TW202312876A - Antimicrobial agent, antimicrobial resin composition and quaternary ammonium salt - Google Patents
Antimicrobial agent, antimicrobial resin composition and quaternary ammonium salt Download PDFInfo
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- TW202312876A TW202312876A TW111129323A TW111129323A TW202312876A TW 202312876 A TW202312876 A TW 202312876A TW 111129323 A TW111129323 A TW 111129323A TW 111129323 A TW111129323 A TW 111129323A TW 202312876 A TW202312876 A TW 202312876A
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- Prior art keywords
- formula
- antibacterial
- antibacterial agent
- quaternary ammonium
- carbon atoms
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- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 50
- 239000011342 resin composition Substances 0.000 title claims description 36
- 239000004599 antimicrobial Substances 0.000 title abstract description 7
- 230000000845 anti-microbial effect Effects 0.000 title description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 51
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 40
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 40
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 7
- 230000000844 anti-bacterial effect Effects 0.000 claims description 108
- 239000003242 anti bacterial agent Substances 0.000 claims description 91
- -1 halide ion Chemical class 0.000 claims description 65
- 229920005989 resin Polymers 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 40
- 239000000126 substance Substances 0.000 claims description 31
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 30
- 125000000524 functional group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 125000004990 dihydroxyalkyl group Chemical group 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 66
- 238000012360 testing method Methods 0.000 description 35
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- 238000004140 cleaning Methods 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 23
- 241000894006 Bacteria Species 0.000 description 22
- 238000010992 reflux Methods 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
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- 238000000034 method Methods 0.000 description 17
- 230000001580 bacterial effect Effects 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
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- YWWNNLPSZSEZNZ-UHFFFAOYSA-N n,n-dimethyldecan-1-amine Chemical compound CCCCCCCCCCN(C)C YWWNNLPSZSEZNZ-UHFFFAOYSA-N 0.000 description 4
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- 241000191963 Staphylococcus epidermidis Species 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- OYQYHJRSHHYEIG-UHFFFAOYSA-N ethyl carbamate;urea Chemical compound NC(N)=O.CCOC(N)=O OYQYHJRSHHYEIG-UHFFFAOYSA-N 0.000 description 2
- 229940050410 gluconate Drugs 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- FFJMLWSZNCJCSZ-UHFFFAOYSA-N n-methylmethanamine;hydrobromide Chemical compound Br.CNC FFJMLWSZNCJCSZ-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
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- 229920000768 polyamine Polymers 0.000 description 2
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- 229920000515 polycarbonate Polymers 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
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- UMGXUWVIJIQANV-UHFFFAOYSA-M didecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC UMGXUWVIJIQANV-UHFFFAOYSA-M 0.000 description 1
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- MBUCQXWFYNYEAP-UHFFFAOYSA-L didecyl-(2-hydroxyethyl)-methylazanium;hexanedioate Chemical compound [O-]C(=O)CCCCC([O-])=O.CCCCCCCCCC[N+](C)(CCO)CCCCCCCCCC.CCCCCCCCCC[N+](C)(CCO)CCCCCCCCCC MBUCQXWFYNYEAP-UHFFFAOYSA-L 0.000 description 1
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- 235000019319 peptone Nutrition 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012137 tryptone Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plant Pathology (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Microbiology (AREA)
- General Health & Medical Sciences (AREA)
- Mycology (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
Description
本發明是有關於抗菌劑、使用此抗菌劑之抗菌性樹脂組合物及四級銨鹽。The present invention relates to an antibacterial agent, an antibacterial resin composition and a quaternary ammonium salt using the antibacterial agent.
近年來，由於住宅的居住空間、汽車的車廂內的衛生上的需要等，在胺甲酸乙酯樹脂等的樹脂中添加抗菌劑的抗菌性樹脂組合物的市場正在擴大。作為添加到樹脂中的抗菌劑，已知有無機系、有機系等的各式各樣的抗菌劑，並且正在針對表現出抗菌性的陽離子系界面活性劑的四級銨鹽進行研究。In recent years, the market for antimicrobial resin compositions in which an antimicrobial agent is added to resins such as urethane resins has been expanding due to hygienic needs in living spaces of houses and interiors of automobiles. Various inorganic and organic antibacterial agents are known as antibacterial agents to be added to resins, and studies are being conducted on quaternary ammonium salts of cationic surfactants that exhibit antibacterial properties.
作為如此的添加到樹脂中的四級銨鹽所形成的抗菌劑，可以列舉，例如，專利文獻1 (國際公開第2016/043202號)中所記載的溴化二癸基二甲基銨、氯化二癸基二甲基銨、氯化烷基二甲基芐基銨、己二酸二癸基二甲基銨等之外、溴化二癸基單甲基羥乙基銨、氯化烷基二甲基羥乙基銨、丙酸N,N-二癸基-N-甲基-聚(氧乙基)銨、己二酸二癸基單甲基羥乙基銨、葡萄糖酸二癸基單甲基羥乙基銨、磺酸二癸基單甲基羥乙基銨、己二酸烷基二甲基羥乙基銨、葡萄糖酸烷基二甲基羥乙基銨、丙酸二癸基甲基聚氧乙烯銨等。As an antibacterial agent formed by such a quaternary ammonium salt added to the resin, for example, didecyldimethylammonium bromide, chloride Didecyl dimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, didecyl dimethyl ammonium adipate, etc., didecyl monomethyl hydroxyethyl ammonium bromide, alkyl chloride Dimethyl hydroxyethyl ammonium, N,N-didecyl-N-methyl-poly(oxyethyl) ammonium propionate, didecyl monomethyl hydroxyethyl ammonium adipate, didecyl gluconate Alkyl monomethyl hydroxyethyl ammonium, didecyl monomethyl hydroxyethyl ammonium sulfonate, alkyl dimethyl hydroxyethyl ammonium adipate, alkyl dimethyl hydroxyethyl ammonium gluconate, dipropionate Decyl methyl polyoxyethylene ammonium, etc.
再者，在專利文獻2 (日本專利第4053635號公報)中記載添加了以下的四級銨鹽(在下述式中，R是氫原子或烴基，x、y是1～4的整數。)的胺甲酸乙酯樹脂。Furthermore, in Patent Document 2 (Japanese Patent No. 4053635), it is described that the following quaternary ammonium salt (in the following formula, R is a hydrogen atom or a hydrocarbon group, and x and y are integers of 1 to 4.) Urethane resin.
[化學式1]
[化學式2]
[化學式3]
[化學式4]
此外，在非專利文獻1中，研究了R(CH 3) 2N +(CH 2CH 2CH 2OH)Br -及R(CH 3) 2N +(CH 2CH 2OH)Br -(R ＝ C 10H 21～C 18H 37)的抗菌活性。 [先前技術文件] [專利文獻] In addition, in Non-Patent Document 1, R(CH 3 ) 2 N + (CH 2 CH 2 CH 2 OH)Br - and R(CH 3 ) 2 N + (CH 2 CH 2 OH)Br - (R =C 10 H 21 ~C 18 H 37 ) antibacterial activity. [Prior Art Documents] [Patent Documents]
[專利文獻1] 國際公開第2016/043202號 [專利文獻2] 日本專利第4053635號公報 [非專利文獻1] D. B. Kudryavtsev, et al., Anticorrosive Effects and Antimicrobial Properties of Alkyldimethyl (Hydroxyl) Ammonium Bromides, Petroleum Chemistry, 2011, Vol. 51, No. 4, pp. 293-298 [Patent Document 1] International Publication No. 2016/043202 [Patent Document 2] Japanese Patent No. 4053635 [Non-Patent Document 1] D. B. Kudryavtsev, et al., Anticorrosive Effects and Antimicrobial Properties of Alkyldimethyl (Hydroxyl) Ammonium Bromides, Petroleum Chemistry, 2011, Vol. 51, No. 4, pp. 293-298
[發明所欲解決的問題][Problem to be solved by the invention]
近年來，對抗菌劑所要求的抗菌活性的水準不斷提高，再者，隨著酒精除菌等的機會的增加，對於酒精清洗的抗菌活性的耐清洗性的要求水準也隨之提高。專利文獻1、專利文獻2、非專利文獻1等所記載的以往的抗菌劑不一定具有充分的抗菌活性、耐酒精清洗性等。In recent years, the level of antibacterial activity required for antibacterial agents has been increasing. Furthermore, as opportunities for alcohol sterilization and the like have increased, the level of antibacterial activity and cleaning resistance required for alcohol cleaning has also increased. Conventional antibacterial agents described in Patent Document 1, Patent Document 2, Non-Patent Document 1, etc. do not necessarily have sufficient antibacterial activity, alcohol cleaning resistance, and the like.
本發明的一個態樣是鑑於上述先前技術所具有的問題而完成的，其目的在於提供一種具有優異的抗菌活性，並且當其添加到樹脂中而形成抗菌性樹脂組合物時，抗菌活性的耐酒精清洗性也優異的抗菌劑；使用此抗菌劑的抗菌性樹脂組合物；以及作為此抗菌劑而發揮功能的新穎的四級銨鹽。 [用以解決問題的手段] One aspect of the present invention is completed in view of the problems of the above-mentioned prior art, and its object is to provide a kind of antibacterial activity that has excellent antibacterial activity, and when it is added in the resin to form antibacterial resin composition, the antibacterial activity resistance An antibacterial agent that is also excellent in alcohol cleaning properties; an antibacterial resin composition using the antibacterial agent; and a novel quaternary ammonium salt that functions as the antibacterial agent. [means used to solve a problem]
本發明提供以下的實施態樣。The present invention provides the following implementation aspects.
[1]一種抗菌劑，由以式(1)表示的四級銨鹽形成。[1] An antibacterial agent comprising a quaternary ammonium salt represented by formula (1).
(R 1) a(R 2) b(R 3) cN +．X -(1) (在式(1)中， R 1是至少一個氫原子被羥基取代的脂肪族烴基， R 1的碳原子數， 當只有一個氫原子被羥基取代時，為4～11， 當有兩個以上的氫原子被羥基取代時，為3～11， R 2是碳原子數10～18的脂肪烴基， R 3是碳原子數1～3的脂肪族烴基， X -是酸的共軛鹼， a表示1或2，b表示1，c表示1或2，且滿足a+b+c = 4，且 以R 1、R 2及R 3表示的脂肪族烴基的碳原子數的總和為15以上、23以下， 當a或c為2時，複數個R 1或R 3可以相同也可以不同。) [2]如[1]所記載之抗菌劑，其中，a為1，c為2，且R 3為甲基。 (R 1 ) a (R 2 ) b (R 3 ) c N + . X - (1) (In formula (1), R 1 is an aliphatic hydrocarbon group in which at least one hydrogen atom is replaced by a hydroxyl group, and the number of carbon atoms in R 1 is 4 to 11 when only one hydrogen atom is replaced by a hydroxyl group, When two or more hydrogen atoms are replaced by hydroxyl groups, it is 3 to 11, R 2 is an aliphatic hydrocarbon group with 10 to 18 carbon atoms, R 3 is an aliphatic hydrocarbon group with 1 to 3 carbon atoms, X - is acidic Conjugate base, a represents 1 or 2, b represents 1, c represents 1 or 2, and satisfies a+b+c=4, and the number of carbon atoms of the aliphatic hydrocarbon group represented by R 1 , R 2 and R 3 The sum is more than 15 and less than 23. When a or c is 2, a plurality of R 1 or R 3 can be the same or different.) [2] The antibacterial agent as described in [1], wherein a is 1, and c is 2, and R 3 is methyl.
[3]如[1]或[2]所記載之抗菌劑，其中，以R 1表示的脂肪族烴基是選自由碳原子數4～11的羥基烷基及碳原子數3～11的二羥基烷基所組成的群組中的至少一種。 [3] The antibacterial agent as described in [1] or [2], wherein the aliphatic hydrocarbon group represented by R is selected from a hydroxyalkyl group having 4 to 11 carbon atoms and a dihydroxy group having 3 to 11 carbon atoms At least one of the group consisting of alkyl groups.
[4]如[1]～[3]中任一項所記載之抗菌劑，其中，在以R 1表示的脂肪族烴基中，滿足以下的條件中的任一項： 只有末端碳原子上的一個氫原子被羥基取代， 末端碳原子上的至少一個氫原子及其相鄰的碳原子上的至少一個氫原子各自被羥基取代。 [4] The antibacterial agent as described in any one of [1] to [3], wherein, in the aliphatic hydrocarbon group represented by R 1 , any one of the following conditions is satisfied: only One hydrogen atom is replaced by a hydroxyl group, and at least one hydrogen atom on a terminal carbon atom and at least one hydrogen atom on an adjacent carbon atom are each replaced by a hydroxyl group.
[5]如[1]～[4]中任一項所記載之抗菌劑，其中，上述脂肪族烴基為直鏈烷基。[5] The antibacterial agent according to any one of [1] to [4], wherein the aliphatic hydrocarbon group is a linear alkyl group.
[6]如[1]～[5]中任一項所記載之抗菌劑，其中，X -為鹵化物離子。 [6] The antibacterial agent according to any one of [1] to [5], wherein X - is a halide ion.
[7]一種抗菌性樹脂組合物，其中，將如[1]～[6]中任一項所記載之抗菌劑固定在包含具有與羥基的反應性的官能基的樹脂上。[7] An antibacterial resin composition in which the antibacterial agent according to any one of [1] to [6] is immobilized on a resin containing a functional group reactive with a hydroxyl group.
[8]如[7]所記載之抗菌性樹脂組合物，其中，上述官能基為異氰酸酯(isocyanate)基。[8] The antibacterial resin composition according to [7], wherein the functional group is an isocyanate group.
[9]如[7]或[8]所記載之抗菌性樹脂組合物，其中，上述樹脂為胺甲酸乙酯(urethane)樹脂。[9] The antibacterial resin composition according to [7] or [8], wherein the resin is a urethane resin.
[10]一種四級銨鹽，以式(2)表示。[10] A quaternary ammonium salt represented by formula (2).
[化學式5]
(在式(2)中，m表示6～11的整數，n表示10～14的整數，且滿足m+n ＝ 16～21，X -表示鹵化物離子。) [11]如[10]所記載之四級銨鹽，以式(3)表示。 (In formula (2), m represents an integer of 6 to 11, n represents an integer of 10 to 14, and satisfies m+n = 16 to 21, and X - represents a halide ion.) [11] As described in [10] The recorded quaternary ammonium salt is represented by formula (3).
[化學式6]
(在式(3)中，n表示12～14的整數，X -表示鹵化物離子。) [12]如[10]所記載之四級銨鹽，以式(4)表示。 (In formula (3), n represents an integer of 12 to 14, and X - represents a halide ion.) [12] The quaternary ammonium salt described in [10], represented by formula (4).
[化學式 7]
(在式(4)中，X -表示鹵化物離子。) [13]一種四級銨鹽，以式(5)表示。 (In formula (4), X - represents a halide ion.) [13] A quaternary ammonium salt represented by formula (5).
[化學式8]
(在式(5)中，n表示12～16的整數，X -表示鹵化物離子。) [發明功效] (In formula (5), n represents an integer of 12 to 16, and X- represents a halide ion.) [Efficacy of the invention]
本發明的一個態樣的抗菌劑，具有優異的抗菌活性，並且當其添加到樹脂中而形成抗菌性樹脂組合物時，抗菌活性的耐酒精清洗性也優異。因此，根據本發明的另一個態樣，能夠得到具有優異的抗菌活性且其耐酒精清洗性亦優異的抗菌性樹脂組合物。再者，在本發明的又一個態樣中，提供一種新穎的四級銨鹽，其作為具有優異的抗菌活性與耐酒精清洗性的抗菌劑而發揮功能。The antibacterial agent according to one aspect of the present invention has excellent antibacterial activity, and when it is added to a resin to form an antibacterial resin composition, the antibacterial activity is also excellent in alcohol cleaning resistance. Therefore, according to another aspect of the present invention, an antibacterial resin composition having excellent antibacterial activity and excellent alcohol cleaning resistance can be obtained. Furthermore, in yet another aspect of the present invention, a novel quaternary ammonium salt is provided, which functions as an antibacterial agent having excellent antibacterial activity and alcohol cleaning resistance.
[用以實施發明的形態][Mode for Carrying Out the Invention]
在下文中，將針對較佳的實施形態而詳細地說明本發明。首先，針對本發明的一個態樣的抗菌劑進行說明。Hereinafter, the present invention will be described in detail for preferred embodiments. First, an antibacterial agent according to one aspect of the present invention will be described.
抗菌劑，是由以式(1)： (R 1) a(R 2) b(R 3) cN +．X -(1) (在式(1)中， R 1是至少一個氫原子被羥基取代的脂肪族烴基， R 1的碳原子數， 當只有一個氫原子被羥基取代時，為4～11， 當有兩個以上的氫原子被羥基取代時，為3～11， R 2是碳原子數10～18的脂肪烴基， R 3是碳原子數1～3的脂肪族烴基， X -是酸的共軛鹼， a表示1或2，b表示1，c表示1或2，且滿足a+b+c = 4，且 以R 1、R 2及R 3表示的脂肪族烴基的碳原子數的總和為15以上、23以下， 當a或c為2時，複數個R 1或R 3可以相同也可以不同。) 表示的四級銨鹽所形成之物。 The antibacterial agent is composed of formula (1): (R 1 ) a (R 2 ) b (R 3 ) c N + . X - (1) (In formula (1), R 1 is an aliphatic hydrocarbon group in which at least one hydrogen atom is replaced by a hydroxyl group, and the number of carbon atoms in R 1 is 4 to 11 when only one hydrogen atom is replaced by a hydroxyl group, When two or more hydrogen atoms are replaced by hydroxyl groups, it is 3 to 11, R 2 is an aliphatic hydrocarbon group with 10 to 18 carbon atoms, R 3 is an aliphatic hydrocarbon group with 1 to 3 carbon atoms, X - is acidic Conjugate base, a represents 1 or 2, b represents 1, c represents 1 or 2, and satisfies a+b+c=4, and the number of carbon atoms of the aliphatic hydrocarbon group represented by R 1 , R 2 and R 3 The sum is more than 15 and less than 23. When a or c is 2, the plurality of R 1 or R 3 may be the same or different.) Formed by quaternary ammonium salt represented by .
在式(1)中，R 3是碳原子數1～3的脂肪族烴基，可以是直鏈狀也可以是支鏈狀，可以是飽和的也可以是不飽和的，以烷基為佳，以直鏈烷基為特佳。如果沒有如此的碳原子數1～3的脂肪族烴基，則四級銨陽離子難以接近細菌，而導致抗菌活性及其耐酒精清洗性降低。作為R 3，可以列舉甲基、乙基、丙基等，其中，從抗菌活性及其耐酒精清洗性趨於進一步提高的觀點考慮，以甲基為佳。R 3的數量(c)是1或2，從抗菌活性及其耐酒精清洗性趨於進一步提高的觀點考慮，c以2為佳。再者，當複數個R 3存在於一個分子中時，它們可以相同也可以不同。 In formula (1), R 3 is an aliphatic hydrocarbon group with 1 to 3 carbon atoms, which can be straight-chain or branched, saturated or unsaturated, preferably alkyl, Straight chain alkyl groups are particularly preferred. Without such an aliphatic hydrocarbon group having 1 to 3 carbon atoms, it is difficult for quaternary ammonium cations to approach bacteria, resulting in a decrease in antibacterial activity and alcohol cleaning resistance. Examples of R 3 include a methyl group, an ethyl group, a propyl group, and the like, and among them, a methyl group is preferable from the viewpoint of further improving the antibacterial activity and its resistance to alcohol cleaning. The number (c) of R 3 is 1 or 2, and c is preferably 2 from the viewpoint that the antibacterial activity and its resistance to alcohol cleaning tend to be further improved. Furthermore, when plural R 3 exist in one molecule, they may be the same or different.
在式(1)中，R 2為碳原子數10～18的脂肪族烴基，可以是直鏈狀也可以是支鏈狀，可以是飽和的也可以是不飽和的，為了提高抗菌活性而以烷基為佳，以直鏈烷基為特佳。R 2的碳原子數為10～18，具體而言是，例如，10、11、12、13、14、15、16、17、18，也可以是以在此所例示的數值中的任意兩個作為上下限以內的範圍。本案發明人推測，R 2是碳原子數10～18的脂肪族烴基，藉此具有充分的疏水性，基於對細胞膜的作用而表現出抗菌性，因此抗菌活性優異。就抗菌活性較高的點而言，作為R 2，可以列舉癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基等作為例子。R 2的數量(b)是1。 In formula (1), R 2 is an aliphatic hydrocarbon group with 10 to 18 carbon atoms, which can be straight-chain or branched, saturated or unsaturated, in order to improve the antibacterial activity Alkyl groups are preferred, and straight chain alkyl groups are particularly preferred. The number of carbon atoms in R2 is 10 to 18, specifically, for example, 10, 11, 12, 13, 14, 15, 16, 17, 18, or any two of the numerical values exemplified here. as a range within the upper and lower limits. The inventors of the present invention speculate that R 2 is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, thereby having sufficient hydrophobicity and exhibiting antibacterial properties based on the action on the cell membrane, so that the antibacterial activity is excellent. In terms of the high antibacterial activity, as R 2 , decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, decadecyl, etc. Heptadecyl, octadecyl, etc. are exemplified. The number (b) of R2 is 1.
在式(1)中，R 1是至少一個氫原子被羥基取代的脂肪族烴基，此脂肪族烴基可以是直鏈狀也可以是支鏈狀，可以是飽和的也可以是不飽和的，為了提高抗菌活性而以烷基為佳，以直鏈烷基為特佳。藉由如此在至少一個脂肪族烴基中導入羥基，在胺甲酸乙酯等的樹脂的製造步驟中添加抗菌劑時，樹脂原料的官能基與羥基反應，藉由共價鍵等的鍵結(較佳為共價鍵)而將抗菌劑固定在樹脂上，因此抗菌活性的耐酒精清洗性得以提高。 In formula (1), R 1 is the aliphatic hydrocarbon group that at least one hydrogen atom is substituted by hydroxyl, and this aliphatic hydrocarbon group can be linear or branched, can be saturated or unsaturated, for Alkyl groups are preferred for improving antibacterial activity, and straight-chain alkyl groups are particularly preferred. By introducing a hydroxyl group into at least one aliphatic hydrocarbon group in this way, when an antibacterial agent is added in the production process of a resin such as urethane, the functional group of the resin raw material reacts with the hydroxyl group, and bonds such as a covalent bond (compared to (preferably covalent bond) to immobilize the antibacterial agent on the resin, so the antibacterial activity and alcohol cleaning resistance can be improved.
因此，當式(1)中的R 1具有一個取代羥基時，必須是碳原子數4～11的脂肪烴基。作為陽離子部位與羥基之間的連接基團(linker)的烴鏈會影響抗菌活性，當取代羥基為一個時，若脂肪族烴基的碳原子數小於4或脂肪族烴基的碳原子數大於11，則抗菌活性降低。式(1)中的R 1具有一個被取代的羥基時，R 1的碳原子數為4～11，也可以為5～11，具體而言是，例如，4、5、6、7、8、9、10 、11，也可以是以在此所例示的數值中的任意兩個作為上下限以內的範圍。作為如此的R 1，以碳原子數4～11的羥基烷基為佳，可以列舉羥基丁基、羥基戊基、羥基己基、羥基庚基、羥基辛基、羥基壬基、羥基癸基、羥基十一烷基等作為例子。羥基鍵結到脂肪族烴基的位置，沒有特別限定，從添加到樹脂中時容易與樹脂的官能基反應的觀點考慮，或是從抗菌活性的耐酒精清洗性趨於進一步提高的觀點考慮，較佳為羥基鍵結到未與N原子鍵結的一側的末端碳原子。 Therefore, when R 1 in formula (1) has one substituted hydroxyl group, it must be an aliphatic hydrocarbon group having 4 to 11 carbon atoms. The hydrocarbon chain as the linker (linker) between the cationic site and the hydroxyl group will affect the antibacterial activity. When the substituted hydroxyl group is one, if the number of carbon atoms of the aliphatic hydrocarbon group is less than 4 or the number of carbon atoms of the aliphatic hydrocarbon group is greater than 11, The antibacterial activity is reduced. When R 1 in formula (1) has one substituted hydroxyl group, R 1 has 4 to 11 carbon atoms, or 5 to 11 carbon atoms, specifically, for example, 4, 5, 6, 7, 8 , 9, 10, 11, and any two of the numerical values exemplified here may be used as the range within the upper and lower limits. Such R 1 is preferably a hydroxyalkyl group having 4 to 11 carbon atoms, such as hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyoctyl, hydroxynonyl, hydroxydecyl, hydroxy Undecyl and the like are exemplified. The position where the hydroxyl group is bonded to the aliphatic hydrocarbon group is not particularly limited, and it is preferable to use it from the viewpoint that it is easy to react with the functional group of the resin when it is added to the resin, or from the viewpoint that the alcohol cleaning resistance of the antibacterial activity tends to be further improved. Preferably, the hydroxyl group is bonded to the terminal carbon atom on the side not bonded to the N atom.
再者，式(1)中的R 1具有兩個以上的被取代的羥基時，必須是碳原子數3～11的脂肪烴基。作為陽離子部位與羥基之間的連接基團(linker)的烴鏈會影響抗菌活性，當被取代的羥基為兩個以上時，若脂肪族烴基的碳原子數小於3或脂肪族烴基的碳原子數大於11，則抗菌活性降低。式(1)中的R 1具有兩個以上的被取代的羥基時，R 1的碳原子數為3～11，具體而言是，例如，3、4、5、6、7、8、9、10 、11，也可以是以在此所例示的數值中的任意兩個作為上下限以內的範圍。作為如此的R1，可以列舉二羥基丙基、二羥基丁基、二羥基戊基、二羥基己基、二羥基庚基、二羥基辛基、二羥基壬基、二羥基癸基、二羥基十一烷基、三羥基丙基、三羥基丁基、三羥基戊基、三羥基己基、三羥基庚基、三羥基辛基、三羥基壬基、三羥基癸基、三羥基十一烷基等作為例子。從抑制添加到樹脂的製造步驟時的不需要的交聯的形成的觀點考慮、或是從進一步提高樹脂的機械物性的觀點考慮，被取代的羥基，以三個以下為佳，以兩個為更佳。作為如此的R 1，以碳原子數3～11的二羥基烷基為佳。再者，羥基鍵結到脂肪族烴基的位置，沒有特別限定，從添加到樹脂中時容易與樹脂的官能基反應的觀點考慮，或是從抗菌活性的耐酒精清洗性趨於進一步提高的觀點考慮，被取代的羥基為兩個以上時，較佳為羥基分別鍵結到未與N原子鍵結的一側的末端碳原子及從末端起算的第二個碳原子。 Furthermore, when R 1 in formula (1) has two or more substituted hydroxyl groups, it must be an aliphatic hydrocarbon group having 3 to 11 carbon atoms. The hydrocarbon chain as the linker between the cationic site and the hydroxyl group will affect the antibacterial activity. When the number of substituted hydroxyl groups is more than two, if the number of carbon atoms of the aliphatic hydrocarbon group is less than 3 or the carbon atoms of the aliphatic hydrocarbon group If the number is greater than 11, the antibacterial activity decreases. When R 1 in formula (1) has two or more substituted hydroxyl groups, R 1 has 3 to 11 carbon atoms, specifically, for example, 3, 4, 5, 6, 7, 8, 9 , 10, 11, and any two of the numerical values exemplified here may be used as the range within the upper and lower limits. Examples of such R1 include dihydroxypropyl, dihydroxybutyl, dihydroxypentyl, dihydroxyhexyl, dihydroxyheptyl, dihydroxyoctyl, dihydroxynonyl, dihydroxydecyl, and dihydroxyundecyl. Alkyl, trihydroxypropyl, trihydroxybutyl, trihydroxypentyl, trihydroxyhexyl, trihydroxyheptyl, trihydroxyoctyl, trihydroxynonyl, trihydroxydecyl, trihydroxyundecyl, etc. example. From the viewpoint of suppressing the formation of unnecessary crosslinks when added to the resin in the production process, or from the viewpoint of further improving the mechanical properties of the resin, the number of hydroxyl groups to be substituted is preferably three or less, and preferably two better. Such R 1 is preferably a dihydroxyalkyl group having 3 to 11 carbon atoms. Furthermore, the position where the hydroxyl group is bonded to the aliphatic hydrocarbon group is not particularly limited, and it is considered from the point of view that it is easy to react with the functional group of the resin when added to the resin, or from the point of view that the antibacterial activity and alcohol cleaning resistance tend to be further improved. Considering that there are two or more hydroxyl groups to be substituted, it is preferable that the hydroxyl groups are respectively bonded to the terminal carbon atom on the side not bonded to the N atom and the second carbon atom from the terminal.
再者，R 1的數量(a)是1或2，需要滿足a+b+c ＝ 4。從抗菌活性趨於進一步提高的觀點考慮，a以1為佳。再者，當複數個R 1存在於一個分子中時，它們可以相同也可以不同。 Furthermore, the number (a) of R 1 is 1 or 2, and a+b+c=4 needs to be satisfied. From the viewpoint that the antibacterial activity tends to be further improved, a is preferably 1. Furthermore, when a plurality of R 1 exist in one molecule, they may be the same or different.
此外，以式(1)表示的四級銨鹽的1個分子中的以R 1、R 2及R 3表示的脂肪族烴基的碳原子數的總和必須為15以上、23以下。與四級銨鹽的N原子鍵結的脂肪族烴基(R 1～R 3)的碳原子數的總數也會影響抗菌活性，當上述碳原子數的總數小於15時，抗菌活性降低，另一方面，若上述碳原子數的總數大於23，則抗菌活性會降低。以R 1、R 2及R 3表示的脂肪族烴基的碳原子數的總和為15以上、23以下，具體而言是，例如，15、16、17、18、19、20、21、22、23，也可以是以在此所例示的數值中的任意兩個作為上下限以內的範圍。 In addition, the total number of carbon atoms of the aliphatic hydrocarbon groups represented by R 1 , R 2 and R 3 in one molecule of the quaternary ammonium salt represented by formula (1) must be 15 or more and 23 or less. The total number of carbon atoms of the aliphatic hydrocarbon group (R 1 ~ R 3 ) bonded to the N atom of the quaternary ammonium salt also affects the antibacterial activity. When the total number of the above-mentioned carbon atoms is less than 15, the antibacterial activity decreases. Another On the one hand, if the total number of the above carbon atoms is greater than 23, the antibacterial activity will decrease. The total number of carbon atoms of the aliphatic hydrocarbon group represented by R 1 , R 2 and R 3 is 15 to 23, specifically, for example, 15, 16, 17, 18, 19, 20, 21, 22, 23. It is also possible to use any two of the numerical values exemplified here as the range within the upper and lower limits.
再者，式(1)中的X -是酸的共軛鹼。較佳為X -是強酸的共軛鹼。使上述的特定的四級銨陽離子與強酸的共軛鹼(陰離子)組合而以鹽的形式使用，藉此能夠作為具有優異的抗菌活性的抗菌劑而發揮功能，並且當其添加到樹脂中而形成抗菌性樹脂組合物時，抗菌活性趨於進一步提高。另一方面，羧酸根離子等的弱酸的共軛鹼，往往不能充分地得到上述的抗菌活性提高的效果。作為強酸的共軛鹼，可以列舉溴(Br)、氯(Cl)、氟(F)、碘(I)等的鹵化物離子、硝酸根離子、硫酸根離子、磷酸根離子、過氯酸根離子等，其中，從抗菌活性趨於進一步提高的觀點考慮，以鹵化物離子為佳，以溴(Br)或氯(Cl)為特佳。 Furthermore, X- in the formula (1) is the conjugate base of the acid. Preferably X - is the conjugate base of a strong acid. Combining the above-mentioned specific quaternary ammonium cation with the conjugate base (anion) of a strong acid and using it in the form of a salt can function as an antibacterial agent with excellent antibacterial activity, and when it is added to the resin, it will When an antibacterial resin composition is formed, the antibacterial activity tends to be further improved. On the other hand, the conjugate base of a weak acid such as carboxylate ion often cannot sufficiently obtain the effect of improving the antibacterial activity mentioned above. Examples of the conjugate base of a strong acid include halide ions such as bromine (Br), chlorine (Cl), fluorine (F), and iodine (I), nitrate ions, sulfate ions, phosphate ions, and perchlorate ions. Among them, halide ions are preferred, and bromine (Br) or chlorine (Cl) is particularly preferred, from the viewpoint of further improvement in antibacterial activity.
作為本發明的一個態樣的抗菌劑(本發明的一個態樣的以式(1)表示的四級銨鹽)的製造方法，沒有特別限定，可以適宜地採用，例如，以下的方法。The method for producing the antibacterial agent of one aspect of the present invention (the quaternary ammonium salt represented by formula (1) of one aspect of the present invention) is not particularly limited, and for example, the following methods can be suitably employed.
＜方法1＞ 一種得到目標的四級銨鹽的方法，此方法將對應於目標的四級銨鹽的以式(1a)： (R 2)(R 3) 2N (1a) (在式(1a)中，R 2、R 3與式(1)中的含義相同。) 表示的三級胺，藉由對應於目標的四級銨鹽的以式(1b)： (R 1)X (1b) (在式(1b)中，R 1、X與式(1)中的含義相同。) 表示的鹵化醇在反應介質中進行四級化反應，並且視需要進行清洗及乾燥。 <Method 1> A method for obtaining the quaternary ammonium salt of the target, which will correspond to the formula (1a) of the quaternary ammonium salt of the target: (R 2 )(R 3 ) 2 N (1a) (in the formula ( In 1a), R 2 , R 3 have the same meaning as in formula (1).) The tertiary amine represented by ), by formula (1b) corresponding to the quaternary ammonium salt of the target: (R 1 )X (1b ) (In formula (1b), R 1 and X have the same meanings as in formula (1).) The halogenated alcohol represented by is subjected to a quaternization reaction in a reaction medium, and washed and dried if necessary.
＜方法2＞ 一種得到目標的四級銨鹽的方法，此方法將對應於目標的四級銨鹽的以式(1c)： (R 1)(R 3) 2N (1c) (在式(1c)中，R 1、R 3與式(1)中的含義相同。) 表示的三級胺，藉由對應於目標的四級銨鹽的以式(1d)： (R 2)X (1d) (在式(1d)中，R 2、X與式(1)中的含義相同。) 表示的鹵化烷在反應介質中進行四級化反應，並且視需要進行清洗及乾燥。 <Method 2> A method for obtaining the quaternary ammonium salt of the target, which will correspond to the formula (1c) of the quaternary ammonium salt of the target: (R 1 )(R 3 ) 2 N (1c) (in the formula ( In 1c), R 1 , R 3 have the same meaning as in formula (1).) The tertiary amine represented by ), by formula (1d) corresponding to the quaternary ammonium salt of the target: (R 2 )X (1d ) (In formula (1d), R 2 and X have the same meanings as in formula (1).) The alkyl halide represented by quaternization reaction is carried out in the reaction medium, and washed and dried if necessary.
＜方法3＞ 一種得到目標的四級銨鹽的方法，此方法將對應於目標的四級銨鹽的以式(1e)： (R 1) 2(R 3)N (1e) (在式(1e)中，R 1、R 3與式(1)中的含義相同。) 表示的三級胺，藉由對應於目標的四級銨鹽的以式(1f)： (R 2)X (1f) (在式(1f)中，R 2、X與式(1)中的含義相同。) 表示的鹵化烷在反應介質中進行四級化反應，並且視需要進行清洗及乾燥。 <Method 3> A method for obtaining the quaternary ammonium salt of the target, which will correspond to the formula (1e) of the quaternary ammonium salt of the target: (R 1 ) 2 (R 3 )N (1e) (in the formula ( In 1e), R 1 , R 3 have the same meaning as in formula (1).) The tertiary amine represented by , by formula (1f) corresponding to the quaternary ammonium salt of the target: (R 2 )X (1f ) (In formula (1f), R 2 and X have the same meanings as in formula (1).) The alkyl halide represented by is subjected to quaternization reaction in the reaction medium, and washed and dried if necessary.
＜方法4＞ 一種得到目標的四級銨鹽的方法，此方法將對應於目標的四級銨鹽的以式(1g)： (R 1) 2(R 2)N (1g) (在式(1g)中，R 1、R 2與式(1)中的含義相同。) 表示的三級胺，藉由對應於目標的四級銨鹽的以式(1h)： (R 3)X (1h) (在式(1h)中，R 3、X與式(1)中的含義相同。) 表示的鹵化烷在反應介質中進行四級化反應，並且視需要進行清洗及乾燥。 <Method 4> A method for obtaining the quaternary ammonium salt of the target, which will correspond to the formula (1g) of the quaternary ammonium salt of the target: (R 1 ) 2 (R 2 )N (1g) (in the formula ( In 1g), R 1 , R 2 have the same meaning as in formula (1).) The tertiary amine represented by the formula (1h) corresponding to the quaternary ammonium salt of the target: (R 3 )X (1h ) (In the formula (1h), R 3 and X have the same meanings as in the formula (1).) The alkyl halide represented by is subjected to quaternization reaction in the reaction medium, and washed and dried if necessary.
四級化反應中使用的反應溶劑，沒有特別限制，可以列舉乙腈、丙腈、二甲基甲醯胺(以下有時稱為DMF)、二甲亞碸(以下有時稱為DMSO)、硝基甲烷、硝基乙烷、苯甲腈、硝基苯、甲醇、乙醇、丙醇、2-丙醇、丁醇、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸異丙酯、乙酸丁酯、乙酸異丁酯、乙酸三級丁酯、甲苯、二甲苯、氯苯、鄰-二氯苯、間-二氯苯、硝基苯等作為例子，其中，從產率良好的觀點考慮，以乙腈為佳。The reaction solvent used in the quaternization reaction is not particularly limited, and examples include acetonitrile, propionitrile, dimethylformamide (hereinafter sometimes referred to as DMF), dimethylsulfoxide (hereinafter sometimes referred to as DMSO), nitric acid Methyl methane, nitroethane, benzonitrile, nitrobenzene, methanol, ethanol, propanol, 2-propanol, butanol, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butylacetate Esters, isobutyl acetate, tertiary butyl acetate, toluene, xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, nitrobenzene, etc. are taken as examples, wherein, from the viewpoint of good yield, Acetonitrile is preferred.
接著，針對本發明的一個態樣的抗菌性樹脂組合物進行說明。抗菌樹脂組合物是將上述抗菌劑固定在包含具有與羥基的反應性的官能基的樹脂上而得到之物。Next, the antimicrobial resin composition of one aspect of this invention is demonstrated. The antibacterial resin composition is obtained by immobilizing the above-mentioned antibacterial agent on a resin having a functional group reactive with a hydroxyl group.
作為具有與羥基的反應性的官能基，可以列舉異氰酸酯基、環氧基等，其中，從在四級銨不會分解的溫度範圍內藉由與羥基的反應形成共價鍵而固定在樹脂上的觀點，且從抗菌活性的耐酒精清洗性趨於進一步提高的觀點考慮，以異氰酸酯基為佳。Examples of functional groups reactive with hydroxyl groups include isocyanate groups, epoxy groups, and the like, which are fixed to the resin by reacting with hydroxyl groups to form a covalent bond within a temperature range in which quaternary ammonium does not decompose. From the standpoint of antibacterial activity and alcohol cleaning resistance tend to be further improved, isocyanate group is preferable.
作為包含如此的官能基的樹脂，沒有特別限定，可以列舉，例如，胺甲酸乙酯樹脂、尿素樹脂、胺甲酸乙酯尿素樹脂、聚醯亞胺樹脂、聚噁唑啶酮樹脂、聚碳二亞胺樹脂、聚異氰脲酸酯樹脂等，其中，從藉由與羥基的反應形成共價鍵而固定在樹脂上的觀點，且從抗菌活性的耐酒精清洗性趨於進一步提高的觀點考慮，以由聚異氰酸酯與多元醇得到的胺甲酸乙酯樹脂；由聚異氰酸酯與多元胺得到的尿素樹脂；由聚異氰酸酯、多元醇與多元胺(單胺)得到的胺甲酸乙酯尿素樹脂為佳。再者，從藉由與羥基的反應形成共價鍵而固定在樹脂上而使抗菌活性的耐酒精清洗性進一步提高，同時使外觀良好而機械性能、耐久性優異的觀點考慮，以由聚異氰酸酯與聚碳酸酯多元醇得到的胺甲酸乙酯樹脂為更佳。The resin containing such a functional group is not particularly limited, and examples thereof include urethane resins, urea resins, urethane urea resins, polyimide resins, polyoxazolidone resins, polycarbonate resins, Imine resins, polyisocyanurate resins, etc., wherein, from the viewpoint of immobilization on the resin by forming a covalent bond through the reaction with hydroxyl groups, and from the viewpoint that the antibacterial activity and alcohol cleaning resistance tend to be further improved , the urethane resin obtained from polyisocyanate and polyol; the urea resin obtained from polyisocyanate and polyamine; the urethane urea resin obtained from polyisocyanate, polyol and polyamine (monoamine) is preferred . Furthermore, from the viewpoint of forming a covalent bond by reacting with a hydroxyl group and immobilizing on the resin so that the antibacterial activity and alcohol cleaning resistance are further improved, and at the same time, the appearance is good and the mechanical properties and durability are excellent. Urethane resins obtained with polycarbonate polyols are even better.
在抗菌性樹脂組合物中的上述抗菌劑的添加量，沒有特別限定，可以根據目的等而適當調整，通常是樹脂組合物中的抗菌劑的添加量為5質量以下，以0.1～5質量%為更佳。The addition amount of the above-mentioned antibacterial agent in the antibacterial resin composition is not particularly limited, and can be adjusted appropriately according to the purpose, etc. Usually, the addition amount of the antibacterial agent in the resin composition is 5 mass or less, with 0.1 to 5 mass % for better.
再者，在抗菌性樹脂組合物中，根據需要可以添加，例如，抗氧化劑、紫外線吸收劑、顏料、塗料、溶劑、阻燃劑、水解抑制劑、潤滑劑、可塑劑、填充材、抗靜電劑、分散劑、催化劑、保存安定劑、界面活性劑、調平劑等的添加劑。Furthermore, in the antibacterial resin composition, you can add, for example, antioxidants, ultraviolet absorbers, pigments, paints, solvents, flame retardants, hydrolysis inhibitors, lubricants, plasticizers, fillers, antistatic Additives for agents, dispersants, catalysts, preservation stabilizers, surfactants, leveling agents, etc.
作為將上述抗菌劑固定在上述樹脂上而得到抗菌性樹脂組合物的方法，沒有特別限定，例如，以採用以下的方法為佳。 (i)在使樹脂的原料(例如，聚異氰酸酯與多元醇)反應的前一步驟中，將抗菌劑混入樹脂形成性組合物中，使所得到的樹脂形成性組合物反應而得到抗菌性樹脂組合物的方法。 (ii)藉由混合機將樹脂丸粒或粉末狀的樹脂與抗菌劑混合之後，藉由擠出機加熱熔融捏揉而得到抗菌性樹脂組合物的方法。 (iii)將高濃度抗菌劑預先混合到樹脂中製備所謂的母料，並用樹脂丸粒或粉末狀的樹脂將其稀釋至預定濃度而得到抗菌性樹脂組合物的方法。 Although it does not specifically limit as a method to obtain an antimicrobial resin composition by immobilizing the said antibacterial agent to the said resin, For example, it is preferable to employ the following method. (i) In the previous step of reacting the raw materials of the resin (for example, polyisocyanate and polyol), an antibacterial agent is mixed into the resin-forming composition, and the resulting resin-forming composition is reacted to obtain an antibacterial resin composition method. (ii) A method of obtaining an antibacterial resin composition by heating, melting and kneading by an extruder after mixing resin pellets or powdery resin and an antibacterial agent by a mixer. (iii) A method in which a high-concentration antibacterial agent is previously mixed into a resin to prepare a so-called masterbatch, and diluted to a predetermined concentration with resin pellets or powdery resin to obtain an antibacterial resin composition.
抗菌性樹脂組合物的形狀等，沒有特別限定，根據用途，可製成塊狀、板狀、片狀、薄膜狀、纖維狀等的各種樹脂成形體，用於在住宅的生活空間、汽車的車廂內等的衛生需求高的各種用途。The shape of the antimicrobial resin composition is not particularly limited, and it can be made into various resin moldings such as blocks, plates, sheets, films, fibers, etc., and used in the living space of houses, automobiles, etc. Various applications that require high sanitation, such as inside a car.
接著，針對本發明的一個態樣的四級銨鹽進行說明。本發明的一個態樣的第一類四級銨鹽，是以式(2)表示的四級銨鹽：Next, the quaternary ammonium salt of one aspect of the present invention will be described. The first class quaternary ammonium salt of an aspect of the present invention is a quaternary ammonium salt represented by formula (2):
[化學式9]
(在式(2)中，m表示6～11的整數，n表示10～14的整數，且滿足m+n ＝ 16～21，X -表示鹵化物離子。) (In formula (2), m represents an integer of 6 to 11, n represents an integer of 10 to 14, and satisfies m+n=16 to 21, and X- represents a halide ion.)
m表示6～11的整數，具體而言是，例如，6、7、8、9、10、11，也可以是以在此所例示的數值中的任意兩個作為上下限以內的範圍。n表示10～14的整數，具體而言是，例如，10、11、12、13、14，也可以是以在此所例示的數值中的任意兩個作為上下限以內的範圍。m+n滿足16～21，具體而言是，例如，16、17、18、19、20、21，也可以是以在此所例示的數值中的任意兩個作為上下限以內的範圍。m represents an integer of 6 to 11, specifically, for example, 6, 7, 8, 9, 10, and 11, and may be within a range within the upper and lower limits of any two of the numerical values exemplified here. n represents an integer of 10 to 14, specifically, for example, 10, 11, 12, 13, and 14, and may be within a range within the upper and lower limits of any two of the numerical values exemplified here. m+n satisfies 16 to 21, specifically, for example, 16, 17, 18, 19, 20, 21, and may be a range within the upper and lower limits of any two of the numerical values exemplified here.
以式(2)表示的四級銨鹽中，以m為6且n為12～14的整數者為佳，如此的四級銨鹽，是以式(3)表示之物：Among the quaternary ammonium salts represented by formula (2), it is better to use m as 6 and n as an integer of 12 to 14. Such quaternary ammonium salts are represented by formula (3):
[化學式10]
(在式(3)中，n表示12～14的整數，X -表示鹵化物離子。) (In formula (3), n represents an integer of 12 to 14, and X - represents a halide ion.)
再者，以式(2)表示的四級銨鹽中，以m為11且n為10者也是較佳的，如此的四級銨鹽，是以式(4)表示之物：Furthermore, among the quaternary ammonium salts represented by formula (2), those with m being 11 and n being 10 are also preferred, such quaternary ammonium salts are represented by formula (4):
[化學式11]
(在式(4)中，X -表示鹵化物離子。) (In formula (4), X- represents a halide ion.)
此外，本發明的一個態樣的第二類四級銨鹽，是以式(5)表示之物：In addition, the second type of quaternary ammonium salt of an aspect of the present invention is represented by formula (5):
[化學式12]
(在式(5)中，n表示12～16的整數，X -表示鹵化物離子。) (In formula (5), n represents an integer of 12 to 16, and X - represents a halide ion.)
以式(2)～(5)表示的四級銨鹽，是作為抗菌劑的新穎化合物，其具有優異的抗菌活性，並且當其添加到樹脂中而形成抗菌性樹脂組合物時，抗菌活性的耐酒精清洗性也優異。The quaternary ammonium salt represented by formulas (2) to (5) is a novel compound as an antibacterial agent, which has excellent antibacterial activity, and when it is added to a resin to form an antibacterial resin composition, the antibacterial activity is significantly improved. It is also excellent in alcohol cleaning resistance.
再者，以式(2)～(5)表示的四級銨鹽，可以按照上述方法1～4而製造，可以實際製造以式(2)表示的四級銨鹽而作為後述的實施例1～5，可以實際製造以式(3)表示的四級銨鹽而作為後述的實施例2～3，可以實際製造以式(4)表示的四級銨鹽而作為後述的實施例1，可以實際製造以式(5)表示的四級銨鹽而作為後述的實施例7～8。Furthermore, the quaternary ammonium salts represented by formulas (2) to (5) can be manufactured according to the above-mentioned methods 1 to 4, and the quaternary ammonium salts represented by formulas (2) can be actually manufactured as the following example 1 ～5, can actually manufacture the quaternary ammonium salt represented by formula (3) and as the embodiment 2～3 described later, can actually manufacture the quaternary ammonium salt represented by formula (4) and as the embodiment 1 described later, can The quaternary ammonium salt represented by the formula (5) was actually produced as Examples 7 to 8 described later.
如以上所說明，本發明的一個態樣的抗菌劑，具有優異的抗菌活性，並且當其添加到樹脂中而形成抗菌性樹脂組合物時，抗菌活性的耐酒精清洗性也優異。因此，根據本發明的另一個態樣，能夠得到具有優異的抗菌活性且其耐酒精清洗性亦優異的抗菌性樹脂組合物。再者，在本發明的又一個態樣，提供一種新穎的四級銨鹽，其作為具有優異的抗菌活性與耐酒精清洗性的抗菌劑而發揮功能。 [實施例] As explained above, the antibacterial agent according to one aspect of the present invention has excellent antibacterial activity, and when it is added to a resin to form an antibacterial resin composition, the antibacterial activity is also excellent in alcohol cleaning resistance. Therefore, according to another aspect of the present invention, an antibacterial resin composition having excellent antibacterial activity and excellent alcohol cleaning resistance can be obtained. Furthermore, in another aspect of the present invention, a novel quaternary ammonium salt is provided, which functions as an antibacterial agent having excellent antibacterial activity and resistance to alcohol cleaning. [Example]
在下文中，將基於實施例及比較例更具體地說明本發明，但本發明並非受到以下的實施例所限定。Hereinafter, the present invention will be more specifically described based on Examples and Comparative Examples, but the present invention is not limited by the following Examples.
又，抗菌劑的結構分析、抗菌劑的抗菌性評價、抗菌加工胺甲酸乙酯樹脂的抗菌性評價分別藉由以下的方法進行評價。Moreover, the structure analysis of an antimicrobial agent, the antibacterial property evaluation of an antimicrobial agent, and the antimicrobial property evaluation of an antimicrobial processed urethane resin were evaluated by the following methods, respectively.
(抗菌劑的結構分析) 各抗菌劑的結構藉由核磁共振(NMR)光譜法確定。使用添加了四甲基矽烷(TMS)的氘代氯仿(Ambridge Isotope Laboratories, Inc.製造，以下表記為CDCl 3)或氘代二甲亞碸(Ambridge Isotope Laboratories, Inc.製造，以下表記為DMSO－d 6)作為化學位移標準，以1質量%的濃度溶解各抗菌劑作為化學位移標準，使用核磁共振設備(Bruker公司製造，「AVANCE II」)，以400 MHz ( 1H-NMR)頻率的進行測定。 (Structural Analysis of Antibacterial Agent) The structure of each antibacterial agent was determined by nuclear magnetic resonance (NMR) spectroscopy. Deuterated chloroform (manufactured by Ambridge Isotope Laboratories, Inc., hereinafter referred to as CDCl 3 ) or deuterated dimethylsulfoxide (manufactured by Ambridge Isotope Laboratories, Inc., hereinafter referred to as DMSO) to which tetramethylsilane (TMS) was added was used- d 6 ) As a chemical shift standard, dissolve each antibacterial agent at a concentration of 1% by mass as a chemical shift standard, and use a nuclear magnetic resonance device (manufactured by Bruker, "AVANCE II") at a frequency of 400 MHz ( 1 H-NMR) Determination.
(抗菌劑的抗菌性評價) 藉由測定最小生長抑制濃度(minimum inhibition concentrationm, MIC)而對各抗菌劑的抗菌性進行評價。 (Evaluation of antibacterial properties of antibacterial agents) The antibacterial activity of each antibacterial agent was evaluated by measuring the minimum growth inhibitory concentration (minimum inhibition concentrationm, MIC).
(1)最小生長抑制濃度的測定方法 將使用營養瓊脂(Nutrient agar)培養基(營養液體培養基(Nutrient broth，Difco公司 製造)+1.5%(w/v)瓊脂在30℃下培養了1天的各試驗菌用滅菌離子交換水稀釋成相當於0.5麥克法蘭(McFarland)而作為懸浮接種用菌液。 試驗菌：表皮葡萄球菌(Staphylococcus epidermidis)NBRC 100911 用離子交換水將水溶性的受試物質的濃度調整至8.0 mg/mL，將過濾除菌後的溶液作為原液。用營養液體培養基將原液稀釋 10 倍，以成為最大稀釋濃度(800 μg/mL)的溶液。另一方面，用二甲基亞碸(東京化成工業試藥公司製造)將難溶於水的受試物質的濃度調整至80 mg/mL的濃度，將未滅菌的溶液作為原液。用營養液體培養基將原液稀釋100倍，以成為最大稀釋濃度(800 μg/mL)的溶液。 (1) Determination method of minimum growth inhibitory concentration Each test bacteria cultured at 30° C. for 1 day using a nutrient agar medium (Nutrient broth (manufactured by Difco) + 1.5% (w/v) agar) was diluted with sterilized ion-exchanged water to an equivalent In 0.5 McFarland (McFarland) as a bacterial solution for suspension inoculation. Test bacteria: Staphylococcus epidermidis NBRC 100911 The concentration of the water-soluble test substance was adjusted to 8.0 mg/mL with ion-exchanged water, and the solution sterilized by filtration was used as the stock solution. Dilute the stock solution 10 times with nutrient broth to obtain a solution with the maximum dilution concentration (800 μg/mL). On the other hand, the concentration of the poorly water-soluble test substance was adjusted to 80 mg/mL with dimethylsulfoxide (manufactured by Tokyo Kasei Koyaku Co., Ltd.), and the unsterilized solution was used as a stock solution. The stock solution was diluted 100 times with nutrient liquid medium to obtain a solution with the maximum dilution concentration (800 μg/mL).
針對受試物質(抗菌劑)，將最大稀釋濃度的溶液設定為最大濃度，以稀釋倍率為2倍，包括最大濃度共11個階段之方式，用營養液體培養基進行稀釋，而調製受試物質溶液。將各受試物質溶液100 μL分裝到96孔微孔板(U型井)中，並將上述各試驗菌的接種用菌液5 μL接種至上述各井中。再者，將不含有受試物質的營養液體培養基(不含受試物質之營養液體培養基)100 μL分裝到96孔微孔板中，並接種各試驗菌的接種用菌液5 μL，作為試驗菌的生長的對照。For the test substance (antibacterial agent), the solution with the maximum dilution concentration is set as the maximum concentration, and the dilution ratio is 2 times, including a total of 11 stages of the maximum concentration, and is diluted with a nutrient liquid medium to prepare a test substance solution . Dispense 100 μL of each test substance solution into a 96-well microplate (U-shaped well), and inoculate 5 μL of the above-mentioned inoculum solution of each test bacteria into each of the above-mentioned wells. Furthermore, 100 μL of nutrient liquid medium (nutrient liquid medium without test substance) was dispensed into a 96-well microplate, and 5 μL of the inoculum solution of each test bacteria was inoculated as The growth control of the test bacteria.
將96孔微孔板用透氣性薄片密封，將試驗液在30℃下靜置培養48小時。培養後，若是用肉眼觀察不到混濁或沉殿的情況，或者即使有沉殿但為1個直徑為1 mm以下的情況，則作為生長抑制的判定基準。確認在對照用的不含受試物質之營養液體培養基中試驗菌的生長後，將肉眼觀察不到細菌生長的井中的最小受試物質濃度作為最小生長抑制濃度(MIC)。針對每種受試物質進行2次測試，取平均值作為測定值。The 96-well microplate was sealed with a gas-permeable sheet, and the test solution was incubated at 30° C. for 48 hours. After cultivation, if no turbidity or sinking is observed with the naked eye, or if there is sinking but one diameter is less than 1 mm, it is used as a criterion for judging growth inhibition. After confirming the growth of the test bacteria in the nutrient liquid medium not containing the test substance for the control, the minimum concentration of the test substance in the well where the growth of the bacteria was not observed with the naked eye was taken as the minimum growth inhibitory concentration (MIC). Two tests were carried out for each test substance, and the average value was taken as the measured value.
(2)最小生長抑制濃度的測定 基於針對各抗菌劑的最小生長抑制濃度的測定結果，根據以下的基準對抗菌劑的抗菌性進行評價。 ＜最小生長抑制濃度的判定基準＞ A：最小生長抑制濃度(μg/mL) ＜ 30 B：最小生長抑制濃度(μg/mL) = 30～100 C：最小生長抑制濃度(μg/mL) ＞ 100。 (2) Determination of minimum growth inhibitory concentration Based on the measurement results of the minimum growth inhibitory concentration for each antibacterial agent, the antibacterial properties of the antibacterial agent were evaluated according to the following criteria. <Judgement criteria for minimum growth inhibitory concentration> A: Minimum growth inhibitory concentration (μg/mL) ＜ 30 B: Minimum growth inhibitory concentration (μg/mL) = 30～100 C: The minimum growth inhibitory concentration (μg/mL) > 100.
(抗菌加工胺甲酸乙酯樹脂的抗菌活性的耐酒精清洗性評價) 各抗菌加工胺甲酸乙酯樹脂的抗菌活性的耐酒精清洗性，是進行作為後處理(清洗)的將製造各抗菌加工胺甲酸乙酯樹脂後浸漬於乙醇中煮沸 6 小時且清洗後，使用各抗菌加工胺甲酸乙酯樹脂測定細菌生長抑制率而進行評價。 (Evaluation of the antibacterial activity of the antibacterial processed urethane resin against alcohol cleaning) The antibacterial activity and alcohol cleaning resistance of each antibacterially treated urethane resin was carried out as a post-treatment (cleaning) after the production of each antibacterially treated urethane resin was immersed in ethanol and boiled for 6 hours. After washing, use each The antibacterial processed urethane resin was evaluated by measuring the bacterial growth inhibition rate.
(1)所用培養基及生理食鹽水的調製 1) NA培養基(2倍濃度的營養液體培養基(Difco公司製造)+5.0 g/L：氯化鈉+15 g/L：瓊脂) 2) NB培養基(普通肉汁培養基，榮研化學公司製造） 3) SCDLP培養基(Daigo，日本製藥公司製造) 4) SA培養基(2.5 g/L：酵母抽出物(yeast extract)，5.0 g/L：胰化蛋白腖(tryptone peptone)，1.0 g/L：葡萄糖(glucose)，15 g/L：瓊脂(agar)） 5) 磷酸緩衝生理食鹽水(42.5 mg/L：磷酸二氫鉀(KH 2PO 4)， 8.5 g/L：氯化鈉， pH：7.2)。 (1) Preparation of culture medium and physiological saline 1) NA medium (2-fold concentration of nutrient liquid medium (manufactured by Difco) + 5.0 g/L: sodium chloride + 15 g/L: agar) 2) NB medium ( Ordinary gravy medium, manufactured by Eiken Chemical Co., Ltd.) 3) SCDLP medium (Daigo, manufactured by Nippon Pharmaceutical Co., Ltd.) 4) SA medium (2.5 g/L: yeast extract, 5.0 g/L: tryptone peptone), 1.0 g/L: glucose (glucose), 15 g/L: agar (agar)) 5) Phosphate buffered saline (42.5 mg/L: potassium dihydrogen phosphate (KH 2 PO 4 ), 8.5 g/L L: sodium chloride, pH: 7.2).
(2)試驗菌及試驗菌液的調製 1) 試驗菌 表皮葡萄球菌(Staphylococcus epidermidis NBRC 100911) 2) 試驗菌液的調製 將冷凍保存的菌株在NA培養基中於35℃下培養24小時。將此培養菌移植到新的NA培養基並在35℃下培養24小時。刮取已生長的菌落，用1/100濃度的NB培養基調整至約1×10 6個/mL，將其作為試驗菌液。 (2) Preparation of Test Bacteria and Test Bacteria Solution 1) Test Bacteria Staphylococcus epidermidis NBRC 100911 2) Preparation of Test Bacteria Solution Cryopreserved strains were cultured in NA medium at 35° C. for 24 hours. This culture was transplanted into a new NA medium and incubated at 35°C for 24 hours. Scrape the grown colonies, adjust to about 1×10 6 colonies/mL with 1/100 concentration of NB medium, and use it as the test bacterial solution.
(3)試驗方法 試驗方法參考「JIS Z2801：2012 抗菌加工製品 抗菌試驗方法．抗菌效果」，且如以下所述而進行。 1) 試驗菌液的接種與培養 切成50 mm見方的正方形，用含有99%乙醇的紙巾擦拭並消毒整個表面，然後將完全乾燥的試驗品(抗菌加工胺甲酸乙酯樹脂及無加工胺甲酸乙酯樹脂)置於培養皿中，滴加試驗菌液0.4 mL。將40 mm見方的被覆膜(聚乙烯膜)被覆在滴加的試驗菌液上，使試驗菌液與試驗品整體緊密接觸。使菌液接種後的試驗品在作用溫濕度條件下作用預定時間。又，試驗品是在各條件下測試分別提供三個樣本(n=3)。 2) 菌數測定 在預定時間的作用後，將SCDLP培養基10 mL 加入到裝有試驗品的培養皿中，使用微量吸管(1000 μL)從試驗品中洗出試驗菌。將洗出的液體作菌數測定用樣品溶液。使用磷酸緩衝生理食鹽水製備樣品溶液的稀釋列，將樣品溶液原液及稀釋溶液各100 μL在SA培養基上展開，並在35℃下培養24小時。計算培養後的生長菌落的數量，求取試驗品每1 cm 2的試驗菌數(定量下限值：0.63個/cm 2)，取平均值作為測定值。 (3) Test method The test method refers to "JIS Z2801:2012 Antibacterial processed products - Antibacterial test method. Antibacterial effect", and it is carried out as follows. 1) Inoculation and cultivation of the test bacteria solution Cut into 50 mm squares, wipe and disinfect the entire surface with a paper towel containing 99% ethanol, and then completely dry the test product (antibacterial processed urethane resin and non-processed urethane Ethyl ester resin) was placed in a Petri dish, and 0.4 mL of the test bacteria solution was added dropwise. Cover the 40 mm square coating film (polyethylene film) on the dropwise test bacteria solution, so that the test bacteria solution and the test product are in close contact. Make the test product inoculated with the bacterial solution act for a predetermined time under the temperature and humidity conditions. In addition, the test product was tested under each condition to provide three samples (n=3). 2) Determination of the number of bacteria After the action of the predetermined time, add 10 mL of SCDLP medium to the petri dish containing the test product, and use a micropipette (1000 μL) to wash out the test bacteria from the test product. The washed liquid was used as a sample solution for the determination of the number of bacteria. A dilution column of the sample solution was prepared using phosphate-buffered saline, and 100 μL each of the original sample solution and the diluted solution were spread on SA medium, and incubated at 35°C for 24 hours. Calculate the number of growing colonies after culture, obtain the number of test bacteria per 1 cm 2 of the test product (quantitative lower limit: 0.63/cm 2 ), and take the average value as the measured value.
(4)細菌增殖抑制率的計算 使用如上述所求取的試驗菌數的測定值，基於以下(算式1)而計算細菌增殖抑制率。 細菌增殖抑制率(%) = {1-(接種24小時後的抗菌加工胺甲酸乙酯樹脂的試驗細菌數)/(接種24小時後的無加工胺甲酸乙酯樹脂的試驗細菌數)}×100 (算式1)。 (4) Calculation of bacterial proliferation inhibition rate Using the measured value of the number of test bacteria obtained as described above, the bacterial growth inhibition rate was calculated based on the following (Equation 1). Bacterial Proliferation Inhibition Rate (%) = {1-(The number of bacteria tested in the antibacterial processed urethane resin 24 hours after inoculation)/(The number of bacteria tested in the non-processed urethane resin 24 hours after the inoculation)}× 100 (Equation 1).
(5)細菌增殖抑制率的判定 基於針對各抗菌加工胺甲酸乙酯樹脂的細菌增殖抑制率的測定結果，根據以下的基準對抗菌加工胺甲酸乙酯樹脂的抗菌性(抗菌活性的耐酒精清洗性)進行評價。 ＜細菌增殖抑制率的判定基準＞ A：細菌增殖抑制率(%) ＞90 B：細菌增殖抑制率(%) = 50-90 C：細菌增殖抑制率(%) ＜ 50。 (5) Determination of bacterial proliferation inhibition rate Based on the measurement results of the bacterial growth inhibition rate for each antibacterially processed urethane resin, the antibacterial properties (resistance to alcohol washing of antibacterial activity) of the antibacterially processed urethane resin were evaluated according to the following criteria. <Judgement criteria for bacterial growth inhibition rate> A: Bacterial proliferation inhibition rate (%) >90 B: Bacterial Proliferation Inhibition Rate (%) = 50-90 C: Bacterial proliferation inhibition rate (%) < 50.
(抗菌劑合成例1：實施例1/抗菌劑A) N-癸基-N-(11-羥基十一烷基)-N,N-二甲基溴化銨的合成 對配備有迴流冷凝管、溫度計的容量 50 mL的3頸圓底燒瓶裝入攪拌子、11-溴-1-十一烷醇(1.50 g，5.97 mmol)、N,N-二甲基癸基胺(1.42 mL，5.98 mmol)、乙腈(10 mL)，並在迴流下(82℃)攪拌5小時。放冷後，減壓蒸餾除去乙腈，用乙酸乙酯清洗所得到的粗製品後，在減壓下進行乾燥，藉此得到N-癸基-N-(11-羥基十一烷基)-N,N-二甲基溴化銨的白色固體(產量：2.58 g，產率：99%)。所得到的抗菌劑的NMR分析結果如下，抗菌性的評價結果顯示於表1。 (antibacterial agent synthesis example 1: embodiment 1/antibacterial agent A) Synthesis of N-decyl-N-(11-hydroxyundecyl)-N,N-dimethylammonium bromide A 3-necked round-bottom flask with a capacity of 50 mL equipped with a reflux condenser and a thermometer was charged with a stirring bar, 11-bromo-1-undecanol (1.50 g, 5.97 mmol), N,N-dimethyldecyl Amine (1.42 mL, 5.98 mmol), acetonitrile (10 mL), and stirred at reflux (82°C) for 5 hours. After cooling, acetonitrile was distilled off under reduced pressure, and the obtained crude product was washed with ethyl acetate and dried under reduced pressure to obtain N-decyl-N-(11-hydroxyundecyl)-N , white solid of N-dimethylammonium bromide (yield: 2.58 g, yield: 99%). The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the evaluation results of antibacterial properties.
1H-NMR (400 MHz, DMSO-d 6): δ 4.34 (m, 1H), 3.40-3.36 (m, 2H), 3.26-3.18 (m, 4H), 2.98 (s, 6H), 1.68-1.56 (m , 4H), 1.44-1.20 (m, 30H), 0.90-0.83 (m, 3H)。 1 H-NMR (400 MHz, DMSO-d 6 ): δ 4.34 (m, 1H), 3.40-3.36 (m, 2H), 3.26-3.18 (m, 4H), 2.98 (s, 6H), 1.68-1.56 (m , 4H), 1.44-1.20 (m, 30H), 0.90-0.83 (m, 3H).
(抗菌劑合成例2：實施例2/抗菌劑B) N-(6-羥基己基)-N,N-二甲基十四烷基溴化銨的合成 對配備有迴流冷凝管、溫度計的容量 100 mL的3頸圓底燒瓶裝入攪拌子、6-二甲胺基-1-己醇(7.49 g，50.0 mmol)、1-溴十四烷(14.3 g，50.0 mmol)、乙腈(25 mL)，並在迴流下(82℃)攪拌5小時。放冷後，減壓蒸餾除去乙腈，用乙酸乙酯清洗所得到的粗製品後，在減壓下進行乾燥，藉此得到N-(6-羥基己基)-N,N-二甲基十四烷基溴化銨的白色固體(產量：20.9 g，產率：99%)。所得到的抗菌劑的NMR分析結果如下，抗菌性的評價結果顯示於表1。 (antibacterial agent synthesis example 2: embodiment 2/antibacterial agent B) Synthesis of N-(6-hydroxyhexyl)-N,N-dimethyltetradecylammonium bromide A 3-neck round-bottomed flask with a capacity of 100 mL equipped with a reflux condenser and a thermometer was charged with a stirring bar, 6-dimethylamino-1-hexanol (7.49 g, 50.0 mmol), 1-bromotetradecane (14.3 g, 50.0 mmol), acetonitrile (25 mL), and stirred at reflux (82°C) for 5 hours. After cooling, acetonitrile was distilled off under reduced pressure, and the obtained crude product was washed with ethyl acetate and dried under reduced pressure to obtain N-(6-hydroxyhexyl)-N,N-dimethyltetradecyl White solid of alkylammonium bromide (yield: 20.9 g, yield: 99%). The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the evaluation results of antibacterial properties.
1H-NMR (400 MHz, DMSO-d 6): δ 4..38 (m, 1H), 3.43-3.36 (m, 2H), 3.26-3.18 (m, 4H), 2.99 (s, 6H), 1.70-1.58 (m , 4H), 1.49-1.18 (m, 28H), 0.89-0.82 (m, 3H)。 1 H-NMR (400 MHz, DMSO-d 6 ): δ 4..38 (m, 1H), 3.43-3.36 (m, 2H), 3.26-3.18 (m, 4H), 2.99 (s, 6H), 1.70-1.58 (m, 4H), 1.49-1.18 (m, 28H), 0.89-0.82 (m, 3H).
(抗菌劑合成例3：實施例3/抗菌劑C) N-十二烷基-N-(6-羥基己基)-N,N-二甲基溴化銨的合成 對配備有迴流冷凝管、溫度計的容量 100 mL的3頸圓底燒瓶裝入攪拌子、6-溴-1-己醇(3.62 g，20.0 mmol)、乙腈(30 mL)、N,N-二甲基十二烷基胺(4.27 g，20.0 mmol)，並在迴流下(82℃)攪拌7小時。放冷後，減壓蒸餾除去乙腈，用乙酸乙酯清洗所得到的粗製品後，在減壓下進行乾燥，藉此得到N-十二烷基-N-(6-羥基己基)-N,N-二甲基溴化銨的無色黏稠物(產量：7.81 g，產率：99%)。所得到的抗菌劑的NMR分析結果如下，抗菌性的評價結果顯示於表1。 (antibacterial agent synthesis example 3: embodiment 3/antibacterial agent C) Synthesis of N-dodecyl-N-(6-hydroxyhexyl)-N,N-dimethylammonium bromide A 3-neck round-bottomed flask with a capacity of 100 mL equipped with a reflux condenser and a thermometer was filled with a stirring bar, 6-bromo-1-hexanol (3.62 g, 20.0 mmol), acetonitrile (30 mL), N,N-di Methyldodecylamine (4.27 g, 20.0 mmol), and stirred at reflux (82° C.) for 7 hours. After standing to cool, acetonitrile was distilled off under reduced pressure, and the resulting crude product was washed with ethyl acetate and dried under reduced pressure to obtain N-dodecyl-N-(6-hydroxyhexyl)-N, Colorless sticky substance of N-dimethylammonium bromide (yield: 7.81 g, yield: 99%). The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the evaluation results of antibacterial properties.
1H-NMR (400 MHz, DMSO-d 6): δ 4..38 (m, 1H), 3.43-3.36 (m, 2H), 3.26-3.18 (m, 4H), 2.99 (s, 6H), 1.70-1.58 (m , 4H), 1.49-1.18 (m, 24H), 0.89-0.82 (m, 3H)。 1 H-NMR (400 MHz, DMSO-d 6 ): δ 4..38 (m, 1H), 3.43-3.36 (m, 2H), 3.26-3.18 (m, 4H), 2.99 (s, 6H), 1.70-1.58 (m, 4H), 1.49-1.18 (m, 24H), 0.89-0.82 (m, 3H).
(抗菌劑合成例4：實施例4/抗菌劑D) N-癸基-N-(6-羥基己基)-N,N-二甲基溴化銨的合成 對配備有迴流冷凝管、溫度計的容量 100 mL的3頸圓底燒瓶裝入攪拌子、6-溴-1-己醇(3.62 g，20.0mmol)、乙腈(30 mL)、N,N-二甲基癸基胺(3.71 g，20.0 mmol)，並在迴流下(82℃)攪拌7小時。放冷後，減壓蒸餾除去乙腈，用乙酸乙酯清洗所得到的粗製品後，在減壓下進行乾燥，藉此得到N-癸基-N-(6-羥基己基)-N,N-二甲基溴化銨的無色黏稠物(產量：7.26g，產率：99%)。所得到的抗菌劑的NMR分析結果如下，抗菌性的評價結果顯示於表1。 (antibacterial agent synthesis example 4: embodiment 4/antibacterial agent D) Synthesis of N-decyl-N-(6-hydroxyhexyl)-N,N-dimethylammonium bromide A 3-neck round-bottomed flask with a capacity of 100 mL equipped with a reflux condenser and a thermometer was filled with a stirring bar, 6-bromo-1-hexanol (3.62 g, 20.0 mmol), acetonitrile (30 mL), N,N-di Methyldecylamine (3.71 g, 20.0 mmol), and stirred at reflux (82° C.) for 7 hours. After cooling, acetonitrile was distilled off under reduced pressure, and the obtained crude product was washed with ethyl acetate and dried under reduced pressure to obtain N-decyl-N-(6-hydroxyhexyl)-N,N- Colorless sticky substance of dimethylammonium bromide (yield: 7.26 g, yield: 99%). The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the evaluation results of antibacterial properties.
1H-NMR (400 MHz, CDCl 3): δ 3.65-3.59 (m, 4H), 3.47-3.43 (m, 2H), 3.36 (s, 6H), 2.79 (brs, 1H), 1.81-1.26 (m, 24H), 0.90-0.87 (m, 3H)。 1 H-NMR (400 MHz, CDCl 3 ): δ 3.65-3.59 (m, 4H), 3.47-3.43 (m, 2H), 3.36 (s, 6H), 2.79 (brs, 1H), 1.81-1.26 (m , 24H), 0.90-0.87 (m, 3H).
(抗菌劑合成例5：實施例5/抗菌劑E) N-癸基-N-(6-羥基己基)-N,N-二甲基氯化銨的合成 對配備有迴流冷凝管、溫度計的容量 100 mL的3頸圓底燒瓶裝入攪拌子、6-氯-1-己醇(3.00 g，22.0 mmol)、乙腈(33 mL)、N,N-二甲基癸基胺(5.22 mL，22.0 mmol)，並在迴流下(82℃)攪拌22小時。放冷後，減壓蒸餾除去乙腈，用二乙基醚及乙酸乙酯清洗所得到的粗製品後，在減壓下進行乾燥，藉此得到N-癸基-N-(6-羥基己基)-N,N-二甲基氯化銨的白色固體(產量：4.04 g，產率：57%)。所得到的抗菌劑的NMR分析結果如下，抗菌性的評價結果顯示於表1。 (antibacterial agent synthesis example 5: embodiment 5/antibacterial agent E) Synthesis of N-decyl-N-(6-hydroxyhexyl)-N,N-dimethylammonium chloride A 3-neck round-bottom flask with a capacity of 100 mL equipped with a reflux condenser and a thermometer was filled with a stirring bar, 6-chloro-1-hexanol (3.00 g, 22.0 mmol), acetonitrile (33 mL), N,N-di Methyldecylamine (5.22 mL, 22.0 mmol), and stirred at reflux (82° C.) for 22 hours. After cooling, acetonitrile was distilled off under reduced pressure, and the obtained crude product was washed with diethyl ether and ethyl acetate, and dried under reduced pressure to obtain N-decyl-N-(6-hydroxyhexyl) - White solid of N,N-dimethylammonium chloride (yield: 4.04 g, yield: 57%). The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the evaluation results of antibacterial properties.
1H-NMR (400 MHz, CDCl 3): δ 3.64-3.59 (m, 4H), 3.46-3.42 (m, 3H), 3.37 (s, 6H), 1.94-1.26 (m, 24H), 0.90-0.86 (m, 3H)。 1 H-NMR (400 MHz, CDCl 3 ): δ 3.64-3.59 (m, 4H), 3.46-3.42 (m, 3H), 3.37 (s, 6H), 1.94-1.26 (m, 24H), 0.90-0.86 (m, 3H).
(抗菌劑合成例6：實施例6/抗菌劑F) N-(4-羥基丁基)-N-十六烷基-N,N-二甲基溴化銨的合成 對配備有迴流冷凝管、溫度計的容量 100 mL的3頸圓底燒瓶裝入攪拌子、4-(二甲基胺)-1-丁醇(5.98 g, 50.0 mmol)、1-溴十六烷(15.9 g，50.0 mmol)、乙腈(25 mL)，並在迴流下(82℃)攪拌5小時。放冷後，減壓蒸餾除去乙腈，用乙酸乙酯清洗所得到的粗製品後，在減壓下進行乾燥，藉此得到N-(4-羥基丁基)-N-十六烷基-N,N-二甲基溴化銨的白色固體(產量：20.4g，產率：97%)。所得到的抗菌劑的NMR分析結果如下，抗菌性的評價結果顯示於表1。 (antibacterial agent synthesis example 6: embodiment 6/antibacterial agent F) Synthesis of N-(4-hydroxybutyl)-N-hexadecyl-N,N-dimethylammonium bromide A 3-neck round-bottomed flask with a capacity of 100 mL equipped with a reflux condenser and a thermometer was filled with a stirring bar, 4-(dimethylamine)-1-butanol (5.98 g, 50.0 mmol), 1-bromohexadecane (15.9 g, 50.0 mmol), acetonitrile (25 mL), and stirred at reflux (82° C.) for 5 hours. After cooling, acetonitrile was distilled off under reduced pressure, and the obtained crude product was washed with ethyl acetate and dried under reduced pressure to obtain N-(4-hydroxybutyl)-N-hexadecyl-N , white solid of N-dimethylammonium bromide (yield: 20.4 g, yield: 97%). The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the evaluation results of antibacterial properties.
1H-NMR (400 MHz, DMSO-d 6): δ 4.56 (m, 1H), 3.48-3.41 (m, 2H), 3.29-3.21 (m, 4H), 3.00 (s, 6H), 1.76-1.59 (m , 4H), 1.48-1.37 (m, 2H), 1.34-1.19 (m, 26H), 0.90-0.83 (m, 3H)。 1 H-NMR (400 MHz, DMSO-d 6 ): δ 4.56 (m, 1H), 3.48-3.41 (m, 2H), 3.29-3.21 (m, 4H), 3.00 (s, 6H), 1.76-1.59 (m , 4H), 1.48-1.37 (m, 2H), 1.34-1.19 (m, 26H), 0.90-0.83 (m, 3H).
(抗菌劑合成例7：實施例7/抗菌劑G) N-(2,3-二羥基丙基)-N-十六烷基-N,N-二甲基溴化銨的合成 對配備有迴流冷凝管、溫度計的容量 100 mL的3頸圓底燒瓶裝入攪拌子、3-溴-1,2-丙二醇(2.35 g, 15.2 mmol)、N,N-二甲基十六烷基胺(4.16 g，15.4 mmol、乙腈(25 mL)，並在迴流下(82℃)攪拌5小時。放冷後，減壓蒸餾除去乙腈，用乙酸乙酯清洗所得到的粗製品後，在減壓下進行乾燥，藉此得到N-(2,3-二羥基丙基)-N-十六烷基-N,N-二甲基溴化銨的白色固體(產量：5.47 g，產率：85%)。所得到的抗菌劑的NMR分析結果如下，抗菌性的評價結果顯示於表1。 (antibacterial agent synthesis example 7: embodiment 7/antibacterial agent G) Synthesis of N-(2,3-dihydroxypropyl)-N-hexadecyl-N,N-dimethylammonium bromide A 3-necked round-bottom flask with a capacity of 100 mL equipped with a reflux condenser and a thermometer was charged with a stirring bar, 3-bromo-1,2-propanediol (2.35 g, 15.2 mmol), N,N-dimethylhexadecane amine (4.16 g, 15.4 mmol, acetonitrile (25 mL), and stirred at reflux (82° C.) for 5 hours. After cooling, the acetonitrile was distilled off under reduced pressure, and the obtained crude product was washed with ethyl acetate, then in Drying was carried out under reduced pressure, thereby obtaining a white solid of N-(2,3-dihydroxypropyl)-N-hexadecyl-N,N-dimethylammonium bromide (yield: 5.47 g, yield : 85%).The NMR analysis result of the obtained antibacterial agent is as follows, and the evaluation result of antibacterial property is shown in Table 1.
1H-NMR (400MHz, DMSO-d 6): δ 5.36 (d, J = 8.2 Hz, 1H), 5.00 (t, J = 5.8 Hz, 1H), 4.00 (m, 1H), 3.45-3.37 (m, 2H), 3.30-3.18 (m, 2H), 3.08 (s, 3H), 3.07 (s, 3H), 1.78-1.56 (m, 2H), 1.47-1.00 (m, 28H), 0.86 (t, J = 6.6 Hz, 3H)。 1 H-NMR (400MHz, DMSO-d 6 ): δ 5.36 (d, J = 8.2 Hz, 1H), 5.00 (t, J = 5.8 Hz, 1H), 4.00 (m, 1H), 3.45-3.37 (m , 2H), 3.30-3.18 (m, 2H), 3.08 (s, 3H), 3.07 (s, 3H), 1.78-1.56 (m, 2H), 1.47-1.00 (m, 28H), 0.86 (t, J = 6.6 Hz, 3H).
(抗菌劑合成例8：實施例8/抗菌劑H) N-十二烷基-N-(2,3-二羥基丙基)-N,N-二甲基溴化銨的合成 對配備有迴流冷凝管、溫度計的容量 100 mL的3頸圓底燒瓶裝入攪拌子、3-溴-1,2-丙二醇(2.35 g, 15.2 mmol)、N,N-二甲基十二烷基胺 (3.29 g，15.4 mmol、乙腈(25 mL)，並在迴流下(82℃)攪拌5小時。放冷後，減壓蒸餾除去乙腈，用乙酸乙酯清洗所得到的粗製品後，在減壓下進行乾燥，藉此得到N-十二烷基-N-(2,3-二羥基丙基)-N,N-二甲基溴化銨的白色固體(產量：4.82g，產率：85%)。所得到的抗菌劑的NMR分析結果如下，抗菌性的評價結果顯示於表1。 (antibacterial agent synthesis example 8: embodiment 8/antibacterial agent H) Synthesis of N-dodecyl-N-(2,3-dihydroxypropyl)-N,N-dimethylammonium bromide A 3-necked round-bottom flask with a capacity of 100 mL equipped with a reflux condenser and a thermometer was charged with a stirring bar, 3-bromo-1,2-propanediol (2.35 g, 15.2 mmol), N,N-dimethyldodecane amine (3.29 g, 15.4 mmol, acetonitrile (25 mL), and stirred at reflux (82° C.) for 5 hours. After cooling, the acetonitrile was distilled off under reduced pressure, and the obtained crude product was washed with ethyl acetate, and then in Drying was carried out under reduced pressure, thereby obtaining a white solid of N-dodecyl-N-(2,3-dihydroxypropyl)-N,N-dimethylammonium bromide (yield: 4.82 g, yield : 85%).The NMR analysis result of the obtained antibacterial agent is as follows, and the evaluation result of antibacterial property is shown in Table 1.
1H-NMR (400MHz, DMSO-d 6): δ 5.36 (d, J = 8.2 Hz, 1H), 5.00 (t, J = 5.8 Hz, 1H), 4.00 (m, 1H), 3.45-3.37 (m, 2H), 3.30-3.18 (m, 2H), 3.08 (s, 3H), 3.07 (s, 3H), 1.78-1.56 (m, 2H), 1.47-1.00 (m, 20H), 0.86 (t, J = 6.6 Hz, 3H)。 1 H-NMR (400MHz, DMSO-d 6 ): δ 5.36 (d, J = 8.2 Hz, 1H), 5.00 (t, J = 5.8 Hz, 1H), 4.00 (m, 1H), 3.45-3.37 (m , 2H), 3.30-3.18 (m, 2H), 3.08 (s, 3H), 3.07 (s, 3H), 1.78-1.56 (m, 2H), 1.47-1.00 (m, 20H), 0.86 (t, J = 6.6 Hz, 3H).
(抗菌劑合成例9：比較例1/抗菌劑I) N-(11-羥基十一烷基)-N-十六烷基-N,N-二甲基溴化銨的合成 對配備有迴流冷凝管、溫度計的容量 50 mL的3頸圓底燒瓶裝入攪拌子、11-溴-1-十一烷醇(1.40 g，5.57 mmol)、N,N-二甲基十六烷基胺(1.88 mL，5.57 mmol)、乙腈(10 mL)，並在迴流下(82℃)攪拌7小時。放冷後，減壓蒸餾除去溶劑，藉由用二乙基醚清洗所得到的粗製品，此得到N-(11-羥基十一烷基)-N-十六烷基-N,N-二甲基溴化銨的白色固體(產量：2.81 g，產率：97%)。所得到的抗菌劑的NMR分析結果如下，抗菌性的評價結果顯示於表1。 (antibacterial agent synthesis example 9: comparative example 1/antibacterial agent 1) Synthesis of N-(11-hydroxyundecyl)-N-hexadecyl-N,N-dimethylammonium bromide A 3-neck round-bottom flask with a capacity of 50 mL equipped with a reflux condenser and a thermometer was charged with a stirring bar, 11-bromo-1-undecanol (1.40 g, 5.57 mmol), N,N-dimethylhexadecanol Alkylamine (1.88 mL, 5.57 mmol), acetonitrile (10 mL), and stirred at reflux (82° C.) for 7 hours. After cooling, the solvent was distilled off under reduced pressure, and the obtained crude product was washed with diethyl ether to obtain N-(11-hydroxyundecyl)-N-hexadecyl-N,N-di White solid of methylammonium bromide (yield: 2.81 g, yield: 97%). The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the evaluation results of antibacterial properties.
1H-NMR (400 MHz, CDCl 3): δ 3.67-3.62 (m, 2H), 3.55-3.48 (m, 4H), 3.40 (s, 6H), 1.74-1.66 (m, 4H), 1.60-1.26 (m, 43H), 0.90-0.86 (m, 3H)。 1 H-NMR (400 MHz, CDCl 3 ): δ 3.67-3.62 (m, 2H), 3.55-3.48 (m, 4H), 3.40 (s, 6H), 1.74-1.66 (m, 4H), 1.60-1.26 (m, 43H), 0.90-0.86 (m, 3H).
(抗菌劑合成例10：比較例2/抗菌劑J) N-丁基-N-(11-羥基十一烷基)-N,N-二甲基溴化銨的合成 對配備有迴流冷凝管、溫度計的容量 50 mL的3頸圓底燒瓶裝入攪拌子、11-溴-1-十一烷醇(1.70 g，6.77 mmol)、N，N-二甲基丁基胺(0.96 mL，6.82 mmol)、乙腈(12 mL)，並在迴流下(82℃)攪拌7小時。放冷後，減壓蒸餾除去溶劑，藉由用乙基醚清洗所得到的粗製品，得到N-丁基-N-(11-羥基十一烷基)-N,N-二甲基溴化銨的白色固體(產量：2.22 g，產率：93%)。所得到的抗菌劑的NMR分析結果如下，抗菌性的評價結果顯示於表1。 (Antibacterial Agent Synthesis Example 10: Comparative Example 2/Antibacterial Agent J) Synthesis of N-butyl-N-(11-hydroxyundecyl)-N,N-dimethylammonium bromide A 3-neck round-bottomed flask with a capacity of 50 mL equipped with a reflux condenser and a thermometer was charged with a stirring bar, 11-bromo-1-undecanol (1.70 g, 6.77 mmol), N,N-dimethylbutyl Amine (0.96 mL, 6.82 mmol), acetonitrile (12 mL), and stirred at reflux (82°C) for 7 hours. After standing to cool, the solvent was distilled off under reduced pressure, and the obtained crude product was washed with ethyl ether to obtain N-butyl-N-(11-hydroxyundecyl)-N,N-dimethyl bromide Ammonium white solid (yield: 2.22 g, yield: 93%). The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the evaluation results of antibacterial properties.
1H-NMR (400 MHz, CDCl 3): δ 3.65-3.62 (m, 2H), 3.56-3.51 (m, 4H), 3.40 (s, 6H), 1.80-1.28 (m, 23H), 1.03-0.99 (m, 3H)。 1 H-NMR (400 MHz, CDCl 3 ): δ 3.65-3.62 (m, 2H), 3.56-3.51 (m, 4H), 3.40 (s, 6H), 1.80-1.28 (m, 23H), 1.03-0.99 (m, 3H).
(抗菌劑合成例11：比較例3/抗菌劑K) N-癸基-N-(3-羥基丙基)-N,N-二甲基溴化銨的合成 對配備有迴流冷凝管、溫度計的容量 100 mL的3頸圓底燒瓶裝入攪拌子、3-溴-1-丙醇(2.78 g，20.0 mmol)、N,N-二甲基癸基胺(3.71 g，20.0 mmol)、乙腈(30 mL)，並在迴流下(82℃)攪拌5小時。放冷後，減壓蒸餾除去乙腈，用乙酸乙酯清洗所得到的粗製品後，在減壓下進行乾燥，藉此得到N-癸基-N-(3-羥基丙基)-N,N-二甲基溴化銨的白色固體(產量：4.45g，產率：69%)。所得到的抗菌劑的NMR分析結果如下，抗菌性的評價結果顯示於表1。 (Antibacterial Agent Synthesis Example 11: Comparative Example 3/Antibacterial Agent K) Synthesis of N-decyl-N-(3-hydroxypropyl)-N,N-dimethylammonium bromide A 3-neck round-bottomed flask with a capacity of 100 mL equipped with a reflux condenser and a thermometer was charged with a stirring bar, 3-bromo-1-propanol (2.78 g, 20.0 mmol), N,N-dimethyldecylamine ( 3.71 g, 20.0 mmol), acetonitrile (30 mL), and stirred at reflux (82°C) for 5 hours. After cooling, acetonitrile was distilled off under reduced pressure, and the obtained crude product was washed with ethyl acetate and dried under reduced pressure to obtain N-decyl-N-(3-hydroxypropyl)-N,N - White solid of dimethylammonium bromide (yield: 4.45 g, yield: 69%). The NMR analysis results of the obtained antibacterial agent are as follows, and Table 1 shows the evaluation results of antibacterial properties.
1H-NMR (400 MHz, CDCl 3): δ 4.55 (brs, 1H), 3.77-3.73 (m, 4H), 3.44-3.39 (m, 2H), 3.31 (s, 6H), 2.54 (brs, 2H), 2.08-2.07 (m, 2H), 1.75 (brs, 2H), 1.33-1.26 (m, 12H), 0.90-0.86 (m, 3H)。 1 H-NMR (400 MHz, CDCl 3 ): δ 4.55 (brs, 1H), 3.77-3.73 (m, 4H), 3.44-3.39 (m, 2H), 3.31 (s, 6H), 2.54 (brs, 2H ), 2.08-2.07 (m, 2H), 1.75 (brs, 2H), 1.33-1.26 (m, 12H), 0.90-0.86 (m, 3H).
(抗菌加工胺甲酸乙酯樹脂製造例1：實施例1/PU-A) 將溫度調整到60℃的聚異氰酸酯(基於六亞甲基二異氰酸酯的異氰脲酸酯型聚異氰酸酯：東曹股份公司製造「Coronate HXR」，NCO平均官能基數3.5，NCO含量21.0%) 45.7g、溫度調整到40℃的多元醇(基於六亞甲基二醇的聚碳酸酯二元醇：東曹股份公司製造「Nippollan 970」，OH官能基數：2，分子量：500) 54.3g、及1g的抗菌劑A混合，添加二月桂酸二辛基錫(東京化成工業股份公司製造「特級試藥」) 0.01g於此作為催化劑並混合，藉此調製胺甲酸乙酯樹脂形成性組合物。將此組合物在5 mmHg的減壓下充分地消泡之後，注入預熱至100～120℃的2 mm厚的平板形成用的模具，在100℃的環境下使其固化30分鐘。之後，取出已經固化的胺甲酸乙酯樹脂組合物，進一步在40～50℃的環境下熟成24小時，藉此得到抗菌性胺甲酸乙酯樹脂組合物(PU-A)。所得到的抗菌性胺甲酸乙酯樹脂組合物的抗菌性的評價結果顯示於表1。 (Antibacterial processed urethane resin production example 1: Example 1/PU-A) Polyisocyanate adjusted to 60°C (hexamethylene diisocyanate-based isocyanurate-type polyisocyanate: "Coronate HXR" manufactured by Tosoh Co., Ltd., NCO average functional group number 3.5, NCO content 21.0%) 45.7g 54.3g and 1g of polyol (hexamethylene glycol-based polycarbonate diol: "Nippollan 970" manufactured by Tosoh Co., Ltd., number of OH functional groups: 2, molecular weight: 500) adjusted to 40°C The antibacterial agent A was mixed, and 0.01 g of dioctyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd. "Special Grade Chemical") was added thereto as a catalyst and mixed to prepare a urethane resin-forming composition. After the composition was sufficiently defoamed under a reduced pressure of 5 mmHg, it was poured into a 2 mm-thick flat plate forming mold preheated to 100 to 120° C., and cured in an environment of 100° C. for 30 minutes. Afterwards, the cured urethane resin composition was taken out, and further aged at 40-50° C. for 24 hours to obtain an antibacterial urethane resin composition (PU-A). Table 1 shows the evaluation results of the antibacterial properties of the obtained antibacterial urethane resin composition.
(抗菌加工胺甲酸乙酯樹脂製造例2～11：實施例2～8/PU-B～PU-H、比較例1～3/PU-I～PU-K) 將抗菌劑A置換成抗菌劑B～K，除此之外，與抗菌加工胺甲酸乙酯樹脂製造例1(實施例1/U-A)同樣地製備，以分別得到抗菌性胺甲酸乙酯樹脂組合物(實施例2～8/PU-B～PU-H)及比較用的抗菌性胺甲酸乙酯樹脂組合物(比較例1～3/PU-I～PU-K)。所得到的抗菌性胺甲酸乙酯樹脂組合物的抗菌性的評價結果顯示於表1。 (Antibacterial processed urethane resin production examples 2 to 11: Examples 2 to 8/PU-B to PU-H, Comparative examples 1 to 3/PU-I to PU-K) The antibacterial agent A was replaced by antibacterial agents B to K, and prepared in the same manner as the antibacterial processed urethane resin production example 1 (Example 1/U-A) to obtain antibacterial urethane resin combinations respectively (embodiment 2～8/PU-B～PU-H) and the antimicrobial urethane resin composition (comparative example 1～3/PU-I～PU-K) of comparative use. Table 1 shows the evaluation results of the antibacterial properties of the obtained antibacterial urethane resin composition.
(無加工胺甲酸乙酯樹脂製造例：對照用的PU-N) 不添加抗菌劑A之外，與抗菌加工胺甲酸乙酯樹脂製造例1(實施例1/U-A)同樣地製備，以得到為了評價抗菌性的對照用的無加工品(無加工胺甲酸乙酯樹脂組合物)。 (Manufacturing example of unprocessed urethane resin: PU-N for comparison) Except not adding the antibacterial agent A, it was prepared in the same manner as the antibacterially processed urethane resin production example 1 (Example 1/U-A) to obtain an unprocessed product (unprocessed urethane resin composition).
[表1]
由表1所示的結果可以了解，已確認的是，相較於比較用的抗菌劑，由本發明的一個態樣的四級銨鹽所形成的本發明的一個態樣的抗菌劑具有優異的抗菌活性，進一步而言，當其添加到樹脂中而形成抗菌性樹脂組合物時，相較於比較用的抗菌性樹脂組合物，本發明的一個態樣的抗菌性樹脂組合物具有優異的抗菌活性的耐酒精清洗性。As can be understood from the results shown in Table 1, it has been confirmed that the antibacterial agent of an aspect of the present invention formed by a quaternary ammonium salt of an aspect of the present invention has excellent Antibacterial activity, further, when it is added in the resin to form antibacterial resin composition, compared with the antibacterial resin composition of comparative use, the antibacterial resin composition of an aspect of the present invention has excellent antibacterial Active alcohol cleaning resistance.
無none
無。none.
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