JPH0386802A - Solvent, emulsifying agent composition and emulsifying agent composition - Google Patents

Abstract

PURPOSE:To obtain a composition having high safety, excellent fluidity and masking effects on smell of destroying agent, comprising a destroying agent such as insecticide and herbicide, terpene-based compound-containing solvent and emulsifying agent of anionic or nonionic surfactant. CONSTITUTION:A composition comprising (A) 1-80wt.% terpene-based compound [e.g. C10H16)n ((n)is 2-4 and oxygen-containing compound derived therefrom] liquid at normal temperature, (B) 10-80wt.% destroying agent (e.g. insecticide, fungicide, acaricide or herbicide) and (C) 1-20wt.% emulsifying agent. An anionic surfactant (e.g. alkylbenzenesulfonate or phosphoric ester salt) and a nonionic surfactant (e.g. polyoxyalkylene alkyl ether) may be cited as the emulsifying agent. When used, 0.1-5.0wt.% of the composition is emulsified and dispersed into water and a scattering solution is prepared.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a solvent for a biocidal emulsion, an emulsifier composition for a biocidal emulsion, and a biocidal emulsion composition.

[Prior Art] Conventionally, xylene, toluene, methyl isobutyl ketone (MIBK), cyclohexane, cellosolves, dimethylformamide (DMF) have been used as solvents for producing biocidal emulsions.
), acetonitrile, etc. have been used.

[Problems to be solved by the invention] However, all of these problems are classified by the EPA (U.S. Environmental Protection Agency) as inactive ingredients with problematic toxicity (EPA Llstl).
) and inert ingredients that are potentially toxic and whose effects must be evaluated (EPA LIst 2), and their use is being regulated in Japan.

[Means for Solving the Problems] In order to solve this problem, the present inventors conducted intensive studies on less toxic solvents, and as a result, they arrived at the present invention.

Specifically, the present invention provides a solvent for a biocidal emulsion characterized by containing a terpene compound that is liquid at room temperature, an emulsifier composition for a biocidal emulsion characterized by comprising a terpene compound that is liquid at room temperature and an emulsifier, and an emulsifier composition for a biocidal emulsion characterized by containing a terpene compound that is liquid at room temperature and an emulsifier. A terpene compound (A), a biocide (B) and an emulsifier (C) which are liquid in
) as an essential component.

The terpene compound in the present invention is the EPA LI
stl and LIst2, and is highly safe for animals and plants.

Examples of terpene compounds in the present invention include (C+
@H+a). Monoterpenes, sesquiterpenes, and diterpenes represented by (n=2 to 4) and oxygenated compounds derived therefrom (alcohols, aldehydes,
ketones, oxides, esters, etc.).

Examples of terpene compounds include the following.

(Limonoterpene (+-1) monoterpene hydrocarbons limonene, ocimene, terpinolene, silvestrene,
dipentene, terpinene, mentene, phelandrene,
Sabinen, Karen, Pinene, Kamphuen, Myrcene, etc.

(1-2) Monoterpene alcohols citronellol, geraniol, borneol, nerol, linalool, terpineol, myrtenol, terepinol, myrcenol, methylgeraniol, hydroxycitronellol, ocimenol, etc.

(1-3) Monoterpene aldehyde Citronellal, citral, phelandol, etc.

(1-4) Monoterpene ketone Kanfer et al.

(+-5) Monoterpene oxide Cineor et al.

(1-8) Monoterpene-based formic acid, acetic acid, propionate ester bornyl acetyl, linallylacetyl, citronellyl acetyl, etc.

(2) Sesquiterpenes (2-1) Sesquiterpene hydrocarbons Curcumen, bisabolene, etc.

(2-2) Sesquiterpene alcohol (2-3) Sesquiterpene ketone cyperone, etc.

(3) Diterpene (3-1) Diterpene hydrocarbon Kangholene, terpene dimer, etc.

(3-2) Diterpene alcohol Fitol et al.

Further, the terpene compounds may be used as they are as a mixture of the above terpene compounds such as orange oil, lemon oil/turpentine oil, fern oil, clover oil, cananga oil, and pine oil. In addition, xylene, toluene, methylnaphthalene, methyl ethyl ketone (MEK), methyl isobutyl ketone (formerly BK), cyclohexanone, and
Ethylene glycol, cellosolves, dimethyl sulfoxide (DMSO), dimethyl formamide (DMF)
, acetonitrile, etc. can also be used in combination.

Among these terpene compounds, mohydrocarbons are preferred.

The terpene compound in the present invention can be used as an emulsifier composition for a biocidal emulsion comprising an emulsifier.

Examples of the emulsifier (C) include anionic surfactants and nonionic surfactants (for details, see Japanese Patent Publication No. 57-396
Described in Publication No. 78. ).

Examples of anionic surfactants include alkylbenzene sulfonates, phosphate ester salts, and mixtures thereof.

77L/+8 carbon atoms as rubenzene sulfonate
Examples include alkylbenzenesulfonic acid salts having at least one branched or straight chain alkyl group of ~20 (preferably ~18).

Salts include alkali metal (such as sodium, potassium and lithium) salts, alkaline earth metal (calcium,
(such as magnesium) salts, alkanolamine (such as jetanolamine) salts, and alkylamine (such as diethylamine) salts.

A specific compound is dodecylbenzenesulfonic acid calcium salt.

Examples of the phosphate salts include alkylaryl phosphate salts, polyoxyalkylene alkyl ether phosphate salts, and polyoxyalkylene alkylaryl ether phosphate salts.

Examples of the salt include those described in the section of the alkylbenzene sulfonate above.

Examples of the alkylaryl phosphate ester salts include phosphoric acid mono- and/or diester salts of alkylphenols or alkylnaphthols having at least one alkyl group, usually having 8 to 12 carbon atoms, such as nonylphenol phosphorus amine salts. .

Polyoxyalkylene alkyl ether phosphate ester salts include ethylene oxide (hereinafter abbreviated as EO) adduct phosphate ester salts of saturated or unsaturated alcohols having usually 6 to 20 carbon atoms, such as stearyl alcohol EO.
Examples include IO molar adduct [10 molar EO adduct is abbreviated as EO(10); the same description will be used hereinafter] phosphoric acid diester monosodium salt.

Polyoxyalkylene alkylaryl ether phosphate ester salts include phosphoric acid mono- and/or diester salts of alkylphenols or alkylnaphthols having at least one alkyl group, usually having 8 to 12 carbon atoms, such as nonylphenol EO(5) phosphoric acid diester jetanolamine Examples include salt.

Also, sulfuric acid ester salts [nonylphenol EO (4) sulfuric ester sodium salt, etc.] and sulfonic acid salts other than alkylbenzene sulfonates [e.g., sulfosuccinic acid ester salts (2-ethylhexyl sulfosuccinic acid ester sodium salt, etc.), alkylnaphthalene sulfonic acid , salts (such as diisopropylnaphthalenesulfonic acid sodium salt), and ligninsulfonates (such as ligninsulfonic acid sodium salt). Examples of the salt include those described in the section of the alkylbenzene sulfonate above.

Among these, preferred are dodecylbenzenesulfonic acid calcium salt and nonylphenol phosphoric acid diester jetanolamine salt.

Examples of nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene styrenated aryl ether, polyoxyalkylene alkylaryl ether, and polyoxyalkylene polyhydric alcohol fatty acid ester.

Examples of the polyoxyalkylene alkyl ether include adducts of alkylene oxide (hereinafter abbreviated as AO) having 2 to 4 carbon atoms to aliphatic alcohols having 6 to 20 carbon atoms, such as cetyl alcohol EO (5) and nonylphenol E.
O(IG)PO(3) [The adduct obtained by adding 16 moles of EO and then adding 3 moles of propylene oxide (hereinafter abbreviated as PO) is abbreviated as EO(1B)PO(3) (the same description will be used hereinafter) . ] can be given.

Polyoxyalkylene styrenated aryl ethers include monocyclic phenols (such as phenols having at least one alkyl group having 8 to 12 carbon atoms) or polycyclic phenols (such as phenols having two or more aromatic rings, such as cumyl phenol), and Stereph 1 AO adducts of reaction products (referred to as styrenated phenols) with ~20 moles (the number of moles of AO added is usually 2 to 50), such as styrenated (3 moles) phenol EO (20), styrenated phenols (2 moles) ) PQ (15) EO (10) etc. [Styrenated (3 mol) Phenol EO (20)
is a compound having a structure in which 20 moles of EO is added to styrenated phenol obtained by reacting phenol and styrene at a molar ratio of 1:3. (hereinafter the same meaning shall apply)].

Examples of the polyoxyalkylene alkylaryl ether include AO adducts of alkylphenols or alkylnaphthols having at least one alkyl group having 8 to 12 carbon atoms (the number of moles of AO added is usually 2 to 50), such as nonylphenol EO (10). can give.

Polyoxyalkylene polyhydric alcohol fatty acid esters include polyhydric alcohols or their intramolecular anhydrides (glycerin, trimethylolpropane, pentaerythritol, sorbitan, sorbitol, sugar, etc.) and fatty acids (
AO adducts of esters with fatty acids having 10 to 2 carbon atoms (the number of moles of AO added is usually 2 to 50), such as sorbitan monoole 1-EO (20), hydrogenated castor oil EO (3
0) etc.

Also included are polyoxyalkylene fatty acid esters (eg, oleic diester of polyethylene glycol (molecular weight: GOO)).

Among these, preferred is cetyl alcohol EO (5
), nonylphe/k EO(IG)PO(3), styrenation (3 mol) 7! EO (20), hydrogenated castor oil EO (30) and sorbitan monooleate EO (20).

The terpene compound (A) in the present invention is a biocide (B)
It can be used as a biocidal emulsion composition containing an emulsifier (C) as an essential component.

Biocides (B) include insecticides, fungicides, acaricides, herbicides, and the like, and include, for example, the following.

Insecticides include diazinon, dimethoate, and CYPl.
D D VPID N TPlE PNlM E P, etc.; Fungicides include isobrothiolane, plasticidin 51EDDP, IBP, etc.; Herbicides include oxacyacin, diquat, bentiocarb, DNBP, etc., used singly or in combination of two or more. are possible, but are not limited to these.

The amounts of each component are as follows based on the weight of the biocidal emulsion composition.

The content of the terpene compound (A) is usually 1 to 80%, preferably 20 to 40%. If it is less than 1%, the effect as a solvent of the present invention cannot be expected, and if it exceeds 80%, it is economically disadvantageous.

The biocide (B) is usually 10 to 80%, preferably 20 to 7%.
It is 0%. The emulsifier (C) is usually 1 to 20%, preferably 5 to IO%.

The method for producing the biocidal emulsion composition may be the same as the conventional method, and the solvent, biocide, and emulsifier of the present invention may be blended in the above-mentioned amounts and uniformly dissolved.

The biocidal emulsion composition of the present invention is poured into water and emulsified and dispersed to prepare a spray solution for use. Killing P++tll against water
-1f1llkf+ c+'? &+ mhnj!
L IJ 7-f: 4-m + 2 Al
l+V + 1 is about 0.1 to 5.0% by weight. The spray liquid is applied in a form depending on the biocide component and is sprayed on fields.

[Examples] The present invention will be further described below with reference to Examples, but the present invention is not limited thereto.

Parts in Examples indicate parts by weight.

Examples 1 to 5 (solvent of the present invention), Comparative Examples 1 to 5 Example 1
d-limonene 2 Pinene 3 Diterpene 4 Myrcene 5 Terpinene Solvents for biocidal emulsions in comparative examples are shown below.

Comparative example 1 Kerosene 2 Polypropylene glycol (molecular weight 200) 3 Methanol PO (5) 4 Butanol EO (3) 5 Xylene qgo 7m n-n-, nl i-1 meeting ^
慴 nl 礒－＾n 1 ＼ Quantity e
1--1 Mu-Examples 6 to 3 Example 6 Dodecylbenzenesulfonic acid calcium salt styrenation (
3 mol) Phenol EO (20)
O(35) d-limonene Example 7 Dodecylbenzenesulfonic acid calcium salt styrenation (
3 mol) Phenol EO (2Q) Hydrogenated castor oil EO (3
0) Diterpene Example 8 Nonylphenol phosphoric acid diester jetanolamine salt Dodecylbenzenesulfonic acid calcium salt Sorbitan monooleate EO (30) Pinene Example 9 Dodecylbenzenesulfonic acid calcium salt Cetyl alcohol EO (5) 35 parts! 0 Nonylphenol EO (IG) PO (3)
25d-limonene 3
The emulsifier composition for biocidal emulsion of Comparative Example 0 is shown below.

Comparative Example 6 Dodecylbenzenesulfonic acid calcium salt 30 parts Styrenated (3 mol) Phenol EO (20) 20 Hydrogenated castor oil EO (35) 35
Xylene 15 Comparative Example 7 Dodecylbenzenesulfonic acid calcium salt 35 @ styrenated (3 mol) Phenol EO (20) 20 Hydrogenated castor oil EO (30) 25 Xylene 20 Comparative Example 8 Nonylphenol phosphoric acid diester jetanolamine salt 40 parts Dodecylbenzene Calcium sulfonate 10 Sorbitan monooleate EO (30) 3G xylene 20 Comparative example 9 Calcium dodecylbenzenesulfonate 35 parts Cetyl alcohol EO (5) 10 Nonylphenol EO (IG) PO (3) 2
5 Xylene 30 Examples 1O to 13 and Comparative Examples 1O to 13 Biocidal emulsion compositions of the present invention were obtained using the formulations shown in Table 1. (Example 1O
~13) Emulsion composition C of Comparative Example 10-13 was obtained using the formulation shown in Table 2.

The biocide (B) used in Examples 1O to 13 and Comparative Examples 1O to 13 is as follows.

Biocide I MEP EPN 3 Diazinon 4 MEP/DDVP= 1/1 (Weight ratio) Units are parts by weight Table 1 Table 2 Units are parts by weight Test Example 1 Examples IO to 13 and Comparative Examples 1O to 13 were carried out by the following method Physical properties were evaluated.

(1) Appearance of emulsion composition Observe the appearance of the emulsion composition at room temperature. It is preferable that the liquid does not separate and precipitate.

(2) Stability of emulsion Dilute the sample 100 times with 3 degree hard water at 20°C, transfer 100ml of this liquid to a 250ml graduated cylinder with a stopper, shake vigorously for 1 minute, and keep at a constant temperature of 20°C. After leaving it in the container for 2 hours, observe the uniformity of the emulsion and the presence or absence of separation of oily matter or coagulated matter. Those without separation of oily substances are better.

(3> Stability of Emulsion Composition - Heating Test The emulsion composition was allowed to stand in a thermostat at 40°C for 14 days, and then the raw material content, appearance, and emulsifying properties were observed.

(2) Cooling test After the emulsion composition is allowed to stand in a thermostat at -5°C for 72 hours, the presence or absence of liquid separation and precipitation is observed.

In both cases, those with little change are considered good.

The evaluation results are shown in Table 3.

Table 3 Table 3 (Continued) [Effects of the Invention] The biocidal emulsion solvent of the present invention is highly safe, has a high solubility of the biocide, and has good emulsifying properties with an emulsifier.

Furthermore, the emulsifier composition for biocidal emulsions of the present invention has good fluidity despite its high concentration.

Claims (1)

[Scope of Claims] 1. A biocidal emulsion solvent characterized by containing a terpene compound that is liquid at room temperature. 2. An emulsifier composition for a biocidal emulsion, characterized by comprising a terpene compound that is liquid at room temperature and an emulsifier. 3. The emulsifier composition according to claim 2, wherein the terpene compound is a compound selected from the group consisting of terpene hydrocarbons and oxygen-containing compounds derived therefrom. 4. The emulsifier composition according to claim 2 or 3, wherein the emulsifier is an anionic surfactant or a nonionic surfactant. 5. The emulsifier composition according to claim 4, wherein the anionic surfactant is an alkylbenzene sulfonate and/or a phosphate ester salt. 6. Claim 4, wherein the nonionic surfactant is a surfactant selected from the group consisting of polyoxyalkylene alkyl ether, polyoxyalkylene styrenated aryl ether, polyoxyalkylene alkylaryl ether, and polyoxyalkylene polyhydric alcohol fatty acid ester. or 5. The emulsifier composition according to 5. 7. A biocidal emulsion composition containing as essential components a terpene compound (A), a biocide (B), and an emulsifier (C) that are liquid at room temperature. 8. The emulsion composition according to claim 7, wherein the biocide is selected from the group consisting of insecticides, fungicides, acaricides, and herbicides. 9. 1-80% (A) based on the weight of the composition, (B
) is 10 to 80%, and (C) is 1 to 20%.
or 8. The emulsion composition according to 8.