Polymer, antimicrobial agent, disinfectant, antimicrobial material, disinfectant material, antimicrobial method, and disinfecting method

Abstract

Provided is a polymer having antimicrobial and disinfecting properties against a wide range of kinds of germs. A polymer, including: a polymer chain having a repeating unit represented by the following formula (1); and a partial structure (excluding the polymer chain) derived from a compound containing a group represented by —NH—. [In formula (1), R.sup.1 represents a hydrogen atom or a methyl group, Z represents a group forming an organic ammonium salt, —NR.sup.5R.sup.6 (where R.sup.5 and R.sup.6 each independently represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group), or a substituted or unsubstituted nitrogen-containing heterocyclic group, and X represents a single bond, or a divalent linking group.] ##STR00001##

Claims

1. A polymer, comprising: a polymer chain ending with a terminal compound and bonded to the terminal compound with a —NH— group present in the compound; wherein the compound comprises a plurality of —NH— groups, wherein the polymer chain comprises a repeating unit of formula (1) and a repeating unit of formula (2): ##STR00018## wherein R.sup.1 represents a hydrogen atom or a methyl group, Z represents an organic ammonium salt or an organic ammonium salt and —NR.sup.5R.sup.6, wherein R.sup.5 and R.sup.6 each independently represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group, the organic ammonium salt is selected from the group consisting of —N.sup.+R.sup.2R.sup.3R.sup.4Y.sup.y−, —(C═O)O.sup.−N.sup.+HR.sup.2R.sup.3R.sup.4, and —(C═O)O.sup.−−A.sup.+ wherein R.sup.2 to R.sup.4 each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, Y.sup.y− represents a y-valent counter anion, and A.sup.+ represents a quaternary ammonium cation, and X represents a single bond, a methylene group, an alkylene group, —(C═O)OR.sup.11-(*), or —(C═O)NHR.sup.12-(*) wherein R.sup.11 and R.sup.12 each represent a methylene group, an alkylene group, or an alkylene oxyalkylene group, and “*” represents a chemical bond bonded to the Z; ##STR00019## wherein R.sup.7 represents a hydrogen atom or a methyl group, and A represents an aromatic hydrocarbon group, —(C═O)OR.sup.8, —(C═O)NHR.sup.9, or —OR.sup.10, wherein R.sup.8 to R.sup.10 each represent a hydrocarbon group or a group having a chain ether structure or a cyclic ether structure.

2. The polymer according to claim 1, wherein a weight average molecular weight (Mw) of the polymer chain is 3,000 or less in terms of polystyrene measured by gel permeation chromatography, wherein a mobile phase is tetrahydrofuran.

3. The polymer according to claim 1, wherein Z is an organic ammonium salt of formula —N.sup.+R.sup.2R.sup.3R.sup.4Y.sup.y−, wherein R.sup.2 to R.sup.4 each independently represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group, and Y.sup.y− represents a y-valet counter anion, or Z is an organic ammonium salt of formula —N.sup.+R.sup.2R.sup.3R.sup.4Y.sup.y− and —NR.sup.5R.sup.6.

4. The polymer according to claim 1, wherein X is —(C═O)OR.sup.11-(*), —(C═O)NHR.sup.12-(*), and wherein R.sup.11 and R.sup.12 each represent a methylene group, an alkylene group, or an alkylene oxyalkylene group.

5. The polymer according to claim 1, wherein the compound is a compound comprising at least one selected from the group consisting of a primary amino group, a secondary amino group, and a carbamoyl group.

6. The polymer according to claim 1, wherein the compound is a polyaziridine-polymer, a modified polyaziridine polymer, a diamine compound, a biguanide compound, an amino acid, an N-acylamino acid, a peptide, an amino sugar, a polyamine sugar, or an antimicrobial drug.

7. The polymer according to claim 1, wherein the terminal compound further comprises a divalent group formed by ring opening of a cyclic ether group bonded to a —NH— group which is different from the group bonded to the polymer chain end.

8. An antimicrobial agent, a disinfectant, or an antimicrobial and disinfecting agent, comprising the polymer according to claim 1 as an active component.

9. An antimicrobial material, a disinfectant material, or an antimicrobial and disinfecting material, comprising the polymer according to claim 1.

10. An antimicrobial method, a disinfecting method, or an antimicrobial and disinfecting method, comprising providing an antimicrobial and/or disinfecting property with the polymer according to claim 1.

11. The polymer according to claim 1, wherein a content of the repeating unit (1) wherein Z is an organic ammonium salt is 60% by mole or more.

Description

EXAMPLES

(1) Hereinafter, the present invention will be described in detail with reference to Examples, however, the present invention is not limited to these Examples.

(2) Abbreviations of, for example, the raw materials used in Examples are as follows.

(3) THF: tetrahydrofuran

(4) PGMEA: propylene glycol monomethyl ether acetate

(5) MMA: methyl methacrylate

(6) nBMA: n-butyl methacrylate (normal butyl methacrylate)

(7) DAMA: dimethylaminoethyl methacrylate

(8) EHMA: 2-ethylhexyl methacrylate

(9) <Measurement Conditions of Mw and Mw/Mn>

(10) Mw and Mn, which measured in the following respective Synthesis Examples, are measured values in terms of polystyrene by gel permeation chromatography with the following specifications.

(11) Device: GPC-104 (manufactured by SHOWA DENKO K.K.)

(12) Column: Three columns of LF-604 were connected with KF-602 to be used

(13) Mobile phase: THF

(14) Temperature: 40° C.

(15) Flow rate: 0.6 mL/min.

(16) <Synthesis of Polymer>

Synthesis Example 1

(17) Into a 300 mL flask, 125 mL of THF, 1.31 g of lithium chloride, and 3.8 g of diisopropylamine were added, the resultant mixture was cooled down to −60° C., and then into the cooled mixture, 23.5 mL of a hexane solution of n-butyllithium (at a concentration of 1.6 mol/L) was added, and the mixture was stirred for 15 minutes. Subsequently, into the resultant mixture, 3.8 g of methyl isobutyrate was added, and the mixture was stirred for 15 minutes, and then into the resultant mixture, a mixture of 7.5 g of MMA, 5 g of nBMA, 7.5 g of EHMA, and 30 g of DAMA was added dropwise, and the reaction was continued for 1 hour. After that, GC was measured, and after the confirmation of the disappearance of monomers, 3.6 g of epichlorohydrin was added into the resultant mixture, and the mixture was stirred for 2 hours. After that, the reaction temperature was raised up to 25° C. over 2 hours, and then 100 mL of water was placed in the flask to wash it with water, layer separation was performed and the water layer was removed, subsequently the resultant solution was adjusted to a PGMEA solution having a concentration of 40% by mass by solvent substitution via vacuum concentration. In this way, a random copolymer a-1 having an epoxy group at the terminal and having repeating units derived from DAMA, MMA, nBMA, and EHMA was obtained. The Mw (weight average molecular weight) of the obtained polymer was 2020, and the Mw/Mn (molecular weight distribution) was 1.21.

(18) Next, into 100.0 g of the obtained 40% by mass polymer solution, 7.0 g of polyethyleneimine 300 (PEI 300), 0.2 g of triphenylphosphine, and 30.0 g of propylene glycol monomethyl ether were added, and the resultant mixture was reacted at 45° C. for 25 hours to react the polymer a-1 with the polyethyleneimine Next, to the resultant mixture, 11.5 g of benzyl chloride was added, and then the mixture was gently stirred, the temperature of the polymer solution was raised to 75° C., this temperature was maintained for 8 hours, and the dimethylamino group derived from DAMA was partially converted to quaternary ammonium. The reaction mixture was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride was disappeared. In this way, a polymer in which repeating units derived from DAMA, MMA, nBMA, and EHMA were provided in the side chain of polyethylene imine, and a part thereof was converted to quaternary ammonium was obtained. The obtained polymer was regarded as a “polymer (A-1)”.

Synthesis Example 2

(19) Into a 300 mL flask, 125 mL of THF, 1.31 g of lithium chloride, and 23.5 mL, of a hexane solution of n-butyllithium (at a concentration of 1.6 mol/L) were added, the resultant mixture was cooled down to −60° C., and then into the cooled mixture, 3.8 g of diisopropylamine was added, and the mixture was stirred for 15 minutes. Subsequently, into the resultant mixture, 3.8 g of methyl isobutyrate was added and the mixture was stirred for 15 minutes, and then into the resultant mixture, a mixture of 5.5 g of MMA, 4 g of nBMA, 5.5 g of EHMA, and 35 g of DAMA was added dropwise, and the reaction was continued for 30 minutes. After that, GC was measured, and after the confirmation of the disappearance of monomers, 3.6 g of epichlorohydrin was added into the resultant mixture, and the mixture was stirred for 2 hours, and then the temperature was raised up to 25° C. over 2 hours. Subsequently, it was washed with 100 mL of water to perform layer separation, and the water layer was removed, and then the resultant solution was adjusted to a PGMEA solution having a concentration of 40% by mass by solvent substitution via vacuum concentration. In this way, a random copolymer a-2 having an epoxy group at the terminal and having repeating units derived from DAMA, MMA, nBMA, and EHMA was obtained. The Mw (weight average molecular weight) of the obtained polymer was 1980, and the Mw/Mn (molecular weight distribution) was 1.23.

(20) Next, into 100.0 g of the obtained 40% by mass polymer solution, 13.9 g of polyethyleneimine 600 (PEI 600), 0.2 g of triphenylphosphine, and 40.0 g of propylene glycol monomethyl ether were added, and the resultant mixture was reacted at 60° C. for 20 hours to react the polymer a-2 with the polyethyleneimine. Next, to the resultant mixture, 16.3 g of benzyl chloride, and 40.0 g of propylene glycol monomethyl ether were added, and then the mixture was gently stirred, the temperature of the polymer solution was raised to 75° C., this temperature was maintained for 8 hours, and the dimethylamino group derived from DAMA was partially converted to quaternary ammonium. The reaction mixture was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride was disappeared. In this way, a polymer in which repeating units derived from DAMA, MMA, nBMA, and EHMA were provided in the side chain of polyethyleneimine, and a part thereof was converted to quaternary ammonium was obtained. The obtained polymer was regarded as a “polymer (A-2)”.

Synthesis Example 3

(21) Into a 300 mL flask, 125 mL of THF, 1.31 g of lithium chloride, and 3.8 g of diisopropylamine were added, and the resultant mixture was cooled down to −60° C. Subsequently, into the cooled mixture, 18.8 mL of a hexane solution of n-butyllithium (at a concentration of 1.6 mol/L) was added, and the mixture was stirred for 5 minutes, and then into the resultant mixture, 3.4 g of methyl isobutyrate was added, and the mixture was stirred for 15 minutes. Into the resultant mixture, a mixture of 7.5 g of MMA, 5 g of nBMA, 7.5 g of EHMA, and 30 g of DAMA was added dropwise, and the reaction was continued for 15 minutes. After that, GC was measured, and after the confirmation of the disappearance of monomers, 3.5 g of epichlorohydrin was added into the resultant mixture, and the mixture was stirred for 2 hours, and then the temperature was raised up to 25° C. over 2 hours to terminate the reaction. Subsequently, it was washed with 100 mL of water to perform layer separation, and the water layer was removed, and then the resultant solution was adjusted to a PGMEA solution having a concentration of 40% by mass by solvent substitution via vacuum concentration. In this way, a random copolymer a-3 having an epoxy group at the terminal and having repeating units derived from DAMA, MMA, nBMA, and EHMA was obtained. The Mw (weight average molecular weight) of the obtained polymer was 2480, and the Mw/Mn (molecular weight distribution) was 1.25.

(22) Next, into 100.0 g of the obtained 40% by mass polymer solution, 4.7 g of polyethyleneimine 300 (PEI 300), 0.2 g of triphenylphosphine, and 40.0 g of propylene glycol monomethyl ether were added, and the resultant mixture was reacted at 70° C. for 16 hours to react the polymer a-3 with the polyethyleneimine Next, to the resultant mixture, 11.5 g of benzyl chloride was added, and then the mixture was gently stirred, the temperature of the polymer solution was raised to 75° C., this temperature was maintained for 8 hours, and the dimethylamino group derived from DAMA was partially converted to quaternary ammonium. The reaction mixture was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride was disappeared. In this way, a polymer in which repeating units derived from DAMA, MMA, nBMA, and EHMA were provided in the side chain of polyethyleneimine, and a part thereof was converted to quaternary ammonium was obtained. The obtained polymer was regarded as a “polymer (A-3)”.

Synthesis Example 4

(23) Into a 300 mL flask, 125 mL of THF, 1.31 g of lithium chloride, and 3.8 g of diisopropylamine were added, the resultant mixture was cooled down to −60° C., and then into the cooled mixture, 23.5 mL of a hexane solution of n-butyllithium (at a concentration of 1.6 mol/L) was added, and the mixture was stirred for 15 minutes. Subsequently, into the resultant mixture, 3.8 g of methyl isobutyrate was added and the mixture was stirred for 15 minutes, and then into the resultant mixture, a mixture of 7.5 g of MMA, 5 g of nBMA, 7.5 g of EHMA, and 30 g of DAMA was added dropwise, and the reaction was continued for 1 hour. After that, GC was measured, and after the confirmation of the disappearance of monomers, 3.6 g of epichlorohydrin was added into the resultant mixture, and the mixture was stirred for 2 hours. After that, the reaction temperature was raised up to 25° C. over 2 hours, and then 100 mL of water was placed in the flask to wash it with water, layer separation was performed and the water layer was removed, subsequently the resultant solution was adjusted to a PGMEA solution having a concentration of 40% by mass by solvent substitution via vacuum concentration. In this way, a random copolymer a-4 having an epoxy group at the terminal and having repeating units derived from DAMA, MMA, nBMA, and EHMA was obtained. The Mw (weight average molecular weight) of the obtained polymer was 2020, and the Mw/Mn (molecular weight distribution) was 1.21.

(24) Next, into 100.0 g of the obtained 40% by mass polymer solution, 5.4 g of phenyl biguanide, 0.2 g of triphenylphosphine, and 30.0 g of propylene glycol monomethyl ether were added, and the resultant mixture was reacted at 70° C. for 16 hours to react the polymer a-4 with the phenyl biguanide. Next, to the resultant mixture, 11.5 g of benzyl chloride was added, and then the mixture was gently stirred, the temperature of the polymer solution was raised to 75° C., this temperature was maintained for 8 hours, and the dimethylamino group derived from DAMA was partially converted to quaternary ammonium. The reaction mixture was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride was disappeared. In this way, a polymer in which a partial structure derived from phenyl biguanide, and repeating units derived from DAMA, MMA, nBMA, and EHMA were provided, and a part thereof was converted to quaternary ammonium was obtained. The obtained polymer was regarded as a “polymer (A-4)”.

Synthesis Example 5

(25) Into a 300 mL flask, 125 mL of THF, 1.31 g of lithium chloride, and 3.8 g of diisopropylamine were added, the resultant mixture was cooled down to −60° C., and then into the cooled mixture, 23.5 mL of a hexane solution of n-butyllithium (at a concentration of 1.6 mol/L) was added, and the mixture was stirred for 15 minutes. Subsequently, into the resultant mixture, 3.8 g of methyl isobutyrate was added and the mixture was stirred for 15 minutes, and then into the resultant mixture, a mixture of 7.5 g of MMA, 5 g of nBMA, 7.5 g of EHMA, and 30 g of DAMA was added dropwise, and the reaction was continued for 1 hour. After that, GC was measured, and after the confirmation of the disappearance of monomers, 3.6 g of epichlorohydrin was added into the resultant mixture, and the mixture was stirred for 2 hours. After that, the reaction temperature was raised up to 25° C. over 2 hours, and then 100 mL of water was placed in the flask to wash it with water, layer separation was performed and the water layer was removed, subsequently the resultant solution was adjusted to a PGMEA solution having a concentration of 40% by mass by solvent substitution via vacuum concentration. In this way, a random copolymer a-5 having an epoxy group at the terminal and having repeating units derived from DAMA, MMA, nEMA, and EHMA was obtained. The Mw (weight average molecular weight) of the obtained polymer was 2020, and the Mw/Mn (molecular weight distribution) was 1.21.

(26) Next, into 100.0 g of the obtained 40% by mass polymer solution, 5.8 g of 1-(o-tolyl)biguanide, 0.2 g of triphenylphosphine, and 30.0 g of propylene glycol monomethyl ether were added, and the resultant mixture was reacted at 70° C. for 16 hours to react the polymer a-5 with the 1-(o-tolyl)biguanide. Next, to the resultant mixture, 11.5 g of benzyl chloride was added, and then the mixture was gently stirred, the temperature of the polymer solution was raised to 75° C., this temperature was maintained for 8 hours, and the dimethylamino group derived from DAMA was partially converted to quaternary ammonium. The reaction mixture was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride was disappeared. In this way, a polymer in which a partial structure derived from 1-(o-tolyl)biguanide, and repeating units derived from DAMA, MMA, nBMA, and EHMA were provided, and a part thereof was converted to quaternary ammonium was obtained. The obtained polymer was regarded as a “polymer (A-5)”.

Synthesis Example 6

(27) Into a 300 mL flask, 125 mL of THF, 1.31 g of lithium chloride, and 3.8 g of diisopropylamine were added, the resultant mixture was cooled down to −60° C., and then into the cooled mixture, 23.5 mL of a hexane solution of n-butyllithium (at a concentration of 1.6 mol/L) was added, and the mixture was stirred for 15 minutes. Subsequently, into the resultant mixture, 3.8 g of methyl isobutyrate was added and the mixture was stirred for 15 minutes, and then into the resultant mixture, a mixture of 7.5 g of MMA, 5 g of nBMA, 7.5 g of EHMA, and 30 g of DAMA was added dropwise, and the reaction was continued for 1 hour. After that, GC was measured, and after the confirmation of the disappearance of monomers, 3.6 g of epichlorohydrin was added into the resultant mixture, and the mixture was stirred for 2 hours. After that, the reaction temperature was raised up to 25° C. over 2 hours, and then 100 mL of water was placed in the flask to wash it with water, layer separation was performed and the water layer was removed, subsequently the resultant solution was adjusted to a PGMEA solution having a concentration of 40% by mass by solvent substitution via vacuum concentration. In this way, a random copolymer a-6 having an epoxy group at the terminal and having repeating units derived from DAMA, MMA, nBMA, and EHMA was obtained. The Mw (weight average molecular weight) of the obtained polymer was 2020, and the Mw/Mn (molecular weight distribution) was 1.21.

(28) Next, into 100.0 g of the obtained 40% by mass polymer solution, 6.6 g of bis(4-aminophenylethyl) adipate, 0.2 g of triphenylphosphine, and 30.0 g of propylene glycol monomethyl ether were added, and the resultant mixture was reacted at 70° C. for 16 hours to react the polymer a-6 with the bis(4-aminophenylethyl) adipate. Next, to the resultant mixture, 11.5 g of benzyl chloride was added, and then the mixture was gently stirred, the temperature of the polymer solution was raised to 75° C., this temperature was maintained for 8 hours, and the dimethylamino group derived from DAMA was partially converted to quaternary ammonium. The reaction mixture was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride was disappeared. In this way, a polymer in which a partial structure derived from bis(4-aminophenylethyl) adipate, and repeating units derived from DAMA, MMA, nBMA, and EHMA were provided, and a part thereof was converted to quaternary ammonium was obtained. The obtained polymer was regarded as a “polymer (A-6)”.

Synthesis Example 7

(29) A polymer a-1 was obtained in a similar manner as in Synthesis Example 1. Next, into 100.0 g of the obtained 40% by mass polymer solution, 4.3 g of N-acetyl-L-glutamine, 0.2 g of triphenylphosphine, and 30.0 g of propylene glycol monomethyl ether were added, and the resultant mixture was reacted at 45° C. for 25 hours to react the polymer a-1 with the N-acetyl-L-glutamine. Next, to the resultant mixture, 11.5 g of benzyl chloride was added, and then the mixture was gently stirred, the temperature of the polymer solution was raised to 75° C., this temperature was maintained for 8 hours, and the dimethylamino group derived from DANA was partially converted to quaternary ammonium. The reaction mixture was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride was disappeared. In this way, a polymer in which a partial structure derived from N-acetyl-L-glutamine, and repeating units derived from DANA, MMA, nBMA, and EHMA were provided, and a part thereof was converted to quaternary ammonium was obtained. The obtained polymer was regarded as a “polymer (A-7)”.

(30) The copolymerization rate (% by mass) to each of the monomers in the polymers a-1 to a-6 obtained in the above respective synthesis examples, and the content ratio (parts by mass) of epichlorohydrin to 100 parts by mass of the total amount of monomers are shown in Table 1.

(31) Further, the Mw and the Mw/Mn of each of the polymers a-1 to a-6 are shown in Table 1.

(32) TABLE-US-00001 TABLE 1 Polymer Polymer Polymer Polymer Polymer Polymer a-1 a-2 a-3 a-4 a-5 a-6 DAMA 60.0 70.0 60.0 60.0 60.0 60.0 (% by mass) MMA 15.0 11.0 15.0 15.0 15.0 15.0 (% by mass) nBMA 10.0 8.0 10.0 10.0 10.0 10.0 (% by mass) EHMA 15.0 11.0 15.0 15.0 15.0 15.0 (% by mass) Repeating 100 100 100 100 100 100 units in total (% by mass) Epichloro- 7.2 7.2 7.0 7.2 7.2 7.2 hydrin (parts by mass) Mw 2020 1980 2480 2020 2020 2020 Mw/Mn 1.21 1.23 1.25 1.21 1.21 1.21

Comparative Synthesis Example 1

(33) Into a 300 mL flask, 125 mL of THF, and 2.62 g of lithium chloride were added, and the resultant mixture was cooled down to 60° C. Into the cooled mixture, 23.5 mL of a hexane solution of n-butyllithium (at a concentration of 1.6 mol/L) was added, and the mixture was stirred for 5 minutes, and then into the resultant mixture, diphenylethylene (6.8 g) was added, and the mixture was stirred for 15 minutes. Into the resultant mixture, a mixture of 7.5 g of MMA, and 5 g of nBMA was added dropwise, and the reaction was continued for 15 minutes. GC was measured, and after the confirmation of the disappearance of monomers, 7.5 g of EHMA was added dropwise into the resultant mixture, and the reaction was continued for 15 minutes after the dropwise addition. GC was measured, and the disappearance of monomers was confirmed. Next, 30 g of DAMA was added dropwise into the resultant mixture, and the reaction was continued for 30 minutes after the dropwise addition. GC was measured, and after the confirmation of the disappearance of monomers, 2 g of ethanol was added into the resultant mixture to terminate the reaction. After that, the resultant solution was adjusted to a PGMEA solution having a concentration of 40% by mass by vacuum concentration. In this way, a block copolymer including a block A having a repeating unit derived from DAMA, a block B1 having a repeating unit derived from EHMA, and a block B2 having repeating units derived from MMA and nEMA was obtained. The Mw (weight average molecular weight) of the obtained polymer was 1100, and the Mw/Mn (molecular weight distribution) was 1.2.

(34) Next, into 100 g of the obtained polymer solution, 13.1 g of benzyl chloride, and 30.0 g of propylene glycol monomethyl ether were added, and then the mixture was gently stirred, the temperature of the polymer solution was raised to 90° C., this temperature was maintained for 8 hours, and the dimethylamino group derived from DAMA was partially converted to quaternary ammonium. The reaction mixture was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride was disappeared. In this way, a block copolymer including a block A having a repeating unit derived from DAMA, of which a part was converted to quaternary ammonium; a block B1 having a repeating unit derived from EHMA; and a block B2 having repeating units derived from MMA and nBMA was obtained. The obtained copolymer was regarded as a “polymer (P-1)”.

(35) The polymers (polymer a-1 to polymer a-6, and polymer p-1) providing respective polymer chains, the compounds providing respective specific partial structures, and the use ratio of benzyl chloride, which were used in each of the above Synthesis Examples and Comparative Synthesis Example, are shown in Table 2.

(36) TABLE-US-00002 TABLE 2 Comparative Synthesis Synthesis Synthesis Synthesis Synthesis Synthesis Synthesis Synthesis Example Example Example Example Example Example Example Example 1 2 3 4 5 6 7 1 (A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7) (P-1) Polymers a-1 to a-6, 40 40 40 40 40 40 40 40 or polymer p-1 (parts by mass) PEI 300 (parts by mass) 7.0 — 4.7 — — — — — PEI 600 (parts by mass) — 13.9 — — — — — — Phenyl biguanide — — — 5.4 — — — — (parts by mass) 1-(o-Tolyl)biguanide — — — — 5.8 — — — (parts by mass) Bis(4-aminophenylethyl) — — — — — 6.6 — — adipate (parts by mass) N-acetyl-L-glutamine — — — — — — 4.3 — (parts by mass) Benzyl chloride 11.5 16.3 11.5 11.5 11.5 11.5 11.5 13.1 (parts by mass) Ratio with respect to 0.8 0.9 0.8 0.8 0.8 0.8 0.8 0.8 DAMA (eq)

Test Example 1

Antimicrobial and Disinfecting Properties Test

(37) Into 500 mL of hexane, 10 g of the polymer obtained in each of the above Synthesis Examples was added dropwise over 2 hours, and then vacuum drying was performed at 40° C. for 24 hours. The powder thus obtained was used for a test.

Example 1

(38) (Preparation of Liquid Medium)

(39) 30.4 g of a medium (Mueller Hinton II) was weighed out, and dissolved in 800 mL of sterile water, and the resultant mixture was subjected to an autoclave treatment at 121° C. and 2 atm for 15 minutes.

(40) (Preparation of Bacterial Liquid)

(41) Each of the bacteria of the following (1) to (8) was suspended in 1 mL of the liquid medium obtained in the above “preparation of liquid medium”, OD600 was measured, and a liquid medium was added so that the amount of bacteria is 1×10.sup.8 cfu/mL to prepare each of the bacterial liquids.

(42) (1) E. coli (drug sensitive strain, DH5α)

(43) (2) S. aureus (drug sensitive strain, ATCC29213)

(44) (3) E. coli (NDM-1 producing strain)

(45) (4) E. coli (IMP-1 producing strain, ST131)

(46) (5) Klebsiella pneumoniae (KPC-2 producing strain, ST258)

(47) (6) A. baumannii (OXA-23 producing strain, ST2)

(48) (7) Pseudomonas aeruginosa (MP-1 producing strain, ST235)

(49) (8) MRSA (S. aureus methicillin-resistant strain)

(50) (Measurement)

(51) A polymer (A-1) and water were mixed to prepare 10 mg/mL of a polymer aqueous solution. Into 897.6 μL of the prepared liquid medium, 102.4 μL of the above-described polymer aqueous solution was added so that the concentration of the polymer is 1024 μg/mL. This solution was diluted 2 times in wells of a 96-well plate to prepare a dilution series of 1024 μg/mL to 0.015625 μg/mL. Next, 5 μL of a bacterial liquid was added to each of the wells and incubated at 37° C. for 16 hours.

(52) The turbidity of each of the wells was visually discriminated and the growing state of the bacteria was confirmed. The concentrations of the dilution series, at which it was visually determined that the antimicrobial action and disinfecting action were performed without cloudiness, are shown in Table 3.

Examples 2 to 7 and Comparative Examples 1 to 4

(53) The antimicrobial and the disinfecting properties were evaluated in a similar manner as in Example 1 except that each of the compounds shown in Table 3 was used in place of the polymer (A-1) in Example 1. The evaluation results are shown in Table 3. In this regard, in the Table, PEI 300 means polyethyleneimine 300 and PEI 600 means polyethyleneimine 600, respectively.

(54) TABLE-US-00003 TABLE 3 Klebsiella Pseudomonas E. coli S. aureus E. coli pneumoniae A. aeruginosa (Drug (Drug E. coli (IMP-1 (KPC-2 baumannii (MP-1 sensitive sensitive (NDM-1 producing producing (OKA-23 producing strain, strain, producing strain, strain, producing strain, Compound DH5α) ATCC29213) strain) ST131) ST258) strain, ST2) ST235) MRSA Examples 1 Polymer 64 64 16 64 128 64 128 64 (A-1) 2 Polymer 64 64 128 128 128 128 64 64 (A-2) 3 Polymer 32 64 32 32 64 64 64 16 (A-3) 4 Polymer 32 64 16 64 256 32 1024 16 (A-4) 5 Polymer 32 64 16 64 256 64 1024 16 (A-5) 6 Polymer 16 64 16 32 64 32 256 16 (A-6) 7 Polymer 64 128 8 128 16 64 1024 32 (A-7) Comparative 1 PEI300 256 512 512 512 512 >1024 32 >1024 Examples 2 PEI600 256 512 512 512 512 >1024 >1024 >1024 3 Phenyl >1024 >1024 1024 1024 >1024 1024 >1024 >1024 biguanide 4 Polymer 32 128 32 — >1024 256 >1024 256 (P-1)

(55) As shown in Table 3, the polymers (A-1) to (A-7) had antimicrobial and disinfecting properties against a wide range of kinds of germs. Of these, the polymers (A-1) to (A-3), and (A-6), particularly the polymers (A-1) to (A-3) had excellent antimicrobial and disinfecting properties even against Pseudomonas aeruginosa.

Test Example 2

Cytotoxicity Test

(56) The cytotoxicity of the polymer (A-3) was evaluated using a CCK-8 assay kit (DOJINDO LABORATORIES).

(57) That is, HepG2 cells were inoculated at 10,000 cells/well in a 96-well cell culture plate (manufactured by IWAKI), and cultured for 24 hours in Dulbecco's MEM containing 10% by mass serum. The polymer (A-3) was made into an aqueous solution of 10 mg/mL, and the final concentration was adjusted to 3 kinds of 1000, 100, and 10 μg/mL with Dulbecco's MEM containing 10% by mass serum. The medium of the cultured plate was removed with an aspirator, and the medium solution containing the polymer (A-3) was added to each of the wells so as to be n=3, and cultured for 24 hours. A CCK-8 reagent was added to each of the wells at 10 μL/well, and after 2 hours cultivation, the absorbance in 450 nm (ref 598 nm) was measured to determine the cell viability for the positive control without the addition of the polymer. The results of the cytotoxicity test are shown in the following Table 4.

(58) TABLE-US-00004 TABLE 4 Polymer concentration (μg/mL) Cell viability (%) 1000 14.1 100 9.1 10 106.7