JP4518781B2 - High concentration concentrated Bordeaux liquid and its production method - Google Patents

Description

  The present invention relates to a concentrated bordeaux solution and a method for producing the same. More specifically, slaked lime powder or slaked lime slurry, copper sulfate aqueous solution or copper sulfate, and a surfactant are mixed, and a solid bordeaux solution is produced by using a high-speed shearing device and a homogenizing stirrer in combination. The present invention relates to a concentrated Bordeaux solution having a high concentration of 40% or more and a method for producing the same.

Bordeaux liquid has long been used as a fungicide for citrus, ume scab, apple spotted leaf disease, peach perforation bacterial disease, and the like. However, the conventional Bordeaux liquid was manufactured by making slaked lime by the reaction of quick lime and water, and then reacting with copper sulfate, but there was a problem that the reaction did not go well, and the produced Bordeaux liquid was a dilute spray liquid itself. There was a problem that a large amount of Bordeaux liquid had to be carried to the place where it was sprayed. In order to solve these problems, for example, in JP-A-2-279610, a copolymer of a carboxyl group-containing vinyl compound and another vinyl compound or a salt of these polymers is added as a dispersant. Concentrated Bordeaux is described. JP-A-2-279612 discloses a concentrated Bordeaux solution to which one of naphthalenesulfonic acid, alkylnaphthalenesulfonic acid, or a formalin condensate thereof is added. Furthermore, JP 2000-26222 A and JP 2000-26223 A include a mixture of slaked lime fine powder having an average particle diameter of 7.5 μm or less and a specific surface area of 20 m ² / g or more, and a copper sulfate solution. A method of reacting is described. Further, JP-A-2002-293707 describes a production method and concentrated bordeaux in which a styrylphenyl ether surfactant and an anionic surfactant are used in combination and wet pulverization is performed after the reaction. However, when a concentrated Bordeaux solution was prepared by these methods, a long time was required for the reaction between slaked lime and copper sulfate, and a pulverization step was further required. Furthermore, problems such as a short storage period and solidification of the preparation may occur, and it has been difficult to prepare a concentrated bordeaux solution with high reproducibility and good storage stability.
JP-A-2-279610 JP-A-2-279612 JP 2000-26222 A JP 2000-26223 A JP 2002-293707 A

  An object of the present invention is to solve these problems and to provide a concentrated Bordeaux liquid having a solid content concentration of 40% or more with good storage stability and a method for producing the same.

As a result of earnest research, the present invention, etc., mixed slaked lime powder or slaked lime slurry, copper sulfate aqueous solution or copper sulfate, and a surfactant, and by using a high-speed shearing device and a homogenizing stirrer in combination, an unprecedented solid content concentration The present invention was completed by finding that a concentrated Bordeaux solution having a high concentration of 40% or more was obtained and the storage stability was excellent.
That is, the present invention mixes slaked lime powder or slaked lime slurry, a copper sulfate aqueous solution or copper sulfate, and a surfactant, and produces a concentrated Bordeaux liquid using a high-speed shearing device and a homogenizing stirrer in combination. The present invention provides a concentrated bordeaux solution having a concentration of 40% or more and a method for producing the same.

  The high concentration concentrated Bordeaux liquid provided by the present invention has a high solid content concentration of 40% or more and excellent storage stability, so that it is very useful for storing a large amount of Bordeaux liquid and transporting it to the place of use.

In the present invention, a high-speed shearing device and a homogenization stirring device used together as a high-speed shearing device and a disperser as a high-speed shearing device and a TK combination using an anchor as a homogenization stirring device (manufactured by Special Machine Industries Co., Ltd.) And a multi-mixer (Mizuho Kogyo Co., Ltd.) that uses a homomixer or a line mixer as a high-speed shearing device, but is not particularly limited, as long as it has a high-speed shearing device and a homogenizing stirring device. It ’s fine.

  The slaked lime powder used in the present invention is not particularly limited in particle diameter and specific surface area, and may be a widely used one. The slaked lime powder may be used as it is, or may be used as a slaked lime slurry with a surfactant such as sodium polyacrylate and water.

  As the copper sulfate, either an aqueous copper sulfate solution or copper sulfate can be used, and the copper sulfate can be used as an anhydride or a hydrate.

  The surfactant used in the present invention is, for example, (1) formaldehyde condensate of sodium naphthalene sulfonate, formaldehyde condensate of sodium alkyl naphthalene sulfonate, polyoxyethylene monostyryl phenyl ether, polyoxyethylene distyryl phenyl ether Phosphate ester and metal salt thereof, polyoxyethylene tristyryl phenyl ether phosphate ester and metal salt thereof, sodium lignin sulfonate, sodium lauryl sulfate, sodium sulfate ester of higher alcohol; (2) sodium polystyrene sulfonate, polyacrylic acid And metal salts thereof, polymethacrylic acid and metal salts thereof; (3) acrylic acid, methacrylic acid, methoxypolyethylene glycol acrylate, methoxypolyethylene methacrylate One or more types selected from the group consisting of (1) to (3), preferably sodium polyacrylate, polysodium methacrylate, polystyrene sulfone; Selected from the group consisting of sodium acid, formaldehyde condensate of sodium naphthalene sulfonate, polyoxyethylene tristyryl phenyl ether phosphate and metal salts thereof, and particularly preferably formaldehyde condensate of sodium naphthalene sulfonate, poly It is selected from a combination of two or more of sodium acrylate, polyoxyethylene tristyrylphenyl ether phosphate, and metal salts thereof. Among the particularly preferred surfactants, sodium polyacrylate may be added in advance together with slaked lime, and the formaldehyde condensate of sodium naphthalenesulfonate may be added in advance or later. It is more effective to add polyoxyethylene tristyryl phenyl ether phosphate and its metal salt together with slaked lime beforehand.

  The mixing ratio of slaked lime and copper sulfate in the present invention can be arbitrarily changed, and can be applied to 4-8 type Bordeaux, 6-6 type Bordeaux, and 4-12 type Bordeaux that are generally used.

  The amount of each component used in the present invention is not particularly limited, but slaked lime is preferably 20 to 50% by weight and copper sulfate is preferably 10 to 30% by weight in order to produce a high concentration concentrated Bordeaux. The surfactant may be added in an amount of 0.01 to 20% by weight, preferably 0.1 to 10%.

  The reaction temperature is not particularly limited, but is preferably 10 to 50 ° C., particularly preferably 20 to 45 ° C., in order to allow the reaction to proceed smoothly. The aging time is not particularly limited, but is preferably 10 minutes to 3 hours, and particularly preferably 10 minutes to 1 hour.

  The rotational speeds of the high-speed shearing device and the homogenizing stirring device in the reaction vary depending on the model and are not particularly limited. K. In the case of using a combination mix (made by Tokushu Kika Kogyo Co., Ltd.), the disper is preferably 100 to 10000 rpm, particularly preferably 500 to 6000 rpm, and the anchor is used in order to make the reaction proceed more smoothly. It is preferably 20 to 500 rpm, and particularly preferably 50 to 300 rpm.

  In the present invention, a nonionic surfactant such as styryl phenyl ether may be used in combination in order to further reduce the viscosity of the preparation for the purpose of improving the handleability of the concentrated bordeaux solution.

  In this invention, 1 type (s) or 2 or more types, such as methanol, ethanol, isopropanol, glycerol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, can be further added as an antifreezing agent. Further, when a phosphate ester of a styryl phenyl ether type or alkylphenyl ether type nonionic surfactant is used, an antifreezing effect can be imparted.

  In the present invention, one or more of polyvinyl alcohol, carboxymethyl cellulose, xanthan gum, bentonite and the like can be further added for the purpose of preventing phase separation of the preparation.

  Any of these antifreezing agents and phase separation preventing agents may be added as necessary, and is preferably added in an amount of 10% by weight or less.

The concentrated Bordeaux liquid of the present invention has a solid content concentration (calculated as quick lime) of 40% or more, preferably 40 to 60%, particularly preferably, based on the whole of quick lime (CaO) and copper sulfate pentahydrate. 40 to 45%. Incidentally, the solid content concentration of the 6-6 type IC Bordeaux liquid commercially available (manufactured by Inoue Lime Co., Ltd.) with respect to the whole of slaked lime (Ca (OH) ₂ ) and copper sulfate pentahydrate is 35% (28.2 in terms of quick lime). The solid content concentration of the slaked lime (Ca (OH) ₂ ) and the copper sulfate pentahydrate of the 4-12 formula IC Bordeaux liquid (manufactured by Inoue Lime Co., Ltd.) and the copper sulfate pentahydrate is 35% (calculated in terms of quick lime 30.%). 2%).

The concentrated Bordeaux liquid of the present invention is produced, for example, as follows.
A solution obtained by dispersing and dissolving a polyacrylic acid-based and / or polymethacrylic acid-based surfactant in water in slaked lime powder having an average particle diameter of 7.8 μm and a specific surface area of 8.4 m ² is described in T.W. K. While stirring at 150 rpm anchor and Disper 5000 rpm with a combimix, copper sulfate pentahydrate is added and aged at about 37 ° C. Next, sodium naphthalene sulfonate formalin condensate is added to produce a concentrated Bordeaux liquid having a solid concentration of 40% or more.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In addition, solid content concentration was shown by weight% with respect to the whole of quicklime (CaO) and copper sulfate pentahydrate.
Example 1
923 g of slaked lime powder (average particle size: 7.8 μm, specific surface area: 8.4 m ² / g) and 20 g of sodium polyacrylate (RDI-09901, manufactured by Nippon Emulsifier Co., Ltd.) were well dispersed and dissolved in 1435 ml of tap water. The solution is T.I. K. While stirring at 150 rpm and Disper 5000 rpm with a combimix, 700 g of copper sulfate pentahydrate is gradually added over about 20 minutes and further aged at about 37 ° C. for 30 minutes. Next, 20 g of sodium naphthalene sulfonate formalin condensate (TPP-12809, manufactured by Nippon Emulsifier Co., Ltd.) was added to produce about 3 kg of 6-6 concentrated Bordeaux liquid having a solid concentration of about 45%.
Example 2
923 g of slaked lime powder (average particle size: 7.8 μm, specific surface area: 8.4 m ² / g) and 20 g of sodium polyacrylate (RDI-09901, manufactured by Nippon Emulsifier Co., Ltd.) were well dispersed and dissolved in 424 ml of tap water. The solution is T.I. K. A solution prepared by dissolving 700 g of copper sulfate pentahydrate in 1400 ml of hot water at 45 ° C. is further aged at about 37 ° C. for 30 minutes while stirring with a combination mix at 150 rpm anchor and 5000 rpm. Next, 20 g of sodium naphthalene sulfonate formalin condensate (TPP-12809, manufactured by Nippon Emulsifier Co., Ltd.) was added to produce about 3 kg of 6-6 concentrated Bordeaux liquid having a solid content of about 40%.
Example 3
923 g of slaked lime powder (average particle size: 7.8 μm, specific surface area: 8.4 m ² / g), 35 g of polyoxyethylene tristyryl phenyl ether phosphate sodium salt (TPP-12808, manufactured by Nippon Emulsifier Co., Ltd.), naphthalene A solution in which 70 g of sodium sulfonate formalin condensate (TPP-12809, manufactured by Nippon Emulsifier Co., Ltd.) was well dispersed and dissolved in 424 ml of tap water was prepared by T.C. K. A solution prepared by dissolving 700 g of copper sulfate pentahydrate in 1400 ml of 45 ° C. warm water while stirring at 150 rpm and Disper 5000 rpm with a combination mix is gradually added over about 20 minutes, and further at about 37 ° C. for 30 minutes. Aging was carried out to produce about 3.5 kg of a 6-6 type concentrated Bordeaux liquid having a solid concentration of about 40%.
Example 4
1625 g of slaked lime powder (average particle size: 7.8 μm, specific surface area: 8.4 m ² / g), polyoxyethylene tristyryl phenyl ether phosphate sodium salt (TPP-12808, manufactured by Nippon Emulsifier Co., Ltd.) 20 g, naphthalene A solution in which 40 g of sodium sulfonate formalin condensate (TPP-12809, manufactured by Nippon Emulsifier Co., Ltd.) was well dispersed and dissolved in 424 ml of tap water was prepared as T.C. K. A solution prepared by dissolving 410 g of copper sulfate pentahydrate in 1000 ml of hot water at 50 ° C. is gradually added over about 20 minutes while stirring at 150 rpm and Disper 5000 rpm with a combination mix, and further at about 37 ° C. for 30 minutes. Aging was carried out to produce about 3.5 kg of a 4-12 concentrated Bordeaux liquid having a solid content of about 45%.
Example 5
1188 g of slaked lime powder (average particle size: 7.8 μm, specific surface area: 8.4 m ² / g), polyoxyethylene tristyrylphenyl ether phosphate sodium salt (TPP-12808, manufactured by Nippon Emulsifier Co., Ltd.) 20 g, naphthalene A solution in which 40 g of sodium sulfonate formalin condensate (TPP-12809, manufactured by Nippon Emulsifier Co., Ltd.) was well dispersed and dissolved in 400 ml of tap water was prepared as T.C. K. A solution prepared by dissolving 450 g of copper sulfate pentahydrate in 900 ml of hot water at 50 ° C. is gradually added over about 20 minutes while stirring at 150 rpm and Disper 5000 rpm with a combination mix, and further at about 37 ° C. for 30 minutes. Aging was carried out to produce about 3 kg of a 4-8 concentrated Bordeaux liquid having a solid concentration of about 45%.

Comparative Example 1
198 g of slaked lime powder, polyoxyethylene tristyrylphenyl ether phosphate sodium salt (TPP-12808, manufactured by Nippon Emulsifier Co., Ltd.) 10 g, sodium naphthalene sulfonate formalin condensate (TPP-12809, manufactured by Nippon Emulsifier Co., Ltd.) 20 g 150 g of copper sulfate pentahydrate is dissolved in 402 ml of hot water at 50 ° C. while stirring at 600 rpm with a three-one motor (type HEIDON, model 1200G) with an anchor wing in a solution dispersed and dissolved in 220 g of tap water. The solution was gradually added over about 20 minutes and then aged for 30 minutes. However, when the stirring was stopped, it solidified and a 6-6 concentrated Bordeaux liquid having a solid content of 35% could not be produced.
Comparative Example 2
317 g of slaked lime powder, polyoxyethylene tristyryl phenyl ether phosphate sodium salt (TPP-12808, manufactured by Nippon Emulsifier Co., Ltd.) 10 g, sodium naphthalene sulfonate formalin condensate (TPP-12809, manufactured by Nippon Emulsifier Co., Ltd.) 20 g 80 g of copper sulfate pentahydrate was dissolved in 253 g of hot water at 50 ° C. while stirring at 600 rpm with a three-one motor (type HEIDON, model 1200G) with an anchor blade in a solution dispersed and dissolved in 250 g of tap water. The solution was gradually added over about 20 minutes and then aged for 30 minutes. However, when the stirring was stopped, it solidified, and a 4-12 concentrated bordeaux liquid having a solid content concentration of 40% could not be produced.
Comparative Example 3
Three-one motor with 60mm propeller blades (model made by TYPE HEIDON, model) 1200G) While stirring at 180 rpm, a solution prepared by dissolving 150 g of copper sulfate pentahydrate in 300 ml of warm water at 45 ° C. was gradually added over 60 minutes, further aged for 1 hour, ground with a bead mill, and a solid content concentration of 28.2. % 6-6 concentrated Bordeaux solution was obtained.
Comparative Example 4
Three-one motor with 60mm propeller blades (manufactured by TYPE HEIDON) , Model 1200G) While stirring at 180 rpm, a solution obtained by dissolving 57 g of copper sulfate pentahydrate in 114 ml of warm water at 45 ° C. was gradually added over 60 minutes, further aged for 1 hour, and pulverized with a bead mill to obtain a solid content of 30 A 2% concentrated 4-12 concentrated Bordeaux solution was obtained.

Observation / Test Examples The concentrated bordeaux solutions produced in the examples and comparative examples were subjected to the following observations / tests and their physical properties were compared. 1) The fluidity in the production process was visually determined from the stirring state. 2) After the prepared preparation was allowed to stand at room temperature for 7 days, 200 g of the preparation was taken into a 500 ml beaker, and a preparation that could be easily transferred to another 500 ml beaker was made good.

Example and comparative formulation types, solids concentration, fluidity in the manufacturing process, aging time, presence or absence of pulverization process, post-thickening agent (sodium naphthalene sulfonate formalin condensate), formulation after 7 days The situation is shown in Tables 1 and 2.

  The preparations of the examples according to the present invention have a solid content concentration of 40% or more, good fluidity in the production process, and can be easily and stably produced in one step without a pulverization process. Excellent in properties. On the other hand, in the conventional method used for the production of a commercial product, as shown in Comparative Examples 3 and 4, in the preparation having the same low solid content concentration as the commercial product, the fluidity in the production process is good and the pulverization process is Concentrated Bordeaux solution with good physical properties after 7 days was obtained by manufacturing in two stages, but the preparations with high solid content in Comparative Example 1 and Comparative Example 2 had poor fluidity in the manufacturing process and stopped stirring. Concentrated Bordeaux could not be produced.

  According to the present invention, a concentrated bordeaux liquid having a high solid content concentration of 40% or more having good storage stability in one step can be obtained, and the concentrated bordeaux liquid can be produced with good reproducibility.

Claims (6)

Solid content concentration 40 including the process of mixing slaked lime powder or slaked lime slurry, copper sulfate aqueous solution or copper sulfate, and surfactant using a disper as a shearing device and a device equipped with an anchor as a stirring device for homogenization. % Of a concentrated Bordeaux solution. The manufacturing method of Claim 1 whose solid content concentration is 40 to 45%. The surfactant is a group of (1) to (3):
(1) Formaldehyde condensate of sodium naphthalene sulfonate, formaldehyde condensate of sodium alkyl naphthalene sulfonate, polyoxyethylene monostyryl phenyl ether, polyoxyethylene distyryl phenyl ether phosphate and its metal salt, polyoxyethylene tristyryl Phenyl ether phosphates and their metal salts, sodium lignin sulfonate, sodium lauryl sulfate, sodium sulfate ester of higher alcohols;
(2) Sodium polystyrene sulfonate, polyacrylic acid and its metal salt, polymethacrylic acid and its metal salt;
(3) A copolymer composed of two or more monomers selected from acrylic acid, methacrylic acid, methoxypolyethylene glycol acrylate, and methoxypolyethylene glycol methacrylate , and a metal salt thereof;
The manufacturing method of Claim 1 or 2 selected from these, or the combination of 2 or more types thereof. The surfactant is selected from a formaldehyde condensate of sodium naphthalenesulfonate, sodium polyacrylate, polyoxyethylene tristyryl phenyl ether phosphate and metal salts thereof , or a combination of two or more thereof. The manufacturing method as described in. The surfactant is selected from a formaldehyde condensate of sodium naphthalenesulfonate, sodium polyacrylate, polyoxyethylene tristyryl phenyl ether phosphate and metal salts thereof , or a combination of two or more thereof. The manufacturing method as described in. It is manufactured by a manufacturing method including a step of mixing a slaked lime powder or slaked lime slurry, a copper sulfate aqueous solution or copper sulfate, and a surfactant using a disper as a shearing device and an apparatus equipped with an anchor as a homogenizing stirring device ;
The surfactant is selected from a formaldehyde condensate of sodium naphthalene sulfonate, sodium polyacrylate, polyoxyethylene tristyryl phenyl ether phosphate and metal salts thereof, or a combination of two or more thereof;
Concentrated Bordeaux solution with a solid content of 40% or more.