WO2000073272A1 - Pyrithione de cuivre de grande purete, et procede de production correspondant - Google Patents

Pyrithione de cuivre de grande purete, et procede de production correspondant Download PDF

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Publication number
WO2000073272A1
WO2000073272A1 PCT/JP2000/003462 JP0003462W WO0073272A1 WO 2000073272 A1 WO2000073272 A1 WO 2000073272A1 JP 0003462 W JP0003462 W JP 0003462W WO 0073272 A1 WO0073272 A1 WO 0073272A1
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WO
WIPO (PCT)
Prior art keywords
copper
purity
aqueous solution
pyrithione
block
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PCT/JP2000/003462
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English (en)
Japanese (ja)
Inventor
Hiroshi Asano
Hideki Ao
Takashi Hamada
Original Assignee
Yoshitomi Fine Chemicals, Ltd.
Kikuchi Color & Chemicals Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by Yoshitomi Fine Chemicals, Ltd., Kikuchi Color & Chemicals Corporation filed Critical Yoshitomi Fine Chemicals, Ltd.
Publication of WO2000073272A1 publication Critical patent/WO2000073272A1/fr

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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

Definitions

  • the present invention relates to a high-purity bis (1-hydroxy-2 (1H) -pyridinethionato-0, S) copper ( ⁇ ) useful as an antifouling agent for ship bottom paints, an antibacterial agent for paints and plastics, and an antifungal agent. ) (Hereinafter referred to as copper pyrithione) and an industrial method for producing copper pyrithione which can be obtained in high yield. Background art
  • copper pyrithione can be roughly classified into (A) aqueous solution of inorganic copper (II) salt at room temperature by adding (1-hydroxy-1- (1H) -pyridinethionato 0, S) (I) (hereinafter referred to as APY) A method of adding an aqueous solution, or conversely, adding an aqueous copper ( ⁇ ) salt solution to an APY aqueous solution (US Pat. No. 2,809,971); (II) A method of adding an alcohol solution of 1-hydroxy_2 (1H) -pyridinethione to an aqueous salt solution (USP 2,809,971) has been performed.
  • copper pyrithione is a substance that is hardly soluble in water. When they are precipitated by, they are formed as very fine particles containing a part of the raw material and by-product alkali sulfate, etc., and are precipitated at once. It is extremely difficult to remove impurities from the fine particles thus precipitated by washing with water, and when the fine particles are dried, the surface of the block after drying becomes hard and agglomerated even when pulverized. Only a powder is obtained. This product has low purity, and when used as an antifouling paint, a good coating film cannot be obtained. In addition, if coarse particles are mixed, the paint preparation will be hindered.
  • the present invention provides a copper pyrithione having a high purity and an optimum particle size which does not cause gelling of a paint when used as a ship bottom paint, and a method for producing the same in a high yield and industrially advantageously. Is to do.
  • the present inventors supply raw materials so that the pH value in the reaction system is kept in a specific range, and heat-treat the obtained slurry-like target product under specific conditions to obtain a high-purity target product in a high yield.
  • the present invention succeeded industrially advantageously, and completed the present invention. That is, the present invention relates to a copper pyrithione having a purity of 97% or more and a particle diameter of 1 to 5 // m and a (1-hydroxy-2 (1H) -pyridinethionato II, S) alkali metal
  • a method for producing copper pyrithione by mixing an aqueous solution and an inorganic copper ( ⁇ ) salt aqueous solution,
  • Both aqueous solutions are mixed and reacted to obtain a slurry so that the pH value in the reaction system is maintained in the range of 1.6 to 3.2.
  • Sodium and sodium hydroxide are typical examples of the alkali metal of the nato (S) alkali metal salt (APY).
  • Inorganic copper (II) salts are divalent copper salts of inorganic acids, and typical examples are copper sulfate (11), copper nitrate (11), and copper chloride (II).
  • an A PY aqueous solution and an inorganic copper ( ⁇ ) salt aqueous solution are prepared, and the two are mixed to carry out the reaction (1).
  • the pH value in the reaction system becomes 1.6 to 1.6. It is an essential requirement to adjust the supply of both aqueous solutions to maintain the range of 3.2, preferably 1.7-3.0.
  • the pH value in the reaction system of (1) is greater than 3.2, rinse with water because the average particle size of the product copper pyrithione will be less than 1 / im even after the heat treatment of (2). The process is difficult, and the block after drying becomes hard and agglomerated, and coarse particles are mixed in the powder after grinding. Also, the purity of the product is low.
  • the type of reaction (1) can be either batch or continuous as long as both aqueous solutions can be supplied so that the pH value in the reaction system is maintained within the range of 1.6 to 3.2. You can do it.
  • the concentrations of the raw material A PY aqueous solution and the inorganic copper (II) salt are usually about 0.1 to 5 mol, preferably about 0.3 to 2 mol.
  • the reaction may be carried out at a temperature of about 60 to 100 ° C, and the stirring speed, the reaction time and the like may be appropriately selected.
  • a slurry is produced by the reaction of (1), and this slurry is 0.5 to 10% by weight, preferably 1.0 to 10% by weight in terms of copper of the inorganic copper ( ⁇ ) salt used in the reaction of (1).
  • the heat treatment of (2) is performed in the presence of 8% by weight of copper ions.
  • the heat treatment of (2) is performed in order to make the fine particles of copper pyrithione produced in (1) into particles having an average particle diameter of 1 to 5 ⁇ m and to remove impurities taken into the particles. If the amount of copper (II) ions present is less than 0.5% by weight, copper pyrithione is not sufficiently formed, and if it is more than 10% by weight, copper ions incorporated into the copper pyrithione particles And the purity of the product decreases.
  • the treatment temperature is preferably about 60 to 100 ° C, and the treatment time is usually 3 hours or more, preferably 5 to 8 hours. Generally, it takes a long time to react at around 60 ° C, and when the temperature is higher than this, the process tends to be completed in a short time.
  • the treatment of (2) may be carried out after washing and removing unnecessary salts produced as a by-product in the reaction of (1), or may be carried out following the reaction of (1).
  • the treatment of (2) can be performed under atmospheric pressure without the need for an autocrepe device or the like.
  • the copper pyrithione thus obtained is particles having an average particle diameter of 1 to 5 ⁇ m, and can be easily washed and filtered. Therefore, after the heat treatment of (2), by washing, solid-liquid separation, drying, and pulverization by a conventional method, a powder having a desired uniform average particle diameter can be obtained.
  • Example 1 Example 1
  • solution B inorganic copper (II) salt aqueous solution: 2.5 g (1.0 mol) of copper sulfate (II) pentahydrate was dissolved in water to prepare a 2.5 liter aqueous solution (hereinafter referred to as solution B).
  • Reaction stage Put 5 liters of water in a container, heat to 80 ° C, and stir solution A and solution B over 4 hours while maintaining the pH value in the reaction system at 1.8 and the temperature at 80 ° C with stirring. At the same time The mixture was reacted while being supplied to obtain a desired slurry.
  • Treatment step 10 g (0.04 mol) of copper (II) sulfate pentahydrate was added to the obtained slurry, and the mixture was treated at 95 ° C for 7 hours, allowed to cool, and filtered with suction. . Subsequently, after suction water washing with 5 liters of warm water at 50 ° C, drying was performed at 90 ° C for 16 hours in a ventilation dryer.
  • the dried block was in a uniform state with no difference between the inside of the block and the surface. Then, the dried product was pulverized using a hammer mill to obtain copper pyrithione fine powder.
  • the obtained copper pyrithione fine powder was green, the yield was 316 g, and the yield compared to the theoretical value was 101%.
  • the copper content was measured by chemical analysis and the purity compared with the theoretical value was more than 99%.
  • the particle size distribution was measured using a centrifugal automatic particle size distribution analyzer (Horiba, Ltd. “CA PA-500”). As a result of the measurement, the average particle size was 2.0 ⁇ .
  • the desired product was obtained in the same manner as in Example 1 except that ⁇ ⁇ ⁇ value of 2.9 was maintained in the reaction stage.
  • the dried block was in a uniform state with no difference between the inside of the block and the surface.
  • the desired product was obtained in the same manner as in Example 1 except that solution A and solution B were simultaneously supplied over 1 hour in the reaction stage.
  • the dried block was in a uniform state with no difference between the inside of the block and the surface.
  • Example 2 The same treatment as in Example 1 was carried out except that 20 g (0.08 mol) of copper sulfate pentahydrate was added in the treatment stage.
  • the dried block was in a uniform state with no difference between the inside of the block and the surface.
  • Example 2 The same treatment as in Example 1 was carried out except that 1.7 g (0.01 mol) of copper (II) chloride dihydrate was added in the treatment stage.
  • the dried block was in a uniform state with no difference between the inside of the block and the surface.
  • Example 7 The treatment was performed in the same manner as in Example 1 except that the heat treatment was performed at 60 ° C. for 15 hours in the treatment stage.
  • the dried block was in a uniform state with no difference between the inside of the block and the surface. Yield: 100%, purity:> 99%, average particle size: 2.8 // m.
  • the treatment was performed in the same manner as in Example 1 except that the heat treatment was performed for 40 hours.
  • the dried block was in a uniform state with no difference between the inside of the block and the surface.
  • Example 2 The desired product was obtained in the same manner as in Example 1 except that the pH value was maintained at 3.8 at the reaction stage.
  • the surface of the dried block was brown and hard compared to the inside of the block. Yield: 103%, purity: 97%, average particle size: 0.6 ⁇ m. Comparative Example 2
  • the desired product was obtained in the same manner as in Example 1 except that the pH value was kept at 1.2 in the reaction stage.
  • the dried block had a fine, sandy overall shape and was rough and hard when touched with fingers.
  • Example 2 Put 5 liters of water and solution A in a container, heat to 80 ° C, and keep the temperature at 80 ° C with stirring. Meanwhile, the target product was obtained in the same manner as in Example 1 except that the solution B was supplied over 4 hours to carry out a mixing reaction.
  • the initial pH value in the reaction system when supplying solution B was 6.8, and the final pH value was 2.2.
  • Example 2 The same as in Example 1 except that 5 liters of water and solution B were placed in a container, heated to 80 ° C, and while maintaining the temperature at 80 ° C with stirring, solution A was supplied over 4 hours to cause a mixing reaction. To obtain the desired product.
  • the initial pH value in the reaction system when supplying solution A was 5.8, and the final pH value was 2.2.
  • the desired product was obtained in the same manner as in Example 1 except that the treatment step was not performed.
  • the desired product was obtained in the same manner as in Example 1 except that 0.75 g (0.003 mol) of copper sulfate pentahydrate was added in the treatment stage.
  • the desired product was obtained in the same manner as in Example 1, except that 35 g (0.14 mol) of copper sulfate pentahydrate was added in the treatment stage.
  • solution C Copper (II) sulfate pentahydrate 250 g (1.0 mol) was dissolved in water to prepare a 20 liter aqueous solution (hereinafter referred to as solution C).
  • solution D 1-Hydroxy-1- (1H) -pyridinethione (254 g, 2.0 mol) was dissolved in ethyl alcohol to prepare a 3 liter solution (hereinafter referred to as solution D).
  • Solution C was placed in a container, heated to 30 ° C, and while maintaining the temperature at 80 ° C with stirring, solution D was supplied over 1 hour to cause a mixing reaction.
  • the generated precipitate was washed, solid-liquid separated and dried by a conventional method.
  • the dried block was in a uniform state with no difference between the inside of the block and the surface. Then, the dried product was pulverized to obtain the desired product.
  • Example A 4 95 7 Good 1U1 99 1.6 Fuse CT d l.8 80 A, B simultaneous 1 Copper sulfate (II) 4 95 7 1UU> 99 1.4
  • Example 4 1.8 80 A, B simultaneous 4 8 95 7 good 101 99 4.6
  • Example 5 1.8 80 ⁇ , ⁇ simultaneous 4 chloride ⁇ ( ⁇ ) 1 95 7 good 100> 99 1.5
  • Example 6 1.8 80 A, B simultaneous 4 sulfuric acid ⁇ (11) 4 60 15 > 99 2.8
  • Comparative example 2 1.2 80 A.B Simultaneous 4 Copper sulfate ( ⁇ ) 4 95 7 Defective 90 97 8.4 Comparative example 3 Fluctuation B at 80 A 4 Copper sulfate (II) 4 95 7 Bad 101 96 0.4 Fluctuation
  • the desired copper pyrithione having an average particle diameter of 1 to 5 ⁇ m which has a high purity of 97% or more and has particularly excellent properties as a pigment, without requiring special raw materials and equipment. Since the powder can be obtained in a high yield, it is useful as an industrial production method.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)

Abstract

Le bis(1-hydroxy-2-(1H)-pyridinethionato-O,S)cuivre(II) (ci-après désigné pyrithione de cuivre) est un composé peu soluble dans l'eau se séparant d'un système réactionnel utilisant un milieu aqueux. Par conséquent, il est difficile d'en éliminer les impuretés par lavage à l'eau, et aucun procédé ne permet d'obtenir avantageusement à l'échelle industrielle un composé d'une grande pureté et d'une granulométrie appropriée pour l'usage. Il est possible d'obtenir un pyrithione de cuivre présentant une pureté supérieure ou égale à 97 % et une granulométrie comprise entre 1 et 5 νm par un procédé consistant à mélanger une solution aqueuse d'un sel de métal alcalin de (1-hydroxy-2(1H)-pyridinethionato-O,S) avec une solution aqueuse d'un sel inorganique de cuivre(II), les deux solutions aqueuses étant mélangées et mises à réagir de manière à maintenir le pH du système réactionnel à une valeur comprise entre 1,6 et 3,2 pour obtenir une bouillie, ladite bouillie étant chauffée en présence de 0,5 à 10 % en poids d'ions cuivre(II) exprimés en terme de cuivre.
PCT/JP2000/003462 1999-05-31 2000-05-29 Pyrithione de cuivre de grande purete, et procede de production correspondant WO2000073272A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP15237599 1999-05-31
JP11/152375 1999-05-31

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004060062A1 (fr) 2002-12-20 2004-07-22 Arch Chemicals, Inc. Pyrithione de cuivre en petites particules
US7481873B2 (en) 2002-12-20 2009-01-27 Arch Chemicals, Inc. Small particle copper pyrithione

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995022905A1 (fr) * 1994-02-28 1995-08-31 Olin Corporation Procede de preparation de pyrithione de cuivre
WO1998041505A1 (fr) * 1997-03-14 1998-09-24 Arch Chemicals, Inc. Procede de production de particules de sels de pyrithione

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995022905A1 (fr) * 1994-02-28 1995-08-31 Olin Corporation Procede de preparation de pyrithione de cuivre
WO1998041505A1 (fr) * 1997-03-14 1998-09-24 Arch Chemicals, Inc. Procede de production de particules de sels de pyrithione

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004060062A1 (fr) 2002-12-20 2004-07-22 Arch Chemicals, Inc. Pyrithione de cuivre en petites particules
US6821326B2 (en) 2002-12-20 2004-11-23 Arch Chemicals, Inc. Small particle copper pyrithione
EP1571905A4 (fr) * 2002-12-20 2008-12-10 Arch Chem Inc Pyrithione de cuivre en petites particules
US7481873B2 (en) 2002-12-20 2009-01-27 Arch Chemicals, Inc. Small particle copper pyrithione

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