio of the monomers was changed to 29.8 parts by weight of acrylonitrile and 0.2 parts by weight of dimethylaminoethyl methacrylate to obtain an acrylonitrile-based polymer in the form of aggregated particles. The evaluation results of the obtained polymer are shown in Table 1.
＜実施例５＞
実施例１において、モノマーの比率をアクリロニトリル２５．５重量部及びジメチルアミノエチルメタクリレート４．５重量部に変更したこと以外は同様に重合を行い、凝集粒子状のアクリロニトリル系重合体を得た。得られた重合体の評価結果を表１に示す。 <Example 5>
In Example 1, polymerization was carried out in the same manner except that the ratio of the monomers was changed to 25.5 parts by weight of acrylonitrile and 4.5 parts by weight of dimethylaminoethyl methacrylate to obtain an acrylonitrile-based polymer in the form of aggregated particles. The evaluation results of the obtained polymer are shown in Table 1.
＜比較例１＞
実施例１において、モノマーをアクリロニトリル３０部のみに変更したこと以外は同様に重合を行い、アミノ基を有しない凝集粒子状のアクリロニトリル系重合体を得た。得られた重合体の評価結果を表１に示す。 <Comparative example 1>
In Example 1, the polymerization was carried out in the same manner except that the monomer was changed to only 30 parts of acrylonitrile to obtain an acrylonitrile-based polymer in the form of aggregated particles having no amino group. The evaluation results of the obtained polymer are shown in Table 1.
＜比較例２＞
市販の粉体状セルロース（ＡＤＶＡＮＴＥＣ製　粉末ろ紙　Ｄ）を使用した評価結果を表１に示す。 <Comparative example 2>
Table 1 shows the evaluation results using commercially available powdered cellulose (powdered filter paper D manufactured by ADVANTEC).
＜比較例３＞
ＮＢＫＰパルプをナイアガラビーターにて叩解して比表面積の大きいセルロースパルプを得た。得られたパルプの評価結果を表１に示す。 <Comparative example 3>
The NBKP pulp was beaten with a Niagara beater to obtain a cellulose pulp having a large specific surface area. The evaluation results of the obtained pulp are shown in Table 1.
＜比較例４＞
市販のセルロース系カチオン性濾過フィルター（吸着デプスフィルターディスク（Ｚｅｔａ　Ｐｌｕｓ（ＴＭ））を使用した評価結果を表１に示す。 <Comparative example 4>
Table 1 shows the evaluation results using a commercially available cellulosic cationic filtration filter (adsorption depth filter disk (Zeta Plus (TM))).
＜比較例５＞
実施例１において、モノマーの比率をアクリロニトリル１９．５重量部及びジメチルアミノエチルメタクリレート１０．５重量部に変更したこと以外は同様に重合を行った。得られたアクリロニトリル系重合体は、アクリロニトリル単位が少なく、微小粒子の分散液状（エマルジョン状）となり、水への再分散性を有するため、濾過助剤としては利用できないものであった。 <Comparative example 5>
In Example 1, polymerization was carried out in the same manner except that the ratio of the monomers was changed to 19.5 parts by weight of acrylonitrile and 10.5 parts by weight of dimethylaminoethyl methacrylate. The obtained acrylonitrile-based polymer has a small amount of acrylonitrile units, becomes a dispersed liquid (emulsion-like) of fine particles, and has redispersibility in water, so that it cannot be used as a filtration aid.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
表１に示すように、実施例１～５のアクリロニトリル系重合体は比較例１のアミノ基を有しないアクリロニトリル系重合体や比較例２～４のセルロース系材料と比較して捕捉率が高く濾過助剤として効果が高いことが分かる。また、実施例１～５のアクリロニトリル系重合体はＳＡＰの膨潤度がブランクの膨潤度（１７．９）よりも高く、赤血球を吸着凝集して除去する効果を有していることが理解できる。
 
  As shown in Table 1, the acrylonitrile-based polymers of Examples 1 to 5 have a higher capture rate than the acrylonitrile-based polymers having no amino group of Comparative Example 1 and the cellulosic materials of Comparative Examples 2 to 4, and are filtered. It can be seen that it is highly effective as an auxiliary agent. Further, it can be understood that the acrylonitrile-based polymers of Examples 1 to 5 have a swelling degree of SAP higher than that of the blank (17.9) and have an effect of adsorbing and agglutinating erythrocytes.

Claims (6)

  1. ７０重量％以上のアクリロニトリル単位および０．０５～２．０ｍｍｏｌ／ｇのアミノ基またはアンモニウム基を含有しており、さらに０．１～４００ｍ２／ｇの比表面積を有しているアクリロニトリル系重合体からなる濾過助剤。 From an acrylonitrile-based polymer containing 70% by weight or more of acrylonitrile units and 0.05 to 2.0 mmol / g of an amino group or an ammonium group, and further having a specific surface area of 0.1 to 400 m2 / g. Filter aid.
  2. アクリロニトリル系重合体が、アミノ基またはアンモニウム基を有するビニル系単量体を構成単位とするものであることを特徴とする請求項１に記載の濾過助剤。 The filtration aid according to claim 1, wherein the acrylonitrile-based polymer has a vinyl-based monomer having an amino group or an ammonium group as a constituent unit.
  3. アクリロニトリル系重合体の形状が凝集粒子状またはパルプ状であることを特徴とする請求項１または２に記載の濾過助剤。 The filtration aid according to claim 1 or 2, wherein the acrylonitrile-based polymer is in the form of aggregated particles or pulp.
  4. 食品、化粧品または医薬品製造用であることを特徴とする請求項１～３のいずれかに記載の濾過助剤。 The filtration aid according to any one of claims 1 to 3, which is for manufacturing foods, cosmetics or pharmaceuticals.
  5. 請求項１～４のいずれかに記載の濾過助剤を含むフィルター。 A filter containing the filtration aid according to any one of claims 1 to 4.
  6. 請求項１～３のいずれかに記載の濾過助剤を含む衛生用品。
     
          A hygienic product containing the filtration aid according to any one of claims 1 to 3.
PCT/JP2019/048394 2019-04-19 2019-12-11 Filter aid, and filter and hygiene product containing filter aid WO2020213208A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4724278B1 (en) * 1969-02-17 1972-07-05
JPS5327257A (en) * 1976-08-27 1978-03-14 Kurita Water Ind Ltd Organic sludge dehydrating assistant
JPS54113954A (en) * 1978-02-24 1979-09-05 Kurita Water Ind Ltd Organic sludge dehydration assistant
JPS57153648A (en) * 1981-02-17 1982-09-22 Kimberly Clark Co Sanitary article containing blood gelling agent
JPH07185333A (en) * 1993-12-28 1995-07-25 Mitsubishi Rayon Co Ltd Novel endotoxine adsorbent

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4724278B1 (en) * 1969-02-17 1972-07-05
JPS5327257A (en) * 1976-08-27 1978-03-14 Kurita Water Ind Ltd Organic sludge dehydrating assistant
JPS54113954A (en) * 1978-02-24 1979-09-05 Kurita Water Ind Ltd Organic sludge dehydration assistant
JPS57153648A (en) * 1981-02-17 1982-09-22 Kimberly Clark Co Sanitary article containing blood gelling agent
JPH07185333A (en) * 1993-12-28 1995-07-25 Mitsubishi Rayon Co Ltd Novel endotoxine adsorbent

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