JP2000290112A - Germicidal composition for industry use and antibiotic treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a germicidal composition for industrial use, capable of exhibiting excellent antibacterial effect in a low concentration, excellent in the durability of antibacterial effect and useful for the antisepsis and disinfection of papermaking process water in a paper and pulp industry by including an o-phthalaldehyde and a specific organic phosphorus compound as effective ingredients. SOLUTION: This germicidal composition for industrial use comprises (A) an o-phthalaldehyde and (B) an organic phosphorus compound [preferably a tetrakis(hydroxymethyl)phosphonium salt such as tetrakis(hydroxymethyl) phosphonium sulfate] of the formula [RnP(CH2OH)3]n+v.nXv- [wherein, R is hydroxymethyl, methyl, ethyl or the like; Xv- is an anion making a compound slightly soluble in water; (n) is 0 or 1; (v) is a valence of X] as effective ingredients. The weight content ratio of the ingredient A to the ingredient B is preferably (1:99)-(99:1). The composition is preferably added to water to be sterilized in a total amount of the ingredients A and B of 1-500 mg/L.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an industrial antibacterial agent composition and an antibacterial method using the same. More specifically, the present invention relates to papermaking process water in the paper and pulp industry, cooling water and washing water for various industries, heavy oil sludge, metalworking oil agent, fiber oil agent, paint, coating liquid for paper, latex, paste, etc. TECHNICAL FIELD The present invention relates to an industrial antibacterial agent composition useful for preserving and disinfecting an antibacterial agent, and a method for antibacterializing the industrial object using the composition.

[0002]

2. Description of the Related Art Conventionally, in the paper making process in the paper and pulp industry and in cooling water systems in various industries, slime due to bacteria and fungi is generated, which may cause obstacles such as deterioration in quality of products and reduction in production efficiency. Are known. Also, many industrial products such as heavy oil sludge, metalworking oils, fiber oils, paints, various latexes, sizing agents, etc., cause decay or contamination by bacteria or fungi, thereby contaminating the products and reducing their commercial value. Such an undesirable situation is caused. Therefore, various antibacterial agents have been used so far in order to prevent such microbial damage. In the past, organic mercury compounds and chlorinated phenol compounds were used, but these drugs are highly toxic to the human body and fish and shellfish and cause environmental pollution, so their use has been regulated. Recently, relatively low toxicity organic nitrogen sulfur compounds, organic halogen compounds and organic sulfur compounds have been used as industrial antibacterial agents. Published by the Mold Society))). Among these antibacterial agents, aldehyde compounds and organic phosphorus compounds have also been developed as effective antibacterial agents having relatively low toxicity. Also, o-phthalaldehyde, one of the active ingredients of the present invention, is known as an industrial antibacterial agent, and tetrakis (hydroxymethyl) phosphonium salt, which is preferably used as another active ingredient, is also commercially available. It is already known as an antibacterial agent. Although the above-mentioned various low-toxicity antibacterial agents have low toxicity, it is desirable to reduce the amount of use as much as possible from the viewpoints of pollution, environmental protection, and reduction of processing costs. Therefore, an antibacterial agent which exhibits an antibacterial effect for a longer time with a minimum amount of addition is inevitably desired. From such a viewpoint, for example, an organic phosphorus compound such as a tetrakis (hydroxymethyl) phosphonium salt is also used as an aldehyde. Attempts have been made to develop a synergistic bactericidal effect in combination with a series compound (Japanese Patent No. 2510748). However, in this case, an aliphatic aldehyde is used as the aldehyde-based compound, and the use of an aromatic aldehyde is not described at all.

[0003]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides an industrial antibacterial agent composition which can exhibit excellent antibacterial effect at a low concentration and has excellent durability. And an antibacterial method using the same.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that by combining o-phthalaldehyde with an organophosphorus compound having a specific structure, the synergistic action of the compound is achieved. The same bactericidal effect is exerted in an amount much smaller than the amount of the drug when used alone,
They have found that the object can be achieved, and have completed the present invention based on this finding. That is, the present invention
(1) (A) o- phthalaldehyde and (B) the general formula _{[R n P (CH 2 OH} ) 3] n + v · nX v- ... [1] ( R in formula hydroxymethyl group, a methyl group, An ethyl or allyl group, X ^v- is an anion that makes the compound slightly water-soluble, n is 0 or 1, and v is the valence of X). Antimicrobial composition,
(2) Component (A) and component (B) are in a weight ratio of 1: 999.
(1) or (3) wherein the organic phosphorus compound as the component (B) is a tetrakis (hydroxymethyl) phosphonium salt. In the industrial antibacterial composition according to the item 2), and (4) the industrial target system to be sterilized, the (1), (2) or
(3) An antibacterial method characterized by adding the industrial antibacterial agent composition described in (3).

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the industrial antibacterial composition of the present invention, o-phthalaldehyde is used as the component (A). This o-phthalaldehyde is

Embedded image Is a relatively low-toxic aromatic dialdehyde, which can be easily produced by a known method, and is also available as a commercial product. On the other hand, the organic phosphorus compound used as the component (B) is a general formula _{[R n P (CH 2 OH} ) 3] n + v · nX v- ... compound having the structure represented by [1]. In the above general formula [1], R represents a hydroxymethyl group, a methyl group,
Either an ethyl group or an allyl group, X ^v- is an anion which makes the compound slightly water-soluble. n is 0 or 1, and v is the valence of X. Examples of the anion X ^v- include Cl ⁻ , S
O ₄ ^2-and PO ₄ ^3- is preferable. Examples of the organic phosphorus compound represented by the general formula [1] include tetrakis (hydroxymethyl) phosphonium salt, methyltris (hydroxymethyl) phosphonium salt, ethyltris (hydroxymethyl) phosphonium salt, allyltris (hydroxymethyl) phosphonium salt and Tris (hydroxymethyl) phosphine, among which,
Tetrakis (hydroxymethyl) phosphonium salts are preferred. Specific examples of the tetrakis (hydroxymethyl) phosphonium salt include tetrakis (hydroxymethyl) phosphonium sulfate, tetrakis (hydroxymethyl) phosphonium chloride, and tetrakis (hydroxymethyl) phosphonium phosphate. In the present invention, this (B)
The component organic phosphorus compounds may be used alone or in combination of two or more. The industrial antimicrobial composition of the present invention, by combining o-phthalaldehyde and the organic phosphorus compound represented by the general formula [1] in this way, has a low bactericidal effect when used alone, but has a synergistic effect. Demonstrate excellent sterilizing effect. The mixing ratio of the component (A) and the component (B) in the composition of the present invention is preferably from 1:99 by weight in terms of synergistic effect.
9 to 99: 1, more preferably 1:99 to 8
0:20, particularly preferably 10:90 to 50:50
Range. The industrial antimicrobial composition of the present invention comprises the above-mentioned components (A), o-phthalaldehyde, and (B) an organic phosphorus compound represented by the general formula [1] as active ingredients. When they are used in combination, it is usually preferable to use them as a one-part preparation in a liquid form. However, they may be individually prepared into a single preparation and separately added to an industrial target system to be antibacterial.

In the case of a one-part preparation, it is usually dissolved or dispersed in a solvent to prepare a solution or suspension. At this time, water or an organic solvent is used as the solvent. Here, examples of the organic solvent include amides such as dimethylformamide and dimethylacetamide, glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and polyethylene glycol, methyl cellosolve, phenyl cellosolve, diethylene glycol monomethyl ether, and diethylene glycol. Glycol ethers and glycol esters such as monoethyl ether ether, dipropylene glycol monomethyl ether, ethylene glycol diacetate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and alcohols having up to 8 carbon atoms Kind,
Methyl acetate, ethyl acetate, butyl acetate, dimethyl maleate, diethyl adipate, ethyl lactate, dimethyl glutarate, dimethyl succinate, dimethyl phthalate, 3-methoxybutyl acetate, 3-methoxybutyl acetate, 2-ethoxymethyl acetate, Esters such as 2-ethoxyethyl acetate and propylene carbonate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and isophorone, ethers such as 1,2-dibutoxyethane, dioxane and tetrahydrofuran, toluene, xylene,
Examples thereof include aromatic solvents such as 1,2-dimethyl-4-ethylbenzene, and dimethyl sulfoxide and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more. In addition, it can be used as a water suspending agent. In this case, using a ball mill or an attritor, the components (A) and (B) and optionally a thickener such as xanthan gum, ramzan gum, and guar gum are added to water. It is preferable to add a dispersant such as a nonionic, anionic, cationic, or amphoteric surfactant and wet-pulverize to prepare an aqueous suspension.
If the industrial target system to be sterilized is an oil system such as heavy oil sludge, cutting oil, or oil paint, use a hydrocarbon oil such as heavy oil, kerosene, or spindle oil as a solvent to prepare a one-part formulation. Preferably, the above-mentioned surfactants may be used. In the industrial antibacterial composition of the present invention, other fungicidally active compounds can be used together with the above-mentioned components (A) and (B), if desired, as long as the object of the present invention is not impaired. The industrial antimicrobial composition of the present invention thus prepared is, for example, in an industrial target system such as a papermaking system of the pulp and paper industry or a cooling water system of a cooling tower, and has an expanded antibacterial spectrum and a remarkable synergistic bactericidal effect. By exhibiting an excellent antibacterial effect and an effect of preventing slime adhesion. Next, in the antibacterial method of the present invention, the industrial antibacterial agent composition is added to various industrial target systems to be sterilized. In this case, the components (A) and (B) They may be added simultaneously or separately. Thereby, in various industrial target systems,
A remarkable bactericidal effect and an effect of suppressing the growth of microorganisms are exhibited.
In particular, when added to a process water system of a papermaking process or an industrial cooling water system, a remarkable antibacterial effect is exhibited. Further, the amount of the antibacterial agent composition of the present invention varies depending on the type of the industrial target system to be sterilized, but generally, the amount of the component (A) and the component (B) relative to the water used. In total, 0.05-
About 1000 mg / liter, preferably 1 to 500 mg / liter
It is chosen to be in the liter range.

[0007]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, o-phthalaldehyde is
A powder reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used, and the tetrakis (hydroxymethyl) phosphonium salt used was "TOLIDE PS75" (containing 75% by weight of tetrakis (hydroxymethyl) phosphonium sulfate) manufactured by Albright & Wilson. . Example 1, Comparative Examples 1 and 2 Pseudomonas, a representative strain of gram-negative bacteria found in process water in the pulp and paper industry, cooling water for various industries, paints, paper coating solutions, latex, and paste
Aeruginosa was used to conduct a test for confirming the bactericidal effect when each drug was combined. A bacterial solution pre-cultured in a bouillon medium was added to sterilized water (0.1 M phosphate buffer, pH 7.0) in advance so that the number of viable bacteria was about 1 × 10 ⁷ CFU / ml. The various compounding agents shown are added so that the total amount of the active ingredient becomes 3 ppm,
Shake for 0 minutes. Then, the viable cell count was measured, and the bactericidal rate (%) with respect to the initial cell count (7.73 × 10 ⁶ CFU / ml) was determined. Table 1 shows the results.

[0008]

[Table 1]

[Note] (a): o-phthalaldehyde (b): glutaraldehyde (c): formaldehyde (B): tetrakis (hydroxymethyl) phosphonium sulfate As is clear from Table 1, o-phthalaldehyde And tetrakis (hydroxymethyl) phosphonium sulfate in a weight ratio of 1:99 to 90:10 in combination (Example 1), a higher bactericidal rate than that of a single agent due to a synergistic effect. Is recognized. Also, a slight synergistic effect is observed with the combination of Comparative Examples 1 and 2, but the effect is extremely small. Example 2, Comparative Examples 3 and 4 A temperature controller, a stirrer, and a thermometer were attached to a polyvinyl chloride water tank having a diameter of 165 mm and a holding water amount of 3000 ml, and a slime measuring plate having a width of 2.5 cm and a length of 4 cm. A stainless steel plate having a thickness of 0.2 mm was mounted so as to be immersed in a water tank. After adding 1% by weight of IBKP pulp and a white water culture solution (a culture solution obtained by culturing white water collected from a newsprint papermaking process in a bouillon liquid medium) to a 1,000-fold diluted broth liquid medium at a rate of 0.1 ml / liter. Then, artificial white water adjusted to pH 5.0 with aluminum sulfate was supplied to this tank at a flow rate of 9 liter / hour, and the same amount of artificial white water was discharged. The chemicals shown in Table 2 were used in a test tank so that the total concentration was 5 ppm, and
Pump 3 times a day (30 times a day) so that it is held for 5 minutes.
Min). After maintaining the white water temperature at 30 ° C. and continuing the stirring for 5 days, the slime adhesion preventing effect was evaluated. The slime evaluation was performed by measuring the slime adhesion thickness using a wet gauge [manufactured by Ket Co., Ltd., for measuring the thickness of undried paint], and comparatively evaluated. Since the amount of slime adhered to each test varies depending on white water and other conditions used, it is a relative and comprehensive evaluation with no slime control agent added and a comparative agent. The results are shown in Table 2.

[0010]

[Table 2]

[Note] (a): o-phthalaldehyde (b): glutaraldehyde (c): formaldehyde (B): tetrakis (hydroxymethyl) phosphonium sulfate As is clear from Table 2, o-phthalic acid By using aldehyde and tetrakis (hydroxymethyl) phosphonium sulfate in combination, an effect of preventing slime adhesion, which is an important performance as an industrial bactericide, is recognized, and the effect is more remarkable than when a single agent is added. high. Example 3, Comparative Examples 5 and 6 Each chemical was added to white water (mainly Bacillus, Pseudomonas, Flavobacterium and Alcaligenes) collected from a paper machine at a certain paper mill, and the mixture was added at 30 ° C. for 30 minutes. Shake. Thereafter, the number of surviving bacteria was measured, and the minimum bactericidal concentration (minimum active ingredient concentration, ppm) at which 99% or more of the initial number of bacteria was killed was determined. The results are shown in Table 3. In addition, the antibacterial agent composition of the composition shown below was used as a medicine of each example. Example 3 Tetrakis (hydroxymethyl) phosphonium sulfate 10% by weight, o-phthalaldehyde 1
0% by weight, dimethylacetamide 60% by weight and water 20
An antibacterial agent composition containing% by weight. Comparative Example 5: An antimicrobial composition containing 20% by weight of tetrakis (hydroxymethyl) phosphonium sulfate and 80% by weight of water. Comparative Example 6: An antimicrobial composition containing 20% by weight of o-glutaraldehyde and 80% by weight of dimethylacetamide.

[0012]

[Table 3]

[Note] A paper white water: pH 7.1, initial bacterial count 8.6 × 10 ⁸ CFU /
Milliliter B paper white water: pH 5.6, initial bacterial count 7.5 × 10 ⁷ CFU /
Milliliter paper white water: pH 4.4, initial bacterial count 1.2 × 10 ⁶ CFU /
Milliliter As can be seen from Table 3, the antibacterial agent composition of the present invention (Example 3) has a wider pH range and a higher bacterial count than that of Comparative Example 5 and Comparative Example 6 in a single preparation. For the system,
It shows a remarkable bactericidal effect.

[0014]

The industrial antibacterial composition of the present invention comprises o-phthalaldehyde and a specific organic phosphorus compound as active ingredients, and exhibits an excellent bactericidal effect in a small amount due to its synergistic action. For example, papermaking process water in the paper and pulp industry, cooling water and washing water for various industries, heavy oil sludge, metalworking oil, fiber oil, paint, paper coating liquid,
It is useful for preserving and sterilizing latex and paste.

Claims (4)

[Claims] 1. A (A) o-phthalaldehyde and (B) the general formula _{[R n P (CH 2 OH} ) 3] n + v · nX v- (R in the formula is a hydroxymethyl group, a methyl group, an ethyl group Or an allyl group, X ^v- is an anion that makes the compound slightly water-soluble, n is 0 or 1, and v is the valence of X). Composition. 2. A weight ratio of component (A) to component (B) of 1:
The industrial antibacterial composition according to claim 1, which is contained at a ratio of 999 to 99: 1. 3. The organic phosphorus compound as the component (B) is a tetrakis (hydroxymethyl) phosphonium salt.
Or the industrial antibacterial composition according to 2. 4. An industrial system to be sterilized according to claim 1,
4. An antibacterial method comprising adding the industrial antibacterial composition according to 2 or 3.