JPS62148405A - Herbicidal composition - Google Patents

Abstract

PURPOSE:A herbicidal composition, containing a dipyridinium quaternary salt as an active ingredient and further at least one selected from blue, red, yellow and green coloring ingredients and having the pH under specific acidic condition, improved dyestuff stability and a wide weeding spectral effect. CONSTITUTION:A herbicial composition containing at least one dipyridinium quaternary salt expressed by formula I (l is 1 or 2; formula II is anion) and/or formula III [m is l; formula IV is anion; two Rs are 1-6C alkyl which may be substituted by OH, lower alkoxy, lower thioalkyl, carboxy, halogen, etc.) as an active ingredient and further at least one coloring ingredient selected from Acid Blue 1, Acid Blue 3, Food Blue Nos. 1 and 2, Food Red Nos. 2, 3, 102 and 104, Red No.504, Food Yellow Nos. 4 and 5, Food Green No.3 and Green No.401, etc., kept under acidic condition of <=5.7pH and used in the form of a formulation, e.g. solution, emulsion, suspension, dust, paste, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a herbicidal composition containing a biviridinium quaternary salt as a main component, and more specifically, it contains a coloring component such as blue, yellow, or green, and has a pHtt. The present invention relates to a herbicidal compound with improved color stability when maintained under specific acidic conditions.

b. Prior art Herbicides containing bipyridium quaternary salts as their main ingredient have a long history.Since their invention in 1955, their husbands have been using them for more than 30 years due to their wide-ranging herbicidal effects and safety. It continues to be used. That is, as with general Ik drugs, if sprayed according to the handling specifications, the agrochemical composition will not cause any harm.

However, even if the agricultural chemical composition is safe for agricultural use, misuse, especially accidental ingestion, can have serious effects on the human body, and various measures must be taken to prevent such misuse. ing. That is, lower aliphatic carboxylic acids as disclosed in JP-A No. 52-9o63, tetrahydrothiophene as disclosed in JP-A-52-114021, or tetrahydrothiophene as disclosed in JP-A-49-7433. One such method is to prevent accidental ingestion and misuse by using an odorant such as the disclosed odorant.

Furthermore, various methods have been proposed for causing the swallowed substance to be vomited in the event of accidental ingestion. In other words, the Special Public Service of 1983-
This corresponds to the S-toIJ7 zolobilicidi/derivatives disclosed in Japanese Patent Publication No. 35641, and the tripolyphosphates and pyrophosphates disclosed in Japanese Patent Application Laid-open No. 56-61301. These preventive measures can be effective. However, coloring these agrochemical compositions to distinguish them from others and to issue certain oak warnings is yet another precaution. This fact is said to be
Japanese Patent Application No. 35641 discloses the use of a layer coloring agent as a means for specializing or distinguishing. However, when a coloring agent is added to an agrochemical composition, its stability becomes very poor. In other words, if the color changes during storage and is misunderstood as something else, the coloring becomes meaningless, and even when mixed with anything else, the penetration of the coloring property and the absence of discoloration are even more breathtaking. This is important. Such matters are not mentioned or disclosed in the above-mentioned Japanese Patent Publication No. 56-35641.

As a result of intensive research on the dye stability in this bipyridium salt agricultural chemical composition, the present inventors discovered the importance of the relationship between the color indicator and its pl (pl), and arrived at the present invention.

Structure of the C1 invention, that is, the present invention is based on the following general formula (I) (wherein l represents a number of 1 or 2, L
' indicates anio/. ” and/or dipyridinium quaternary salt represented by the following general formula (11).
A herbicidal composition containing as an active ingredient, the composition comprising:
7-side glue 1.7-end blue 3. Acid Blue 99 Edible T-Shi No. 1 1 Edible Blue No. 2 0 Edible Red No. 2 8 Edible Aka Tomoe No. 3 9 Edible Red No. 102 No. 1 Edible Red No. 104 0 Edible Red No. 105 1 Edible Red No. 106, Zen Color 5L No. 14.

Food Yellow No. 4 1 Food Yellow No. 5 1 Textile Green No. 3 and Green 4
This herbicidal composition contains at least one type of component 7II selected from the group consisting of No. 01 and is maintained under acidic conditions with a pH of 171'5.7 or less.

The dye used in the present invention is L]11'' Pt color, red.

It is a yellow and green pigment. This is because such pigments are not only easy to distinguish from those of dragons, but also have a warning meaning. The dyes used in the present invention can be prepared by any method as long as they are of these colors.
It may also be something that was given to you. As a specific example of these pigments, I would like to cite something like an arrow.

[Blue]

(ll Acid Flu One ill (C01,420
45°RN29-17-9) gthanaminium, N-(4-((4-die
thylamino)phenyl)-(2+4-d
i 5ulf ophyl)methylene
)-2+5-cyclohexadien-1-yl
jdene-N-ethyl-+hydroxide
1nner 5alt sodium 5a
lt(9CI).

(2) γ site 7゛ Loosely (31 (C6I, 4
2051゜1ζN3536 49 0) gthanaminium+N-(4-((4-(di
eth)'lamino)phenyl)-(5-hy
droxy-2e4-djsulfophenyl)m
ethylene)-2+5-eyelohexadi
en-1-ylidene)-N-ethyl-+hy
droxide 1nner 5alt cal
ciumsalt (2:1) (9C1).

(3) Acid Blue Nine (91 (C, 1,420
913゜RN2560-18-2) Arnmonlum, e*h71-(4-(p-eth
yl (m-!Iulfob-enzyl)amin
o-a (o-mulfophsnyl)benzyl
ine)-2,5-cyclohexadien-1-
ylidene) (m-sulfob-enzyl-+
hydroxide) winner 5 alt d
iammonium salt (9C1).

(4) Food Blue No. 1 Puri IJ A/D Blue FOF
4-((-t-(N-ethyl-m-aulfobe
nzylamfno)-phenyl)-(2-sul
fonium phenyl)-methylene)-
(1-(N-ethyl-N-+5ulfobenzy
l)-8”-eyclo-hexadienimine
) clisodium sin.

(51 meals) H1T color No. 2 I/Jigokarumi 11-4nl
l11-4ndi, 5'-digulfonic ac
id+diaodium 5alt [Red] (6) Red No. 2 for A″ Amaranth 1-(4-sulfo-1-naphthylazo)
-2-naphthol-C6-disulfonic
acidvtrisodium 5alt(7)
Food Red No. 3 Erythrosi/ 1etraiodofluoreaeein+diso
dium gilt (8) Food red No. 102 Two knees; comb/So, Na 1-(4-gul fo-1-naphthylazo
)-2-naphthol-6v8-disulfo
nie acid w trisodium salt (9
) *Akaba IU4q Furo Senshi/C1 terabromo-tetrachlororo-f l
uoresceindisodium 5alt 01 Sound Red No. 1435 Low Spec/Gal ■ e tetrachloro-terraiodof 1u
orescein +-disodium 5alt Oυ Food Red No. 106 Ashitudrend 80, Na 9-(2'-sulfonium-4'-5ulfop
henyl)-6-diethylamino-3-
(N+N-diethylimino)-3-Liox
anthen-sodium 113 Red No. 504 (Bo/Bon-5X) 1-(4,6
-dimethyl-3-sulfonyl sod
iumazo)-(7-sulfonyl sodi
um-2-Naphtol) [Yellow] Yellow No. 4 for UNIX Tartrazine δU, Na 5-hydroxy-1-p-sulfopheuyl
-4-(p-sulfophenylazo)pyrm
zoL-3-earboxyLicael(1+trj
80dlum 5altI Food Yellow No. 5 Sunset Yellow FCF1-p-sulfophanylazo
-2-naphthol-6-sulfonic ac
id+disodium 5alt [green] α5 Food green No. 3 Fast Cree-7FCF4-1 (
4-(N-eLhyl-m-sulfobenzyla
mino)-phenyl)-(4-hydroxy-
2-sulfonium phenyl)-msthy
leneJ-(1-(N-ethyl-m-sulfo
benzyl)-△2°5-cyclohexadie
nimins) disodium 5alt member green 4
No. 0.1 (Naphthol Green B) Ferric-1
-nitroso-8chaef fer”1β-ac
idal t These pigments are generally used in herbicidal compositions containing bipyridium quaternary salts as active ingredients (101118 to 2% in blood volume, preferably 100III in water volume or solid matter).
A range of N to 1.0% is used. If the m degree is too low, it may be affected by various constituents and is not preferred. On the other hand, the upper limit is up to m dissolution of the dye into the composition, and
However, even in this case, as long as it is a water-soluble composition, the upper limit bath P! The above range is preferably used for economical reasons.

The color used may be any of the above blue, red, yellow, and green. However, colors such as f are particularly preferably used as colors that are naturally rare.

However, when using dyes such as these, 1 cpH is particularly important for their stability. That is, the pH at which this product is used is preferably 5.7 or less, particularly 5.5 or less. P) When L is brought into neutral or centrally negative alkaline conditions with a concentration of 6 or more, not only does a subtle color change occur in fi-colored objects, but also the long-term stability of stability vf increases rapidly, resulting in a loss of stability as a colored object. The effect will be faded and confusion with the colors will likely occur. That is, the stability of the yellow phase, which is not recognized in short-term tests, is maintained by adjusting the above pH conditions. That is, by maintaining the pH in the above-mentioned range in the herbicidal composition containing the above-mentioned dye containing dipyridium quaternary salt as an active ingredient, that is, by adjusting the pH to 5.5 or less when the pH is 5.7 or less. Therefore, it is possible to use a herbicidal composition containing diviridium 4M salt as an active ingredient, which has a stable pigment over a long period of time and is safer.

There is no lower limit to the acidic conditions, but if the conditions are too strong, the soil quality may change during use. The lower limit of the pH of stool is preferably 1 or more, particularly 1.5 or more.

The diviridinium quaternary salt in the present invention will be described in detail below. One of the pyridinium quaternary salts of the present invention is represented by the following general formula [I].

(However, β in the formula indicates 1 or 2 feasts, (X)”:J
indicates an anion. ) Here, the selection of 720/ is made as appropriate based on, for example, price. 7Nio/ is preferably one that produces a salt with appropriate water solubility. Examples of 7-ions that can be monovalent or polyvalent include e: acid radical, benzene/sulfone radical, benzene tR radical, bromate radical, bromide ion, butyrate radical, chlorate radical, chloride ion, citric acid radical. , gi #l root, fluorogui am, fumal iron root, fluoroborate root, iodine io/, lactic acid root, malic acid root, maleic acid root, methyl sulfate root, nitrate #1 root, propio/acid, root, phosphate root, salici I #! root, sulfamic acid root, co-phosphate s1m
Mention may be made of the root, thiocyanate, tartrate and p-)luenesulfone root. Preferred are bromide ions, chloride ions, iodide ions or methyl sulfur.
It is.

Examples of compounds of the above general formula (l) include bil 11
1'-ethyne 7-212'-bipyridylium dipromide (diquat dichloride)
romids) (Mei 1,1'-Echire 7-212'
-bipyridinium dichloride (.→ill'-ethyle7-212'-bipyridinium difluoride, etc.) can be obtained.

The method for producing such a compound is not particularly limited. For example, when diquat 7 dinoroma 1 is used as this compound, this compound is used as a raw material, and then pyridine is quaternized using 22' bipyridyl and ethyle/bromide, which are diphenolicized using a mononickel catalyst. The present invention is suitably applied to products manufactured by this method.

On the other hand, other dipyridinium salts are represented by the following general formula [■].

R-ζ)iW-m-' [YJmθ...
-L■] As the anion/binding agent in the diviridinium quaternary salt of the general formula (11), the same one as explained in the general formula (1) can be used.

Examples of such compounds of general formula (IL) include: 1)
1'-dimethyl-4,4'-bipyridinium dichloride (balactate dichloride) (e) l, 1'-
Di-2-hydroxyethyl-4,4'-bipyridinium dichloride () 1-(2-hydroxyethyl)-1'-methyl-4,4'-bipyridinium dichloride ()l
1,1'-di(carbamoylmethyl)-4,4
'-Bipyridinium dichloride (T) 1.1''-Bis-N,N-dimethylcarbamoylmethyl-4,4'-bipyridinium dichloride (Sl) 1.1'-Bis-N t N'-Diethylcarbamoylmethyl-4 ,4'-bipyridinium dichloride diagram 1.1'-diacetonyl-4,4'-bipyridinium dichloride 4 Ll'-jethoxycarbonylmethyl-4941-
Bipyridinium dichloride (W) l*1'-Diallyl-4,4'-bipyridinium dibu-mite (W1.1.1'-Dimethylthio-4,4'-bipyridinium dichloride, etc.).

The compound of Kahero's general formula [■] can be produced, for example, by the method shown by the following anticentric formula, that is, the method of reacting dipyridi/ with furkyl halide〇ζ')-/JIN+ 2R-Y This invention The active ingredient in the herbicidal composition may contain the general formula (1) or [■], or a mixture of (1) and (11), but considering the stability of the dye at the flowering stage, It is recommended that the active ingredient contains diviridinium quaternary salt (1). That is, the effects of the present invention are significantly superior to herbicidal compositions containing (13 alone or a mixture of [I] and (11) as active ingredients).

In particular, when (1) and [■] are used in combination, preferred combinations include, for example, ge)-ni).

(b)-ni), (Il-e→, (b)-ri→
, Kl-()l or (c+l-(t1).

When the herbicidal composition of the present invention is an aqueous solution, the amount of cations in the bipyridium quaternary salt is 20 to 4001//
1, and in the case of a solid star object, it is preferable that these weights are included when it is made into an aqueous solution with water or the like.

In the present invention, in addition to the above-mentioned active ingredient 1, the pigment compound, in order to avoid disasters such as misuse, especially accidental ingestion, an emetic agent,
Alternatively, it is also possible to create safer herbicidal compositions by adding additives such as odorants or bittering agents.
That may generally be preferable. In the present invention, the emetic agent 1 odorant, bittering agent, etc. are not particularly limited as long as they satisfy the conditions in the method of the present invention.

However, when the emetic agent 1 odorant, bittering agent, etc. is an organic type, and is a furkyl type or a heterocyclic type compound, it may be used in a preferable manner.

In addition to these warning substances, additives commonly used in herbicidal compositions can also be added. That is, furkyl vE acid ester, furkyl sulfone polyoxyethylene glycol ethers, and polyoxyethylene furkyl furyl ether.

Surfactants, emulsifiers or dispersants, or urea agents such as polyoxyethylene/Nruvita/monofluthiolate, dinaphthylmethane disulfonate, or urea agents: carboxymethyl cellulose. 7
It is prepared using 1 g or 2 a [or more] of each of the 4 adjuvants, such as Ravi 7 Gum.

The composition of the present invention comprises S'e. They can be used as preparations in conventional forms such as emulsions, suspensions, powders, pastes or granules.

Such preparations include, for example, talc, bentonite.

Klee, Kaori/. Diatomaceous earth, white carb/.

Solid carriers such as vermiculite, fP lime, ammonium sulfate, urea; water. Alcohol, dioxane, 7setone, xylene/.
Liquid carriers include cyclohexa/, methylphthalene, and dimethylformamide.

Among these forms, the form of a water hydration solution is particularly preferably used. However, a solid form is used for certain special purposes, such as a method in which a solid substance containing a gluing agent is added to water or drinking water to form a gel and prevent misuse.

The present invention will be described in detail below with reference to Examples.

Example 1 (composition containing acid blue IY)
1.1'-dimethyl-4,4'-bipyridylium dichloride (hereinafter referred to as 1) Q-012 with a weight of 35.0% by weight. ) rich water bath Q 355.1 # and 30. A thick aqueous solution of 1.1'-ethyle/2 + 2'-bipyridylium dichloride (hereinafter abbreviated as DQ-Br2.
(& sex agent (furkylphenyl needle A) 20.
Add 10,000 liters of Ol, 40.0 liters of Polio 1,000 ethylene/alkyl 7 amine surfactant, and approximately 10,011 tons of water using iV.

The pH was adjusted to 5.4 with Takeshi Isoshio.

Add to this the heterocyclic emetics o, Ao y and colorants (acid,
Added 6.501 m of 20% water-soluble fatigue of Blue 1), added an odorant (amine type) at 8.0:J5S, and then added water to make the whole '41. It was set as fJII liter.

The main composition of this herbicidal composition was as follows.

Example 2 (Preparation of a composition rich in Acid Blue 9) A composition with a pH of 4.0 was prepared in the same manner as in Example 1, except that 7-Synde Blue 9 was used as the colorant.

Examples 3 to 6 and Comparative Examples 1 to 3 In Example 1, the dyes in Table 1 below were used, p
Herbicidal compositions with H adjusted to various values were prepared.

Table 1 Example 7 (Stability Test) Each of the herbicidal compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 above was tested at the temperature and atmosphere F shown in Clothing 2 below for the time shown in the same table. held. The results were expressed as a rate of change (%) in wavelength absorbance. That is, the absorbance of the composition was diluted 250 times with water at a wavelength of 750 to 4 in an IcIII quartz cell.
61 at the unique wavelength of each dye at 00 nmM.
11, and the increase/decrease rate after storage is shown as a relative value (%) when the time of preparation of the composition is set as 100.

Table 2 * In the table, diviridinium quaternary salt does not contain PQ-Br, but durability was investigated in a system containing PQ-C1,22, (lit%).

Claims (1)

[Claims] The following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (However, in the formula, l represents an integer of 1 or 2, and [X] ^l^■ Anion) and/or the following general formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... [II] [However, in the formula, m represents an integer of 1 or 2, [Y] ＾ m ＾ ■ indicates an anion. The two R's are the same or different alkyl groups having 1 to 5 carbon atoms, and the alkyl groups include a hydroxy group, a lower alkoxy group, a lower thioalkyl group, a lower alkylcarbonyl group, a lower alkoxycarbonyl group, a carboxy group, and a carbonylamide group. , may be substituted with a halogen group. ] A herbicidal composition containing as an active ingredient at least one of diviridinium quaternary salts represented by Acid Blue 1, Acid Blue 3, Acid Blue 9,
Food Blue No. 1, Food Blue No. 2, Food Red No. 2, Food Red No. 3, Food Red No. 102, Food Red No. 104, Food Red No. 105, Food Red No. 106, Red No. 504, Food Yellow No. 4, Food Red A herbicidal composition containing at least one coloring component selected from the group consisting of Yellow No. 5, Edible Green No. 3, and Green No. 401, and maintained under acidic conditions with a pH of 5.7 or less.