JP2015093260A - Solid water treatment agent having sustained release, and production method thereof - Google Patents
Solid water treatment agent having sustained release, and production method thereof Download PDFInfo
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本発明は、水系において徐放性を有する固形水処理剤、及びその製造方法に関し、詳しくは、共重合体中に水溶性の水処理薬剤が固溶体または分散体として存在する水処理剤であって、該共重合体がＮ−ビニルカプロラクタム、酢酸ビニルおよびポリエチレングリコールの３成分からなる共重合体である固形水処理剤、及びその製造方法に関する。 The present invention relates to a solid water treatment agent having sustained release properties in an aqueous system and a method for producing the same, and more specifically, a water treatment agent in which a water-soluble water treatment agent is present as a solid solution or dispersion in a copolymer. The present invention relates to a solid water treatment agent, wherein the copolymer is a copolymer composed of three components of N-vinylcaprolactam, vinyl acetate and polyethylene glycol, and a method for producing the same.
工業用水系、冷却水系、冷温水系、ボイラ水系、工程水系、排水系などの各種水系には、水系内で使用されている金属の腐食防止及びスケール防止、水系内の原生動物、細菌、藻類等の微生物を防除するために、防食剤、スケール防止剤や、抗菌剤、防黴剤または防藻剤などの様々な微生物防除剤等の水処理薬剤が使用されており、その多くは、長期間に渡って、高い効果が持続することが求められている。そのため、通常、薬注ポンプを使用して液体の水処理薬剤を連続的に注入して薬剤の効果を持続させる方法が採用されているが、薬注ポンプによる水処理薬剤の注入が設備面等で困難な施設では簡便な方法で薬剤の効果が持続する徐放性の固形水処理剤が望まれている。徐放製剤は、医薬品や農薬の製剤技術として開発され、例えば、水溶性薬物を含む溶液を内水相とし、高分子重合物を含む溶液を油相としたＷ／Ｏ型乳化物を水中乾燥させて作られるマイクロカプセルが報告されている（例えば、特許文献１参照）。 For various water systems such as industrial water systems, cooling water systems, cold / hot water systems, boiler water systems, process water systems, and drainage systems, corrosion prevention and scale prevention of metals used in water systems, protozoa, bacteria, algae, etc. in water systems In order to control microorganisms, water treatment agents such as anticorrosives, scale inhibitors, antibacterial agents, antifungal agents, or algae inhibitors are used, and many of them are used for a long time. Therefore, it is demanded that a high effect is sustained. For this reason, a method in which a liquid water treatment chemical is continuously infused using a chemical injection pump to maintain the effect of the chemical is usually adopted. In a difficult and difficult facility, a sustained-release solid water treatment agent in which the effect of the drug is sustained by a simple method is desired. Sustained release formulations were developed as pharmaceutical and agrochemical formulation technologies. For example, W / O emulsions in which a solution containing a water-soluble drug is an inner aqueous phase and a solution containing a polymer is an oil phase are dried in water. A microcapsule produced by this method has been reported (for example, see Patent Document 1).
一方、農薬成分に樹脂成分をコーテイングすることにより徐放製剤化する方法、例えば、農薬成分とエマルジョン状態にした融点６０℃以上のワックスおよび撥水性粉末を芯材にコーテイングする徐放性農薬の製造方法がある（例えば、特許文献２参照）。 On the other hand, a method for preparing a sustained-release formulation by coating a resin component with an agrochemical component, for example, a sustained-release agrochemical that coats a core material with an agrochemical component and a wax having a melting point of 60 ° C. or higher and water-repellent powder There is a method (see, for example, Patent Document 2).
また、熱可塑性有機高分子に有機系抗菌剤を溶融混練して成る抗菌性樹脂組成物が提案されている（例えば、特許文献３参照）。この樹脂組成物は、徐放性の抗菌剤を含むカテーテルなどの医療用具や包装材料などの樹脂成形品の製造に用いられる。 Further, an antibacterial resin composition obtained by melting and kneading an organic antibacterial agent with a thermoplastic organic polymer has been proposed (see, for example, Patent Document 3). This resin composition is used for the production of a resin molded product such as a medical device such as a catheter or a packaging material containing a sustained-release antibacterial agent.
また、農薬活性成分、スチレン無水マレイン酸共重合体またはスチレン無水共重合体混合樹脂および溶出制御剤からなる溶出制御された農薬製剤が報告されている（特許文献４、５）。 In addition, there has been reported an elution-controlled agricultural chemical formulation comprising an agricultural chemical active ingredient, a styrene maleic anhydride copolymer or a styrene anhydrous copolymer mixed resin, and an elution control agent (Patent Documents 4 and 5).
本発明に用いられるN-ビニルカプロラクタム、酢酸ビニルおよびポリエチレングリコールの３成分からなる共重合体は、難水溶性化合物の医薬品原薬の腸管吸収性を改良するために、溶融混練して押出造粒するポリマーとして開発されたものである（非特許文献１）。しかしながら、提案された３成分からなる共重合体が徐放性を有する固形水処理剤に用いられることや、長期に渡って安定的に適度な水処理薬剤の徐放性が得られることに関しての開示も示唆もされていない。 The three-component copolymer of N-vinylcaprolactam, vinyl acetate and polyethylene glycol used in the present invention is melt-kneaded and extrusion granulated to improve the intestinal absorbability of the drug substance as a poorly water-soluble compound. It has been developed as a polymer (Non-patent Document 1). However, the proposed three-component copolymer is used for a solid water treatment agent having a sustained release property, and a stable release property of an appropriate water treatment agent can be obtained stably over a long period of time. There is no disclosure or suggestion.
本発明は、長期保存性に優れ、使用に際しては有効成分が経時安定的に水系に徐々に放出される徐放性を有する固形水処理剤を提供することを目的とする。 An object of the present invention is to provide a solid water treatment agent that has excellent long-term storage stability and has a sustained release property in which an active ingredient is gradually released into an aqueous system in a stable manner over time.
固形水処理剤で用いられる共重合体としての望ましい要件は、共重合体が水処理薬剤といわゆる「固溶体」を形成可能であることである。「固溶体」という用語は、ある物質が、微粒分散の形態、又は理想的な場合には、固体マトリクス（例えばポリマーマトリクス）中の分子分散の形態である状態を意味する。そのような固溶体によって、例えば水処理薬剤を固形水処理剤の形状で用いる場合に有効成分の放出が改善される。また、固溶体の限度容量も重要であり、有効成分の最大量を含んでも安定な固溶体を形成する能力が要求される。 A desirable requirement for a copolymer used in a solid water treatment agent is that the copolymer can form a so-called “solid solution” with the water treatment agent. The term “solid solution” means a state in which a substance is in the form of a finely divided dispersion or, ideally, in the form of a molecular dispersion in a solid matrix (eg, a polymer matrix). Such a solid solution improves the release of the active ingredient, for example when the water treatment agent is used in the form of a solid water treatment agent. The limit capacity of the solid solution is also important, and the ability to form a stable solid solution is required even when the maximum amount of the active ingredient is included.
共重合体が水処理薬剤と固溶体を形成するという基本的な能力だけではなく、共重合体の吸湿性もまた、固溶体の形成に重要な役割を果たしている。周囲空気から過度の水分を吸収する共重合体は固溶体の液状化を引き起こし、結果として、有効成分の望ましくない偏在を導く。過剰な吸湿性はまた水処理剤の加工時にも問題を引き起こしうる。重要な要件は、長期間にわたって貯蔵した場合であってもそのような固溶体が安定であることが要求される。 Not only the basic ability of the copolymer to form a solid solution with the water treatment agent, but also the hygroscopicity of the copolymer plays an important role in the formation of the solid solution. Copolymers that absorb excessive moisture from the ambient air cause liquefaction of the solid solution, resulting in undesirable uneven distribution of active ingredients. Excessive hygroscopicity can also cause problems when processing water treatment agents. An important requirement is that such solid solutions be stable even when stored for long periods of time.
本発明の第１の発明は、共重合体中に水溶性の水処理薬剤が固溶体または分散体として存在する水処理剤であって、該共重合体がN-ビニルカプロラクタム、酢酸ビニルおよびポリエチレングリコールの３成分からなる共重合体である、徐放性を有する固形水処理剤である。
本発明の第２の発明は、第１の発明において、前記水溶性の水処理薬剤が防食剤である、徐放性を有する固形水処理剤である。
本発明の第３の発明は、第２の発明において、前記防食剤がアゾール系化合物である、徐放性を有する固形水処理剤である。
本発明の第４の発明は、第１の発明において、前記水溶性の水処理薬剤が微生物防除剤である、徐放性を有する固形水処理剤である。
本発明の第５の発明は、第１の発明〜第４の発明の何れかにおいて、前記共重合体と前記水溶性の水処理薬剤の質量比が５：９５から４０：６０である、徐放性を有する固形水処理剤である。
本発明の第６の発明は、第１の発明〜第５の発明の何れかに記載の徐放性を有する固形水処理剤を製造する方法であって、前記共重合体と前記水溶性の水処理薬剤に溶媒を組み合わせて分散および／または溶解された形態にある液状物を作製し、前記液状物から溶媒を除去する、徐放性を有する固形水処理剤の製造方法である。
本発明の第７の発明は、第１の発明〜第５の発明の何れかに記載の徐放性を有する固形水処理剤を製造する方法であって、前記共重合体と前記水溶性の水処理薬剤の混合物を水処理薬剤の融点よりも高い温度で溶融し、該融点よりも低い温度に冷却する、徐放性を有する固形水処理剤の製造方法である。
A first invention of the present invention is a water treatment agent in which a water-soluble water treatment agent is present as a solid solution or dispersion in a copolymer, the copolymer comprising N-vinylcaprolactam, vinyl acetate and polyethylene glycol. It is a solid water treatment agent having a sustained release property, which is a copolymer comprising the following three components.
A second invention of the present invention is the solid water treatment agent having sustained release, wherein the water-soluble water treatment agent is an anticorrosive agent in the first invention.
A third invention of the present invention is a solid water treatment agent having sustained release, wherein the anticorrosive agent is an azole compound in the second invention.
A fourth invention of the present invention is the solid water treatment agent having sustained release, wherein the water-soluble water treatment agent is a microorganism control agent in the first invention.
According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the mass ratio of the copolymer to the water-soluble water treatment agent is 5:95 to 40:60. It is a solid water treatment agent having releasability.
A sixth invention of the present invention is a method for producing a solid water treatment agent having sustained release properties according to any one of the first to fifth inventions, wherein the copolymer and the water-soluble treatment agent are produced. This is a method for producing a solid water treatment agent having sustained release, wherein a liquid material in a form dispersed and / or dissolved by combining a solvent with a water treatment agent is prepared, and the solvent is removed from the liquid material.
A seventh invention of the present invention is a method for producing a solid water treating agent having sustained release properties according to any one of the first to fifth inventions, wherein the copolymer and the water-soluble treatment agent are produced. This is a method for producing a solid water treatment agent having sustained release, wherein a mixture of water treatment agents is melted at a temperature higher than the melting point of the water treatment agent and cooled to a temperature lower than the melting point.
本発明は、Ｎ−ビニルカプロラクタム、酢酸ビニルおよびポリエチレングリコールの３成分からなる共重合体中に水溶性の水処理薬剤が固溶体または分散体として存在する、徐放性を有する固形水処理剤、及びその製造法であり、本固形水処理剤は、長期保存性に優れ、有効成分が経時安定的に水系に徐々に放出されるという効果を示す。本発明で固形水処理剤が水系への徐放性を有するとは、含有される有効成分である水溶性の水処理薬剤が概ね一週間以上に渡って水系中に安定して徐々に放出される特性を有することを意味する。 The present invention relates to a solid water treatment agent having sustained release, wherein a water-soluble water treatment agent is present as a solid solution or dispersion in a three-component copolymer of N-vinylcaprolactam, vinyl acetate and polyethylene glycol, and This solid water treatment agent is a method for producing the same, and is excellent in long-term storage stability and exhibits an effect that an active ingredient is gradually released into an aqueous system stably over time. In the present invention, the solid water treatment agent has a sustained release property to the aqueous system. The water-soluble water treatment agent that is an active ingredient contained therein is stably and gradually released into the aqueous system over approximately one week. It has the following characteristics.
本発明の共重合体は、N-ビニルカプロラクタム、酢酸ビニルおよびポリエチレングリコールの３成分からなる共重合体であり、各成分の好ましい比率は４０〜６０質量％、１５〜３５質量％、及び１０〜３０質量％である。好ましい共重合体の例として、ＢＡＳＦ ＳＥ株式会社製のソルプラス（商標）が挙げられる。 The copolymer of the present invention is a copolymer composed of three components of N-vinylcaprolactam, vinyl acetate and polyethylene glycol, and the preferred ratio of each component is 40 to 60% by mass, 15 to 35% by mass, and 10 to 10%. 30% by mass. As an example of a preferable copolymer, Solplus (trademark) manufactured by BASF SE Ltd. may be mentioned.
本発明で、固形水処理剤が水系への徐放性を有するとは、含有される有効成分である水溶性の水処理薬剤が概ね１週間以上に渡って水系中に安定して徐々に放出される特性を有することを意味する。固形水処理剤は、徐放性により処理効果が長期に渡って持続することが添加の間隔を延ばすためには好ましく、特に２週間以上の安定的な徐放性が望ましい。 In the present invention, the solid water treatment agent has a sustained release property to the aqueous system, and the water-soluble water treatment agent as the active ingredient contained therein is stably and gradually released into the aqueous system over a week or more. Means having the properties In order to extend the interval of addition, it is preferable that the solid water treatment agent has a long-lasting treatment effect due to the sustained release property, and a stable sustained release property of 2 weeks or more is particularly desirable.
固形水処理剤の水系への溶解性が高い場合は一錠の固形水処理剤を大きくすることにより溶解終了までの時間を延ばすことが可能であるが、加工性や取扱い性に問題があり、溶解性が低い場合は一錠の固形水処理剤を微細化して比表面積を大きくすることで溶解性を高めることが可能であるが、溶解終了までの時間が短くなるので好ましくない。本発明では、実用性から、一錠の固形水処理剤の大きさや形状として、少なくとも１週間以上に渡って１ｇ／日以上、３０ｇ／日以下で固形水処理剤が安定的に溶解、分散により減量していくような加工が必要であり、加工性や取扱い性からは２ｇ／日以上、２０ｇ／日以下で減量することが好ましい。 If the solubility of the solid water treatment agent in the aqueous system is high, it is possible to extend the time to the end of dissolution by increasing the size of one tablet of the solid water treatment agent, but there are problems in workability and handleability, When the solubility is low, it is possible to increase the solubility by refining one tablet of the solid water treatment agent to increase the specific surface area, but this is not preferable because the time until the dissolution is completed is shortened. In the present invention, from the practical point of view, the size and shape of one tablet of the solid water treatment agent is stably dissolved and dispersed at least 1 g / day and 30 g / day for at least one week. Processing that reduces the weight is necessary, and it is preferable to reduce the amount at 2 g / day or more and 20 g / day or less from the viewpoint of workability and handleability.
本発明の水溶性の水処理薬剤としては、本発明の共重合体と徐放性を有する固形水処理剤にすることが可能な各種公知の防食剤、微生物防除剤、スライム防止剤、防藻剤、スケール防止剤、等から１種または２種以上を選択して使用でき、異なる効果を有する薬剤を併用して一つの固形水処理剤とすることもできる。 As the water-soluble water treatment agent of the present invention, various known anticorrosive agents, microorganism control agents, antislime agents, and algae preventives that can be made into a solid water treatment agent having sustained release properties with the copolymer of the present invention. One or two or more types can be selected and used from agents, scale inhibitors, etc., and a single solid water treatment agent can be obtained by using agents having different effects.
本発明の防食剤としては、公知の各種化合物から選択されるが、好ましくはアゾール系化合物であり、特に好ましくは、ベンゾトリアゾール、トリルトリアゾール、メルカプトベンゾチアゾール、及びそれらの誘導体が挙げられる。 The anticorrosive agent of the present invention is selected from various known compounds, but is preferably an azole compound, and particularly preferably includes benzotriazole, tolyltriazole, mercaptobenzothiazole, and derivatives thereof.
本発明の微生物防除剤としては、公知の各種化合物から選択され、例えば、トリアジン系化合物、ピリジニウム塩系化合物、イソチアゾリン系化合物、ピリチオン系化合物、ジチオール系化合物、メチレンビスチオシアネート、ジブロモニトリルプロピオンアミド、２−ブロモ−２−ニトロ−プロパン−１，３−ジオール、グルタルアルデヒド、フタルアルデヒド、ヨーネンポリマー、３−（３，４−ジクロロフェニル）−１，１−ジメチル尿素、等が挙げられる。 The microorganism control agent of the present invention is selected from various known compounds such as triazine compounds, pyridinium salt compounds, isothiazoline compounds, pyrithione compounds, dithiol compounds, methylene bis thiocyanate, dibromonitrile propionamide, 2 -Bromo-2-nitro-propane-1,3-diol, glutaraldehyde, phthalaldehyde, ionene polymer, 3- (3,4-dichlorophenyl) -1,1-dimethylurea and the like.
本発明のスケール防止剤としては、公知の各種化合物から選択され、例えば、アクリル酸系、マレイン酸系、メタクリル酸系、スルホン酸系、イタコン酸系、または、イソブチレン系の各種重合体やこれらの共重合体、燐酸系重合体、ホスホン酸、ホスフィン酸、あるいはこれらの水溶性塩等が挙げられる。 The scale inhibitor of the present invention is selected from various known compounds, such as various acrylic acid-based, maleic acid-based, methacrylic acid-based, sulfonic acid-based, itaconic acid-based, or isobutylene-based polymers, and these. Examples thereof include copolymers, phosphoric acid polymers, phosphonic acids, phosphinic acids, and water-soluble salts thereof.
本発明の徐放性を有する固形水処理剤における共重合体と水溶性の水処理薬剤の質量比は、２：９８から８０：２０であり、好ましくは３：９７から５０：５０であり、より好ましくは５：９５から４０：６０である。水処理剤における共重合体の比が２質量部より小さいと長期に渡って安定的に有効成分の徐放性が得にくく、８０質量部より多いと固形水処理剤の作製が困難となりやすい。 The mass ratio of the copolymer and the water-soluble water treatment agent in the solid water treatment agent having sustained release of the present invention is 2:98 to 80:20, preferably 3:97 to 50:50, More preferably, it is 5:95 to 40:60. When the ratio of the copolymer in the water treatment agent is less than 2 parts by mass, it is difficult to stably obtain a sustained release of the active ingredient over a long period of time, and when it is more than 80 parts by mass, it is difficult to produce a solid water treatment agent.
本発明の共重合体と水溶性の水処理薬剤から徐放性を有する固形水処理剤を作製する際の容易性には水処理薬剤の水溶解度が影響し、含有される共重合体と水処理薬剤との質量比がより広い範囲で作製を可能とするには、水処理薬剤の水溶解度は２５℃の純水で１ｇ／リットル以上、６０ｇ／リットル以下が好ましく、より好ましくは１ｇ／リットル以上、４０ｇ／リットル以下である。 The ease with which a solid water treatment agent having sustained release properties can be produced from the copolymer of the present invention and a water-soluble water treatment agent is affected by the water solubility of the water treatment agent. In order to enable production in a wider range of mass ratio with the treatment chemical, the water solubility of the water treatment chemical is preferably 1 g / liter or more and 60 g / liter or less, more preferably 1 g / liter with 25 ° C. pure water. The amount is 40 g / liter or less.
本発明の徐放性を有する固形水処理剤において、共重合体中に水溶性の水処理薬剤を固溶体または分散体として存在させる方法としては、共重合体と水溶性の水処理薬剤に溶媒を組み合わせて分散および／または溶解された形態にある液状物を作製し、スプレドライにより液状物から溶媒を除去する方法、または、共重合体と水溶性の水処理薬剤の混合物を水処理薬剤の融点よりも高い温度で溶融し、融点よりも低い温度に冷却する方法が挙げられる。好ましい方法は、共重合体と水処理薬剤の両方の融点よりも高い温度で溶融し、両方の融点よりも低い温度に冷却する方法により、より長期の安定的な薬剤の徐放性が得られる。 In the solid water treatment agent having sustained release according to the present invention, as a method for allowing a water-soluble water treatment agent to be present in the copolymer as a solid solution or dispersion, a solvent is added to the copolymer and the water-soluble water treatment agent. A method of removing a solvent from a liquid material by spray drying, or a mixture of a copolymer and a water-soluble water treatment chemical by preparing a liquid material in a dispersed and / or dissolved form in combination, or a melting point of the water treatment chemical And a method of melting at a higher temperature and cooling to a temperature lower than the melting point. A preferred method is to melt at a temperature higher than the melting point of both the copolymer and the water treatment drug, and to cool to a temperature lower than both of the melting points, thereby obtaining a longer-term stable sustained release of the drug. .
本発明の徐放性を有する固形水処理剤において、N-ビニルカプロラクタム、酢酸ビニルおよびポリエチレングリコールの３成分からなる共重合体と水溶性の水処理薬剤以外に、本発明の効果を損なわない範囲で、各種バインダー、増量材、色素、香料、安定化剤、界面活性剤、比重調整剤などや有機、無機の溶媒を適時加えることが出来る。 In the solid water treatment agent having sustained release properties of the present invention, a range that does not impair the effects of the present invention other than a copolymer composed of three components of N-vinylcaprolactam, vinyl acetate, and polyethylene glycol and a water-soluble water treatment agent. In addition, various binders, extenders, dyes, fragrances, stabilizers, surfactants, specific gravity adjusters, and organic and inorganic solvents can be added in a timely manner.
こうして得られる徐放性を有する固形水処理剤は、共重合体と水溶性の水処理薬剤が溶融状態や溶媒中の分散および／または溶解状態である液状物を容器に流し込んで冷却、または溶媒除去することで種々の形状に加工することが可能である。 The solid water treatment agent having sustained release obtained in this way is cooled by pouring a liquid material in which a copolymer and a water-soluble water treatment agent are in a molten state or dispersed and / or dissolved in a solvent into a container, or a solvent. By removing it, it can be processed into various shapes.
本発明による加熱溶融方法について、好適な装置は、原則的に当業者に知られている通常のニーダーである。 For the heating and melting method according to the invention, the preferred apparatus is in principle a conventional kneader known to those skilled in the art.
本発明による固形水処理剤の製造方法によって、水溶性の水処理薬剤成分の含有比率が高い場合でも、均質な固溶性、分散性を有し、良好な保存安定性や安定的な徐放性を有する固形水処理剤の製造が可能になる。 Even if the content ratio of the water-soluble water treatment chemical component is high by the method for producing a solid water treatment agent according to the present invention, it has homogeneous solid solubility and dispersibility, and has good storage stability and stable sustained release. It becomes possible to produce a solid water treatment agent having
以下の実施例において、本発明の固形水処理剤の製造及び使用をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。 In the following examples, the production and use of the solid water treatment agent of the present invention will be described in more detail, but the present invention is not limited to these examples.
（実施例１）
１，２，３−ベンゾトリアゾール（融点９８．５℃、２５℃水溶解度２０ｇ／リットル）２２８ｇ、ソルプラス（商標、ＢＡＳＦ ＳＥ株式会社製 N-ビニルカプロラクタム/酢酸ビニル/ポリエチレングリコール共重合体、融点＜１００℃）１2ｇの粉末を粉状態で混ぜて、混合物をステンレス製容器に入れ、オイルバスに浸漬して１１３℃に加熱、攪拌しながら溶解し、１分後にシリコンゴム製の型枠に流し込み、室温まで冷却後、取り出して２２９ｇの固形水処理剤を得た。
Example 1
228 g of 1,2,3-benzotriazole (melting point 98.5 ° C., 25 ° C. water solubility 20 g / liter), Solplus (trademark, NSF-caprolactam / vinyl acetate / polyethylene glycol copolymer manufactured by BASF SE Ltd., melting point < (100 ° C.) 12 g of powder is mixed in a powder state, the mixture is put in a stainless steel container, immersed in an oil bath, heated to 113 ° C., dissolved with stirring, poured into a silicon rubber mold after 1 minute, After cooling to room temperature, it was taken out to obtain 229 g of a solid water treatment agent.
（実施例２）
１，２，３−ベンゾトリアゾール２１６ｇ、ソルプラス２４ｇの粉末を粉状態で混ぜて、混合物をステンレス製容器に入れ、オイルバスに浸漬して１１３℃に加熱、攪拌しながら溶解し、１分後にシリコンゴム製の型枠に流し込み、室温まで冷却後、取り出して２１６ｇの固形水処理剤を得た。
(Example 2)
216 g of 1,2,3-benzotriazole and 24 g of Solplus are mixed in powder form, and the mixture is placed in a stainless steel container, immersed in an oil bath, heated to 113 ° C., dissolved with stirring, and after 1 minute silicon It was poured into a rubber mold, cooled to room temperature, and then taken out to obtain 216 g of a solid water treatment agent.
（実施例３）
１，２，３−ベンゾトリアゾール１９２ｇ、ソルプラス４８ｇの粉末を粉状態で混ぜて、混合物をステンレス製容器に入れ、オイルバスに浸漬して１１３℃に加熱、攪拌しながら溶解し、１分後にシリコンゴム製の型枠に流し込み、室温まで冷却後、取り出して２１４ｇの固形水処理剤を得た。
(Example 3)
192 g of 1,2,3-benzotriazole and 48 g of Solplus are mixed in powder form, and the mixture is placed in a stainless steel container, immersed in an oil bath, heated to 113 ° C. and dissolved with stirring, and after 1 minute silicon The product was poured into a rubber mold, cooled to room temperature, and then taken out to obtain 214 g of a solid water treatment agent.
（実施例４）
１，２，３−ベンゾトリアゾール１９２ｇ、ポリエチレングリコール（数平均分子量２００００）１２ｇ、ソルプラス３６ｇの粉末を粉状態で混ぜて、混合物をステンレス製容器に入れ、オイルバスに浸漬して１０６℃に加熱、攪拌しながら溶解し、１分後にシリコンゴム製の型枠に流し込み、室温まで冷却後、取り出して２１６ｇの固形水処理剤を得た。
Example 4
192 g of 1,2,3-benzotriazole, 12 g of polyethylene glycol (number average molecular weight 20000) 12 g, and Solplus 36 g were mixed in powder form, the mixture was put in a stainless steel container, immersed in an oil bath and heated to 106 ° C., It melt | dissolved, stirring, after 1 minute, poured into the silicone rubber mold, cooled to room temperature, and then taken out to obtain 216 g of a solid water treatment agent.
（実施例５）
１，２，３−ベンゾトリアゾール１６８ｇ、ソルプラス７２ｇの粉末を粉状態で混ぜて、混合物をステンレス製容器に入れ、オイルバスに浸漬して１４６℃に加熱、攪拌しながら溶解し、１分後にシリコンゴム製の型枠に流し込み、室温まで冷却後、取り出して２１４ｇの固形水処理剤を得た。
(Example 5)
168 g of 1,2,3-benzotriazole and 72 g of Solplus are mixed in powder form, and the mixture is placed in a stainless steel container, immersed in an oil bath, heated to 146 ° C. and dissolved with stirring, and after 1 minute silicon The product was poured into a rubber mold, cooled to room temperature, and then taken out to obtain 214 g of a solid water treatment agent.
（実施例６）
１，２，３−ベンゾトリアゾール１４４ｇ、ソルプラス９６ｇの粉末を粉状態で混ぜて、混合物をステンレス製容器に入れ、オイルバスに浸漬して１５０℃に加熱、攪拌しながら溶解し、１分後にシリコンゴム製の型枠に流し込み、室温まで冷却後、取り出して２０５ｇの固形水処理剤を得た。
(Example 6)
1,2,3-benzotriazole (144 g) and Solplus (96 g) powder are mixed in a powder state, the mixture is placed in a stainless steel container, immersed in an oil bath, heated to 150 ° C. and dissolved with stirring, and after 1 minute silicon It was poured into a rubber mold, cooled to room temperature, and then taken out to obtain 205 g of a solid water treatment agent.
（実施例７）
１，２，３−ベンゾトリアゾール１４５ｇ、ソルプラス１４５ｇの粉末を粉状態で混ぜて、混合物をステンレス製容器に入れ、オイルバスに浸漬して１５０℃に加熱、攪拌しながら溶解し、１分後にシリコンゴム製の型枠に流し込み、室温まで冷却後、取り出して２２２ｇの固形水処理剤を得た。
(Example 7)
145 g of 1,2,3-benzotriazole and 145 g of Solplus are mixed in powder form, and the mixture is placed in a stainless steel container, immersed in an oil bath, heated to 150 ° C. and dissolved with stirring, and after 1 minute silicon It was poured into a rubber mold, cooled to room temperature, and then taken out to obtain 222 g of a solid water treatment agent.
（実施例８）
トリルトリアゾール（融点７６〜８７℃、２５℃水溶解度６ｇ／リットル）１９２ｇ、ソルプラス４８ｇの粉末を粉状態で混ぜて、混合物をステンレス製容器に入れ、オイルバスに浸漬して１０４℃に加熱、攪拌しながら溶解し、１分後にシリコンゴム製の型枠に流し込み、室温まで冷却後、取り出して２０８ｇの固形水処理剤を得た。
(Example 8)
192 g of trilltriazole (melting point: 76-87 ° C., 25 ° C. water solubility: 6 g / liter) and sol plus 48 g of powder are mixed in powder form, the mixture is placed in a stainless steel container, immersed in an oil bath, heated to 104 ° C. and stirred. 1 minute later, it was poured into a mold made of silicon rubber, cooled to room temperature, and then taken out to obtain 208 g of a solid water treatment agent.
（比較例１）
１，２，３−ベンゾトリアゾール２４０ｇの粉末をステンレス製容器に入れ、オイルバスに浸漬して１１３℃に加熱、攪拌しながら溶解し、１分後にシリコンゴム製の型枠に流し込み、室温まで冷却後、取り出して２２９ｇの固形水処理剤を得た。
(Comparative Example 1)
Put 240g of 1,2,3-benzotriazole powder in a stainless steel container, immerse it in an oil bath, dissolve it with heating and stirring at 113 ° C, pour it into a silicone rubber mold after 1 minute, and cool it to room temperature. Thereafter, it was taken out to obtain 229 g of a solid water treatment agent.
（比較例２）
１，２，３−ベンゾトリアゾール１９２ｇ、ポリエチレングリコール（数平均分子量４０００）４８ｇの粉末を粉状態で混ぜて、混合物をステンレス製容器に入れ、オイルバスに浸漬して１１３℃に加熱、攪拌しながら溶解し、１分後にシリコンゴム製の型枠に流し込み、室温まで冷却後、取り出して２２６ｇの固形水処理剤を得た。
(Comparative Example 2)
While 192 g of 1,2,3-benzotriazole and 48 g of polyethylene glycol (number average molecular weight 4000) are mixed in powder form, the mixture is placed in a stainless steel container, immersed in an oil bath and heated to 113 ° C. while stirring. 1 minute later, it was poured into a mold made of silicon rubber, cooled to room temperature, and then taken out to obtain 226 g of a solid water treatment agent.
（比較例３）
１，２，３，−ベンゾトリアゾール１９２ｇ、ポリエチレングリコール（数平均分子量６０００）４８ｇの粉末を粉状態で混ぜて、混合物をステンレス製容器に入れ、オイルバスに浸漬して１１３℃に加熱、攪拌しながら溶解し、１分後にシリコンゴム製の型枠に流し込み、室温まで冷却後、取り出して２２７ｇの固形水処理剤を得た。
(Comparative Example 3)
192 g of 1,2,3, -benzotriazole and 48 g of polyethylene glycol (number average molecular weight 6000) are mixed in powder form, the mixture is placed in a stainless steel container, immersed in an oil bath, heated to 113 ° C. and stirred. 1 minute later, it was poured into a mold made of silicon rubber, cooled to room temperature, and then taken out to obtain 227 g of a solid water treatment agent.
（比較例４）
１，２，３−ベンゾトリアゾール１９２ｇ、ポリエチレングリコール（数平均分子量２００００）４８ｇの粉末を粉状態で混ぜて、混合物をステンレス製容器に入れ、オイルバスに浸漬して１１３℃に加熱、攪拌しながら溶解し、１分後にシリコンゴム製の型枠に流し込み、室温まで冷却する。取り出して２２３ｇの固形水処理剤を得た。
(Comparative Example 4)
While mixing 192 g of 1,2,3-benzotriazole and 48 g of polyethylene glycol (number average molecular weight 20000) in a powder state, the mixture is placed in a stainless steel container, immersed in an oil bath, heated to 113 ° C. and stirred. Dissolve, and after 1 minute, pour into a silicone rubber mold and cool to room temperature. It was taken out to obtain 223 g of a solid water treatment agent.
（比較例５）
トリルトリアゾール２４０ｇをステンレス製容器に入れ、オイルバスに浸漬して９０℃に加熱、攪拌しながら溶解し、１分後にシリコンゴム製の型枠に流し込み、室温まで冷却後、取り出して２１５ｇの固形水処理剤を得た。
(Comparative Example 5)
Put 240g of triltriazole in a stainless steel container, soak in an oil bath, dissolve at 90 ° C with heating and stirring, pour into a silicone rubber mold after 1 minute, cool to room temperature, take out, and take out 215g of solid water A treating agent was obtained.
実施例１から実施例８、比較例１から比較例５で作製した約２００ｇの固形水処理剤を、作製から１日後に多孔性のプラスチック製容器に入れ、２５℃に制御されたつくば市水道水６０リットルが入れられ、攪拌されているタンクに投入した。１日に１回、一定時刻に水を３０リットル残して放水し、新しい水道水を追加してタンク内の水総量を６０リットルにした後、固形水処理剤を取り出して残留量を測定してから再度投入する工程を２８日間実施する溶解性試験を行った。
尚、実施例3において、1日毎に行う一定時刻での放水前にタンク内の水に含まれる１，２，３−ベンゾトリアゾール濃度を分光光度計により測定することで溶解性データに比例して安定的に薬剤が放出されていることを確認した。
About 200 g of the solid water treatment agent prepared in Example 1 to Example 8 and Comparative Example 1 to Comparative Example 5 was put into a porous plastic container one day after the preparation, and the water was controlled at 25 ° C. 60 liters of water was placed in a stirred tank. Once a day, 30 liters of water is left at a fixed time and discharged, and new tap water is added to make the total amount of water in the tank 60 liters. Then, the solid water treatment agent is taken out and the remaining amount is measured. A solubility test was carried out in which the step of re-injection was conducted for 28 days.
In Example 3, the concentration of 1,2,3-benzotriazole contained in the water in the tank was measured with a spectrophotometer before water discharge at a certain time every day, which was proportional to the solubility data. It was confirmed that the drug was stably released.
図１に実施例の代表的な経時での減量データとして実施例３で作製した固形水処理剤の結果を折れ線グラフで示す。 FIG. 1 is a line graph showing the results of the solid water treatment agent produced in Example 3 as typical weight loss data of the example.
図１のグラフより、実施例３の固形水処理剤は２０日以上に亘って良好な徐放性が確認された。固形水処理剤は概ねその表面積に比例して溶解するので経時により一日当たりの溶解量は少なくなり、実施例３では２１日以降は１日当たりの溶解量が２ｇ／日以下となるので新たな固形処理剤の添加が好ましくなる。 From the graph of FIG. 1, it was confirmed that the solid water treatment agent of Example 3 had good sustained release over 20 days or more. Since the solid water treatment agent dissolves almost in proportion to its surface area, the dissolved amount per day decreases with time, and in Example 3, the dissolved amount per day is 21 g or less after 21 days. Addition of a treatment agent is preferred.
実施例3以外の実施例１から実施例６の固形水処理剤についても、良好な経時減量データが得られ、実施例３同様に２０日以上に亘って良好な徐放性を示した。実施例７は、固形水処理剤を作製する際の加熱での均一溶解に若干時間がかかったが徐放性は問題の無い範囲であった。実施例８の固形水処理剤についても、実施例３同様に良好な徐放性であった。
尚、実施例１から実施例８で得られた固形水処理剤について、作製から一カ月間を常温、常湿で静置した後に同様の溶解性試験を行い、良好な徐放性を示すことを確認した。
Good aging loss data were also obtained for the solid water treatment agents of Examples 1 to 6 other than Example 3, and showed good sustained release properties over 20 days as in Example 3. In Example 7, it took some time for uniform dissolution by heating when producing the solid water treatment agent, but the sustained release was in a range where there was no problem. The solid water treating agent of Example 8 also had good sustained release properties as in Example 3.
In addition, about the solid water treatment agent obtained in Example 1 to Example 8, after carrying out the same solubility test after leaving still for one month from preparation at normal temperature and normal humidity, showing favorable sustained release property It was confirmed.
比較例１は、4日間で固形水処理剤が溶解し消失した。比較例２、比較例３、比較例４、比較例５はいずれも１日以内で固形水処理剤が溶解し消失した。 In Comparative Example 1, the solid water treatment agent dissolved and disappeared in 4 days. In all of Comparative Example 2, Comparative Example 3, Comparative Example 4, and Comparative Example 5, the solid water treatment agent dissolved and disappeared within one day.
工業用プラントや空調設備などの工業用水系や冷却水系、及び冷温水系で本発明の徐放性を有する固形水処理剤を用いることで、水処理薬剤を安定的に長期に渡って徐放することが可能となる。 By using the solid water treatment agent having sustained release characteristics of the present invention in industrial water systems such as industrial plants and air conditioning equipment, cooling water systems, and cold / hot water systems, water treatment chemicals can be stably released over a long period of time. It becomes possible.
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| JP2012532099A (en) * | 2009-06-29 | 2012-12-13 | ベンデル・アナリティカル・ホールディング・ビー．ブイ． | Drug delivery system comprising polyoxazoline and bioactive substance |
| JP2013528225A (en) * | 2010-06-10 | 2013-07-08 | アボット・ラボラトリーズ | Solid composition |
| JP2013540823A (en) * | 2010-10-29 | 2013-11-07 | アッヴィ・インコーポレイテッド | Solid dispersion containing apoptosis inducer |
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