JP6114643B2 - Agricultural and horticultural compositions - Google Patents

Description

  The present invention relates to an agricultural or horticultural or industrial pharmaceutical composition. More specifically, the present invention relates to a solid or suspension agricultural or horticultural or industrial pharmaceutical composition containing a fat-soluble ascorbic acid derivative as an active ingredient and excellent in storage stability.

  Ascorbic acid and its derivatives are known as one of the substances exhibiting preventive and therapeutic effects against viral diseases of plants (Patent Document 1). However, ascorbic acid and its derivatives have low chemical or physical stability, and are altered by long-term storage or cause particle growth due to dissolution and reprecipitation. Difficult to handle as a formulation. In particular, fat-soluble ascorbic acid derivatives have low solubility in water and many other solvents, making it difficult to make emulsions and EC agents.

WO2011 / 030816 JP 2005-187466 A JP 2007-99670 A JP 2009-249325 A JP-T-2001-513076 JP-A-62-240364 JP-A-8-92008 JP 2000-44403 A JP 2001-342102 A JP 2012-12299 A JP-A-8-63735 JP 2001-214111 A

  By the way, as a composition which tried to improve the storage stability of an ascorbic acid derivative, for example, Patent Document 2 discloses a salt of a higher fatty acid ester of ascorbic acid-2-phosphate, a water-soluble synthetic polymer compound, An external skin preparation containing water is disclosed. Patent Document 3 discloses a skin external preparation containing an ascorbic acid derivative such as ascorbic acid-2-phosphate-6-palmitic acid and edetic acid or a salt thereof. Patent Document 4 discloses a skin external preparation containing a fatty acid ester of L-ascorbic acid-2-phosphate or a salt thereof, a liquid oil having an IOB value of 0.07 to 0.65, a surfactant, and water. doing. Patent document 5 is disclosing the composition for skin treatment containing ascorbic-acid fatty acid ester etc., solvents, such as ethoxydiglycol, and an acetylcholine derivative. All of the compositions disclosed therein are related to a skin external preparation.

  On the other hand, ascorbic acid and its derivatives are sometimes used to improve the storage stability of medical and agrochemical components. For example, Patent Document 6 discloses the use of long-chain fatty acid esters of ascorbic acid to disperse carotenoids in water. Patent Document 7 proposes the use of acids including ascorbic acid and the like to increase the stability and durability of propenazole. U.S. Patent No. 6,057,077 proposes the use of ascorbic acid to inhibit the degradation of imazosulfuron, diimron and pentoxazone. Patent Document 9 proposes the use of ascorbic acid to suppress the degradation of bifenazate. In addition, US Pat. No. 6,057,059 proposes the use of an acidic substance such as ascorbic acid to control the release of active ingredients such as imazosulfuron. These proposals use ascorbic acid derivatives as adjuvants.

  Ascorbic acid and its derivatives are sometimes used in industrial applications. For example, it is used for the purpose of preventing deterioration of industrial products. Patent Document 11 describes an example in which L-ascorbyl palmitate or the like is used as an antioxidant contained in a magnetic recording medium. Patent Document 12 describes an example in which ascorbic acid dipalmitate or the like is added to oil-based ballpoint pen ink to prevent blurring due to deterioration.

  An object of the present invention is to provide a solid or suspension-like agricultural or horticultural or industrial pharmaceutical composition containing a fat-soluble ascorbic acid derivative as an active ingredient and having excellent storage stability.

  As a result of intensive studies to achieve the above object, the present inventors have completed the invention of the following aspect.

[1] A compound (A) that is at least one selected from the group consisting of the compound represented by the formula (A1) or the formula (A2) and a salt thereof and is fat-soluble, and the formula (B1) or the formula (B2 A substance (B) that is at least one selected from the group consisting of compounds represented by the formula (1) and salts thereof and is water-soluble.
A liquid agricultural or horticultural or industrial pharmaceutical composition comprising a solid or suspended substance (A).

［式（A1）中、Ｒ¹〜Ｒ⁴は、それぞれ独立して、水素原子、無置換の若しくは置換基を有するグリコシル基、−ＣＨＯ、−Ｃ（＝Ｏ）Ｒ^a、−ＣＯＯＨ、−ＣＯＯＲ^a、−ＣＯＮＨ₂、−ＣＯＮＨＲ^a、−ＣＯＮＲ^aＲ^b、−ＳＯ₂Ｈ、−ＳＯ₂Ｒ^a、−ＰＯ₃Ｈ₂、−ＰＯ（ＯＨ）ＯＲ^a、−ＳＯ₂ＮＨ₂、−ＳＯ₂ＮＨＲ^a、または−ＳＯ₂ＮＲ^aＲ^bを示す。ただし、Ｒ¹〜Ｒ⁴の少なくとも一つは−Ｃ（＝Ｏ）Ｒ^aである。
Ｒ^aおよびＲ^bは、それぞれ独立して、無置換の若しくは置換基を有するＣ１〜３０アルキル基、無置換の若しくは置換基を有するＣ２〜３０アルケニル基、無置換の若しくは置換基を有するＣ２〜３０アルキニル基、無置換の若しくは置換基を有するＣ３〜２０シクロアルキル基、無置換の若しくは置換基を有するＣ４〜２０シクロアルケニル基、無置換の若しくは置換基を有するＣ８〜２０シクロアルキニル基、無置換の若しくは置換基を有するＣ６〜１０アリール基、または無置換の若しくは置換基を有する５〜１０員ヘテロ環基を示す。］

[In the formula (A1), R ^{1 to} R ⁴ each independently represents a hydrogen atom, an unsubstituted or substituted glycosyl group, —CHO, —C (═O) R ^a , —COOH, —COOR; _{^{a, -CONH 2, -CONHR a,}} -CONR a R b, -SO 2 H, -SO 2 R a, -PO 3 H 2, -PO (OH) OR a, -SO 2 NH 2, -SO 2 NHR ^a or —SO ₂ NR ^a R ^b is shown. Provided that at least one of R ¹ to R ⁴ is -C (= O) R ^a.
R ^a and R ^b are each independently an unsubstituted or substituted C 1-30 alkyl group, an unsubstituted or substituted C 2-30 alkenyl group, an unsubstituted or substituted C 2- 30 alkynyl group, unsubstituted or substituted C3-20 cycloalkyl group, unsubstituted or substituted C4-20 cycloalkenyl group, unsubstituted or substituted C8-20 cycloalkynyl group, none A substituted or substituted C6-10 aryl group, or an unsubstituted or substituted 5-10 membered heterocyclic group is shown. ]

［式（A2）中、Ｒ⁵およびＲ⁶は、それぞれ独立して、水素原子、無置換の若しくは置換基を有するグリコシル基、−ＣＨＯ、−Ｃ（＝Ｏ）Ｒ^c、−ＣＯＯＨ、−ＣＯＯＲ^c、−ＣＯＮＨ₂、−ＣＯＮＨＲ^c、−ＣＯＮＲ^cＲ^d、−ＳＯ₂Ｈ、−ＳＯ₂Ｒ^c、−ＰＯ₃Ｈ₂、−ＰＯ（ＯＨ）ＯＲ^c、−ＳＯ₂ＮＨ₂、−ＳＯ₂ＮＨＲ^c、または−ＳＯ₂ＮＲ^cＲ^dを示す。ただし、Ｒ⁵とＲ⁶の少なくとも一つは−Ｃ（＝Ｏ）Ｒ^cである。
Ｒ^cおよびＲ^dは、それぞれ独立して、無置換の若しくは置換基を有するＣ１〜３０アルキル基、無置換の若しくは置換基を有するＣ２〜３０アルケニル基、無置換の若しくは置換基を有するＣ２〜３０アルキニル基、無置換の若しくは置換基を有するＣ３〜２０シクロアルキル基、無置換の若しくは置換基を有するＣ４〜２０シクロアルケニル基、無置換の若しくは置換基を有するＣ８〜２０シクロアルキニル基、無置換の若しくは置換基を有するＣ６〜１０アリール基、または無置換の若しくは置換基を有する５〜１０員ヘテロ環基を示す。］

[In the formula (A2), R ⁵ and R ⁶ each independently represents a hydrogen atom, an unsubstituted or substituted glycosyl group, —CHO, —C (═O) R ^c , —COOH, —COOR; _{^{c, -CONH 2, -CONHR c,}} -CONR c R d, -SO 2 H, -SO 2 R c, -PO 3 H 2, -PO (OH) OR c, -SO 2 NH 2, -SO 2 NHR ^c or —SO ₂ NR ^c R ^d is shown. However, at least one of R ⁵ and R ⁶ is —C (═O) R ^c .
R ^c and R ^d are each independently an unsubstituted or substituted C1-30 alkyl group, an unsubstituted or substituted C2-30 alkenyl group, an unsubstituted or substituted C2_ 30 alkynyl group, unsubstituted or substituted C3-20 cycloalkyl group, unsubstituted or substituted C4-20 cycloalkenyl group, unsubstituted or substituted C8-20 cycloalkynyl group, none A substituted or substituted C6-10 aryl group, or an unsubstituted or substituted 5-10 membered heterocyclic group is shown. ]

［式（B1）中、Ｒ⁷〜Ｒ¹⁰は、それぞれ独立して、水素原子、−ＳＯ₃Ｈ、−ＰＯ₃Ｈ₂、無置換の若しくは置換基を有するグリコシル基、または−ＣＨＯを示す。］

[In the formula (B1), R ^{7 to} R ¹⁰ each independently represent a hydrogen atom, —SO ₃ H, —PO ₃ H ₂ , an unsubstituted or substituted glycosyl group, or —CHO. ]

［式（B2）中、Ｒ¹¹およびＲ¹²は、それぞれ独立して、水素原子、−ＳＯ₃Ｈ、−ＰＯ₃Ｈ₂、無置換の若しくは置換基を有するグリコシル基、または−ＣＨＯを示す。］
〔２〕 物質（B）が、アスコルビン酸またはその塩を含有するものである、〔１〕に記載の農園芸用または工業用製剤組成物。

[In the formula (B2), R ¹¹ and R ¹² each independently represent a hydrogen atom, —SO ₃ H, —PO ₃ H ₂ , an unsubstituted or substituted glycosyl group, or —CHO. ]
[2] The agricultural or horticultural or industrial preparation composition according to [1], wherein the substance (B) contains ascorbic acid or a salt thereof.

[3] At least one selected from the group consisting of compounds represented by formula (A1) or formula (A2) and salts thereof and a fat-soluble substance (A), and chemical stability of substance (A) Carrier (C) which can be enhanced and is solid at room temperature
A solid agricultural or horticultural or industrial preparation composition comprising
[4] The agriculture according to [3], wherein the carrier (C) contains at least one selected from the group consisting of calcium sulfate, calcium carbonate, ammonium sulfate, potassium sulfate, starch, starch derivatives, and trehalose. Horticultural or industrial formulation composition.
[5] The agricultural or horticultural or industrial solid preparation composition according to [3] or [4], which is a granule wettable powder or granule.

[6] Increasing the solubility of at least one substance (A) selected from the group consisting of the compound represented by the formula (A1) or the formula (A2) and a salt thereof and the fat-soluble substance, and the substance (A) No surfactant (D)
An agricultural or horticultural or industrial pharmaceutical composition containing
[7] The agricultural or horticultural or industrial preparation composition according to [6], wherein the surfactant (D) contains a lignin surfactant.
[8] The agricultural or horticultural or industrial preparation composition according to [7], wherein the lignin surfactant is lignin sulfonate.
[9] The agricultural or horticultural or industrial preparation composition according to [7] or [8], which is a liquid in which the substance (A) is suspended.

[10] a substance (A) that is at least one selected from the group consisting of the compound represented by the formula (A1) or the formula (A2) and a salt thereof and is fat-soluble;
A solid containing the substance (A) comprising mixing a carrier (C) containing at least one selected from the group consisting of calcium sulfate, calcium carbonate, ammonium sulfate, potassium sulfate, starch, starch derivatives, and trehalose Of stabilizing a pharmaceutical composition for agricultural or horticultural use.
[11] A substance (A) which is at least one selected from the group consisting of the compound represented by the formula (A1) or the formula (A2) and a salt thereof and is fat-soluble,
In the presence of a surfactant (D) that does not increase the solubility of the substance (A),
A method for stabilizing a liquid agricultural or horticultural or industrial pharmaceutical composition comprising a substance (A) suspended, comprising suspending in a liquid medium.

  The agricultural or horticultural or industrial pharmaceutical composition of the present invention prevents chemical changes in the fat-soluble ascorbic acid derivative, and does not change in properties even after long-term storage. The solid agricultural or horticultural or industrial preparation composition according to one embodiment of the present invention has almost the same disintegration and dispersibility when added to water as after the production, even after long-term storage. The suspension-like agricultural or horticultural or industrial preparation composition according to one embodiment of the present invention does not show particle growth even during long-term storage, and maintains a suspended state immediately after production. Moreover, the agricultural and horticultural or industrial preparation composition of the present invention has high activity such as virus control and anti-oxidation, as well as the activity immediately after production, even after long-term storage.

  The agricultural or horticultural or industrial preparation composition according to the first embodiment of the present invention is a solid or liquid agricultural or horticultural material containing the substance (A) and the substance (B) and formed by suspending the substance (A). Or industrial pharmaceutical composition.

(Substance (A))
The substance (A) is at least one selected from the group consisting of a compound represented by the formula (A1) or the formula (A2) and a salt thereof, and a fat-soluble substance, preferably represented by the formula (A1) It is at least one selected from the group consisting of a compound or a salt thereof and a fat-soluble substance. Specifically, the fat-soluble substance (A) has an octanol / water partition coefficient (Log Pow) of preferably more than 0, more preferably 1 or more.

In formula (A1), R ^{1 to} R ⁴ each independently represent a hydrogen atom, an unsubstituted or substituted glycosyl group, —CHO, —C (═O) R ^a , —COOH, —COOR ^a , —CONH ₂ , —CONHR ^a , —CONR ^a R ^b , —SO ₂ H, —SO ₂ R ^a , —PO ₃ H ₂ , —PO (OH) OR ^a , —SO ₂ NH ₂ , —SO ₂ NHR ^a , or —SO ₂ NR ^a R ^b ; preferably each independently, a hydrogen atom, an unsubstituted or substituted glycosyl group, —C (═O) R ^a , —SO ₂ H, or —PO ₃ H ₂ is shown. Provided that at least one of R ¹ to R ⁴ is a -C (= O) R ^a

R ^a and R ^b are each independently an unsubstituted or substituted C 1-30 alkyl group, an unsubstituted or substituted C 2-30 alkenyl group, an unsubstituted or substituted C 2- 30 alkynyl group, unsubstituted or substituted C3-20 cycloalkyl group, unsubstituted or substituted C4-20 cycloalkenyl group, unsubstituted or substituted C8-20 cycloalkynyl group, none A substituted or substituted C6-10 aryl group, or an unsubstituted or substituted 5-10 membered heterocyclic group is shown.

In formula (A2), R ⁵ and R ⁶ are each independently a hydrogen atom, an unsubstituted or substituted glycosyl group, —CHO, —C (═O) R ^c , —COOH, —COOR ^c. , —CONH ₂ , —CONHR ^c , —CONR ^c R ^d , —SO ₂ H, —SO ₂ R ^c , —PO ₃ H ₂ , —PO (OH) OR ^c , —SO ₂ NH ₂ , —SO ₂ NHR ^c , or —SO ₂ NR ^c R ^d ; preferably each independently, a hydrogen atom, an unsubstituted or substituted glycosyl group, —C (═O) R ^c , —SO ₂ H, or —PO ₃ H ₂ is shown. However, at least one of R ⁵ and R ⁶ is —C (═O) R ^c .

R ^c and R ^d are each independently an unsubstituted or substituted C1-30 alkyl group, an unsubstituted or substituted C2-30 alkenyl group, an unsubstituted or substituted C2_ 30 alkynyl group, unsubstituted or substituted C3-20 cycloalkyl group, unsubstituted or substituted C4-20 cycloalkenyl group, unsubstituted or substituted C8-20 cycloalkynyl group, none A substituted or substituted C6-10 aryl group, or an unsubstituted or substituted 5-10 membered heterocyclic group is shown.
The compounds represented by the formula (A1) or the formula (A2) include those isomers.

In the present specification, the term “unsubstituted” means that the group is only a group serving as a mother nucleus. In addition, when there is no description of “having a substituent” and only the name of the group serving as a mother nucleus is described, it means “unsubstituted” unless otherwise specified.
On the other hand, the term “having a substituent” means that any hydrogen atom of a group serving as a mother nucleus is substituted with a group having a structure different from or the same as that of the mother nucleus. Therefore, the “substituent” is another group substituted with a group serving as a mother nucleus. The number of substituents may be one, or two or more. Two or more substituents may be the same or different. For example, in a C1-30 alkyl group having a substituent, a group serving as a mother nucleus is a C1-30 alkyl group, and any one of these hydrogen atoms is substituted with a group having a different structure ("substituent") It is.

  The glycosyl group is a sugar residue such as a monosaccharide or a low molecular weight oligosaccharide (specifically, a partial structure of a molecule in which the hemiacetal hydroxy group of the sugar moiety is removed to form a binding position). Examples of monosaccharides include glucose, galactose, fructose, rhamnose and the like. Examples of oligosaccharides include rutinose, vicyanose, lactose, maltose, sucrose and the like. Accordingly, the glycosyl group includes, for example, a glucosyl group, a galactosyl group, a fructosyl group, a rhamnosyl group, and the like. The glycosyl group also includes a group in which any combination of these groups is bonded by a 1 → 2 bond, a 1 → 3 bond, a 1 → 4 bond, or a 1 → 6 bond to form a disaccharide.

  As C1-30 alkyl group, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, i-propyl group, i -Butyl group, s-butyl group, t-butyl group, i-pentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, i-hexyl group, heptyl group, octyl, nonyl group, decyl group , Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, triacontyl group and the like.

  C2-30 alkenyl groups include vinyl, 1-propenyl, isopropenyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3- Pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-heptenyl group, 6-heptenyl group, 1-octenyl group, 7- Octenyl group, 1-methyl-allyl group, 2-methyl-allyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, etc. Is mentioned.

  Examples of the C2-30 alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group, 2-methyl-3 -Butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-2-butynyl group, 2-methyl-3-pentynyl group, 1-hexynyl group, 1,1 -A dimethyl- 2-butynyl group etc. are mentioned.

  Examples of the C3-20 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

  Examples of the C4-20 cycloalkenyl group include a 2-cyclopentenyl group, a 3-cyclohexenyl group, and a 4-cyclooctenyl group.

  Examples of the C8-20 cycloalkynyl group include a cyclooctynyl group, a cyclononyl group, and a cyclodecynyl group.

  Examples of the C6-10 aryl group include a phenyl group and a naphthyl group.

The 5- to 10-membered heterocyclic group contains 1 to 4 heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom as atoms constituting the ring. The heterocyclic group may be a heteroaryl group such as a 5-membered heteroaryl group or a 6-membered heteroaryl group, or a saturated heterocyclic group. The heterocyclic group may be a monocyclic group or a polycyclic group.
Examples of the 5-membered heteroaryl group include pyrrolyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, etc. .
Examples of the 6-membered heteroaryl group include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, and a triazinyl group.
Examples of the condensed heteroaryl group include indolyl group, benzofuranyl group, benzothiophenyl group, benzimidazolyl group, benzoxazolyl group, benzothiazolyl group, quinolinyl group and the like.
Examples of other heterocyclic groups include aziridinyl group, epoxy group, pyrrolidinyl group, tetrahydrofuranyl group, piperidinyl group, piperazinyl group, morpholinyl group and the like.

  Glycosyl group, C1-30 alkyl group, C2-30 alkenyl group, C2-30 alkynyl group, C3-20 cycloalkyl group, C4-20 cycloalkenyl group, C8-20 cycloalkynyl group, C6-10 aryl group, or 5 Examples of a group that can be a “substituent” of a 10-membered heterocyclic group include hydroxyl group, mercapto group, amino group, nitro group, halogen atom such as chlorine atom, fluorine atom, bromine atom, methoxy group, ethoxy group, isopropoxy Group, n-propoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group and other alkoxy groups; phenoxy group, 1-naphthyloxy group and other aryloxy groups; fluoromethoxy group, difluoromethoxy group , Trifluoromethoxy group, 2-chloroethoxy group, 2,2,2-trichloroethoxy group Haloalkoxy groups such as methylthio groups, alkylthio groups such as ethylthio groups; arylthio groups such as phenylthio groups and 1-naphthylthio groups; alkylamino groups such as methylamino groups and diethylamino groups; anilino groups and 1-naphthylamino groups Arylamino group; cyano group; and the like.

Of the above, R ^a , R ^b , R ^c and R ^d are preferably an unsubstituted or substituted C12-30 alkyl group or an unsubstituted or substituted C12-30 alkenyl group.
Examples of the “C12-30 alkyl group” include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, 1-heptyldecyl group, 1-hexylnonyl group, An 11-methyldodecyl group, a 13-methyltetradecyl group, etc. are mentioned. Examples of the “C12-30 alkyl group having a substituent” include a 2-hydroxytridecyl group, a 1-hydroxypentadecyl group, an 11-hydroxyheptadecyl group, and a 1-aminoheptadecyl group.

  Examples of the “C12-30 alkenyl group” include dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group and the like. Examples of the “substituted C12-30 alkenyl group” include 7-hydroxy-8-pentadecenyl group, 1-hydroxy-8-peptadecenyl group, 1-amino-8-heptadecenyl group and the like.

  The salt of the compound represented by the formula (A1) or the formula (A2) is not limited as long as it is a salt formed from the compound and a metal or a cationic compound. Specifically, alkali metal salts such as sodium salt, potassium salt and lithium salt; alkaline earth metal salts such as calcium salt and magnesium salt; other metal salts such as copper salt, iron salt and zinc salt; ammonium salt and amine Salt, quaternary ammonium salt, ethanolamine salt and the like.

  Specific examples of the substance (A) include ascorbic acid-6-myristate, ascorbic acid-6-palmitate, ascorbic acid-6-stearate, ascorbic acid-2-myristate, ascorbic acid-2- Palmitate, Ascorbic acid-2-isopalmitate, Ascorbic acid-2-stearate, Ascorbic acid-2-isostearate, Ascorbic acid-2-isomyristate, Ascorbic acid-2,6-Dimyristate, Ascorbic acid-2,6 -Dipalmitate, ascorbic acid-2,6-diisopalmitate, ascorbic acid-2,6-distearate, ascorbic acid-2,3,5,6-tetrahexyl decanoate and the like.

  In the agricultural or horticultural or industrial pharmaceutical composition according to the first embodiment of the present invention, one substance (A) may be used alone or in combination of two or more substances (A).

(Substance (B))
The substance (B) is at least one selected from the group consisting of the compound represented by the formula (B1) or the formula (B2) and a salt thereof, and is a water-soluble substance, preferably ascorbic acid or a salt thereof. .
In formula (B1), R ^{7 to} R ¹⁰ each independently represent a hydrogen atom, —SO ₃ H, —PO ₃ H ₂ , an unsubstituted or substituted glycosyl group, or —CHO.
In the formula (B2), R ¹¹ and R ¹² each independently represent a hydrogen atom, —SO ₃ H, —PO ₃ H ₂ , an unsubstituted or substituted glycosyl group, or —CHO.
The unsubstituted or substituted glycosyl group is the same as that described in the explanation relating to the substance (A).
The compounds represented by the formula (B1) or the formula (B2) include those isomers.

  The salt of the compound represented by the formula (B1) or the formula (B2) is not limited as long as it is a salt formed from the compound and a metal or a cationic compound, and is described in the explanation relating to the substance (A) And the same salts.

  Specific examples of the substance (B) include ascorbic acid, ascorbic acid-2-phosphate ester, ascorbic acid-3-phosphate ester, ascorbic acid-2-sulfate ester, ascorbic acid-3-sulfate ester and the salt thereof. Ascorbic acid-2-glucoside; erythorbic acid or a salt thereof; Among these, ascorbic acid or a sodium salt, potassium salt, magnesium salt or calcium salt thereof is preferable, and ascorbic acid is more preferable.

  The content of the substance (B) in the agricultural / horticultural or industrial preparation composition according to the first embodiment of the present invention is preferably 0.001 to 1000 parts by mass, preferably 1 part by mass of the substance (A). Is 0.1 to 10 parts by mass, more preferably 0.5 to 2 parts by mass.

The agricultural or horticultural or industrial preparation composition according to the first embodiment of the present invention is in a solid form or a suspension form.
The solid agricultural or horticultural or industrial preparation composition according to the first embodiment of the present invention is in the form of powder, granules, lumps or the like. Formulation forms for agricultural chemicals include powders, wettable powders, granular wettable powders, granules, tablets and the like. The preparation form of the solid agricultural or horticultural or industrial preparation composition as an agrochemical is preferably a wettable powder, a granular wettable powder or a granule, and more preferably a granular wettable powder or a granule. The content of the substance (A) in the solid agricultural or horticultural or industrial preparation composition according to the first embodiment of the present invention is preferably 1 to 80% by mass, more preferably 1 to 50% by mass. The content of the substance (B) is preferably 1 to 80% by mass, more preferably 1 to 50% by mass.

  The suspension-like agricultural / horticultural or industrial preparation composition according to the first embodiment of the present invention is formed by suspending the substance (A) in a liquid medium. Examples of formulation forms for agricultural chemicals include suspensions and flowables. Water is preferably used as the liquid medium. In the suspension-like agricultural or horticultural or industrial preparation composition according to the first embodiment of the present invention, the content of the substance (A) is preferably 1 to 80% by mass, more preferably 1 to 50% by mass. The content of the substance (B) is preferably 0.1 to 50% by mass, more preferably 1 to 50% by mass, and the water content is preferably 10 to 98.9% by mass, more preferably Is 20-98 mass%.

  The agricultural or horticultural or industrial preparation composition according to the second embodiment of the present invention is a solid agricultural or horticultural or industrial preparation composition containing a substance (A) and a carrier (C). The substance (A) is the same as that described in the description of the first embodiment.

(Carrier (C))
The carrier (C) is not particularly limited as long as it can enhance the chemical stability of the substance (A) and is solid at room temperature.
Even if the carrier alone cannot enhance the chemical stability of the substance (A) or is not solid at room temperature, the chemical stability of the substance (A) can be improved by using it in combination with other carriers. The combination of the carriers can be used as the carrier (C) in the present invention as long as it can be increased and is solid at room temperature.

  Examples of solid carriers (C) that can be combined include clay, bentonite, talc, dikelite, kaolin, montmorillonite, mica, sericite, acid clay, silica, silt, diatomaceous earth, pumice, zeolite, vermiculite, perlite, Water-insoluble solid carriers such as silica, zinc oxide, titanium dioxide or poorly water-soluble solid carriers; water-soluble salts such as potassium chloride, potassium carbonate, sodium carbonate, sodium sulfate, potassium phosphate, ammonium chloride, monosodium phosphate, magnesium sulfate Water-soluble solid carriers such as: polysaccharides such as cellulose (excluding starch, starch derivatives and trehalose); oligosaccharides such as glucose, maltose, sucrose and lactose; sugar alcohols such as mannitol and xylitol; urea; The

The carrier (C) suitably used in the present invention contains at least one selected from the group consisting of calcium sulfate, calcium carbonate, ammonium sulfate, potassium sulfate, starch, starch derivatives, and trehalose.
Examples of the starch include raw starch such as corn starch, tapioca starch, and potato starch, pregelatinized starch, and the like.
Examples of the starch derivative include carboxymethyl starch, methyl hydroxypropyl starch, phosphate starch, oxidized starch and the like.
Of these, calcium sulfate, calcium carbonate, ammonium sulfate, potassium sulfate, starch, and trehalose are particularly preferred.

  The content of the carrier (C) in the agricultural or horticultural or industrial preparation composition according to the second embodiment of the present invention is preferably 0.01 to 100 parts by mass with respect to 1 part by mass of the substance (A). Preferably it is 0.1-50 mass parts.

  The agricultural or horticultural or industrial preparation composition according to the second embodiment of the present invention is solid. The solid agricultural or horticultural or industrial preparation composition is in the form of powder, granules, lumps or the like. Formulation forms for agricultural chemicals include powders, wettable powders, granular wettable powders, granules, tablets and the like. The preparation form of the solid agricultural or horticultural or industrial preparation composition as an agrochemical is preferably a wettable powder, a granular wettable powder or a granule, and more preferably a granular wettable powder or a granule. The content of the substance (A) in the solid agricultural or horticultural or industrial preparation composition according to the second embodiment of the present invention is preferably 1 to 80% by mass, more preferably 1 to 50% by mass. The content of the carrier (C) is preferably 1 to 99% by mass, more preferably 5 to 80% by mass, and particularly preferably 20 to 60% by mass.

  The agricultural or horticultural or industrial preparation composition according to the third embodiment of the present invention is an agricultural or horticultural or industrial preparation composition containing a substance (A) and a surfactant (D). The substance (A) is the same as that described in the description of the first embodiment.

(Surfactant (D))
The surfactant (D) is not particularly limited as long as it is a surfactant that does not increase the solubility of the substance (A). In the surfactant (D), the solubility of the substance (A) in the liquid medium to which the surfactant (D) is added is equal to the solubility of the substance (A) in the liquid medium to which the surfactant (D) is not added. Equal or lower. The method for measuring the solubility is not particularly limited. The liquid medium used for the measurement of solubility is diluted when applying the liquid medium used for the liquid agricultural or horticultural or industrial preparation composition of the present invention or the solid agricultural or horticultural or industrial preparation composition of the present invention. It is a liquid medium used for suspension, emulsification and the like. Examples of the liquid medium include water and an organic solvent described later. The temperature of the liquid medium at the time of measurement is usually 20 to 80 ° C. The concentration of the surfactant (b3) at the time of measurement is usually 2 to 10% by mass.

In addition, even if the surfactant alone increases the solubility of the substance (A), the surfactant may be used as long as it does not increase the solubility of the substance (A) by using in combination with another surfactant. These combinations can be used as the surfactant (D) in the present invention.
Surfactants (D) that can be combined to form polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkylate, polyoxyethylene Nonionic surfactants such as ethylene phenyl ether polymer, polyoxyethylene alkylene aryl phenyl ether, polyoxyethylene alkylene glycol, polyoxyethylene / polyoxypropylene block polymer, polyoxyethylene vegetable oil ether; alkyl aryl sulfonate, alkyl Aryl sulfate salt, alkyl aryl phosphate salt, dialkyl sulfosuccinate, alkyl naphthalene sulfonate, Anionic surfactants such as formalin condensates of tarene sulfonates and polycarboxylates; cationic surfactants such as alkyl quaternary ammonium salts, alkylamine salts and alkylpyridinium salts; alkylbetaines and amine oxides And amphoteric surfactants such as alkyl amino acid salts.

  As the surfactant (D), a lignin surfactant is preferable. A lignin-based surfactant is a substance having a surfactant activity derived from lignin, which is a natural polymer compound. Examples of the lignin surfactant include lignin sulfonic acid or a salt thereof, lignin carboxylic acid or a salt thereof, a glycidyl ether derivative of lignin, and a glycol derivative of lignin. Of these, lignin sulfonate is preferred.

  The content of the surfactant (D) in the agricultural or horticultural or industrial preparation composition according to the third embodiment of the present invention is preferably 0.01 to 10 parts by mass with respect to 1 part by mass of the substance (A). More preferably, it is 0.05-1 mass part.

  The agricultural or horticultural or industrial preparation composition according to the third embodiment of the present invention may be either liquid or solid. The solid agricultural or horticultural or industrial preparation composition is in the form of powder, granules, lumps or the like. Formulation forms for agricultural chemicals include powders, wettable powders, granular wettable powders, granules, tablets and the like. The preparation form of the solid agricultural or horticultural or industrial preparation composition as an agrochemical is preferably a wettable powder, a granular wettable powder or a granule, and more preferably a granular wettable powder or a granule. The content of the substance (A) in the solid agricultural or horticultural or industrial pharmaceutical composition according to the third embodiment of the present invention is preferably 1 to 80% by mass, more preferably 1 to 50% by mass. The content of the surfactant (D) is preferably 1 to 50% by mass, more preferably 1 to 30% by mass.

  The liquid agricultural or horticultural or industrial preparation composition according to the third embodiment of the present invention includes the substance (A) in the liquid medium. Formulation forms for agricultural chemicals include suspensions, flowables, emulsifiers, solutions and the like. Water is preferably used as the liquid medium. The liquid agricultural or horticultural or industrial pharmaceutical composition according to the third embodiment of the present invention is preferably a liquid in which the substance (A) is suspended.

  In the liquid agricultural or horticultural or industrial preparation composition according to the third embodiment of the present invention, the content of the substance (A) is preferably 1 to 80% by mass, more preferably 1 to 50% by mass, The content of the surfactant (D) is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, and the water content is preferably 10 to 98.9% by mass, more preferably. Is 20-90 mass%.

The agricultural or horticultural or industrial preparation composition of the present invention may contain an agricultural or horticultural active ingredient other than the substance (A), if necessary.
The active ingredients for agricultural and horticultural use include fungicides, insecticides, acaricides, nematicides, herbicides, algaecides, pest repellents, antiviral agents, plant growth regulators, plant vital agents, fertilizers And the like.

  In combination with the agricultural and horticultural active ingredient, the antiviral efficacy of the substance (A) may be enhanced, or the agricultural and horticultural active ingredient may be stabilized to enhance its efficacy.

  The agricultural or horticultural or industrial preparation composition of the present invention comprises, as necessary, a binder (or thickener), an organic solvent, an antifoaming agent, an ultraviolet ray inhibitor, an antioxidant, an antiseptic, a colorant, An antifreezing agent or the like may be contained within a range that does not inhibit the action of the substance (B), the carrier (C), or the surfactant (D).

  Examples of the organic solvent include vegetable oils, mineral oils; aromatic hydrocarbons such as petroleum aromatic hydrocarbons, benzene, toluene, xylene, and ethylbenzene; halogenated hydrocarbons such as dichloromethane and trichloroethylene; ethyl alcohol, isopropyl alcohol, alcohols such as n-butyl alcohol, benzyl alcohol, octyl alcohol, lauryl alcohol, ethylene glycol, propylene glycol, glycerin; aliphatic or alicyclic hydrocarbons such as n-hexane, cyclohexane, isopropyl ether, ethylene oxide, tetrahydrofuran, etc. Ethers; ketones such as acetone, methyl ethyl ketone, cyclohexanone; ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, methyl laurate, phthalic acid Esters such as ethylhexyl; acid amides such as dimethylformamide, propionitrile, nitriles such as acrylonitrile; dimethyl sulfoxide sulfoxides such as diethylene glycol, alcohol ethers such as ethylene glycol monoethyl ether; and the like. The amount of the organic solvent used in the suspension-like agricultural or horticultural or industrial preparation composition of the present invention is preferably 70% by mass or less, more preferably 30% by mass or less, based on the entire composition. A water-miscible organic solvent such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin can be used as an antifreezing agent.

  Examples of the binder or thickener include dextrin, cellulose, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, pullulan, sodium alginate, ammonium alginate, propylene glycol alginate, guar gum, locust bean gum, arabic Examples include rubber, xanthan gum, gelatin, casein, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, ethylene / propylene block polymer, sodium polyacrylate, polyvinyl pyrrolidone, carrageenan, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol and the like.

  The agricultural or horticultural or industrial formulation composition of the present invention is suitable for agricultural and horticultural use as an antiviral agent, a plant growth regulator, a plant vitality agent and the like. Suitable for preservatives, antibacterial agents, preservatives and the like. Preferred examples of the industrial product include wood, paper, fiber, resin, rubber, leather, adhesive, paint, fats and oils, industrial water, ceramic, metal, and various products made of these.

  The present invention will be described more specifically with reference to the following examples. However, the scope of the present invention is not limited by these examples. In the following description, “part” is “part by mass” unless otherwise specified.

Example 1 (granular wettable powder)
31.5 parts of L-ascorbic acid-6-palmitate, 30 parts of sodium ascorbate, 4 parts of sodium alkyl sulfate, 10 parts of sodium salt of formalin naphthalene sulfonate formalin, 1 part of yellow iron oxide and 23.5 parts of corn starch are mixed. Then, water was added thereto, and then kneaded with a bench kneader (Irie Shokai Co., Ltd.). The kneaded product was extruded and granulated to a diameter of 0.7 mm with a micro-shaped granule manufacturing machine (manufactured by Tsutsui Rika Kikai Co., Ltd.) to obtain a granulated wet product. This was dried with a fluidized bed dryer at 50 ° C. for 20 minutes to obtain a granular wettable powder.

Storage stability test 1
The following tests were performed on the granular wettable powder immediately after production and the granular wettable powder placed in an aluminum laminate bag and allowed to stand at 54 ° C. for 14 days. The results are shown in Table 1.

(Underwater disintegration)
100 mL of hard water was added to a 100 mL Spitz tube, and 100 mg of granular wettable powder was added thereto. The spitz tube was stoppered so that air did not enter and allowed to stand for 30 seconds. Thereafter, the Spitz tube was inverted at a rate of 30 times per minute. The number of inversions performed until the granule wettable powder completely disintegrated and dispersed was recorded as the number of collapsed falls.

(Suspension rate)
100 mL of hard water was added to a 100 mL Spitz tube, and 100 mg of granular wettable powder was added thereto, and the granular wettable powder was completely disintegrated to obtain a dispersed liquid. The mass (C) of L-ascorbic acid-6-palmitate contained in the dispersion was measured.
The dispersion was allowed to stand for 30 minutes. 90 ml of the supernatant was extracted. The mass (Q) of L-ascorbic acid-6-palmitate contained in 10 ml of the remaining liquid was measured. The suspension rate was calculated based on the following formula.
Suspension rate (%) = (10/9) × (100 (C−Q) / C)

(Survival rate)
The mass (C0) of L-ascorbic acid-6-palmitate contained in 100 mg of the granular wettable powder immediately after production was measured.
The mass (C1) of L-ascorbic acid-6-palmitate contained in 100 mg of granular wettable powder placed in an aluminum laminate bag and allowed to stand at 54 ° C. for 14 days was measured. The residual rate at 54 ° C. for 14 days was calculated based on the following formula. The higher the residual rate, the higher the chemical stability.
Residual rate (%) at 54 ° C. for 14 days = C1 / C0 × 100

The mass of L-ascorbic acid-6-palmitate contained in the granular wettable powder was measured as follows. 100 mg of granular wettable powder was placed in a 50 mL glass tube bottle. To this, 20 mL of methanol, 10 mL of homocysteine solution (1 g homocysteine / 100 mL distilled water) and 5 mL of internal standard solution (2000 ppm O-terphenyl / methanol solution) were added and mixed until a uniform solution was obtained. This solution was analyzed using high performance liquid chromatography (HPLC), and the mass of L-ascorbic acid-6-palmitate was measured.
The L-ascorbic acid-6-palmitate analysis standard solution was prepared as follows. 50 mg of L-ascorbic acid-6-palmitate was placed in a 50 mL volumetric flask and the volume was adjusted with methanol to obtain a solution adjusted to a predetermined concentration. 20 mL of the resulting solution was placed in a 50 mL glass tube bottle. A homocysteine solution (1 g homocysteine / 100 mL distilled water) 10 mL and an internal standard solution (2000 ppm O-terphenyl / methanol solution) 5 mL were added thereto.
HPLC conditions:
・ Equipment: Shimadzu HPLC Class-VP
Column: YMC-Pack ODS-AM
・ Temperature: 40 ℃
Mobile phase: methanol / water (mixed after adjusting to pH 6.5 with sodium acetate) = 850/150
・ Flow rate: 1.0 mL / min
・ Injection volume: 1 μL
・ Detection wavelength: 265 nm

  As shown in Table 1, the granule wettable powder which is one example of the present invention has practical levels of disintegration in water, suspension rate and chemical stability even after long-term storage at high temperature.

Example 2-1 (granular wettable powder)
20 parts of L-ascorbic acid-6-palmitate and 80 parts of calcium sulfate were mixed. Water was added to the mixture and kneaded with a bench kneader (manufactured by Irie Shokai Co., Ltd.). The kneaded product was extruded and granulated to a diameter of 0.7 mm with a micro-shaped granule manufacturing machine (manufactured by Tsutsui Rika Kikai Co., Ltd.) to obtain a granulated wet product. This was allowed to stand at 40 ° C. and dried to obtain a granular wettable powder. The granule wettable powder was subjected to a storage stability test 1 and the residual rate at 54 ° C. for 14 days was calculated. The results are shown in Table 2.

Example 2-2
A granular wettable powder was obtained in the same manner as in Example 2-1, except that calcium carbonate was used instead of calcium sulfate. The granule wettable powder was subjected to a storage stability test 1 and the residual rate at 54 ° C. for 14 days was calculated. The results are shown in Table 2.

Example 2-3
A granular wettable powder was obtained in the same manner as in Example 2-1, except that ammonium sulfate was used instead of calcium sulfate. The granule wettable powder was subjected to a storage stability test 1 and the residual rate at 54 ° C. for 14 days was calculated. The results are shown in Table 2.

Example 2-4
A granular wettable powder was obtained in the same manner as in Example 2-1, except that potassium sulfate was used instead of calcium sulfate. The granule wettable powder was subjected to a storage stability test 1 and the residual rate at 54 ° C. for 14 days was calculated. The results are shown in Table 2.

Comparative Example 2-1
A granular wettable powder was obtained in the same manner as in Example 2-1, except that potassium chloride was used instead of calcium sulfate. The granule wettable powder was subjected to a storage stability test 1 and the residual rate at 54 ° C. for 14 days was calculated. The results are shown in Table 2.

Example 2-5
A granular wettable powder was obtained in the same manner as in Example 2-1, except that corn starch was used instead of calcium sulfate. The granule wettable powder was subjected to a storage stability test 1 and the residual rate at 54 ° C. for 14 days was calculated. The results are shown in Table 2.

Example 2-6
A granular wettable powder was obtained in the same manner as in Example 2-1, except that trehalose was used instead of calcium sulfate. The granule wettable powder was subjected to a storage stability test 1 and the residual rate at 54 ° C. for 14 days was calculated. The results are shown in Table 2.

Comparative Example 2-2
A granular wettable powder was obtained in the same manner as in Example 2-1, except that lactose was used instead of calcium sulfate. The granule wettable powder was subjected to a storage stability test 1 and the residual rate at 54 ° C. for 14 days was calculated. The results are shown in Table 2.

  As shown in Table 2, the granule wettable powder according to the embodiment of the present invention containing calcium sulfate, calcium carbonate, ammonium sulfate, potassium sulfate, corn starch and trehalose as a stabilizer is L-ascorbic acid- The chemical stability of 6-palmitate is high.

Example 3 (granule)
21 parts of L-ascorbic acid-6-palmitate, 20 parts of sodium ascorbate, 1 part of sodium salt of alkylbenzene sulfonate, 10 parts of sodium salt of formalin sulfonate formalin condensate, 1 part of yellow iron oxide, 5 parts of starch and 42 parts of trehalose The mixture was mixed, and water was added thereto and kneaded. The kneaded product was extruded and granulated. This was dried to obtain granules.

Example 4 (suspension)
25 parts of L-ascorbic acid-6-palmitate, 2.5 parts of sodium lignin sulfonate, 1.0 part of a silicon-based antifoaming agent and 71.5 parts of distilled water are mixed and wet-ground with a planetary mill. A turbid agent was obtained. Table 4 shows the solubility of L-ascorbic acid-6-palmitate in an aqueous medium to which sodium lignin sulfonate was added and the solubility of L-ascorbic acid-6-palmitate in water.

Storage stability test 2
The following tests were conducted on the suspension immediately after production, and the suspension encapsulated in an ampoule tube and allowed to stand at 54 ° C. for 7 days and allowed to stand for 14 days. The results are shown in Table 3.

(Liquidity)
The ampoule was held in hand and shaken. The state at that time was visually observed and evaluated according to the following criteria.
○: The liquid flowed quickly.
Δ: The liquid flowed, but thickening was observed.
X: The liquid did not flow.

(Survival rate)
The mass (C2) of L-ascorbic acid-6-palmitate contained in 100 mg of the suspension immediately after production was measured.
The mass (C3) of L-ascorbic acid-6-palmitate contained in 100 mg of the suspension encapsulated in an ampule tube and allowed to stand at 54 ° C. for 7 days was measured.
The mass (C4) of L-ascorbic acid-6-palmitate contained in 100 mg of the suspension that was sealed in an ampule tube and allowed to stand at 54 ° C. for 14 days was measured.
Based on the following formula, the remaining rate at 54 ° C. for 7 days and the remaining rate at 54 ° C. for 14 days were calculated. The higher the residual rate, the higher the chemical stability.
Residual rate (%) at 54 ° C. for 7 days = C3 / C2 × 100
Residual rate (%) at 54 ° C. for 14 days = C 4 / C 2 × 100
In addition, the measurement of the mass of L-ascorbic acid-6-palmitate contained in the suspension was included in the granular wettable powder except that 100 mg of the suspension was used instead of 100 mg of the granular wettable powder. The measurement was performed in the same manner as the measurement of the mass of L-ascorbic acid-6-palmitate.

(Particle size)
100 mg of hard water was added to a 100 mL Spitz tube and diluted with 100 mg of the suspension immediately after production. The volume average particle diameter (D0) of the suspended particles in the diluted solution was measured.
A suspension of 100 mg suspended in an ampule tube and allowed to stand at 54 ° C. for 7 days was diluted by adding 100 mL of hard water three times to a 100 mL Spitz tube. The volume average particle diameter (D1) of the suspended particles in the diluted solution was measured.
100 mg of hardened water, which was sealed in an ampoule tube and allowed to stand at 54 ° C. for 14 days, was diluted by adding 100 mL of hard water to a 100 mL Spitz tube. The volume average particle diameter (D2) of the suspended particles in the diluted solution was measured.
The volume average particle diameter of the suspended particles was measured with a laser diffraction / scattering particle size distribution measuring apparatus Microtrack 9320-X-100 (Nikkiso Co., Ltd.).
Based on the following formula, the particle size growth rate at 54 ° C. for 7 days and the particle size growth rate at 54 ° C. for 14 days were calculated. The smaller the grain growth rate, the higher the stability.
Particle size growth magnification at 54 ° C for 7 days = (D1-D0) / (D0)
Particle size growth magnification at 54 ° C. for 14 days = (D1-D0) / (D0)

Comparative Example 4-1
A suspension was obtained in the same manner as in Example 4 except that 2.5 parts of sodium naphthalenesulfonate formalin condensate was used instead of 2.5 parts of sodium lignin sulfonate. This suspension was subjected to a storage stability test 2 to calculate the residual rate and particle size growth rate at 54 ° C. for 7 days. The results are shown in Table 3.

Comparative Example 4-2
A suspension was obtained in the same manner as in Example 4 except that 2.5 parts of sodium polycarboxylate was used instead of 2.5 parts of sodium lignin sulfonate. This suspension was subjected to a storage stability test 2 to calculate the residual rate and particle size growth rate at 54 ° C. for 7 days. The results are shown in Table 3.

Comparative Example 4-3
A suspension was obtained in the same manner as in Example 4 except that 2.5 parts of sodium alkylnaphthalene sulfonate was used instead of 2.5 parts of sodium lignin sulfonate. This suspension was subjected to a storage stability test 2 to calculate the residual rate and particle size growth rate at 54 ° C. for 7 days. The results are shown in Table 3.

Comparative Example 4-4
A suspension was obtained in the same manner as in Example 4 except that 2.5 parts of alkyl sulfate sodium was used instead of 2.5 parts of lignin sulfonic acid. This suspension was subjected to a storage stability test 2 to calculate the residual rate and particle size growth rate at 54 ° C. for 7 days. The results are shown in Table 3.

Comparative Example 4-5
A suspension was obtained in the same manner as in Example 4 except that 2.5 parts of sodium alkylbenzene sulfonate was used instead of 2.5 parts of lignin sulfonic acid. This suspension was subjected to a storage stability test 2 to calculate the residual rate and particle size growth rate at 54 ° C. for 7 days. The results are shown in Table 3.

Comparative Example 4-6
10 parts of L-ascorbic acid-6-palmitate, 1.25 parts of sodium lignin sulfonate, 10 parts of polyoxyethylene tristyryl phenyl ether sulfate, 2.25 parts of silicon-based antifoaming agent, and 76.5 parts of distilled water The mixture was mixed and wet pulverized with a planetary mill to obtain a suspension. The suspension was subjected to a storage stability test 2 and the residual rate and particle size growth rate at 54 ° C. for 14 days were calculated. The results are shown in Table 3. Table 4 shows the solubility of L-ascorbic acid-6-palmitate in an aqueous medium to which polyoxyethylene tristyryl phenyl ether sulfate was added.

Reference example 1
92.5 parts of distilled water, 5 parts of L-ascorbic acid-6-palmitate and 2.5 parts of sodium lignin sulfonate were mixed, and wet-pulverized with a planetary mill to obtain a suspension. This suspension was allowed to stand for 7 days at 30 ° C., 40 ° C., and 54 ° C. Thereafter, the suspension was filtered to obtain a filtrate. The obtained filtrate was analyzed using high performance liquid chromatography (HPLC) to measure the concentration of L-ascorbic acid-6-palmitate. The results are shown in Table 4.

Reference example 2
Distilled water (95 parts) and L-ascorbic acid-6-palmitate (5 parts) were mixed and wet-ground with a planetary mill to obtain a suspension. This suspension was allowed to stand for 7 days at 30 ° C., 40 ° C., and 54 ° C. Thereafter, the suspension was filtered to obtain a filtrate. The obtained filtrate was analyzed using high performance liquid chromatography (HPLC) to measure the concentration of L-ascorbic acid-6-palmitate. The results are shown in Table 4.

Reference example 3
85 parts of distilled water, 5 parts of L-ascorbic acid-6-palmitate, and 10 parts of polyoxyethylene tristyryl phenyl ether sulfate were mixed and wet-ground with a planetary mill to obtain a suspension. This suspension was allowed to stand for 7 days at 30 ° C., 40 ° C., and 54 ° C. Thereafter, the suspension was filtered to obtain a filtrate. The obtained filtrate was analyzed using high performance liquid chromatography (HPLC) to measure the concentration of L-ascorbic acid-6-palmitate. The results are shown in Table 4.

Claims (3)

And ascorbic acid-6-palmitate, calcium sulfate, calcium carbonate, ammonium sulfate, sulfuric acid potassium, solid agricultural and horticultural compositions containing at least one selected from the group consisting of cornstarch Contact and trehalose.   The composition according to claim 1, which is a granule wettable powder or a granule. And ascorbic acid-6-palmitate, calcium sulfate, calcium carbonate, ammonium sulfate, solid containing ascorbic acid-6-palmitate comprising mixing at least a bract a selected from the group consisting of sulfate potassium, corn starch Contact and trehalose Method for stabilizing agricultural and horticultural compositions.