KR100365390B1 - Antimicrobial water bottle - Google Patents

Antimicrobial water bottle Download PDF

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Publication number
KR100365390B1
KR100365390B1 KR1019950007338A KR19950007338A KR100365390B1 KR 100365390 B1 KR100365390 B1 KR 100365390B1 KR 1019950007338 A KR1019950007338 A KR 1019950007338A KR 19950007338 A KR19950007338 A KR 19950007338A KR 100365390 B1 KR100365390 B1 KR 100365390B1
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South Korea
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antimicrobial
silver
bucket
weight
zeolite
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KR1019950007338A
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Korean (ko)
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KR960034298A (en
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김준영
박동일
이수정
인주환
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주식회사 엘지화학
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/28Applications of food preservatives, fungicides, pesticides or animal repellants
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds

Abstract

PURPOSE: Provided is an antimicrobial water bottle preventing the propagation of bacteria and not being faded, which contains a silver-based inorganic antimicrobial agent containing nitrate ion(NO3-). CONSTITUTION: The antimicrobial water bottle comprises: 87-98.95wt% of a high density polyethylene resin having a melt index of 0.01-8.0g/10min(190deg.C/2.16kg) and a density of 0.945-0.965g/cm3; 0.05-3wt% of the silver-based inorganic antimicrobial agent containing the nitrate ion(NO3-), which is an antimicrobial zeolite containing the nitrate ion(NO3-) and substituting total or partial ion-exchangeable cations in the zeolite by at least one metal ion selected from the group consisting of silver, zinc, copper, calcium, magnesium, ammonium, and potassium; and 1-10wt% of TiO2.

Description

항균 물통Antibacterial bucket

본 발명은 항균기능을 갖는 물통에 관한 것으로서, 더욱 상세하게는 반 영구적인 항균력을 부여하여 세균의 번식을 억제함으로서 위생적으로 사용할 수 있는 항균 물통에 관한 것이다.The present invention relates to a bucket having an antimicrobial function, and more particularly, to an antibacterial bucket that can be used hygienically by imparting a semi-permanent antibacterial power to suppress the growth of bacteria.

종래에 사용되고 있는 일반 합성수지로 만든 물통의 경우 장시간 식수 보관시 세균 및 곰팡이의 번식이 용이하여 위생적으로 부적합하여 단기적으로 사용할 수 밖에 없는 문제점이 있으며 가습기 등에 사용되는 물통의 경우 생활 식수 보관용으로 사용하지는 않지만, 역시 세균 번식의 용이함으로 인해 많은 위생상의 문제점을 안고 있다.In the case of a bucket made of general synthetic resin used in the past, there is a problem in that it is easy to breed bacteria and molds for long periods of drinking water, so it is not hygienic and inadequate to be used for a short time. In the case of a bucket used for a humidifier, it is not used for storing drinking water. However, there are also many hygiene problems due to the ease of bacterial propagation.

이러한 문제점을 해결하기 위해 합성수지에 항균제를 배합하여 합성 수지를 제조하게 되는데, 이러한 항균제에는 유기계 및 무기계 두 종류가 있고 유기계 항균제는 표면으로의 이행에 의해 항균력을 나타내는데 이러한 이행에 의해 장기 지속성이 열등하게 되며 항균력을 주기위해 다량 사용시 독성의 문제점이 있으며, 무기계 항균제는 독성이 없으며 장기 지속성이 뛰어나나 유기, 무기 항균제 모두 변색을 일으키는 것이 문제점으로 지적되어 왔다.In order to solve this problem, synthetic resins are prepared by blending antimicrobial agents with synthetic resins. There are two kinds of antimicrobial agents, organic and inorganic, and organic antimicrobial agents exhibit antimicrobial activity by transitioning to the surface. In addition, there is a problem of toxicity when a large amount of antimicrobial activity is used. Inorganic antimicrobial agents have no toxicity and have excellent long-term persistence.

따라서 본 발명의 목적은 상기 문제점을 해결하여 세균의 번식을 억제함으로써 장시간 물을 보관하여도 위생상 별 문제가 없는 위생적인 물통을 제공하는데 있다.Accordingly, an object of the present invention is to provide a hygienic bucket that does not have a problem in hygiene even when water is stored for a long time by solving the above problems and suppressing the growth of bacteria.

이러한 본 발명의 목적에 따라 본 발명에서는 상기의 문제점을 개선한 항균 물통으로서 합성수지, 특히 고밀도 폴린에틸렌 수지에 항균력이 우수하고 변색이 되지 않는 무기계 항균제인 나이트레이트 이온(NO3 -)을 함유하는 은계 무기 항균제를 함유하는 항균 물통을 제공한다.According to the object of the present invention, in the present invention, the antimicrobial bucket which improves the above problems is a silver-containing nitrate ion (NO 3 ), which is an inorganic antimicrobial agent that is excellent in antibacterial activity and does not discolor in synthetic resins, especially high density polyethylene resin. It provides an antibacterial bucket containing an inorganic antimicrobial agent.

즉, 본 발명은That is, the present invention

(가) 190℃/2.16kg에서 용융지수가 0.01-8.0g/10분이고 밀도가 0.945-0.965g/㎤인 고밀도 폴리에틸렌 수지 87-98.95 중량%;(A) 87-98.95% by weight of a high density polyethylene resin having a melt index of 0.01-8.0 g / 10 min and a density of 0.945-0.965 g / cm 3 at 190 ° C./2.16 kg;

(나) 나이트레이트 이온(NO3 -)을 함유한 은계 무기 항균제 0.05-3 중량%; 및(B) 0.05-3% by weight of a silver inorganic inorganic antibacterial agent containing nitrate ions (NO 3 ); And

(다) TiO21-10 중량%로 구성됨을 특징으로 하는 항군 물통에 관한 것이다.(C) relates to an anti-water bottle, characterized in that consisting of 1-10% by weight of TiO 2 .

본 발명을 상세히 설명하면 다음과 같다.The present invention is described in detail as follows.

본 발명의 가)성분인 고밀도 폴리에틸렌 수지는 지글러(Ziegler)공법, 필립스(Phillips) 공법, 스탠다드(Standard) 공법으로 제조되는 주쇄에 부착된 단량체 단위의 측쇄가 거의 없는 선상 중합체로 190℃/2.16kg에서의 용융지수가 0.01-8.0 이고, 밀도가 0.945-0.965g/㎤의 값을 갖는 것을 사용할 수 있다. 그 사용량은 87-98.95 중량%가 바람직하며 90-98.5 중량%가 더욱 바람직하다.The high-density polyethylene resin of the a) component of the present invention is a linear polymer having almost no side chains of monomer units attached to the main chain manufactured by the Ziegler method, the Phillips method, or the Standard method, and is 190 ° C./2.16 kg. A melt index of 0.01-8.0 and a density of 0.945-0.965 g / cm 3 can be used. The amount is preferably 87-98.95% by weight, more preferably 90-98.5% by weight.

나) 성분인 나이트레이트 이온(NO3 -)을 함유하는 은계 무기 항균제는 본 발명에서 항균제로 사용되어 항균 물통의 항균성 및 변색방지 효과를 부여하는 것이다. 본 발명에서 사용된 무기 항균제는 양이온과 함께 나이트레이트 이온(NO3 -)을 함유함을 특징으로 하는 열적 및 광학적으로 안정하여 변색되지 않은 항균성 제올라이트이다.B) A silver-based inorganic antimicrobial agent containing nitrate ions (NO 3 ) is used as an antimicrobial agent in the present invention to impart antimicrobial and discoloration preventing effects of the antimicrobial bucket. The inorganic antimicrobial agent used in the present invention is a thermally and optically stable antimicrobial zeolite characterized by containing nitrate ions (NO 3 ) together with a cation.

종래에 사용된 항균성 제올라이트로는, 은을 활성탄, 알루미나 혹은 실리카등에 지지시켜 사용할 경우 은이온이 지지제로부터 빠르게 누출되어 그 항균력이 오래 지속되지 않는 문제점을 해결하기 위해 은과 구리 또는 아연을 동시에 치환시킨 항균성 제올라이트가 있으나 이러한 항균성 제올라이트는 150-300℃ 에 클러스터링(Clustering)되어 노란색 혹은 갈색으로 변하며, 이러한 변색은 또한 빛에 의해 서도 일어나 실제 용융된 상품의 가치를 현저하게 떨어뜨린다. 이러한 현상은 초기에 Ag3 +가 형성되어 클러스터가 노란색을 띄고, 더욱 진행됨에 따라 Ag6 +혹은 Ag9 n+(n은 1 또는 2 이다)이 형성되어 적색 또는 갈적색을 띄게 된다. 이러한 클리스터링은 은 이온들이 제올라이트 채널안에서 움직이는 것으로 인한 것이며, 소오다라이트 케이지(Sodalite cage)산소의 육각 고리를 통해서 은 이온들이 이동해 그 케이지 안에서 클러스터가 형성된다. 이온들의 움직임은 온도가 높을수록 용이하여 변속을 가속화한다. 본 발명에서는 이러한 문제점을 개선하여, 나이트레이트이온(NO3 -)을 항균성 제올라이트의 채널 안에 존재케하여 은 이온의 움직임을 방해하고 환원성 클러스터링을 막아 변색을 방지하고자 하였다. 이러한 나이트레이트 이온(NO3 -)을 함유한 열적 및 광학적으로 안정하여 변색되지 않는 은계 무기 항균제는 제올라이트 내의 이온교환 가능한 양이온의 전부 또는 일부가 은, 아연, 구리, 칼슘, 마그네슘, 암모늄 및 칼륨으로 구성되는 군으로 부터 선택된 한가지 이상의 금속 이온으로 치환되고 나이트레이트 이온을 함유한 항균성 제올라이트로서 0.05-3 중량% 의 양으로 사용하며, 바람직하게는 0.1-1.0 중량%를 사용한다.Conventionally used antimicrobial zeolites, when silver is supported on activated carbon, alumina, or silica, silver ions quickly leak from the support agent and replace silver, copper or zinc at the same time to solve the problem that the antimicrobial activity does not last long. These antimicrobial zeolites are clustered at 150-300 ° C., turning yellow or brown, and this discoloration is also caused by light, which significantly reduces the value of the actual molten product. This phenomenon is initially Ag 3 + is formed in the cluster is yellow, and as the progress is further Ag 6 + or Ag 9 n + (n is 1 or 2) is formed to become red or brown red. This clustering is due to the movement of silver ions in the zeolite channel, where silver ions move through a hexagonal ring of a sodalite cage, forming clusters within the cage. The movement of the ions is easier at higher temperatures to accelerate shifts. According to the present invention to improve this problem, the nitrate ion was to the cake in the presence of antimicrobial zeolite channels interfere with the movement of the ions and to prevent color fading preventing the clustering-reducing (NO 3). The thermally and optically stable silver-based inorganic antimicrobial agent containing these nitrate ions (NO 3 ) does not discolor all or part of the ion exchangeable cations in the zeolite with silver, zinc, copper, calcium, magnesium, ammonium and potassium. An antimicrobial zeolite containing nitrate ions substituted with one or more metal ions selected from the group consisting of is used in an amount of 0.05-3% by weight, preferably 0.1-1.0% by weight.

본 발명의 다)성분인 TiO2는 1-10 중량%의 양으로 사용한다. 본 발명은 상기 성분 이외에 항균제의 분산을 위한 활제, 완제품의 색상을 미려하게 하기 위한 무기계 안료, 그리고 컴파운딩시 열에 의한 분해를 방지하기 위 한 열안정제를 첨가할 수 있다.TiO 2 , a multicomponent component of the present invention, is used in an amount of 1-10% by weight. In the present invention, in addition to the above components, a lubricant for dispersing the antimicrobial agent, an inorganic pigment for the beautiful color of the finished product, and a thermal stabilizer for preventing decomposition by heat during compounding may be added.

본 발명의 최종 목적물인 항균 물통의 제조방법은 상기한 성분들의 혼합 조성물을 100-150℃의 온도에서 밴버리 믹서에서 용융혼련후 100-200℃ 의 압출온도에서 단축 압출기에서 압출시켜 제조한 다음 중공 성형기를 이용하여 일정한 형태의 물통을 제조한다.The final object of the present invention is a method for producing an antimicrobial bucket prepared by extruding the mixed composition of the above components in a banbury mixer at a temperature of 100-150 ℃ extruded in a single screw extruder at an extrusion temperature of 100-200 ℃ Using to prepare a bucket of a certain form.

이하 본 발명을 실시예에 의해 구체적으로 설명하나 본 발명의 범위가 이에 제한되는 것은 아니다.Hereinafter, the present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.

실시예 1Example 1

고밀도 폴리에틸렌(LUTENE-H, (주)LG 화학) 100 중량부, 나이트레이트 이온(NO3 -)함유 은계 무기 항균제 0.2 중량부, TiO23 중량부, 및 Iganox 1076(시바가이기사 제품) 0.1 중량부를 밴버리 믹서에서 용융 혼련 후 압출온도에서 단축 압출기에서 압출시켜 제조한 다음 프리스에서 190℃, 5분 동안 예열하여 2mm 두께의 쉬트를 제작하였으며 본 발명의 컴파운드를 이용하여 항균 물통을 제작한 후 물성을 측정하였다.100 parts by weight of high density polyethylene (LUTENE-H, LG Chemical Co., Ltd.), 0.2 parts by weight of a silver inorganic inorganic antibacterial agent containing nitrate ions (NO 3 ), 3 parts by weight of TiO 2 , and 0.1 parts by weight of Iganox 1076 (manufactured by Shivagai Co., Ltd.) After melt-kneading the parts in a Banbury mixer and extruded in a single screw extruder at the extrusion temperature, preheated for 190 minutes at a freeze for 5 minutes to produce a sheet of 2mm thickness and after producing an antibacterial bucket using the compound of the present invention Measured.

본 발명에서 항균성 시험은 컴파운드와 최종 목적물인 항균 물통으로 나누어 실시하였으며 항균측정 방법은 쉐이크 플라스크 방법(shake flask method)로서 0.1M 인산염 완충용액(phosphate buffer solution(배양액))을 팔콘튜브에 넣고 E. coli ATCC 10536(대장균)을 접종한 후 37℃ 배양기 중에서 18시간 동안 균을 증식시켰다. 증식 후 E. coli 의 수는 대략 3 × 10cfu/㎖이었으며 상기에서 배양한 균주의 갯수를 포토미터를 이용하여 1 × 10cfu/㎖로 맞춘 후 여기에 상기에서 제작한 쉬트를 넣고 오토클래이브에서 살균하였다(이때 사용되는 시편은 1cm × 1cm 크기에 두께가 2mm인 정사면체 30개이다). 그 후 시간대 별로(6, 24, 48 시간) 팔콘튜브에서 완충액을 100㎖씩 추출하여 균주의 갯수를 측정하는데 추출한 배양액을 적당량 탑아가(top agar)에 넣고 플레이트한 한천에 뿌려 고정시킨 다음 배양기에서 18시간 동안 키우면 콜로니가 육안으로 관찰되며 이의 갯수를 측정한다. 상기와 같이 측정한 항균성은 다음과 같다. 세균수는 골수에 희석배수를 곱하여 계산하였으며 억제율은 초기 농도에서 시간대별 농도를 뺀 다음 초기농도로 나누어 백분율로 표기하였다.In the present invention, the antimicrobial test was carried out by dividing the compound and the antimicrobial bucket of the final target. The antimicrobial measurement method was shake shake method (shake flask method) and put 0.1M phosphate buffer solution (culture solution) into the Falcon tube. After inoculating coli ATCC 10536 (E. coli), the bacteria were grown for 18 hours in a 37 ℃ incubator. After propagation, the number of E. coli was about 3 × 10 cfu / ㎖, and the number of strains cultured above was adjusted to 1 × 10 cfu / ㎖ by using a photometer, and the sheet prepared above was added and sterilized in an autoclave. (The specimens used were 30 tetrahedrons with a size of 1 cm x 1 cm and a thickness of 2 mm). Thereafter, 100 ml of buffer solution was extracted from the falcon tube at each time interval (6, 24, 48 hours) to measure the number of strains. The extracted culture solution was placed in an appropriate amount of top agar, sprinkled on plate agar, and fixed in the incubator. When grown for 18 hours, colonies are visually observed and their number is measured. Antimicrobial activity measured as described above is as follows. The bacterial count was calculated by multiplying the bone marrow by the dilution factor, and the inhibition rate was expressed as a percentage by subtracting the concentration at each time from the initial concentration and then dividing by the initial concentration.

[컴파운드][Compound]

[항균 물통][Antibacterial bucket]

[옥외 폭로 시험][Outdoor Exposure Test]

태양광선에 의한 색상 경시변화를 측정하기 위해 옥외 폭로시험을 실시하였다. 본 발명의 항균 물통을 30일동안 옥외 폭로시킨 후 백색도를 측정한 결과 색상변화는 일어나지 않았으며 측정치는 다음과 같다. 백색도 측정은 ASTM E 313에 의거하여 가드너사의 스픽트로 포토미터로 측정하였다.Outdoor exposure test was conducted to measure the change in color over time caused by sunlight. After the exposure of the antimicrobial bucket of the present invention for 30 days outdoors, the whiteness was measured, and the color change did not occur. Whiteness measurement was measured with a photometer with a Gardner company's pit according to ASTM E 313.

Claims (3)

(가) 190℃/2.16kg에서 용융지수가 0.01-8.0g/10분이고 밀도가 0.945-0.965g/㎤인 고밀도 폴리에틸렌 수지 87-98.95 중량%;(A) 87-98.95% by weight of a high density polyethylene resin having a melt index of 0.01-8.0 g / 10 min and a density of 0.945-0.965 g / cm 3 at 190 ° C./2.16 kg; (나) 나이트레이트 이온(NO3 -)을 함유한 은계 무기 항균제 0.05-3 중량%; 및(B) 0.05-3% by weight of a silver inorganic inorganic antibacterial agent containing nitrate ions (NO 3 ); And (다) TiO21-10 중량%로 구성됨을 특징으로 하는(C) TiO 2 It is characterized by consisting of 1-10% by weight 항균 물통.Antibacterial bucket. 제 1 항에 있어서,The method of claim 1, 상기 나이트레이트 이온을 함유한 은계 무기 항균제는 양이온과 함께 나이트레이트 이온을 함유한 항균성 제올라이트임을 특징으로 하는The silver-based inorganic antimicrobial agent containing nitrate ions is an antimicrobial zeolite containing nitrate ions together with a cation. 항균 물통.Antibacterial bucket. 제 1 항 또는 제 2 항에 있어서,The method according to claim 1 or 2, 상기 나이트레이트 이온을 함유한 은계 무기 항균제는 제올라이트내의 이온교환 가능한 양이온의 전부 또는 일부가 은, 아연, 구리, 칼슘, 마그네슘, 암모늄 및 칼륨으로 구성되는 군으로부터 선택된 한가지 이상의 금속 이온으로 치환되고 나이트레이트 이온을 함유한 항균성 제올라이트임을 특징으로 하는The silver-based inorganic antimicrobial agent containing nitrate ions is substituted with one or more metal ions selected from the group consisting of silver, zinc, copper, calcium, magnesium, ammonium and potassium, in which all or part of the ion exchangeable cations in the zeolite are nitrate Characterized by being an antimicrobial zeolite containing ions 항균 물통.Antibacterial bucket.
KR1019950007338A 1995-03-31 1995-03-31 Antimicrobial water bottle KR100365390B1 (en)

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KR100768601B1 (en) * 2006-11-07 2007-10-18 전근민 Method for manufacturing anti-microbial resolvability container
KR102046799B1 (en) * 2017-11-29 2019-12-02 주식회사 알앤에프케미칼 Biodegradable film for filter for sink drain with insect repellent effect and high tearing strength

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59133235A (en) * 1983-01-21 1984-07-31 Kanebo Ltd Zeolite particle-containing polymer and its production
KR910000401A (en) * 1989-06-28 1991-01-29 파네스 오드 Anti-skid chain tools and mounting means
KR910007590A (en) * 1989-10-23 1991-05-30 후루다 노리마사 Painting Dryer
KR940011355A (en) * 1992-11-09 1994-06-21 최근선 Antimicrobial Zeolite with Nitrate Ion (NO₃ ^-)
JPH07112771A (en) * 1993-10-15 1995-05-02 Heiwa Kagaku Kogyosho:Kk Antibacterial multilayer container
KR960003801A (en) * 1994-07-22 1996-02-23 고지마 아끼로 Carbonylation Catalyst System and Carbonylation Process

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59133235A (en) * 1983-01-21 1984-07-31 Kanebo Ltd Zeolite particle-containing polymer and its production
KR910000401A (en) * 1989-06-28 1991-01-29 파네스 오드 Anti-skid chain tools and mounting means
KR910007590A (en) * 1989-10-23 1991-05-30 후루다 노리마사 Painting Dryer
KR940011355A (en) * 1992-11-09 1994-06-21 최근선 Antimicrobial Zeolite with Nitrate Ion (NO₃ ^-)
JPH07112771A (en) * 1993-10-15 1995-05-02 Heiwa Kagaku Kogyosho:Kk Antibacterial multilayer container
KR960003801A (en) * 1994-07-22 1996-02-23 고지마 아끼로 Carbonylation Catalyst System and Carbonylation Process

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