JP5732639B1 - Copper pyrithione aggregate and use thereof - Google Patents

Abstract

[PROBLEMS] The future issue of copper pyrithione, which has been recognized worldwide as the main antifouling agent for ship bottom paint, is to control the elution from the coating film from the viewpoint of protecting the marine environment. There were two ways to develop a product with a shape that would increase the duration of the product and how to develop a product with less dusting in order to improve safety at the work site. The present inventor uses conventional composite copper pyrithione by using a composite salt of an inorganic copper (II) salt and an inorganic ammonium salt in place of the inorganic copper (II) salt that is a raw material of the conventional copper pyrithione production method. We succeeded in obtaining copper pyrithione aggregates composed of small cylindrical and tabular grains different from the needle-like crystals. As a result, copper pyrithione aggregate particles having an average particle size in the range of less than 5.5-9 μm, which are mainly spherical and elliptical, can control the elution of the ship bottom antifouling coating film into seawater, and dust inhalation at work sites The above problem was solved by finding that the risk of the risk could be reduced.

Description

  The present invention relates to a copper pyrithione aggregate and its use. Specifically, a water-soluble metal pyrithione or a composite salt of ammonium pyrithione, an inorganic copper (II) salt and an inorganic ammonium salt, or a composite salt obtained by substituting a part of the inorganic ammonium salt with an inorganic alkali metal salt has a pH of more than 4 and less than -9 The present invention relates to a copper pyrithione aggregate produced by reacting in an aqueous medium and a method for producing the same. In addition, a water-soluble metal pyrithione or a complex salt of ammonium pyrithione, an inorganic copper (II) salt and an inorganic ammonium salt, or a complex salt obtained by substituting a part of the inorganic ammonium salt with an inorganic alkali metal salt for water having a pH of less than 1-9 The present invention relates to an underwater antifouling agent in a range of less than 5.5-9 μm on the assumption that particles of a copper pyrithione aggregate produced by reaction in a medium have a particle size range of 1 peak.

  Patent Document 1 discloses a method of adding a surfactant for the purpose of preventing gelation occurring in the production process and promoting the reaction in producing copper pyrithione. When inorganic copper (II) salt is added to an aqueous solution of pyrithione alkali metal salt under the conditions of pH 3-8 described in the claims of the present patent, before copper pyrithione is formed, first, fine crystals of the basic copper salt are formed. Precipitate. Copper pyrithione is obtained by the reaction of a slightly soluble basic copper salt precipitate and a pyrithione alkali metal salt, but it becomes a highly viscous liquid. This is the actual state of the phenomenon called gelation. Although the reaction proceeds by adding a surfactant, the produced copper pyrithione particles are as small as several microns, and have the disadvantage of poor filterability. Further, 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 the ship bottom paint.

  In Patent Document 2, 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, then an inorganic copper (II) salt is added, and heat treatment is performed. A process for producing copper pyrithione is disclosed. In the first step of this method, bispyrithione (dimer) is easily formed by oxidation of pyrithionic acid from the production conditions of reacting at low pH and high temperature for a long time, and in the second step, bispyrithione is thermally decomposed, At the same time, a method of increasing the purity of copper pyrithione by replenishing inorganic copper (II) salt has been taken. Although high-purity copper pyrithione can be obtained, it has the disadvantage that the production cost increases due to an increase in the number of steps. In the second step, although the amount of production is limited, the production of the basic copper salt as described above is unavoidable. The average particle size of copper pyrithione obtained by the production method of this patent is much larger than the average particle size of copper pyrithione obtained by the production method of Patent Document 1 because there are few basic copper salts to be produced. As shown in the Examples, when the centrifugal particle size distribution measuring device “CAPA500” (Horiba Seisakusho) is used, it does not exceed 5 μm.

  Patent Document 3 discloses an antifouling composition containing a pyrithione metal salt having a certain particle size range as a constituent element and a range of the ratio as an antifouling active ingredient. Among copper pyrithione among pyrithione metal salts, four examples of D (0.5) showing median values are shown in Examples and Comparative Examples. The breakdown includes one example of a pulverized product, one example of a wet filtered product, one example of a mixture of a pulverized product and an unground product, and one example of a non-ground product (comparative example). The measured value of the pulverized product and the wet filtered product is 2-3 μm, whereas the mixture of the pulverized product and the unground product shows 5 μm or more. However, the copper pyrithione product can be obtained by pulverizing a dry block as described in Example 1 of Patent Document 2 mentioned above. In the production process, the wet cake obtained after washing and filtering is always solidified in the drying process to form a dry block. Of course, an unground product cannot be a product. The method of obtaining an undried product having an average particle size of a product level is limited to a case where a special treatment not premised on commercialization is performed in a laboratory with a small amount of sample. A method of subjecting the wet cake to an aqueous dispersion as it is for particle size distribution measurement is also possible. However, even though this method can be adopted in the laboratory, the measured values obtained by this method are considered to be because the bottom antifouling paint and fishing net antifouling preparation are oil-based products and they dislike water very much. It can be said that it does not reflect the measured values of copper pyrithione products. Therefore, the measured value of 5.8 μm for the mixture of the pulverized product and the unground product and the measured value of 8.3 μm for the unground product are inappropriate values for the average particle size of the copper pyrithione product and may be used industrially. From this point of view, only the measured value of the ground product should be referred to.

Japanese Patent No. 3062825 Japanese Patent No. 3532500 Japanese Patent No. 4563642 Japanese Patent No. 5594619

  The future challenge for copper pyrithione, which has been recognized globally as the main antifouling agent for ship bottom paint, is to control the elution from the coating film and maintain the antifouling effect from the viewpoint of protecting the sea environment. There were two ways to develop a product with a shape that can extend the length of the product, and how to develop a product with less dusting in order to increase safety at the work site.

The present inventor uses a composite salt of an inorganic copper (II) salt and an inorganic ammonium salt in place of the inorganic copper (II) salt, which is a raw material of the conventional copper pyrithione production method, to thereby form a conventional needle crystal of copper pyrithione. We have succeeded in obtaining copper pyrithione aggregates composed of small cylindrical and tabular grains. As a result, copper pyrithione aggregate particles having an average particle size in the range of less than 5.5-9 μm, which are mainly spherical and elliptical, can control the elution of the ship bottom antifouling coating film into seawater, and dust inhalation at work sites The above problem was solved by finding that the risk of the risk could be reduced.
That is, the present invention
(1) General formula (I):
(Wherein M represents a monovalent or divalent metal or ammonium, Py represents a 2-pyridylthio-N-oxide group, and n represents 1 or 2), and a water-soluble metal pyrithione or ammonium pyrithione,
General formula (II):
(Wherein X represents an anion of Cl, 1 / 2SO ₄ or NO ₃ , M ′ represents ammonium or an alkali metal) and a composite of an inorganic copper (II) salt and an inorganic ammonium salt A copper pyrithione aggregate produced by reacting a salt or a composite salt in which a part of the inorganic ammonium salt is replaced with an inorganic alkali metal salt in an aqueous medium having a pH of more than 4 and less than -9,
(2) General formula (I):
(Wherein M represents a monovalent or divalent metal or ammonium, Py represents a 2-pyridylthio-N-oxide group, and n represents 1 or 2), and a water-soluble metal pyrithione or ammonium pyrithione,
General formula (II):
(Wherein X represents an anion of Cl, 1 / 2SO ₄ or NO ₃ , M ′ represents ammonium or an alkali metal) and a composite of an inorganic copper (II) salt and an inorganic ammonium salt A method for producing a copper pyrithione aggregate, characterized by being produced by reacting a salt, or a composite salt obtained by substituting a part of an inorganic ammonium salt with an inorganic alkali metal salt in an aqueous medium having a pH of more than 4 and less than -9,
(3) General formula (I):
(Wherein M represents a monovalent or divalent metal or ammonium, Py represents a 2-pyridylthio-N-oxide group, and n represents 1 or 2), and a water-soluble metal pyrithione or ammonium pyrithione,
General formula (II):
(Wherein X represents an anion of Cl, 1 / 2SO ₄ or NO ₃ , M ′ represents ammonium or an alkali metal) and a composite of an inorganic copper (II) salt and an inorganic ammonium salt The median diameter of copper pyrithione aggregate particles produced by reacting a salt or a composite salt obtained by substituting a part of the inorganic ammonium salt with an inorganic alkali metal salt in an aqueous medium having a pH of less than 1-9 has one particle size distribution. A copper pyrithione aggregate in the range of less than 5.5-9 μm, provided that it has a peak,
(4) M is a copper pyrithione assembly according to (1) or (3) above, which is a metal selected from the group consisting of sodium, potassium, calcium and magnesium,
(5) The method for producing a copper pyrithione aggregate according to (2) above, wherein M is a metal selected from the group consisting of sodium, potassium, calcium and magnesium,
(6) The inorganic copper (II) salt is copper (II) chloride or copper (II) sulfate, the inorganic ammonium salt is ammonium chloride or ammonium sulfate, and the inorganic alkali metal salt is sodium chloride or sodium sulfate. The copper pyrithione aggregate according to (1), (3) or (4) above,
(7) The inorganic copper (II) salt is copper (II) chloride or copper (II) sulfate, the inorganic ammonium salt is ammonium chloride or ammonium sulfate, and the inorganic alkali metal salt is sodium chloride or sodium sulfate. A method for producing a copper pyrithione aggregate according to (2) or (5) above,
(8) The copper pyrithione aggregate according to (3) above, wherein the median diameter of the copper pyrithione aggregate particles is in the range of less than 5.5-9 μm on the premise that a pulverizer is used.
(9) An underwater antifouling agent containing the copper pyrithione aggregate of (1) above,
(10) The underwater antifouling agent containing the copper pyrithione aggregate of (3) or (8) above, and (11) The above (9) wherein the underwater antifouling agent is an antifouling agent for ship bottom paints or an antifouling agent for fishing nets. Or an underwater antifouling agent according to (10).

  As a preferable metal pyrithione used when producing the copper pyrithione aggregate of the present invention, sodium pyrithione is preferable, and as a preferable inorganic copper (II) salt, copper (II) sulfate or copper (II) chloride is preferable inorganic ammonium. Examples of the salt include ammonium sulfate and ammonium chloride, and preferable inorganic alkali metal salts include sodium sulfate and sodium chloride.

Examples of the composite salt of inorganic copper (II) salt and inorganic ammonium salt used in the present invention include a composite salt of copper chloride and ammonium chloride (CuCl ₂ · 2 (NH ₄ ) Cl · 2H ₂ O), copper sulfate As a composite salt of copper sulfate and ammonium sulfate (CuSO ₄ · (NH ₄ ) ₂ SO ₄ · 6H ₂ O), inorganic copper (II) salt and inorganic alkali metal salt, for example, composite salt of copper sulfate and sodium sulfate (CuSO ₄ · Na ₂ SO ₄ · 2H ₂ O), and a composite salt of copper sulfate and potassium sulfate (CuSO ₄ · K ₂ SO ₄ · 6H ₂ O). These composite salts are generally obtained as crystals by concentrating a calculated amount of an inorganic copper (II) salt and an aqueous sulfuric acid or hydrochloric acid solution of an inorganic alkali metal salt or an inorganic ammonium salt. However, it is efficient and preferable to use it as it is as a raw material aqueous solution for producing the copper pyrithione aggregate of the present invention as it is, without taking out crystals from the concentrated liquid, for the reaction with the aqueous metal pyrithione solution.
When a part of the inorganic ammonium salt is used instead of the inorganic alkali metal salt, the ratio of the inorganic alkali metal salt is 10 to 90%, preferably 30 to 70%. If it is less than 10%, there is no substitute effect, and if it exceeds 90%, aggregate formation by ammonium cannot be obtained. The merit of using a part of the inorganic ammonium salt in place of the inorganic alkali metal salt is obtained when the reaction is performed in a high pH range or at a relatively high temperature. Under such reaction conditions, the effect of controlling the amount of ammonia generated from inorganic ammonium and smoothing the stirring can be expected. However, since removal of inorganic alkali metal salt impurities contained in the obtained copper pyrithione aggregate is not easy, the content of this impurity tends to increase and the shape of the particles becomes elongated, so the quality of the obtained copper pyrithione aggregate May adversely affect particle size control. Accordingly, when the reaction is carried out at a low pH range and at a low temperature, that is, when there is almost no generation of ammonium, it is recommended to use only an inorganic ammonium salt without using an inorganic alkali metal salt. Which one is selected depends on manufacturing conditions, manufacturing scale, and manufacturing equipment.

In the conventional method of obtaining copper pyrithione by reacting an aqueous solution of metal pyrithione and an aqueous solution of inorganic copper (II) salt, a basic copper salt (for example, basic copper sulfate, CuSO _4. Since Cu (OH) ₂ )) is generated, the reaction becomes solid-liquid reaction, resulting in not only poor reaction efficiency but also high viscosity. As described in Patent Document 1 mentioned above, a surfactant is used. The reaction will not proceed unless is used. However, when the metal pyrithione aqueous solution of the present invention, a composite salt aqueous solution of an inorganic copper (II) salt and an inorganic ammonium salt, or a composite salt aqueous solution in which a part of the inorganic ammonium salt is replaced with an inorganic alkali metal salt is reacted, Since an inorganic ammonium salt or inorganic alkali metal salt having a stronger binding strength than copper is bonded to an inorganic copper (II) salt, a basic copper salt is not generated, and a liquid-liquid reaction is maintained. Therefore, the reaction proceeds smoothly, and there is an advantage that there is no need to add a surfactant in the reaction under pH 4-8 conditions. The pH range suitable for producing the copper pyrithione aggregate of the present invention is less than 1-9. Regarding the range of pH 1-4, a patent application has already been filed by the present inventor (Patent Document 4). When the pH exceeds 9, the inorganic ammonium salt, which is an essential raw material, is replaced with an inorganic alkali salt to prevent aggregate formation, and ammonia is generated to cause a problem of odor.

  In the conventional method of obtaining copper pyrithione by reacting an aqueous metal pyrithione aqueous solution with an inorganic copper (II) salt aqueous solution, the reaction is carried out at a high temperature of 70 ° C. or higher. On the other hand, in the method of reacting a metal pyrithione aqueous solution, a composite salt aqueous solution of an inorganic copper (II) salt and an inorganic ammonium salt, or a composite salt aqueous solution in which a part of the inorganic ammonium salt is replaced with an inorganic alkali metal salt, Is carried out at room temperature of 10-40 ° C, preferably 15-30 ° C. When the reaction is carried out at a high temperature, the particles become large, a preferable aggregate cannot be obtained, and a problem of odor generation may occur.

  Based on the method for producing a copper pyrithione aggregate of the present invention, a copper pyrithione aggregate obtained by using a composite salt of sodium pyrithione, copper sulfate (II) and ammonium sulfate as a raw material is pulverized into particles having an average particle diameter of about 10 μm. When dispersed in water and heated at 80 ° C. for 30 minutes, it emits a faint ammonia odor and breaks the aggregate by several tens of percent. From this, it is considered that the substance that contributes to the formation of the copper pyrithione aggregate is an ammonium ion having an affinity for copper. However, the presence of ammonium sulfate was not recognized by X-ray diffraction analysis, and this substance could not be specified as a substance. Compared to the X-ray diffraction analysis chart of copper pyrithione, no difference is observed, so ammonium is considered to be in close contact with copper pyrithione and amorphous. The copper pyrithione purity by HPLC of the copper pyrithione aggregate sufficiently washed with Na to 1 ppm or less was 98.2-98.6%. From this, the ammonium content in the copper pyrithione aggregate is estimated to be about 1.4%. On the other hand, regarding the possibility that sodium sulfate contributes to the formation of copper pyrithione aggregates, if the copper pyrithione aggregates are sufficiently washed with water, as shown in Example 2, the Na content is about 0.1 ppm. Since it is clear that it is not held in the body, it is judged that there is no possibility.

  Based on the manufacturing method of the copper pyrithione aggregate of the present invention, the solid obtained by washing and filtering the reaction product and drying is aggregate coarse particles having a diameter of several hundred μm. When this coarse particle is pulverized by applying a shearing force, for example, a force such as rubbing with a mortar, a part of the particle becomes a fine particle, and two peaks appear in the fine particle region and the large particle region in the particle size distribution (see Patent Document 4). . However, when the surface is pulverized by applying a pressing force, for example, when pulverized by a ball mill as a fine pulverizer, a normal distribution or a particle size distribution of one peak close thereto can be obtained. Such a state of the particle size distribution is confirmed by a laser diffraction type particle size distribution measuring apparatus, for example, LA-920 (Horiba Seisakusho). Since the copper pyrithione aggregate obtained by the pulverization method of the present invention does not substantially contain microparticles, it is compared with the aggregate particles having the above-mentioned microparticle region and large particle region, and the ship bottom antifouling paint or fishing net antifouling preparation Excellent elution control function from coating film. A preferable particle size range for the antifouling agent for ship bottom antifouling paints or fishing net antifouling preparations is 1-30 μm, and the median value is less than 5.5-9 μm. However, it is a precondition that the lower limit of 5.5 μm is a value measured by a centrifugal particle size distribution device, CAPA-500 (Horiba Seisakusho). This is because the average particle diameter of 1-5 μm, which is the claim of Patent Document 2, is a value measured by CAPA-500.

  In the past, when copper pyrithione was handled in the form of powder, there was a concern that it would harm health at the work site due to inhalation by powdering. In particular, the problem that conventional copper pyrithione is a relatively hard needle-like crystal is regarded as a problem, and a method of coarsening particles using a surfactant or the like, a method of coating with an oil-based resinous material, and the like are proposed. I came. Although these methods are effective, since the copper pyrithione powder is secondarily treated, an increase in cost is inevitable. Since the copper pyrithione aggregate of the present invention is large in particle size and fluid, it is not only easy to handle and difficult to dust, but also has no problems due to needle-like crystals. Even if it is handled in powder form, it has the advantage that the risk of health damage is greatly reduced compared to the prior art.

The elution rate of copper pyrithione eluted from the paint film of ship bottom paints and fishing net antifouling preparations includes the surface area of copper pyrithione, seawater temperature, the nature of the paint film, the ship's navigation speed or ocean current speed, and the status of fouling organisms. Factors are involved. The surface area of the copper pyrithione assembly of the present invention having an average particle size (median value) of less than 5.5-9 μm is not limited by the ratio of the copper pyrithione surface area. It is 1.5-4 times larger than the surface area, and the elution delay effect is produced in the copper pyrithione aggregate due to the inclusion of the aggregate-forming substance, so that the elution rate into seawater is significantly slower than that of conventional copper pyrithione. As a result, not only the durability of the antifouling effect under high water temperature conditions such as in tropical waters is improved, but also the amount of copper pyrithione discharged into the ocean can be reduced, which is preferable from the viewpoint of protecting the sea environment.
The copper pyrithione aggregate of the present invention is a ship bottom antifouling paint based on a silyl acrylic resin, a zinc acrylic resin, a copper acrylic resin and a copolymer resin thereof, and a flexible resin such as an acrylic resin as a base material. It is added to the fishing net antifouling preparation. Both ship bottom antifouling paints and fishing net antifouling preparations are usually formulated with cuprous oxide.

  In the copper pyrithione aggregate of the present invention, the conventional copper pyrithione is a needle-like crystal having a median diameter of 5 μm or less, whereas the median diameter is large as less than 5.5-9 μm, and a granular aggregate of small particles having a short length Because it is a body, it has good fluidity, greatly reducing the risk of inhalation at the work site, and when used as an antifouling agent for ship bottom antifouling paints and fishing net antifouling preparations, It is greatly reduced and the durability of the antifouling effect is improved.

These are the charts which show the diffraction pattern by the X-ray diffraction analysis of the copper pyrithione aggregate | assembly obtained in Example 1. FIG. These are the charts which show the diffraction pattern by the X-ray diffraction analysis of commercial copper pyrithione. These are the charts which show the exothermic peak temperature in DTA / TGA of the copper pyrithione aggregate obtained in Example 1. These are charts which show a median value (50%) from the particle size distribution of the copper pyrithione aggregate obtained in Example 1. (Centrifuge type “CAPA-500” (Horiba)) These are charts which show a median value (50%) from the particle size distribution of the copper pyrithione aggregate obtained in Example 1. (Laser diffraction type “LA-920” (Horiba)) These are the electron micrographs of the copper pyrithione aggregate obtained in Example 1. These are charts which show a median value (50%) from the particle size distribution of the copper pyrithione aggregate obtained in Example 2. (Laser diffraction type "LA-920" (Horiba)) These are charts which show a median value (50%) from the particle size distribution of the copper pyrithione aggregate obtained in Example 3. (Laser diffraction type "LA-920" (Horiba)) These are the electron micrographs of the copper pyrithione aggregate obtained in Example 3. These are the charts which show the diffraction pattern by the X-ray diffraction analysis of the copper pyrithione aggregate | assembly obtained in Example 4. FIG. These are charts which show a median value (50%) from the particle size distribution of the copper pyrithione aggregate obtained in Example 4. (Centrifuge type “CAPA-500” (Horiba)) These are the electron micrographs of the copper pyrithione aggregate obtained in Example 4.

  The present invention will be specifically described below with reference to examples.

Into a 5 L reactor, 125 g (0.5 mol) of copper sulfate pentahydrate and 66 g (0.5 mol) of ammonium sulfate were added to make a 1.8 L aqueous solution, and then 20 mL of 10% sulfuric acid was added to adjust the pH to 2. Adjusted. Next, 300 mL of a 40% aqueous solution of sodium pyrithione (specific gravity 1.22) was diluted with water to obtain a 1.2 L aqueous solution. To 1.8 L of copper sulfate / ammonium sulfate aqueous solution, 1.2 L of sodium pyrithione aqueous solution was added dropwise at 20 ° C. over 2 hours with stirring. 3 L of the obtained copper pyrithione assembly slurry liquid was subjected to suction filtration under reduced pressure. The solid remaining after the filtration was once again transferred to the original container, and water was added to make 3 L of copper pyrithione aggregate slurry again. After stirring, suction filtration was performed again. This operation was repeated twice. The obtained solid was put in a dryer at 80 ° C. overnight, dried, crushed into small pieces, and crushed with a ball mill over 40 minutes. Yield was about 150 g.
A small amount of the sample was taken and subjected to X-ray diffraction analysis. As a result, the same diffraction pattern as that of commercially available copper pyrithione (manufactured by KOLON Life Science Co., Ltd.) was shown (FIGS. 1 and 2). Further, the value of the exothermic peak temperature of DTA / TGA was 280 ° C., and no endothermic or exothermic peak indicating the inclusion of impurities was observed (FIG. 3). The exothermic peak temperature of the copper pyrithione recrystallized product is 276 ° C., and the exothermic peak temperature of commercially available copper pyrithione is 282-285 ° C. Therefore, the copper pyrithione aggregate obtained in this example contains a trace amount of bound ammonium. Nevertheless, it was shown to be highly pure, and in fact the HPLC purity was 98.2%. The average particle size is 5.9 μm (Fig. 4) for the centrifugal “CAPA-500” (Horiba Seisakusho), and 6.48 μm (FIG. 5) for the laser diffraction type “LA-920” (Horiba Seisakusho) (respectively). Median value, dispersion medium: 0.2% demole N aqueous solution). Moreover, it was confirmed by the SEM photograph that the copper pyrithione aggregate obtained in this example was an aggregate of columnar or tabular grains having a small aspect ratio (FIG. 6).

  The synthesis was carried out in the same manner as in Example 1, and the obtained copper pyrithione aggregate slurry was dispensed into a 500 mL beaker and filtered with water washing using 18 cm diameter 5A filter paper. The filtration residue was again transferred to a beaker, water was added, and after stirring, the operation of washing and filtering with 5A filter paper was repeated three times. The solid from which water was squeezed was put into a drier, dried at 60 ° C. for 6 hours, and the obtained small piece was pulverized by a ball mill for 40 minutes. A small amount of the sample was taken and subjected to X-ray diffraction analysis. As a result, the same pattern as that of copper pyrithione was shown. The average particle size was 5.79 μm (FIG. 7) (median value, dispersion medium: 0.2% demole N aqueous solution) of laser diffraction type “LA-920” (Horiba Seisakusho). Furthermore, when the sodium content of this product was determined by atomic absorption analysis, it was 0.09 μg / mg and almost no by-product sodium sulfate remained.

In a 1 L beaker, 12.5 g of copper sulfate pentahydrate and 6.6 ammonium sulfate were combined to form a 360 mL aqueous solution, and then the pH was adjusted to 4.1 with a 1% aqueous sodium hydroxide solution. Next, 30 mL of a 40% aqueous solution of sodium pyrithione (specific gravity 1.22) was diluted with water to obtain a 240 mL aqueous solution. Formation of basic copper sulfate was not observed. To 360 mL of copper sulfate / ammonium sulfate aqueous solution, 240 mL of sodium pyrithione aqueous solution was added dropwise at 26 ° C. over 30 minutes with stirring. The pH after completion of the reaction was 7.3. After the reaction, 600 mL of the copper pyrithione assembly slurry liquid was left overnight and washed with water using 5A filter paper. The liquid solid remaining on the filter paper was once again transferred to a beaker, water was added, and the mixture was stirred and filtered again. This operation was repeated twice. The solid from which water was squeezed was put into a drier, dried at 60 ° C. for 6 hours, and the obtained small piece was pulverized with a ball mill for 30 minutes. Yield was about 150 g. The HPLC purity was 98.6%.
A small amount of the sample was taken and subjected to X-ray diffraction analysis. As a result, the same pattern as that of copper pyrithione was shown. The average particle diameter was 7.43 μm (FIG. 8) (median value, dispersion medium: 0.2% demole N aqueous solution) when pulverized with a laser diffraction type “LA-920” (Horiba Seisakusho) for 30 minutes. It was. The copper pyrithione aggregate obtained in this example was confirmed to be an aggregate of cylindrical or tabular grains having a small aspect ratio by SEM photography (FIG. 9).

  6.6 g of ammonium sulfate in Example 3 was replaced with 3.3 g of ammonium sulfate and 3.6 g of sodium sulfate, and the pH was adjusted to 6.4 with a 1% aqueous sodium hydroxide solution and reacted at 30 ° C. in the same manner as in Example 3. . The pH after completion of the reaction was 7.8. The ammonia odor was not perceivable. The copper pyrithione aggregate slurry after the reaction was washed with water and filtered in the same manner as in Example 3, and the small pieces obtained by drying were pulverized with a ball mill for 15 minutes. A small amount of the sample was taken and subjected to X-ray diffraction analysis. As a result, the same pattern as that of copper pyrithione was shown (FIG. 10). The average particle size was 8.5 μm (FIG. 11) (median value, dispersion medium: 0.2% demole N aqueous solution) by centrifugal “CAPA-500” (Horiba Seisakusho). Moreover, it was confirmed by the SEM photograph that the copper pyrithione obtained in this example was an aggregate of cylindrical particles having a small aspect ratio (FIG. 12).

In order to examine the dissolution property of the antifouling agent from the fishing net antifouling preparation coating film, the components of the following composition except for other components that might affect the dissolution property were uniformly mixed to obtain a fishing net antifouling preparation.
Note: Commercially available copper pyrithione; copper pyrithione (needle crystal) manufactured by Company A Average particle size 4.8 μm (CAPA-500)
A knotless net made of polyethylene (6 sections, 400 denier, 6 pieces) was immersed in the anti-fouling preparations of the above-mentioned formulas I and II and dried. The speed of elution of the copper pyrithione aggregate and copper pyrithione in the fishing net antifouling preparation composition into the water was investigated by measuring the elution copper concentration over time.
The sample was immersed in a fishing net antifouling preparation of Formulation I and II of Example 6 and the dried polyethylene knotless net was cut off so that the application amount of the antifouling agent was 1 g. Each sample immersed in 250 mL of ultrapure water was stirred at room temperature for 1 day, 4 days, and 7 days (total 6 samples). Next, the mixture was filtered using a 5C filter paper and then a membrane filter having an average pore diameter of 0.45 μm, and then a solution in which nitric acid was added to the filtrate to 0.1 mol / L was subjected to measurement.
For comparison, the solubility (dissolved copper) of copper pyrithione aggregate of formulation I and copper pyrithione of formulation II in water was measured by stirring for 24 hours in the same manner.
Measuring method
ICP emission spectroscopic analysis (Instrument: Shimadzu Corporation ICPS-2000)
The measurement results are shown in Table 1.

Table 1 Concentration of eluted copper components (mg / L)
Sample I. Copper pyrithione aggregate of Example 1 Average particle size; 5.9 μm (CAPA-500)
II. Copper pyrithione average particle size manufactured by Company A: 4.8 μm (CAPA-500)
The results in the above table indicate that the copper pyrithione aggregate of the present invention has a slower elution into the water from the fishing net antifouling preparation coating film than the difference in the average particle diameter with copper pyrithione compared to the commercially available copper pyrithione. Yes. In other words, the shape of the aggregate may have contributed. As for the dissolution property of the ship bottom antifouling paint film into water, this measurement method cannot be applied because the ship bottom antifouling paint is usually formulated together with cuprous oxide. However, considering the similarity to the fishing net antifouling preparation that the resin used for the ship bottom antifouling paint is an acrylic resin, the results of this example show a similar or similar tendency for the bottom antifouling paint. I guess it will be.

The following components were uniformly mixed to obtain a ship bottom paint.
No abnormalities such as gelation were observed at the time of preparing the paint and after 3 months.

The copper pyrithione aggregate of the present invention is easy to handle because it has less powdering during operation than the conventional commercially available copper pyrithione, and has a large average particle diameter of less than 5.5-9 μm in median diameter. As a result of delaying elution of ship bottom antifouling paints and fishing net antifouling preparations from paint films, it is useful as an antifouling agent that exhibits long-term antifouling performance, particularly in tropical seas, and as an antifouling agent with low environmental emissions. There is a possibility.

Claims (11)

Formula (I):
(Wherein M represents a monovalent or divalent metal or ammonium, Py represents a 2-pyridylthio-N-oxide group, and n represents 1 or 2), and a water-soluble metal pyrithione or ammonium pyrithione,
General formula (II):
(Wherein X is, Cl, 1 / 2SO ₄ or one of the anions of NO _3, M 'represents. The ammonium beam) complex salts with inorganic copper (II) salt and an inorganic ammonium salt represented by Copper pyrithione aggregate produced by reacting in an aqueous medium having a pH of more than 4 and less than -9. Formula (I):
(Wherein M represents a monovalent or divalent metal or ammonium, Py represents a 2-pyridylthio-N-oxide group, and n represents 1 or 2), and a water-soluble metal pyrithione or ammonium pyrithione,
General formula (II):
(Wherein X is, Cl, 1 / 2SO ₄ or one of the anions of NO _3, M 'represents. The ammonium beam) complex salts with inorganic copper (II) salt and an inorganic ammonium salt represented by A process for producing a copper pyrithione aggregate, wherein the copper pyrithione aggregate is produced by reacting in an aqueous medium having a pH of more than 4 and less than -9. Formula (I):
(Wherein M represents a monovalent or divalent metal or ammonium, Py represents a 2-pyridylthio-N-oxide group, and n represents 1 or 2), and a water-soluble metal pyrithione or ammonium pyrithione,
General formula (II):
(Wherein X is, Cl, 1 / 2SO ₄ or one of the anions of NO _3, M 'represents. The ammonium beam) complex salts with inorganic copper (II) salt and an inorganic ammonium salt represented by the median diameter of the copper pyrithione aggregate particles are Seise by reacting in an aqueous medium of less than pH1-9 is, as a prerequisite to have one peak in the particle size distribution is in the range of less than 5.5-9μm Copper pyrithione aggregate.   The copper pyrithione aggregate according to claim 1 or 3, wherein M is a metal selected from the group consisting of sodium, potassium, calcium, and magnesium. The method for producing a copper pyrithione aggregate according to claim 2, wherein M is a metal selected from the group consisting of sodium, potassium, calcium and magnesium. The inorganic copper (II) salt is copper (II) chloride or copper (II) sulfate, the inorganic ammonium salt is ammonium chloride or ammonium sulfate, and the inorganic alkali metal salt is sodium chloride or sodium sulfate. The copper pyrithione aggregate according to claim 3 or claim 4. The inorganic copper (II) salt is copper (II) chloride or copper (II) sulfate, the inorganic ammonium salt is ammonium chloride or ammonium sulfate, and the inorganic alkali metal salt is sodium chloride or sodium sulfate. Or the manufacturing method of the copper pyrithione aggregate | assembly of Claim 5.   4. The copper pyrithione aggregate according to claim 3, wherein the median diameter of the copper pyrithione aggregate particles is in the range of less than 5.5-9 [mu] m on the assumption that a fine pulverizer is used.   An underwater antifouling agent containing the copper pyrithione aggregate of claim 1.   An underwater antifouling agent comprising the copper pyrithione aggregate according to claim 3 or 8.   The underwater antifouling agent according to claim 9 or 10, wherein the underwater antifouling agent is a ship bottom paint antifouling agent or a fishing net antifouling agent.