JP2000169304A - Germicide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a germicide which can exert an excellent germicidal effect or algicidal effect without precipitating polymers by adding a specific compound to a quaternary ammonium salt polymer as a scale inhibitor. SOLUTION: This germicide is obtained by including (A) a quaternary ammonium salt polymer (preferably an alkylated polyalkylenepolyamine quaternary ammonium salt, a polyalkylene-polyamine quaternary ammonium salt, an N,N,N ',N'-tetramethylpropylenediamine-bromo-chloropropane polycondensation product or the like) and (B) an N-(2-aminoethyl)acrylamide polymer (it is favorable to be 1,000-100,000 in the molecular weight). The germicide can be used as a germicide or algicide in a wide range without being restricted to the use for cooling water, for example, in the sterilization for fibers and resins or the sterilization for slime control agents or the like on the process of paper pulp or paper manufacture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a bactericide.

[0002]

2. Description of the Related Art When cooling water is circulated or used for long-term continuous operation, various obstacles such as corrosion, scale, slime, and generation of sludge occur. For this reason, it is common to add agents such as an anticorrosive, a scale inhibitor, a bactericide, and an algicide to the cooling water.

[0003] Quaternary ammonium salt polymers are widely used as fungicides and algicides. The quaternary ammonium salt polymer has low oral toxicity and skin irritation, and damage to equipment is one of the smallest among various fungicides. However, in water treatment, a bactericide and an algicide are rarely added alone, and a corrosion inhibitor, a scale inhibitor and the like are often added at the same time.

Since a carboxylic acid such as polyacrylic acid is generally used as a scale inhibitor, a cationic quaternary ammonium salt polymer forms an ionic complex with polyacrylic acid and precipitates. . As a result, the use of quaternary ammonium salt polymers has been severely limited.

[0005]

This is a quaternary ammonium salt polymer which has excellent characteristics that oral toxicity and skin irritation are low and damage to equipment is one of the smallest among various fungicides. However, because of the problem that it cannot be used at the same time as the polyacrylic acid as a scale inhibitor, its use for cooling water and the like is limited. Therefore, there has been a demand for the development of a quaternary ammonium salt-based germicide which does not cause precipitation even when combined with a scale inhibitor.

[0006]

Means for Solving the Problems As a result of intensive studies on the quaternary ammonium salt polymer-based bactericide, the present inventors have found that a quaternary ammonium salt-added N- (2-aminoethyl) acrylamide polymer is added as a scale inhibitor. The present inventors have found a novel fact that an ammonium salt polymer exhibits excellent bactericidal and algicidal properties without causing precipitation, thereby completing the present invention.

That is, the present invention is a fungicide containing a quaternary ammonium salt polymer and an N- (2-aminoethyl) acrylamide polymer.

Hereinafter, the present invention will be described in more detail.

[0009] The fungicide of the present invention comprises a quaternary ammonium salt polymer and an N- (2-aminoethyl) acrylamide polymer.

In the present invention, the term "quaternary ammonium salt polymer" is a general term for polymers having a quaternary ammonium structure in the main chain skeleton, and is not particularly limited, and alkylated polyalkylene polyamine quaternary ammonium salt, Polyalkylene polyamine quaternary ammonium salt,
N, N, N ', N'-tetramethylpropylenediamine / bulmochloropropane polycondensate, tetramethylethylenediamine / dichloroethylether polycondensate, tetramethylpropylenediamine / halogenated ethyl ether polycondensate, N, N , N ', N'-tetramethyl-1,6
Examples thereof include polycondensates of -hexanediamine and 1,6-dichlorohexane, and other quaternary salt polymers having sterilizing and algicidal properties may be used.

The quaternary ammonium salt polymer is generally obtained by reacting an amine with a halide such as a chlorinated product or a brominated product. Examples of the amine compound include triethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, N ″, N '' -Pentamethyldiethylenetriamine, N, N, N ', N'
-Tetramethylpropanediamine, bis (dimethylaminopropyl) urea, N, N, N ', N'-tetramethyl-2-butene-1,4-diamine. Examples of the halide include dichloropropane, dichloropropanol, dichlorobutene, dichloroethyl ether, 1,2-bis (2-chloroethoxy) ethane, dichloroxylene, bis (chloromethyl) biphenyl, bis (chloroacetyl) piperazine, and adipine. Acid chloroacetate, epichlorohydrin, benzyl chloride, dibromopropane, dibromopropanol, dibromobutane, dibromobutene, dibromobutanediol, dibromopentane, dibromohexane, dibromodecane, dibromododecane, dibromodiethylether, bisbromomethylazobenzene, xylene dibromide, etc. Is exemplified.

[0012] N- used in the fungicide of the present invention
As the (2-aminoethyl) acrylamide polymer, a homopolymer may be used, or a copolymer of N- (2-aminoethyl) acrylamide and another monomer may be used. As the constituent monomer of the copolymer, for example, vinyl chloride,
Vinyl halides such as vinyl bromide and vinyl fluoride; vinylidene halides such as vinylidene chloride; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid and maleic anhydride and salts thereof, and (meth) acrylic (Meth) acrylates such as methyl acrylate and ethyl (meth) acrylate, unsaturated ketones such as methyl vinyl ketone and methyl isopropenyl ketone, vinyl esters such as vinyl acetate and vinyl benzoate, methyl vinyl ether and ethyl Vinyl ethers such as vinyl ether, (meth) acrylamide and alkyl-substituted products thereof, vinylsulfonic acid, (meth) allylsulfonic acid, p-styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, (meth) acryloyloxyethyl Unsaturated sulfone such as sulfonic acid Etc. and their salts, styrene, alpha-methyl styrene, styrene and alkyl or halogen-substituted derivatives such as chlorostyrene, allyl alcohol and its esters or ethers, vinyl pyridine,
Basic vinyl compounds such as vinylpyrimidine, vinylimidazole, dimethylaminoethyl methacrylate, vinylbenzyldimethylamine, and vinylimidazoline.

The N- (2-aminoethyl) acrylamide polymer used in the bactericide of the present invention can be easily obtained by hydrolyzing a vinylimidazoline polymer by a known method.

[0014] N- used in the fungicide of the present invention
(2-Aminoethyl) acrylamide polymers exhibit the effect of scale inhibitors. That is, by adding the N- (2-aminoethyl) acrylamide polymer, the growth of crystals can be suppressed, and the precipitation and deposition of crystals can be prevented. The molecular weight of the N- (2-aminoethyl) acrylamide polymer is preferably from 1,000 to 100,000. Even if the molecular weight is smaller than 1,000 or more than 100,000, the scale preventing ability is reduced.

The quaternary ammonium salt polymer and the N- (2-aminoethyl) acrylamide polymer in the fungicide of the present invention do not precipitate an insoluble salt even if mixed at any ratio. However, it can be arbitrarily determined in view of the sterilization performance and scale prevention performance.

Other agents such as anticorrosives can be added to the fungicide of the present invention.

The bactericide of the present invention is not limited to use in cooling water,
It can be widely used as fungicide and algicide,
It can be used for sterilization of fiber and resin, slime control agent in paper pulp and paper making processes, and sterilization of pools and baths.

Although the specific method of use and the amount of the fungicide of the present invention vary depending on each application, it cannot be unconditionally stated, but in principle, it is significantly different from the general use in each application. There is nothing. However, the bactericide of the present invention can be expected to use examples that have never existed before because of its excellent functions and effects, and it goes without saying that the use amount can be reduced for achieving the same level of effects. .

[0019]

Industrial Applicability The present invention provides a quaternary ammonium salt-based germicide which does not cause precipitation even when combined with a scale inhibitor, and is industrially extremely significant.

[0020]

EXAMPLES Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

Example 1 A 0.1 M aqueous solution of calcium chloride was added to 1 ml of a 1 M aqueous solution of N- (2-aminoethyl) acrylamide polymer (weight average molecular weight: 10,000) in terms of N- (2-aminoethyl) acrylamide. 10 ml of a 1 M aqueous sodium carbonate solution was added. When the crystal diameter and shape of the generated calcium carbonate were observed with a microscope, it was found to be amorphous crystals of 1 μm or less.

Poly (oxyethylene (dimethylimino)
5% by weight of ethylene (dimethylimino) ethylene dichloride, 10% by weight of N- (2-aminoethyl) acrylamide polymer, 0.7% of benzotriazole as an anticorrosive
An aqueous solution containing% by weight was prepared. This aqueous solution did not precipitate even after standing.

In order to test the sterilization performance of this aqueous solution, the aqueous solution was impregnated into filter paper, and a mold resistance test was performed. The filter paper was placed on a medium (glucose, peptone, agar medium) and the mold spore suspension was sprinkled evenly. The cells were cultured at 28 ° C. in a wet manner, and the growth of hypha was observed. As a result, even after 2 weeks, the growth of hypha was not observed in the test piece (filter paper) portion and the contact portion.

Example 2 5% by weight of a polycondensate of N, N, N ', N'-tetramethylhexamethylenediamine and 1,6-dichlorohexane, and N- (2-aminoethyl) acrylamide-acrylamide copolymer Combined (N- (2-aminoethyl) acrylamide: acrylamide = 9: 1, weight average molecular weight 5
Aqueous solution containing 10% by weight was prepared. This aqueous solution did not precipitate even after standing. The sterilization performance of this aqueous solution was tested in the same manner as in Example 1. As a result, even after 2 weeks, the growth of hypha was not observed in the test piece (filter paper) portion and the contact portion.

Comparative Example 1 A 0.1 M aqueous solution of calcium chloride and a 0.1 M aqueous solution of sodium carbonate were mixed in amounts of 10 ml each. When the crystal diameter and shape of the generated calcium carbonate were observed with a microscope, it was a tetragonal crystal having a size of 11 μm or less.

Comparative Example 2 When a fungicide poly (oxyethylene (dimethylimino) ethylene (dimethylimino) ethylenedichloride) was added to an aqueous solution of polyacrylic acid (weight average molecular weight: 2,000), a white precipitate was formed. The sterilization performance of this aqueous solution was tested in the same manner as in Example 1. As a result, two weeks later, hyphal growth was observed on a part of the test piece (filter paper).

Comparative Example 3 An aqueous solution containing 5% by weight of a polycondensate of N, N, N ', N'-tetramethylhexamethylenediamine and 1,6-dichlorohexane and 10% by weight of polyacrylic acid was prepared. This aqueous solution became cloudy. The sterilization performance of this aqueous solution was tested in the same manner as in Example 1. As a result, 10 days later,
Hyphal growth was observed in a part of the test piece (filter paper).

Comparative Example 4 10 ml of a 0.1 M aqueous solution of calcium chloride, 10 ml of a 0.1 M aqueous solution of sodium carbonate, and 1 M poly (oxyethylene (dimethylimino) ethylene in terms of oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride An aqueous solution of (dimethylimino) ethylene dichloride) (1 ml) was mixed, and the crystal diameter and shape of the resulting calcium carbonate were observed with a microscope.

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Claims (3)

[Claims] 1. A quaternary ammonium salt polymer and N-
A fungicide containing a (2-aminoethyl) acrylamide polymer. 2. The quaternary ammonium salt polymer is an alkylated polyalkylene polyamine quaternary ammonium salt, a polyalkylene polyamine quaternary ammonium salt,
N, N, N ', N'-tetramethylpropylenediamine / bulmochloropropane polycondensate, tetramethylethylenediamine / dichloroethylether polycondensate, tetramethylpropylenediamine / halogenated ethyl ether polycondensate, and N, N N, N ', N'-tetramethyl-
The disinfectant according to claim 1, wherein the disinfectant is at least one member selected from the group consisting of polycondensates of 1,6-hexanediamine and 1,6-dichlorohexane. 3. The disinfectant according to claim 1, wherein the molecular weight of the N- (2-aminoethyl) acrylamide polymer is from 1,000 to 100,000.