JPH0456810B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aqueous dispersion of a solid aromatic hydroxy compound, and more specifically, the above-mentioned hydroxy compound has antibacterial and/or antifungal properties, has a boiling point of 100°C or higher, a flash point of 50°C or higher, and a solubility in water of 30wt.
%, the solubility of solid aromatic hydroxy compounds is
Organic solvent of 50wt% or more, polyoxyalkylene alkyl ether (HLB12.5~
17.5) and an aqueous dispersion consisting of an aqueous medium. Aromatic hydroxy compounds, such as alkylphenols, have been known to have antibacterial (preservative) and/or antifungal effects, and have been used for these purposes. In this field of application, alkylphenols in particular are often used as aqueous dispersions. However, since solid aromatic hydroxy compounds hardly dissolve in aqueous media, a solution to this problem has been desired. The conventional aqueous solution method converts the OH group of a solid alkylphenol into a Na salt to make it water-soluble, but it was only possible to prepare an aqueous solution of about 10% at most. A method of making water dispersible using an emulsifier has also been adopted, but in the case of a solid alkylphenol, it has the disadvantage that it is difficult to obtain a particularly stable aqueous dispersion. In the process of investigating aqueous dispersion of solid aromatic hydroxy compounds, the present inventor used, for example, isophorone as an organic solvent and polyoxyethylene oleyl ether (HLB13.6) as an emulsifier, and added an aqueous medium. I learned that by stirring or shaking, a highly concentrated and stable aqueous dispersion can be obtained compared to conventional methods, and the desired purpose can be achieved.
As a result of further studies, we have arrived at the following invention. That is, the present invention provides a solid aromatic hydroxy compound represented by the general formula (), () or ().
(a), an organic solvent (b), an emulsifier (c), and an aqueous medium (d). general formula (Here, R and R' are substituents having 1 to 30 carbon atoms, and represent an alkyl group, a cycloalkyl group, or an aryl group, and may be the same or different. X and X' are halogen or represents a nitro group,
They may be the same or different. m is an integer from 1 to 6, n and p are integers from 0 to 5, and 0<m+n+p
≦6. Y represents a lower alkylidene group.
q is 0 or 1. r, s, t and u are integers from 0 to 4, respectively, and 00≦r+t≦4 and 0
≦s+u≦4. v is an integer of 1 to 8, w and z are each integers of 0 to 7, and 0≦v+w
+z≦8. In addition, in the general formula ()
Each of OH, R and X can be distributed at any position on the two aromatic nuclei. ) It is known to use organic solvents or plasticizers in the aqueous dispersion of solid chemicals for the purpose of turning the solid into a liquid. For example, when aqueous dispersion of a hydrocarbon resin is carried out, linseed oil is added to the hydrocarbon resin as a plasticizer, and the liquid state is aqueous dispersed using an emulsifier, or polyoxypropylene is added to the solid aromatic hydroxy compound of the present invention as a plasticizer. A method of obtaining a stable aqueous dispersion by adding glycol and further adding an emulsifier to obtain a stable aqueous dispersion by a phase inversion method (W/O→O/W) different from the present invention, ) to which ortho-xylene is added as an organic solvent and an emulsifier is added to prepare an aqueous mold-preventing emulsion. However, for the purpose of aqueous dispersion of a solid aromatic hydroxy compound, as in the present invention, an aqueous dispersion with excellent dilution stability is prepared using, for example, isophorone as an organic solvent and a polyoxyalkyl ether as an emulsifier. No results were reported. The solid aromatic hydroxy compound used in the present invention is represented by any of the following general formulas (), (), and (), is solid at around room temperature (25°C), and has antibacterial and/or Refers to something that has a fungicidal effect. general formula (Here, R and R' are substituents having 1 to 30 carbon atoms, and represent an alkyl group, a cycloalkyl group, or an aryl group, and may be the same or different. X and X' are halogen or represents a nitro group,
They may be the same or different. m is an integer from 1 to 6, n and p are integers from 0 to 5, and 0<m+n+p
≦6. Y represents a lower alkylidene group.
q is 0 or 1. r, s, t and u are each integers from 0 to 4, 00≦r+t≦4 and 0≦
s+u≦4. v is an integer from 1 to 8, w and z
are integers from 0 to 7, and 0≦v+w+
Satisfy z≦8. In addition, in the general formula ()
Each of OH, R and X can be distributed at any position on the two aromatic nuclei. ) These solid aromatic hydroxy compounds include:
Examples include: (1) Alkylphenol: 4-sec-butylphenol, 4-tert-butylphenol, 4-tert-amylphenol, 4
-hexylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-isopropyl-5-methylphenol, 5-isopropyl-2-methylphenol, 3-methyl-4- isopropylphenol,
2,6-diethylphenol, 2-sec-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 4-butyl-2-methylphenol, 2-amyl-4-methylphenol, 2,
6-diethyl-4-methylphenol, 3,5-
Dimethyl-2-ethylphenol, 2,4,6-
Tri-tert-butylphenol, 2,6-di-
tert-butyl-4-methylphenol, (2) Arylphenol and aralkylphenol: 2-phenylphenol, p-cumylphenol, (3) Cycloalkylphenol: 2-cyclohexylphenol, 4-cyclohexylphenol, (4) Phenol combining two or more groups selected from the above alkyl group, aryl group and cycloalkyl group: 2-cyclohexyl-6-ethylphenol,
2-cyclohexyl-4-methylphenol, 2
-cyclohexyl-4-tert-butylphenol, 2,6-dicyclohexyl-4-methylphenol, 2-cumyl-4-methylphenol,
2,6-dicumyl-4-methylphenol, (5) Phenol containing halogen: 3-chloro-2,6-diisopropylphenol, 4-chloro-2-isopropylphenol,
2,4,4'-trichloro-2'-hydroxyphenyl ether, pentachlorophenol, p-chloro-m-xylenol, p-chloro-m-cresol, 2,4,6-trichlorophenol, 2,
4,6-tribromophenol, (6) Phenol containing a nitro group: dinitrophenols, dinatro-o-cresol, dinitro-o-chlorophenol, (7) dihydroxydiphenyl: o,o'-dihydroxydiphenyl, p,p'-dihydroxydiphenyl, p,p'-dihydroxy-m,m'-dimethyldiphenyl, p,p'-dihydroxy-m,m'-dichlorodiphenyl, o,o'-
Dihydroxy-p-chloro-p'-bromidiphenyl, (8) Bisphenols: Bis(p-hydroxyphenyl)methane (commonly known as bisphenol F), bis(p-hydroxyphenyl)ethane, 2,2-bis( p-hydroxyphenyl)propane (commonly known as bisphenol A), bis(o-hydroxyphenyl)methane, 2,2-
Bis(p-hydroxyphenyl-o-bromo)propane, (9) Naphthols: Methyl-β-naphthol, Tribromo-β-naphthol. The following are examples of particularly preferred solid aromatic hydroxy compounds. 4-tert-amylphenol, 4-methyl-
Isopropylphenol, dialkylphenols containing both methyl and isopropyl groups,
2-amyl-4-methylphenol, dialkylphenols containing both amyl and methyl groups, o-phenylphenol, p-cumylphenol, 2-cumyl-4-methylphenol, 3-chloro-2,6 -diisopropylphenol, other haloisopropylphenols, p-chloro-m-xylenol, p,p'-dihydroxydiphenyl, p,p'-
dihydroxy-m,m'-dimethyldiphenyl, methyl-β-naphthol, tribrome-β-
Naphthol, the organic solvent used in the present invention has a boiling point
100℃ or higher, flash point 50℃ or higher, solubility in water at room temperature (25℃) of 30wt% or less, and solubility of solid aromatic hydroxy compounds in the organic solvent (25%).
°C) is a solvent with physical properties of 50wt% or more,
Preferably, it has physical properties such as a boiling point of 130°C or more, a flash point of 55°C, a solubility in water (25°C) of 25wt% or less, and a solubility of the solid aromatic hydroxy compound in the organic solvent (25°C) of 50wt% or more. . For example, holone, isophorone, cyclohexanone, acetophenone, n-amyl alcohol, 2
-ethoxyethyl acetate, ethylene glycol diacetate, etc., among which isophorone, amyl alcohol, and 2-ethoxyethyl acetate are particularly preferred. The amount of organic solvent used is usually 20 to 20% per solid aromatic hydroxy compound.
90wt%, preferably within the range of 30-60wt%. The emulsifier used in the present invention includes anionic,
Among cationic and nonionic emulsifiers, nonionic emulsifiers are most suitable, and those with an HLB value of 12.5 to 17.5, preferably 13.0 to 16.5 are used. Examples of suitable emulsifiers are shown in the table below.

[Table] Since polyoxyethylene oleyl ether (HLB13.6) is the most suitable among these, it was used as an emulsifier in the examples of the present invention. The amount of emulsifier used is usually 15 to 90 wt%, based on the total amount of solid aromatic hydroxy compound and solvent.
Preferably it is 30wt% to 60wt%. The aqueous dispersion of the present invention is produced by adding an organic solvent and an emulsifier to a solid aromatic hydroxy compound, melting the mixture uniformly under heating (70 to 80°C), and then bringing the mixture to room temperature, stirring or shaking the mixture. This is done by addition to water, resulting in highly homogeneous and stable aqueous dispersions. The solid aromatic hydroxy compound of the present invention, an organic solvent, and an emulsifier that are heated and melted are stable even if kept at room temperature for a long period of time without crystal precipitation of the solid aromatic hydroxy compound, and the aqueous dispersion thereof is Even when diluted 10 to 5,000 times its volume with water, it remains uniform even after 24 hours. In addition, the aqueous dispersion of the present invention can be widely used as a preservative or fungicide for agricultural, horticultural, and industrial products (e.g., raw materials, paints, papermaking, adhesives, clothing), which were previously considered difficult to use. I can do it. Next, the present invention will be explained with reference to Examples. Example 1 100 g of 4-tert-amylphenol, 100 g of isophorone, and 120 g of polyoxyethylene oleyl ether (HLB13.6) were placed in a 500 ml flask and heated to 70 to 80°C with stirring to uniformly dissolve. After dissolution, let it cool to room temperature, collect 2.5 g of it into a 50 ml marked dilution stability test tube (φ25 mm), fill it up to the marked line with distilled water (dilute 20 times), and transfer it to a shaker for the test. The tube was installed, shaken at 250 spm (number of shakes per minute, the same applies hereinafter) for 10 minutes, and then allowed to stand at room temperature for a dilution stability test. As a result, the dispersion liquid maintained a homogeneous phase even after 24 hours and was sufficiently stable. Example 2 The operation of Example 1 was repeated using 100 g of p-cumylphenol, 70 g of 2-ethoxyethyl acetate, and 110 g of polyoxyethylene oleyl ether (HLB13.6) to obtain a dissolved mixture. Collect 2.5g of it in a dilution stability test tube and dilute it with distilled water for 50 g.
Fill it up to the ml mark and place it on a shaker.
After shaking at 250 spm for 10 minutes, the mixture was allowed to stand at room temperature for a dilution stability test. As a result, the dispersion liquid maintained a homogeneous phase even after 24 hours and was sufficiently stable. Example 3 50 g of 4-tert-amylphenol, 50 g of p-cumylphenol, 70 g of n-amyl alcohol, and 100 g of polyoxyethylene oleyl ether (HLB13.6) were placed in a 500 ml flask and heated to 70 to 80°C while stirring. It was heated and dissolved uniformly.
After dissolution, the solution was allowed to cool to room temperature, and 2.5 g of the solution was placed in a dilution stability test tube, which was filled to the 50 ml mark with distilled water. Place the test tube in a shaker and shake at 250 spm.
After shaking for 10 minutes, a dilution stability test was performed by standing at room temperature. As a result, the dispersion maintained a homogeneous phase even after 24 hours and was sufficiently stable. Example 4 100 g of p-chloro-m-xylenol, 110 g of isophorone, and 140 g of polyoxyethioleyl ether (HLB13.6) were placed in a 500 ml flask, heated to 80°C while stirring, and allowed to cool to room temperature after uniformly dissolving. did. Place 2.5 g of the dissolution mixture in a dilution stability test tube and fill to the 50 ml mark with distilled water.
The test tube was placed in a shaker and shaken at 250 spm for 10 minutes. After shaking, a dilution stability test was performed by allowing the dispersion to stand at room temperature. As a result, the dispersion maintained a homogeneous phase even after 24 hours and was sufficiently stable. Example 5 100 g of dinitro-o-cresol, 80 g of n-amyl alcohol, and 120 g of polyoxyethylene oleyl ether (HLB13.6) were placed in a 500 ml flask, heated to 80°C while stirring, and after uniformly dissolving, allowed to cool to room temperature. It got cold. 2.5 g of the dissolved mixture was placed in a dilution stability test tube, filled to the 50 ml mark with distilled water, and then placed in a shaker and shaken at 250 spm for 10 minutes. After shaking, a dilution stability test was performed by allowing the dispersion to stand at room temperature. As a result, the dispersion maintained a homogeneous phase even after 24 hours and was sufficiently stable. Example 6 100 g of methyl-β-naphthol, 80 g of 2-ethoxyethyl acetate, and 150 g of polyoxyethylene oleyl ether (HLB13.6) were placed in a 500 ml flask, heated to 80°C with stirring, and dissolved uniformly. It was allowed to cool to room temperature. Collect 2.5g of it, put it in a dilution stability test tube, fill it up to the 50ml mark with distilled water, and place it on a shaker.
Shake at 250 spm for 10 minutes. After shaking, a dilution stability test was performed by allowing the dispersion to stand at room temperature.
It remained a homogeneous phase even after 24 hours and was sufficiently stable. Comparative Example 1 The procedure of Example 1 was repeated except that xylene was used instead of isophorone. As a result, in the dilution stability test, the dispersion caused an oil layer to settle at the bottom of the vessel. Comparative Example 2 The operation of Example 2 was repeated except that polyoxyethylene oleyl ether with HLB of 10.0 was used instead of polyoxyalkylene ether with HLB of 13.6 g. As a result, in the dilution stability test, the dispersion liquid caused an oil layer to settle at the bottom of the vessel. Comparative Example 3 The operation of Example 3 was repeated except that the amount of polyoxyethylene oleyl ether (HLB13.6) added as an emulsifier was changed from 100 g to 27 g. As a result, in the dilution stability test, the dispersion liquid immediately separated into oil and water. Comparative Example 4 The operation of Example 4 was repeated except that the amount of isophorone added was changed from 110 g to 25 g. As a result, in the dilution stability test, the dispersion caused an oil layer to settle at the bottom of the vessel. Comparative Example 5 The operation of Example 5 was repeated except that an anionic emulsifier, sodium dodecylbenzenesulfonate, was used instead of the emulsifier, polyoxyethylene oleyl ether. As a result, in the dilution stability test, the dispersion liquid caused an oil layer to settle at the bottom of the vessel. Comparative Example 6 The operation of Example 6 was repeated except that a cationic emulsifier, lauryltrimethylammonium chloride, was used instead of polyoxyethylene oleyl ether as an emulsifier. the result,
In the dilution stability test, the dispersion caused an oil layer to settle at the bottom of the vessel.

Claims (1)

[Claims] 1. A solid aromatic hydroxy compound (a) represented by the general formula (), () or (), boiling point of 100°C or higher, flash point of 50°C or higher, solubility in water (25°C)
30 wt% or less, and the solubility of the solid aromatic hydroxy compound in the organic solvent is 50 wt% or more; and a nonionic emulsifier that is a polyoxyalkylene ether with an HLB value of 12.5 to 17.5.
Mix (c) to obtain a homogeneous solution, which is then added to the aqueous medium (d).
A method for producing an aqueous dispersion, characterized by separating the two. general formula (Here, R and R' are substituents having 1 to 30 carbon atoms, and represent an alkyl group, a cycloalkyl group, or an aryl group, and may be the same or different. X and X' are halogen or represents a nitro group,
They may be the same or different. m is an integer from 1 to 6, n and p are integers from 0 to 5, and 0<m+n+p
≦6. Y represents a lower alkylidene group.
q is 0 or 1. r, s, t and u are integers from 0 to 4, respectively, and 00≦r+t≦4 and 0
≦s+u≦4. v is an integer of 1 to 8, w and z are each integers of 0 to 7, and 1 ≦v+w
+z≦8. In addition, in the general formula ()
Each of OH, R and X can be distributed at any position on the two aromatic nuclei. ) 2 The organic solvent is isophorone, amyl alcohol,
2. A method according to claim 1, wherein the ester is selected from 2-ethoxyethyl acetate. 3. The method according to claim 1, wherein the emulsifier is polyoxyethylene oleyl ether (HLB13.6).