JPH10287511A - Antimicrobial and algicidal agent for nonmedical use and prevention of microorganism and alga - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject antimicrobial and algicidal agent, showing strongly and immediately antimicrobial and algicidal effects on a wide range of microorganisms by use in a low concentration, by including o-phthalaldehyde, glutaraldehyde and a quaternary ammonium salt. SOLUTION: This antimicrobial and algicidal agent comprises (A) o- phthalaldehyde, (B) 1-50 pts.wt. based on 1 pt.wt. of the component A of glutaraldehyde, (C) O.01-O.2 pts.wt. based on 1 pt.wt. of the total of the components A and B of a quaternary ammonium salt and optionally (D) a stabilizer and other additives. A compound of the formula (R<1> is a straight-chain or branched 1-18C alkyl; R<2> is R<1> , benzyl or hydroxylethyl; X is chlorine, bromine, OH or propionato) is preferably used as the component C. The antimicrobial and algicidal agent is dissolved in a solvent (e.g. water) and is used for a slime-producing water system in production of paper or pulp.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-medical germicidal and algicide. In more detail, products such as water-based systems for papermaking in paper pulp mills, metalworking oils, fiber oils, water-based paints, coating solutions for paper, latex, paste, leather, etc. The present invention relates to an antibacterial and antialgal agent used for controlling bacteria, filamentous fungi, yeast, algae, and the like generated in a cooling water system for cooling and heating equipment, a circulating water system in various factories, and the like.

[0002]

2. Description of the Related Art Conventionally, products such as water system, metal working oil agent, fiber oil agent, water-based paint, coating liquid for paper, latex, glue, leather, etc. of the paper making process of a paper pulp mill and the water system of the manufacturing process, building Bacteria, microorganisms, and the like increase and increase in the cooling water system of the cooling and heating equipment and the circulating water system of various factories, causing a decrease in productivity, product quality, and the like. In particular, in the water systems of paper mills and pulp mills, there is a problem that bacteria, filamentous fungi, and yeasts proliferate at locations where the flow velocity is slow, and slime, that is, slime is formed. The slime is also formed on a refiner wall, a screen, an inlet, and a chest wall of a raw water system, which are part of a white water circulation process in a papermaking and pulp mill. When a large amount of slime is generated, what adheres to the walls and the like drops off and is made together with other raw materials, causing defects such as so-called eyeballs on the paper to lower the paper quality and balance the wet paper strength. Damage and often cause paper breaks. Such a phenomenon causes a great decrease in productivity particularly when producing paper and pulp using a high-speed machine, and causes enormous economic loss. On the other hand, in recent years, in these irrigation systems, eutrophication has been promoted by closing irrigation water, and since irrigation water contains a reducing agent through the use of bleaching agents such as hydrosulfite and sodium sulfite, it has a strong effect under reducing conditions. It is becoming difficult to control slime and the like unless the drug has a sterilizing power. Also, products such as metalworking oils, fiber oils, aqueous paints, paper coating liquids, latexes, printing pastes, pastes containing starch as a component, leather, etc. This causes problems such as deterioration of the working environment due to fouling of the product and generation of offensive odor. Also, in a cooling water system of a cooling and heating facility such as a building and a circulating water system of various factories, the occurrence of algae in a water tank causes problems such as blockage and corrosion of pipes and a decrease in heat exchange efficiency.

[0003] Meanwhile, various types of microbial control agents have been proposed for such water systems.
For example, typical examples include isothiazolone-based compounds such as 3-isothiazolone described in JP-B-46-21240 and metal salt complex of 3-isothiazolone described in JP-B-54-23968, and 1,1-described in JP-B-46-4199. Benzisothiazolone compounds such as 2-benzisothiazolone, bromonitroalcohol described in JP-B-40-8917, 2,2-dibromo-3-nitrilopropionamide described in JP-B-56-202841, and JP-B-3-14801. There are algicides in which a quaternary ammonium salt is added to the glutaraldehyde described.

[0004] In order to improve these microbial control agents, that is, to cope with a decrease in potency due to the emergence of resistant bacteria and bacterial replacement phenomena, skin irritation of isothiazolone compounds, and bubbling of quaternary ammonium salts. In order to overcome the disadvantages such as severe properties, various control agents containing orthophthalaldehyde as an active ingredient have been proposed. For example, orthophthalaldehyde alone or in combination with glutaraldehyde or formaldehyde to control adherent microorganisms in a recirculating cooling tower or an aqueous system of an oil field water flood system (Japanese Patent Application Laid-Open No. 6-23368), or orthophthalaldehyde Using slime as a slime control agent for papermaking (Japanese Unexamined Patent Publication No.
No. 264,397), a compound having a bromonitro alcohol compound blended with orthophthalaldehyde to enhance its effectiveness as a slime controlling agent for papermaking (Japanese Patent Application Laid-Open No. Hei 7-116669).
Nos. 8-157307), and a controlling agent obtained by blending an isothiazolone-based compound or an ionene polymer with orthophthalaldehyde (JP-A-7-116669, 8-188).
504). Regarding the antimicrobial activity of orthophthalaldehyde, prior to each of the above prior arts, D.A.
Reported by Lane et al. (D. Rehn et al., Zbl. Bak
T. Hyg. Abt. Orig. B 172, 508-519 (1981)), then, as a medical disinfectant, orthophthalaldehyde alone (Japanese Patent Laid-Open No. 313705/1988), glutaraldehyde was added to orthophthalaldehyde. Compounds (US Pat. No. 4,847,304) and those containing a mixture of orthophthalaldehyde with a linear dialdehyde and a quaternary ammonium salt (French Patent No. 2,718,923) have been proposed. I have. However, even though orthophthalaldehyde is effective in medical disinfectant applications, it has various problems in the manufacturing process of a paper pulp mill and in the antibacterial and algae control of industrial water. First, orthophthalaldehyde alone has a problem that the microbial control ability is extremely reduced at a concentration of about 10 mg / liter. On the other hand, use at a higher concentration than this is not desirable for practical use, in part because the cost of orthophthalaldehyde is much higher than the conventional one. For this reason, as described above, orthophthalaldehyde and other control agents have been proposed for the purpose of increasing the control effect at a low concentration by mixing with other control agents.
It is still inadequate because of its inadequate efficacy against the above-mentioned reducing water system that has been generalized in recent pulp and paper mills and the need to incorporate a relatively large amount of expensive orthophthalaldehyde. It was not something.

In addition, the above-mentioned French Patent No. 2,718,9
The disinfectant described in No. 23 contains a high proportion of quaternary ammonium salts, has excellent foaming properties, and is useful as a disinfectant, but is practically used in water circulation systems such as paper and pulp mills. I couldn't do it. In other words, foaming properties in applications relating to papermaking pulp are not only undesirable because they cause aqueous foaming, and the quaternary ammonium salt compound itself is cationic and tends to be deactivated by adsorbing on cellulose fibers. is there. Therefore, as a bactericide (conversely, a quaternary ammonium salt compound is sometimes used as a drainage improver, etc. by utilizing such a property that it is easily adsorbed on cellulose fibers due to cationic properties) In practice, use has been avoided. In addition, in the case of industrial products and their manufacturing processes, cationic quaternary ammonium salts are generally adsorbed to organic compounds to be preserved in many cases. Therefore, avoid using them in industrial preservatives. Was customary. In addition, as an algicide using a quaternary ammonium salt,
No. 14801 describes glutaraldehyde mixed with a quaternary ammonium salt such as benzalkonium chloride. In this example, however, foaming is severe in a circulating water system such as an air-conditioning cooling tower. The use is limited to non-circulating water systems. From these facts, even a water system containing a reducing substance exhibits a high antibacterial and algicidal effect with a small amount of use, and has low foaming and can be used even in a circulating water system. Development of an anti-algal method was desired.

[0006]

Accordingly, the present invention provides
For a wide range of microorganisms such as bacteria, filamentous fungi, yeast, and algae, using a low concentration, even in the presence of a reducing substance, shows a powerful and immediate antibacterial and algic effect, and can prevent the regeneration of microorganisms for a long time, An object of the present invention is to provide a low-cost non-medical germicidal and algicidal agent and a germicidal and algal prevention method capable of suppressing foaming which is a problem.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above problems, and as a result, by using glutaraldehyde, orthophthalaldehyde and a quaternary ammonium salt together, even a small amount of bacteria can be used to kill a wide range of microorganisms. It was found to be effective for water systems containing reducing substances, and it was found that foaming was reduced, and that a fungicidal and algicidal agent with excellent antibacterial and algicidal effects could be obtained. Invented the invention. That is, the present invention provides (1) a non-medical antibacterial and algicidal agent characterized by comprising orthophthalaldehyde, glutaraldehyde and a quaternary ammonium salt, and (2) a glutaraldehyde content of orthophthalaldehyde. 1 to 50 parts by weight for 1 part by weight,
The content of the quaternary ammonium salt is 0.01 to 0.2 parts by weight based on 1 part by weight of the total of glutaraldehyde and orthophthalaldehyde (1).
(3) The non-medical bactericidal anti-algal agent according to (1) or (2), wherein the quaternary ammonium salt is represented by the following general formula (I). Anti-algal agents,

[0008]

Embedded image

(Wherein R ¹ may be the same or different,
Represents a linear or branched alkyl group having 1 to 18 carbon atoms,
R ² represents a linear or branched alkyl group having 8 to 18 carbon atoms, a benzyl group or a hydroxyethyl group; X represents chlorine;
Represents a bromine, hydroxyl or propionate group. (4) Non-medical antibacterial and algicidal agents according to (1), (2) or (3), which are for slime generating water systems in paper or pulp production, (5) air conditioning or industrial use (1), (2) or (3)
(6) water-based paint, coating liquid for paper, latex, paste, leather or oil agent, or water-based in the production process thereof. , (2) or (3) the non-medical antibacterial and algicidal agent according to (7), (7) the antibacterial and algicidal agent according to (2) above, with orthophthalaldehyde, The total concentration of glutaraldehyde and quaternary ammonium salt is 2 to 200
(8) Non-medical bactericidal protection according to (1), (2) or (3), in a slime generating water system in paper or pulp production. An anti-algal and anti-algal method characterized by adding an anti-algal agent,
(9) (1), (2) or (3) for air conditioning or industrial water systems
A method of adding a non-medical antibacterial and algicidal agent according to the above item, and (10) a water-based paint, a coating liquid for paper,
An antiseptic method characterized by adding the non-medical antibacterial and antialgal agent according to (1), (2) or (3) to latex, glue, leather or oil or an aqueous system in the production process thereof. Is what you do.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The antibacterial and antialgal agent of the present invention is characterized by comprising orthophthalaldehyde (hereinafter referred to as OPA), glutaraldehyde (hereinafter referred to as GDA) and a quaternary ammonium salt. I do. The quaternary ammonium salt is preferably represented by the above general formula (I). In the general formula (I), R ¹ may be the same or different from each other, and is a linear or branched alkyl group having 1 to 18 carbon atoms. In this case, at least one of R ¹ has 8 to 8 carbon atoms.
In the alkyl group of 18, other R ¹ may be a lower alkyl group. R ² is a linear or branched alkyl group having 8 to 18 carbon atoms, a benzyl group or a hydroxyethyl group which may have a substituent on a benzene ring. Among R ² , an alkyl group having 8 to 18 carbon atoms or a benzyl group is preferable. X
Is a chlorine, bromine, hydroxyl or propionate group. In the quaternary ammonium salt represented by the general formula (I), at least one of R ¹ is a linear or branched alkyl group having 8 to 18 carbon atoms, and R ² has 8 to 18 carbon atoms.
Those which are 18 alkyl groups or benzyl groups are particularly preferred. Specific examples of the quaternary ammonium salt represented by the general formula (I) include didecyldimethylammonium chloride, diisononyldimethylammonium chloride, dioctyldimethylammonium chloride, octyldecyldimethylammonium chloride, and an alkyl group having 8 to 16 carbon atoms. Alkyldimethylbenzylammonium chloride, didecyldimethylammonium hydroxide,
Diisononyldimethylammonium hydroxide, dioctyldimethylammonium hydroxide, octyldecyldimethylammonium hydroxide, alkyldimethylbenzylammonium hydroxide having 8 to 16 carbon atoms in the alkyl group, didecylmethylhydroxyethylammonium propionate, tetradecyltrimethylammonium Bromide and the like. In the present invention, the quaternary ammonium salts may be used alone or in combination of two or more.

In the present invention, GDA is preferably used in an amount of 1 to 50 parts by weight per 1 part by weight of OPA.
5 parts by weight is more preferable, and 4 to 15 parts by weight is particularly preferable. If OPA is too small relative to GDA, the antibacterial and algicidal effects may be insufficient. On the other hand, when the amount is too large, the antibacterial and algal effects are saturated, which is not economical. In addition, since OPA has relatively low solubility in water, it is water-soluble (water-miscible) when it is formulated with water as a solvent. It may be necessary to use a large amount of the solvent. In the present invention, the amount of the quaternary ammonium salt used is the total amount of GDA and OPA of 1
With respect to parts by weight, 0.01 to 0.2 parts by weight is preferable,
0.02 to 0.15 part by weight is more preferable,
-0.1 parts by weight is particularly preferred. If the amount of the quaternary ammonium salt is too small, the antibacterial and algicidal effect is too low. If the amount is too large, foaming during use becomes severe, and use in a circulating water system may be difficult.

In the antibacterial and antialgal agent of the present invention, the above OP
A, GDA and a quaternary ammonium salt are essential components, but other commonly used additives such as a stabilizer can be added as necessary. The antibacterial and antialgal agent of the present invention is usually used by dissolving it in a solvent, and water is preferred as the solvent. This is because the GDA used in the present invention is generally industrially available as an aqueous solution having a concentration of about 50% by weight, and OPA having a solubility in water of about 6% by weight at room temperature is preferred in the present invention. GDA in percentage
This is because they coexist with each other to be in a compatible state and can be prepared as a uniform aqueous solution without adding a water-soluble organic solvent. As a solvent other than water, a water-soluble organic solvent inert to OPA, GDA and a quaternary ammonium salt can be used.
Glycol-based solvents such as polyethylene glycol having a molecular weight of about 300, polyethylene glycol monomethyl ether having an average molecular weight of about 225,
An aprotic solvent such as -methyl-2-pyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide is particularly preferably used. In order to prevent freezing in a severe winter, these organic solvents can be blended to lower the freezing point. Water and the organic solvent may be used singly or as a mixture of two or more kinds.
The weight ratio is preferably 0.1 to 20 times the total amount of the active ingredients of A, GDA and the quaternary ammonium salt.

In the present invention, as described above, each component may be mixed and used as a formulation, but OPA, GDA
Each of the quaternary ammonium and the quaternary ammonium can be used as it is or as a solution, and simultaneously added to the antibacterial and algal target. In any method, the total of OPA, GDA and quaternary ammonium is 2 to 200 mg / liter, preferably 20 to 100, based on the total weight of the water system.
It is preferable to use it in a concentration of mg / liter.

When slime control is performed, for example, in a papermaking process using the antibacterial and antialgal agent of the present invention, the slime is preferably added to circulating process water, such as a seed box, a reflower flow box, and a white water pit. The place of addition can be appropriately selected. In addition, the antibacterial and antialgal agents of the present invention have less foaming,
It can be used for air conditioning and industrial cooling water systems.
It can also be used for products such as water-based paints, paper coating liquids, latex, printing pastes, pastes containing starch, leather, metalworking oils, fiber oils and the like and water-based preservatives in the production process thereof.

[0015]

The antibacterial and antialgal agent and the antibacterial and antialgal method of the present invention, by using OPA, GDA and a quaternary ammonium salt together, have a low concentration of each component and a high immediate bactericidal effect and sustaining effect. Can be obtained, and can be used as a drug with a low bubbling and a high antibacterial and algal effect, and can be used for a wide range of antibacterial and algal targets including circulating water systems. In particular, the germicidal and anti-algal agent and the germicidal and anti-algal method of the present invention exert a strong germicidal and anti-algal effect even in a reducing water system containing a reducing agent such as sodium hydrosulfite and sodium sulfite, and furthermore, the bactericidal and anti-algal effect of microorganisms for a long time Reproduction can be prevented.

[0016]

Next, the present invention will be described in more detail with reference to examples. Example 1 Sample No. 1 was prepared according to the following formulation. 1 to 10 antibacterial and antialgal agents were prepared. (Sample No. 1) Component (% by weight) Orthophthalaldehyde 10.0 Glutaraldehyde 41.0 Didecyldimethylammonium chloride 5.0 Water 44.0 Total 100.0

(Sample No. 2) Ingredient (% by weight) Orthophthalaldehyde 10.0 Glutaraldehyde 50.0 Didecyldimethylammonium chloride 5.0 Polyethylene glycol (average molecular weight 200) 15.0 Water 20.0 Total 100. 0

(Sample No. 3) Ingredient (% by weight) Orthophthalaldehyde 8.0 Glutaraldehyde 44.0 Didecyldimethylammonium chloride 2.5 Water 45.5 Total 100.0

(Sample No. 4) Component (% by weight) Orthophthalaldehyde 8.0 Glutaraldehyde 30.0 Didecyldimethylammonium chloride 2.5 Water 59.5 Total 100.0

(Sample No. 5) Ingredient (% by weight) Orthophthalaldehyde 4.0 Glutaraldehyde 45.0 Didecyldimethylammonium chloride 2.5 Water 48.5 Total 100.0

(Sample No. 6) Ingredient (% by weight) Orthophthalaldehyde 5.0 Glutaraldehyde 30.0 Didecylmethylhydroxyethyl ammonium propionate 3.0 N, N-dimethylacetamide 22.0 Water 40.0 Total 100.0

(Sample No. 7) Ingredient (% by weight) Orthophthalaldehyde 5.0 Glutaraldehyde 40.0 Benzalkonium chloride 3.0 Water 52.0 Total 100.0

(Sample No. 8) Ingredient (% by weight) Orthophthalaldehyde 12.0 Glutaraldehyde 33.0 Tetradecyltrimethylammonium bromide 4.0 Polyethylene glycol (average molecular weight 200) 14.0 Water 37.0 Total 100. 0

(Sample No. 9) Component (% by weight) Orthophthalaldehyde 10.0 Glutaraldehyde 40.0 Diisononyldimethylammonium chloride 4.0 Polyethylene glycol (average molecular weight 200) 6.0 Water 40.0 Total 100.0

(Sample No. 10) Ingredient (% by weight) Orthophthalaldehyde 5.0 Glutaraldehyde 25.0 Didecyldimethylammonium chloride 2.5 Polyethylene glycol (average molecular weight 200) 15.0 Water 52.5 Total 100. 0

Comparative Example 1 For comparison, Comparative Sample No. 1-6
Were prepared. (Comparative sample No. 1) Component (% by weight) Orthophthalaldehyde 10.0 Polyethylene glycol (average molecular weight 200) 90.0 Total 100.0

(Comparative Sample No. 2) Ingredient (% by weight) Glutaraldehyde 50.0 Water 50.0 Total 100.0

(Comparative Sample No. 3) Ingredient (% by weight) Didecyldimethylammonium chloride 50.0 Water 50.0 Total 100.0

(Comparative sample No. 4) Ingredient (% by weight) Orthophthalaldehyde 5.0 Glutaraldehyde 25.0 Polyethylene glycol (average molecular weight 200) 45.0 Water 25.0 Total 100.0

(Comparative Sample No. 5) Ingredient (% by weight) Orthophthalaldehyde 5.0 Didecyldimethylammonium chloride 2.5 Water 92.5 Total 100.0

(Comparative Sample No. 6) Ingredient (% by weight) Glutaraldehyde 25.0 Didecyldimethylammonium chloride 2.5 Water 72.5 Total 100.0

Example 2 White water A (pH 6.0) containing no reducing substance, which was collected from a white water pit of a paper company A, was placed in an L-type test tube, and was subjected to Table 1.
OPA, GDA and didecyldimethylammonium chloride (hereinafter referred to as DDAC) were added at the concentrations shown in
Shaking culture was performed at 30 ° C. After 30 minutes and 90 minutes, the number of viable bacteria was measured. Table 1 shows the results.

[0033]

[Table 1]

From the results shown in Table 1, the sample of the present invention shows much higher bactericidal activity than the comparative sample.
It can be seen that the combined use of GDA and a quaternary ammonium salt allows each component to have a lower concentration and a higher antibacterial effect.

Example 3 The same white water A as used in Example 2 was tested for bactericidal activity in the same manner as in Example 2 by adding OPA, GDA and DDAC at the concentrations shown in Table 2. Table 2 shows the results.

[0036]

[Table 2]

Example 4 Na ₂ S ₂ O ₄ collected from a white water pit of a paper company B
B containing 25 ppm as a reducing substance (pH
6.0) at the concentrations shown in Table 3 for OPA, GDA,
DDAC was added and the bactericidal activity was tested as in Example 2. Table 3 shows the results. Comparing the results in Table 3 with those in Table 1, the bactericidal effect of OPA alone was significantly lower under the reducing water than in the case where no reducing substance was contained,
It can be seen that the bactericidal effect is maintained according to the sample of the present invention.

[0038]

[Table 3]

Example 5 The same white water B as used in Example 4 was tested for bactericidal activity in the same manner as in Example 2 by adding OPA, GDA and DDAC at the concentrations shown in Table 4. Table 4 shows the results.

[0040]

[Table 4]

Example 6 Na ₂ S ₂ O ₄ collected from a white water pit of a paper company C
C containing 28 ppm as a reducing substance (pH
5.5) and Na ₂ S ₂ O ₄ as a reducing substance
pm containing white water D (pH 5.5) with respect to the sample No. prepared in Example 1. 3 and Vitox K and V-Tech R-80 (both trade names, manufactured by KI Kasei Co., Ltd.) were added at the concentrations shown in Tables 5 and 6, and the bactericidal activity was tested in the same manner as in Example 2. Table 5 shows the results for white water C.
Are shown in Table 6. From the results of Tables 5 and 6, the sample of the present invention has a high bactericidal activity even at a low concentration even in the presence of a reducing substance, unlike the conventional bactericide,
It turns out that immediate effect is high.

[0042]

[Table 5]

[0043]

[Table 6]

Example 7 The white water C used in Example 6 was replaced with the sample No. 1 prepared in Example 1. 6 to 9 were added at the concentrations shown in Table 7, and the bactericidal activity was tested in the same manner as in Example 2. The results are shown in Table 7. Sample No. of the present invention Nos. 6 to 9 exhibit high bactericidal activity at a low concentration, and have an immediate bactericidal action even in an aqueous system containing a reducing substance.

[0045]

[Table 7]

Example 8 Sample No. 1 prepared in Example 1 Nos. 1, 4 and 5, and Comparative Sample No. prepared in Comparative Example 1 for comparison. 4 and 6
Of starch slurries (pH 5.6) at the concentrations shown in Tables 8 and 9 in a small beaker, and add starch spoilage bacteria to a concentration of 10 ⁵ to 10 ⁶ N / ml. It was covered with foil and stored in a thermostat at 32 ° C. After 6 hours, 1 day, 7 days, and 14 days, the number of viable bacteria in the starch slurry, pH measurement, odor, and appearance were observed, and the antiseptic effect was examined. In addition, in order to clarify the continuity of the effect, the spoilage bacterium was re-inoculated after counting the number of bacteria one day and seven days later. The results are shown in Tables 8 and 9. From Tables 8 and 9, the sample of the present invention has a higher preservative effect than the comparative sample,
Also, it can be seen that the effect has a high persistence.

[0047]

[Table 8]

[0048]

[Table 9]

Example 9 A sample N prepared in Example 1 was applied to a starch-coated color liquid.
o. 5 and 6, and Comparative Sample No. prepared in Comparative Example 1 for comparison. 2 and 4 were added at a formulation concentration of 150 ppm, and the viable cell count and pH were measured after 6 hours, 1 day, and 7 days. After counting the number of bacteria one day later, the spoilage bacteria were inoculated again. Table 10 shows the results. From the results shown in Table 10, it is understood that the sample of the present invention can be effectively used as a preservative for a starch coating color liquid.

[0050]

[Table 10]

Example 10 Green algae (Chlorella vulgaris) and blue algae (Oshiratoria neglector) commonly observed in an air-conditioning cooling tower were collected and cultured. After diluting these algae with distilled water so that the actual concentration becomes about 3.0 × 10 ⁶ / ml, the pH was adjusted to 8.5. To this, the sample No. prepared in Example 1 was added. Nos. 1, 6, and 8 and Comparative Sample No. prepared in Comparative Example 1. 2 and 4 at an active ingredient concentration of 1.0, 2.
After adding 5, 5, 10, 20, and 30 ppm, respectively, it was collected in an L-shaped test tube. These were shake-cultured at 25 ° C. while irradiating with light every 12 hours, and the algicidal effect was examined on the third day, with the whitened concentration as the minimum algicidal concentration. Table 11 shows the results. From the results in Table 11, it can be seen that the sample of the present invention can kill green algae and cyanobacteria at a low concentration, and is effective in preventing algae from cooling water such as air conditioning.

[0052]

[Table 11]

Test Example A sample containing OPA, GDA and DDAC was shaken vertically at room temperature at a shaking frequency of 270 times / min for 60 seconds, allowed to stand, and the volume of the foam after 15 seconds and 30 seconds was measured. .
Samples A to H were OPA, GDA and D at the concentrations shown in Table 12.
Diluent containing DAC, 50ml with stopper 100ml
It was placed in a measuring cylinder and shaken. The following six types of water were used for dilution, and the foaming property (residual foaming property) was examined for each of the following six kinds. (Types of water) a: distilled water b: 0.1% pulp added to distilled water c: white water A (same as used in Example 2) d: white water B (same as used in Example 4) E) White water C (same as used in Example 6) f: White water D (same as used in Example 6) The results are shown in Table 13.

[0054]

[Table 12]

[0055]

[Table 13]

From the results shown in Table 13, it can be seen that Samples B to H of the present invention do not have high foaming properties (residual foaming properties), but the foaming properties are particularly large between Samples E and F. For this reason, when the content of the quaternary ammonium salt is in the range of 0.01 to 0.2 parts by weight with respect to 1 part by weight of the total of GDA and OPA, the antibacterial and antibacterial properties are particularly low in foaming properties (residual foaming properties). It can be seen that an algal agent is obtained and is preferable.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hisatake Ogura 328 Shionitahamano, Fukuda-cho, Iwata-gun, Shizuoka Pref. 328 Hamano K-I Kasei Co., Ltd.

Claims (10)

[Claims] 1. A non-medical antibacterial and algicidal composition comprising orthophthalaldehyde, glutaraldehyde and a quaternary ammonium salt. 2. The glutaraldehyde content is 1 to 50 parts by weight per 1 part by weight of orthophthalaldehyde,
2. The non-medical germicidal composition according to claim 1, wherein the content of the quaternary ammonium salt is 0.01 to 0.2 part by weight based on 1 part by weight of the total of glutaraldehyde and orthophthalaldehyde. Algae repellent. 3. The non-medical germicidal and algicidal agent according to claim 1, wherein the quaternary ammonium salt is represented by the following general formula (I). Embedded image (Wherein R ¹ may be the same or different and represents a linear or branched alkyl group having 1 to 18 carbon atoms, and R ² represents a linear or branched alkyl group having 8 to 18 carbon atoms, a benzyl group or Represents a hydroxyethyl group, and X represents a chlorine, bromine, hydroxyl or propionate group. 4. The non-medical antibacterial and algicidal composition according to claim 1, which is used for a slime generating water system in paper or pulp production. 5. The non-medical germicidal and algicidal agent according to claim 1, which is used for cooling water systems for air conditioning or industrial use. 6. The non-medical protection according to claim 1, 2 or 3, characterized in that it is used for aqueous paints, paper coating liquids, latexes, pastes, leather or oils, or aqueous systems in the production process thereof. Fungicide for fungi. 7. A non-medical antibacterial and algicidal agent according to claim 2, wherein the total concentration of orthophthalaldehyde, glutaraldehyde and quaternary ammonium salt is 2 to 2.
A method for preventing germs and algae, which is added so as to be 00 mg / liter. 8. A method for preventing germs and alga, comprising adding the non-medical germicidal and algicidal agent according to claim 1, 2 or 3 to an aqueous slime-producing system in paper or pulp production. 9. A method for preventing germs and alga, comprising adding the non-medical germicidal and algicidal agent according to claim 1, 2 or 3 to an air conditioning system or an industrial water system. 10. A water-based paint, a coating liquid for paper, a latex,
An antiseptic method comprising adding the non-medical antibacterial and antialgal agent according to claim 1, 2 or 3 to a paste, leather or oil agent or an aqueous system in the production process thereof.