JP3018729B2 - Industrial antibacterial agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel industrial antibacterial agent, and more particularly to an industrial antibacterial agent which exhibits excellent antibacterial activity stably against a wide range of microorganisms over a long period of time.

[0002]

2. Description of the Related Art In a cooling water system of various plant plants, slime composed of bacteria, filamentous fungi, algae, etc. is generated in the system, and slime such as deterioration of thermal efficiency, blockage of water flow pipes, corrosion of pipe metal materials, and the like. It is known that disability often occurs. In the paper pulp papermaking system, slime containing bacteria, filamentous fungi and the like as main constituent microorganisms is formed on the inner wall surface of the system using various additives such as cellulose and starch as a nutrient source. Such slime peels off from the wall surface and mixes as foreign matter in the product, lowering product quality or causing paper breakage in the papermaking process, impeding continuous operation and greatly reducing production efficiency. Such as undesired situations. Especially in the pulp and paper industry, starch, latex, casein, etc. are used in large quantities as additives, and all of these additives are nutrients for the propagation of microorganisms, so they are spoiled by microorganisms and cause deterioration of products. It is a big cause. In addition, in related fields such as water-based paints, emulsion paints, emulsion adhesives, metalworking oils, latex, starch paste liquids, and paper coating liquids that are rich in organic substances, product quality and productivity are reduced by microorganisms. It is known that various obstacles such as the above occur. Conventionally, such microorganisms in various industrial fields, filamentous fungi, yeast, against microbial disorders such as algae, its implementation is relatively simple and economical,
Treated with antibacterial agent. Conventionally, thiocyanate-based compounds, halocyanoacetamide-based compounds, isothiazolone-based compounds, and the like have been frequently used as the antibacterial agent. However, the thiocyanate-based compound has a weak bactericidal activity and has a drawback that when used for a long period of time, it tends to be resistant to slime-constituting bacteria, and particularly has a weak antibacterial activity against microbacterium that often appears as slime-constituting bacteria. ing. In addition, the halocyanoacetamide-based compound has excellent fast-acting bactericidal properties, and shows a stable bactericidal effect with little influence of the number of bacteria in the treated water. Although it can be said that the fungicide is an effective fungicide, this kind of fungicide has a drawback that its effect is poor and its antibacterial activity against filamentous fungi is weak. On the other hand, isothiazolone-based compounds have a drawback that they have poor stability in water, especially in neutral to alkaline water or water containing a reduced product. Therefore, conventionally, a method of coexisting a metal salt or using a complex compound thereof has been attempted in order to enhance the stability in water, but this method is not necessarily sufficient in terms of the persistence of the effect, and it is not suitable for latex and the like. When it is applied, it has disadvantages such as the emulsion being destroyed by the contained metal salt. Furthermore, the isothiazolone-based compound also has a problem that its antibacterial activity is weak against spore bacteria involved in spoilage of industrial products such as color coating solutions and latex. On the other hand, a compounding agent of an isothiazolone compound and glutaraldehyde has been proposed (JP-A-58-1891).
03 publication). However, although this compound has excellent antibacterial activity against a wide range of microorganisms, it has the disadvantage of poor stability (precipitation and coagulation in a short period of time).

[0003]

SUMMARY OF THE INVENTION Under the above circumstances, an object of the present invention is to provide an industrial antibacterial agent which shows a stable and excellent antibacterial activity against a wide range of microorganisms over a long period of time. It was done as.

[0004]

The present inventors have conducted intensive studies to develop an industrial antibacterial agent having the above-mentioned preferable properties, and as a result, by combining an isothiazolone-based clathrate compound with glutaraldehyde. They have found that the object can be achieved, and have completed the present invention based on this finding. That is, the present invention provides an industrial antibacterial agent containing an isothiazolone-based clathrate compound and glutaraldehyde as active ingredients. Hereinafter, the present invention will be described in detail. The isothiazolone-based clathrate compound used in the antibacterial agent of the present invention is a compound obtained by including an isothiazolone-based compound as a guest compound and clathrating it with a host compound capable of including the same, and the isothiazolone-based compound serving as the guest compound includes: General formula

[0005]

Embedded image

(Wherein R is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group, X ¹ and X ²
Is a hydrogen atom or a halogen atom, which may be the same or different, or may be condensed with each other to form a benzene ring). Specific examples of the compound represented by the general formula [1] include 5-chloro-2-methyl-4.
-Isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-octyl-4-
Preferred are isothiazolin-3-one, 1,2-benzoisothiazolin-3-one and the like.

On the other hand, the clathrate compound is not particularly limited as long as it can form the clathrate compound by clathrate the isothiazolone compound. Such clathrates include, for example, 1,1,6,6-tetraphenyl-2,4
-Hexadiyne-1,6-diol, 1,1-bis (2,
4-dimethylphenyl) -2-propyn-1-ol,
1,1,4,4-tetraphenyl-2-butyne-1,4-diol, 1,1′-bi-2-naphthol, 1,1,6,6-
Tetrakis (2,4-dimethylphenyl) -2,4-hexadiyne-1,6-diol, 9,10-bis (4-methylphenyl) -9,10-dihydroanthracene-9,1
0-diol, 1,1-bis (4-hydroxyphenyl) cyclohexane, N, N, N'N '-(tetracyclohexyl)-[1,1'-biphenyl] -2,2'-dicarboxamide, 5 , 5'-Dichloro-2,2'-dihydroxydiphenylmethane, deoxycholic acid, 2,5-di-t
A host compound such as -butylhydroquinone is preferably used.

[0008] These host compounds and 5-chloro-2-
The inclusion compound with methyl-4-isothiazolin-3-one is usually in a solid state. The content of 5-chloro-2-methyl-4-isothiazolin-3-one in the clathrate compound is usually selected in the range of 10 to 40% by weight. The industrial antimicrobial agent of the present invention contains the above-mentioned isothiazolone-based clathrate and glutaraldehyde as active ingredients, and their use ratio is usually the weight ratio of the isothiazolone-based clathrate and glutaraldehyde. 10:
Both components are blended so as to be in the range of 1 to 1:50, preferably 1: 1 to 1:10. At this time, one kind of the isothiazolone-based inclusion compound may be used, or two or more kinds thereof may be used in combination.

The method of using the industrial antibacterial agent of the present invention is not particularly limited, but at least an isothiazolone-based clathrate compound among the active ingredients of the industrial antibacterial agent is dispersed in water or an organic dispersion medium (flowable). It is preferable to use them. In this case, from the viewpoint of dispersibility in a dispersion medium, the isothiazolone-based clathrate is preferably as small as possible in particle size, and is practically a fine powder that passes through 100 mesh. The organic dispersion medium is not particularly limited, for example, ethylene glycol, propylene glycol, glycerin, alcohols such as polyglycerin, diethylene glycol monomethyl ether, glycol ethers such as ethylene glycol monobutyl ether, liquid paraffin, further xylene, Alkylbenzenes such as toluene, vegetable oils such as castor oil, soybean oil, olive oil, rapeseed oil, terpenes such as hinoki oil, and surfactants such as polyoxyethylene alkyl ether can be used. One of these dispersion media may be used, or two or more of them may be used as a mixture.

In the industrial antibacterial agent of the present invention, as a stabilizer, if desired, for example, carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, sodium alginate, xanthan gum, ramzan gum,
Sodium polyacrylate, polyacrylamide, alkyl methacrylate / diethylaminoethyl methacrylate copolymer, alkyl methacrylate / N-vinyl-
2-pyrrolidone acrylate copolymer, alkyl methacrylate / polyethylene glycol methacrylate copolymer, dodecyl fumarate / diethylaminoethyl methacrylate copolymer, styrene / maleic acid copolymer,
Sodium naphthalene sulfonate formalin condensate, sodium melamine sulfonate formalin condensate, sodium lauryl sulfate, sodium lauryl benzene sulfonate, polyoxyethylene alkyl ether, succinimide, succinate, polyalkyl glycol carbonate, polyalkylene glycol carbamine Acid esters, alkylbenzene sulfonic acids, nonionic surfactants and the like can be used. The addition amount of the industrial antibacterial agent of the present invention is appropriately selected depending on the type of the sterilization target to which the antibacterial agent is applied.In general, when the sterilization target is a paper pulp papermaking system, that is, when used as a slime control agent. The total amount of the active ingredients of the isothiazolone-based inclusion compound and glutaraldehyde is 0.1 to 25 g / m ^3, and the object to be sterilized is a synthetic resin emulsion;
In the case of starch paste, paint, metalworking oil, and color coating fluid,
That is, when used as a preservative, the total amount of the active ingredients is preferably selected so as to be 1 to 5000 g / m ³ .
The industrial antimicrobial agent of the present invention is used not only as a slime control agent in the paper and pulp industry, but also as a preservative for starch and casein, as a preservative for SBR latex, paints, adhesives, and as a preservative in metalworking oil-based systems. Can be

[0011]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention. In addition, each code | symbol in an Example and a comparative example means the following. IA: 1,1,6,6-tetrakis (2,4-dimethylphenyl) containing 30% by weight of a guest compound containing 5-chloro-2-methyl-4-isothiazolin-3-one (hereinafter abbreviated as CMI) ) Inclusion compound containing 70% by weight of 2,2,4-hexadiyne-1,6-diol as a host compound. IB: containing 20 wt% of CMI as a guest compound,
Inclusion compound containing 80 wt% of 5,5'-dichloro-2,2'-dihydroxydiphenylmethane as a host compound IC: 25 wt% of 4,5-dichloro-2-octyl-4-isothiazolin-3-one as a guest compound Inclusion compound containing 75% by weight of 1,1-bis (4-hydroxyphenyl) cyclohexane as a host compound II-A: Aqueous solution containing 10% by weight of CMI II-B: 10% by weight of CMI, 10% by weight of MgCl ₂ and Mg
Aqueous solution of CMI complex compound containing 5 wt% of (NO ₃ ) ₂ II-C: Ethylene glycol solution containing 10 wt% of CMI GA: Glutaraldehyde

Example 1, Comparative Example 1 Preparation stability test Formulations having the compositions shown in Table 1 were prepared and prepared at 25 ° C. and 40 ° C.
For one month, and its stability was determined according to the following criteria. For the antibacterial activity, the minimum inhibitory concentration (MIC ₂₄ ) was determined using Pseudomonas bacteria, and the rate of decrease in the activity was examined. The results are shown in Table 1. Appearance change ○: No change ×: Liquid turns brown to form a precipitate Antibacterial activity ○: Maintains 90% or more △: Less than 90% 50% or more ×: Less than 50%

[0013]

[Table 1]

Note 1) Kelzan: thickener As can be seen from Table 1, C dissolved in water or an organic solvent.
Formulations using MI have poor stability and reduced antibacterial activity, whereas the formulations of the present invention are stable for long periods of time. It is considered that the preparation of the present invention is stabilized by inclusion of CMI.

[0015] Example 2, against the Comparative Example 2 the coating color liquid
The antiseptic effect of the antibacterial agent was examined using a coating color liquid used in the pulp and paper industry. That is, a test solution prepared by adding 5% by weight of a solution pre-rotted to the coated starch color solution to a coated starch color solution (test solution pH 9.2, viable cell count 3.2 × 10 ⁴ cells / ml) was used. The antibacterial agents in the ratios shown in Table 2 were added to the test solution at 25 ppm, and after standing at 30 ° C. for 72 hours, the number of viable bacteria was measured by the agar plate method (medium 10 wt% broth medium). The results are shown in Table 2.

[0016]

[Table 2]

As can be seen from Table 2, the antibacterial agent of the present invention has a synergistic bactericidal effect as compared with the case where IB and GA are used alone.

[0018] Example 3, Comparative Example 3 starch slurry
Antiseptic test paper The antibacterial agent of the compounding ratio shown in Table 3 was added to the 2 wt% phosphate esterified starch slurry used for the interlayer adhesive at the pulp mill, and the mixture was allowed to stand at 30 ° C for 7 days. The minimum concentration effective for preservation was determined by measuring the degree of spoilage from the pH drop and odor of the liquid. Table 3 shows the results.

[0019]

[Table 3]

As can be seen from Table 3, the antimicrobial agent of the present invention has a synergistic antiseptic effect as compared with the case where IA and GA are used alone.

[0021] Example 4, for Comparative Example 4 Latex
Antiseptic test The antiseptic effect of the antibacterial agent was examined by an antiseptic test using emulsion latex. That is, 200 ppm of an antibacterial agent having the compounding ratio shown in Table 4 was added to a styrene-butadiene emulsion latex (pH 9.0), and the number of bacteria spoiled by this product was adjusted to 10 ⁶ / ml. After the addition, the mixture was stored at 30 ° C. After adding the spoilage bacterium at a frequency of 10 ⁶ cells / ml once every two weeks, the number of viable bacteria was measured on the seventh day. The antiseptic effect is 10 ³
The number of days to prevent putrefaction was determined on the basis of the number of cells per ml or less. Table 4 shows the results.

[0022]

[Table 4]

As can be seen from Table 4, the antibacterial agent of the present invention has a long term anti-rot effect compared to the case where IB and GA are added alone. Also,
The antibacterial agent of the present invention shows more excellent effect persistence due to the stabilized CMI as compared with the case where II-B and II-C are added together with GA.

Example 5 and Comparative Example 5 Water-based paint antifungal test A water-based paint was used as a sample and the method (J
The antifungal effect was examined according to IS Z2911). The test was performed as follows. First, filter paper was immersed in a paint containing 0.2% by weight of an antibacterial agent having the composition shown in Table 5, and the stock was uniformly applied and dried (temperature: 20 ° C, humidity: 75%, 4%).
8 hours). Next, the filter paper was cut into a circular shape having a diameter of 30 mm and immersed in water at 20 ° C. Test pieces were prepared by changing the water immersion period to 1, 7, and 14 days, respectively. Next, after drying each test piece, it was stuck on an agar plate medium based on glucose and peptone, and a mixed spore suspension of the following five molds was placed thereon, and the number of mold spores was 10 ⁵ / ml. After culturing at 30 ° C. for one week, the effect was examined according to the following evaluation criteria by observing the appearance. For comparison, the same test was carried out for the case where no additive was added. The results are shown in Table 5.

Mixed spores Aspergillus niger, Penicillium funiculosum, Cladosporium cladosporioides, Aureobasidium pullulans, Gliocladium virens. Evaluation Criteria 3: No mold growth was observed on the test piece. 2: Mold growth on the test piece does not exceed 1/3 of the total area. 1: The growth of the mold on the test piece exceeded 1/3 of the total area.

[0026]

[Table 5]

From Table 5, it can be seen that the antibacterial agent of the present invention has an excellent antifungal effect and also has an excellent sustainability of the effect.

Example 6, Comparative Example 6 Latex emulsion
® emission breakdown test styrene - examined the effect of antimicrobial agents against butadiene emulsion latex. That is, 1 ml of a latex emulsion was dispersed in a circular shape on a glass petri dish, and two or three drops of an antibacterial agent were dropped at the center of the sample. After standing for 30 seconds, the mixture was gently mixed with a glass rod, and the presence or absence of solidification of the emulsion was observed. Table 6 shows the results.

[0029]

[Table 6]

From Table 6, it was confirmed that the antibacterial agent of the present invention was more stable to the emulsion than the conventional preparation.

[0031]

The industrial antibacterial agent of the present invention (1) exhibits a synergistic antibacterial effect and exhibits excellent antibacterial properties against a wide range of microorganisms. (2) The isothiazolone-based inclusion compound can produce a stable preparation with glutaraldehyde. (3)
Isothiazolone-based clathrates are stable in water, and as a result, good antimicrobial effect can be maintained for a long period of time. (4) Isothiazolone-based clathrates can be formulated stably without complex salts with metal salts Therefore, when applied to an emulsion product such as a latex, it does not cause any obstacle such as breaking the emulsion.

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-3-112908 (JP, A) JP-A-2-28102 (JP, A) JP-A-1-272506 (JP, A) JP-A-58-58 189103 (JP, A) JP-A-58-150577 (JP, A) JP-A-5-247011 (JP, A) JP-A-1-190602 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 43/80 A01N 35/02

Claims (1)

(57) [Claims] 1. An industrial antibacterial agent comprising an isothiazolone-based clathrate compound and glutaraldehyde as active ingredients.