KR102646264B1 - Antibacterial polymer composition - Google Patents
Antibacterial polymer composition Download PDFInfo
- Publication number
- KR102646264B1 KR102646264B1 KR1020190060052A KR20190060052A KR102646264B1 KR 102646264 B1 KR102646264 B1 KR 102646264B1 KR 1020190060052 A KR1020190060052 A KR 1020190060052A KR 20190060052 A KR20190060052 A KR 20190060052A KR 102646264 B1 KR102646264 B1 KR 102646264B1
- Authority
- KR
- South Korea
- Prior art keywords
- antibacterial
- polymer composition
- formula
- compound
- polymer
- Prior art date
Links
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 29
- 229920000642 polymer Polymers 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 239000002952 polymeric resin Substances 0.000 claims abstract description 14
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 14
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 125000002347 octyl 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])[H] 0.000 claims description 2
- 239000003504 photosensitizing agent Substances 0.000 abstract description 8
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000001580 bacterial effect Effects 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003642 reactive oxygen metabolite Substances 0.000 description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- -1 butoxy methyl Chemical group 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- SFPNZPQIIAJXGL-UHFFFAOYSA-N 2-ethoxyethyl 2-methylprop-2-enoate Chemical compound CCOCCOC(=O)C(C)=C SFPNZPQIIAJXGL-UHFFFAOYSA-N 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000191070 Escherichia coli ATCC 8739 Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- PCELSSNUBBRCHW-UHFFFAOYSA-N butoxymethyl 2-methylprop-2-enoate Chemical compound CCCCOCOC(=O)C(C)=C PCELSSNUBBRCHW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000001332 colony forming effect Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
- C07D487/14—Ortho-condensed systems
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Materials Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
본 발명에 따른 화학식 1로 표시되는 화합물은 광감응제로서 고분자에 대한 상용성이 우수하고 유기 용매에 대한 용해도가 우수하여, 고분자 수지와 함께 상기 화합물을 항균제로서 포함하는 항균성 고분자 조성물로 유용하게 사용할 수 있다. The compound represented by Formula 1 according to the present invention is a photosensitizer and has excellent compatibility with polymers and excellent solubility in organic solvents, so it can be usefully used as an antibacterial polymer composition containing the compound as an antibacterial agent along with a polymer resin. You can.
Description
본 발명은 항균성 고분자 조성물에 관한 것이다. The present invention relates to antibacterial polymer compositions.
광감응제(photosensitizer)는 빛을 흡수하여 활성산소종(ROS)을 생성시키는 물질로서, 외부에서 특정 파장의 빛을 조사하여 광감응제로부터 활성 산소종 또는 자유 라디칼을 발생시켜 각종 병변 부위나 암세포의 세포 사멸을 유도하여 파괴하는 광역동 치료(photodynamic therapy, PDT) 등이 널리 사용되고 있다. A photosensitizer is a substance that absorbs light and generates reactive oxygen species (ROS). By irradiating light of a specific wavelength from the outside, reactive oxygen species or free radicals are generated from the photosensitizer, which can be used to treat various lesions or cancer cells. Photodynamic therapy (PDT), which destroys cells by inducing their death, is widely used.
이러한 광감응제로서 포피린(porphyrin)계 화합물이 알려져 있으며, 산소와의 반응하여 ROS 및 singlet oxygen을 생성한다고 알려져 있다. 이의 대표적인 예로 TCPP(4,4',4'',4'''-(porphrin-5,10,15,20-tetrayl)tetrakis(benzoic acid))가 알려져 있다. Porphyrin-based compounds are known as such photosensitizers, and are known to generate ROS and singlet oxygen by reacting with oxygen. A representative example of this is known as TCPP (4,4',4'',4'''-(porphrin-5,10,15,20-tetrayl)tetrakis(benzoic acid)).
이러한 광동역학 반응(photodynamic reaction)을 이용하여 항균성을 갖는 고분자 재료를 개발하려는 다양한 시도가 있으며, 예를 들어 고분자 수지 등을 용융시킨 후 용융된 수지와 광감응제를 혼합하는 방법이나 고분자 수지 및 광감응제를 용매에 녹여서 형성된 코팅액을 이용하는 방법이 알려져 있다.There are various attempts to develop polymer materials with antibacterial properties using this photodynamic reaction. For example, a method of melting a polymer resin and then mixing the melted resin with a photosensitizer, or a method of mixing the polymer resin and light There is a known method of using a coating solution formed by dissolving a sensitizer in a solvent.
그런데, TCPP와 같은 광감응제는 물에 친화력이 좋은 카르복시기를 치환기로 가지고 있어, 고분자 수지와의 상용성이 좋지 않고, 또한 코팅액 제조를 위한 유기 용매의 용해도 또한 좋지 않다는 문제점이 있다. 이에 따라 광감응제의 분산성이 떨어져 항균 효과 또한 떨어지는 문제가 있다.However, photosensitizers such as TCPP have a carboxyl group with good affinity for water as a substituent, so they have poor compatibility with polymer resins and also have poor solubility in organic solvents for preparing coating solutions. Accordingly, there is a problem that the dispersibility of the photosensitizer decreases and the antibacterial effect also decreases.
본 발명은 고분자에 대한 상용성이 우수하고 유기 용매에 대한 용해도가 우수한 신규한 화합물을 항균제로서 포함하는 항균성 고분자 조성물을 제공하기 위한 것이다. The present invention is intended to provide an antibacterial polymer composition containing a novel compound with excellent compatibility with polymers and excellent solubility in organic solvents as an antibacterial agent.
상기 과제를 해결하기 위하여, 본 발명은 항균제로서 하기 화학식 1로 표시되는 화합물과 고분자 수지를 포함하는 항균성 고분자 조성물을 제공한다:In order to solve the above problems, the present invention provides an antibacterial polymer composition comprising a polymer resin and a compound represented by the following formula (1) as an antibacterial agent:
[화학식 1] [Formula 1]
상기 화학식 1에서, In Formula 1,
R은 각각 독립적으로 -R', -O-R', -CO-R', 또는 -CO-O-R'이고,Each R is independently -R', -O-R', -CO-R', or -CO-O-R',
R'는 C1-60 알킬, 또는 C6-60 아릴이고, R' is C 1-60 alkyl, or C 6-60 aryl,
단, R 중 적어도 2개가 -CO-R' 또는 -CO-O-R'이다. However, at least two of R are -CO-R' or -CO-O-R'.
상기 화학식 1로 표시되는 화합물은 종래에 사용되던 TCPP의 화합물에서 말단의 카르복시기 대신 에스터기, 또는 케톤기를 포함하는 것을 특징으로 한다.The compound represented by Formula 1 is characterized by containing an ester group or a ketone group instead of the carboxyl group at the terminal of the conventionally used TCPP compound.
카르복시기는 물에 대한 친화력이 좋기 때문에, TCPP를 포함하는 조성물이 물과 접촉하면 TCPP가 물에 용출되는 문제점이 있다. 또한, 카르복시기로 인하여 유기 용매에 대한 용해도가 낮아 TCPP를 코팅할 때 사용할 수 있는 용매의 제한이 있다. 그러나, 본 발명에서는 상기 카르복시기를 에스터기, 또는 케톤기로 치환함으로써, 상기의 문제를 해결할 수 있을 뿐만 아니라, 향균제로서의 효과도 향상된다. Since the carboxyl group has good affinity for water, there is a problem in that when a composition containing TCPP comes in contact with water, TCPP is eluted into the water. In addition, due to the carboxyl group, the solubility in organic solvents is low, so there is a limit to the solvents that can be used when coating TCPP. However, in the present invention, by replacing the carboxyl group with an ester group or a ketone group, not only can the above problem be solved, but the effect as an antibacterial agent is also improved.
상기 화학식 1에서, R은 총 4개가 존재하며 서로 동일하거나 상이할 수 있다. 바람직하게는, R'는 C1-10 알킬이다. 보다 바람직하게는, R'는 옥틸이다. In Formula 1, there are a total of 4 R and may be the same or different from each other. Preferably, R' is C 1-10 alkyl. More preferably, R' is octyl.
바람직하게는, R은 모두 -CO-O-R'이다. Preferably, all R's are -CO-O-R'.
상기 화학식 1로 표시되는 화합물의 대표적인 예는 하기와 같다:Representative examples of compounds represented by Formula 1 are as follows:
상기 화학식 1로 표시되는 화합물 중 R이 -CO-O-R'인 경우 하기 반응식 1과 같은 방법으로 제조할 수 있으며, 나머지에 대해서도 유사하게 적용할 수 있다. Among the compounds represented by Formula 1, when R is -CO-O-R', it can be prepared by the method shown in Scheme 1 below, and can be similarly applied to the rest.
[반응식 1][Scheme 1]
상기 반응식 1은, 카르복시기를 에스터 또는 케톤으로 치환시키는 반응으로서, 당업계에서 알려진 방법을 제한 없이 사용할 수 있다. 상기 제조 방법은 후술할 실시예에서 보다 구체화될 수 있다.Reaction Scheme 1 is a reaction for substituting a carboxyl group with an ester or ketone, and methods known in the art can be used without limitation. The manufacturing method may be further detailed in examples to be described later.
후술할 실험예와 같이 상기 화합물은 박테리아와 같은 미생물의 생장이나 생존을 억제할 수 있는바, 항균제로서 사용할 수 있다. As shown in the experimental examples described later, the compound can inhibit the growth or survival of microorganisms such as bacteria and can be used as an antibacterial agent.
또한, 본 발명에서 사용되는 고분자 수지는 특별히 제한되지 않으며, 고분자의 용도에 따라 항균성이 필요한 고분자에 제한 없이 적용할 수 있다.In addition, the polymer resin used in the present invention is not particularly limited, and can be applied without limitation to polymers requiring antibacterial properties depending on the use of the polymer.
상술한 바와 같이, 상기 화학식 1로 표시되는 화합물은 고분자에 대한 상용성이 우수하므로, 고분자와 함께 상기 화학식 1로 표시되는 화합물을 포함하는 고분자 조성물로 항균성이 필요한 물품에 적용할 수 있다. 또한, 본 발명에 따른 항균성 고분자 조성물은 코팅 용액으로도 적용이 가능하며, 항균성이 필요한 물품의 표면을 코팅하는 방식으로도 적용할 수 있다. As described above, the compound represented by Formula 1 has excellent compatibility with polymers, so a polymer composition containing the compound represented by Formula 1 together with a polymer can be applied to articles requiring antibacterial properties. In addition, the antibacterial polymer composition according to the present invention can be applied as a coating solution, and can also be applied by coating the surface of an article requiring antibacterial properties.
이러한 항균성이 필요한 물품의 예로는 가습기, 수조, 냉장고, 에어워셔, 수족관, 공기청정기 등, 유해한 박테리아가 쉽게 성장하는 물품에 적용 가능하다.Examples of items requiring antibacterial properties include humidifiers, water tanks, refrigerators, air washers, aquariums, air purifiers, etc., which can be applied to items in which harmful bacteria easily grow.
상기 항균성 고분자 조성물은, 고분자 수지를 용융시킨 후 용융된 수지와 본 발명에 따른 화합물을 혼합하는 방법이나, 또는 고분자 수지 및 상기 화학식 1로 표시되는 화합물을 용매에 함께 용해시키는 방법으로 제조할 수 있다. 또는, 후술할 고분자 수지의 단량체와 상기 화학식 1로 표시되는 화합물을 용매에 함께 용해시킨 후 상기 단량체를 중합하는 방법으로도 제조할 수 있다.The antibacterial polymer composition can be prepared by melting the polymer resin and then mixing the molten resin with the compound according to the present invention, or by dissolving the polymer resin and the compound represented by Formula 1 together in a solvent. . Alternatively, it can be prepared by dissolving the monomer of the polymer resin described later and the compound represented by Formula 1 together in a solvent and then polymerizing the monomer.
또한, 상기 항균성 고분자 조성물을 이용하여 필름을 제조하고, 이러한 필름을 상기 항균성이 필요한 물품에 적용하는 방식으로도 적용할 수 있다. In addition, it can be applied by manufacturing a film using the antibacterial polymer composition and applying this film to an article requiring antibacterial properties.
한편, 상기 항균성 고분자 조성물 내에서, 상기 화학식 1로 표시된느 화합물과 상기 고분자 수지의 중량비는 1:10 내지 1000이고, 보다 바람직하게는 1:10 내지 100이다.Meanwhile, in the antibacterial polymer composition, the weight ratio of the compound represented by Formula 1 and the polymer resin is 1:10 to 1000, more preferably 1:10 to 100.
바람직하게는, 상기 고분자 수지는 아크릴 수지이다. 이때, 상기 아크릴 수지는 (메트)아크릴계 단량체를 주성분으로 포함하는 것으로, (메트)아크릴계 단량체로 이루어진 호모폴리머 수지뿐 아니라 (메트)아크릴계 단량체 이외에 다른 단량체가 공중합된 공중합체 수지를 포함하는 개념이다.Preferably, the polymer resin is an acrylic resin. At this time, the acrylic resin contains a (meth)acrylic monomer as a main component, and includes not only a homopolymer resin made of a (meth)acrylic monomer, but also a copolymer resin in which monomers other than the (meth)acrylic monomer are copolymerized.
이때, 상기 (메트)아크릴계 단량체는 아크릴레이트 및 메타크릴레이트 뿐만 아니라 아크릴레이트 및 메타크릴레이트의 유도체를 포함하는 개념으로, 예컨대 메틸 메타크릴레이트, 에틸 메타크릴레이트, 프로필 메타크릴레이트, n-부틸 메타크릴레이트, t-부틸 메타크릴레이트, 시클로헥실 메타크릴레이트, 페닐 메타크릴레이트, 벤질메타크릴레이트, 메톡시에틸 메타크릴레이트, 에톡시에틸 메타크릴레이트, 부톡시메틸 메타크릴레이트, 메틸 아크릴레이트, 에틸 아크릴레이트, 프로필 아크릴레이트, n-부틸 아크릴레이트, t-부틸 아크릴레이트, 시클로헥실아크릴레이트, 페닐 아크릴레이트, 벤질 아크릴레이트, 메톡시에틸 아크릴레이트, 에톡시에틸 아크릴레이트, 부톡시 메틸 아크릴레이트 또는 이들의 올리고머 등 일 수 있으며, 그 중에서도 메틸 메타크릴레이트, 메틸 아크릴레이트 등의 알킬 (메트)아크릴레이트인 것이 보다 바람직하나, 반드시 이에 한정되는 것은 아니다. 이들은 단독으로 또는 혼합하여 사용될 수 있다.At this time, the (meth)acrylic monomer includes not only acrylates and methacrylates, but also derivatives of acrylates and methacrylates, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl. Methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, butoxymethyl methacrylate, methyl acrylic acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxy methyl. It may be an acrylate or an oligomer thereof, and more preferably an alkyl (meth)acrylate such as methyl methacrylate or methyl acrylate, but is not necessarily limited thereto. These can be used alone or in combination.
또한, 필요에 따라 상기 아크릴 수지는 필요에 따라 상기 (메트)아크릴계 단량체 이외에 다른 단량체를 추가로 포함할 수 있으며, 상기 상기 (메트)아크릴계 단량체와 공중합 가능한 단량체이면 특별히 제한되지 않으며, 일례로 디펜타에리트리롤 핵사아크릴레이트를 사용할 수 있다. In addition, if necessary, the acrylic resin may further include other monomers in addition to the (meth)acrylic monomer, and is not particularly limited as long as it is a monomer that can be copolymerized with the (meth)acrylic monomer. For example, dipenta Erythrol hexaacrylate can be used.
또한, 상술한 단량체와 상기 화학식 1로 표시되는 화합물을 용매에 함께 용해시킨 후 상기 단량체를 중합하는 방법으로도 제조할 수 있으며, 상기 중합은 열중합 또는 광중합의 방법으로 수행할 수 있다. 또한, 상기 광중합을 적용하는 경우 자외선 조사 등의 방법으로 수행할 수 있다. In addition, it can also be prepared by dissolving the above-described monomer and the compound represented by Formula 1 together in a solvent and then polymerizing the monomer, and the polymerization can be performed by thermal polymerization or photopolymerization. In addition, when applying the photopolymerization, it can be performed by methods such as ultraviolet irradiation.
상술한 화학식 1로 표시되는 화합물은 광감응제로서 고분자 수지에 대한 상용성이 우수하고 유기 용매에 대한 용해도가 우수하여, 항균성 고분자 조성물로 유용하게 사용할 수 있다. The compound represented by the above-mentioned formula 1 is a photosensitizer and has excellent compatibility with polymer resins and excellent solubility in organic solvents, so it can be usefully used as an antibacterial polymer composition.
도 1은, 본 발명의 실시예 및 비교예의 화합물에 대한 항균성 평가 결과를 나타낸 것이다.
도 2은, 본 발명의 실시예 및 비교예의 화합물에 대한 용해도 평가 결과를 나타낸 것이다. Figure 1 shows the results of antibacterial evaluation of the compounds of Examples and Comparative Examples of the present invention.
Figure 2 shows the solubility evaluation results for the compounds of Examples and Comparative Examples of the present invention.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해 본 발명의 내용이 한정되는 것은 아니다.Below, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are provided only to make the present invention easier to understand, and the content of the present invention is not limited thereto.
실시예Example
1) TOCPP의 제조1) Manufacturing of TOCPP
Sigma-Aldrich에서 구매한 TCPP(4,4',4'',4'''-(porphrin-5,10,15,20-tetrayl)tetrakis(benzoic acid)); 1 eq)를 DMF에 녹인 후, 0℃에서 syringe를 통해 1-옥타놀(10 eq)을 넣었다. 0℃에서 10분 후 DMAP(4-(dimethylamino)pyridine; 1 eq)를 넣었다. 0℃에서 30분 후 EDC·HCl(N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride; 10 eq)를 넣었다. 반응이 완료되면, 용매로 사용한 DMF를 건조시켜 제거하고, 물을 이용하여 추출하였다. 추출물을 황산 마그네슘을 이용하여 수분을 제거한 후 컬럼 크로마토그라피로 정제하여 상기 화합물을 제조하였다. TCPP (4,4',4'',4'''-(porphrin-5,10,15,20-tetrayl)tetrakis(benzoic acid)) purchased from Sigma-Aldrich; After dissolving 1 eq) in DMF, 1-octanol (10 eq) was added through a syringe at 0°C. After 10 minutes at 0°C, DMAP (4-(dimethylamino)pyridine; 1 eq) was added. After 30 minutes at 0°C, EDC·HCl (N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride; 10 eq) was added. When the reaction was completed, DMF used as a solvent was removed by drying and extracted using water. The extract was dried using magnesium sulfate and then purified by column chromatography to prepare the above compound.
1H NMR(500 MHz, CDCl3, ppm): 8.82 (s, 8H), 8.46-8.44 (d, 8H), 8.30-8.29 (d, 8H), 4.52-4.50 (t, 8H), 1.95-1.89 (m, 8H), 1.61-1.57 (m, 8H), 1.48-1.26 (m, 32H), 0.93-0.90 (t, 12H), -2.30 (s, 2H) 1 H NMR (500 MHz, CDCl 3 , ppm): 8.82 (s, 8H), 8.46-8.44 (d, 8H), 8.30-8.29 (d, 8H), 4.52-4.50 (t, 8H), 1.95-1.89 (m, 8H), 1.61-1.57 (m, 8H), 1.48-1.26 (m, 32H), 0.93-0.90 (t, 12H), -2.30 (s, 2H)
ESI-MS: m/z 1239 [M+H]+ ESI-MS: m/z 1239 [M+H] +
2) 시험편의 제조2) Preparation of test specimens
메틸메타아크릴레이트(MMA) 36 중량부, 디펜타에리트리롤 핵사아크릴레이트(DPHA) 7 중량부, 앞서 제조한 TOPCC 화합물 1 중량부, 계면활성제(상품명: F477 DIC社) 0.1 중량부, 및 톨루엔 55.6 중량부를 혼합하여 코팅 용액을 제조하였다. 그리고 위의 코팅액을 #20 bar를 이용해 코팅한 후, 0.2 J/cm2의 UV 램프를 이용하여, 2 m/min 속도로 경화를 진행 하였으며, 10 ㎛ 두께로 필름을 제조하였다.36 parts by weight of methyl methacrylate (MMA), 7 parts by weight of dipentaerythrol hexaacrylate (DPHA), 1 part by weight of the TOPCC compound prepared previously, 0.1 part by weight of surfactant (Product name: F477 DIC), and toluene A coating solution was prepared by mixing 55.6 parts by weight. After coating the above coating solution using #20 bar, curing was carried out at a speed of 2 m/min using a UV lamp of 0.2 J/cm 2 , and a film with a thickness of 10 ㎛ was manufactured.
비교예Comparative example
상기 실시예의 제조에 사용된 출발 물질인 TCPP를 비교예로서 사용하여 필름을 제조하였다. 구체적으로, 메틸메타아크릴레이트(MMA) 36 중량부, 디펜타에리트리롤 핵사아크릴레이트(DPHA) 7 중량부, TCPP 화합물 1 중량부, 계면활성제(상품명: F477 DIC社) 0.1 중량부, 및 디메틸포름아미드(DMF) 55.6 중량부를 혼합하여 코팅 용액을 제조하였다. 그리고 위의 코팅액을 #20 bar를 이용해 코팅한 후, 0.2 J/cm2의 UV 램프를 이용하여, 2 m/min 속도로 경화를 진행 하였으며, 10 ㎛ 두께로 필름을 제조하였다.A film was manufactured using TCPP, the starting material used in the preparation of the above examples, as a comparative example. Specifically, 36 parts by weight of methyl methacrylate (MMA), 7 parts by weight of dipentaerythrol hexaacrylate (DPHA), 1 part by weight of TCPP compound, 0.1 part by weight of surfactant (Product name: F477 DIC), and dimethyl A coating solution was prepared by mixing 55.6 parts by weight of formamide (DMF). After coating the above coating solution using #20 bar, curing was carried out at a speed of 2 m/min using a UV lamp of 0.2 J/cm2, and a film with a thickness of 10 ㎛ was manufactured.
실험예 1: 항균성 평가Experimental Example 1: Antibacterial evaluation
1) 박테리아 현탁액의 제조1) Preparation of bacterial suspension
시험 박테리아로서 KS L ISO 27447 규격에 명시된 표준 대장균인 E.coli ATCC 8739를 사용하였다. 상기 E.coli ATCC 8739 균주를 백금 루프를 사용하여 LB 영양 배지에 접종하고, 37℃에서 16 내지 24시간 동안 배양한 후, 5℃ 냉장고에 보관하였다. 1개월 이내에 상기 과정을 모사하여 2차 배양을 반복하였다. 2차 배양할 때 CFU(colony forming unit)의 최대 개수는 10이여야 한다. LB 영양 배지는 25 g/L Luria Broth powder와 15 g/L agar powder (Sigma-Aldrich에서 구매 가능)를 증류수에 섞은 후 autoclave에 멸균한 후 ~40℃까지 온도가 떨어지면 petri dish에 적정량 정량하여 제조하였다. As a test bacterium, E.coli ATCC 8739, a standard E. coli specified in the KS L ISO 27447 standard, was used. The E. coli ATCC 8739 strain was inoculated into LB nutrient medium using a platinum loop, cultured at 37°C for 16 to 24 hours, and then stored in a 5°C refrigerator. The secondary culture was repeated by simulating the above process within 1 month. During secondary culture, the maximum number of CFU (colony forming units) should be 10. LB nutrient medium is prepared by mixing 25 g/L Luria Broth powder and 15 g/L agar powder (available from Sigma-Aldrich) in distilled water, sterilizing it in an autoclave, and then weighing the appropriate amount in a petri dish when the temperature drops to ~40℃. did.
상기 박테리아 배양액을 원심분리하여 박테리아와 LB 액체 배지를 분리시킨 후 박테리아를 식염수에 이동하였다. Spectrophotometer를 이용하여 600 nm에서 박테리아-식염수 액의 흡수 값이 0.5가 되도록 현탄액을 희석시키고, 상기 박테리아 현탄액을 시험에 사용하였다. The bacterial culture was centrifuged to separate the bacteria and LB liquid medium, and then the bacteria were transferred to saline solution. Using a spectrophotometer, the suspension was diluted so that the absorption value of the bacterial-saline solution was 0.5 at 600 nm, and the bacterial suspension was used in the test.
구체적인 희석 방법은, 각 plate는 1/10씩 희석시킨 것이므로 CFU 개수도 1/10씩 줄어든다. Plating에 사용된 현탁액의 양은 0.1 ml이다. C4의 CFU 개수가 299이며 사용된 액의 양이 0.1 ml이므로 299 CFU / 0.1ml = 2,990 CFU/ml이 된다 C1의 CFU 개수는 1,000를 곱한 ~3.0 × 106 CFU/ml 이며 C1은 박테리아 원액(C0)을 1/10 희석시킨 것이므로 박테리아 현탄액의 CFU 개수는 3.0 × 107 CFU/ml이다.The specific dilution method is that each plate is diluted by 1/10, so the number of CFU is reduced by 1/10. The amount of suspension used for plating is 0.1 ml. Since the number of CFU in C 4 is 299 and the amount of liquid used is 0.1 ml, 299 CFU / 0.1 ml = 2,990 CFU/ml. The number of CFU in C 1 is ~3.0 × 10 6 CFU/ml multiplied by 1,000, and C 1 is Since the bacterial stock solution (C 0 ) is diluted by 1/10, the number of CFU in the bacterial suspension is 3.0 × 10 7 CFU/ml.
2) 시험편에 박테리아 접종2) Bacteria inoculation on test specimen
앞서 제조한 시험편 위에, 박테리아 현탄액(C1, C2, C3, C4) 0.2 mL을 각각 정량한 후, 그 위에 투과율이 80% 이상인 폴리프로필렌 접착 필름을 배치하여, 광촉매 시료를 담지한 고분자 필름과 접착 필름의 사이에 위치한 미생물 현탁액을 포함하는 샌드위치 구조로 제조하였다. After quantifying 0.2 mL of bacterial suspension (C 1 , C 2 , C 3 , C 4 ) on the test piece prepared previously, a polypropylene adhesive film with a transmittance of 80% or more was placed on it to support the photocatalyst sample. It was manufactured as a sandwich structure containing a microbial suspension located between a polymer film and an adhesive film.
3) 항균 시험(광 조건; light)3) Antibacterial test (light conditions; light)
각 시험편을 광원 아래에 위치시키고, 34℃에서 6시간 동안 광을 조사하였다. 상기 사용한 광은 백색 가시광으로서, 430 nm blue 영역대의 peak을 기반으로 만들어진 LED를 조도계로 측정했을 때 1,000 lux를 사용하며, 시험편과 광원의 거리는 1 cm이었다. Each test piece was placed under a light source and irradiated with light at 34°C for 6 hours. The light used was white visible light, and when measured with an illuminance meter using an LED made based on the peak in the 430 nm blue range, 1,000 lux was used, and the distance between the test piece and the light source was 1 cm.
4) 항균 시험(암 조건; dark)4) Antibacterial test (cancer condition; dark)
상기 3)의 항균 시험과 동일한 방법으로 실시하되, 광을 조사하지 않고 암실에서 진행하여, 향균성을 평가하였다. It was conducted in the same manner as the antibacterial test in 3) above, but conducted in a dark room without irradiation of light to evaluate antibacterial properties.
상기 실험의 결과를 도 1에 나타내었다. 도 1에 나타난 바와 같이, 실시예의 화합물이 비교예의 화합물에 비하여 광 조건에서 더 좋은 항균성을 나타내었으며, 이론적으로 제한되는 것은 아니나 실시예의 화합물이 고분자에 대한 상용성이 보다 우수하여 분산성이 향상된 것에 기인하는 것으로 판단된다.The results of the above experiment are shown in Figure 1. As shown in Figure 1, the compounds of the Examples showed better antibacterial properties under light conditions compared to the compounds of the Comparative Examples. Although not limited theoretically, the compounds of the Examples had better compatibility with polymers and improved dispersibility. It is believed to be caused by
실험예 2: 용해도 평가Experimental Example 2: Solubility evaluation
상기 실시예의 화합물(TOCPP) 및 비교예의 화합물(TCPP)를 각각 툴루엔과 DMF에 0.1 wt%, 0.3 wt% 및 0.5 wt%가 되도록 첨가하여 용해도를 평가하였으며, 그 결과를 도 2에 나타내었다. The solubility of the compound of the above example (TOCPP) and the compound of the comparative example (TCPP) was added to toluene and DMF at 0.1 wt%, 0.3 wt%, and 0.5 wt%, respectively, and the results are shown in FIG. 2.
도 2에 나타난 바와 같이, 실시예의 TOCPP는 0.5 wt%인 경우에도 용해되지 않은 부분이 육안으로 관찰되지 않았다. 반면, 비교예의 TCPP는 0.3 wt%인 경우에도 용해되지 않은 부분이 관찰되었다. As shown in Figure 2, even when the TOCPP of the example was 0.5 wt%, undissolved portions were not observed with the naked eye. On the other hand, undissolved portions of TCPP in the comparative example were observed even at 0.3 wt%.
Claims (6)
고분자 수지를 포함하는,
항균성 고분자 조성물:
[화학식 1]
상기 화학식 1에서,
R은 모두 -CO-O-R'이고,
R'는 C1-60 알킬이다.
As an antibacterial agent, a compound represented by the following formula (1),
Containing polymer resin,
Antibacterial polymer composition:
[Formula 1]
In Formula 1,
All R is -CO-O-R',
R' is C 1-60 alkyl.
R'는 C1-10 알킬인,
항균성 고분자 조성물.
According to paragraph 1,
R' is C 1-10 alkyl,
Antibacterial polymer composition.
R'는 옥틸인,
항균성 고분자 조성물.
According to paragraph 1,
R' is octyl,
Antibacterial polymer composition.
상기 화학식 1로 표시되는 화합물은 하기 화합물인,
항균성 고분자 조성물:
According to paragraph 1,
The compound represented by Formula 1 is the following compound,
Antibacterial polymer composition:
상기 고분자 수지는 아크릴 수지인,
항균성 고분자 조성물.According to paragraph 1,
The polymer resin is an acrylic resin,
Antibacterial polymer composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020180115320 | 2018-09-27 | ||
| KR20180115320 | 2018-09-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20200035832A KR20200035832A (en) | 2020-04-06 |
| KR102646264B1 true KR102646264B1 (en) | 2024-03-11 |
Family
ID=70282207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020190060052A KR102646264B1 (en) | 2018-09-27 | 2019-05-22 | Antibacterial polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR102646264B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115011047B (en) * | 2022-07-04 | 2023-07-25 | 广东裕泰实业有限公司 | Preparation method of antibacterial PVC packaging film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015134204A1 (en) | 2014-03-07 | 2015-09-11 | University Of Cincinnati | Silver nanoparticle-enhanced photosensitizers |
| WO2016030528A1 (en) | 2014-08-28 | 2016-03-03 | Pci Biotech As | Compound and method |
| WO2016051361A1 (en) | 2014-09-30 | 2016-04-07 | Biolitec Unternehmensbeteiligungs Ii Ag | Specifically meso-substituted porphyrins and chlorins for photodynamic therapy |
| WO2016151458A1 (en) | 2015-03-20 | 2016-09-29 | Luzitin, S.A. | Atropisomers of halogenated tetraphenylbacteriochlorins and chlorins and their use in photodynamic therapy |
-
2019
- 2019-05-22 KR KR1020190060052A patent/KR102646264B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015134204A1 (en) | 2014-03-07 | 2015-09-11 | University Of Cincinnati | Silver nanoparticle-enhanced photosensitizers |
| WO2016030528A1 (en) | 2014-08-28 | 2016-03-03 | Pci Biotech As | Compound and method |
| WO2016051361A1 (en) | 2014-09-30 | 2016-04-07 | Biolitec Unternehmensbeteiligungs Ii Ag | Specifically meso-substituted porphyrins and chlorins for photodynamic therapy |
| WO2016151458A1 (en) | 2015-03-20 | 2016-09-29 | Luzitin, S.A. | Atropisomers of halogenated tetraphenylbacteriochlorins and chlorins and their use in photodynamic therapy |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20200035832A (en) | 2020-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100752150B1 (en) | Photocurable monomoers having imidazolium salts, antibacterial photocurable compositions comprising the same, and antibacterial polymer materials prepared therefrom | |
| US8753570B2 (en) | Structure, synthesis, and applications for oligo phenylene ethynylenes | |
| Liu et al. | Antimicrobial property of halogenated catechols | |
| JP7277930B2 (en) | Phenalen-1-one containing photosensitizer composition, phenalen-1-one compound and use thereof | |
| Goel et al. | Functionalization of cotton fabrics by radiation induced grafting of quaternary salt to impart antibacterial property | |
| JP5523948B2 (en) | Resin molded body and protective plate for display | |
| Santos et al. | Light-activated antimicrobial surfaces using industrial varnish formulations to mitigate the incidence of nosocomial infections | |
| KR102646264B1 (en) | Antibacterial polymer composition | |
| CN105793304A (en) | Novel copolymer with cyclic halamine structure | |
| Chen et al. | Stability, antibacterial ability, and inhibition of “zinc burning” of amitrole as thermal stabilizer for transparent poly (vinyl chloride) | |
| Liu et al. | Preparation of surface self-concentration and contact-killing antibacterial coating through UV curing | |
| US11891494B2 (en) | Antimicrobial resin and coating material | |
| CN112368341B (en) | Antimicrobial polymer coating composition and antimicrobial polymer film | |
| KR102578739B1 (en) | Novel compound, antibacterial agent, and antibacterial polymer coating composition comprising the same | |
| CA2884128C (en) | Uv cured benzophenone terminated quaternary ammonium antimicrobials for surfaces | |
| Zhang et al. | Inserting Menthoxytriazine into Poly (Ethylene Terephthalate) for Inhibiting Microbial Adhesion | |
| KR101488701B1 (en) | Antibacterial imidazolium compound and antibacterial photocurable thiol-ene compositions comprising the same, and antibacterial polymer coatings prepared therefrom | |
| GB2373787A (en) | Phenothiazinium derivatives and their use to reduce pathogenic contaminants | |
| Li et al. | Antimicrobial modification of PET by insertion of menthoxy-triazine | |
| JP7258155B2 (en) | Polymerizable composition, compound, polymer, resin composition, ultraviolet shielding film and laminate | |
| KR102557941B1 (en) | Antibacterial polymer coating composition and antibacterial polymer film | |
| Shevchenko et al. | Effect of some metal β-diketonates on the bactericidal activity of polymer | |
| CN116253834A (en) | Polymer, preparation method thereof, antibacterial and antiviral product and application thereof | |
| Lone et al. | Urushiol-Acrylate Terpolymers: Synthesis, Characterization, and Antibacterial Effects Against Staphylococcus aureus | |
| KR20210067737A (en) | Antibacterial and anti-allegic polymer coating composition, and antibacterial and anti-allegic polymer film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |