JP2985714B2 - Antimicrobial composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial composition, and more particularly to 5-chloro-2-methyl-4-isothiazoline-3.
The present invention relates to a novel antibacterial composition in which -on (hereinafter abbreviated as "Cl-MIT") is improved in handleability, stability, workability and the like.

[0002]

2. Description of the Prior Art Cl-MIT represented by the following formula (I), which is an isothiazoline-based water-soluble bactericide, is:
Because of its excellent antibacterial activity, it is conventionally used for various water-based slime control agents such as cooling water systems, paper pulp, aqueous emulsion paints, aqueous emulsion adhesives, cutting oils, antibacterial agents, algicides, and fungicides Widely used as.

[0003]

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[0004] This Cl-MIT has excellent bactericidal activity, but is difficult to handle. Further, since Cl-MIT is a compound that is easily decomposed, a large amount of Mg salt is contained in currently marketed water-soluble germicides to stabilize Cl-MIT. For this reason, it could not be used in the field of latex or emulsion in which Mg salts are not used.

Although Cl-MIT can be fractionated from a commercially available water-soluble bactericide by an extraction method using an organic solvent, the extracted Cl-MIT is unstable and is particularly resistant to heat. , It decomposes in about 1 to 2 days even at a temperature of about 40 ° C. Therefore, precautions for storage such as refrigeration are required.

[0006] In order to solve such a problem, the present applicant has proposed 4,4'-ethylidenebisphenol and Cl-MI
An inclusion compound with T was previously proposed (Japanese Patent Application No. 5-2468).
No. 88. Hereinafter, it is referred to as “first application”. ).

[0007]

However, since the clathrate compound proposed in the above-mentioned prior application is in a powder form, there is a problem that workability at the time of addition is poor. That is, the powdery clathrate compound has problems such as contamination of the working environment due to scattering of fine powder during use and poor weighing workability.

An object of the present invention is to provide an antibacterial composition having improved handleability and workability of the clathrate compound according to the above-mentioned prior application.

[0009]

The antibacterial composition of the present invention comprises 5-chloro-2-methyl-4-isothiazoline-3.
An inclusion compound comprising -one and 4,4'-ethylidenebisphenol is dispersed in a dispersion medium to obtain a fluid preparation.

Hereinafter, the present invention will be described in detail.

The antibacterial composition of the present invention comprises a clathrate compound obtained by clathrating Cl-MIT with 4,4'-ethylidenebisphenol (bisphenol E) as a dispersoid, and dispersing this in a dispersion medium to form a suspension. A liquid antimicrobial composition.

The dispersion medium used in the present invention is one that keeps the above-mentioned clathrate compound in a stable suspension state. Even if Cl-MIT which is a bactericide component is partially eluted into the dispersion medium, Any material that does not decompose and stably retains the antibacterial activity may be used. There is no particular limitation, and the following materials can be used.

Water, alcohols such as ethylene glycol, propylene glycol, glycerin and polyglycerin, mineral oils such as liquid paraffin, xylene and toluene;
Vegetable oils such as castor oil, soybean oil, olive oil, rapeseed oil,
Terpenes such as hinoki oil, surfactants such as polyoxyalkyl ether, and silicone oil. Of these, water is suitable in consideration of the handling and safety of the dispersion medium.

The inclusion compound serving as a dispersoid preferably has a smaller particle size.
It is appropriate that the fine powder has a size of 0 μm or less. There are various methods for pulverizing the clathrate compound. In the present invention, the wet pulverization method in the above-mentioned dispersion medium is preferable. The pulverization may be performed by any of a batch system and a continuous system, and a sand mill, an attritor, a ball mill, or the like can be used as an apparatus.

The suspension obtained by dispersing the clathrate compound in a suitable dispersing medium has a higher concentration of the clathrate compound.
Although advantageous in terms of use and stability of Cl-MIT, generally, the concentration of the clathrate is 1 to 50% by weight,
As the l-MIT concentration, a concentration of about 0.1 to 20% by weight is practical.

In the present invention, a dispersant is added during the pulverizing treatment of the clathrate compound for the purpose of improving the pulverization efficiency in wet pulverization and preventing aggregation of the clathrate particles after pulverization. Can also. As dispersants, polystyrene sulfonic acid, lignin sulfonic acid, isoprene sulfonic acid, dialkyl sulfosuccinate, naphthalene sulfonic acid formalin condensate, melamine sulfonic acid formalin condensate, lauryl sulfate, lauryl benzene sulfonic acid, polystyrene sulfonic acid and maleic anhydride Examples include acid copolymers and salts thereof, but are not limited thereto.

When the prepared suspension has a low viscosity and precipitates in a stationary state, a proper amount of a suspending agent (thickener) is added to obtain a stable suspension. You can also. In this case, as the suspending agent used, the polymer polysaccharides (rhamsan, xanthan gum, guar gum, etc.), cellulose scan derivatives (methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, etc.), starches (hydroxypropyl starch), synthetic polymers (Polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, polyacrylamide, carboxymethyl cellulose, etc.) and inorganic compounds (talc, mica, smectite, smectite clay, bentonite, magnesium aluminum silicate, etc.), but are not limited thereto. It is not something to be done.

Further, in the present invention, the following additives may be blended for the purpose of imparting another function to the prepared suspension.

That is, for example, as a corrosion inhibitor, tolyltriazole, benzotriazole, methylbenzotriazole, molybdic acid, tungstic acid, silicic acid, nitrous acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, hydroxyethylidene diacid Phosphonic acid, hexametaphosphoric acid, tripolyphosphoric acid, orthophosphoric acid and salts thereof,
Zinc chloride, zinc chloride hydrochloride, zinc sulfate, zinc ligninsulfonate, hydrazine, etc .; and polyacrylic acid, copolymers of acrylic acid / hydroxyethylidene methacrylate, acrylic acid / hydroxyethylidene methacrylate as scale inhibitors / Methyl acrylate copolymer, acrylic acid / allyl glycidyl ethers copolymer, acrylic acid / 2-hydroxy-3-allyloxy-1-propanesulfonic acid copolymer, acrylic acid /
Isoprene sulfonic acid copolymer, acrylic acid / vinyl sulfonic acid copolymer, acrylic acid / allyl sulfonic acid copolymer, maleic acid or maleic anhydride / isobutylene copolymer, maleic acid or maleic anhydride / Styrenesulfonic acid copolymer, maleic acid or maleic anhydride / acrylic acid copolymer, maleic acid or maleic anhydride / acrylate acid copolymer, maleic acid or maleic anhydride / 2-acrylamido-2-methyl A copolymer of propanesulfonic acid, a copolymer of maleic acid or maleic anhydride / amylene acid, a copolymer of maleic acid or maleic anhydride / allylated fluorescent substance (such as 5-allylbenzosuberenol), polyacrylamide, Polyitaconic acid and salts thereof; and further, as an antibacterial agent, halogenated aliphatic nitrite. Alcohol (2-bromo-2-nitro-1,3-propanediol, 2,2-dibromo -2
-Nitroethanol, etc.) and their esters, isothiazolone-based compounds (4,5-dichloro-2-octylisothiazolin-3-one, 2-octylisothiazolin-3-one, 1,2-benzoisothiazolone, etc.) and the like. Salts, dibromonitrilopropionamide,
Alkylenebisthiocyanate (methylenebisthiocyanate, etc.), 1,4-bisbromoacetoxy-2-butene, hexabromodimethylsulfone, isophthalonitrile-based compound (5-chloro-2,4,6-trifluoroisophthalonitrile, tetra Chloroisophthalonitrile, etc.), dimethyldithiocarbamate, 4,5-dichloro-1,2-dithiol-3-one, 3,3,4,4-tetrachlorotetrahydrothiophen-1,1-dioxide, triiodoallyl alcohol , Bromonitrostyrene, aldehyde compounds (glutaraldehyde, phthalaldehyde, isophthalaldehyde, terephthalaldehyde, etc.), dichloroglyoxime, benzaldoxime compounds (α-chlorobenzaldoxime acetate,
α-chlorobenzaldoxime), 5,5-dimethylhydantoin and the like; furthermore, a silicone-based or non-silicon-based antifoaming agent as an antifoaming agent; It is not limited to these, and other various additives can also be used.

The antimicrobial composition of the present invention is prepared by adding these additives to, for example, the following composition.

Formulation (% by weight) Cl-MIT / 4,4'-ethylidenebisphenol inclusion compound: 1 to 50 Precipitating agent such as high molecular polysaccharide: 0.01 to 0.5 Dispersant: 0.1 to 0.5 5 Scale inhibitor: 0 to 50 Corrosion inhibitor: 0 to 50 Antibacterial agent: 0 to 30 Antifoaming agent: 0 to 10 Algaeproofing agent: 0 to 20 Dispersion medium such as water and propylene glycol: 30 to 95 The fluid preparation comprising a suspension of the Cl-MIT clathrate obtained as described above is added and used depending on the purpose, for example, so as to have the following Cl-MIT concentration.

In the case of paper / pulp papermaking system or cooling water slime prevention purpose: Cl-MIT concentration is 0.1 to 25 g /
m ³ synthetic resin emulsion, starch paste, starch slurry, paint, antiseptic purpose of metalworking fluid: Cl-MIT concentration 1～5000G / m ³

[0023]

The antibacterial composition of the present invention comprises Cl-MIT / 4,
Since it is a fluid preparation prepared by dispersing the 4'-ethylidenebisphenol inclusion compound in a dispersion medium, the handleability and workability are good. And Cl-MIT is 4,
By making the inclusion compound with 4′-ethylidenebisphenol, the solubility of Cl-MIT in water is suppressed, and its skin irritation and the like are also reduced. In addition, the antimicrobial activity is prevented from lowering due to the reaction with other substances during storage and use, and is also excellent in heat stability and the like.

Therefore, the antibacterial composition of the present invention is a sustained-release bactericide capable of maintaining bactericidal activity for a long time,
It can be used effectively with good handling and workability.

[0025]

EXAMPLES The present invention will be described more specifically with reference to production examples and examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Production Example: Production of Cl-MIT / 4,4'-ethylidenebisphenol clathrate compound In a 1-liter separable flask, 75 g of methanol and 50 g of the host compound 4,4'-ethylidenebisphenol were added.
The host compound was completely dissolved by stirring with a meniscus stirring blade (length: 5 cm). Keep this separable flask at 20 ° C
While keeping the contents in a thermostat and stirring the contents at a rotation speed of 500 rpm, 300 g of a water-soluble bactericide containing Cl-MIT as a main component (Cl-MIT concentration of 10 to 12% by weight) was added to 3 parts.
The mixture was continuously poured over 0 minutes to precipitate an inclusion compound precipitate. After completion of the pouring, stirring was continued for 1 hour to sufficiently precipitate the clathrate. Then, the precipitate was filtered by suction, and the precipitate was washed three times with 75 ml of demineralized water and air-dried to remove the clathrate. Obtained. The obtained clathrate was 79.8 g, and the Cl-MIT content in the clathrate was 35% by weight.

Production Example 2: Production of suspension In a stainless steel beaker, 142.37 g of demineralized water and 3.0 g of sodium polystyrenesulfonate were added and dissolved by stirring, and the clathrate compound 51 obtained in Example 1 was added thereto. .43
g and 3.0 g of propylene glycol in which 0.1 g of a high molecular weight polysaccharide (ramzan gum) was dispersed, and the mixture was sufficiently stirred for 30 minutes. Next, 500 g of glass beads having a diameter of 1.3 mm was added, and the mixture was stirred for 45 minutes with a batch-type tabletop sand mill (manufactured by Campe) (peripheral speed: 8 m / s).
ec) Wet pulverization. After pulverization, the glass beads and the suspension were separated by a mill separator to obtain 190 g of a suspension A. The resulting suspension A has a Cl-MIT content of 9% by weight and a dispersed clathrate having a particle size of 10%.
μm or less. The suspension A is stable at room temperature for 1 month or more and at 40 ° C. for 2 weeks or more, and has no change in Cl-MIT content, viscosity and aggregation of inclusion compound particles, and is stored without causing phase separation or the like. We were able to.

Examples 1-3: Preparation of various formulations of fluid preparations and stability test Using the suspension A produced in Production Example 2, fluid formulations were prepared according to the formulation shown in Table 1.

For each of the fluid preparations, at 40 ° C.
And stability when stored at room temperature, that is, Cl-MIT.
Examination of the period during which there was no change in the content, viscosity and aggregation of the inclusion compound particles and no phase separation revealed that all of the fluid preparations were stable for a long period of time, as shown in Table 1. Was.

[0030]

[Table 1]

Example 4: Cl-MIT dissolution test of a flowable preparation The flowable preparation prepared in Example 1 (total Cl-MIT concentration: 3.06% by weight) was filtered using a 5 ° filter paper, and then filtered. The filtrate was further filtered using a 0.1 μm Millipore filter, and the Cl-MIT concentration in the filtrate was measured.
As a result, the Cl-MIT concentration was 280 mg / l. In addition, this fluid preparation is kept at 40 ° C. for 2 months, or
As a result of performing the same measurement on those stored at room temperature for 6 months, no change was found in the Cl-MIT concentration in water.

From these results, it was found that C in water of this fluid preparation
The amount of l-MIT is 0.9% by weight based on the total amount of Cl-MIT, and the remaining Cl-MIT will remain in the clathrate. Therefore, Cl-MIT is 3.06% by weight.
Compared to a drug dissolved in water, it is expected that the skin irritation and the like are reduced, and that the antibacterial activity can be prevented from lowering due to the reaction with other substances during storage and use.

Example 5: Antibacterial test of a fluid preparation The growth inhibiting effect of the fluid preparation (Cl-MIT concentration: 3.06% by weight) prepared in Example 1 using Bacilus subtillus was determined.

The test conditions were as follows: a liquid medium (containing 1 g / l of peptone and 1 g / l of yeast extract) based on peptone-yeast extract having a pH of 7 was inoculated with the bacteria at a concentration of 10 ⁶ cells / ml. 1 was prepared using Cl-M
The IT concentration was adjusted to the prescribed concentration shown in Table 2, and 3
Shaking culture was performed at 0 ° C. for 24 hours. For comparison, a water-soluble disinfectant containing Cl-MIT as a main component (Cl-MIT concentration of 10 to 12% by weight) used as a Cl-MIT raw material in Production Example 1 was diluted with water to reduce the Cl-MIT concentration to 3%. The test was carried out in the same manner for the case of 0.06% by weight and the case where no drug was added (blank).

Table 2 shows the results. Table 2 shows that the antibacterial composition according to the present invention has the same growth inhibitory effect as the comparative product. It is considered that the reason why the same effect is exhibited is that the clathrate compound is dissolved or Cl-MIT is released from the clathrate compound at the added amount shown in Table 2.

[0036]

[Table 2]

[0037]

As described above in detail, the antibacterial composition of the present invention is obtained by dispersing Cl-MIT / 4,4'-ethylidenebisphenol inclusion compound in a dispersion medium to obtain a fluid preparation. Since it is a stable suspension with fluidity, it has good handling and workability, there is no problem of fine powder scattering, and the work environment is greatly improved. Since it does not contain a metal salt, it can be effectively used in a wide range of treated water systems without breaking the aqueous emulsion. The skin irritation of Cl-MIT is reduced. It is possible to prevent Cl-MIT from reacting with other substances and reducing the antibacterial activity. And so on, and are extremely useful industrially.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-279373 (JP, A) JP-A-1-190602 (JP, A) JP-A-1-316301 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) A01N 43/80 A01N 25/04 A01N 25/22 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] An inclusion compound comprising 5-chloro-2-methyl-4-isothiazolin-3-one and 4,4′-ethylidenebisphenol is dispersed in a dispersion medium to obtain a fluid preparation. An antibacterial composition characterized by the following.