JPS6021564B2 - Antibacterial and algal agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an antibacterial and antilacquer agent, and more particularly to an antibacterial lacquer agent for controlling bacteria, mold, yeast, algae, etc. that are harmful to water systems and industrial products in the production process of industrial products. This invention relates to antibacterial and algae inhibitors.

Water systems such as paper making processes in paper mills and pulp factories, industrial cooling water circulation processes, metal processing oil circulation processes, and water-based paints;
It is known that the microorganisms mentioned above multiply in industrial products such as paper coating liquids, latex, printing paste, and leather. This phenomenon causes a decrease in productivity and product quality, resulting in economic loss. BACKGROUND OF THE INVENTION Slime is formed in water systems in paper and pulp mills when bacteria, fungi, and yeasts breed. This slime is attached to the riffler wall or screen that is part of the whitewater water system, the inlet, or the chest arm of the raw water system, and falls off when it becomes large. The slime that falls off is made into paper together with the raw materials, causing spots on the paper and deteriorating the quality of the paper.
It also disrupts the strength balance of Junjun paper and causes the paper to break. In the water system for metalworking oil circulation, microorganisms multiply using the metalworking oil as nutrients, reducing the cooling properties of the processing oil.
This impedes emulsification, generates a bad odor, and causes problems such as deterioration of the working environment.

Furthermore, in industrial cooling water systems, algae and the like occur frequently, which clog pipes and reduce cooling efficiency such as heat exchange rate.

Therefore, although it is inefficient, it is currently necessary to increase the size of the device and take measures to avoid this damage. Other problems caused by microorganisms occur in water-based paints, paper coating fluids, polymer latex, paper pulp, printing pastes, leather, metal processing fluids, etc. These industrial products are spoiled by microorganisms and contaminated by filamentous fungi. Therefore, it is desired to develop a control agent that is effective in controlling microorganisms in industrial water systems as well as in industrial products. As a result, organometallic compounds such as mercury agents have been used as control agents for these harmful microorganisms, but their use has been regulated because these agents are highly toxic to the human body or to fish and shellfish.

In recent years, organic chlorine agents, organic sulfur agents, or quaternary ammonium agents have been used as substitute agents for these organometallic compounds, but their efficacy is insufficient. Especially industrial products,
For example, products such as metal processing oils, water-based paints, paper coating fluids, and latex are all alkaline, and the antibacterial and blinding agents used for these must be stable for long periods of time in the alkaline range and maintain their effectiveness. However, various drugs other than organic mercury compounds do not meet these conditions. The development of microbial damage control agents that can be applied to a wide range of products is strongly desired from many fields. The present invention was made in view of the current situation, and its purpose is to provide a method that does not cause environmental pollution and is effective in controlling microorganisms that proliferate in water systems, industrial products, and their production processes. To provide an antibacterial and blinding agent.

The antibacterial and algal agent of the present invention has the following general formula (wherein, Y represents a hydrogen atom, an alkyl group, a lower alkenyl group, a lower alkynyl group, or a pendyl group, R,
R' represents a hydrogen atom or a chloro atom, and R and R'
It may also combine with to form a benzene ring.

M represents a group 0 metal or N5, and Z represents CI or N03. Further, a represents an integer of 1 or 2, and n represents an integer such that the anion of Z satisfies the valence of the intestinal ion of M. ) and 2-hydroxymethyl-2-nitro-1,3-propanediol (hereinafter referred to as H
It's called MNP. ) as an active ingredient. The present inventors conducted a multifaceted study in order to develop an antibacterial and groove-preventing agent suitable for the above-mentioned purpose.・The composition containing 3-propanediol is an industrially harmful microorganism such as filamentous fungi, bacteria,
It has been discovered that these agents have extremely superior properties as described below, compared to when each agent is used alone as a control agent for yeast and the like.

In other words, isothiazolone of general formula [1] is
This compound is described in the specification of Japanese Patent No. 148465, and shows activity against a relatively wide range of bacteria and algae at high concentrations, but its antibacterial spectrum is narrow at low concentrations, so it is used as a slime control agent for paper manufacturing. It is inappropriate for

On the other hand, HMNP is based on the Merck Index (MERKIN).
DEX) [8th edition, 1 female page 2], and many reports regarding its biological activity have been made since ancient times. However, this substance does not have sufficient biological activity against any harmful microorganisms, and its activity against filamentous fungi and yeasts is particularly poor. Thus, the isothiazolone and HMNP
As antibacterial and algae-proofing agents, the former cannot be expected to have sufficient efficacy by itself because it maintains a stable effect and range of application at low concentrations, and the latter lacks efficacy against filamentous fungi and yeasts. Furthermore, it has the disadvantage that it cannot deal with microbial contamination in current closed water systems and microbial damage in complicated industrial products. According to the present invention, when HMNP is mixed and used in a ratio of 0.01 to 5 parts by weight with respect to 1 part by weight of the above-mentioned isothiazolone, each has unexpected activity even at low concentrations that do not show activity when used alone. Moreover, it exhibits fast-acting bactericidal power.

This fast-acting bactericidal power is fully demonstrated in the paper manufacturing process, cooling water-related processes, coating fluids, paint manufacturing processes, etc., and can inhibit the growth of microorganisms even in a state where microbial contamination has already progressed. In addition to the above characteristics, as shown in the test examples, the agent of the present invention is highly stable even in alkaline products and maintains stable bactericidal efficacy for a long period of time. These properties are not found in organochlorine agents and organosulfur agents used as substitutes for organometallic compounds. The above general formula [1
] The following compounds are mentioned as isothiazolones.

2-methyl-3-isothiazolone, 2-ethyl-3-isothiazolone, 2-octyl-4-chloro-3-isothiazolone, 2-
Penzyl-4,5-dichloro-3-isothiazolone 2
-Allyl-3-isothiazolone, 2-propynyl-3-isothiazolone, 2-methyl-5-chloro-3-isothiazolone, 1.2
- Tsuba compounds with zinc chloride, calcium chloride, magnesium chloride, barium chloride, ammonium chloride, magnesium nitrate, such as penzothiazolone, etc.

Among the above, particularly preferred combinations are calcium (0) chloride or magnesium (
0) This is the case of a mixture of one or two chlorides and HMNP.

Typical formulation forms of the antibacterial and screen protectant of the present invention are as follows.

That is, the antibacterial and algae-proofing agent of the present invention is formulated into a solution or a wettable powder, but it is particularly preferable to use it when it is formulated into a liquid preparation. To prepare this solution, use a polyhydric alcohol such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, or polypropylene glycol, acetonitrile, dioxane, N-methylmorpholine, water, etc. as a solvent to uniformly dissolve, They may be mixed together, and to prepare a wettable powder, they may be adsorbed and mixed with a filler such as diatom, clay, or talc together with a small amount of a surfactant as a wetting agent or dispersant, and then uniformly ground.

Furthermore, the antibacterial and algae-preventing agent of the present invention can be used with the addition of 2-bromo-2-nitropropane-1,3-diol (hereinafter referred to as BNP).

BNP is a compound described in Japanese Patent Publication No. 52-61221, and when used as an industrial preservative, BNP is a gram-negative bacterium called Pseudomonas aeruginosa (
Although it is highly effective against Pseadomo Msaeruglnosa), its activity against filamentous fungi and yeasts is significantly inferior. However, when BNP is blended into the antibacterial and blinding agent of the present invention, it has the effect of improving antiseptic activity. next,
Although the present invention will be explained by showing examples, the present invention is not limited to these in any way. Parts in the examples indicate parts by weight, and Compounds 1 to 13 each indicate the following. Compound
1 2-Methyl-5-chloro-3-isothiazolone calcium (0) chloride compound 2 2-Methyl-3-isothiazolone calcium (0).

Ride compound 3 2-methyl-5-chloro-3-isothiazolone ammonium chloride compound 4 Bis(2-methyl-3-isothiazolone) zinc (0)
Chloride compound 5 2-octyl-4-chloro-3-isothiazolone calcium (0) chloride compound 6 2-penzyl-4,5-dichloro-3-isothiazolone magnesiwam (0) chloride compound 7 2-aryl-3-isothiazolone ammonium chloride compound 8 2-propynyl-3- Isothiazolone calcium (0)
Chloride compound 9 2-ethyl-3-isothiazolone calcium (□) chloride compound 10 1,2-penzothiazolone magnesium (0) chloride compound 115-chloro-2-methyl-3-isothiazolone magnesium (0) chlorite compound 12 2-methyl-3-isothiazolone Magnesium (□) chloride compound 13 2-methyl-3-isothiazolone magnesium (b) nitrate Example 1 Liquid compound 1 15 parts Compound 1 5 parts HMNP
5 parts Diethylene glycol 75 parts Example 2
Liquid agent class compound 3 Tsuyoshi NP Misaki propylene glycol 75 parts Example 3 Liquid agent compound 4 2 Edge part H
MNP I part water
2 Diethylene glycol 5 parts Examples 4 Liquid compound 5 3 Boto H
MNP O. 5 parts Diethylene glycol 69.5 parts Example 5 Liquid compound 6 15 parts H
MNP 15 parts diethylene glycol 7 Base part Examples 6 Liquid compound 7 2 Base part HM
NP 2 parts potassium bromide 3 parts water
Female part Diethylene glycol 65 parts Examples 7 Liquid compound 8 Tateto HM
NP 5 parts Diethylene glycol 65 parts Example 8
Liquid compound 9 Isobe HMNP 2-part diethylene glycol Isobe example
9 compounds 10 female part HMNP 5 parts sodium bromide 5 parts water
Hattori diethylene glycol 7 parts Example 10 Hydrating agent 3:1 mixture of Compound 1 and Compound 2 15 parts Skin N
P side Neoberex (registered trademark Kao Atlas ■ wetting agent)
2.5 parts Sanjekiss (registered trademark)
Wetting agent manufactured by Kao Atlas ■)
2.5 part quartzite
7 Anchor Example 11 Solution 3:1 mixture of Compound 1 and Compound 2 15 parts HM
NP 3rd part BN
P 15 parts Propylene glycol 6 Hiragi part Example 1
2-part compound 4 2 part H
MNP 5th part BN
P 2 Ikari Sodium Niobide 5 parts Water
15 parts Propylene glycol 35 parts Example 13 Liquid compound 7 15 parts H
MNP 5th part BN
P Isobe Diethylene Glycol 6 Foundation Example 1
4 Hydrating agent compound 9 15 parts Skin NP Misaki BNP
Megun Neoberetschus (previous life) 5th part Keikan±
Isobe Example 15 Solution 3:1 mixture of compound 1 and compound 2 15 parts HM
NP I part BNP
15 parts sodium bromide female part water
Diethylene glycol 3$ Example 16 Liquid compound 11 3 parts Compound 12 1 part HMNP
I part BNP
2 parts sodium bromide, part water
Vertical portion: 35 parts of diethylene glycol Next, the effects of the antibacterial and algal agent of the present invention will be explained using test examples.

Comparative examples for single use are 15% liquid (intiazolones) or 3
A 0% solution (HMNP and BNP) was formulated and used.
Test Example 1 Test for Minimum Inhibitory Concentration of Microbial Growth The minimum inhibitory concentration of the drug of the present invention in a bouillon liquid medium was determined.

The broth liquid medium was adjusted to pH 7.5 for bacteria and pH 4.2 for filamentous fungi. The precultured mystery bacteria and the drug of the present invention diluted to a predetermined concentration were added to an L-shaped tube containing a liquid medium, and cultured with shaking using a mono-type shaker.
After 2 hours in the field, the growth inhibition concentration (skin) of the drug was determined by observing the turbidity of the medium.

The results are shown first. The microorganisms A to F in the table are as follows. Microorganism A: Aerobacter aerogenes 8: Snephylococcus aureus C: Pseudomonas aeruginosa
Bonito nosa) D: Geotrichum candeidium (G
.

triCh Candidum) E: Bacteria isolated from pink slime (bacteria) F: Bacteria isolated from pink slime (filamentous fungus) The number in parentheses in the mixture ratio column of Table 1 is 3:1 of compound 1 and compound 2.
Indicates the amount of mixture (the same applies below).

The drug of the present invention containing isothiazolone and HMNP as active ingredients showed an extremely lower bottom growth-inhibiting concentration than when each was used alone.

Furthermore, those containing BNP have further improved activity against bacteria. Test Example 2 Antibacterial test of cutting oil for metal processing Already putrid cutting oil collected at a metal processing factory was added to a broth liquid column, cultured with shaking for 2 hours, and activated to obtain test bacteria.

Cutting oil 3" sound diluted emulsion (pH
9.3) 17', 1' liquid medium for bacterial growth;
Add 1 part of the above test bacterial solution and 1 part of the drug solution diluted to the specified concentration, totaling 20 parts, and place in a 30°C incubator, shake for 8 hours a day, and let stand for 1 hour. The cells were cultured for 28 days.

The number of viable bacteria in the cutting oil was measured after 3 hours, 7 days, 14 days, 21 days, and 28 days.

In addition, for the purpose of examining the sustained efficacy of the drug, after measuring the number of viable bacteria after 7, 14, and 21 days, a fresh batch of bacterial solution was added. The results are shown in Table 2. 2. The agent of the present invention exhibits rapid bactericidal activity and stable preservative activity over a long period of time under alkaline conditions such as cutting oil for metal processing, as evidenced by the investigation of the number of viable bacteria after 3 hours.

Test Example 3 Test for inhibiting the growth of white water fungi in a paper mill. Circulating white water collected from the high-quality paper manufacturing process at a certain paper mill was added to a bouillon liquid tower and incubated in a shaking tower for 2 hours to activate it. do.

Next, take the bouillon liquid medium to which each drug has been added to a predetermined concentration into an L-shaped tube, inoculate it with the above-mentioned test bacteria, and
Culture with shaking. After culturing, the turbidity of the medium between the four anchorages was observed to determine the effect of inhibiting the growth of the whitewater fungus. The results are shown in Table 3.

Display in Table 3: 0.1 to 5 indicates the degree of turbidity, and 5 indicates that the medium becomes cloudy and slime is formed in the medium.

Test Example 4 Green algae (Cosmarium) and occipital algae (Oscillatoria) attached to the screen killing test cooler were collected and cultured.
This was immersed for 1 hour in solutions diluted with each drug at formulation concentrations of 1, 3, and 1, and then further immersed in distilled water for 2 hours.

The state of death was determined by observing the state of protoplasm separation of the algae, and the minimum concentration of the active ingredient required to kill the algae was determined. 4th Test Example 5 Preservation test for papermaking coating solution A bouillon liquid medium and a previously spoiled coating solution are added to the papermaking coating solution (starch coating solution with a pH of 9.6), and the predetermined concentration is achieved after the coating solution has been mixed into a paste. Each drug was added in the same way.

After culturing this for 5 days in a 3P0 mackerel egg container, the number of viable bacteria, filamentous fungi, and yeast in each journal material was measured, and the preservative effect of each drug was determined. The results are shown in Table 5.

No. 5 The agent of the present invention was also extremely effective for coating liquids containing starch as the main binder compared to single use.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, Y represents a hydrogen atom, an alkyl group, a lower alkenyl group, a lower alkynyl group, or a benzyl group, and R,
R' represents a hydrogen atom or a chloro atom, and R and R'
It may also combine with to form a benzene ring. M represents Group II metal or NH_4, Z represents Cl or N
Indicates O_3. In addition, a represents an integer of 1 or 2, and n
represents an integer such that the anion of Z satisfies the valence of the cation of M. ) and one or more isothiazolones represented by
An antibacterial and algal agent characterized by containing hydroxymethyl-2-nitro-1,3-propanediol as an active ingredient.