JP2006056784A - Stabilized water-based herbicide composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition which is a water-based herbicide composition containing sodium salt of N-phosphonomethylglycine and sodium salt of 2,2,3,3-tetrafluoropropionic acid in a herbicidally effective mixing ratio and which does not undergo crystal deposition even at low temperatures to thereby show excellent stability during production and storage. <P>SOLUTION: The water-based herbicide composition comprises sodium salt of N-phosphonomethylglycine as a first component, sodium salt of 2,2,3,3-tetrafluoropropionic acid as a second component, and an organic base and has a pH of 6.5 to 7.5. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is a novel, storage-stable, aimed at controlling various broad-leaved weeds, gramineous weeds, camellia weeds, and cyperaceae weeds, among others reeds, pampas grasses, ogis, and scorpions. The present invention relates to an aqueous herbicide composition having excellent properties.

  Currently, many herbicides are used for cultivated land or non-agricultural land, but weeds to be controlled have many types and long-term occurrence, so they have a higher herbicidal effect and have a broad herbicidal spectrum. Development of herbicides is desired. Perennial highly harmful weeds such as reeds, Japanese pampas grass, sasa and hamasges flourish especially on non-agricultural lands and watersides such as riverbeds, waterways, road edges, and dispatched areas. Pest control. However, since these mechanical controls are hard work and always involve the risk of injury, there is a need for a drug that can suppress the generation and growth of these highly harmful weeds for a long period of time.

Among these weeds, the formula to control weeds such as reed, hamasuge, Japanese pampas grass, Sasa, Japanese pampas grass:

2,2,3,3-tetrafluoropropionic acid or its sodium salt (tetrapion) is used as a herbicide for Japanese pampas grass and sasa in non-agricultural land and forest land, and when treated before germination to early germination, It is known that its generation and growth can be suppressed over time (Non-Patent Document 1). However, the amount of the drug to be dropped is quite large, and the required active ingredient per 10 ares may be 1 kg. From the viewpoint of environmental considerations and labor reduction, the dosage should be reduced by combining with other drugs. Is desired.

Meanwhile, the formula:

Is also used for weeding various annual and perennial weeds in non-agricultural lands or cultivated lands before plowing or before planting (Non-patent Document 2). .

  Patent Document 1 discloses a herbicide composition containing glyphosate or a salt thereof and 2,2,3,3-tetrafluoropropionic acid or a salt thereof as an active ingredient on agricultural land and non-agricultural land, particularly non-agricultural land. Controls a wide range of weeds such as broad-leaved weeds, gramineous weeds, camellia weeds, cyperaceae weeds, and in particular repels reeds, pampas grasses, ogis or scorpions, and their herbicidal effects are effective. It is described that it increases synergistically compared to when the components are used alone.

  On the other hand, Non-Patent Document 3 shows that a composition of isopropylamine salt of glyphosate and tetrapion does not show a synergistic herbicidal action but a additive herbicidal action against a specific grass weed, Coolatai grass. Are listed. However, in this document, there is no description of herbicidal action against weeds other than Coolatai grass, and there is no description of glyphosate other than isopropylamine salt or a composition containing a salt thereof.

  These 2,2,3,3-tetrafluoropropionic acid and glyphosate are inferior in terms of long-term storage stability when not in the form of a salt, and the glyphosate does not necessarily exhibit a good effect when it is not a salt. For these reasons, when these ingredients are used in combination as an herbicidal composition, an aqueous preparation containing both ingredients in a salt form at a sufficient concentration that can satisfy herbicidal activity is used. It was also considered to be suitable in terms of preparation, storage stability, and biological effects.

However, glyphosate is a tribasic acid and takes 5 different dissociation forms depending on the pH and forms mono-, di- or tribasic salts, so glyphosate is also a water-dissociable compound 2,2, In the case of an aqueous mixed preparation formulated with 3,3-tetrafluoropropionic acid, an appropriate salt and the pH of the preparation are adjusted so that both components can be dissolved in water and exhibit herbicidal activity. There was a need to choose. However, when 2,2,3,3-tetrafluoropropionic acid sodium salt and glyphosate isopropylamine or ammonium salt are blended, isopropylamine or ammonia is liberated. Further, when a sodium salt of glyphosate and a sodium salt of 2,2,3,3-tetrafluoropropionic acid are blended, there is a problem that crystals of glyphosate sodium salt are precipitated depending on pH.
JP 2000-247817 A The Pesticide Manual, 11th edition, pages 585-586 (1997) The Pesticide Manual, 11th edition, pages 646-649 (1997) Australian Journal of Experimental Agriculture 34, 479-485 (1994)

  Therefore, an aqueous herbicidal composition comprising the above-mentioned salts of both components in a blending ratio capable of exhibiting herbicidal effects, which does not cause crystal precipitation even at low temperatures and has excellent stability during production and storage. Development was required. As a result of intensive studies to develop such a herbicide composition, the present inventors have found that an aqueous herbicide composition containing glyphosate sodium salt and 2,2,3,3-tetrafluoropropionic acid sodium salt It has been found that by adding a specific organic base to a product, the pH of the composition is adjusted to 6.5 to 7.5, whereby a composition having excellent stability during production and storage can be obtained. The present invention has been completed.

  The present invention provides the first component as a formula:

で表されるＮ−ホスホノメチルグリシンのナトリウム塩；

A sodium salt of N-phosphonomethylglycine represented by:

As the second component, the formula:

A sodium salt of 2,2,3,3-tetrafluoropropionic acid represented by: and an organic base;
And an aqueous herbicidal composition characterized in that the pH of the composition is 6.5 to 7.5.

  The present invention also provides a method for producing the above aqueous herbicide composition, comprising preparing an aqueous mixture containing N-phosphonomethylglycine and 2,2,3,3-tetrafluoropropionic acid, and adding sodium hydroxide. The present invention relates to a method characterized in that both components are converted to sodium salts by addition, and then the pH of the resulting aqueous herbicidal composition is adjusted to 6.5 to 7.5 by adding an organic base.

  The present invention also provides a method for producing the above aqueous herbicidal composition, comprising an aqueous solution of a sodium salt of N-phosphonomethylglycine and an aqueous solution of a sodium salt of 2,2,3,3-tetrafluoropropionic acid. And then adding an organic base to adjust the pH of the resulting aqueous herbicidal composition to 6.5-7.5.

  Furthermore, the present invention relates to a method for weeding reeds, Susuki, Ogi or Sasa, characterized by spraying the above-mentioned aqueous herbicidal composition.

  The aqueous herbicidal composition of the present invention contains a sodium salt of N-phosphonomethylglycine and a sodium salt of 2,2,3,3-tetrafluoropropionic acid in a blending ratio capable of showing a herbicidal effect, It does not cause crystal precipitation even at low temperatures and has excellent stability during production and storage. Specifically, the aqueous herbicidal composition of the present invention does not show crystal precipitation at the time of production, and even after the composition is subdivided into bottles after production, the crystal precipitation is within the range of -15 to 50 ° C. No two-layer separation or turbidity occurs. Moreover, even if crystal precipitation or freezing occurs under extremely cold conditions such as −15 ° C., when the temperature is returned to a normal room temperature (that is, the temperature at which the aqueous herbicidal composition can be used), these phenomena are quickly observed. Disappears.

  The aqueous herbicidal composition of the present invention comprises, as a first component, a sodium salt of N-phosphonomethylglycine; as a second component, a sodium salt of 2,2,3,3-tetrafluoropropionic acid; and an organic base. And the pH of the composition is about 6.5 to 7.5, preferably about 6.5 to 7.0.

  A 1st component and a 2nd component can be mix | blended in arbitrary ratios as needed. The amount of the first component is preferably about 5 to 20 parts by mass in 100 parts by mass of the composition, and particularly preferably about 10 to 20 parts by mass in 100 parts by mass of the composition. The amount of the second component is preferably about 10 to 25 parts by mass in 100 parts by mass of the composition, and particularly preferably about 15 to 25 parts by mass in 100 parts by mass of the composition.

  The organic base blended in the aqueous herbicidal composition of the present invention is added to adjust the pH of the present composition to ensure the stability during production and the stability during storage. Such an organic base is not particularly limited as long as it has a nitrogen atom in its molecular structure, is not volatile under natural conditions, or has a high boiling point of 100 ° C. or higher. Can be used. Among them, piperazine, piperidine, benzylamine, monoethanolamine, diethanolamine, triethanolamine and the like can be mentioned, and in particular, an organic base selected from monoethanolamine, diethanolamine, or triethanolamine can be preferably used.

  The blending amount of the organic base can be determined in the range where the pH of the herbicidal composition finally obtained is about 6.5 to 7.5, preferably about 6.5 to 7.0. However, it should not be added in such an amount that the sodium salt of the active ingredient in the aqueous herbicidal composition according to the present invention is completely replaced by the additional base.

  In addition to the above-described components, a surfactant may be added to the aqueous herbicidal composition of the present invention as necessary in order to maximize the herbicidal effect.

  As such a surfactant, any surfactant can be used as long as it is a surfactant that is usually used for wet spreading of agrochemical formulations. Common anionic surfactants, nonionic surfactants, Various surfactants such as a cationic surfactant or an amphoteric surfactant can be used. Examples of the anionic surfactant include alkyl phosphate ester salt, alkyl sulfate ester salt, polyoxyalkylene alkyl ether phosphate ester salt, polyoxyethylene alkyl ether sulfate ester salt, alkylaryl phosphate ester salt, alkylaryl sulfate ester salt , Polyoxyalkylene alkylaryl ether phosphate ester salt, polyoxyalkylene alkylaryl ether sulfate ester salt, alkylphenol phosphate salt, alkylphenol phosphate ester salt, alkylphenol sulfate salt, alkylphenol sulfate ester salt, polyoxyalkylene alkylphenol phosphate salt, Polyoxyalkylene alkylphenol phosphate ester salt, polyoxyalkylene alkylphenol sulfate, polyoxyalkylene Rulylphenol sulfate, styrylphenol phosphate, styrylphenol phosphate, styrylphenol sulfate, styrylphenol sulfate, polyoxyalkylene styrylphenol phosphate, polyoxyalkylene styrylphenol phosphate, poly Oxyalkylene styrylphenol sulfate, polyoxyalkylene styryl phenol sulfate, distyrylphenol phosphate, distyrylphenol phosphate, distyrylphenol sulfate, distyrylphenol sulfate, polyoxyalkylene distyrylphenol Phosphate, polyoxyalkylene distyrylphenol phosphate ester salt, polyoxyalkylene distyrylphenol sulfate, polyoxyalkyl Distyrylphenol sulfate, tristyrylphenol phosphate, tristyrylphenol phosphate, tristyrylphenol sulfate, tristyrylphenol sulfate, polyoxyalkylene tristyrylphenol phosphate, polyoxyalkylene tristyryl Phenol phosphate salt, polyoxyalkylene tristyryl phenol sulfate, polyoxyalkylene tristyryl phenol sulfate salt, alkyl succinate sulfonate, dialkyl succinate sulfonate or polyoxyalkylene dialkyl succinate sulfonate Can be used. As the cationic surfactant, an aliphatic tertiary amine or a salt thereof, an aliphatic tertiary amine, an aliphatic amine alkylene oxide adduct or a salt thereof, an aliphatic quaternary amine salt, or the like can be used. Nonionic surfactants include aliphatic alcohol alkylene oxide adducts, polyalkyleneoxy fatty acid esters, sorbitan surfactants or their alkylene oxide adducts, polyglycerin fatty acid esters, alkyl polysaccharide surfactants, and sucrose glyceride. Polyoxyalkylene alkyl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl aryl ether, polyoxyalkylene alkyl phenol ether, polyoxyalkylene styryl phenol ether, polyoxyalkylene distyryl phenol ether, polyoxyalkylene tristyryl phenol ether, etc. Can be used. In addition, as the amphoteric surfactant, alkyldimethylbetaine, alkylaminopropionate, or the like can be used. The compounding quantity of these surfactants can be suitably determined according to the kind.

  In addition to the above components, the aqueous herbicidal composition of the present invention may further contain stabilizers, auxiliaries, and the like that improve storage stability. As such a stabilizer, piperazine, piperidine, benzylamine, monoethanolamine, diethanolamine, or triethanolamine can be used. The amount can be appropriately determined according to the type of stabilizer.

The aqueous herbicide composition of the present invention may further contain other herbicides or insecticides, acaricides, nematicides, fungicides, plant growth regulators, and the like.
The aqueous herbicidal composition of the present invention comprises the above components in an aqueous solvent. As such an aqueous solvent, water or a water-miscible polar solvent can be used. As the water-miscible polar solvent, alcohol solvents, glycol ether solvents, and mixtures thereof can be used. Specific examples of such water-miscible polar solvents include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin; methanol, ethanol, propanol, isopropanol, butanol, isobutanol, hexanol, Monohydric alcohols such as cyclohexanol, octanol, 3-methyl-3-methoxybutanol; methyl glycol, methyl diglycol, methyl triglycol, methyl polyglycol, isopropyl glycol, butyl glycol, butyl diglycol, butyl triglycol , Isobutyl glycol, isobutyl diglycol, hexyl glycol, hexyl diglycol, 2-ethylhexyl glycol, 2-ethylhexyl diglycol, Lyl glycol, phenyl glycol, benzyl glycol, benzyl diglycol, methyl propylene glycol, methyl propylene diglycol, methyl propylene triglycol, propyl propylene glycol, propyl propylene diglycol, butyl propylene glycol, butyl propylene diglycol, phenyl propylene glycol, methyl Examples include glycol ethers such as propylene glycol acetate, dimethyl glycol, dimethyl diglycol, dimethyl triglycol, diethyl diglycol, dibutyl diglycol, and dimethylpropylene diglycol. However, it is preferable to use only water.

  The aqueous herbicidal composition of the present invention is prepared by preparing an aqueous mixture containing N-phosphonomethylglycine and 2,2,3,3-tetrafluoropropionic acid, and adding both sodium hydroxide to add sodium hydroxide. It can be prepared by adjusting the pH of the resulting aqueous herbicidal composition to about 6.5-7.5 by salting and then adding an organic base. The amount of sodium hydroxide in which both components are sodium salts is sodium hydroxide in an amount of about 1.1 mol per mol of the component. Specifically, a predetermined amount of a solvent such as water is added to each component to form a slurry, and then a predetermined amount of sodium hydroxide is added to form a sodium salt. The pH is adjusted to about 6.5 to 7.5 by adding an agent and the like, then adding an appropriate amount of organic base, and further adding an appropriate amount of solvent to a predetermined amount.

  Alternatively, the aqueous herbicidal composition of the present invention comprises mixing an aqueous solution of a sodium salt of N-phosphonomethylglycine and an aqueous solution of a sodium salt of 2,2,3,3-tetrafluoropropionic acid, and then an organic base. Can also be prepared by adjusting the pH of the resulting aqueous herbicidal composition to about 6.5-7.5.

  Alternatively, a sodium salt of the other component may be added after forming a sodium salt with sodium hydroxide using only the free acid of one component.

  Even when the aqueous herbicidal composition of the present invention produced using this production method is produced in a low temperature environment, the active herbicidal composition is used in a preparation tank, a circulation pump, a filtration device or a subdivision facility at the time of production. There is no precipitation of crystals and storage stability is excellent.

  The aqueous herbicidal composition of the present invention can be used as it is or diluted with water or the like, for example, in fallow fields, paddy shores, orchards, pastures, forests or non-agricultural lands.

  The aqueous herbicidal composition of the present invention can be applied, for example, to weeds or their surroundings before or after emergence of weeds.

The aqueous herbicidal composition of the present invention can be used for controlling various weeds. For example, buckwheat, Sanaetade, Rhizogiri, Subicille, Jacobe, Shiroza, Blue-headed dragonfly, Japanese radish, Noharagarashi, Nazuna, Japanese horned fox, American horned fox Broad-leaved weeds such as pearl-bellied grass, red-bellied grass, white-bellied grass, red-bellied grass, red-bellied grass, red-bellied grass, sun-buckthorn , Oats, oats, seiban sorghum, shibamugi, umanochahiki, gyoshiba It can be used and Cyperus Iria, the control of such Cyperaceae weeds such as Cyperus; commelinaceae weeds such as Commelina communis; Miscanthus such, Ogi acids, bamboo grass, Imperata cylindrica, Gramineae weeds such as reeds acids. The aqueous herbicidal composition of the present invention exhibits a remarkable herbicidal effect particularly against grass weeds, especially reeds, Susuki, Ogi and Sasa.
The application amount of the aqueous herbicidal composition of the present invention varies depending on the mixing ratio of active ingredients, formulation form, type of target weeds, weather conditions, etc., but the total active ingredient amount per hectare is usually 100 g to 10 kg. The weight is preferably 200 g to 8 kg. When applying, usually, the predetermined amount is diluted with 100 to 1000 liters of water per hectare. If necessary, an auxiliary agent such as a spreading agent may be added to the water to be diluted. As an auxiliary agent, in addition to the above-mentioned surfactant, polyoxyethylene resin acid and its ester, lignin sulfonate, abieticin Acid salts, dinaphthylmethane disulfonate, paraffin, petroleum oil and the like can be used.
Next, the present invention will be described in more detail with reference to examples and test examples.

Example 1
Under an ambient temperature of 10 to 15 ° C. and in a 10-L stainless steel vat under stirring conditions by a three-one motor, 13.34 parts by mass of glyphosate base (purity 95.0%) with respect to 31.48 parts by mass of water Added to the slurry of glyphosate base, 13.18 parts by mass of 25% liquid caustic soda solution (Kureha Chemical Co., Ltd.) Sodium hydroxide) was gradually added to obtain an aqueous glyphosate sodium solution. The pH of the aqueous glyphosate sodium salt solution at this time was 4.2. Next, 35.14 parts by mass of the Frenoc bulk material (2,2,3,3-tetrafluoropropionic acid sodium salt, tetrapion 60.0% aqueous solution) was added to obtain a mixed solution of glyphosate sodium and tetrapion. Next, 2.0 parts by mass of New Coal TA420 (manufactured by Nippon Emulsifier Co., Ltd., beef tallow amine ethylene oxide 20 mol adduct) was added to this mixed solution, and then monoethanolamine (manufactured by Nippon Shokubai Co., Ltd., purity 99.000). (0% or more) 3.8 parts by mass was added, and water was finally added to 100 parts by mass. The composition was finally applied to Buchner funnel with filter paper no. 2 (manufactured by Advantech), followed by filtration under pre-coated radiolite # 200 to obtain a clear aqueous herbicidal composition containing 14.31 parts by mass of glyphosate sodium and 21.08 parts by mass of tetrapion. The trial production amount of the composition at this time was 6.0 kg, and the stock solution pH of the composition was 6.80. The resulting composition was then subdivided into 10 500 ml single-layer plastic bottles of approximately 500 ml each.

Comparative Example 1
In the same manner as in Example 1, 7.96 parts by mass of glyphosate raw material (purity 95.0%) was added to 31.48 parts by weight of water under the same outside air temperature conditions to obtain a slurry of glyphosate raw material. 25% liquid caustic soda solution (NaOH 25.0% aqueous solution; manufactured by Kureha Chemical Industry Co., Ltd.) 8.29 parts by mass (sodium hydroxide corresponding to 1.1 moles per mole of glyphosate) Was gradually added to obtain an aqueous solution of sodium glyphosate. At this time, the liquid temperature rose to 40 ° C. due to heat generation due to heat of neutralization. The pH of the aqueous glyphosate sodium salt solution at this time was 4.1. Next, 22.17 parts by mass of the Frenoc base material (tetrapion purity 60.0% aqueous solution) was added to obtain a mixed solution of sodium glyphosate and tetrapion. The composition was finally applied to Buchner funnel with filter paper no. 2 (manufactured by Advantech), followed by filtration under pre-coated radiolite # 200 to obtain a clear aqueous herbicidal composition containing 9.0 parts by weight of glyphosate sodium and 13.3 parts by weight of tetrapion. The trial production amount of the composition at this time was 6.0 kg, and the stock solution pH was 4.10. Subsequently, the obtained composition was prepared and subdivided under the same ambient temperature conditions by the same method as in Example 1.

Comparative Example 2
The sample was prepared and subdivided under the same ambient temperature conditions as in Example 1 except that no monoethanolamine was added. Finally, a clear aqueous herbicidal composition was obtained. The stock solution pH of the composition at this time was 4.25.

Comparative Example 3
The mixture was prepared and subdivided under the same ambient temperature conditions as in Example 1 except that 4.3 parts by mass of sodium hydroxide (96.0%, Wako Reagent) was further added instead of monoethanolamine. During the filtration step, crystal precipitation occurred from the filtrate adhering to the wall of the filtrate collection container, but the solution was warmed and redissolved by stirring. Finally, a clear aqueous herbicidal composition was obtained. The stock solution pH of the composition at this time was 7.87.

Comparative Example 4
The mixture was prepared and subdivided under the same ambient temperature conditions as in Example 1 except that 2.61 parts by mass of sodium hydroxide (96.0%, Wako Reagent) was further added instead of monoethanolamine. During the filtration step, crystal precipitation occurred from the filtrate adhering to the wall of the filtrate collection container, but the solution was warmed and redissolved by stirring. Finally, a clear aqueous herbicidal composition was obtained. The stock solution pH of the composition at this time was 6.88.

Comparative Example 5
The mixture was prepared and subdivided under the same ambient temperature conditions as in Example 1 except that 3.2 parts by mass of monoethanolamine was further added. The stock solution pH of the composition at this time was 6.23.

Test Example 1 Presence or absence of crystal precipitation at the time of trial production In all trial production steps of the comparative example (including filtration operation and subdivision operation), the composition in the trial container, the composition after filtration, and the single-layer plastic bottle after subdivision The crystal precipitation of the composition was confirmed by visual observation. The results are shown in Table 1.

Test Example 2 Cooling and cold resistance test Examples and comparative examples (500 ml × 10 pieces) of the composition were capped and left for 7 days in a Nagano thermostat at −5 ° C. and −15 ° C. . The results are shown in Table 2.

Test Example 3 Crystal Precipitate Identification Crystal precipitates generated in Test 1 and Test 2 were washed with a solvent of methanol: water = 50: 50, collected by filtration, and identified by HPLC analysis. The results are shown in Table 3.

なお、全実施例、比較例とも４０℃×９０日による虐待経時試験による両有効成分の分解は認められなかった。

In all Examples and Comparative Examples, no degradation of both active ingredients was observed in the aging test at 40 ° C. for 90 days.

  The herbicidal composition of the present invention has excellent storage stability without glyphosate sodium salt and sodium salt of 2,2,3,3-tetrafluoropropionic acid as active ingredients being crystallized during production and storage. An aqueous herbicidal composition.

Claims (8)

As the first component, the formula:

A sodium salt of N-phosphonomethylglycine represented by:
As the second component, the formula:

A sodium salt of 2,2,3,3-tetrafluoropropionic acid represented by: and an organic base;
And an aqueous herbicidal composition characterized in that the pH of the composition is 6.5 to 7.5.   The sodium salt of N-phosphonomethylglycine as the first component is contained in 5 to 20 parts by mass in 100 parts by mass of the composition, and the sodium salt of 2,2,3,3-tetrafluoropropionic acid as the second component is added. The aqueous herbicidal composition according to claim 1, comprising 10 to 25 parts by mass in 100 parts by mass of the composition.   The aqueous herbicidal composition according to claim 1 or 2, wherein the organic base is selected from monoethanolamine, diethanolamine, or triethanolamine.   The aqueous herbicidal composition according to any one of claims 1 to 3, further comprising a cation, an anion, a nonion, or an amphoteric surfactant.   The aqueous herbicidal composition according to any one of claims 1 to 4, which is used for herbicides of reeds, Susuki, Ogi or Sasa.   A method for producing an aqueous herbicidal composition according to any one of claims 1 to 5, wherein an aqueous mixture containing N-phosphonomethylglycine and 2,2,3,3-tetrafluoropropionic acid is prepared. And adding sodium hydroxide to make both components sodium salts, and then adding an organic base to adjust the pH of the resulting aqueous herbicidal composition to 6.5-7.5. how to.   A method for producing an aqueous herbicidal composition according to any one of claims 1 to 5, comprising an aqueous solution of a sodium salt of N-phosphonomethylglycine and 2,2,3,3-tetrafluoropropionic acid. A method characterized in that the pH of the resulting aqueous herbicidal composition is adjusted to 6.5-7.5 by mixing an aqueous solution of sodium salt and then adding an organic base.   A method for weeding reeds, Susuki, Ogi or Sasa, comprising spraying the aqueous herbicidal composition according to any one of claims 1 to 5.