KR20140131980A - Copper pyrithione aggregate and use of same - Google Patents

Abstract

Conventional copper pyrithione products have been considered to be too fast to dissolve in seawater in tropical waters, and the development of copper pyrithione having a large average particle diameter has also been required in order to make the dissolution into seawater slower. In addition, until now, copper pyrithione products are likely to be powdered at the worksite, and once inhaled into the lungs, the bedding crystals have been anxious about their health. By using the inorganic copper (II) -inorganic ammonium complex salt instead of the inorganic copper (II) salt as a conventional raw material for production, the resulting small particles of copper pyrithione are made into a large granular aggregate having an average particle diameter of 9-13 μm , Both of which were solved simultaneously.

Description

Copper pyrithione aggregates and their uses {Copper pyrithione aggregate and use of same}

The present invention relates to copper pyrithione aggregates and uses thereof. More specifically, the present invention relates to a copper pyrithione aggregate produced by reacting a water-soluble metal pyrithione or ammonium pyrithione, a complex salt of an inorganic copper (II) salt and an inorganic ammonium salt in a water medium at pH 1-4, and a use thereof. More specifically, the water-soluble metal pyrithione or ammonium pyrithione and a complex salt of an inorganic copper (II) salt and an inorganic ammonium salt are reacted in a water medium of pH 1-4 to prepare a copper pyrithione aggregate, And having a diameter in the range of 9 to 13 占 퐉.

Japanese Patent No. 3062825 discloses a method of preventing the gelation occurring in the production process in the production of copper pyrithione and adding a surfactant to accelerate the reaction. When an inorganic copper (II) salt is added to an aqueous solution of an alkali metal pyrithione under the condition of pH 3 to 8 described in the claims of this patent, microcrystals of the basic copper salt are precipitated before the copper pyrithione is produced. This is the actual phenomenon called gelation. Copper pyrithione can be obtained by reacting a basic copper salt with a poorly soluble basicity and an alkali metal pyrithione, but the crystal of the product is small and the average particle diameter does not exceed 5 탆. Further, the basic copper salt remaining as an impurity in the copper pyrithione product causes gelation at the time of storage of the paint when incorporated into the bottom antifouling paint.

Japanese Patent No. 3532500 discloses a process for producing copper (II) salt by reacting an aqueous solution of a pyrithione metal salt and an aqueous solution of an inorganic copper (II) salt at a pH in the range of 1.6 to 3.2, A method for producing pyrithione is disclosed. In the first step of the present method, bispyrithione (dimer) is easily formed due to oxidation of pyrithione acid (acid) in a production condition under which the reaction is carried out for a long time at a low pH and a high temperature. In the second step, pyrethion And at the same time, an inorganic copper (II) salt is supplemented to increase the purity of the copper pyrithione. Therefore, in the second step, the amount of formation is limited, but the basic copper salt precipitates first as described above. The average particle diameter of the copper pyrithione obtained by the present patented production method is much larger than the average particle diameter of the copper pyrithione obtained by the method of the Japanese Patent No. 3062825 because the amount of the basic copper salt to be produced is small, As shown, it does not exceed 5 탆.

Patent Document 1: Japanese Patent No. 3062825 Patent Document 2: Japanese Patent No. 3532500

When the copper pyrithione is incorporated into the bottom coating, the maximum factor that determines the antifouling effect is the rate of dissolution to sea water, that is, its solubility in water, and is determined according to the surface area of the particles. In one sea area, the average particle diameter of copper pyrithione obtained in Japanese Patent No. 3062825 is suitable, and in the temperate region, the average particle diameter of copper pyrithione obtained in Japanese Patent No. 3532500 is considered to be suitable. However, in the tropical waters, copper pyrithione, which can be obtained from Japanese Patent No. 3532500, is thought to be too fast for sea water, and in order to further delay the release into seawater, the development of copper pyrithione having a larger average particle diameter is required . Also, the copper pyrithione products so far tend to be powdered at the work site, and once they are inhaled into the lungs, there are concerns about their health due to the needle crystals.

The inventors of the present invention have discovered a process for collecting small particles of copper pyrithione and succeeded in simultaneously solving the above two problems by using copper pyrithione as a granular aggregate having an average particle diameter of 9-13 μm.

That is,

(1) General formula (I)

Or a compound represented by the general formula (I '):

(Wherein M represents a monovalent or divalent metal or ammonium, and Py represents a 2-pyridylthio-N-oxide group).

Soluble metal pyrithione or ammonium pyrithione represented by the formula

In general formula (II)

(Wherein X represents any one of Cl, 1 / 2SO _4, and NO ₃ ).

(II) salt and an inorganic ammonium salt represented by the general formula (I) in a pH-4 aqueous medium.

(2) General formula (I)

Or a compound represented by the general formula (I '):

(Wherein M represents a monovalent or divalent metal, or ammonium, and Py represents a 2-pyridylthio-N-oxide group.)

A water-soluble metal pyrithione or ammonium pyrithione represented by the general formula

In general formula (II)

(Wherein X represents any one of Cl, 1 / 2SO ₄ , and NO ₃ ).

And a complex salt of an inorganic copper (II) salt and an inorganic ammonium salt represented by the general formula (I) in a water medium having a pH of 1-4.

(3) The copper pyrithione aggregate according to (1), wherein M is selected from metals consisting of sodium, potassium, calcium and magnesium.

(4) The method for producing a copper pyrithione aggregate according to (2), wherein M is selected from metals consisting of sodium, potassium, calcium and magnesium.

(5) The copper pyrithione aggregate according to (1) or (3), wherein the inorganic copper (II) salt is copper (II) chloride or copper (II) chloride and the inorganic ammonium salt is ammonium chloride or ammonium sulfate.

(6) The process for producing a copper pyrithione aggregate according to (2) or (4), wherein the inorganic copper (II) salt is copper (II) chloride or copper (II) chloride and the inorganic ammonium salt is ammonium chloride or ammonium sulfate.

(7) The method according to (1), (3) or (5), wherein the median diameter of the copper pyrithione aggregate particles is in the range of 9 to 13 μm on condition that the major part of the particle size distribution exhibits a normal distribution Copper pyrithione aggregate.

(8) The copper-pyrithione aggregate particles according to (2), (4) or (6), wherein the median diameter of the copper pyrithione aggregate particles is in the range of 9 to 13 μm on condition that the major part of the particle size distribution exhibits a normal distribution Gt; pyrithione < / RTI >

(9) A bottom coat paint containing a copper pyrithione aggregate of (1).

(10) The bottom coat paint according to (9), wherein the median diameter of the copper pyrithione aggregate particles is in the range of 9 to 13 μm on condition that a major part of the particle size distribution shows a normal distribution.

M represents a monovalent or divalent metal. For example, monovalent metals such as sodium and potassium, and bivalent metals such as calcium and magnesium. Preferably monovalent sodium.

As the inorganic copper (II) salt used in producing the copper pyrithione granular aggregate of the present invention, there are copper (II) chloride or copper (II) sulfate, and used in the production of the copper pyrithione granular aggregate of the present invention Examples of the inorganic ammonium salt include ammonium chloride or ammonium sulfate. As the composite salt of the inorganic copper (II) salt and the inorganic ammonium salt used in producing the copper pyrithione granular aggregate of the present invention, a complex salt of copper chloride and ammonium chloride (for example, CuCl ₂ .2 (NH ₄ ) Cl), a complex salt of copper sulfate and ammonium sulfate (e.g. CuSO _4. (NH ₄ ) ₂ SO ₄ ), a complex salt of copper nitrate and ammonium nitrate (for example, Cu (NO ₃ ) ₄ ) NO ₃ ), and hydrates of the complex salts thereof. Preferably, a complex salt of copper chloride and ammonium chloride (for example, CuCl ₂揃 2 (NH ₄ ) Cl), a complex salt of copper sulfate and ammonium sulfate (for example, CuSO ₄揃 (NH ₄ ) ₂ SO ₄ ) And hydrates of the complex salts thereof. For example, CuCl ₂ · 2 (NH ₄ ) Cl · 2H ₂ O which is commercially available as a dye fixing agent can be used. However, even when a crystal obtained by concentrating a hydrochloric acid aqueous solution of calculated amounts of copper (II) chloride and ammonium chloride good. Similarly, a sulfuric acid acidic solution of a calculated amount of copper sulfate (II) and ammonium sulfate can be concentrated to obtain blue crystals of CuSO _4. (NH ₄ ) ₂ SO ₄ .6H ₂ O. Or efficiently. The crystals may be directly supplied to the reaction with the aqueous pyrithione metal salt solution as the raw material aqueous solution for producing the copper pyrithione granular aggregate of the present invention without the necessity of taking out crystals from the concentrated liquid. The amount of the inorganic copper salt and the inorganic ammonium salt of the composite salt is 1: 2 by molar ratio, and the amount of the complex salt and sodium pyrithione is 1: 2 by molar ratio. The formation of a complex salt of an inorganic copper (II) salt with an inorganic ammonium salt and the reaction of the inorganic copper (II) -ammonium complex salt of the present invention with a pyrithione metal salt preferably proceeds in the range of pHI-4. The reaction temperature is preferably room temperature of 10 to 30 占 폚. When the reaction temperature is high, the primary particles of the copper pyrithione are stretched too long, and aggregates are not formed well. Since the aggregates after the reaction by the method of the present invention form a granular aggregate having an average particle diameter of several hundreds of micrometers, the filtration properties are much better than those of the conventional copper pyrithione. When crushed to have an average particle diameter of less than 9 mu m, single particles of 0.1 to 1.0 mu m at the time of crushing easily occur so as not to be negligible, and it is easy to affect the elution of the copper pyrithione aggregate of the present invention into seawater. When the average particle diameter is more than 13 占 퐉, the proportion of large particles of 50 占 퐉 or more may be 10% or more, which may affect the paint film performance of the paint. Therefore, it is appropriate to use this powder as an antifogging agent for bottom paints (FIG. 1 and FIG. 6) so as to have an average particle diameter of 9 to 13 μm. When the average particle diameter is in the range of 9 to 13 占 퐉, the particle size distribution exhibits a normal distribution, and this normal distribution is a prerequisite for the median diameter measurement. This was pulverized to have an average particle diameter of 9 to 13 占 퐉 (Fig. 1), and used as a solvent for the bottom paint.

When the granular aggregates (average particle diameter of about 10 占 퐉) of the present invention are dispersed in water and heated at 80 占 폚 for 30 minutes, a faint ammonia odor is emitted and aggregates are broken by several 10%. From this, the entity of the aggregate is considered to be a complex of copper pyrithione with an inorganic ammonium salt. On the other hand, SEM photographs (FIG. 2 and FIG. 3) of the aggregate show only a copper pyrithione form, and in the chart of the X-ray diffraction analysis (FIGS. 4 and 5), only the same peak as the conventional copper pyrithione is observed. Judging from the above results, it is assumed that the substance of the aggregate of the present invention is a complex of copper pyrithione and a trace amount of an inorganic ammonium salt. That is, most of the inorganic ammonium salt dissociated in the reaction is dissolved in the reaction solution and removed by water washing.

When copper pyrithione is handled in powder form, there has been a risk of harm to health due to inhalation by powder at the work site. Particularly, it has been pointed out that copper pyrithione is a relatively hard needle-like crystal, and a method of enlarging the particle size, a method of coating with a resinous material, and the like have been proposed. These methods are effective, but cost increases are inevitable. Since the granular aggregates of the present invention are large in particle size and have fluidity, they are not only difficult to be powdered but also have no problem of needle bed crystals, so that even if they are handled in powder form without requiring such special treatment, The risk of damage is greatly reduced.

The elution rate of the copper pyrithione eluted from the bottom coating film depends on factors such as the surface area of the copper pyrithione and the sea water temperature as well as the properties of the coating film, the speed of the ship, and the adherence status of contaminated organisms. The surface area of the copper pyrithione granular aggregate having a median diameter of 9-13 탆 according to the present invention is 2-6 times larger than the surface area of commercially available copper pyrithione as a result of the elution on seawater It is considered that the speed is considerably slowed, which not only improves the sustainability of the antifouling effect at high temperature conditions such as the tropical waters, but also reduces the copper pyrithione emission to the ocean, which is also preferable from the viewpoint of environmental protection.

The copper pyrithione granular aggregate of the present invention is mixed with a bottom antifouling paint based on a silyl acrylic resin, a zinc acrylic resin, a copper acrylic resin and a copolymer resin thereof, and is ordinarily formulated together with copper oxide.

Since the copper pyrithione obtained in the present invention is a granular aggregate of small particles having a median particle diameter of 9 to 13 占 퐉 and a relatively small median particle diameter of not more than 5 占 퐉, The risk of inhalation on site is greatly reduced, and when it is used as a base paints for use as bottom paints, the dissolution into seawater is greatly reduced and the durability of the antifouling effect is improved.

Fig. 1 is a chart showing the median diameter of the copper pyrithione aggregate particles obtained in Example 1. Fig. (Laser diffraction particle size distribution device, HORIBA, Inc. LA-920, without ultrasonic treatment)
Fig. 2 is an electron micrograph (600O times) of the copper pyrithione aggregate obtained in Example 1. Fig.
3 is an electron micrograph (3000O times) of the copper pyrithione aggregate obtained in Example 1. Fig.
4 is a chart showing an X-ray diffraction pattern of the copper pyrithione aggregate obtained in Example 1. Fig.
5 is a chart showing an X-ray diffraction pattern of commercially available copper pyrithione powder (manufactured by Kolon Life Science).
6 is a chart showing the median diameter of the copper pyrithione aggregate particles obtained in Example 2 (laser diffraction particle size distribution apparatus, Horiba Works, LA-920, ultrasonic treatment for 1 minute).

Hereinafter, the present invention will be described in detail by way of examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Example 1

3.0 g of copper sulfate (II) pentahydrate and 1.5 g of ammonium sulfate were added to 40 mL of water contained in the beaker, and an aqueous copper sulfate (II) sulfate complex salt aqueous solution (A) adjusted to pH 2 with 5% . Subsequently, 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 an aqueous solution (B) of diluted sodium pyrithione. The mixture was maintained at 25 占 폚, and (A) and (B) were added dropwise with stirring (stirring) for 30 minutes. Meanwhile, 5% sulfuric acid was appropriately added so that the pH did not exceed 3.

The resulting green copper pyrithione slurry was filtered, and the filtration residue was dissolved in 100 mL of water. After stirring (stirring) and then filtration was repeated three times, the obtained solid was dried, ) To obtain 3.6 g of a green particulate material.

The median particle diameter of this green particulate material dispersed in an aqueous solution of 0.1% demol N (Kao Corporation) was 10.6 μm as measured by a laser diffraction particle size distribution analyzer, Horiba Corp. "LA-920" (Fig. 1). The median diameter when the ultrasonic function of this device was operated for 1 minute was 9.5 mu m. The tendency that the numerical value is lowered due to the increase of the ultrasonic operating time is the same as in the case of the commercial copper pyrithione.

In order to observe the internal state of the particles, photographs were taken at 6000 times (FIG. 2) and 30,000 times (FIG. 3) using an electron microscope. As a result, it was found that the inside was a collection of materials considered as elliptical spherical, rod-shaped copper pyrithione having a length of 0.1 to 1.0 μm.

Then, X-ray diffraction analysis was carried out to examine the chemical composition of the aggregate. As a result, it was confirmed that the peak position recognized on this chart of the green granular aggregate and the commercial copper pyrithione (Kolon Life Science Co.) (FIGS. 4 and 5) was at the very same point that the nature of the green granular aggregate was in the copper pyrithione .

When this copper pyrithione granular aggregate was dispersed in water and stirred (stirred) at 80 캜 for 30 minutes, there was a slight ammonia odor, and the aggregate was broken by several 10%.

This indicates that the water-soluble ammonia compound is contained in the aggregate. Considering the situation in which copper pyrithione is generated from the copper (II) sulfate ammonium complex sulfate salt and sodium pyrithione, the ammonium sulfate dissociated during the reaction becomes copper pyrithione And it is presumed that copper pyrithione is bound to each other. That is, a complex has been formed. Since the trace is not judged on the X-ray diffraction chart, the content of ammonium sulfate is estimated to be very small.

Example 2

To the beaker, 50 mL of water was added 0.05 mmol (2.7 g) of ammonium chloride and 0.025 mol (4.3 g) of copper (II) chloride dihydrate (pH 3) and 2N hydrochloric acid was added thereto to prepare a copper chloride ammonium chloride complex salt To prepare an aqueous solution (A).

To 40 mL of water in another beaker was added 18.6 g of a 40% aqueous solution of sodium pyrithione to prepare 0.05 molar aqueous solution (B) of sodium pyrithione. (A) and (B) were added dropwise at room temperature (20 占 폚) while stirring (stirring) for 10 minutes. During this time, 2N hydrochloric acid was added appropriately and the pH of the reaction end point was adjusted to 3. Stirring (stirring) continued at room temperature for 30 minutes. The obtained green slurry was filtered, and the filtration residue was returned to 10 mlL of water. After stirring for 10 minutes again, filtration was repeated three times. The obtained solid was dried, To obtain 7.6 g of a copper pyrithione granular aggregate.

The median particle diameter of this green particulate material dispersed in an aqueous solution of 0.1% of DEMOL N (Kao Co., Ltd.) was measured with a laser diffraction particle size distribution analyzer, Horiba Laboratories "LA-920" The median diameter when operating the ultrasound function for 1 minute was 12.1 m (Fig. 6).

Comparative Example 1

The copper pyrithione granular aggregate obtained in Example 1 was immersed in water, ground more finely with a pestle mortar and finely pulverized, and its median diameter was measured in the same manner as in Example 2 to find that 5.0 μm (without ultrasonic treatment) , 3.3 μm (ultrasonic treatment for 1 minute).

Comparative Example 2

The copper pyrithione granular aggregate obtained in Example 2 was made finer in the same manner as in Comparative Example 1 and its median diameter was measured in the same manner. As a result, it was found that 4.3 μm (without ultrasonic treatment) and 3.1 μm Value.

Example 3

The solubility of the copper pyrithione granular aggregates obtained in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 in water was measured.

1. Sample Preparation

0.05 g of each sample was dispersed in 250 mL of ultrapure water, and the mixture was stirred (stirred) at room temperature for 24 hours. Next, the filtrate was filtered using a filter paper of 5C, followed by an average pore diameter of 0.45 μm membrane filter, and then a solution in which nitric acid was added so as to be 0.1 mol / L in the filtrate was used for the measurement.

2. Measuring method

ICP emission spectroscopic analysis (instrument; Shimadzu Corporation "ICPS-2000")

The measurement results are shown in Table 1.

Table 1 Solubility in water sample Copper Measurements (mg / L) Concentration in terms of copper pyrithione (mg / L) The copper pyrithione aggregate of Example 1 &Lt; 0.05 <0.25 The copper pyrithione aggregate of Example 2 &Lt; 0.05 <0.25 The copper pyrithione aggregate of Comparative Example 1 0.08 0.40 The copper pyrithione aggregate of Comparative Example 2 0.09 0.45

In the results of Table 1, the solubility of the copper pyrithione aggregates of Examples 1 and 2 in water is 2/3 to 1/2 of that of the copper pyrithione aggregates of Comparative Examples 1 and 2.

Example 4

The following components were uniformly mixed to obtain a bottom coating.

36% by weight of a 2: 3 copolymer of methyl methacrylate and triisopropylsilyl acrylate (50% xylene solution)

32% by weight of copper oxide

Zinc powder 4 weight%

3% by weight of the copper pyrithione granular aggregate of Example 2

Titanium bag 2 wt%

2% by weight of bengala

Fatty acid amide wax (20%) 2%

Xylene 19 wt%

100 weight%

No abnormality such as gelation was found even after half a year at the time of coating preparation.

Since the copper pyrithione granular aggregate of the present invention has a large particle diameter of 9 to 13 占 퐉 at the median diameter which can not be obtained by conventional commercial copper pyrithione, the rate of elution of the bottom paints in the coating film is reduced, There is a possibility of being useful as an antifouling agent exhibiting long-term antifouling performance in the sea area and also as an antifouling agent having a small emission amount to the environment.

Claims (10)

The compound of formula (I)
(7)

Or a compound represented by the general formula (I '):
[Chemical Formula 8]

(Wherein M represents a monovalent or divalent metal, or ammonium, and Py represents a 2-pyridylthio-N-oxide group.)
Soluble metal pyrithione or ammonium pyrithione represented by the formula
In general formula (II)
[Chemical Formula 9]

(Wherein X represents any one of the anion of Cl, 1 / 2S0 ₄ or N0 _3.)
(II) salt with an inorganic ammonium salt in a water medium having a pH of 1-4, thereby producing a copper pyrithione aggregate. The compound of formula (I)
[Chemical formula 10]

Or a compound represented by the general formula (I '):
(11)

(Wherein M represents a monovalent or divalent metal or ammonium, and Py represents a 2-pyridylthio-N-oxide group).
Soluble metal pyrithione or ammonium pyrithione represented by the formula
In general formula (II)
[Chemical Formula 12]

(Wherein X represents any one of the anion of Cl, 1 / 2S0 ₄ or N0 _3.)
And a complex salt of an inorganic copper (II) salt and an inorganic ammonium salt represented by the general formula (I) in a water medium having a pH of 1-4. The method according to claim 1,
M is selected from metals consisting of sodium, potassium, calcium and magnesium. 3. The method of claim 2,
And M is selected from metals consisting of sodium, potassium, calcium and magnesium. The method according to claim 1 or 3,
Wherein the inorganic copper (II) salt is copper (II) chloride or copper (II) sulfate, and the inorganic ammonium salt is ammonium chloride or ammonium sulfate. The method according to claim 2 or 4,
Wherein the inorganic copper (II) salt is copper (II) chloride or copper (II) sulfate, and the inorganic ammonium salt is ammonium chloride or ammonium sulfate. The method according to claim 1, 3, or 5,
Wherein the median diameter of the copper pyrithione aggregate particles is in the range of 9-13 占 퐉, provided that the major part of the particle size distribution exhibits a normal distribution. The method according to claim 2, 4, or 6,
Wherein the median diameter of the copper pyrithione aggregate particles is in the range of 9-13 μm, provided that the major part of the particle size distribution exhibits a normal distribution. A bottom coat paint containing the copper pyrithione aggregate of claim 1. 10. The method of claim 9,
The median diameter of the copper pyrithione aggregate particles is in the range of 9-13 μm, assuming that the major part of the particle size distribution shows a normal distribution.

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