Pesticide Additives

Abstract

To provide an additive for agricultural chemicals, exhibiting stable spreading performance.SOLUTION: An additive for agricultural chemicals contains a copolymer which includes as the constitutional units, a constitutional unit (I) derived from a monomer represented by general formula (1), and a constitutional unit (II) derived from a monomer represented by general formula (2), and has an average molecular weight in the range of 15,000-150,000. The additive for agricultural chemicals is such that the copolymer includes the constitutional unit (II) in the range of 1-6 mol based on 1 mol of the constitutional unit (I).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an agricultural chemical additive. [Background technology]

[0002] In agricultural fields such as rice paddies, it is preferable to spread the pesticide from the application site in order to make it easier for the pesticide to exert its effect, reduce residual pesticide, and increase safety. For this reason, pesticides are sprayed together with a spreader that has spreading properties.

[0003] Such spreaders are expected to spread the pesticide over a wider area from the point of application on the water surface after coming into contact with the water. Therefore, it is important to consider the distance the pesticide will travel, to disperse the pesticide quickly before it settles, and to prevent it from agglomerating on the water surface.

[0004] For such agricultural chemical additives (spreaders), ether-type surfactants having a polyoxyalkylene alkyl ether moiety have been used. Patent Document 1 discloses a mixture of a monoester salt and a diester salt of a phosphoric acid ester salt of an alkylene oxide adduct of an alkyl alcohol as an ether-type surfactant having a polyoxyalkylene alkyl ether moiety. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Document 1: JP 2002-128605 A DISCLOSURE OF THE PRESENT DISCLOSURE However, in Patent Document 1, the performance was sometimes unstable depending on the mixing ratio of the mixture of monoester salt and diester salt of the phosphate ester salt, and there was room for improvement in the effect of the agricultural chemical water surface spreader depending on the mixing ratio.

[0006] Therefore, an object of the present invention is to provide an agricultural chemical additive that exhibits stable spreading performance. Summary of the Invention [Means for solving the problem]

[0007] As a result of extensive efforts, the inventors have achieved the solution of the problems of the present invention by the following configuration. That is, the present invention relates to the following [1] to [4]. [1] A pesticide additive comprising a copolymer having an average weight molecular weight of 15,000 to 150,000, the copolymer comprising a structural unit (I) derived from a monomer represented by the following general formula (1) and a structural unit (II) derived from a monomer represented by the following general formula (2) as structural units:

[0008] [ka] (In the formula, R 1 , R 2 and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; p represents an integer of 0 to 2, and q represents an integer of 0 to 1; A1O are the same or different and represent an oxyalkylene group having 2 to 18 carbon atoms; n represents an integer of 20 to 300. R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.

[0009] [ka] (In the formula, R 5 , R 6 , and R 7 are each independently a hydrogen atom, -CH3 or -(CH2) r COOM 2 represents -CH3 or -(CH2) r COOM 2 Each other -COOM 1 or -(CH2) r COOM 2 When an anhydride is formed, the M 1 , M 2 does not exist. 1 and M. 2are the same or different and represent a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a substituted alkylammonium group; and r represents an integer of 0 to 2. [2] The agricultural chemical additive according to [1], wherein the copolymer further contains a structural unit (III) derived from a monomer represented by the following general formula (3):

[0010] [ka] (In the formula, R 8 , R 9 and R 10 R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 11 represents a hydrocarbon group having 1 to 4 carbon atoms which may contain a heteroatom; and s represents an integer of 0 to 2. [3] The agricultural chemical additive according to any one of [1] to [2], wherein the copolymer contains 1 to 6 mol of the structural unit (II) per 1 mol of the structural unit (I). [4] A pesticide composition comprising the pesticide additive according to any one of [1] to [3]. Effect of the Invention

[0011] The present invention can provide an agricultural chemical additive that exhibits stable spreading performance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] That is, the present invention is an agricultural chemical additive characterized by containing, as structural units, a structural unit (I) derived from a monomer represented by the following general formula (1) and a structural unit (II) derived from a monomer represented by the following general formula (2), and containing a copolymer having an average weight molecular weight in the range of 15,000 to 150,000.

[0013] (Structural unit (I)) The structural unit (I) is a structural unit derived from a monomer represented by general formula (1).

[0014] [ka]

[0015] R in general formula (1) 1 , R 2 and R 3 R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. 3 is preferably a hydrogen atom. The alkyl group having 1 to 3 carbon atoms may have a substituent (however, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkyl group). 1 is preferably a hydrogen atom. 2 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. In the general formula (1), p represents an integer of 0 to 2. In the general formula (1), q represents an integer of 0 to 1.

[0016] A in general formula (1) 1 O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. Examples of the oxyalkylene group (alkylene glycol unit) include an oxyethylene group (ethylene glycol unit), an oxypropylene group (propylene glycol unit), and an oxybutylene group (butylene glycol unit), with an oxyethylene group and an oxypropylene group being preferred.

[0017] The above-mentioned "same or different" means that A 1 If multiple Os are included (n is 2 or more), each A 1 This means that O may be the same oxyalkylene group or may be different (two or more types) of oxyalkylene groups. 1In the case where a plurality of O's are contained, there may be mentioned an embodiment in which two or more oxyalkylene groups selected from the group consisting of oxyethylene, oxypropylene and oxybutylene groups are mixed, and an embodiment in which an oxyethylene group and an oxypropylene group are mixed, or an embodiment in which an oxyethylene group and an oxybutylene group are mixed, is preferable, and an embodiment in which an oxyethylene group and an oxypropylene group are mixed is more preferable. In an embodiment in which different oxyalkylene groups are mixed, the addition of two or more kinds of oxyalkylene groups may be in a block form or a random form. In addition, in the general formula (1), when q is 0, the alkylene group having the carbon number p and A 1 It bonds to O via an oxygen atom.

[0018] In the general formula (1), n ​​is the average number of moles of oxyalkylene groups added and represents an integer of 20 to 300. n is preferably 30 to 100, more preferably 40 to 100, and further preferably 40 to 80. The average number of moles added means the average value of the number of moles of oxyalkylene groups added to 1 mole of monomer.

[0019] This allows the compound to exhibit appropriate steric repulsion on the water surface, thereby enabling good water surface spreadability to be obtained, particularly when used in combination with an agricultural chemical.

[0020] R in general formula (1) 4 R represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. 4 is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and most preferably a hydrogen atom or a methyl group. Within this range, the number of carbon atoms is not too large, and the cement admixture exhibits good cement dispersibility.

[0021] Examples of the method for producing the monomer represented by the general formula (1) include a method in which 20 to 300 moles of alkylene oxide are added to an unsaturated alcohol such as allyl alcohol, methal alcohol, or 3-methyl-3-buten-1-ol. Examples of monomers that can be produced by this method include (poly)ethylene glycol allyl ether, (poly)ethylene glycol methallyl ether, (poly)ethylene glycol 3-methyl-3-butenyl ether, (poly)ethylene (poly)propylene glycol allyl ether, (poly)ethylene (poly)propylene glycol methallyl ether, (poly)ethylene (poly)propylene glycol 3-methyl-3-butenyl ether, (poly)ethylene (poly)butylene glycol allyl ether, (poly)ethylene (poly)butylene glycol methallyl ether, (poly)ethylene (poly)butylene glycol 3-methyl-3-butenyl ether, methoxy(poly)ethylene Examples of the methacrylic acid include ethylene glycol allyl ether, methoxy(poly)ethylene glycol methallyl ether, methoxy(poly)ethylene glycol 3-methyl-3-butenyl ether, methoxy(poly)ethylene (poly)propylene glycol allyl ether, methoxy(poly)ethylene (poly)propylene glycol methallyl ether, methoxy(poly)ethylene (poly)propylene glycol 3-methyl-3-butenyl ether, methoxy(poly)ethylene (poly)butylene glycol allyl ether, methoxy(poly)ethylene (poly)butylene glycol methallyl ether, and methoxy(poly)ethylene (poly)butylene glycol 3-methyl-3-butenyl ether. Among these, (poly)ethylene glycol (meth)allyl ether, (poly)ethylene (poly)propylene glycol (meth)allyl ether, (poly)ethylene glycol 3-methyl-3-butenyl ether, and (poly)ethylene (poly)propylene glycol 3-methyl-3-butenyl ether are preferred from the viewpoint of the balance between hydrophilicity and hydrophobicity.

[0022] In this specification, "(poly)" means that the subsequently described component or raw material is bonded in multiples and / or only one is present. "(Meth)allyl" means methallyl and / or allyl, "(meth)acrylate" means methacrylate and / or acrylate, and "(meth)acrylic acid" means methacrylic acid and / or acrylic acid.

[0023] Another example of a method for producing the monomer represented by general formula (1) is the esterification of an unsaturated monocarboxylic acid such as (meth)acrylate (hereinafter, "(meth)acrylate" means "acrylate or methacrylate") with a (poly)alkylene glycol such as (poly)ethylene glycol, (poly)ethylene (poly)propylene glycol, (poly)ethylene (poly)butylene glycol, methoxy(poly)ethylene glycol, methoxy(poly)ethylene (poly)propylene glycol, or methoxy(poly)ethylene (poly)butylene glycol. Examples of monomers that can be produced by this method include (poly)ethylene glycol (meth)acrylate, (poly)ethylene (poly)propylene glycol (meth)acrylate, (poly)ethylene (poly)butylene glycol (meth)acrylate, methoxy (poly)ethylene glycol (meth)acrylate, methoxy (poly)ethylene (poly)propylene glycol (meth)acrylate, methoxy (poly)ethylene (poly)butylene glycol (meth)acrylate, and other (poly)alkylene glycol (meth)acrylates. Among these, (poly)alkylene glycol (meth)acrylate and methoxy (poly)ethylene glycol (meth)acrylate are preferred, with methoxy (poly)ethylene glycol (meth)acrylate being more preferred.

[0024] The copolymer used in the present invention may contain one type of structural unit (I), or may contain two or more types of structural units (I) derived from mutually different monomers.

[0025] (Structural unit (II)) The structural unit (II) is a structural unit derived from a monomer represented by general formula (2).

[0026] [ka]

[0027] R in general formula (2) 5 , R 6 and R 7 are each independently a hydrogen atom, -CH3 or -(CH2)rCOOM 2 represents -CH3 or (CH2)rCOOM 2 Each other -COOM 1 or -(CH2)rCOOM 2 and may form an anhydride, and when an anhydride is formed, M 1 , M 2 does not exist. R 5 is preferably a hydrogen atom. R 6 is preferably a hydrogen atom or -CH3. 7 is preferably a hydrogen atom.

[0028] In general formula (2), M 1 and M. 2 are the same or different and each represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group or a substituted alkylammonium group; M 1 , M 2 are preferably a hydrogen atom, an alkali metal, or an alkaline earth metal.

[0029] In formula (2), r represents an integer of 0 to 2. It is preferable that r is 0.

[0030] Examples of the monomer represented by the general formula (2) include unsaturated monocarboxylic acid monomers and unsaturated dicarboxylic acid monomers. Examples of the unsaturated monocarboxylic acid monomers include acrylic acid, methacrylic acid, crotonic acid, and the like, and their monovalent metal salts, ammonium salts, and organic amine salts. Examples of the unsaturated dicarboxylic acid include maleic acid, itaconic acid, citraconic acid, fumaric acid, and the like, and their monovalent metal salts, ammonium salts, and organic amine salts, or their anhydrides. As the monomer (II), acrylic acid, methacrylic acid, and maleic acid are preferred.

[0031] The copolymer used in the present invention may contain one type of structural unit (II), or may contain two or more types of structural units (II) derived from mutually different monomers.

[0032] (Structural unit (III)) The copolymer used in the present invention preferably contains a structural unit (III), and such a structural unit (III) is a structural unit derived from a monomer represented by general formula (3).

[0033] [ka]

[0034] In general formula (3), R 8 , R 9 and R 10 Each of the groups independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include R 1 , R 2 and R 3 Similar to the example in R 8 is preferably a hydrogen atom. 9 is preferably a hydrogen atom. 10 is preferably a hydrogen atom.

[0035] In general formula (3), R 11R represents a hydrocarbon group having 1 to 4 carbon atoms which may contain a heteroatom. The number of carbon atoms is preferably 1 to 3, more preferably 2 to 3, and even more preferably 3. Examples of the heteroatom include an oxygen atom, a nitrogen atom, a phosphorus atom, and a silicon atom, and an oxygen atom is preferred. Examples of the hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, and a glyceryl group. 11 The number of heteroatoms contained in may be 1 or may be 2 or more. When two or more heteroatoms are contained, the respective heteroatoms may be the same or different from each other.

[0036] R 11 is preferably a hydrocarbon group containing a heteroatom and having 1 to 4 carbon atoms, and more preferably a hydrocarbon group containing an oxygen atom and having 1 to 4 carbon atoms. Examples of such groups include a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, and a glyceryl group, of which the 2-hydroxypropyl group is preferred.

[0037] In formula (3), s represents an integer of 0 to 2. s is preferably 0.

[0038] Examples of the monomer represented by the general formula (3) include monoesters of unsaturated monocarboxylic acids. Examples of the unsaturated monocarboxylic acid monoesters include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glyceryl (meth)acrylate.

[0039] The polymer used in the present invention may contain one type of structural unit (III), or may contain two or more types of structural units (III) derived from mutually different monomers.

[0040] (Structural unit (IV)) The copolymer used in the present invention may contain a structural unit (IV) in addition to the structural units (I) to (III). The structural unit (IV) is a structural unit derived from a monomer copolymerizable with the monomers represented by the general formulas (1) to (3). The monomers copolymerizable with the monomers represented by the general formulas (1) to (3) are structurally distinct from the monomers represented by the general formulas (1) to (3). The monomers constituting the structural unit (IV) are not particularly limited, but may include, for example, the following monomers, and one or more of these may be used.

[0041] General formula (IV-1):

[0042] [ka]

[0043] Diallyl bisphenols represented by the formula: for example, 3- and 3'-allyl substituted 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, and 4,4'-dihydroxydiphenylsulfone;

[0044] General formula (IV-2):

[0045] [ka]

[0046] monoallyl bisphenols represented by the following formula (I): for example, 3-allyl substituted bisphenols of 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, and 4,4'-dihydroxydiphenylsulfone;

[0047] General formula (IV-3):

[0048] [ka]

[0049] Allylphenol represented by the formula:

[0050] Half esters and diesters of unsaturated dicarboxylic acids, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic acid, with alcohols having 1 to 30 carbon atoms; Half amides and diamides of the above unsaturated dicarboxylic acids with amines having 1 to 30 carbon atoms;

[0051] half esters and diesters of alkyl (poly)alkylene glycols obtained by adding 1 to 500 moles of alkylene oxide having 2 to 18 carbon atoms to the above alcohols or amines, and the above unsaturated dicarboxylic acids;

[0052] Half esters and diesters of the above unsaturated dicarboxylic acids with glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 moles of such glycols;

[0053] Half amides of maleamic acid with glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 moles of such glycols;

[0054] Esters of alkoxy (poly)alkylene glycols obtained by adding 1 to 500 moles of alkylene oxide having 2 to 18 carbon atoms to alcohol having 1 to 30 carbon atoms, and unsaturated monocarboxylic acids such as (meth)acrylic acid;

[0055] (poly)ethylene glycol monomethacrylate, (poly)propylene glycol monomethacrylate, (poly)butylene glycol monomethacrylate, and other adducts of 1 to 500 moles of alkylene oxide having 2 to 18 carbon atoms to unsaturated monocarboxylic acids such as (meth)acrylic acid (excluding monomers represented by general formulas (1) to (3));

[0056] (poly)alkylene glycol di(meth)acrylates such as triethylene glycol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and (poly)ethylene glycol (poly)propylene glycol di(meth)acrylate;

[0057] Polyfunctional (meth)acrylates such as hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trimethylolpropane di(meth)acrylate;

[0058] (Poly)alkylene glycol dimaleates such as triethylene glycol dimaleate and polyethylene glycol dimaleate;

[0059] unsaturated sulfonic acids such as vinyl sulfonate, (meth)allyl sulfonate, 2-(meth)acryloxyethyl sulfonate, 3-(meth)acryloxypropyl sulfonate, 3-(meth)acryloxy-2-hydroxypropyl sulfonate, 3-(meth)acryloxy-2-hydroxypropyl sulfophenyl ether, 3-(meth)acryloxy-2-hydroxypropyloxysulfobenzoate, 4-(meth)acryloxybutyl sulfonate, (meth)acrylamidomethyl sulfonic acid, (meth)acrylamidoethyl sulfonic acid, 2-methylpropanesulfonic acid (meth)acrylamide, and styrenesulfonic acid, as well as their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts;

[0060] Amides of unsaturated monocarboxylic acids and amines having 1 to 30 carbon atoms, such as methyl (meth)acrylamide;

[0061] vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene;

[0062] Alkanediol mono(meth)acrylates such as 1,5-pentanediol mono(meth)acrylate and 1,6-hexanediol mono(meth)acrylate (excluding monomers represented by general formula (3));

[0063] Dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, and 2-chloro-1,3-butadiene;

[0064] Unsaturated amides such as (meth)acrylamide, (meth)acrylalkylamide, N-methylol (meth)acrylamide, and N,N-dimethyl (meth)acrylamide;

[0065] Unsaturated cyanides such as (meth)acrylonitrile and α-chloroacrylonitrile;

[0066] Unsaturated esters such as vinyl acetate and vinyl propionate;

[0067] Unsaturated amines such as aminoethyl (meth)acrylate, methylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, and vinylpyridine (excluding monomers represented by general formula (3));

[0068] Divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate;

[0069] Allyls such as (meth)allyl alcohol and glycidyl (meth)allyl ether;

[0070] Vinyl ethers or allyl ethers such as methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono(meth)allyl ether, polyethylene glycol mono(meth)allyl ether, etc. (excluding the monomer represented by the general formula (1)); and

[0071] Siloxane derivatives such as polydimethylsiloxane propylaminomaleamic acid, polydimethylsiloxane aminopropylene aminomaleamic acid, polydimethylsiloxane bis-(propylaminomaleamic acid), polydimethylsiloxane bis-(dipropyleneaminomaleamic acid), polydimethylsiloxane-(1-propyl-3-acrylate), polydimethylsiloxane-(1-propyl-3-methacrylate), polydimethylsiloxane bis-(1-propyl-3-acrylate), and polydimethylsiloxane bis-(1-propyl-3-methacrylate) (however, excluding the monomer represented by general formula (3)).

[0072] The copolymer used in the present invention may contain one type of structural unit (IV), or may contain two or more types of structural units (IV) derived from mutually different monomers.

[0073] <Method of producing copolymer> The copolymer used in the present invention can be produced by copolymerizing each of the predetermined monomers by a known method, such as polymerization in a solvent or bulk polymerization.

[0074] (Reaction Solvent) Examples of the solvent used in the polymerization in a solvent include water, lower alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, etc., aromatic hydrocarbons such as benzene, toluene, xylene, etc., aliphatic hydrocarbons such as cyclohexane, n-hexane, etc., esters such as ethyl acetate, etc., ketones such as acetone, methyl ethyl ketone, etc. From the viewpoint of the solubility of the raw material monomers and the resulting copolymer, it is preferable to use one or more selected from the group consisting of water and lower alcohols, and among them, it is more preferable to use water.

[0075] When copolymerization is carried out in a solvent, each monomer and the polymerization initiator may be continuously added dropwise to a reaction vessel, or a mixture of each monomer and the polymerization initiator may be continuously added dropwise to a reaction vessel. Alternatively, a solvent may be charged into a reaction vessel, and a mixture of the monomers and the solvent and a polymerization initiator solution may be continuously added into the reaction vessel, or a part or all of the monomers may be charged into a reaction vessel, and the polymerization initiator may be continuously added dropwise.

[0076] (Initiator) The polymerization initiator that can be used for copolymerization is not particularly limited. Examples of polymerization initiators that can be used when copolymerizing in an aqueous solvent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; and water-soluble peroxides such as t-butyl hydroperoxide and hydrogen peroxide. In this case, accelerators such as L-ascorbic acid, sodium hydrogen sulfite, and Mohr's salt may be used in combination. Examples of polymerization initiators that can be used when copolymerizing in a solvent such as lower alcohol, aromatic hydrocarbon, aliphatic hydrocarbon, esters, or ketones include peroxides such as benzoyl peroxide and lauryl peroxide; hydroperoxides such as cumene peroxide; and aromatic azo compounds such as azobisisobutyronitrile. In this case, accelerators such as amine compounds may be used in combination. The polymerization initiator that can be used when copolymerizing in a water-lower alcohol mixed solvent may be appropriately selected from the above-mentioned polymerization initiators or combinations of polymerization initiators and accelerators. The polymerization temperature varies depending on the polymerization conditions such as the solvent used and the type of polymerization initiator, but is usually 50 to 120°C.

[0077] (Chain transfer agent) In the copolymerization, a chain transfer agent can be used to adjust the molecular weight, if necessary. Examples of the chain transfer agent used include known thiol compounds such as mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, and 2-mercaptoethanesulfonic acid; phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionous acid, metabisulfite, and salts thereof (sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.), lower oxides and salts thereof; and the like. These may be used alone or in combination of two or more. To adjust the molecular weight of the copolymer, a monomer (V) having high chain transfer properties other than the monomers represented by the general formulas (1) to (3) and the monomers constituting the structural unit (VI) may be used. An example of the monomer (V) having high chain transferability is a (meth)allylsulfonic acid (salt) monomer. The content of the monomer (V) in the copolymer is usually 20% by weight or less, and preferably 10% by weight or less. The above content is the content when the content of the monomer represented by general formula (1) + the content of the monomer derived from the monomer represented by general formula (2) + the content of the monomer represented by general formula (3) + the content of the monomer constituting the structural unit (IV) is taken as 100% by weight when the copolymer is produced.

[0078] (neutralization) When copolymerization is performed in an aqueous solvent to obtain a copolymer, the pH during polymerization is usually strongly acidic due to the influence of the monomer having an unsaturated bond, but this may be adjusted to an appropriate pH. If pH adjustment is required during polymerization, the pH may be adjusted using an acidic substance such as phosphoric acid, sulfuric acid, nitric acid, alkyl phosphoric acid, alkyl sulfuric acid, alkyl sulfonic acid, or (alkyl)benzenesulfonic acid. Among these acidic substances, phosphoric acid is preferred because of its pH buffering effect. However, in order to eliminate the instability of the ester bond of the ester monomer, it is preferable to perform polymerization at a pH of 1 to 7. There is no particular limitation on the alkaline substance that can be used to adjust the pH, but alkaline substances such as NaOH and Ca(OH)2 are common. The pH adjustment may be performed on the monomer before polymerization, or on the copolymer solution after polymerization. In addition, a part of the alkaline substance may be added before polymerization to perform polymerization, and then the pH of the copolymer may be further adjusted.

[0079] (molecular weight) The weight-average molecular weight of the copolymer used in the present invention is preferably 15,000 or more, more preferably 20,000 or more, and even more preferably 35,000 or more. The upper limit of the weight-average molecular weight is preferably 150,000 or less, more preferably 100,000 or less, and even more preferably 80,000 or less. This makes it easier for the localization to be uniform when used in combination with an agricultural chemical, and allows the copolymer to effectively exhibit its spreading performance.

[0080] The molecular weight distribution (Mw / Mn) of the copolymer is preferably 1.0 or more, more preferably 1.20 or more. The upper limit is preferably 3.0 or less, more preferably 2.50 or less. The molecular weight distribution is preferably in the range of 1.2 to 3.0.

[0081] The weight average molecular weight in the present invention can be measured by a known method using gel permeation chromatography (GPC) in terms of polyethylene glycol.

[0082] Although there are no particular limitations on the GPC measurement conditions, the following conditions can be mentioned as examples. The weight average molecular weight in the examples below is the value measured under these conditions. Measuring device: Tosoh Columns used: Shodex Column OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ Eluent: 0.05 mM sodium nitrate / acetonitrile 8 / 2 (v / v) Standard material: Polyethylene glycol (Tosoh, GL Science) Detector: Differential refractometer (manufactured by Tosoh) Calibration curve; Polyethylene glycol standard

[0083] The copolymer used in the present invention preferably contains 1 to 6 mol of the structural unit (II) per mol of the structural unit (I), more preferably 1 to 5.5 mol. The structural unit (II) is hydrophilic, so it quickly wets and spreads when it comes into contact with water, but if there is not a certain amount of the structural unit (I) that exhibits a nonionic effect, it is difficult to exhibit spreading performance on the water surface. Therefore, it is preferable that the copolymer used in the present invention satisfies the above range.

[0084] The contents of the structural units (I) and (II) in the copolymer can be considered to be those in which the entire amounts of the monomers representing the respective structural units used in the copolymerization reaction have reacted, and can be obtained from the amounts of the monomers added during the reaction.

[0085] (optional ingredient) The agricultural chemical additive of the present invention may contain optional components in addition to the copolymer, so long as the effects of the present invention are not impaired. Examples of the optional components include disintegrants, other dispersants, chelating agents, detergents, flocculants, thickeners, stabilizers, spreading agents, water retention agents, protective colloids, binders, water-absorbent resins, etc. EXAMPLES

[0086] The present invention will be described in detail below with reference to examples. The following examples are provided to better explain the present invention, and are not intended to limit the present invention. The methods for measuring physical properties and the like are the same as those described above unless otherwise specified. In the examples, "%" means % by weight, and "parts" means parts by weight, unless otherwise specified.

[0087] (Production Example 1) In a glass reaction vessel equipped with a thermometer, agitator, reflux device, nitrogen inlet tube and dropping device, 192.5 parts of water, 192 parts (0.08 mol) of ethylene oxide adduct of methallyl alcohol (average number of moles of ethylene oxide added: 53, molecular weight: 2404), and 0.5 parts of hydrogen peroxide were charged, and the reaction vessel was replaced with nitrogen while stirring. After heating to 40°C under a nitrogen atmosphere, an aqueous monomer solution containing 5.76 parts (0.08 mol) of acrylic acid (molecular weight: 72), 0.1 parts of 3-mercaptopropionic acid, and 35 parts of water was continuously dropped into the reaction vessel held at 40°C for 2 hours, and an aqueous solution containing 1.4 parts of sodium hydroxymethanesulfonate dissolved in 48.6 parts of water was continuously dropped into the reaction vessel held at 40°C for 2.5 hours. After the dropping was completed, the mixture was reacted for another hour while maintaining the temperature, and neutralized to pH 4 with sodium hydroxide and water was added at the same time to obtain an aqueous solution of copolymer 1. The copolymer 1 in the liquid had a weight average molecular weight of 50,800 and Mw / Mn of 1.97 (structural unit (II)) / structural unit (I)=1.0).

[0088] (Production Example 2) In a glass reaction vessel equipped with a thermometer, agitator, reflux device, nitrogen inlet tube and dropping device, 58 parts of water, 60 parts (0.025 mol) of ethylene oxide adduct of methallyl alcohol (average number of moles of ethylene oxide added: 53, molecular weight: 2404), and 1.3 parts of hydrogen peroxide were charged, and the reaction vessel was replaced with nitrogen while stirring. After heating to 40°C under a nitrogen atmosphere, an aqueous monomer solution containing 9 parts (0.125 mol) of acrylic acid, 0.1 parts of 3-mercaptopropionic acid and 209 parts of water was continuously dropped into the reaction vessel held at 40°C for 2 hours, and an aqueous solution containing 0.1 parts of sodium hydroxymethanesulfonate dissolved in 99.9 parts of water was continuously dropped into the reaction vessel held at 40°C for 2.5 hours. After the dropping was completed, the mixture was reacted for another hour while maintaining the temperature, and neutralized to pH 4 with sodium hydroxide and water was added at the same time to obtain an aqueous solution of copolymer 2. The copolymer 2 in the liquid had a weight average molecular weight of 65,300 and Mw / Mn of 2.19 (structural unit (II) / structural unit (I)=5.0).

[0089] (Production Example 3) In a glass reaction vessel equipped with a thermometer, agitator, reflux device, nitrogen inlet tube and dropping device, 113 parts of water, 168 parts (0.07 mol) of ethylene oxide adduct of methallyl alcohol (average number of moles of ethylene oxide added: 53, molecular weight: 2404), and 1.8 parts of ascorbic acid were charged, and the reaction vessel was replaced with nitrogen while stirring. After heating to 40°C under a nitrogen atmosphere, an aqueous monomer solution containing 10.1 parts (0.14 mol) of acrylic acid, 0.1 parts of 3-mercaptopropionic acid and 85.8 parts of water was continuously dropped into the reaction vessel held at 40°C for 2 hours, and a mixed solution of 0.7 parts of hydrogen peroxide and 49.3 parts of water was continuously dropped into the reaction vessel held at 40°C for 2.5 hours. After the dropping was completed, the mixture was reacted for another hour while maintaining the temperature, neutralized to pH 4 with sodium hydroxide and water was added at the same time to obtain an aqueous solution of copolymer 3. The copolymer 3 in the liquid had a weight average molecular weight of 55,700 and Mw / Mn of 1.68 (structural unit (II) / structural unit (I)=2.0).

[0090] (Production Example 4) In a glass reaction vessel equipped with a thermometer, agitator, reflux device, nitrogen inlet tube and dropping device, 113 parts of water, 168 parts (0.07 mol) of ethylene oxide adduct of methallyl alcohol (average number of moles of ethylene oxide added: 53, molecular weight: 2404), and 1.8 parts of ascorbic acid were charged, and the reaction vessel was replaced with nitrogen while stirring. After heating to 40°C under a nitrogen atmosphere, an aqueous monomer solution containing 10.1 parts (0.14 mol) of acrylic acid, 0.2 parts of 3-mercaptopropionic acid and 83 parts of water was continuously dropped into the reaction vessel held at 40°C for 2 hours, and an aqueous solution containing 2.4 parts of 30% hydrogen peroxide dissolved in 47.6 parts of water was continuously dropped into the reaction vessel held at 40°C for 2.5 hours. After the dropping was completed, the mixture was reacted for another hour while maintaining the temperature, and neutralized to pH 4 with sodium hydroxide and water was added at the same time to obtain an aqueous solution of copolymer 4. The copolymer 4 in the liquid had a weight average molecular weight of 39,700 and Mw / Mn of 1.47 (structural unit (II) / structural unit (I)=2.0).

[0091] (Production Example 5) Into a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen inlet tube, and a dropping device, 127 parts of water, 63.6 parts (0.0265 mol) of an ethylene oxide adduct of methallyl alcohol (average number of moles of ethylene oxide added: 53, molecular weight: 2404), and 0.7 parts of 30% hydrogen peroxide were charged, and the atmosphere in the reaction vessel was replaced with nitrogen while stirring. After heating to 40°C under a nitrogen atmosphere, a monomer aqueous solution containing 13.4 parts (0.186 mol) of acrylic acid, 0.6 parts of 3-mercaptopropionic acid, and 192 parts of water was stirred for 2 hours, and an aqueous solution containing 0.6 parts of sodium hydroxymethanesulfonate dissolved in 24.4 parts of water was stirred for 2 hours. Over a period of 2.5 hours, the mixture was continuously added dropwise to a reaction vessel maintained at 40°C. After completion of the addition, the mixture was allowed to react for an additional hour while maintaining the temperature, and was then neutralized to pH 6 with sodium hydroxide and water was added at the same time to obtain an aqueous solution of copolymer 5. The copolymer 5 in the solution had a weight average molecular weight of 24,100 and Mw / Mn of 1.98 (structural unit (II) / structural unit (I)=7.0).

[0092] (Production Example 6) 291 parts of water was charged into a stainless steel reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen inlet tube and a dropping device, and the reaction vessel was replaced with nitrogen under stirring. After heating to 100°C under a nitrogen atmosphere, an aqueous monomer solution containing 61 parts (0.034 mol) of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added: 18, molecular weight: 892), 2.0 parts (0.03 mol), 7.37 parts (0.086 mol) of methacrylic acid (molecular weight: 86), and 50 parts of water was continuously dropped into the reaction vessel held at 100°C for 2 hours, and an aqueous solution in which 0.9 parts of sodium persulfate were dissolved in 49.1 parts of water was continuously dropped into the reaction vessel held at 100°C over 2.5 hours. The polymerization reaction was carried out for 1 hour while the temperature was held at 100°C. After that, the mixture was cooled to 70°C in an additional device located at the rear of the reaction vessel, neutralized to pH 4 with sodium hydroxide, and water was added at the same time to obtain an aqueous solution of copolymer 6. The copolymer 6 in the liquid had a weight average molecular weight of 14,800 and Mw / Mn of 1.49 (structural unit (II) / structural unit (I)=3.4).

[0093] (Examples 1 to 5, Comparative Example 1) <Water surface spreading test> A plastic container measuring 10 cm in length and 40 cm in width was filled with distilled water with a hardness of 0.4, and 0.2 g of calcium stearate powder was floated on the water surface of the plastic container as a lump. Then, copolymers 1 to 6 each diluted to 0.1 wt% were added to the water surface from the edge of the plastic container, and the diffusion capacity (cm) and stopping time (sec) of the calcium stearate powder on the water surface were measured. The results are shown in Table 1.

[0094] <Surface tension> Measurements were made by the plate method (vertical plate method, Wilhelmy method). A platinum plate was hung using a Kyowa CBVP surface tensiometer CBVP-A3 (Kyowa Interface Science Co., Ltd.), and the agricultural chemical additives of Production Examples 1 to 6 were prepared into 10% aqueous solutions. The liquid bath was raised and brought into contact with the platinum plate, and the force (dyn / cm) with which the platinum plate was pulled by the liquid bath was measured. The results are shown in Table 1.

[0095] <Foaming property> The copolymers obtained in Production Examples 1 to 6 were adjusted to 1% aqueous solutions, and 20 mL of each was measured in a 100 mL graduated cylinder. Then, the graduated cylinder was covered with a lid, shaken manually 20 times, and then left to stand horizontally. The amount (mL) of the foam layer that was generated without delay was read and measured using the graduated cylinder. The results are shown in Table 1.

[0096] [Table 1]

[0097] (Examples 6 to 10, Comparative Example 2) <Water surface spread test of granular pesticides> Granular agricultural chemicals were prepared by adding 82 parts of calcium carbonate, 15 parts of bentonite, and 50 parts of any of copolymers 1 to 6 adjusted to 6 wt% and kneading the mixture uniformly. After cutting into pieces with a diameter of 3 mm and a length of 5 mm, the pieces were dried at 105°C for 30 minutes and then at 50°C overnight to obtain granular agricultural chemicals 1 to 6 containing each copolymer. Each of granular chemicals 1 to 6 was gently placed on the edge of a plastic container, and the diffusion capacity (cm) of calcium stearate powder on the water surface for 10 minutes was measured in the same manner. The results are shown in Table 2.

[0098] [Table 2]

Claims

1. A structural unit (I) derived from a monomer represented by the following general formula (1) and a structural unit (I) derived from a monomer represented by the following general formula (2): The present invention relates to a copolymer having an average weight molecular weight of 15,000 to 150,000, and a structural unit (II) derived from a monomer represented by the following general formula (1), wherein the structural unit (II) is contained in an amount of 1 to 6 mol per 1 mol of the structural unit (I), and the average weight molecular weight is 15,000 to 150,000, and the average added mole number n of the A 1 O group in the following general formula (1) is 40 to 80. 【Chemistry 1】 (In the formula, R 1 , R 2 and R 3 Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. p represents an integer of 0 to 2, and q represents an integer of 0 to 1. A 1 O are the same or different and represent an oxyalkylene group having 2 to 18 carbon atoms. R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. 【Chemistry 2】 (In the formula, R 5 , R 6 , and R 7 each independently represents a hydrogen atom, -CH 3 Or - (CH 2 ) r COOM 2 represents -CH 3 Or - (CH 2 ) r COOM 2 Each other -COOM 1 Or - (CH 2 ) r COOM 2 When an anhydride is formed, the M 1 , M. 2 does not exist. 1 and M. 2 are the same or different and represent a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a substituted alkylammonium group; and r represents an integer of 0 to 2.

2. The agricultural chemical water surface spreader according to claim 1, characterized in that the copolymer further contains a structural unit (III) derived from a monomer represented by the following general formula (3). 【Chemistry 3】 (In the formula, R 8 , R 9 and R 10 R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 11 represents a hydrocarbon group having 1 to 4 carbon atoms which may contain a heteroatom; and s represents an integer of 0 to 2.

3. 3. An agricultural chemical composition comprising the agricultural chemical water surface spreader according to claim 1.

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