KR102599259B1 - Antibacterial coating composition with improved durability and laminate using same - Google Patents
Antibacterial coating composition with improved durability and laminate using same Download PDFInfo
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- KR102599259B1 KR102599259B1 KR1020230049738A KR20230049738A KR102599259B1 KR 102599259 B1 KR102599259 B1 KR 102599259B1 KR 1020230049738 A KR1020230049738 A KR 1020230049738A KR 20230049738 A KR20230049738 A KR 20230049738A KR 102599259 B1 KR102599259 B1 KR 102599259B1
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- antibacterial
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 94
- 239000008199 coating composition Substances 0.000 title claims abstract description 35
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 55
- 238000000576 coating method Methods 0.000 claims abstract description 45
- 239000011248 coating agent Substances 0.000 claims abstract description 44
- 229920001709 polysilazane Polymers 0.000 claims abstract description 35
- 239000011521 glass Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000004480 active ingredient Substances 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- TUGGFUSCPLPUFY-UHFFFAOYSA-N 3-triethoxysilylpropan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCN.CCO[Si](OCC)(OCC)CCCN TUGGFUSCPLPUFY-UHFFFAOYSA-N 0.000 claims description 3
- PFYBXKBLFFEPRJ-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN.CO[Si](OC)(OC)CCCN PFYBXKBLFFEPRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002928 artificial marble Substances 0.000 claims description 3
- 239000002969 artificial stone Substances 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 238000001723 curing Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 241000191967 Staphylococcus aureus Species 0.000 description 6
- 239000007844 bleaching agent Substances 0.000 description 6
- 241000588724 Escherichia coli Species 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 239000002956 ash Substances 0.000 description 4
- 230000003385 bacteriostatic effect Effects 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 241001360526 Escherichia coli ATCC 25922 Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- FJQXCDYVZAHXNS-UHFFFAOYSA-N methadone hydrochloride Chemical compound Cl.C=1C=CC=CC=1C(CC(C)N(C)C)(C(=O)CC)C1=CC=CC=C1 FJQXCDYVZAHXNS-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Classifications
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- 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
-
- 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/40—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Nanotechnology (AREA)
- Paints Or Removers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
본 발명은 내구성이 개선된 항균 코팅 조성물 및 이를 이용한 적층체에 관한 것으로, 더욱 상세하게는 유기폴리실라잔, 무기폴리실라잔, 경화촉매 및 무기 항균제를 유효성분으로 포함하며, 상기 무기 항균제는 아연이온(Zn2+)을 유효성분으로 하는 유리계 항균제임을 특징으로 한다. 본 발명에 의하면, 도막 내 무기 항균제간 평균 거리를 제한하여 항균활성을 극대화하면서도 도막의 품질을 개선하고, 도막의 내구성을 개선하여 우수한 초기 항균성은 물론, 장기간에 걸쳐 지속적으로 우수한 항균성을 갖도록 한다는 장점이 있다.The present invention relates to an antibacterial coating composition with improved durability and a laminate using the same. More specifically, the present invention relates to an antibacterial coating composition with improved durability and a laminate using the same. More specifically, it contains organic polysilazanes, inorganic polysilazanes, a curing catalyst, and an inorganic antibacterial agent as active ingredients, and the inorganic antibacterial agent is zinc. It is characterized as a glass-based antibacterial agent containing ions (Zn 2+ ) as an active ingredient. According to the present invention, the quality of the coating film is improved while maximizing the antibacterial activity by limiting the average distance between inorganic antibacterial agents in the coating film, and the durability of the coating film is improved to provide excellent initial antibacterial properties as well as continuously excellent antibacterial properties over a long period of time. There is.
Description
본 발명은 내구성이 개선된 항균 코팅 조성물 및 이를 이용한 적층체에 관한 것으로, 더욱 상세하게는 유기폴리실라잔과 무기폴리실라잔을 주수지로 포함하고, 아연이온(Zn2+)을 유효성분으로 하는 유리계 항균제를 무기 항균제로 포함하는 내구성이 개선된 항균 코팅 조성물 및 이를 이용한 적층체에 관한 것이다.The present invention relates to an antibacterial coating composition with improved durability and a laminate using the same, and more specifically, to an antibacterial coating composition with improved durability and a laminate using the same. More specifically, it contains organic polysilazane and inorganic polysilazane as the main resin, and zinc ion (Zn 2+ ) as the active ingredient. It relates to an antibacterial coating composition with improved durability containing a glass-based antibacterial agent as an inorganic antibacterial agent and a laminate using the same.
일반적으로 주거공간에서 사용되는 각종 생활용품은 물론, 창문, 도어핸들과 같은 인테리어 소재로 활용되는 유리, SUS, 플라스틱, 목재 등의 기재는 생활 밀접 특성상 오염에 취약하다.In general, materials such as glass, SUS, plastic, and wood used as interior materials such as windows and door handles, as well as various household items used in residential spaces, are vulnerable to contamination due to their close nature.
상기한 소재들의 표면이 세균이나 악취의 원인균 등에 오염될 경우, 이를 접촉한 사용자가 관련 질병에 감염될 확률이 높아지고, 오염된 소재는 그 기본 기능을 다할 수 없게 되는 문제가 있다.If the surfaces of the above-mentioned materials are contaminated with bacteria or bacteria that cause bad odors, the probability that users who come into contact with them will become infected with related diseases increases, and there is a problem in that the contaminated materials cannot perform their basic functions.
이에 각종 생활 밀접 소재에 항균 기능성을 부여하기 위한 다양한 방법이 제안되어 왔다.Accordingly, various methods have been proposed to impart antibacterial functionality to various materials closely related to daily life.
이 중 하나의 방법은 가시광 영역에서 촉매 활성을 띠는 광 촉매를 이용하는 방법이다. 그러나 가시광 촉매 중 백금 담지 산화 텅스텐은 다른 광 촉매에 비하여 큰 비중을 가지기 때문에, 코팅층 내에서 표면을 향하여 부상하지 못하고, 분산성이 불량하여 코팅층의 하단부에 위치하여 항균 효과를 나타내지 못하였으며, 코팅층의 코팅성이 크게 저하되어 기재와의 부착성이 좋지 못한 문제가 있었다.One of these methods is to use a photocatalyst that is catalytically active in the visible light region. However, among visible light catalysts, platinum-supported tungsten oxide has a larger specific gravity than other photocatalysts, so it cannot float toward the surface within the coating layer, and due to poor dispersibility, it is located at the bottom of the coating layer and does not exhibit an antibacterial effect. There was a problem of poor adhesion to the substrate due to greatly reduced coating properties.
이러한 단점을 해소하기 위하여, 대한민국 공개특허 제10-2022-0061884호에서는 광촉매, 실리콘 함유 화합물을 포함하는 코팅 조성물을 제안하였다. 상기 선공개 특허는 기재와의 반응성을 향상시켜 우수한 부착력, 내마모성, 코팅 균일성을 갖도록 하였다.In order to solve these shortcomings, Republic of Korea Patent Publication No. 10-2022-0061884 proposed a coating composition containing a photocatalyst and a silicon-containing compound. The pre-published patent improved reactivity with the substrate to provide excellent adhesion, wear resistance, and coating uniformity.
또한, 대한민국 공개특허 제10-2023-0000987호에서는 광촉매, 유기폴리실라잔 수지를 포함함으로써, 기재와의 반응성을 향상시켜 우수한 코팅 균일성을 갖고, 표면층 위에 소정의 비율로 광 촉매가 노출되어 우수한 표면 항균성을 갖도록 하였다.In addition, in Korean Patent Publication No. 10-2023-0000987, by including a photocatalyst and an organic polysilazane resin, the reactivity with the substrate is improved, resulting in excellent coating uniformity, and the photocatalyst is exposed at a predetermined ratio on the surface layer, resulting in excellent coating quality. It was designed to have surface antibacterial properties.
그러나 상기 선공개 특허들은 초기 항균성은 우수하나, 제품의 사용 환경에 따라 도막의 내구성이 저하됨에 따라 항균성 역시 급속도로 저하된다는 단점이 있었다.However, the above-mentioned pre-published patents had excellent initial antibacterial properties, but had the disadvantage that antibacterial properties also rapidly deteriorated as the durability of the coating film deteriorated depending on the product use environment.
따라서, 초기 항균성은 물론, 장기간에 걸쳐 지속적으로 우수한 항균성을 갖는 항균 코팅 조성물의 개발이 요구되고 있는 실정이다. Therefore, there is a need for the development of an antibacterial coating composition that not only has initial antibacterial properties but also has consistently excellent antibacterial properties over a long period of time.
따라서, 본 발명의 목적은 유기폴리실라잔과 무기폴리실라잔을 주수지로 포함하고, 아연이온(Zn2+)을 유효성분으로 하는 유리계 항균제를 무기 항균제로 포함함으로써, 도막의 내구성을 개선하여 우수한 초기 항균성은 물론, 장기간에 걸쳐 지속적으로 우수한 항균성을 갖도록 하는 내구성이 개선된 항균 코팅 조성물 및 이를 이용한 적층체를 제공하는 데 있다.Therefore, the object of the present invention is to improve the durability of the coating film by including organic polysilazane and inorganic polysilazane as the main resin and a glass-based antibacterial agent containing zinc ions (Zn 2+ ) as an active ingredient as an inorganic antibacterial agent. The aim is to provide an antibacterial coating composition with improved durability that not only has excellent initial antibacterial properties but also continues to have excellent antibacterial properties over a long period of time, and a laminate using the same.
본 발명의 다른 목적은, 무기 항균제의 평균 입도 및 배합비를 한정함으로써, 도막 내 무기 항균제 간 평균 거리를 제한하여 우수한 항균성, 촉감 및 외감을 갖도록 하는 내구성이 개선된 항균 코팅 조성물 및 이를 이용한 적층체를 제공하는 데 있다.Another object of the present invention is to provide an antibacterial coating composition with improved durability and a laminate using the same, which has excellent antibacterial properties, feel and appearance by limiting the average particle size and mixing ratio of the inorganic antibacterial agent, thereby limiting the average distance between the inorganic antibacterial agents in the coating film. It is to provide.
상기한 목적을 달성하기 위한 본 발명의 내구성이 개선된 항균 코팅 조성물은, 유기폴리실라잔, 무기폴리실라잔, 경화촉매 및 무기 항균제를 유효성분으로 포함하며, 상기 무기 항균제는 아연이온(Zn2+)을 유효성분으로 하는 유리계 항균제임을 특징으로 한다.The antibacterial coating composition with improved durability of the present invention for achieving the above object includes organic polysilazane, inorganic polysilazane, a curing catalyst, and an inorganic antibacterial agent as active ingredients, and the inorganic antibacterial agent contains zinc ions (Zn 2 It is characterized as a glass-based antibacterial agent containing + ) as an active ingredient.
표면용 첨가제를 더 포함하되, 상기 표면용 첨가제는 실리콘계 계면활성제인 것을 특징으로 한다.It further includes a surface additive, wherein the surface additive is a silicone-based surfactant.
용제를 더 포함하는 것을 특징으로 한다.It is characterized in that it further contains a solvent.
유기폴리실라잔 30~60중량%, 무기폴리실라잔 5~10중량%, 경화촉매 10~20중량%, 무기 항균제 0.5~2.0중량%, 표면용 첨가제 0.1~2.0중량% 및 잔부의 용제로 구성되는 것을 특징으로 한다.Consists of 30 to 60% by weight of organic polysilazane, 5 to 10% by weight of inorganic polysilazane, 10 to 20% by weight of curing catalyst, 0.5 to 2.0% by weight of inorganic antibacterial agent, 0.1 to 2.0% by weight of surface additive, and the remaining solvent. It is characterized by being
상기 경화촉매는 3-(트라이에톡시실릴)프로필아민(3-Aminopropyl triethoxysilane) 및 3-(트라이메톡시실릴)프로필아민(3-Aminopropyl trimethoxysilane) 중 1종 이상의 것임을 특징으로 한다.The curing catalyst is characterized in that it is one or more of 3-(triethoxysilyl)propylamine (3-Aminopropyl triethoxysilane) and 3-(trimethoxysilyl)propylamine (3-Aminopropyl trimethoxysilane).
상기 무기 항균제의 평균 입도는 3~10㎛인 것을 특징으로 한다.The average particle size of the inorganic antibacterial agent is 3 to 10 ㎛.
그리고 본 발명에 의한 적층체는, 기재; 상기 기재 상에 형성되며, 상기한 항균 코팅 조성물로 구성되는 도막;을 포함하는 것을 특징으로 한다. And the laminate according to the present invention includes a base material; A coating film formed on the substrate and composed of the antibacterial coating composition described above.
상기 도막 내 무기 항균제 간 평균 거리는 50~200㎛인 것을 특징으로 한다.The average distance between the inorganic antibacterial agents in the coating film is characterized in that it is 50 to 200㎛.
상기 코팅층의 두께는 1~10㎛이고, 상기 기재는 플라스틱, 금속, 목재, 유리, 인조대리석 및 석재 중 1종 이상의 것임을 특징으로 한다.The thickness of the coating layer is 1 to 10㎛, and the substrate is characterized in that it is one or more types of plastic, metal, wood, glass, artificial marble, and stone.
본 발명의 내구성이 개선된 항균 코팅 조성물 및 이를 이용한 적층체에 의하면, 도막 내 무기 항균제 간 평균 거리를 제한하여 항균활성을 극대화하면서도 도막의 품질을 개선하고, 도막의 내구성을 개선하여 우수한 초기 항균성은 물론, 장기간에 걸쳐 지속적으로 우수한 항균성을 갖도록 한다는 장점이 있다.According to the antibacterial coating composition with improved durability of the present invention and the laminate using the same, the quality of the coating film is improved while maximizing antibacterial activity by limiting the average distance between inorganic antibacterial agents in the coating film, and the durability of the coating film is improved to provide excellent initial antibacterial properties. Of course, it has the advantage of maintaining excellent antibacterial properties over a long period of time.
도 1은 본 발명의 실시예 1에 의해 형성된 도막의 광학 현미경 사진.1 is an optical micrograph of a coating film formed in Example 1 of the present invention.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 유기폴리실라잔과 무기폴리실라잔을 주수지로 포함하고, 아연이온(Zn2+)을 유효성분으로 하는 유리계 항균제를 무기 항균제로 포함함으로써, 최소한의 항균제만으로 항균활성을 극대화하고, 도막의 내구성을 개선하여 장기간에 걸쳐 지속적으로 우수한 항균성을 갖도록 한다는 데 가장 큰 특징이 있다.The present invention includes organic polysilazanes and inorganic polysilazanes as the main resin, and a glass-based antibacterial agent with zinc ions (Zn 2+ ) as an active ingredient as an inorganic antibacterial agent, thereby maximizing antibacterial activity with a minimum amount of antibacterial agents. , the biggest feature is that it improves the durability of the coating film and ensures that it continues to have excellent antibacterial properties over a long period of time.
보다 구체적으로, 본 발명의 내구성이 개선된 항균 코팅 조성물은, 유기폴리실라잔, 무기폴리실라잔, 경화촉매 및 무기 항균제를 유효성분으로 포함하며, 상기 무기 항균제는 아연이온(Zn2+)을 유효성분으로 하는 유리계 항균제임을 특징으로 한다.More specifically, the antibacterial coating composition with improved durability of the present invention includes organic polysilazane, inorganic polysilazane, a curing catalyst, and an inorganic antibacterial agent as active ingredients, and the inorganic antibacterial agent contains zinc ions (Zn 2+ ). It is characterized as a glass-based antibacterial agent used as an active ingredient.
먼저, 상기 유기폴리실라잔(Organic Polysilazane)은 항균 도막을 구성하는 주수지로, 기재와의 반응성 및 접착성이 우수하며, 내오염성도 우수하다. 따라서, 본 발명의 주수지로 사용된다. First, the organic polysilazane is the main resin that makes up the antibacterial coating film, and has excellent reactivity and adhesion with the substrate and excellent contamination resistance. Therefore, it is used as the main resin of the present invention.
본 발명에서 상기 유기폴리실라잔은 그 구체적인 구조를 한정하지 않으며, 치환기가 유기 치환기인 경우 어떠한 유기폴리실라잔도 적용 가능하다. 상업적으로 구할 수 있는 제품으로는, Merck사의 Durazane 1500 RC, Durazane 1500 SC, Durazane 1800 등이 있다.In the present invention, the specific structure of the organopolysilazane is not limited, and any organopolysilazane can be applied if the substituent is an organic substituent. Commercially available products include Durazane 1500 RC, Durazane 1500 SC, and Durazane 1800 from Merck.
상기 유기폴리실라잔은 항균 코팅 조성물 100중량%를 기준으로, 30~60중량%로 포함됨이 바람직한데, 그 함량이 30중량% 미만이면 적절 도막 두께 수준보다 낮아지고, 60중량%를 초과하면 적절 도막 두께 수준보다 높아져 도막의 형성이 어렵기 때문이다.The organic polysilazane is preferably included in an amount of 30 to 60% by weight based on 100% by weight of the antibacterial coating composition. If the content is less than 30% by weight, it is lower than the appropriate film thickness level, and if it exceeds 60% by weight, it is appropriate. This is because it becomes difficult to form a coating film as it becomes higher than the coating film thickness level.
상기 무기폴리실라잔(Inorganic Polysilazane) 역시 항균 도막을 구성하는 수지로, 내구성을 개선해준다. 즉, 유기폴리실라잔만을 주수지로 포함할 경우 도막의 내구성이 떨어져 장기간에 걸쳐 지속적인 항균성을 확보할 수 없으나, 무기폴리실라잔을 혼용하면 도막의 내구성을 현저히 높일 수 있어, 지속적인 항균성의 확보가 가능하게 된다.The inorganic polysilazane is also a resin that makes up the antibacterial coating film and improves durability. In other words, if only organic polysilazanes are included as the main resin, the durability of the coating film is low and continuous antibacterial properties cannot be secured over a long period of time. However, if inorganic polysilazanes are mixed, the durability of the coating film can be significantly increased, thereby ensuring continuous antibacterial properties. It becomes possible.
상기 무기폴리실라잔 역시 그 구체적인 구조를 한정하지 않으며, 치환기가 수소인 경우 어떠한 무기폴리실라잔도 적용 가능하다. 상업적으로 구할 수 있는 제품으로는, Merck사의 Durazane 2400, Durazane 2800 등이 있다.The specific structure of the inorganic polysilazane is not limited, and if the substituent is hydrogen, any inorganic polysilazane can be applied. Commercially available products include Merck's Durazane 2400 and Durazane 2800.
상기 무기폴리실라잔은 항균 코팅 조성물 100중량%를 기준으로, 5~10중량%로 포함됨이 바람직한데, 그 함량이 5중량% 미만이면 내구성의 확보가 어렵고, 10중량%를 초과하더라도 더 이상의 내구성 개선이 어려우므로 경제성이 떨어지기 때문이다.The inorganic polysilazane is preferably included in an amount of 5 to 10% by weight based on 100% by weight of the antibacterial coating composition. If the content is less than 5% by weight, it is difficult to secure durability, and even if it exceeds 10% by weight, durability is no longer achieved. This is because improvement is difficult and economic feasibility is low.
상기 경화촉매는 상기 유기폴리실라잔 및 무기폴리실라잔의 경화를 촉진하기 위한 것으로, 경화 온도를 낮추고, 경화 시간을 단축하기 위한 것이다.The curing catalyst is used to promote curing of the organic polysilazane and inorganic polysilazane, lower the curing temperature, and shorten the curing time.
상기 경화촉매로는 3-(트라이에톡시실릴)프로필아민(3-Aminopropyl triethoxysilane) 및 3-(트라이메톡시실릴)프로필아민(3-Aminopropyl trimethoxysilane) 중 1종 이상의 것을 사용함이 바람직하다.As the curing catalyst, it is preferable to use at least one of 3-(triethoxysilyl)propylamine (3-Aminopropyl triethoxysilane) and 3-(trimethoxysilyl)propylamine (3-Aminopropyl trimethoxysilane).
상기 경화촉매는 항균 코팅 조성물 100중량%를 기준으로, 10~20중량%로 포함됨이 바람직한데, 그 함량이 10중량% 미만이면 경화 촉진의 효과가 미미하고, 과량의 경우 경화속도가 너무 빨라 도막의 백탁, 핀홀과 같은 외관불량이 발생하며, 작업성이 좋지 못하기 때문이다.The curing catalyst is preferably contained in an amount of 10 to 20% by weight based on 100% by weight of the antibacterial coating composition. If the content is less than 10% by weight, the effect of promoting curing is minimal, and if the amount is excessive, the curing speed is too fast and the coating film This is because appearance defects such as white clouding and pinholes occur and workability is poor.
상기 무기 항균제는 도막 표면에서 항균성을 발휘하기 위한 것이다.The inorganic antibacterial agent is intended to exert antibacterial properties on the surface of the coating film.
본 발명에서는 상기 무기 항균제로 아연이온(Zn2+)을 유효성분으로 하는 유리계 항균제를 사용함이 바람직한데, 아연이온이 세균 및 곰팡이를 유인하여 세포 내부의 Thiol기 및 Hydroxyl기에 결합하여 세포를 변성시킴으로써, 항균활성을 발휘하는 것이다. In the present invention, it is preferable to use a glass-based antibacterial agent containing zinc ions (Zn 2+ ) as an active ingredient as the inorganic antibacterial agent. Zinc ions attract bacteria and fungi and bind to thiol and hydroxyl groups inside cells, denaturing cells. By doing so, it exerts antibacterial activity.
이러한 유리계 항균제는, 구체적으로 Ag2O 0.1∼2.0중량%, B2O3 30∼40중량%, SiO2 6∼9중량%, CaO 2~10중량%, Na2O 6~7중량% 및 잔부의 ZnO로 이루어진 원료를 1100∼1300℃에서 가열 용융, 냉각 및 분쇄하여 얻을 수 있다. 상기한 조성의 유리계 항균제는 유리의 골격을 형성하는 성분 및 항균 성분의 배합비를 최적화하여 항균성을 극대화하며, 가공 중 항균성이 저하되는 문제를 개선한 것이다. 아울러, 상업적으로 구할 수 있는 유리계 항균제로, TOAGOSEI사의 Novaron VZ를 사용할 수도 있다. 다만, 상기 유리계 항균제의 평균 입도는 3~10㎛인 것이 바람직한데, 그 입도가 3㎛ 미만이면 도막 내로 묻히는 입자가 많아 충분한 항균성의 확보가 어려워 과량을 배합해야 하고, 10㎛를 초과할 경우 도막으로부터 탈락되는 입자가 많아 경제성이 떨어지기 때문이다.These glass-based antibacterial agents specifically include 0.1 to 2.0% by weight of Ag 2 O, 30 to 40% by weight of B 2 O 3 , 6 to 9% by weight of SiO 2 , 2 to 10% by weight of CaO, and 6 to 7% by weight of Na 2 O. The raw material consisting of ZnO and the remaining portion can be obtained by heating and melting at 1100 to 1300°C, cooling and pulverizing. The glass-based antibacterial agent of the above-described composition maximizes antibacterial properties by optimizing the mixing ratio of the components that form the skeleton of the glass and the antibacterial components, and improves the problem of deterioration of antibacterial properties during processing. In addition, TOAGOSEI's Novaron VZ can be used as a commercially available glass-based antibacterial agent. However, the average particle size of the glass-based antibacterial agent is preferably 3 to 10㎛. If the particle size is less than 3㎛, there are many particles embedded in the coating film, making it difficult to secure sufficient antibacterial properties, so an excessive amount must be mixed. If the particle size is less than 10㎛, it is difficult to secure sufficient antibacterial properties. This is because many particles fall off from the paint film, making it less economical.
상기 무기 항균제는 항균 코팅 조성물 100중량%를 기준으로, 0.5~2.0중량%로 포함됨이 바람직하다. 이는 상기 무기 항균제는 도막 형성 시, 도막 내 무기 항균제 간 평균 거리가 50~200㎛이어야만 충분한 항균활성을 발휘하면서도 표면에 너무 많은 항균제가 노출되어 외관 및 촉감을 해치는 문제를 해소할 수 있는데, 상기한 배합비를 벗어날 경우 상기한 무기 항균제 간 평균 거리를 만족시킬 수 없기 때문이다.The inorganic antibacterial agent is preferably contained in an amount of 0.5 to 2.0% by weight based on 100% by weight of the antibacterial coating composition. This means that when forming a coating film, the inorganic antibacterial agent must have an average distance of 50-200㎛ between the inorganic antibacterial agents in the coating film to exert sufficient antibacterial activity, while solving the problem of damaging the appearance and feel due to too much antibacterial agent being exposed to the surface. This is because if the mixing ratio is exceeded, the average distance between the above-described inorganic antibacterial agents cannot be satisfied.
한편, 본 발명의 항균 코팅 조성물은 표면용 첨가제를 더 포함하는 것이 바람직하다.Meanwhile, the antibacterial coating composition of the present invention preferably further includes a surface additive.
상기 표면용 첨가제는 코팅 표면의 레벨링성 조절을 위해 사용되는 것으로, 실리콘계 계면활성제 중 어떠한 것이라도 적용 가능하다. 예시적으로, 상업적으로 구할 수 있는 제품으로는 Evonik 사의 Glide 450K이 있다.The surface additive is used to control the leveling properties of the coating surface, and any silicone-based surfactant can be applied. By way of example, a commercially available product is Glide 450K from Evonik.
상기 표면용 첨가제는 항균 코팅 조성물 100중량%를 기준으로, 0.1~2.0중량%로 포함됨이 바람직한데, 그 함량이 너무 적으면 그 역할이 미미하고, 과량이 되더라도 더 이상의 증진된 작용효과를 나타내지 못해 경제성이 떨어지기 때문이다.The surface additive is preferably included in an amount of 0.1 to 2.0% by weight based on 100% by weight of the antibacterial coating composition. If the content is too small, its role is insignificant, and even if it is excessive, it does not show any further enhanced effect. This is because economic feasibility is low.
아울러, 본 발명의 항균 코팅 조성물은 고형분의 함량을 낮추고, 점도를 낮추기 위해 용제를 더 포함함이 바람직하다.In addition, the antibacterial coating composition of the present invention preferably further includes a solvent to lower the solid content and viscosity.
상기 용제로는 비알콜성 유기용제라면 어떠한 것이라도 사용 가능한바, 예시적으로, n-Buthyl acetate, PGMEA, DGMEA 중 1종 이상을 사용할 수 있다. Any non-alcoholic organic solvent can be used as the solvent. For example, one or more of n-Buthyl acetate, PGMEA, and DGMEA can be used.
상기 용제는 항균 코팅 조성물 내 잔부로서 포함된다.The solvent is included as the remainder in the antibacterial coating composition.
상기와 같이 구성되는 본 발명의 항균 코팅 조성물은, 앞서 설명된 바와 같이, 초기 항균성이 우수함은 물론, 내구성이 우수하여 장기간에 걸친 항균성 역시 우수하다는 장점이 있다. 아울러, 도막 내 무기 항균제 간 최적의 거리를 갖도록 함으로써, 최소한의 무기 항균제만으로 항균활성을 극대화할 수 있으며, 기재와의 접착성, 도막 균일성 등의 기본 물성 역시 우수하다는 장점이 있다.As described above, the antibacterial coating composition of the present invention, composed as described above, has the advantage of not only having excellent initial antibacterial properties, but also excellent durability and long-term antibacterial properties. In addition, by ensuring the optimal distance between inorganic antibacterial agents in the coating film, antibacterial activity can be maximized with only a minimum amount of inorganic antibacterial agents, and basic physical properties such as adhesion to the substrate and coating uniformity are also advantageous.
한편, 본 발명의 항균 코팅 조성물은 항균 코팅 조성물 100중량%를 기준으로, 탄산화 발전회 0.1~2중량%를 추가로 포함할 수 있다. Meanwhile, the antibacterial coating composition of the present invention may additionally include 0.1 to 2% by weight of carbonated power ash based on 100% by weight of the antibacterial coating composition.
상기 탄산화 발전회는 도막의 물성을 개선해주는 것으로, 이를 통해 장기적으로 항균성이 유지되도록 한다.The carbonated power ash improves the physical properties of the coating film, thereby maintaining antibacterial properties over a long period of time.
상기 탄산화 발전회는 발전회(비회, fly ash)에 물을 1:1~2중량비로 혼합하고, 이에 이산화탄소를 pH가 9~10이 될때까지 주입한 후, 여과 및 건조하고, 상기 건조된 건조물을 2~3부피배의 인산염 수용액에 20~30℃의 온도에서 30~40분간 침지한 후, 건조하고 1~10㎛로 분쇄하는 것이다. 이때, 상기 인산염 수용액으로는 3~10중량% 농도의 인산암모늄 수용액을 사용하면 족한바, 인산염의 종류 및 농도를 제한하지 않는다.The carbonated power ash is made by mixing water with power ash (fly ash) at a weight ratio of 1:1 to 2, injecting carbon dioxide into the mixture until the pH is 9 to 10, filtering and drying, and the dried product. is immersed in 2 to 3 times the volume of phosphate aqueous solution at a temperature of 20 to 30°C for 30 to 40 minutes, then dried and ground to 1 to 10㎛. At this time, it is sufficient to use an ammonium phosphate aqueous solution with a concentration of 3 to 10% by weight as the aqueous phosphate solution, and the type and concentration of the phosphate are not limited.
이하, 본 발명에 의한 적층체에 대하여 상세히 설명한다. 다만, 설명의 중복을 피하기 위하여, 상기에서 충분히 설명된 항균 코팅 조성물에 대한 추가 설명은 생략한다.Hereinafter, the laminate according to the present invention will be described in detail. However, in order to avoid duplication of explanation, further description of the antibacterial coating composition fully described above will be omitted.
본 발명에 의한 적층체는, 기재; 상기 기재 상에 형성되며, 상기한 항균 코팅 조성물로 구성되는 도막;을 포함하는 것을 특징으로 한다.The laminate according to the present invention includes a base material; A coating film formed on the substrate and composed of the antibacterial coating composition described above.
본 발명에서 상기 기재로는 그 종류와 무관하게 적용 가능한데, 예시적으로 플라스틱, 금속, 목재, 유리, 인조대리석, 석재 중 1종 이상의 것일 수 있다. 이는 본 발명에 의한 항균 코팅 조성물은 기재와의 반응성 및 접착성이 우수하므로, 기재의 종류와 상관없이 적용이 가능한 것이다.In the present invention, the substrate can be applied regardless of its type, and may be exemplified by one or more of plastic, metal, wood, glass, artificial marble, and stone. This is because the antibacterial coating composition according to the present invention has excellent reactivity and adhesion to the substrate, so it can be applied regardless of the type of substrate.
상기 도막은 본 발명에 의한 항균 코팅 조성물로 구성되는 것으로, 상기 도막의 형성방법은 기재를 깨끗이 세척한 후, 이에 항균 코팅 조성물을 코팅하고, 50~150℃에서 5~60분간 경화 및 냉각시키는 것이다. 이때, 기재가 금속일 경우 높은 온도에서 열경화하고, 플라스틱일 경우 변형이 없는 낮은 온도에서 진행함은 당연하다. The coating film is composed of an antibacterial coating composition according to the present invention. The method of forming the coating film is to clean the substrate, coat it with an antibacterial coating composition, and cure and cool at 50 to 150 ° C. for 5 to 60 minutes. . At this time, if the base material is metal, heat curing is carried out at a high temperature, and if the base material is plastic, it is natural to carry out heat curing at a low temperature without deformation.
아울러, 본 발명에서 상기 코팅 방법은 제한하지 않는바, 담지법, 함침법, 스피닝 및 스프레이를 이용한 분사법 등, 공지된 다양한 방법을 모두 적용할 수 있다.In addition, the coating method is not limited in the present invention, and various known methods such as supporting method, impregnating method, spinning method, and spraying method can be applied.
이때, 상기 도막의 두께는 1~10㎛임이 바람직한데, 이는 충분한 항균성의 발현을 위함이다. At this time, the thickness of the coating film is preferably 1 to 10㎛ in order to develop sufficient antibacterial properties.
또한, 앞서 설명된 바와 같이 도막 내 무기 항균제 간 평균 거리는 50~200㎛인 것으로, 그 평균 거리가 작으면 표면에 너무 많은 항균제가 노출되어 외관, 촉감의 측면에서 부적절하고, 그 평균 거리가 너무 크면 충분한 항균성을 확보하기 어렵기 때문이다.In addition, as explained previously, the average distance between inorganic antibacterial agents in the coating film is 50 to 200㎛. If the average distance is small, too much antibacterial agent is exposed to the surface, which is inappropriate in terms of appearance and feel, and if the average distance is too large, This is because it is difficult to secure sufficient antibacterial properties.
이하, 본 발명을 구체적인 실시예를 통해 상세히 설명한다.Hereinafter, the present invention will be described in detail through specific examples.
(실시예 1)(Example 1)
유기폴리실라잔(Merck 사 Durazane 1500 RC) 30중량%, 무기폴리실라잔(Merck 사 Durazane 2400) 7.5중량%, 경화촉매(3-Aminopropyl trimethoxysilane) 10중량%, 무기 항균제(Toagosei 사 Novaron VZ 900) 1.5중량%, 표면용 첨가제(Evonik사 Glide 450K) 1중량% 및 잔부의 용제(n-Buthyl acetate)를 혼합하여 항균 코팅 조성물을 제조하였다. 이때, 무기 항균제의 평균 입도는 3~10㎛ 였다.Organic polysilazane (Merck company Durazane 1500 RC) 30% by weight, inorganic polysilazane (Merck company Durazane 2400) 7.5% by weight, curing catalyst (3-Aminopropyl trimethoxysilane) 10% by weight, inorganic antibacterial agent (Toagosei Novaron VZ 900) An antibacterial coating composition was prepared by mixing 1.5% by weight, 1% by weight of surface additive (Glide 450K from Evonik) and the remainder of solvent (n-Buthyl acetate). At this time, the average particle size of the inorganic antibacterial agent was 3 to 10㎛.
(실시예 2)(Example 2)
실시예 1과 동일하게 실시하되, 무기 항균제를 1.0중량%만큼 사용하였다.The same procedure as in Example 1 was performed, except that 1.0% by weight of an inorganic antibacterial agent was used.
(실시예 3)(Example 3)
실시예 1과 동일하게 실시하되, 무기 항균제를 0.5중량%만큼 사용하였다.The same procedure as Example 1 was performed, but 0.5% by weight of an inorganic antibacterial agent was used.
(비교예 1)(Comparative Example 1)
실시예 1과 동일하게 실시하되, 유기폴리실라잔을 36.5중량%만큼, 무기폴리실라잔을 1.0중량%만큼 사용하였다.The same procedure as Example 1 was performed, except that 36.5% by weight of organic polysilazane and 1.0% by weight of inorganic polysilazane were used.
(비교예 2)(Comparative Example 2)
실시예 1과 동일하게 실시하되, 무기폴리실라잔을 대신하여 유기폴리실라잔을 사용하였다.The same procedure as Example 1 was performed, except that organic polysilazane was used instead of inorganic polysilazane.
(비교예 3)(Comparative Example 3)
실시예 1과 동일하게 실시하되, 무기 항균제를 3.0중량%만큼 사용하였다.The same procedure as Example 1 was performed, but 3.0% by weight of an inorganic antibacterial agent was used.
(비교예 4)(Comparative Example 4)
실시예 1과 동일하게 실시하되, 무기 항균제를 0.1중량%만큼 사용하였다.The same procedure as Example 1 was performed, but 0.1% by weight of an inorganic antibacterial agent was used.
(시험예 1)(Test Example 1)
상기 실시예 1, 비교예 1, 비교예 2에 대하여 항균성, 항균 지속력을 테스트 하였다.Example 1, Comparative Example 1, and Comparative Example 2 were tested for antibacterial properties and antibacterial durability.
구체적으로, 강화유리 기재에 각 코팅 조성물을 스프레이 코팅방법으로 5㎛ 두께의 도막을 형성하고, 120℃에서 30분간 열경화한 후, 실온에서 냉각시켜 시편을 제조한 후, 이의 초기 항균력을 테스트 하였다.Specifically, each coating composition was spray coated on a tempered glass substrate to form a 5㎛ thick coating film, heat cured at 120°C for 30 minutes, cooled to room temperature to prepare a specimen, and its initial antibacterial activity was tested. .
이때, 시험 균주로는 대장균(Escherichia Coli ATCC 25922)과 황색포도상구균(Staphylococcus aureus ATCC 6538)을 사용하였으며, 36℃ 배양기에서 상기 균을 각각 16시간 배양하여 배양액을 준비하였다. 준비된 시편에 각 시험 균주 배양액을 20,000배 희석하여 1ml씩 시편에 적하한 후 25℃에서 24시간 보존 후 꺼내고, 이를 멸균 처리된 한천배지에서 48시간 배양하고 습식 평판 배양법으로 조사하여 생균수를 측정하였다. 그리고 정균감소율(%)을 하기의 식에 따라 계산한 후, 그 결과를 하기 표 1에 나타내었다.At this time, Escherichia Coli ATCC 25922 and Staphylococcus aureus ATCC 6538 were used as test strains, and the culture medium was prepared by culturing each of the bacteria in an incubator at 36°C for 16 hours. The culture medium of each test strain was diluted 20,000 times and 1 ml of each test strain was added dropwise to the prepared specimen, stored at 25°C for 24 hours, taken out, cultured on sterilized agar medium for 48 hours, and examined by wet plate culture to measure the number of viable cells. . Then, the bacteriostatic reduction rate (%) was calculated according to the formula below, and the results are shown in Table 1 below.
정균감소율(%)=[(대조군의 24시간 후 균수-시편의 24시간 후 균수) / 대조군의 24시간 후 균수] × 100Bacteriostatic reduction rate (%) = [(Bacterial count after 24 hours in control group - Bacterial count after 24 hours in specimen) / Bacterial count after 24 hours in control group] × 100
또한, 시편의 항균 지속력은, 마모 테스트 후, 락스 침지 후, 내열 Cycle 후 항균력을 측정함으로써 판단하였는바, 구체적으로 마틴데일 마모 시험기를 사용하여 3M 스카치브라이트 제로스크래치 수세미를 마모자로 활용하여 6N 하중에서 5200회 마모 후 항균력을 측정(마모 테스트 후의 항균력)하였으며, 시판 락스와 물을 1:1 중량비로 혼합한 액에 시편을 30분간 완전 침지한 후, 증류수로 세척하고 항균력을 측정(락스 침지 후의 항균력)하였고, 시편을 80℃, 85% R.H.에서 3h -> 25℃, 50% R.H에서 1h ->40℃, 20% R.H.에서 3 hr -> 25℃, 50% R.H에서 1h -> 50℃ 95% R.H에서 7h ->25℃, 50% R.H에서 1h 방치하는 일련의 과정을 240시간 동안 실시한 후, 항균력을 측정(내열 Cycle 후의 항균력)하였다. 그리고 그 결과 역시 하기 표 1에 나타내었다.In addition, the antibacterial durability of the specimen was determined by measuring the antibacterial power after an abrasion test, immersion in bleach, and after a heat resistance cycle. Specifically, the antibacterial power was measured using a Martindale abrasion tester and a 3M Scotchbright Zero Scrub scrubber as an abraser under a 6N load. The antibacterial activity was measured after abrasion 5,200 times (antibacterial activity after abrasion test). The specimen was completely immersed in a mixture of commercially available bleach and water in a 1:1 weight ratio for 30 minutes, then washed with distilled water and the antibacterial activity was measured (antibacterial activity after immersion in bleach). ), and the specimen was heated at 80°C, 85% R.H. for 3 h -> 25°C, at 50% R.H. for 1 h -> 40°C, 20% R.H. for 3 hr -> at 25°C, 50% R.H. for 1 h -> 50°C 95%. After performing a series of processes of 7h -> 25°C at R.H. and 1h at 50% R.H. for 240 hours, the antibacterial activity was measured (antibacterial activity after heat resistance cycle). And the results are also shown in Table 1 below.
(정균감소율, %)antibacterial
(Bacteriostatic reduction rate, %)
항균성Early
antibacterial
상기 표 1에서와 같이, 본 발명에 의한 실시예 1은 초기 항균성이 우수함은 물론, 마모 테스트 후, 락스 침지 후, 내열 사이클 후 그 항균성이 유지되었으나, 비교예 1, 2는 초기 항균성은 우수하나, 마모 테스트 항균성이 현저히 감소하고, 락스 침지 후, 내열 사이클 후 항균성이 다소 감소함을 확인할 수 있었다.As shown in Table 1, Example 1 according to the present invention not only has excellent initial antibacterial property, but also maintains the antibacterial property after the wear test, after immersion in bleach, and after the heat resistance cycle. However, Comparative Examples 1 and 2 have excellent initial antibacterial property. , it was confirmed that the antibacterial activity in the wear test was significantly reduced, and that the antibacterial activity was slightly reduced after immersion in bleach and after a heat resistance cycle.
(시험예 2)(Test Example 2)
상기 실시예 1 내지 3, 비교예 3, 비교예 4에 대하여 도막 내 항균제 간 평균 거리, 도막 촉감 및 외관, 항균성을 테스트하고, 그 결과를 하기 표 2에 나타내었다. 이때, 상기 항균제 간 평균 거리는 도막 표면을 현미경으로 관찰하여 측정하였으며, 도 1은 실시예 1의 광학 현미경 사진이다.Examples 1 to 3, Comparative Example 3, and Comparative Example 4 were tested for the average distance between antibacterial agents in the coating film, feel and appearance of the coating film, and antibacterial property, and the results are shown in Table 2 below. At this time, the average distance between the antibacterial agents was measured by observing the surface of the coating film under a microscope, and Figure 1 is an optical microscope photo of Example 1.
(정균감소율, %)antibacterial
(Bacteriostatic reduction rate, %)
(> 99.9)> 5.7
(>99.9)
(> 99.9)> 5.5
(>99.9)
(> 99.9)> 5.6
(>99.9)
(> 99.9)> 3.8
(>99.9)
(> 98.5)> 1.8
(>98.5)
(> 99.9)> 5.6
(>99.9)
(> 99.9)> 5.3
(>99.9)
(> 99.9)> 4.9
(>99.9)
(> 99.9)> 3.3
(>99.9)
(> 95.4)> 1.3
(>95.4)
상기 표 2에서 확인할 수 있는 바와 같이, 본 발명의 실시예 1 내지 3은 양호한 수준의 촉감 및 외관을 보였으며, 항균성 역시 우수함을 확인할 수 있었다. 다만, 실시예 1은 다소 거친 표면을 보였으나, 실사용 제품에 적용 가능한 수준이었다.As can be seen in Table 2, Examples 1 to 3 of the present invention showed a good level of texture and appearance, and were also confirmed to have excellent antibacterial properties. However, Example 1 showed a somewhat rough surface, but was at a level applicable to actual products.
반면, 비교예 3은 촉감이 매우 거칠고, 외관이 좋지 못하여 실사용 제품에의 적용이 어려운 정도였으며, 비교예 4는 충분한 항균성이 발현되지 못하였다.On the other hand, Comparative Example 3 had a very rough feel and poor appearance, making it difficult to apply to actual products, and Comparative Example 4 did not exhibit sufficient antibacterial properties.
상기에서는 본 출원의 바람직한 실시예를 참조하여 설명하였지만, 해당 기술 분야의 숙련된 당업자는 하기의 특허 청구 범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 출원을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.Although the present application has been described above with reference to preferred embodiments, those skilled in the art may modify and change the present application in various ways without departing from the spirit and scope of the present invention as set forth in the claims below. You will understand that it is possible.
Claims (9)
유기폴리실라잔 30~60중량%, 무기폴리실라잔 5~10중량%, 경화촉매 10~20중량%, 무기 항균제 0.5~2.0중량%, 표면용 첨가제 0.1~2.0중량% 및 잔부의 용제를 포함하며,
상기 무기 항균제는 아연이온(Zn2+)을 유효성분으로 하는 유리계 항균제이고,
상기 무기 항균제의 평균 입도는 3~10㎛이며,
상기 표면용 첨가제는 실리콘계 계면활성제이고,
상기 경화촉매는 3-(트라이에톡시실릴)프로필아민(3-Aminopropyl triethoxysilane) 및 3-(트라이메톡시실릴)프로필아민(3-Aminopropyl trimethoxysilane) 중 1종 이상의 것임을 특징으로 하는 내구성이 개선된 항균 코팅 조성물.
Active ingredients include organic polysilazanes, inorganic polysilazanes, curing catalysts, inorganic antibacterial agents, surface additives, and solvents.
Contains 30 to 60% by weight of organic polysilazane, 5 to 10% by weight of inorganic polysilazane, 10 to 20% by weight of curing catalyst, 0.5 to 2.0% by weight of inorganic antibacterial agent, 0.1 to 2.0% by weight of surface additive, and the remaining solvent. And
The inorganic antibacterial agent is a glass-based antibacterial agent containing zinc ions (Zn 2+ ) as an active ingredient,
The average particle size of the inorganic antibacterial agent is 3 to 10㎛,
The surface additive is a silicone-based surfactant,
The curing catalyst is an antibacterial agent with improved durability, characterized in that it is one or more types of 3-(triethoxysilyl)propylamine (3-Aminopropyl triethoxysilane) and 3-(trimethoxysilyl)propylamine (3-Aminopropyl trimethoxysilane) Coating composition.
탄산화 발전회 0.1~2중량%를 더 포함하며,
상기 탄산화 발전회는 발전회에 물을 1:1~2중량비로 혼합하고, 이에 이산화탄소를 pH가 9~10이 될 때까지 주입한 후 여과 및 건조하고, 상기 건조된 건조물을 2~3부피배의 인산염 수용액에 20~30℃의 온도에서 30~40분간 침지한 후 건조하고 1~10㎛로 분쇄한 것을 특징으로 하는 내구성이 개선된 항균 코팅 조성물.
According to paragraph 1,
It further contains 0.1 to 2% by weight of carbonated power ash,
The carbonated power ash is mixed with water at a weight ratio of 1:1 to 2, carbon dioxide is injected into the ash until the pH is 9 to 10, filtered and dried, and the dried product is mixed by 2 to 3 volumes. An antibacterial coating composition with improved durability, characterized in that it is immersed in an aqueous phosphate solution at a temperature of 20-30°C for 30-40 minutes, dried, and ground to 1-10㎛.
상기 기재 상에 형성되며, 제1항 또는 제2항의 항균 코팅 조성물로 구성되는 도막;을 포함하고,
상기 도막 내 무기 항균제 간 평균 거리는 50~200㎛이며,
상기 도막의 두께는 1~10㎛이고,
상기 기재는 플라스틱, 금속, 목재, 유리, 인조대리석 및 석재 중 1종 이상의 것임을 특징으로 하는 적층체.write;
A coating film formed on the substrate and composed of the antibacterial coating composition of claim 1 or 2,
The average distance between inorganic antibacterial agents in the coating film is 50 to 200㎛,
The thickness of the coating film is 1 to 10㎛,
A laminate, wherein the substrate is one or more of plastic, metal, wood, glass, artificial marble, and stone.
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| KR20110044606A (en) * | 2009-10-23 | 2011-04-29 | 재원금속 주식회사 | Surface-treatment agent composition |
| JP2022008038A (en) * | 2020-05-25 | 2022-01-13 | ハドラスホールディングス株式会社 | Coating material and coating method |
| KR20220061884A (en) | 2020-11-06 | 2022-05-13 | (주)엘엑스하우시스 | Coating composition comprising photocatalyst and laminate using same |
| KR20220069239A (en) * | 2020-11-20 | 2022-05-27 | (주)엘엑스하우시스 | Coating method of artificial marble with excellent stain resistance and matte properties |
| JP2022098378A (en) * | 2020-12-21 | 2022-07-01 | 株式会社甑園 | SiOC FILM, LAMINATE STRUCTURE, AND ANTIBACTERIAL PRODUCT |
| KR20230000987A (en) | 2021-06-25 | 2023-01-03 | (주)엘엑스하우시스 | Composition comprising photocatalyst and polysilazane resin, laminate and method for manufacturing same |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20110044606A (en) * | 2009-10-23 | 2011-04-29 | 재원금속 주식회사 | Surface-treatment agent composition |
| JP2022008038A (en) * | 2020-05-25 | 2022-01-13 | ハドラスホールディングス株式会社 | Coating material and coating method |
| KR20220061884A (en) | 2020-11-06 | 2022-05-13 | (주)엘엑스하우시스 | Coating composition comprising photocatalyst and laminate using same |
| KR20220069239A (en) * | 2020-11-20 | 2022-05-27 | (주)엘엑스하우시스 | Coating method of artificial marble with excellent stain resistance and matte properties |
| JP2022098378A (en) * | 2020-12-21 | 2022-07-01 | 株式会社甑園 | SiOC FILM, LAMINATE STRUCTURE, AND ANTIBACTERIAL PRODUCT |
| KR20230000987A (en) | 2021-06-25 | 2023-01-03 | (주)엘엑스하우시스 | Composition comprising photocatalyst and polysilazane resin, laminate and method for manufacturing same |
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