JPH07118191A - Flowable formulation of clathrate compound - Google Patents

Abstract

PURPOSE:To provide the flowable clathrate compound formulation containing a tetrakisphenol compound as a host compound and a biocide, etc., as guest compounds. CONSTITUTION:A tetrakisphenol compound of the formula [X is (CH2)n; n is 0-3; R1 to R8 are H, lower alkyl, halogen, lower alkoxy, phenyl] as a host compound is reacted with various kinds of biocides such as a bactericidal agent, an antifungal agent, an insecticidal agent, antimicrobial agent, an acaricidal agent, and a herbicide as guest compounds, if necessary, in a solvent at the ordinary temperature to 100 deg.C to form a clathrate compound. The clathrate is finely ground, mixed with a surfactant and other auxiliary agents, and subsequently suspended in water or an organic dispersion medium to obtain the objective flowable formulation. The majority of the clathrate compounds containing the tetrakisphenol compound as the host compound are crystalline powder, thereby enabling to avoid troubles such as the pollution of working environments and the deterioration of workability, e.g. measurement, due to the scattering of the fine powder caused by its property. Since the flowable formulation is homogeneously mixed with various kinds of solvents such as water, the efficacy of the active ingredient is homogeneously exhibited.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a preparation of an inclusion compound of a biocide, and more particularly to a flowable preparation of an inclusion compound containing a tetrakisphenol as a host compound and a biocide as a guest compound.

[0002]

2. Description of the Related Art An inclusion compound is a crystalline powder in which guest molecules are embedded in the cavities of host molecules or in the cavities between host molecules, and the present technology reduces toxicity, chemically stabilizes, and residual efficacy. Has been applied to

Specifically, the host compound is tetrakis (hydroxyphenyl) for the purpose of reducing toxicity, separation and sustained release of 5-chloro-2-methyl-4-isothiazolin-3-one, which is a water-soluble bactericide. ) Ethane (JP-A-5-497)
8) 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol (Japanese Patent Publication No. 3-4990)
7) 1,1'-bi-2-naphthol (Japanese Patent Publication No. 3-33)
121), 1,1-di (4-hydroxyphenyl) -cyclohexane (Japanese Patent Publication No. 2-57046) and other inclusion compounds are known. Furthermore, an optical resolution method of dialkyl sulfoxides using 1,1′-bi-2-naphthol as a host compound (Japanese Patent Publication No. 5-21104), 1, 1,
6,6-tetraphenyl-2,4-hexadiyne-1,
A method for separately collecting 3-picoline using 1-dione as a host compound (Japanese Patent Publication No. 19548/1993), an underwater antifouling coating material containing an inclusion compound (JP-A-62-115072) and the like are known.

[0004]

However, these clathrate compounds are crystalline powders, and there are problems such as contamination of the work environment due to the scattering of fine powders due to their properties, and deterioration of workability such as weighing. is there. The present invention provides a flowable clathrate (liquid suspension) of a clathrate compound using a tetrakisphenol compound as a host compound, which solves these problems.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that tetrakisphenol compounds as host compounds and various biocides such as insecticides as guest It was found that a flowable powder obtained by finely pulverizing a powder of a clathrate compound as a compound and suspending it in water or an organic dispersion medium by adding a surfactant or other auxiliary agent can avoid the above problems. The present invention has been completed. The present invention will be described in detail below.

The present invention is a flowable composition comprising at least one clathrate compound containing a tetrakisphenol compound as a host compound and a biocide as a guest compound, a surfactant and a dispersion medium.

(Host Compound) The host compound used in the present invention is a tetrakisphenol compound represented by the following general formula 2.

[0008]

[Chemical 2]

(In the formula, X represents (CH ₂ ) n, n represents 0, ₁ , 2 or 3, and R _{1 to} R ₈ are each a hydrogen atom, a lower alkyl group, a halogen atom, a lower alkoxy group and It represents any one selected from the group consisting of an optionally substituted phenyl group.)

As the host compound of the present invention, for example,
1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-
Tetrakis (3-bromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1,2,2-
Tetrakis (3-t-butyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-4-hydroxyphenyl) ethane, 1,1,2,2-
Tetrakis (3,5-dichloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) ethane, 1,1,2,2
-Tetrakis (3,5-difluoro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methoxy-4-hydroxyphenyl) ethane, 1,1,
2,2-Tetrakis (3,5-dimethoxy-4-hydroxyphenyl) ethane, 1,1,2,2-Tetrakis (3-chloro-5-methyl-4-hydroxyphenyl)
Ethane, 1,1,2,2-tetrakis (3-chloro-5
-Phenyl-4-hydroxyphenyl) ethane, 1,
1,2,2-Tetrakis [4-hydroxy-3-phenyl) phenyl] ethane, 1,1-bis (4-hydroxyphenyl) -2,2-bis (3-methyl-4-hydroxyphenyl) ethane, 1 , 1,3,3-Tetrakis (4
-Hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-methyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1,3,3
-Tetrakis (3-chloro-4-hydroxyphenyl)
Propane, 1,1,3,3-tetrakis (3,5-dichloro-4-hydroxyphenyl) propane, 1,1,
3,3-tetrakis (3-fluoro-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,3
5-difluoro-4-hydroxyphenyl) propane,
1,1,3,3-tetrakis (3-phenyl-4-hydroxyphenyl) propane, 1,1,4,4-tetrakis (4-hydroxyphenyl) butane, 1,1,4,4
-Tetrakis (3-methyl-4-hydroxyphenyl)
Butane, 1,1,4,4-tetrakis (3,5-dimethyl-4-hydroxyphenyl) butane, 1,1,4,4
-Tetrakis (3-chloro-4-hydroxyphenyl)
Butane, 1,1,4,4-tetrakis (3,5-dichloro-4-hydroxyphenyl) butane, 1,1,4,-
Tetrakis (3-fluoro-4-hydroxyphenyl)
Examples include butane and 1,1,4,4-tetrakis (3,5-difluoro-4-hydroxyphenyl) butane.

(Guest Compound) The guest compound used in the present invention is not particularly limited as long as it is included in the above host compound, but in particular, a bactericidal agent, an antibacterial agent,
Various biocides such as insecticides, microbicides, acaricides and herbicides can be used.

For example, 5-chloro-2-methyl-4-isothiazolin-3-one (CMI), 2-methyl-4-
Isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2,3,5,6-tetrachloro-4-
(Methylsulfonyl) pyridine, 2-n-octyl-
4-isothiazolin-3-one, 2-methoxycarbonylbenzimidazole, 4,5-dichloro-1,2-dithiolan-3-one, 5-chloro-4-phenyl-1,
2-dithiolan-3-one, ethyl alcohol, thymol, cineol, hinokitiol, menthol, borneol, menthone, carvone, eugenol, terpineol, citral, geraniol, N ¹ -[(6-chloro-3-pyridyl) methyl] -N ² -cyano-N ^1-
Methyl acetamidine, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-3-n-octyl-
Isothiazolin-3-one, 2-benzisothiazolin-3-one, 2-methoxycarbonylbenzimidazole, 2,3,5,6-tetrachloro-4-methanesulfonylpyridine, 2-thiocyanomethylbenzothiazole, 2,2 -Dithio-bis- (pyridine-1-oxide), 3,3,4,4-tetrahydrothiophene-
1,1-dioxide, 4,5-dichloro-1,2-dithiolan-3-one, 5-chloro-4-phenyl-1,
2-dithiolan-3-one, N-methylpyrrolidone, phenyl- (2-cyano-2-chlorovinyl) sulfone,
Methylenebisthiocyanate, 2-bromo-2-nitropropane 1,3-diol, 2,2-dibromo-2-nitroethanol, 2-bromo-4′-hydroxyacetophenone, zymromnitrile pyropionamide, 2-bromo- 2-bromomethylglutarnitrile, 2,4
5,6-tetrachloroisophthalonitrile etc. can be mentioned.

It is also possible to mix two or more clathrate compounds having these as guests, or non-inclusion biocides in addition to the clathrate compounds having these as guests to form a flowable compound.

(Clathrate compound) The clathrate compound used in the present invention usually comprises a guest organic compound and a host compound, optionally in the presence of an inert solvent, at room temperature to 10 ° C.
It can be easily obtained by stirring at 0 ° C. for several minutes to several hours to react.

The content of the inclusion compound and the above non-inclusion inclusion biocide in the flowable composition of the present invention is usually 0.1% to 70% by weight, preferably 1% to 40% by weight. .

(Dispersion Medium) As the dispersion medium used in the present invention, water is most preferable from the viewpoint of toxicity and flammability, but if necessary, paraffinic hydrocarbon, cycloparaffinic hydrocarbon, aromatic It is also possible to use mineral oils such as hydrocarbons, vegetable oils such as corn oil and soybean oil, and organic solvents such as alcohols, ethers and esters that do not dissolve the inclusion compound. The content of the dispersion medium in the flowable is usually 30% by weight to 99% by weight.

(Surfactant) The surfactant used in the present invention is generally used as a wetting agent and a dispersant, and examples thereof include anionic surfactants and nonionic surfactants. There is.

As the anionic surfactant, for example,
Various alkyl sulfates, alkylbenzene sulfonates, dialkylsulfosuccinates, alkylnaphthalene sulfonates, formalin condensates of naphthalene sulfonates, formalin condensates of alkylnaphthalene sulfonates, lignin sulfonates, polyoxy Examples thereof include ethylene alkyl aryl ether sulfuric acid ester salts, polyoxyethylene alkyl aryl ether phosphoric acid ester salts, and polycarboxylic acid salts. Examples of the salts include alkali metal salts, ammonium salts, and amine salts.

As the dispersant, formalin condensate of sodium naphthalene sulfonate, formalin condensate of sodium alkylnaphthalene sulfonate, and sodium polycarboxylate are particularly preferable. Although addition of sodium dioctyl sulfosuccinate, which is mainly used as a wetting agent, sometimes causes gelation, addition of a small amount can be expected to have a thickening effect.

Examples of the nonionic surfactant include, for example,
Examples include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene alkylaryl phenyl ether, polyoxyethylene sorbitan alkyl ether, polyoxyethylene polyoxypropylene block copolymer, and acetylene glycol type. Depending on the HLB, May aggregate and separate. Even if the common name is the same, the physical properties may differ greatly depending on the manufacturer.

The content of these surfactants in the flowable is usually 0.1% by weight to 10% by weight.

Further, a suspension stabilizer, a pH adjusting agent, a freezing point depressant, a defoaming agent, a specific gravity adjusting agent and the like can be added to the flowable material of the present invention as required.

Examples of the suspension stabilizer include sodium polyacrylate, carboxymethyl cellulose, polyvinyl alcohol, guar gum, xanthan gum, sodium montmorillonite, silica and the like. Particularly, xanthan gum and montmorillonite to which a trace amount of alkali metal salt is added are useful. Is.

The pH adjusting agent is added mainly for stabilizing the bactericidal agent, and an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, maleic acid, malic acid, adipic acid, or a salt or ester thereof is added to them. Is mentioned.

Examples of the freezing point depressant when water is used as the dispersion medium include hydrophilic solvents such as ethylene glycol, propylene glycol and glycerin. The defoaming agent is mainly added to prevent foaming during wet pulverization, and a silicon-based defoaming agent is useful.

The specific gravity adjusting agent serves to bring the specific gravity of the dispersion medium closer to the specific gravity of the clathrate compound for suspension stabilization. When the dispersion medium is water, a soluble compound such as urea can be added.

(Preparation of flowable) As a method for preparing the flowable of the present invention, for example, a method in which all the components are sufficiently mixed and then finely pulverized by a wet pulverizer, or the clathrate is preliminarily jet-milled, etc. A method of pulverizing with a dry pulverizer, adding other components, and thoroughly mixing is preferable, but the former is preferable in terms of working environment. The average particle size of the inclusions in the preparation is approximately 10 microns or less, preferably 5 microns or less.

[0028]

EXAMPLES Hereinafter, the present invention will be described more specifically by way of examples. Example 1 Using 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane as a host, 5-chloro-2-
60 g of an inclusion compound having methyl-4-isothiazolin-3-one (CMI) as a guest compound, 6 g of Newcalgen PS-P (Takemoto Yushi Co., Ltd.), SH-5505
(Toray Dow Corning Silicone Co., Ltd.) 0.4
g and 73.6 g of water were thoroughly mixed and pulverized with an Eiger motor mill (4500 rpm, 40 minutes). To 70 g of this pulverized product, 6 g of a 2% aqueous solution of Rhodpole-23 (Rhone-Poulin Japan) prepared beforehand and 2 g of water were added.
4 g was added and sufficiently stirred again to obtain a flowable containing 30% of the clathrate compound.

Example 2 Using 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane as a host, 5-
60 g of an inclusion compound having chloro-2-methyl-4-isothiazolin-3-one (CMI) as a guest, 4 g of Newkalgen PS-P (Takemoto Yushi Co., Ltd.), SH55
05 (Toray Dow Corning Silicone Co., Ltd.)
0.4 g and 75.6 g of water were thoroughly mixed and pulverized with an Eiger motor mill (4500 rpm, 40 minutes). Kunipia-F (Kunimine Industries Co., Ltd.) water (Kunipia-F: water = 8: 9) prepared in advance in 70 g of this pulverized product
After 25 g of 2) was added and sufficiently dispersed by stirring, 1 g of sodium dihydrogen phosphate dihydrate and 4 g of water were added and further stirred and mixed to obtain a flowable containing 30% of the clathrate compound.

Example 3 Using 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane as a host, 5-
Inclusion compound 60 g having chloro-2-methyl-4-isothiazolin-3-one (CMI) as a guest, Soprofol FLK (Rhone Poulin Japan Co., Ltd.) 4
g, SH5505 (Toray Dow Corning Silicone Co., Ltd.) 0.4 g, and water 75.6 g were thoroughly mixed and pulverized with an Eiger motor mill (4500 rpm, 40 minutes). To 70 g of this pulverized product, 4 g of a 2% aqueous solution of Rhodpole 23 (Rhone-Poulin Japan) and 26 g of water, which had been prepared in advance, were added, and the mixture was thoroughly stirred again to obtain a flowable product containing 30% of the clathrate compound.

Example 4 Using 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane as a host, 5
Inclusion compound 60 g containing -chloro-2-methyl-4-isothiazolin-3-one as a guest compound, Newcalgen LX-C (Takemoto Yushi Co., Ltd.) 2 g, Newkalgen RX-B (Takemoto Yushi Co., Ltd.) 8 g, SH5505 (Toray Dow Corning Silicone Co., Ltd.) 0.4 g,
Mix 69.6 g of water thoroughly and mix with Eiger motor mill (4
It was crushed at 500 rpm for 40 minutes. 70g of this crushed product
6 g of a 2% aqueous solution of Rhodpole-23 (Rhone-Poulin Japan) and 24 g of water, which had been prepared in advance, were added and sufficiently stirred to obtain a flowable containing 30% of the clathrate compound.

Example 5 Using 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane as a host, 5
-Chloro-2-methyl-4-isothiazolin-3-one as a guest compound in an inclusion compound of 40 g, Newcalgen PS-P (Takemoto Yushi Co., Ltd.) 8 g, SH5505
(Toray Dow Corning Silicone Co., Ltd.) 0.8
g and 51.2 g of water were sufficiently mixed and pulverized with an Eiger motor mill (4500 rpm, 40 minutes). This crushed product 1
12% of a 2% aqueous solution of Rhodpole-23 (Rhone-Poulin Japan Co., Ltd.) previously prepared to 2.5 g
g and water (75.5 g) were added, and the mixture was thoroughly stirred again to obtain a flowable product containing 5% of the clathrate compound.

[0033]

As described above, according to the present invention, a clathrate compound comprising a tetrakisphenol compound as a host compound and a guest compound of a biocide such as various fungicides and insecticides is pulverized to obtain a surfactant, It is a flowable product obtained by adding an auxiliary agent and suspending it in water or an organic dispersion medium.

Most of the clathrate compounds having a tetrakisphenol compound as a host are crystalline powders, and due to their properties, there are problems such as contamination of the work environment due to scattering of fine powders and deterioration of workability such as weighing. there were. The present invention is a flowable clathrate compound using a tetrakisphenol compound as a host, which solves these problems. Further, since the flowable of the present invention is uniformly mixed with various solvents such as water,
The efficacy of the active ingredient is uniformly exerted.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 43/23 C 7419-4H

Claims (4)

[Claims] 1. A flowable clathrate comprising an inclusion compound comprising a guest compound and a tetrakisphenol compound represented by the following general formula 1, a surfactant and a dispersion medium. [Chemical 1] (In the formula, X represents (CH ₂ ) n, n represents 0, ₁ , 2 or 3, and R _{1 to} R ₈ are each a hydrogen atom, a lower alkyl group, a halogen atom, a lower alkoxy group and a substituted group. May be any one selected from the group consisting of optionally phenyl groups.) 2. The clathrate compound flowable according to claim 1, wherein the guest compound is a biocide. 3. The surfactant is at least one selected from the group consisting of alkylnaphthalene sulfonates, formalin condensates of naphthalene sulfonates, and formalin condensates of alkylnaphthalene sulfonates. A flowable clathrate according to item 1. 4. The flowable inclusion compound according to claim 1, wherein the dispersion medium is water or a non-aqueous dispersion medium.