JPH0616508A - Sterilizer - Google Patents

Abstract

PURPOSE:To provide the sterilizer containing a polyphosphonium salt as an active ingredient, having a wide sterilizing spectrum, having a sufficient sterilizing effect on its contact for a short time, and useful as a sterilizer for external uses, a sterilizer for hygienic processing, etc. CONSTITUTION:The sterilizer contains a polyphosphonium salt of formula I [n is an integer of 0 or more; X is anion; Y, R1 are 1-12C alkylene, xylylene of formula II (Z is H, halogen, OH, methyl, acid amide, nitrile, amino; m is 1-3); R2 is 1-12C alkyl, xylyl], or a polyphosphonium salt of formula III as an active ingredient. The phosphonium salt of formula I includes @{9146/[ethyenebis(diphenylphosphonio)]butylene dibromide], and the compound of formula III includes ethylene-bis(diphenylethylphosphonium) dibromide. The compounds are useful as sterilizers and can simultaneously impart antistaticity, flame retardancy, and an antifouling property, too.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fungicide, and more specifically, the present invention relates to a fungicide containing a polyphosphonium salt as an active ingredient.

[0002]

2. Description of the Related Art At present, a great variety of fungicides are used in various fields such as industry, agriculture and food. Most of the bactericides that have been used so far have been synthetic bactericides with a high degree of toxicity, but recently, research aimed at reducing the toxicity of bactericides has progressed, and particularly high functionality has been achieved. Researches on molecular compounds are actively conducted. Polymers and oligomers having biological activity have been synthesized, and in addition to studies on their properties and functions, the relationship between structure and biological activity has been examined regarding molecular weight, composition of copolymers, chain morphology, and the like. This polymer type bactericide can impart a bactericidal function to the surface of various substances, and is used in many fields including, for example, antibacterial and deodorant fibers fixed to the surface of fibers. Polymer type germicide
Polyvinyl, polyacrylate, polymethacrylate,
It has been reported that a bactericide is fixed in a pendant type to a polymer such as polyester and polyamide. For example, a polyvinyl chain having an alkylpyridinium salt and an alkyldimethylbenzylammonium salt fixed thereto, a polyacrylate chain and a polymethacrylate chain having biguanides fixed thereto, or a polyester chain and a polyamide chain having an alkylpyridinium salt fixed thereto. The thing etc. are mentioned. Among these, most of the polymer-type bactericides that have been put to practical use or under research are quaternary ammonium salt-based ones. Further, the phosphonium salt compound is known as a biologically active chemical substance having a broad activity spectrum in bacteria, fungi and algae, similarly to various nitrogen-containing compounds (JP-A-57- 204286, JP 6
3-60903, JP 62-114903, JP 1-9359
No. 6, JP-A No. 2-240090).

[0003]

However, although the quaternary ammonium salt-based polymer type bactericide has a wide sterilization spectrum, the bactericidal effect of acting on microorganisms by contact in a short time is not yet sufficient. Furthermore, the phosphonium salt compound-based bactericide does not have a bactericidal power with practicality, and there is no disclosure of the polyphosphonium salt according to the present invention. DISCLOSURE OF THE INVENTION The present inventors have solved the conventional problems as described above, and have a polyphosphonium salt as an active ingredient, and have a broad sterilization spectrum and an object of the present invention to provide a bactericidal agent having a sufficient bactericidal effect by contact for a short time. It is what

[0004]

As a result of earnest studies, the present inventors were able to solve the above-mentioned conventional problems. That is, the present invention has the general formula (1)

[0005]

[Chemical 5]

[In the formula, n represents an integer of 0 or more, X represents an anion, and Y and R ₁ are the same or different alkylene groups having 1 to 12 carbon atoms or the general formula (2).

[0007]

[Chemical 6]

(In the formula, Z is hydrogen, halogen, hydroxyl group,
A methyl group, an acid amide group, a nitrile group, a substituted or unsubstituted amino group, m represents 1 to 3), and a substituted or unsubstituted xylylene group, and R ₂ represents the same or different carbon number 1 to 12 represents an alkyl group or a xylyl group] is provided as an active ingredient.

The present invention will be described in detail below. The bactericide according to the present invention contains, as an active ingredient, the polymer of the phosphonium salt represented by the general formula (1) as described above. In the general formula (1) of the fungicide of the present invention, X in the formula
Is an anion, for example, halogen ion of fluorine, chlorine, bromine or iodine, carboxyl ion such as formic acid, acetic acid, oxalic acid, sulfate ion, phosphate ion, methyl or dimethyl phosphate, ethyl or diethyl phosphate, antimony fluoride. Ions, phosphorus fluoride ions, arsenic fluoride ions, boron fluoride ions, perchlorate ions and the like can be mentioned, with halogen ions being preferred. Y and R ₁
Is an alkylene group having 1 to 12 carbon atoms such as methylene, ethylene, propylene, butylene, and amylene, and / or a substituted or unsubstituted xylylene group represented by the general formula (2). In addition, Y and R ₁ may be the same or different. R ₂ is, for example, an alkyl group having 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl or the like, or a p-, m- or o-xylyl group. Note that R ₂ may be the same or different.

The bactericide according to the present invention has the general formula (1) above.
As shown in, a phosphonium salt polymer comprising a repeating unit of a phosphonium salt having a P—C bond in the main chain and a substituent is used as an active ingredient, and its molecular weight is 500 to 10,000. It is preferably 1000 to 5000. Therefore, the polymer has a relatively low degree of polymerization of about dimer to oligomer. The bactericidal activity and the solubility in water are affected by the degree of polymerization, and the higher the degree of polymerization, the higher the bactericidal activity and the tendency to become poorly soluble. In the present invention, in particular, the following general formula (3)

[0011]

[Chemical 7]

(In the formula, R ₂ is the same or different carbon number 1
~ 12 alkyl groups or xylyl groups, Y and X having the same meanings as above) are preferred.

The bactericide according to the present invention includes, for example, poly [(ethylene-bis (diphenylphosphonio)) butylene dibromide] and poly [(ethylene-bis (diphenylphosphonate) as the polyphosphonium salt represented by the general formula (1). Nio)) hexylenedibromide], poly [(butylene-bis (diphenylphosphonio)) butylene dibromide], poly [(diphenylphosphonio) -P-xylylene bromide], poly [(butylene-bis (diphenylphosphonoid) Nio))-P-xylylene dibromide], poly [(diphenylphosphonio) -2,5-dihydroxy-
p-xylylene bromide], poly [(diphenylphosphonio) -2,5-diamino-p-xylylene bromide], poly [(diphenylphosphonio) -2,5-dicyano-p-xylylene bromide] and the like. Can be mentioned.

The phosphonium salt dimer represented by the general formula (3) includes ethylene-bis (diphenylethylphosphonium) dibromide, butylene-bis (diphenylethylphosphonium) dibromide, p-xylylene-bis (diphenylbutylphosphonium). Dibromide, 2,5-dihydroxy-p-xylylene-bis (diphenylethylphosphonium) dibromide, 2,5-
Examples thereof include diamino-p-xylylene-bis (diphenylbutylphosphonium) dibromide.

Bactericidal activity (MIC) of the bactericide according to the present invention
Is not uniform depending on the type of polyphosphonium salt compound, the type of preparation or the type of various fungi and the environment, but is generally exhibited when the concentration of the polyphosphonium salt compound is 1 ppm or more. Higher bactericidal activity than fungicides. The bactericide according to the present invention is used in various industrial fields depending on the form of the preparation, for example, a slime preventive or control agent in papermaking, water, oils and fats, emulsions, paper, wood, rubber, plastics, fibers, films, paints, etc. A bactericidal function can be imparted. The fungicide according to the present invention can be either water-soluble or oil-soluble depending on the physical properties of the polyphosphonium salt, and therefore, in its use, the compound itself should be directly used as a powder according to the intended purpose. Of course, it can be provided in any formulation such as water-soluble, wettable powder, emulsifier or powder by a desired solvent or carrier such as powder.
Further, in the preparation, in addition to the carrier, auxiliary agents such as surfactants, binders, colorants, dispersants, wetting agents and other organic or inorganic bactericides may be added, if necessary.

Method for producing bactericide according to the present invention The method for producing the polyphosphonium salt represented by the general formulas (1) and (3) is not particularly limited.
An example of the industrial manufacturing method is shown below. General formula (4)

[0017]

[Chemical 8]

(Wherein Y has the same meaning as described above) and the general formula (5)

[0019]

[Chemical 9]

(Wherein R ₁ has the same meaning as described above)

Or the general formula (6)

[0022]

[Chemical 10]

It can be produced by reacting a compound represented by the formula (wherein R ₂ and X have the same meanings as described above) in a polar solvent. That is, the polyphosphonium salt represented by the general formula (1) is produced, for example, by the reaction of 1,2-bis (diphenylphosphino) ethane of the general formula (4) with 1,9-dichlorononane of the general formula (5). The dimer of the polyphosphonium salt of the general formula (3) can be obtained, for example, by reacting 1,2-bis (diphenylphosphino) ethane of the general formula (4) with ethyl chloride of the general formula (6). be able to.

The reaction conditions are as follows: the phosphine compound of the general formula (4) and the compound of the general formula (5) or the general formula (6) are dissolved in a polar solvent, and the temperature is 10 to 200 ° C., preferably 40 to 100 ° C. The time is 1 to 24 hours, preferably 2 to
It is suitable to react for 10 hours. The use ratio of each raw material used in this case is preferably such that the compound of the general formula (5) or the general formula (6) is equimolar to the phosphine compound of the general formula (4). The reaction can be carried out under normal pressure or increased pressure.

Examples of the phosphine compound represented by the general formula (4) used in the production of the fungicide according to the present invention include 1,2-
Bis (diphenylphosphino) ethane, 1,4-bis (diphenylphosphino) butane, 1,6-bis (diphenylphosphino) hexane, 2,5-bis (diphenylphosphinomethyl) -catechol, 2,5- Bis (diphenylphosphinomethyl) -hydroquinone, 3,6
-Bis (diphenylphosphinomethyl) -1,2-dichlorobenzene, 3,6-bis (diphenylphosphinomethyl) -1,4-dichlorobenzene, 3,6-bis (diphenylphosphinomethyl) -1 , 5-dichlorobenzene, 3,6-bis (diphenylphosphinomethyl)-
1,2-Diaminocarbonylbenzene, 3,6-bis (diphenylphosphinomethyl) -1,4-diaminocarbonylbenzene, 3,6-bis (diphenylphosphinomethyl) -1,2-dicyanobenzene, 3,6 -Bis (diphenylphosphinomethyl) -1,2-diaminobenzene, 3,6-bis (diphenylphosphinomethyl)
-1,2-alkylaminobenzene etc. can be mentioned.

Further, as the compound represented by the general formula (5), 1,9-dichlorononane, 1,6-dichlorohexene, ortho-xylylene chloride, meta-xylylene chloride, para-xylylene chloride, 4 , 6-
Dimethyl-meta-xylylene chloride, ortho-xylylene bromide, meta-xylylene bromide, para-xylene bromide, 4,6-dimethyl-meta-xylylene bromide, 1,6-hexamethylene ditosylate, para-xylyl Examples include range tosylate.

Further, examples of the compound represented by the general formula (6) include ethyl chloride, butyl chloride, hexyl chloride, propyl chloride, ethyl bromide, butyl bromide, hexyl bromide, propyl bromide and the like. As the polar solvent, dialkylamides such as dimethylformamide, dimethylacetamide and diethylacetamide, sulfoxides such as dimethylsulfoxide and sulfolane, and alcohols such as methanol and ethanol are preferably used.

[0028]

EXAMPLES The present invention will be further described below with reference to examples. Example 1 A pressure-resistant reaction vessel was charged with 1.00 g (2.3 mmol) of butylene bis- (diphenylphosphine), 3.21 g (23.5 mmol) of butyl bromide, and 10 ml of chloroform, which were well dissolved and sufficiently replaced with nitrogen. After doing, 80 ℃
And reacted for 8 hours. After the reaction was completed, the product was poured into excess diethyl ether to precipitate crystals, and white crystals were obtained. The product was filtered and dried to obtain 1.64 g of white crystalline butylene-bis (diphenylbutylphosphonium) dibromide (hereinafter referred to as sample A).

Example 2 1.99 g (5.0 mmol) of ethylene-bis (diphenylphosphine) and 0.1% of dibromoethane were placed in a pressure resistant reactor.
Charge 94 g (5.0 mmol) and 10 ml of chloroform, dissolve them well, and replace with nitrogen sufficiently, and then at 8O 0 C for 8 hours.
Reacted for hours. After the reaction was completed, the product was poured into excess diethyl ether to precipitate crystals, and white crystals were obtained. The product was filtered and dried to obtain 1.42 g of poly [(ethylene-bis (diphenylphosphonio)) ethylene dibromide]. As a result of measuring the weight average molecular weight by a light scattering method, it was 1700 (hereinafter referred to as sample B).

Example 3 1.99 g (5.0 mmol) of ethylene-bis (diphenylphosphine) and 1.0 of dibromobutane were placed in a flask container.
Charge 8 g (5.0 mmol) and 30 ml of chloroform,
After being well dissolved and sufficiently replaced with nitrogen, reaction was carried out at 80 ° C. for 8 hours. After the reaction was completed, the product was poured into excess diethyl ether to precipitate crystals, and white crystals were obtained. The product was filtered and dried to give poly [(ethylene-bis (diphenylphosphonio)) butylene dibromide].
1.09 g of was obtained. As a result of measuring the weight average molecular weight by a light scattering method, it was 2300 (hereinafter referred to as sample C).

Example 4 1.99 g (5.0 mmol) of ethylene-bis (diphenylphosphine) and 1.bromodihexane in a flask container.
Charge 22 g (5.0 mmol) and 30 ml of chloroform, dissolve them well, and replace with nitrogen sufficiently, and then at 8O 0 C for 8 hours.
Reacted for hours. After the reaction was completed, the product was poured into excess diethyl ether to precipitate crystals, and white crystals were obtained. The product was filtered and dried to obtain 1.70 g of poly [(ethylene-bis (diphenylphosphonio)) hexylene dibromide]. As a result of measuring the weight average molecular weight by a light scattering method, it was 1100 (hereinafter referred to as sample D).

Example 5 2.13 g (5.0 mmol) of ethylene-bis (diphenylphosphine) and 1.0 of dibromobutane were placed in a flask container.
Charge 8 g (5.0 mmol) and 30 ml of chloroform,
After being well dissolved and sufficiently replaced with nitrogen, reaction was carried out at 80 ° C. for 8 hours. After the reaction was completed, the product was poured into excess diethyl ether to precipitate crystals, and white crystals were obtained. The product was filtered and dried to give poly [(butylene-bis (diphenylphosphonio)) butylene dibromide].
1.63 g was obtained. As a result of measuring the weight average molecular weight by a light scattering method, it was 1400 (hereinafter referred to as sample E).

EXAMPLE 6 1.73 g (4.0 mmol) of butylene-bis (diphenylphosphine) and 0.9% of dibromobutane were placed in a pressure resistant reactor.
87 g (4.0 mmol) and 30 ml of chloroform were charged, well dissolved, sufficiently replaced with nitrogen, and then reacted at 160 ° C. for 6 hours. After the reaction was completed, the product was poured into excess diethyl ether to precipitate crystals, and white crystals were obtained.
The product was filtered and dried to obtain 2.39 g of poly [(butylene-bis (diphenylphosphonio)) butylene dibromide]. As a result of measuring the weight average molecular weight by a light scattering method, it was 4500 (hereinafter referred to as sample F).

Example 7 2.13 g (5.0 mmol) of butylene-bis (diphenylphosphine) and 1.35 of dibromohexane were placed in a flask container.
Charge 22 g (5.0 mmol) and 30 ml of chloroform, dissolve them well, and replace with nitrogen sufficiently, and then at 8O 0 C for 8 hours.
Reacted for hours. After the reaction was completed, the product was poured into excess diethyl ether to precipitate crystals, and white crystals were obtained. The product was filtered and dried to obtain 1.63 g of poly [(butylene-bis (diphenylphosphonio)) hexylene dibromide]. As a result of measuring the weight average molecular weight by a light scattering method, it was 1300 (hereinafter referred to as sample G).

EXAMPLE 8 1.00 g (2.1 mmol) of p-xylylenebis (diphenylphosphine), 1.79 g (10.5 mmol) of benzyl bromide and 30 ml of chloroform were placed in a flask container.
After being charged and dissolved, the mixture was reacted at 80 ° C. for 8 hours under reflux in a nitrogen atmosphere. After the reaction was completed, the product was poured into excess diethyl ether to precipitate a precipitate. When the product was filtered and dried, 1.22 g of p-xylylenebis (diphenylbenzylphosphonium) dibromide was obtained (hereinafter referred to as sample H).

Example 9 1.00 g (2.1 mmol) of p-xylylene bis (diphenylphosphine), 0.55 g (2.1 mmol) of p-xylylene bromide and 30 m of chloroform were placed in a pressure resistant container.
After l was charged and dissolved, the mixture was reacted at 80 ° C. for 8 hours while refluxing under a nitrogen atmosphere. After the reaction was completed, the product was poured into excess diethyl ether to precipitate a precipitate. When the product was filtered and dried, 1.09 g of poly [(p-xylylenebis (diphenylphosphonio)) p-xylylenedibromide] was obtained. As a result of measuring the weight average molecular weight by a light scattering method, it was 1500 (hereinafter referred to as sample I).

(Bactericidal activity test) As a representative of Gram-positive bacteria, Staphylococcus aureus
aureus) IFO12732 and Escherichia Coli IFO3806 as representatives of Gram-negative bacteria, and samples of various polyphosphonium salt compounds obtained in the examples at the concentrations and the action times shown in Table 1 and Table 2. Let it work. The obtained bactericidal activity results are shown in Tables 1 and 2. The bactericidal activity was evaluated by a solution dilution method in which a predetermined amount of bacteria was ingested and brought into contact with the bacteria, and the number of bacteria was measured thereafter. It is indicated that the bactericidal activity is stronger as the number of bacteria is significantly reduced with respect to the contact time.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

[Table 5]

[0043]

[Table 6]

[0044]

INDUSTRIAL APPLICABILITY According to the present invention, a bactericidal agent having a broad bactericidal spectrum and having a sufficient bactericidal effect by contact for a short time can be obtained. These bactericidal tastes are, for example, external bactericidal agents,
It can be used as a sanitizer for sanitary processing of fibers, cloths, medical instruments, paints and building materials, pools, industrial water, and the like. At the same time, antistatic property, flame retardancy, and antifouling property can be imparted. The compound of the present invention can be used in the form of spheres and pellets, as a filter, and by descending them, various sterilizing industrial materials.

Claims (2)

[Claims] 1. A compound represented by the general formula (1): [In the formula, n represents an integer of 0 or more, X represents an anion, and Y and R ₁ are the same or different carbon numbers 1 to 12
Or an alkylene group of the general formula (2) (In the formula, Z is hydrogen, halogen, hydroxyl group, methyl group, acid amide group, nitrile group, substituted or unsubstituted amino group, m
Represents a substituted or unsubstituted xylylene group represented by the formula (1) to (3), and R ₂ represents the same or different C 1 to C 1
Represents an alkyl group or a xylyl group of 2] as the active ingredient. 2. A general formula (3): [In the formula, X represents an anion, Y is an alkylene group having 1 to 12 carbon atoms or a compound represented by the general formula (2): (In the formula, Z is hydrogen, halogen, hydroxyl group, methyl group, acid amide group, nitrile group, substituted or unsubstituted amino group, m
Represents a substituted or unsubstituted xylylene group represented by the formula (1) to (3), and R ₂ is the same or different from 1 to 12 carbon atoms.
Which represents an alkyl group or a xylyl group of the above] as an active ingredient.