WO2014042117A1 - 銅ピリチオン集合体及びその用途 - Google Patents
銅ピリチオン集合体及びその用途 Download PDFInfo
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- WO2014042117A1 WO2014042117A1 PCT/JP2013/074216 JP2013074216W WO2014042117A1 WO 2014042117 A1 WO2014042117 A1 WO 2014042117A1 JP 2013074216 W JP2013074216 W JP 2013074216W WO 2014042117 A1 WO2014042117 A1 WO 2014042117A1
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- copper
- pyrithione
- salt
- copper pyrithione
- ammonium
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
Definitions
- the present invention relates to a copper pyrithione aggregate and its use. More specifically, the present invention relates to an aggregate of copper pyrithione produced by reacting a water-soluble metal pyrithione or ammonium pyrithione with a composite salt of an inorganic copper (II) salt and an inorganic ammonium salt in an aqueous medium of pH 1-4, and its use. More specifically, the particle size of a copper pyrithione aggregate produced by reacting a water-soluble metal pyrithione or ammonium pyrithione with a composite salt of an inorganic copper (II) salt and an inorganic ammonium salt in an aqueous medium of pH 1-4.
- the present invention relates to an antifouling agent for ship bottom paints having a median diameter of 9-13 ⁇ m.
- Japanese Patent No. 3062825 discloses a method of adding a surfactant for the purpose of preventing the gelation that occurs in the production process and promoting the reaction in the production of copper pyrithione.
- an inorganic copper (II) salt is added to an aqueous pyrithione alkali metal salt solution under the conditions of pH 3-8 described in the claims of this patent, before the copper pyrithione is formed, first, fine crystals of the basic copper salt are formed. Precipitate. This is the actual state of the phenomenon called gelation.
- Copper pyrithione is obtained by the reaction of a slightly soluble basic copper salt and a pyrithione alkali metal salt, but the crystals of the product are small and the average particle diameter does not exceed 5 ⁇ m.
- the basic copper salt remaining as an impurity in the copper pyrithione product can cause gelation when the paint is stored when it is blended in a ship bottom antifouling paint.
- a pyrithione metal salt aqueous solution and an inorganic copper (II) salt aqueous solution are reacted at a high temperature in the range of pH 1.6 to 3.2, and then an inorganic copper (II) salt is added, followed by heat treatment.
- a process for producing copper pyrithione is disclosed.
- the dissolution rate in seawater that is, the solubility in water, and is determined by the surface area of the particles.
- the average particle size of copper pyrithione obtained in Japanese Patent No. 3062825 is suitable in the cold zone
- the average particle size of copper pyrithione obtained in Japanese Patent No. 3532500 is suitable in the temperate zone.
- copper pyrithione obtained in Japanese Patent No. 3532500 is considered to be too fast to be dissolved in seawater in the tropical sea area, and development of copper pyrithione with a larger average particle size is required to make the dissolution into seawater slower. Was demanded.
- conventional copper pyrithione products are easily powdered at the work site, and once inhaled into the lungs, health concerns have been shown due to their needle-like crystals.
- the present inventor has found a production method for aggregating copper pyrithione of small particles, and succeeded in solving the above two problems simultaneously by making the copper pyrithione into a granular aggregate having an average particle diameter of 9-13 ⁇ m. . That is, the present invention (1) General formula (I) Or general formula (I ') (Wherein M represents a monovalent or divalent metal or ammonium, and Py represents a 2-pyridylthio-N-oxide group.) Water-soluble metal pyrithione or ammonium pyrithione represented by the general formula (II) (In the formula, X represents an anion of Cl, 1 / 2SO 4 , or NO 3.
- a copper pyrithione aggregate produced by reacting a composite salt of an inorganic copper (II) salt and an inorganic ammonium salt represented by the above in an aqueous medium having a pH of 1-4.
- II General formula (I) Or general formula (I ')
- M represents a monovalent or divalent metal or ammonium
- Py represents a 2-pyridylthio-N-oxide group.
- Water-soluble metal pyrithione or ammonium pyrithione represented by the general formula (II) In the formula, X represents an anion of Cl, 1 / 2SO 4 , or NO 3.
- a process for producing a copper pyrithione aggregate which is produced by reacting a composite salt of an inorganic copper (II) salt and an inorganic ammonium salt represented by formula (1) in an aqueous medium having a pH of 1-4.
- the median diameter of the copper pyrithione aggregate particles is in the range of 9-13 ⁇ m on the premise that the main part of the particle size distribution shows a normal distribution, as described in (1), (3) or (5) Of copper pyrithione.
- the median diameter of the copper pyrithione aggregate particles is in the range of 9-13 ⁇ m, on the premise that the main part of the particle size distribution shows a normal distribution, as described in (2), (4) or (6) Of producing a copper pyrithione aggregate.
- M represents a monovalent or divalent metal.
- Monovalent sodium is preferred.
- inorganic copper (II) salt used when manufacturing the copper pyrithione granular aggregate of the present invention is copper chloride (II) or copper (II) sulfate
- inorganic ammonium salt used in the above include ammonium chloride or ammonium sulfate.
- a composite salt of inorganic copper (II) salt and inorganic ammonium salt used for producing the copper pyrithione granular aggregate of the present invention a composite salt of copper chloride and ammonium chloride (for example, CuCl 2 ⁇ 2 (NH 4 ) Cl), a composite salt of copper sulfate and ammonium sulfate (for example, CuSO 4 ⁇ (NH 4 ) 2 SO 4 ), a composite salt of copper nitrate and ammonium nitrate (for example, Cu (NO 3 ) 2 ⁇ 2 (NH 4 ) NO 3 )) and hydrates of these complex salts.
- a composite salt of copper chloride and ammonium chloride for example, CuCl 2 ⁇ 2 (NH 4 ) Cl
- a composite salt of copper sulfate and ammonium sulfate for example, CuSO 4 ⁇ (NH 4 ) 2 SO 4
- a composite salt of copper nitrate and ammonium nitrate for
- a composite salt of copper chloride and ammonium chloride eg, CuCl 2 ⁇ 2 (NH 4 ) Cl
- a composite salt of copper sulfate and ammonium sulfate eg, CuSO 4 ⁇ (NH 4 ) 2 SO 4
- a composite thereof It is a salt hydrate.
- the commercially available CuCl 2 ⁇ 2 (NH 4 ) Cl ⁇ 2H 2 O can be used as a dye fixing agent, but it is obtained by concentrating a calculated amount of copper (II) chloride and ammonium chloride acidic aqueous solution. The obtained crystal may be used.
- the amount of inorganic copper salt and inorganic ammonium salt used in the composite salt is 1 to 2 in molar ratio, and the amount of composite salt and sodium pyrithione used is 1 to 2 in molar ratio.
- the formation of a composite salt of an inorganic copper (II) salt and an inorganic ammonium salt, and the reaction of the inorganic copper (II) / ammonium composite salt of the present invention with a pyrithione metal salt are preferably carried out in the range of pH 1-4.
- the reaction temperature is preferably 10-30 ° C. When the reaction temperature is high, the primary particles of copper pyrithione extend too long and the aggregates are not formed well.
- the filterability is very good as compared with the conventional copper pyrithione.
- the average particle size is pulverized to be less than 9 ⁇ m, it is easy to produce 0.1-1.0 ⁇ m single particles at the time of pulverization, and the elution into the seawater of the copper pyrithione aggregate of the present invention is likely to be affected.
- the ratio of coarse particles of 50 ⁇ m or more may be 10% or more, which may affect the coating film performance of the paint.
- this product is appropriate to pulverize this product so as to have an average particle size of 9-13 ⁇ m (FIGS. 1 and 6) and use it as an antifouling agent for ship bottom paint. If the average particle diameter is in the range of 9-13 ⁇ m, the particle size distribution shows a normal distribution, and this normal distribution is a precondition for the median diameter measurement.
- This product is pulverized so as to have an average particle size of 9-13 ⁇ m (FIG. 1) and used as an antifouling agent for ship bottom paint.
- the aggregate entity may be a complex of copper pyrithione and an inorganic ammonium salt.
- the shape of copper pyrithione is recognized in the SEM photograph of the aggregate (FIGS. 2 and 3), and only the same peak as that of the conventional copper pyrithione is recognized in the charts of X-ray diffraction analysis (FIGS. 4 and 5).
- the aggregate of the present invention is a complex of copper pyrithione and a trace amount of inorganic ammonium salt. That is, most of the inorganic ammonium salt dissociated during the reaction is dissolved in the reaction solution and removed by washing with water.
- copper pyrithione is considered to be a relatively hard needle crystal, and a method of coarsening particles, a method of coating with a resinous substance, and the like have been proposed. These methods are effective, but cost increases are inevitable. Since the granular aggregate of the present invention has large particles and fluidity, it is not only difficult to powder, but also has no problem due to needle-like crystals. However, the risk of health damage is greatly reduced compared to conventional cases.
- the elution rate of copper pyrithione eluted from the ship bottom paint film is related to factors such as the surface properties of copper pyrithione and seawater temperature, the nature of the film, the navigation speed of the ship, and the adherence of fouling organisms. Although the difference cannot be discussed simply by the surface area ratio, the surface area of the copper pyrithione granular aggregate having a median diameter of 9-13 ⁇ m of the present invention is 2-6 times larger than the surface area of commercially available copper pyrithione.
- the elution rate for seawater is thought to be significantly slower, not only improving the antifouling effect sustainability under high water temperature conditions like in tropical waters, but also reducing copper pyrithione emissions into the ocean, It is also preferable from the viewpoint of environmental protection.
- the copper pyrithione granular aggregate of this invention is mix
- the copper pyrithione obtained by the production method of the present invention is a needle-like crystal having a median particle diameter of 5 ⁇ m or less, whereas the conventional copper pyrithione is a large particle having a median particle diameter of 9-13 ⁇ m and a small particle size with a short length. Because it is an assembly, the risk of inhalation at the work site is greatly reduced, and when used as an antifouling agent for ship bottom paint, elution into seawater is greatly reduced, and the antifouling effect is sustained. Improved.
- Copper (II) sulfate / ammonium sulfate complex salt in which 3.0 g of copper (II) sulfate pentahydrate and 1.5 g of ammonium sulfate were added to 40 mL of water in a beaker, and 5% sulfuric acid was added to adjust the pH to 2.
- An aqueous solution (A) was prepared.
- 8.85 g of a 40% aqueous solution of sodium pyrithione (specific gravity 1.20) was added to 50 mL of water in a beaker to prepare a dilute aqueous solution of sodium pyrithione (B). While maintaining at 25 ° C., (B) was added dropwise to (A) with stirring over 30 minutes.
- ammonium sulfate was adsorbed on copper pyrithione and bound copper pyrithione. That is, it is considered that a complex was formed. However, since the trace is not recognized on the X-ray diffraction chart, the content of ammonium sulfate is estimated to be very small.
- Example 1 The copper pyrithione granular aggregate obtained in Example 1 was moistened with water, ground further strongly in a mortar and finely pulverized, and the median diameter of this was measured in the same manner as in Example 2 to obtain 5.0 ⁇ m (ultrasound No treatment) A fine particle aggregate having a value of 3.3 ⁇ m (sonication for 1 minute) was obtained.
- Example 2 The copper pyrithione granular aggregate obtained in Example 2 was refined in the same manner as in Comparative Example 1, and the median diameter was measured in the same manner. As a result, 4.3 ⁇ m (no sonication), 3.1 ⁇ m (ultrasound A value of 1 minute of treatment) was obtained.
- Example 1 For the copper pyrithione granular aggregates obtained in Example 1, Example 2, Comparative Example 1, and Comparative Example 2, the solubility in water was measured.
- Sample Preparation A sample in which 0.05 g of each sample was dispersed in 250 mL of ultrapure water was stirred at room temperature for 24 hours. Next, the mixture was filtered using a 5C filter paper, and subsequently with an average pore diameter of 0.45 ⁇ m membrane filter, and then a solution in which nitric acid was added to the filtrate to 0.1 mol / L was subjected to measurement. 2.
- Measurement Method ICP Emission Spectroscopic Analysis (Equipment: Shimadzu Corporation “ICPS-2000”) The measurement results are shown in Table 1.
- the copper pyrithione granular aggregate of the present invention has a large median diameter of 9 to 13 ⁇ m as a median diameter that cannot be obtained by conventional commercial copper pyrithione, the dissolution rate from the paint film of the ship bottom paint is reduced.
- it may be useful as an antifouling agent exhibiting long-term antifouling performance in a tropical sea area and as an antifouling agent with a small amount of discharge to the environment.
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Abstract
Description
日本特許第3532500号には、pH1.6~3.2の範囲でピリチオン金属塩水溶液と無機銅(II)塩水溶液を高温下で反応させ、次いで無機銅(II)塩を追加し、加熱処理を行うという銅ピリチオンの製造法が開示されている。本方法の第1工程では、低pH・高温下で長時間反応させるという製造条件から、ピリチオン酸の酸化によるビスピリチオン(2量体)ができやすく、第2工程でビスピリチオンを熱分解させ、同時に無機銅(II)塩を補充することにより、銅ピチオンの純度を高めるという手法が取られている。従い、第2工程においては、生成量は限られているものの、先ずは上述のように塩基性銅塩が沈殿する。本特許の製造法で得られる銅ピリチオンの平均粒子径は、生成する塩基性銅塩が少ないため、上記日本特許第3062825号の製造法で得られる銅ピリチオンの平均粒子径より格段に大きくなるが、それでも特許請求範囲に示されるように、5μmを超えない。
即ち、本発明は、
(1)一般式(I)
で示される水可溶性金属ピリチオン又はアンモニウムピリチオンと
一般式(II)
で示される無機銅(II)塩と無機アンモニウム塩との複合塩をpH1-4の水媒体中で反応させて製せられる銅ピリチオン集合体。
(2)一般式(I)
で示される水可溶性金属ピリチオン又はアンモニウムピリチオンと
一般式(II)
で示される無機銅(II)塩と無機アンモニウム塩との複合塩をpH1-4の水媒体中で反応させて製せられることを特徴とする、銅ピリチオン集合体の製造方法。
(3)Mは、ナトリウム、カリウム、カルシウム及びマグネシウムからなる金属から選ばれるものである、(1)に記載の銅ピリチオン集合体。
(4)Mは、ナトリウム、カリウム、カルシウム及びマグネシウムからなる金属から選ばれるものである、(2)に記載の銅ピリチオン集合体の製造方法。
(5)無機銅(II)塩は、塩化銅(II)又は硫酸銅(II)であり、無機アンモニウム塩は、塩化アンモニウム又は硫酸アンモニウムである、(1)又は(3)に記載の銅ピリチオン集合体。
(6)無機銅(II)塩は、塩化銅(II)又は硫酸銅(II)であり、無機アンモニウム塩は、塩化アンモニウム又は硫酸アンモニウムである、(2)又は(4)に記載の銅ピリチオン集合体の製造方法。
(7)銅ピリチオン集合体粒子のメジアン径が、粒度分布の主要部分が正規分布を示すことを前提条件として、9-13μmの範囲にある、(1)、(3)又は(5)に記載の銅ピリチオン集合体。
(8)銅ピリチオン集合体粒子のメジアン径が、粒度分布の主要部分が正規分布を示すことを前提条件として、9-13μmの範囲にある、(2)、(4)又は(6)に記載の銅ピリチオン集合体の製造方法。
(9)(1)の銅ピリチオン集合体を含有する船底塗料用防汚剤。
(10)銅ピリチオン集合体の粒子のメジアン径が、粒度分布の主要部分が正規分布を示すことを前提条件として、9-13μmの範囲にある、(9)に記載の船底塗料用防汚剤。
平均粒子径が9μm未満になるよう粉砕すると、粉砕時0.1-1.0μmの単粒子が無視できないほどできやすく、本発明の銅ピリチオン集合体の海水への溶出性に影響を与えやすい。また平均粒子径が13μmを超えるよう粉砕すると、50μm以上の粗大粒子の比率が10%以上になる可能性があり、塗料の塗膜性能に影響を与えるおそれがある。従って、このものを平均粒子径が9-13μmになるよう粉砕し(図1及び図6)、船底塗料用防汚剤として用いるのが適当である。平均粒子径が9-13μmの範囲にあれば、粒度分布は正規分布を示すので、この正規分布がメジアン径測定の前提条件となる。このものを平均粒子径が9-13μmになるよう粉砕し(図1)、船底塗料用防汚剤として用いる。
本発明の銅ピリチオン粒状集合体は、シリルアクリル樹脂、亜鉛アクリル樹脂、銅アクリル樹脂及びこれらの共重合樹脂を基材とする船底防汚塗料に配合され、通常亜酸化銅とともに処方される。
この緑色粒状物を0.1%デモールN(花王株式会社)水溶液に分散させたもののメジアン粒子径は、レーザ回折式粒度分布測定装置、堀場製作所「LA-920」で測定した結果、10.6μmであった(図1)。またこの装置の超音波機能を1分間作動させたときのメジアン径は、9.5μmであった。この超音波作動時間の増加により、数値が低下する傾向は、市販銅ピリチオンの場合と同様である。
粒子の内部の状態を観察するため、電子顕微鏡を用いて、6000倍(図2)、及び30000倍(図3)の写真を撮影した。その結果、内部は0.1~1.0μmの長さを有する楕円球状、棒状の銅ピリチオンと思われる物質の集合体であることが判明した。
次に集合体の化学成分を調べるため、X線回折分析を行った。その結果この緑色粒状集合体と市販銅ピリチオン(Kolon生命科学社製)のチャート(図4及び5)上で認められるピーク位置は全く同一であることから、緑色粒状集合体の本質は銅ピリチオンであることを確認した。
さらにこの銅ピリチオン粒状集合体を水に分散させ、80℃で30分撹拌したところ、かすかなアンモニア臭があり、集合体は数10%程度壊れた。このことは、集合体に水可溶性のアンモニア化合物が含まれていることを示しており、硫酸銅(II)・硫酸アンモニウム複合塩とナトリウムピリチオンから銅ピリチオンが生成した経緯を考えると、反応時解離した硫酸アンモニウムが銅ピリチオンに吸着され、銅ピリチオン同士を結びつけたと推測される。即ち複合体が形成されたと考えられる。ただX線回折チャート上ではその形跡が認められないことから、硫酸アンモニウムの含量は微量であると推定される。
(II)2水和物0.025モル(4.3g)を加え(pH3)、さらに2N塩酸を加えてpH2の塩化銅・塩化アンモニウム複合塩水溶液(A)を調製した。別のビーカーに入れた40mLの水にナトリウムピリチオン40%水溶液18.6gを加え、ナトリウムピリチオンの0.05モル水溶液(B)を調製した。室温(20℃)で(A)に(B)を10分かけて撹拌しながら滴下した。この間適宜2N塩酸を加え、反応終点のpHが3になるよう調整した。さらに30分間室温で撹拌を続けた。得られた緑色スラリーをろ過し、ろ過残を100mLの水に戻し、10分間撹拌後次いでろ過を行うという操作を3回繰り返した後、得られた固体を乾燥し、乳鉢で粉砕して7.6gの銅ピリチオン粒状集合体を得た。
この緑色粒状物を0.1%デモールN(花王株式会社)水溶液に分散させたもののメジアン粒子径は、レーザ回折式粒度分布測定装置、堀場製作所「LA-920」で測定した結果、この装置の超音波機能を1分間作動させたときのメジアン径は、12.1μmであった(図6)。
1.試料調製
各試料0.05gをそれぞれ超純水250mLに分散させたものを、室温で24時間撹拌した。次に5Cのろ紙、続いて平均穴径0.45μmメンブランフィルタを用いてろ過した後、ろ液に0.1モル/Lになるよう硝酸を添加した溶液を測定に供した。
2.測定方法
ICP発光分光分析(機器;島津製作所「ICPS-2000」)
測定結果を表1に示す。
メチルメタクリレートとトリイソプロピルシリルアクリレートの2:3共重合体(50%キシレン溶液) 36重量%
亜酸化銅 32重量%
亜鉛華 4重量%
実施例2の銅ピリチオン粒状集合体 3重量%
チタン白 2重量%
弁柄 2重量%
脂肪酸アマイドワックス(20%) 2重量%
キシレン 19重量%
合計 100重量%
塗料調製時また半年後もゲル化等の異常は認められなかった。
Claims (10)
- Mは、ナトリウム、カリウム、カルシウム及びマグネシウムからなる金属から選ばれるものである、請求項1に記載の銅ピリチオン集合体。
- Mは、ナトリウム、カリウム、カルシウム及びマグネシウムからなる金属から選ばれるものである、請求項2に記載の銅ピリチオン集合体の製造方法。
- 無機銅(II)塩は、塩化銅(II)又は硫酸銅(II)であり、無機アンモニウム塩は、塩化アンモニウム又は硫酸アンモニウムである、請求項1又は請求項3に記載の銅ピリチオン集合体。
- 無機銅(II)塩は、塩化銅(II)又は硫酸銅(II)であり、無機アンモニウム塩は、塩化アンモニウム又は硫酸アンモニウムである、請求項2又は請求項4に記載の銅ピリチオン集合体の製造方法。
- 銅ピリチオン集合体粒子のメジアン径が、粒度分布の主要部分が正規分布を示すことを前提条件として、9-13μmの範囲にある、請求項1、3又は5に記載の銅ピリチオン集合体。
- 銅ピリチオン集合体粒子のメジアン径が、粒度分布の主要部分が正規分布を示すことを前提条件として、9-13μmの範囲にある、請求項2、4又は6に記載の銅ピリチオン集合体の製造方法。
- 請求項1の銅ピリチオン集合体を含有する船底塗料用防汚剤。
- 銅ピリチオン集合体の粒子のメジアン径が、粒度分布の主要部分が正規分布を示すことを前提条件として、9-13μmの範囲にある、請求項9に記載の船底塗料用防汚剤。
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SG11201407771RA SG11201407771RA (en) | 2012-09-12 | 2013-09-09 | Copper pyrithione aggregate and use of same |
JP2014514961A JP5594619B2 (ja) | 2012-09-12 | 2013-09-09 | 銅ピリチオン集合体及びその用途 |
CN201380017535.3A CN104203917B (zh) | 2012-09-12 | 2013-09-09 | 吡啶硫酮铜集合体及其用途 |
KR1020147027375A KR101630560B1 (ko) | 2012-09-12 | 2013-09-09 | 구리피리티온 집합체 및 그 용도 |
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JP2021123589A (ja) * | 2020-02-03 | 2021-08-30 | 有限会社 ワイエイチエス | 銅ピリチオン集合体の製造方法 |
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CN104203917B (zh) | 2016-08-24 |
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