WO2005063017A1

WO2005063017A1 - Surfactant for agricultural chemical and agricultural chemical composition containing the same

Info

Publication number: WO2005063017A1
Application number: PCT/JP2004/019375
Authority: WO
Inventors: Akira Yoshikawa; Toshihiro Kohara; Tetsuo Kubota; Toshio Mizuno
Original assignee: Nippon Soda Co., Ltd.
Priority date: 2003-12-26
Filing date: 2004-12-24
Publication date: 2005-07-14
Also published as: AR047170A1; JP2005187418A

Abstract

A surfactant comprising a polyoxyalkylene higher-alkyl ether sulfuric ester salt as an anionic surfactant and a higher alcohol/alkylene oxide adduct as a nonionic surfactant. It has excellent suspensibility and water dispersibility when used as a surfactant for agricultural chemicals. Use of this surfactant can provide an agricultural chemical composition with no fear of emitting an environmental hormone.

Description

Agrochemical surfactant and agrochemical composition using the same

Technical field

The present invention relates to a non-alkylphenol-based agricultural chemical surfactant free from environmental hormones and an agricultural chemical composition using the same. More specifically, a surfactant for agrochemicals, which is an alkylene oxide adduct of a polyalkylene higher alkyl ether sulfate and a non-ionic surfactant higher alcohol, and an agrochemical composition using the same. About things.

Background art

[0002] Conventional alkylphenol-based surfactants, for example, alkylphenol ethoxylates, are described in Tomoyuki Funamizu, Oils and Fats, Vol. 51, No. 9, pp. 95-103 (1998) and Iguchi Yasuizumi, Chemistry and Education, 47 vol. As pointed out in Vol. 2, p. 132-246 (1999), the problem is that, at the same time as its biodegradability, alkylphenol, which is a degradation product, remains in the environment as an environmental hormone for a long period of time. . In addition, alkylphenol ethoxylates are produced in substantial quantities worldwide, not only in Japan and the United States, but the development of alternatives that do not have the potential for endocrine disruptors was an urgent issue. In order to solve these problems, for example, Japanese Patent Application Laid-Open No. 2001-3263 and Japanese Patent Application Laid-Open No. 2001-279292 disclose a fiber refining agent comprising an aliphatic alcohol alkylene oxide adduct, cyclohexanol alkylene oxide. Detergents for clothing made of calorie have been proposed, but the problem is that the suspension and hydration properties of agricultural chemicals, especially as a dispersant for agricultural chemicals, are insufficient compared to alkylphenol-based surfactants. was there.

Non-Patent Document 1: Tomoyuki Funamizu, Oils and Fats, Vol. 51, No. 9, pp. 95-103 (1998)

Non-Patent Document 2: Yasumi Iguchi, Chemistry and Education, Vol. 47, No. 132, pp. 246 (1999) Non-Patent Document 3: Yuji Tabata, Fine Chemical, Vol. 30, No. 11, pp. 10 to 18 (2001) Patent Reference 1: JP 2001-3263

Patent Document 2: JP 2001-279292 A

Disclosure of the invention Problems the invention is trying to solve

[0003] The present invention solves these problems, has a surfactant activity comparable to that of an alkylphenol-based surfactant, and has no fear of environmental hormones such as an alkylphenol-based surfactant! An object of the present invention is to provide an agricultural chemical surfactant and an agricultural chemical composition using the same.

Means for solving the problem

[0004] The inventors of the present invention have conducted intensive studies and have found that a surfactant consisting of an alkylene oxide adduct of a polyionic alkylene higher alkyl ether sulfate and a nonionic surfactant higher alcohol has been obtained. The present inventors have found that a pesticidal composition having excellent susceptibility and hydration properties as a surfactant for pesticides and using the same can achieve the above object, and completed the present invention.

That is, the present invention relates to a surfactant for agricultural chemicals comprising a polyoxyalkylene higher alkyl ether sulfate ester salt of an aionic surfactant and an alkylene oxide adduct of a higher alcohol as a nonionic surfactant. Provide the agent.

The present invention also relates to a surfactant for agricultural chemicals comprising a polyoxyalkylene higher alkyl ether sulfate ester salt of an aionic surfactant and an alkylene oxide adduct of a higher alcohol as a nonionic surfactant. An agricultural chemical composition comprising the agent is provided.

The invention's effect

[0007] The surfactant for agricultural chemicals provided by the present invention has excellent susceptibility and water as an alternative to the alkylphenol-based surfactant which has been pointed out as a danger as an environmental hormone (exogenous endocrine disrupting substance). A pesticidal composition using the compound is useful because it has no fear of environmental hormones and can be used safely.

BEST MODE FOR CARRYING OUT THE INVENTION

[0008] The polyoxyalkylene higher alkyl ether sulfate salt of an aionic surfactant used in the present invention is a sulfuric acid of an alkylene oxide adduct of a saturated or unsaturated higher alcohol having 8 to 18 carbon atoms. Ester salt, higher alcohols such as oleyl alcohol, octyl alcohol, decyl alcohol, lauryl alcohol , Myristinoleanolonecole, setinoleanoleconeole, stearinoleanoleconeole, behe-noreanolecohol, preferably oleyl alcohol, lauryl alcohol, cetyl alcohol, and particularly preferably. Is oleyl alcohol. Alkylene oxides preferably include ethylene oxide and propylene oxide, and when the type of alkylene oxide is different, random adducts and block adducts are preferred, and particularly preferred are ethylene oxide adducts. Is mentioned. The number of moles of the adduct is preferably from 2 to 100 moles, more preferably from 5 to 50 moles, based on the higher alcohol. The ester sulfate is preferably an ammonium salt, a sodium salt, a potassium salt, a magnesium salt, a calcium salt or the like, and particularly preferably an ammonium salt, a sodium salt or a potassium salt.

[0009] The a-ionic surfactant polyoxyalkylene higher alkyl ether sulfate salt is prepared by a method well known in the art, that is, an alkylene oxide is added to a higher alcohol in the presence of an alkali catalyst, and then sulfuric acid is added. It is produced by converting it to an ester salt.

[0010] A surfactant comprising a nonionic surfactant, a nonionic surfactant, an alkylene oxide adduct of a higher alcohol, and a higher alcohol such as oleyl alcohol, octyl alcohol, decyl alcohol, and lauryl alcohol , Myristyl alcohol, cetyl alcohol, stearyl alcohol, and behyl alcohol, preferably oleyl alcohol, lauryl alcohol, and cetyl alcohol, and particularly preferably cetyl alcohol. Alkylene oxides preferably include ethylene oxide and propylene oxide, and when the type of alkylene oxide is different, random adducts and block adducts are preferred, and particularly preferred are ethylene oxide adducts. Is mentioned. The number of moles of the adduct is preferably from 1 to 50 moles, more preferably from 1 to 20 moles, based on the higher alcohol.

[0011] Nonionic surfactants, non-ionic surfactants and alkylene oxide adducts of higher alcohols. Surfactants that are well known in the art for higher alcohols, namely, alkali catalysts It is easily prepared by adding an alkylene oxide in the presence.

[0012] From these aionic surfactant polyoxyalkylene higher alkyl ether sulfate ester salt and nonionic surfactant higher alcohol alkylene oxide adduct. The pesticidal active ingredient of the pesticidal composition using the pesticidal surfactant is not particularly limited, but may be thiuram, maneb, ziram, capitan, chlorothaloninole, josetinole, benomyl, thiophanate methyl, thiabendazole, iprodion, procymidone. , Fluorimide, Oxycarboxin, Taleoxime methyl, Azoxystrobin, Metominostrobin, Mepa-pyrim, Triadimefon, Hexaconazole, Triflumizole, Imazalil, Polyoxin, Probenazole, Dithianon, Fluazinam, Tricyclazole, oxolinic acid, simoxal, dietofencalp, acetamiprid, imidacloprid, ditenviram, fiprole, NAC, dicophor, propael, and more preferably NAC, thiophanate Chill and the like, particularly preferably a thiophanate methyl.

[0013] In order to enhance dispersibility, a pesticidal composition containing these pesticide active ingredients as active ingredients contains a dispersing aid such as sodium carboxymethylcellulose or white carbon, and a fine mineral carrier in order to enhance dispersibility. Can be used. Mineral powder carriers include inorganic salts such as potassium chloride, calcium carbonate, ammonium sulfate, potassium phosphate, and sodium phosphate, diatomaceous earth, bentonite, pyrophyllite clay, and kaolinite sauce. These may be used alone or in combination of two or more.

[0014] In the present invention, a silicone-based surfactant, a sodium or calcium salt of a higher fatty acid or a mixture thereof, an acetylene-based surfactant, or the like is added as an antifoaming agent to reduce foaming. You can also.

[0015] The amount of each component in the pesticidal composition of the present invention varies depending on the kind of the pesticidal active ingredient, but is usually 1 to 90% by weight, preferably 10 to 80% by weight, based on the whole. % By weight, and particularly preferably from 20 to 80% by weight, which is an alkylene oxide adduct of a polyionic alkylene higher alkyl ether sulfate and a nonionic surfactant higher alcohol. The amount of the surfactant for agrochemicals is from 1 to 30% by weight, preferably from 1 to 20% by weight, particularly preferably from 2 to 15%. The agent makes up the remaining weight components.

[0016] The surfactant for agricultural chemicals of the present invention can be used for various applications for agricultural chemicals, for example, wettable powders (wetting agents, dispersants) and granular wettable powders (wetting agents, dispersants) in the field of agricultural formulations. ), Granules (dispersant, disintegrant It can be used for disintegrants), flowable preparations (wetting agents, dispersants), etc.

Example

The present invention will be described with reference to examples and test examples, but the present invention is not limited to these examples. In this example, "%" means "% by weight" and "parts" means "parts by weight".

Example 1

Thiophanate methyl (73.02 parts), Kunilite 201 (manufactured by Kunimine Industries, Ltd .; 18.85 parts), amorphous form of diacid sodium (Carplex # 67, manufactured by Shionogi & Co., Ltd .; 0.89 parts) ) And the following dispersion sample (7.24 parts) were mixed well, pulverized with an air pulverizer (trade name: Urmax; manufactured by Nisso Engineering Co., Ltd.), and mixed with a preparation sample (mean particle size: 6.037 m). did. Dispersed samples were surfactant Newcol 1230SNC (polyoxyethylene oleyl ether sulfate sodium ester sodium salt (oxyethylene chain = 30), manufactured by Nippon Emulsifier Co., Ltd.) (25 parts), Newcol 1602 (polyoxyethylene cetyl ether ( (Oxyethylene chain = 2), Nippon Emulsifier Co., Ltd.) (10 parts), Newcol 1607 (polyoxyethylene cetyl ether (oxyethylene chain = 6, 8 (ratio 1: 1), Nippon Emulsifier Co., Ltd.)) (10 parts) ), CMC-Na (10 parts) and amorphous silicon oxynitride (45 parts) were mixed well, and the mixture was ground into a pulverizer and used.

Example 2

Thiophanate methyl (73.02 parts), Kunilite 201 (manufactured by Kunimine Industries, Ltd .; 18.85 parts), amorphous form of diacid sodium (Carplex # 67, manufactured by Shionogi & Co., Ltd .; 0.89 parts) ) And the following dispersion sample (7.24 parts) were mixed well, and pulverized with the air pulverizer of Example 1 to give a preparation sample (average particle size: 5.924 μm). The dispersion samples were surfactant Newcol 1230SNC (polyoxyethylene oleyl ether sulfate sodium salt (oxyethylene chain = 30), manufactured by Nippon Emulsifier Co., Ltd.) (20 parts), Newcol 1602 (polyoxyethylene cetyl ether (oxyethylene (Chain = 2), manufactured by Nippon Emulsifier Co., Ltd.) (11.25 parts), Newcol 1607 (polyoxyethylene cetyl ether (oxyethylene chain = 6, 8 (ratio 1: 1), manufactured by Nippon Dairyaku Co., Ltd.) ) (11.25 parts), CMC-Na (10 parts) and amorphous dioxygenated silicon (45 parts) were mixed well and used as a crushed powder in a pulverizer.

Example 3

NAC (77 parts), Kunilite 201 (manufactured by Kunimine Industry Co., Ltd .; 15 parts), amorphous diacid silicate silicon ( 3 parts), and pulverized into a powder to obtain an agricultural chemical sample. Surfactant Newcol 123 OSNC (polyoxyethylene oleyl ether sulfate sodium salt (oxyxylene chain = 30), manufactured by Nippon Milk Dairy Co., Ltd.) (25 parts), Newcol 1602 (polyoxyethylene cetyl ether (oxyethylene) (Chain = 2), Nippon Emulsifier Co., Ltd.) (10 parts), Newcol 160 7 (polyoxyethylene cetyl ether (oxyethylene chain = 6, 8 (ratio 1: 1), Nippon Dairyaku Co., Ltd.)) (10 parts), CMC-Na (10 parts) and amorphous dioxygenated silicon (45 parts) were mixed well and crushed with a pulverizer to obtain a dispersion sample of the powder. 19.0 g was added, and the mixture was pulverized and mixed in a mortar to prepare a preparation sample.

Example 4

TMTD (83.3 parts), clay (9.46 parts) and the following dispersed sample (7.24 parts) were mixed well, and pulverized with the air pulverizer of Example 1 to prepare a preparation sample (mean particle size: 3.876 parts). / zm). Dispersion samples are surfactant Newcol 1230SNC (polyoxyethylene oleyl ether sulfate sodium salt (oxyethylene chain = 30), manufactured by Nippon Emulsifier Co., Ltd.) (25 parts), Newcol 1602 (polyoxyethylene cetyl ether ( (Oxyethylene chain = 2), Nippon Emulsifier Co., Ltd.) (10 parts), Newcol 1607 (polyoxyethylene cetyl ether (oxyshethylene chain = 6, 8 (ratio 1: 1), Nippon Emulsifier Co., Ltd.)) Parts), CMC-Na (10 parts) and amorphous silicon dioxide (45 parts) were mixed well and crushed into a pulverizer to form a powder.

Example 5

Dithianon (75 parts), minerals (17.76 parts) and the following dispersed sample (7.24 parts) were mixed well, and pulverized with the air pulverizer of Example 1 to prepare a preparation sample (mean particle size 3.652 / zm). Dispersion samples were surfactant Newcol 1230SNC (polyoxyethylene oleyl ether sulfate sodium salt (oxyethylene chain = 30), manufactured by Nippon Emulsifier Co., Ltd.) (25 parts), Newcol 1602 (polyoxyethylene cetyl ether ( (Oxyethylene chain = 2), Nippon Dairyaku Co., Ltd. (10 parts), Newcol 1607 (polyoxyethylene cetyl ether (oxyethylene chain = 6, 8 (ratio 1: 1), Nippon Emulsifier Co., Ltd.) ) (10 parts), CMC-Na (10 parts) and amorphous silicon dioxide (45 parts) were mixed well and used as a powder in a pulverizer.

Josetyl (42.8 parts), captan (46.2 parts), clay (3.76 parts) and the following dispersion test The mixture (7.24 parts) was mixed well and pulverized with the air pulverizer of Example 1 to obtain a preparation sample (average particle size: 2.552 μm). Dispersed samples were surfactant Newcol 1230SNC (polyoxyethylene oleyl ether sulfate sodium salt (oxyethylene chain = 30), manufactured by Nippon Emulsifier Co., Ltd.) (25 parts), Newcol 1602 (polyoxyethylene cetyl ether (oxyxylene chain = 2), Nippon Emulsifier Co., Ltd.) (10 parts), Newcol 1607 (Polyoxyethylene acetyl ether (oxyethylene chain = 6, 8 (ratio 1: 1), Nippon Emulsifier Co., Ltd.)) (10 parts), C MC—Na (10 parts) and amorphous silicon dioxide (45 parts) were mixed well and used in a pulverizer to form a powder.

Example 7

Mix well with thiophanate methyl (21.6 parts), emdifer (63.8 parts), clay (61.46 parts) and the following dispersed sample (7.24 parts), pulverize with the air pulverizer of Example 1. Formulation sample (average particle size 1.082 / zm). Dispersed samples were surfactant Newcol 1230SNC (polyoxyethylene oleyl ether sulfate sodium salt (oxyethylene chain = 30), manufactured by Nippon Emulsifier Co., Ltd.) (25 parts), Newcol 1602 (polyoxyethylene cetyl ether (oxyethylene) Chain = 2), Nippon Emulsifier Co., Ltd.) (10 parts), Newcol 1607 (polyoxyethylene cetyl ether (oxyethylene chain = 6, 8 (ratio 1: 1), Nippon Milk Dillant Co., Ltd.)) 10 parts), CMC-Na (10 parts) and amorphous dioxygenated silicon (45 parts) were mixed well, and then pulverized using a pulverizer.The powder containing no surfactant of the present invention was used. Thiophanate methyl 70% wettable powder (trade name: Topgin M wettable powder. Lot No. TAK-016, average particle size 5.391 m, manufactured by Nippon Soda Co., Ltd.) A hydration test was performed and compared with Examples 1 and 2.

2

While not containing the surfactant of the present invention, a suspension ratio, a foaming property and a hydration property were tested using a commercially available denabone wettable powder (manufactured by Nissan Chemical Industries, Ltd.), and compared with Example 3.

Test examples are shown below. In Test Examples 1 and 2, it was confirmed that the physical properties of the particularly preferred target drugs thiophanate and NAC were good in comparison with the commercial preparations. Trial In Experimental Example 3, it was confirmed that a pharmaceutical preparation with good physical properties can be prepared for a preferred target drug.

Test examples 1 and 2: Comparison of suspension ratio, foamability, hydration test method and physical properties

Suspension rate (%)

The suspension rate was measured in accordance with the CIPAC MT-15 test method of “CIPAC ^ J APAC” issued by the Japanese Agricultural Chemicals Committee.

[0019] A 250 ml graduated cylinder equipped with a stopper is charged with CIPAC standard hard water D (342 ppm) at 30 ± 1 ° C and 0.25 g of the above preparation, and 250 ml of a dispersion liquid is prepared. Leave it in the constant temperature water bath of C, and after 30 minutes, draw out the upper 225 ml with a suction glass tube over 10 to 15 seconds and remove it. The active ingredients in the formulation and in the bottom 25 ml of the cylinder were measured, and the suspension ratio was calculated by the following formula.

[0020] Suspension rate (%) = (10/9) X (100 (C-Q) / C)

Cg = amount of active ingredient in sample, Qg = amount of active ingredient in bottom 25ml Foaming property (mm, whole agricultural method)

Foamability was measured in accordance with the “Physical Properties Standards and Specification Test Methods for Wettable Powders” presented on February 25, 1975 by the Research Center for Fertilizers and Agriculture, All National Agricultural Technology Center.

[0021] Into a 250-ml stoppered measuring cylinder containing 250 ml of distilled water at 20 ° C, 0.5 g of the above-mentioned preparation sample was placed, and it was turned 10 times every 2 seconds, and left standing for 1 minute. The foam height was measured.

[0022] The foaming property (bubble height) is low and the value is good, and the suspension ratio is high and the value is good.

[0023] Hydration test (Second, pesticide official inspection method)

Hydration was measured in accordance with the “Physical Property Test Method” published in No. 71 of February 3, 1960.

[0024] In a 500ml beaker, 200ml of water at 20 ° C and hardness of 3 degrees was put and passed through a 360μm pore size standard screen in advance. 5. Quiet the Og preparation sample so that it spreads thinner than about 10cm above the water surface And the time (seconds) that all the samples sank below the water surface was measured.

[0025] The hydratability is preferably a value with a small number of seconds.

Results of test and test example 1

The suspension samples, foamability and hydration tests were performed on the preparation samples of Example 1 and Example 2 and compared. The suspension ratio, foaming property and hydration property of Example 1 were compared. Table 1 shows the results.

[Table 1]

[0027] The preparations of Example 1 and Example 2 exhibited excellent suspension ratio and low foaming property as compared with the preparation of Comparative Example 1 which is commercially available.

Results of test and test example 2

The suspension sample, foaming property and hydration property of the preparation sample of Example 3 were tested, and the suspension rate, foaming property and hydration property of Comparative Example 2 were compared. Table 2 shows the results.

[Table 2]

[0029] The preparation of Example 3 exhibited excellent suspension ratio and low foaming property. Hydration was good within one minute.

Parliament 3

Example 4 One of the preparation samples of Example 7 was subjected to the foaming and hydration tests and the suspension test described below. The results are shown in Table 3.

[0030] In the suspension test, 0.1 lg of the preparation sample was placed in a 100 ml colorimetric tube with a stopper and 100 ml of 3 degree water at 20 ° C. Immediately after inverting the colorimeter tube 30 times for Z minutes, the tube was allowed to stand still in a constant temperature water bath at 20 ° C, and immediately after, 30 minutes, 3 hours, and 24 hours, the foam height and sedimentation amount were measured.

[0031] This method is a simple dilution property measurement method for judging the overall dilution properties of a preparation and the possibility of mixing. [0032] The suspension property is defined as a substance having an effect equivalent to that of a commercially available agent.

[0033] [Table 3]

Example 4 One of the preparations of Example 7 exhibited low foaming properties and good hydration properties.

Industrial applicability

[0035] The surfactant for non-alkylphenol-based pesticides of the present invention and the pesticide composition using the same, which have the same suspending properties and hydration properties as those of the alkylphenol-based surfactants, and are free from environmental hormones. The use of products can avoid the negative effects of environmental hormones, which have become a serious problem worldwide.

Claims

The scope of the claims

[1] A surfactant for agricultural chemicals comprising a polyoxyalkylene higher alkyl ether sulfate ester salt of an aionic surfactant and an alkylene oxide adduct of a higher alcohol as a nonionic surfactant.

[2] The surfactant for agricultural chemicals according to claim 1, wherein the ionic surfactant is polyoxyethylene oleyl ether sulfate, and the nonionic surfactant is cetyl alcohol ethoxylate.

[3] Polyoxyethylene oleyl ether sulfate, a fermented surfactant,

0 to 70% by weight, and the nonionic surfactant cetyl alcohol ethoxylate

3. The surfactant for pesticides according to claim 2, wherein the amount is 30 to 60% by weight.

[4] The agricultural chemical surfactant according to claim 3, comprising a polyoxyethylene oleyl ether sulfate ester salt having an oxyethylene chain of 20 to 40 and a cetyl alcohol ethoxylate having an oxyethylene chain of 2 to 20.

[5] A pesticidal composition containing a pesticidal surfactant comprising a polyoxyalkylene higher alkyl ether sulfate ester salt of an a-ionic surfactant and an alkylene oxide adduct of a higher alcohol as a nonionic surfactant. .

6. The pesticidal composition according to claim 5, wherein the ionic surfactant is polyoxyethylene oleyl ether sulfate, and the nonionic surfactant is cetyl alcohol ethoxylate.

[7] The polyoxyethylene oleyl ether sulfate, an ionic surfactant, is

0 to 70% by weight, and the nonionic surfactant cetyl alcohol ethoxylate

7. The pesticidal composition according to claim 6, wherein the amount is 30 to 60% by weight.

[8] The pesticidal composition according to claim 7, comprising a polyoxyethylene oleyl ether sulfate ester salt having an oxyethylene chain of 20 to 40 and a cetyl alcohol ethoxylate having an oxyethylene chain of 2 to 20.

[9] The pesticidal composition according to claim 5, wherein the pesticide drug substance is NAC and Z or thiophanate methyl.