WO2016010211A1 - Oxygen absorbing resin composition for stopper gasket - Google Patents

Oxygen absorbing resin composition for stopper gasket Download PDF

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Publication number
WO2016010211A1
WO2016010211A1 PCT/KR2014/012786 KR2014012786W WO2016010211A1 WO 2016010211 A1 WO2016010211 A1 WO 2016010211A1 KR 2014012786 W KR2014012786 W KR 2014012786W WO 2016010211 A1 WO2016010211 A1 WO 2016010211A1
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Prior art keywords
oxygen
resin composition
absorbent
weight
resin
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PCT/KR2014/012786
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French (fr)
Korean (ko)
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민동훈
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삼화화학공업주식회사
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Priority to JP2016534549A priority Critical patent/JP2016532753A/en
Priority to CN201480002896.5A priority patent/CN105593282A/en
Publication of WO2016010211A1 publication Critical patent/WO2016010211A1/en

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    • 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
    • C08K3/10—Metal 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the present invention relates to an oxygen-absorbing resin composition suitable for use in a bottle cap gasket, and more particularly, to oxygen absorbing in the head space of the bottle when the bottle cap gasket is manufactured with a high oxygen absorption rate.
  • the present invention relates to an oxygen-absorbing resin composition for a bottle cap gasket capable of preventing the deterioration of a product contained in a bottle by removing at a speed.
  • Alcohol, beverages, etc. are produced and distributed in containers such as glass bottles or plastic bottles.
  • containers such as glass bottles or plastic bottles.
  • oxygen remains in the head space between the contents and the lid, and the contents contained in the container may be altered by the remaining oxygen.
  • Patent Publication No. 10-2005-0119543 discloses a resin composition capable of absorbing oxygen and absorbing moisture.
  • the composition is composed of oxygen absorbers, ethylene vinyl alcohol copolymers (EVOH), polyvinyl alcohols (PVA), super absorbent polymers (SAP), poly ethylene oxide (PEO) and calcium carbonate (CaCO 3 ), which are transition metal salts in thermoplastic olefin resins. It is a mixture of moisture absorbents selected from.
  • Patent registration No. 10-0953352 (2010. 04. 09. registration) discloses an oxygen-absorbing resin composition, an oxygen-absorbing container cap and an oxygen-absorbing container cap using the same.
  • This patent uses an oxygen absorbent containing 20% or more of a particle size of 1000 ⁇ m or less in order to solve the problem that occurs when an oxygen absorbent having high oxygen absorbency but low compatibility with a base resin is included. The absorbent is dispersed and blended at a ratio of 20% or less with respect to the base resin.
  • the composition of this patent further comprises an absorbent material which is a fatty acid ester and has an HLB value of 4.3 or more and 10 or less.
  • Korean Patent Publication No. 194-0014098 published on July 16, 1994
  • Patent Publication No. 10-2007-0118283 published on December 14, 2007
  • Utility Model Registration No. 20-0421312 2006. 07
  • Registration discloses an oxygen absorbent container cap.
  • the contents can be prevented from being deteriorated by removing oxygen remaining in the head space between the contents and the lid in a container such as a glass bottle or a plastic bottle, but more completely preventing the contents deterioration.
  • a container such as a glass bottle or a plastic bottle
  • an object of the present invention is to prevent the deterioration of the product contained in the bottle by rapidly removing the oxygen present in the head space (head space) of the bottle when manufacturing the bottle cap gasket with a fast oxygen absorption rate
  • An oxygen absorbing resin composition in particular, an oxygen absorbing resin composition for a bottle cap gasket.
  • Oxygen absorbing resin composition according to the present invention for achieving the above object is, according to an aspect of the present invention, 60 to 98% by weight of a base resin of a thermoplastic resin; 0.1-20% by weight of a water absorbent resin; 1-20% by weight of an oxygen absorbent; And 0.1 to 5% by weight of blowing agent.
  • the oxygen absorbing resin composition may further comprise 0.1 to 20% by weight of a porous material.
  • the oxygen absorption resin composition of the present invention 60 to 98% by weight of the base resin of the thermoplastic resin; 0.1-20% by weight of a water absorbent resin; 1-20% by weight of an oxygen absorbent; And 0.1-20% by weight of porous material.
  • the said oxygen absorbent is a compound which has reducibility, and especially the said oxygen absorber is sodium sulfite or potassium sulfite.
  • the particle size of the oxygen absorbent is preferably 1 ⁇ 900 nm.
  • the moisture absorbent resin is preferably an ethylene vinyl alcohol copolymer (EVOH).
  • the porous material is silica.
  • the said base resin consists of a polyolefin resin and a rubber component, and the weight ratio of the said polyolefin resin and the said rubber component is 2: 1-1: 2.
  • the said rubber component is a mixture of alpha olefin rubber and styrene butadiene rubber, and the weight ratio of the said alpha olefin rubber and the styrene butadiene rubber is 2: 1-1: 2.
  • the present invention also provides an oxygen absorbing product produced by the oxygen absorbing resin composition described above.
  • the product may be a bottle cap provided with a gasket manufactured by the oxygen absorbing resin composition.
  • Oxygen-absorbing resin composition according to the present invention is a high rate of oxygen absorption by producing a bottle cap gasket with it can quickly remove the oxygen present in the head space of the bottle to prevent deterioration of the product contained in the bottle. Therefore, it can be usefully used to manufacture a bottle cap provided with a gasket.
  • FIG. 1 is a view schematically showing the detailed structure of the bottle cap gasket manufactured by the oxygen absorbing resin composition according to the prior art.
  • FIG. 2 is a view schematically showing the detailed structure of the bottle cap gasket manufactured by the oxygen absorbing resin composition according to the present invention.
  • oxygen absorbent 300 pore or porous material
  • the oxygen-absorbing resin composition of the present invention is 60 to 98% by weight of the base resin of the thermoplastic resin; 0.1-20% by weight of a water absorbent resin; 1-20% by weight of an oxygen absorbent; And 0.1 to 5% by weight of blowing agent.
  • the oxygen absorbing resin composition may further comprise 0.1 to 20% by weight of a porous material.
  • the oxygen-absorbing resin composition of the present invention is 60 to 98% by weight of the base resin of the thermoplastic resin; 0.1-20% by weight of a water absorbent resin; 1-20% by weight of an oxygen absorbent; And 0.1-20% by weight of porous material.
  • the oxygen absorbent is strongly oxidized when it encounters oxygen.
  • oxygen existing in the head space of the bottle may be removed to prevent deterioration of the product contained in the bottle.
  • FIG. 1 is a view schematically showing the detailed structure of the bottle cap gasket 10 manufactured by the oxygen absorbing resin composition according to the prior art.
  • the oxygen absorbent 200 is dispersed in a base resin such as a thermoplastic resin, as shown in FIG.
  • This base resin forms the substrate, ie the matrix 100, in the capping gasket 10.
  • the base resin does not have perfect oxygen barrier properties, but since it has some oxygen barrier properties, the oxidation reaction of the oxygen absorbent is somewhat hindered by the base resin. Therefore, in the bottle cap gasket having the structure in which the oxygen absorbent is dispersed in the base resin, the oxygen absorption performance is insufficient.
  • the prior art has mixed a water absorbent such as ethylene vinyl alcohol copolymer in addition to the oxygen absorbent into the base resin.
  • the water absorbent may be mixed with the base resin uniformly. That is, the water absorbent forms the same phase as the base resin.
  • the oxygen absorbent is only dispersed in the base resin to form a different phase.
  • the bottle cap gasket 10 has a structure in which the base resin and the water absorbent resin are uniformly mixed to form a matrix 100 and the oxygen absorbent 200 is uniformly dispersed therein. .
  • the oxygen absorbent 200 is mainly oxidized by a reaction indirectly made by the moisture absorbent than when the oxygen absorbent 200 is directly reacted with oxygen and oxidized.
  • This indirect oxidation reaction is first started by the absorption of moisture by the moisture absorbent.
  • water absorbed by the water absorbent may be referred to as water vapor rather than liquid, and water vapor present in the head space is absorbed by the water absorbent. This water absorption takes place preferentially at the surface of the gasket.
  • the water absorbed by the water absorbent on the surface of the gasket may be transferred or moved along a network formed by the water absorbent in a matrix formed by the base resin and the water absorbent resin together. The transferred water can meet with the oxygen absorbent.
  • the oxygen absorbent is then oxidized by water and the water is converted to hydrogen. Hydrogen generated from the water chemically reacts with oxygen present in the headspace to produce water again. Therefore, it can be seen that in this overall reaction, water only serves to catalyze the oxidation of the oxygen absorbent.
  • the indirect oxidation of the oxidizing absorber it is essential that the water meets the oxidizing absorber by the water absorption by the water absorbent and the movement of water through the water absorbent network, and if such a process is rapid, the oxygen absorption performance is improved. do.
  • the present invention has developed a factor for making such a process fast, which is to improve the oxidation rate of the oxidizing absorber by shortening the water transport path by the water absorbent network.
  • FIG. 2 is a view schematically showing the detailed structure of the bottle cap gasket manufactured by the oxygen absorbing resin composition according to the present invention.
  • the first method of shortening the water migration path by the water absorbent network is to further include a blowing agent in the coral absorbent resin composition of the present invention to form a bottle cap gasket prepared by the composition to form a structure having pores therein.
  • the bottle cap gasket 10 manufactured by the oxygen absorbing resin composition of the present invention has pores 300 formed in a matrix 100 formed of a base resin and a water absorbent resin. ), The oxygen absorbent 200 is uniformly dispersed.
  • the pores 300 are not closed but are open, so that they are in communication with the head space. Thus, the pores 300 are filled with oxygen and moisture.
  • the oxygen absorbent 200 and the pores 300 are somewhat exaggerated.
  • the pores 300 are formed substantially uniformly in the matrix 100. Therefore, not only the surface of the gasket 10 but also the inside thereof, the distance from the oxygen absorbent 200 to the water, that is, the path is shortened.
  • the water absorption by the water absorbent is active not only on the surface of the gasket 10, but also inside the gasket 10, and also the path to move to the oxygen absorbent 200 after the water is absorbed by the water absorbent.
  • the time is shorter, so that the time until the oxygen absorbent is oxidized by water is shortened. In other words, it means that the oxygen absorption rate by the oxygen absorbent is improved.
  • the pores 300 are formed by foaming in the matrix 100
  • the same effect can be obtained even by a structure in which a porous material such as silica is uniformly dispersed in a phase different from that of the matrix 100. have.
  • the porous material has many pores inside it. Therefore, the porous material, as well as the pores 300 formed by foaming in the bottle cap gasket manufactured by the oxygen absorbing resin composition of the present invention by containing oxygen and moisture therein as well as speed up the water absorption by the moisture absorbent. After the absorption of water, the path to the oxygen absorbent is shortened to improve the oxygen absorption rate.
  • the porous material together with the pores 300 by foaming, the synergistic effect of the two is exerted, and the oxygen absorption rate is further improved.
  • thermoplastic resin used as the base resin.
  • the thermoplastic resin used in the present invention is not particularly limited as long as it is a thermoplastic resin generally used for producing a bottle cap gasket. Polyolefin resins such as polyethylene and polypropylene are preferably used.
  • the base resin can also be formed only from the above-mentioned polyolefin resin, it is preferable to include a rubber component in addition to the polyolefin resin in order to improve the sealing force by elasticity as a gasket.
  • the weight ratio of the polyolefin resin and the rubber component in the base resin is preferably in the range of 2: 1 to 1: 2.
  • the rubber component generally known synthetic rubbers can be used alone, but it is more preferable to use a mixture of alphaolefin rubber and styrenebutadiene rubber. It is also possible to use a mixture of alphaolefin rubber and styrene-ethylene-butylene-styrene copolymer (SEBS) rubber.
  • SEBS styrene-ethylene-butylene-styrene copolymer
  • the weight ratio of the alphaolefin rubber to the styrenebutadiene rubber or the SEBS rubber in the rubber component is preferably 2: 1 to 1: 2.
  • alpha olefin rubber isobutene-isoprene rubber, butyl rubber, ethylene-propylene rubber such as EPM and EPDM and the like can be used.
  • the water absorbent resin may be a water absorbent generally known as long as it has a water absorbing function, but is preferably an ethylene vinyl alcohol copolymer (EVOH).
  • EVOH ethylene vinyl alcohol copolymer
  • Oxygen absorbers in the present invention can be used without particular limitation as long as the compound having a reducing property. Specifically, sodium sulfite, potassium sulfite, reducing iron powder, reducing tin powder, reducing zinc powder, ferrous oxide, iron carbide, silicon iron, carbonyl iron, iron hydroxide, and the like may be used. Among them, sodium sulfite or potassium sulfite can be preferably used.
  • Oxygen absorbers are present in a dispersed state, not mixed with the matrix resin 100 in a powder form. For uniform dispersion and improved oxygen absorption performance, the particle size of the oxygen absorbent is composed of nano-sizes such as 1 to 900 nm. It is desirable to.
  • the foaming agent in the present invention is not particularly limited as long as it is used for foaming the polymer resin.
  • One embodiment of the present invention provides an example in which citric acid and sodium bicarbonate are used as a blowing agent.
  • the porous material is not particularly limited as long as it includes a pore therein and has a powder.
  • the porous material is not mixed with the matrix resin in the composition of the present invention but merely dispersed.
  • Particularly preferred porous materials which can be used in the present invention are porous silica.
  • the component ratio of each component in this invention has the range as described. If the component ratio of any component is added in an amount less than the stated range, it becomes difficult to achieve the performance desired by the component. On the contrary, if the component ratio of a certain component is added in an amount greater than the stated range, the performance to be obtained by the component can be sufficiently achieved, but since the amount of other components becomes smaller, it is difficult to achieve the overall balance of physical properties.
  • Example 1 Parts by weight
  • Example 2 Parts by weight
  • Example 3 parts by weight
  • Hardness 99A 45.00 45.00 45.00
  • Alphaolefin rubber 0.870
  • Melting Point 58 ° C
  • Hardness 70A 22.85 22.45 22.40
  • hardness 70A, styrene content: 31% by weight 22.85 22.45 22.40
  • Oxygen Absorber Na 2 SO 3 ) 7.00 7.00 7.00 7.00 7.00
  • Antioxidant 1010 four 0.10 0.10 0.10 blowing agent citric acid + sodium bicarbonate 0.20 0.20 Porous silica Average particle size: 2 micrometers 1.00 1.00
  • Oxygen uptake was measured for the products of the above examples.
  • a specimen prepared according to the above-described examples was prepared. Specimens were prepared by thermally pressing a certain amount of sample to a thickness of 0.4 mm or less. Specifically, 600 mg of pellet type sample to measure the oxygen absorption rate was measured in the specimen maker, and heated at 180 ° C. for 15 minutes to prepare a sheet of 0.4 mm or less using a pressure press.
  • a 20 ml glass bottle (a Bayer bottle for injection liquid) was prepared.
  • a stopper for injection an inner stopper made of butyl rubber and an outer cover made of aluminum capable of sealing the container were prepared.
  • the glass bottle was a standard product with a bottle diameter of 20 mm.
  • a crimper for a diameter of 20 mm was prepared as a sealing mechanism for sealing an aluminum outer lid to a glass bottle.
  • Oxygen-absorbing liner specimens were placed in a container of water. At this time, the specimen was fixed to the inner surface of the inner container stopper so as not to contact with water. In the fixing method, the pin and the fastener of the butyl rubber material were fixed.
  • the aluminum outer cap was completely sealed using a crimper.
  • the sealed container was pretreated for a period of time at 50 °C constant temperature conditions.
  • the known product specimens are the same as those of Examples 1 to 3, but do not include a blowing agent and porous silica.
  • Oxygen absorbance was calculated by measuring the oxygen content remaining in the glass bottle after a certain time for the treated specimens.
  • the oxygen concentration in the vessel treated as above was measured using gas chromatography (GC).
  • GC measurement conditions were as follows.
  • the oxygen absorption rate was calculated by the following equation by measuring the difference between the amount of oxygen in the blank vessel (glass bottle without specimen) and the amount of oxygen in the vessel into which the specimen was placed.
  • Oxygen Absorption Rate (A-B) x 100 / A
  • A is the amount of oxygen in the blank vessel and B is the amount of oxygen in the specimen injection vessel.
  • Example product according to the present invention can absorb oxygen at a faster rate than the known product.
  • Example products of the present invention it was confirmed that the Example 3 product having pores by being foamed by a blowing agent and also including porous silica showed the fastest oxygen absorption rate. This is a result of overlapping the effect by the foamed pores and the effect by the porous silica.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Closures For Containers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

Disclosed is an oxygen absorbing resin composition, containing: 60-98 wt% of a base resin formed of a thermoplastic resin; 0.1-20 wt% of a moisture absorbent resin; 1-20 wt% of an oxygen absorbent; and 0.1-5 wt% of a foaming agent. The oxygen absorbing resin composition according to the present invention has a fast oxygen absorption rate, and thus, when a stopper gasket is manufactured using the oxygen absorbing resin composition, the stopper gasket removes the oxygen present in a headspace of a bottle at a fast speed, thereby preventing the degradation of products put in the bottle. Accordingly, the oxygen absorbing resin composition can be favorably used to manufacture a stopper with a gasket.

Description

병마개 가스켓용 산소흡수 수지 조성물Oxygen Absorption Resin Composition for Bottle Cap Gasket
본 발명은 병마개 가스켓용으로 사용하기에 적합한 산소흡수 수지 조성물에 관한 것으로서, 더욱 상세하게는 산소흡수 속도가 빨라 그것으로 병마개 가스켓을 제조하였을 때 병의 헤드 스페이스(head space)에 존재하는 산소를 빠른 속도로 제거함으로써 병에 내장된 제품의 변질을 방지할 수 있는 병마개 가스켓용 산소흡수 수지 조성물에 관한 것이다. The present invention relates to an oxygen-absorbing resin composition suitable for use in a bottle cap gasket, and more particularly, to oxygen absorbing in the head space of the bottle when the bottle cap gasket is manufactured with a high oxygen absorption rate. The present invention relates to an oxygen-absorbing resin composition for a bottle cap gasket capable of preventing the deterioration of a product contained in a bottle by removing at a speed.
술, 음료 등은 유리병 또는 플라스틱 병과 같은 용기에 담겨 생산 및 유통되고 있다. 이러한 용기에서 내용물과 뚜껑 사이의 헤드 스페이스(head space)에는 산소가 잔존하게 되는데, 이렇게 잔존하는 산소에 의하여 용기에 담긴 내용물이 변질될 수 있다. Alcohol, beverages, etc. are produced and distributed in containers such as glass bottles or plastic bottles. In such a container, oxygen remains in the head space between the contents and the lid, and the contents contained in the container may be altered by the remaining oxygen.
특허공개 제10-2005-0119543호(2005. 12. 21. 공개)는 산소 흡수 및 수분 흡수가 가능한 수지 조성물을 개시한다. 이 조성물은 열가소성 올레핀 수지에 전이금속염으로 되는 산소흡수제, 에틸렌 비닐 알콜 공중합체(EVOH), 폴리비닐 알콜(PVA), SAP(Super Absorbent Polymer), PEO(Poly Ethylene Oxide) 및 탄산칼슘(CaCO3) 중에서 선택되는 수분흡수제를 혼합한 것이다. Patent Publication No. 10-2005-0119543 (published on Dec. 21, 2005) discloses a resin composition capable of absorbing oxygen and absorbing moisture. The composition is composed of oxygen absorbers, ethylene vinyl alcohol copolymers (EVOH), polyvinyl alcohols (PVA), super absorbent polymers (SAP), poly ethylene oxide (PEO) and calcium carbonate (CaCO 3 ), which are transition metal salts in thermoplastic olefin resins. It is a mixture of moisture absorbents selected from.
특허등록 제10-0953352호(2010. 04. 09. 등록)는 산소흡수성 수지 조성물 및 이것을 사용한 산소흡수성 용기캡 및 산소흡수성 용기마개부를 개시한다. 이 특허는 산소흡수성은 높지만 베이스 수지와의 상용성이 낮은 산소흡수제를 포함하는 경우 발생하는 문제점을 해결하기 위하여 산소흡수제로는 1000㎛ 이하의 입도분을 20% 이상 포함하는 것을 사용하고, 그러한 산소흡수제를 베이스 수지에 대하여 20% 이하의 비율로 분산 배합하는 것이다. 또한 이 특허의 조성물은 지방산 에스테르로 되고 HLB 값이 4.3 이상 10 이하인 흡수성 재료를 더 포함한다. Patent registration No. 10-0953352 (2010. 04. 09. registration) discloses an oxygen-absorbing resin composition, an oxygen-absorbing container cap and an oxygen-absorbing container cap using the same. This patent uses an oxygen absorbent containing 20% or more of a particle size of 1000 μm or less in order to solve the problem that occurs when an oxygen absorbent having high oxygen absorbency but low compatibility with a base resin is included. The absorbent is dispersed and blended at a ratio of 20% or less with respect to the base resin. In addition, the composition of this patent further comprises an absorbent material which is a fatty acid ester and has an HLB value of 4.3 or more and 10 or less.
이외에도, 특허공개 제1994-0014098호(1994. 07. 16. 공개), 특허공개 제10-2007-0118283호(2007. 12. 14. 공개) 및 실용신안등록 제20-0421312호(2006. 07. 05. 등록)에 산소흡수성 용기캡이 개시되어 있다. In addition, Korean Patent Publication No. 194-0014098 (published on July 16, 1994), Patent Publication No. 10-2007-0118283 (published on December 14, 2007) and Utility Model Registration No. 20-0421312 (2006. 07) 05. Registration) discloses an oxygen absorbent container cap.
상기한 종래기술들에 의하면, 유리병 또는 플라스틱 병과 같은 용기 내에서 내용물과 뚜껑 사이에 있는 헤드 스페이스에 잔존하는 산소를 제거함으로써 내용물이 변질되는 것을 방지할 수 있지만, 내용물 변질을 더욱 완벽하게 방지하기 위해서는 산소흡수성능에 대한 개선이 요구된다. According to the above-mentioned prior arts, the contents can be prevented from being deteriorated by removing oxygen remaining in the head space between the contents and the lid in a container such as a glass bottle or a plastic bottle, but more completely preventing the contents deterioration. In order to improve the oxygen absorption performance is required.
이에, 본 발명의 목적은 산소흡수 속도가 빨라 그것으로 병마개 가스켓을 제조하였을 때 병의 헤드 스페이스(head space)에 존재하는 산소를 빠른 속도로 제거함으로써 병에 내장된 제품의 변질을 방지할 수 있는 산소흡수 수지 조성물, 특히 병마개 가스켓용 산소흡수 수지 조성물을 제공하는 것이다. Accordingly, an object of the present invention is to prevent the deterioration of the product contained in the bottle by rapidly removing the oxygen present in the head space (head space) of the bottle when manufacturing the bottle cap gasket with a fast oxygen absorption rate An oxygen absorbing resin composition, in particular, an oxygen absorbing resin composition for a bottle cap gasket.
또한 본 발명의 목적은 그러한 조성물에 의하여 제조되는 산소흡수 제품, 특히 그러한 조성물에 의하여 제조되는 가스켓이 마련된 병마개를 제공하는 것이다. It is also an object of the present invention to provide an oxygen absorbing product made by such a composition, in particular a bottle cap provided with a gasket made by such a composition.
상기한 목적을 달성하기 위한 본 발명에 따른 산소흡수 수지 조성물은 본 발명의 한 양태에 따르면, 열가소성 수지로 된 베이스 수지 60~98 중량%; 수분흡수제 수지 0.1~20 중량%; 산소흡수제 1~20 중량%; 및 발포제 0.1~5 중량%를 포함한다. Oxygen absorbing resin composition according to the present invention for achieving the above object is, according to an aspect of the present invention, 60 to 98% by weight of a base resin of a thermoplastic resin; 0.1-20% by weight of a water absorbent resin; 1-20% by weight of an oxygen absorbent; And 0.1 to 5% by weight of blowing agent.
이러한 산소흡수 수지 조성물은 다공성 물질 0.1~20 중량%를 더 포함할 수 있다. The oxygen absorbing resin composition may further comprise 0.1 to 20% by weight of a porous material.
또한 본 발명의 산소흡수 수지 조성물은 본 발명의 다른 양태에 따르면, 열가소성 수지로 된 베이스 수지 60~98 중량%; 수분흡수제 수지 0.1~20 중량%; 산소흡수제 1~20 중량%; 및 다공성 물질 0.1~20 중량%를 포함한다. In addition, the oxygen absorption resin composition of the present invention, according to another embodiment of the present invention, 60 to 98% by weight of the base resin of the thermoplastic resin; 0.1-20% by weight of a water absorbent resin; 1-20% by weight of an oxygen absorbent; And 0.1-20% by weight of porous material.
상기 산소흡수제는 환원성을 갖는 화합물이고, 특히 상기 산소흡수제는 아황산나트륨 또는 아황산칼륨인 것이 바람직하다.It is preferable that the said oxygen absorbent is a compound which has reducibility, and especially the said oxygen absorber is sodium sulfite or potassium sulfite.
상기 산소흡수제의 입자크기는 1~900 nm인 것이 바람직하다.The particle size of the oxygen absorbent is preferably 1 ~ 900 nm.
상기 수분흡수제 수지는 에틸렌 비닐 알콜 공중합체(Ethylene Vinyl Alcohol Copolymer; EVOH)인 것이 바람직하다.The moisture absorbent resin is preferably an ethylene vinyl alcohol copolymer (EVOH).
상기 다공성 물질은 실리카인 것이 바람직하다.Preferably, the porous material is silica.
상기 베이스 수지는 폴리올레핀 수지와 고무 성분으로 이루어지고, 상기 폴리올레핀 수지와 상기 고무 성분의 중량비는 2:1~1:2인 것이 바람직하다.It is preferable that the said base resin consists of a polyolefin resin and a rubber component, and the weight ratio of the said polyolefin resin and the said rubber component is 2: 1-1: 2.
상기 고무 성분은 알파올레핀 고무와 스티렌부타디엔 고무의 혼합물이고, 상기 알파올레핀 고무와 상기 스테렌부타디엔 고무의 중량비는 2:1~1:2인 것이 바람직하다.It is preferable that the said rubber component is a mixture of alpha olefin rubber and styrene butadiene rubber, and the weight ratio of the said alpha olefin rubber and the styrene butadiene rubber is 2: 1-1: 2.
본 발명은 또한 상기한 산소흡수 수지 조성물에 의하여 제조되는 산소흡수 제품을 제공한다. 상기 제품은 특히 상기 산소흡수 수지 조성물에 의하여 제조되는 가스켓이 마련된 병마개일 수 있다. The present invention also provides an oxygen absorbing product produced by the oxygen absorbing resin composition described above. In particular, the product may be a bottle cap provided with a gasket manufactured by the oxygen absorbing resin composition.
본 발명에 따른 산소흡수 수지 조성물은 산소흡수 속도가 빨라 그것으로 병마개 가스켓을 제조하면 병의 헤드 스페이스에 존재하는 산소를 빠른 속도로 제거하여 병에 내장된 제품의 변질을 방지할 수 있다. 따라서, 가스켓이 마련된 병마개를 제조하는데 유용하게 사용될 수 있다. Oxygen-absorbing resin composition according to the present invention is a high rate of oxygen absorption by producing a bottle cap gasket with it can quickly remove the oxygen present in the head space of the bottle to prevent deterioration of the product contained in the bottle. Therefore, it can be usefully used to manufacture a bottle cap provided with a gasket.
도 1은 종래기술에 따른 산소흡수 수지 조성물에 의하여 제조되는 병마개 가스켓의 세부구조를 모식적으로 도시한 도면이다.1 is a view schematically showing the detailed structure of the bottle cap gasket manufactured by the oxygen absorbing resin composition according to the prior art.
도 2는 본 발명에 따른 산소흡수 수지 조성물에 의하여 제조되는 병마개 가스켓의 세부구조를 모식적으로 도시한 도면이다. 2 is a view schematically showing the detailed structure of the bottle cap gasket manufactured by the oxygen absorbing resin composition according to the present invention.
* 도면 중 주요 부호에 대한 설명 * Description of the main symbols in the drawings
10: 가스켓 100: 매트릭스10: gasket 100: matrix
200: 산소흡수제 300: 기공 또는 다공성 물질200: oxygen absorbent 300: pore or porous material
이하, 본 발명을 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
한 양태에 따르면, 본 발명의 산소흡수 수지 조성물은 열가소성 수지로 된 베이스 수지 60~98 중량%; 수분흡수제 수지 0.1~20 중량%; 산소흡수제 1~20 중량%; 및 발포제 0.1~5 중량%를 포함한다. 상기 산소흡수 수지 조성물은 다공성 물질 0.1~20 중량%를 더 포함할 수 있다.In one embodiment, the oxygen-absorbing resin composition of the present invention is 60 to 98% by weight of the base resin of the thermoplastic resin; 0.1-20% by weight of a water absorbent resin; 1-20% by weight of an oxygen absorbent; And 0.1 to 5% by weight of blowing agent. The oxygen absorbing resin composition may further comprise 0.1 to 20% by weight of a porous material.
다른 양태에 따르면, 본 발명의 산소흡수 수지 조성물은 열가소성 수지로 된 베이스 수지 60~98 중량%; 수분흡수제 수지 0.1~20 중량%; 산소흡수제 1~20 중량%; 및 다공성 물질 0.1~20 중량%를 포함한다. According to another aspect, the oxygen-absorbing resin composition of the present invention is 60 to 98% by weight of the base resin of the thermoplastic resin; 0.1-20% by weight of a water absorbent resin; 1-20% by weight of an oxygen absorbent; And 0.1-20% by weight of porous material.
본 발명의 산소흡수 수지 조성물에서 산소흡수제는 산화되려는 성질이 강하여 산소를 만나면 산화된다. 그럼으로써 본 발명의 산소흡수 수지 조성물로 병마개에 부착되는 가스켓을 제조하면, 병의 헤드 스페이스에 존재하는 산소를 제거하여 병에 내장된 제품의 변질을 막을 수 있게 된다. In the oxygen absorbing resin composition of the present invention, the oxygen absorbent is strongly oxidized when it encounters oxygen. As a result, when the gasket attached to the bottle cap is manufactured by the oxygen absorption resin composition of the present invention, oxygen existing in the head space of the bottle may be removed to prevent deterioration of the product contained in the bottle.
도 1은 종래기술에 따른 산소흡수 수지 조성물에 의하여 제조되는 병마개 가스켓(10)의 세부구조를 모식적으로 도시한 도면이다. 그런데, 산소흡수제(200)는 도 1에 도시된 바와 같이, 열가소성 수지와 같은 베이스 수지에 분산되어 있다. 이러한 베이스 수지는 병마개 가스켓(10)에서 기재, 즉 매트릭스(100)를 형성한다. 1 is a view schematically showing the detailed structure of the bottle cap gasket 10 manufactured by the oxygen absorbing resin composition according to the prior art. By the way, the oxygen absorbent 200 is dispersed in a base resin such as a thermoplastic resin, as shown in FIG. This base resin forms the substrate, ie the matrix 100, in the capping gasket 10.
베이스 수지는 완벽한 산소차단성을 가지지는 않지만, 어느 정도의 산소차단성을 가지기 때문에 산소흡수제의 산화반응은 베이스 수지에 의하여 어느 정도 방해를 받게 된다. 따라서, 베이스 수지에 산소흡수제가 분산된 구조의 병마개 가스켓에서는 산소흡수성능이 미흡하게 된다. The base resin does not have perfect oxygen barrier properties, but since it has some oxygen barrier properties, the oxidation reaction of the oxygen absorbent is somewhat hindered by the base resin. Therefore, in the bottle cap gasket having the structure in which the oxygen absorbent is dispersed in the base resin, the oxygen absorption performance is insufficient.
이러한 구조적 문제를 개선하기 위하여 종래기술은 산소흡수제에 더하여 에틸렌 비닐 알콜 공중합체와 같은 수분흡수제를 베이스 수지에 혼합시켰다. 여기에서 수분흡수제는 베이스 수지와 균일하게 혼합될 수 있다. 즉, 수분흡수제는 베이스 수지와 동일한 상을 이루게 된다. 반면에 산소흡수제는 베이스 수지에 분산될 뿐이어서 서로 다른 상을 이루게 된다. 이러한 구조의 병마개 가스켓(10)은 도 1에 도시된 바와 같이 베이스 수지와 수분흡수제 수지가 균일하게 혼합되어 매트릭스(100)를 형성하고 그것 내에 산소흡수제(200)가 균일하게 분산되어 있는 구조를 가진다. In order to improve this structural problem, the prior art has mixed a water absorbent such as ethylene vinyl alcohol copolymer in addition to the oxygen absorbent into the base resin. Here, the water absorbent may be mixed with the base resin uniformly. That is, the water absorbent forms the same phase as the base resin. On the other hand, the oxygen absorbent is only dispersed in the base resin to form a different phase. As shown in FIG. 1, the bottle cap gasket 10 has a structure in which the base resin and the water absorbent resin are uniformly mixed to form a matrix 100 and the oxygen absorbent 200 is uniformly dispersed therein. .
이러한 구조의 가스켓(10)에서는 산소흡수제(200)가 산소와 직접적으로 반응하여 산화되는 경우보다 수분흡수제에 의한 간접적으로 이루어지는 반응에 의하여 주로 산화된다. 이러한 간접적인 산화반응은 먼저 수분흡수제에 의한 수분의 흡수에 의하여 시작된다. 여기에서, 수분흡수제에 의하여 흡수되는 수분은 액체라기보다는 수증기라고 할 수 있으며, 헤드 스페이스에 존재하는 수증기가 수분흡수제에 의하여 흡수되는 것이다. 이러한 수분흡수는 가스켓의 표면에서 우선적으로 이루어진다. 다음으로, 가스켓의 표면에서 수분흡수제에 의하여 흡수된 수분은 베이스 수지와 수분흡수제 수지가 함께 형성하는 매트릭스에서 수분흡수제에 의하여 형성되는 망(network)에 따라 전달되거나 이동될 수 있다. 이렇게 이동된 수분은 산소흡수제와 만날 수 있게 된다. 그러면 산소흡수제는 수분에 의하여 산화되고 수분은 수소로 변하게 된다. 수분으로부터 생성된 수소는 헤드 스페이스에 존재하는 산소와 화학반응을 하여 다시 수분을 생성하게 된다. 따라서, 이러한 전체적인 반응에서 수분은 산소흡수제의 산화를 촉매하는 역할을 할 뿐임을 알 수 있다. In the gasket 10 having such a structure, the oxygen absorbent 200 is mainly oxidized by a reaction indirectly made by the moisture absorbent than when the oxygen absorbent 200 is directly reacted with oxygen and oxidized. This indirect oxidation reaction is first started by the absorption of moisture by the moisture absorbent. Here, water absorbed by the water absorbent may be referred to as water vapor rather than liquid, and water vapor present in the head space is absorbed by the water absorbent. This water absorption takes place preferentially at the surface of the gasket. Next, the water absorbed by the water absorbent on the surface of the gasket may be transferred or moved along a network formed by the water absorbent in a matrix formed by the base resin and the water absorbent resin together. The transferred water can meet with the oxygen absorbent. The oxygen absorbent is then oxidized by water and the water is converted to hydrogen. Hydrogen generated from the water chemically reacts with oxygen present in the headspace to produce water again. Therefore, it can be seen that in this overall reaction, water only serves to catalyze the oxidation of the oxygen absorbent.
이와 같은 산화흡수제의 간접적인 산화방식을 살펴보면, 수분흡수제에 의한 수분 흡수와 수분흡수제 망을 통한 수분 이동에 의하여 수분이 산화흡수제와 만나는 것이 필수적 사항이며, 그러한 과정이 빠르게 이루어진다면 산소흡수성능이 향상된다. Looking at the indirect oxidation of the oxidizing absorber, it is essential that the water meets the oxidizing absorber by the water absorption by the water absorbent and the movement of water through the water absorbent network, and if such a process is rapid, the oxygen absorption performance is improved. do.
본 발명은 그러한 과정이 빠르게 이루어지게 하는 요인을 개발하였는데, 그것은 수분흡수제 망에 의한 수분 이동 경로를 짧게 함으로써 산화흡수제의 산화속도를 향상시키는 것이다. The present invention has developed a factor for making such a process fast, which is to improve the oxidation rate of the oxidizing absorber by shortening the water transport path by the water absorbent network.
도 2는 본 발명에 따른 산소흡수 수지 조성물에 의하여 제조되는 병마개 가스켓의 세부구조를 모식적으로 도시한 도면이다.2 is a view schematically showing the detailed structure of the bottle cap gasket manufactured by the oxygen absorbing resin composition according to the present invention.
수분흡수제 망에 의한 수분 이동 경로를 짧게 하는 첫번째 방법은 본 발명의 산호흡수 수지 조성물에 발포제를 더욱 포함시킴으로써 그 조성물에 의하여 제조되는 병마개 가스켓이 발포되어 그 내부에 기공을 가지는 구조로 형성하는 것이다. 도 2에 도시된 바와 같이, 본 발명의 산소흡수 수지 조성물에 의하여 제조되는 병마개 가스켓(10)은 베이스 수지와 수분흡수제 수지로 이루어지는 매트릭스(100)에 기공(300)이 형성되어 있고, 매트릭스(100)에는 산소흡수제(200)가 균일하게 분산되어 있다. 이러한 구조의 병마개 가스켓(10)에서 기공(300)은 폐쇄된 것이 아니라 오픈된 것이기 때문에 외부, 구체적인 예로서 헤드 스페이스와 소통되는 것이다. 그래서 그러한 기공(300)에는 산소 및 수분이 채워져 있다. The first method of shortening the water migration path by the water absorbent network is to further include a blowing agent in the coral absorbent resin composition of the present invention to form a bottle cap gasket prepared by the composition to form a structure having pores therein. As shown in FIG. 2, the bottle cap gasket 10 manufactured by the oxygen absorbing resin composition of the present invention has pores 300 formed in a matrix 100 formed of a base resin and a water absorbent resin. ), The oxygen absorbent 200 is uniformly dispersed. In the bottle cap gasket 10 of this structure, the pores 300 are not closed but are open, so that they are in communication with the head space. Thus, the pores 300 are filled with oxygen and moisture.
도 2에는 산소흡수제(200) 및 기공(300)이 다소 과장되게 표현되어 있는데, 기공(300)은 매트릭스(100)에서 대체로 균일하게 형성되어 있다. 따라서, 가스켓(10)의 표면뿐만 아니라 내부에서도 산소흡수제(200)에서 수분까지의 거리 즉, 경로는 짧아지게 된다. 이것은 수분흡수제에 의한 수분 흡수가 가스켓(10)의 표면에서뿐만 아니라 가스켓(10)의 내부에서도 활발하게 일어나는 것을 의미하고, 또한 수분흡수제에 의하여 수분이 흡수된 후 산소흡수제(200)까지 이동하여야 할 경로가 짧아진다는 것을 의미하고, 그래서 수분에 의하여 산소흡수제가 산화하기까지 시간이 짧아진다는 것을 의미한다. 다시 말하면, 산소흡수제에 의한 산소흡수 속도가 향상된다는 것을 의미한다. In FIG. 2, the oxygen absorbent 200 and the pores 300 are somewhat exaggerated. The pores 300 are formed substantially uniformly in the matrix 100. Therefore, not only the surface of the gasket 10 but also the inside thereof, the distance from the oxygen absorbent 200 to the water, that is, the path is shortened. This means that the water absorption by the water absorbent is active not only on the surface of the gasket 10, but also inside the gasket 10, and also the path to move to the oxygen absorbent 200 after the water is absorbed by the water absorbent. Means that the time is shorter, so that the time until the oxygen absorbent is oxidized by water is shortened. In other words, it means that the oxygen absorption rate by the oxygen absorbent is improved.
한편, 상기에서는 매트릭스(100) 내부에 발포에 의한 기공(300)이 형성된 예를 설명하였지만, 실리카와 같은 다공성 물질이 매트릭스(100)와는 다른 상으로 균일하게 분산된 구조에 의해서도 동일한 효과를 얻을 수 있다. 다공성 물질은 그것 내부에 많은 기공을 가진다. 따라서, 다공성 물질은 본 발명의 산소흡수 수지 조성물에 의하여 제조되는 병마개용 가스켓에서 발포에 의하여 형성된 기공(300)과 마찬가지로 산소 및 수분을 그것 내부에 함유함으로써 수분흡수제에 의한 수분 흡수를 빠르게 할 뿐만 아니라 수분 흡수 후에 산소흡수제까지의 이동경로를 짧게 하여 산소흡수속도를 향상시키는 것이다. On the other hand, while the above described an example in which the pores 300 are formed by foaming in the matrix 100, the same effect can be obtained even by a structure in which a porous material such as silica is uniformly dispersed in a phase different from that of the matrix 100. have. The porous material has many pores inside it. Therefore, the porous material, as well as the pores 300 formed by foaming in the bottle cap gasket manufactured by the oxygen absorbing resin composition of the present invention by containing oxygen and moisture therein as well as speed up the water absorption by the moisture absorbent. After the absorption of water, the path to the oxygen absorbent is shortened to improve the oxygen absorption rate.
본 발명에서 발포에 의한 기공(300)과 함께 다공성 물질을 포함하면 그것들 둘의 시너지 효과가 발휘되어 산소흡수속도가 더욱 향상된다. In the present invention, if the porous material together with the pores 300 by foaming, the synergistic effect of the two is exerted, and the oxygen absorption rate is further improved.
본 발명의 산소흡수 수지 조성물이 이러한 작용을 하기 위하여, 베이스 수지로는 열가소성 수지가 사용된다. 본 발명에서 사용되는 열가소성 수지는 병마개 가스켓을 제조하기 위하여 일반적으로 사용되는 열가소성 수지라면 특별히 제한되지 않는데, 폴리에틸렌, 폴리프로필렌과 같은 폴리올레핀 수지가 바람직하게 사용된다. In order for the oxygen-absorbing resin composition of the present invention to perform this function, a thermoplastic resin is used as the base resin. The thermoplastic resin used in the present invention is not particularly limited as long as it is a thermoplastic resin generally used for producing a bottle cap gasket. Polyolefin resins such as polyethylene and polypropylene are preferably used.
베이스 수지는 상기한 폴리올레핀 수지로만 형성하는 것도 가능하지만, 가스켓으로서의 탄성에 의한 밀봉력을 높이기 위하여 폴리올레핀 수지에 더하여 고무 성분을 포함하는 것이 바람직하다. 베이스 수지에서 고무 성분이 포함되는 경우, 베이스 수지에서 폴리올레핀 수지와 고무 성분의 중량비는 2:1~1:2의 범위인 것이 바람직하다.Although the base resin can also be formed only from the above-mentioned polyolefin resin, it is preferable to include a rubber component in addition to the polyolefin resin in order to improve the sealing force by elasticity as a gasket. When the rubber component is included in the base resin, the weight ratio of the polyolefin resin and the rubber component in the base resin is preferably in the range of 2: 1 to 1: 2.
고무 성분으로는 일반적으로 알려진 합성고무가 단독으로 사용될 수 있지만, 알파올레핀 고무와 스티렌부타디엔 고무의 혼합물이 사용되는 것이 더욱 바람직하다. 또한 알파올레핀 고무와 스티렌-에틸렌-부틸렌-스티렌 공중합체(SEBS) 고무의 혼합물이 사용되는 것도 좋다. 고무 성분으로서 혼합물이 사용되는 경우, 고무 성분에서 알파올레핀 고무와 스티렌부타디엔 고무 또는 SEBS 고무의 중량비는 2:1~1:2인 것이 바람직하다. As the rubber component, generally known synthetic rubbers can be used alone, but it is more preferable to use a mixture of alphaolefin rubber and styrenebutadiene rubber. It is also possible to use a mixture of alphaolefin rubber and styrene-ethylene-butylene-styrene copolymer (SEBS) rubber. When a mixture is used as the rubber component, the weight ratio of the alphaolefin rubber to the styrenebutadiene rubber or the SEBS rubber in the rubber component is preferably 2: 1 to 1: 2.
알파올레핀 고무로는 이소부텐-이소프렌 고무, 부틸고무, EPM 및 EPDM과 같은 에틸렌-프로필렌 고무 등이 사용될 수 있다. As the alpha olefin rubber, isobutene-isoprene rubber, butyl rubber, ethylene-propylene rubber such as EPM and EPDM and the like can be used.
본 발명에서 수분흡수제 수지는 수분흡수기능이 있는 것이라면 일반적으로 알려진 수분흡수제를 사용할 수 있지만, 에틸렌 비닐 알콜 공중합체(Ethylene Vinyl Alcohol Copolymer; EVOH)인 것이 바람직하다.In the present invention, the water absorbent resin may be a water absorbent generally known as long as it has a water absorbing function, but is preferably an ethylene vinyl alcohol copolymer (EVOH).
본 발명에서 산소흡수제는 환원성을 갖는 화합물이라면 특별히 제한없이 사용할 수 있다. 구체적으로 아황산 나트륨, 아황산 칼륨, 환원성 철 분말, 환원성 주석 분말, 환원성 아연 분말, 산화 제일철, 탄화철, 규소철, 카르보닐철, 수산화철 등이 사용될 수 있다. 그 중에서 아황산 나트륨 또는 아황산 칼륨이 바람직하게 사용될 수 있다. 산소흡수제는 분말 형태로 매트릭스 수지(100)와는 혼합되지 않고 단지 분산된 상태로 존재하게 되는데, 균일한 분산 및 산소흡수성능의 향상을 위하여 그것의 입자크기는 1~900 nm와 같은 나노크기로 구성하는 것이 바람직하다. Oxygen absorbers in the present invention can be used without particular limitation as long as the compound having a reducing property. Specifically, sodium sulfite, potassium sulfite, reducing iron powder, reducing tin powder, reducing zinc powder, ferrous oxide, iron carbide, silicon iron, carbonyl iron, iron hydroxide, and the like may be used. Among them, sodium sulfite or potassium sulfite can be preferably used. Oxygen absorbers are present in a dispersed state, not mixed with the matrix resin 100 in a powder form. For uniform dispersion and improved oxygen absorption performance, the particle size of the oxygen absorbent is composed of nano-sizes such as 1 to 900 nm. It is desirable to.
본 발명에서 발포제는 고분자 수지의 발포를 위하여 사용되는 것이라면 특별히 한정되지 않는다. 본 발명의 한 실시예는 시트르산(citric acid)와 소듐 바이카보네이트(sodium bicarbonate)를 발포제로 사용한 예를 제시하였다. The foaming agent in the present invention is not particularly limited as long as it is used for foaming the polymer resin. One embodiment of the present invention provides an example in which citric acid and sodium bicarbonate are used as a blowing agent.
본 발명에서 다공성 물질은 그것 내에 기공을 포함하면서 분말상을 가지는 물질이라면 특별히 한정되지 않는다. 다공성 물질은 본 발명의 조성물에서 매트릭스 수지와 혼합되지 않는 것이며 단지 분산될 뿐이다. 본 발명에서 특히 바람직하게 사용할 수 있는 다공성 물질은 다공성 실리카이다. In the present invention, the porous material is not particularly limited as long as it includes a pore therein and has a powder. The porous material is not mixed with the matrix resin in the composition of the present invention but merely dispersed. Particularly preferred porous materials which can be used in the present invention are porous silica.
본 발명에서 각 성분들의 성분비는 기재된 범위를 가지는 것이 바람직하다. 만약 어떤 성분의 성분비가 기재된 범위보다 적은 양으로 첨가된다면 그 성분에 의하여 얻고자 하는 성능을 달성하기 어렵게 된다. 반대로 어떤 성분의 성분비가 기재된 범위보다 많은 양으로 첨가된다면 그 성분에 의하여 얻고자 하는 성능은 충분히 달성될 수 있으나, 다른 성분들의 양이 적어지게 되므로 전체적인 물성의 조화를 이루기 어렵게 된다. It is preferable that the component ratio of each component in this invention has the range as described. If the component ratio of any component is added in an amount less than the stated range, it becomes difficult to achieve the performance desired by the component. On the contrary, if the component ratio of a certain component is added in an amount greater than the stated range, the performance to be obtained by the component can be sufficiently achieved, but since the amount of other components becomes smaller, it is difficult to achieve the overall balance of physical properties.
이하, 본 발명을 실시예에 의하여 더욱 구체적으로 설명한다. 다만, 하기의 실시예는 본 발명을 예시하는 것에 불과하므로, 본 발명의 범위가 하기의 실시예에 의하여 제한되는 것으로 이해되어서는 아니 된다. Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are merely to illustrate the invention, it should not be understood that the scope of the present invention is limited by the following examples.
실시예Example
실시예 1 내지 3Examples 1 to 3
하기 표의 성분비에 따라 형성된 산소흡수 수지 조성물로부터 병마개용 가스켓으로 사용할 수 있는 제품을 제조하였다. From the oxygen-absorbing resin composition formed according to the component ratio of the following table was prepared a product that can be used as a gasket for a bottle cap.
표 1
구분 특징 실시예 1(중량부) 실시예 2(중량부) 실시예 3(중량부)
LDPE 비중=0.915, 융점=105℃, 경도=99A 45.00 45.00 45.00
알파올레핀 고무 비중=0.870, 융점=58℃, 경도=70A 22.85 22.45 22.40
스티렌부타디엔 고무 비중=0.94, 경도=70A, 스티렌함량: 31중량% 22.85 22.45 22.40
산소흡수제(Na2SO3) 7.00 7.00 7.00
수분흡수수지(EVOH) 2.00 2.00 2.00
산화방지제 1010 사 0.10 0.10 0.10
발포제 citric acid + sodium bicarbonate 0.20 0.20
다공성 실리카 평균입자사이즈: 2 마이크로미터 1.00 1.00
Table 1
division Characteristic Example 1 (parts by weight) Example 2 (parts by weight) Example 3 (parts by weight)
LDPE Specific Gravity = 0.915, Melting Point = 105 ° C, Hardness = 99A 45.00 45.00 45.00
Alphaolefin rubber Specific Gravity = 0.870, Melting Point = 58 ° C, Hardness = 70A 22.85 22.45 22.40
Styrenebutadiene rubber Specific gravity = 0.94, hardness = 70A, styrene content: 31% by weight 22.85 22.45 22.40
Oxygen Absorber (Na 2 SO 3 ) 7.00 7.00 7.00
Water Absorption Resin (EVOH) 2.00 2.00 2.00
Antioxidant 1010 four 0.10 0.10 0.10
blowing agent citric acid + sodium bicarbonate 0.20 0.20
Porous silica Average particle size: 2 micrometers 1.00 1.00
산소흡수율 측정Oxygen Absorption Rate Measurement
상기한 실시예들의 제품에 대하여 산소흡수율을 측정하였다. 산소흡수율을 측정하기 위하여 상기한 실시예들에 따라 제조한 시편을 준비하였다. 일정량의 시료를 두께 0.4mm 이하로 열 가압하여 시편을 제작하였다. 구체적으로 시편제조기에 산소흡수율을 측정할 펠릿 타입(Pellet Type) 시료 600 mg을 투여하고, 180℃에서 15분간 가열유지한 후 가압 프레스를 이용하여 0.4mm 이하의 시트를 제조하였다. Oxygen uptake was measured for the products of the above examples. In order to measure the oxygen absorption rate, a specimen prepared according to the above-described examples was prepared. Specimens were prepared by thermally pressing a certain amount of sample to a thickness of 0.4 mm or less. Specifically, 600 mg of pellet type sample to measure the oxygen absorption rate was measured in the specimen maker, and heated at 180 ° C. for 15 minutes to prepare a sheet of 0.4 mm or less using a pressure press.
한편, 20ml 유리병(주사액용 바이엘 병)을 준비하였다. 주사액용 마개로서, 이 용기를 밀봉할 수 있는 부틸 러버(Butyl Rubber) 재질의 속마개와 알루미늄 재질의 겉마개를 준비하였다. 유리병은 병구 지름이 20mm인 표준 규격 제품을 사용하였다.Meanwhile, a 20 ml glass bottle (a Bayer bottle for injection liquid) was prepared. As a stopper for injection, an inner stopper made of butyl rubber and an outer cover made of aluminum capable of sealing the container were prepared. The glass bottle was a standard product with a bottle diameter of 20 mm.
또한 유리병에 알루미늄 재질의 겉마개를 밀봉하기 위한 실링기구로 직경 20mm용 크림퍼(Crimper)를 준비하였다. In addition, a crimper for a diameter of 20 mm was prepared as a sealing mechanism for sealing an aluminum outer lid to a glass bottle.
다음으로, 20ml 용기 내에 1ml의 물(H2O)를 투여하였다. 이때 물은 불순물 등으로 인한 시험오차를 없애기 위하여 증류수를 사용하였다. Next, 1 ml of water (H 2 O) was administered in a 20 ml container. At this time, distilled water was used to eliminate the test error due to impurities.
물이 투여된 용기에 산소흡수 라이너(Liner) 시편을 넣었다. 이때 시편이 물과 접촉하지 않도록 용기 속마개 내측 상면부위에 고정시켰다. 고정방법은 핀을 사용하여 시편과 부틸 러버 재질의 속마개를 고정시켰다.Oxygen-absorbing liner specimens were placed in a container of water. At this time, the specimen was fixed to the inner surface of the inner container stopper so as not to contact with water. In the fixing method, the pin and the fastener of the butyl rubber material were fixed.
시편이 고정되어 있는 속마개를 용기에 밀봉한 후 알루미늄 재질의 겉마개를 크림퍼를 사용하여 완벽하게 밀폐시켰다. 밀폐시킨 용기를 50℃ 항온조건에서 일정시간 동안 전처리를 실시하였다. After sealing the fastener to which the specimen was fixed in the container, the aluminum outer cap was completely sealed using a crimper. The sealed container was pretreated for a period of time at 50 ℃ constant temperature conditions.
한편, 비교를 위하여 시편이 없는 유리병을 동일한 조건에서 처리하였고, 또한 공지제품 시편을 투여한 유리병을 동일한 조건에서 처리하였다. 여기에서 공지제품 시편은 실시예 1 내지 3과 동일하지만, 발포제 및 다공성 실리카가 포함되지 않은 제품을 의미한다. On the other hand, for comparison, a glass bottle without a specimen was treated under the same conditions, and a glass bottle to which a known product specimen was administered was treated under the same conditions. Herein, the known product specimens are the same as those of Examples 1 to 3, but do not include a blowing agent and porous silica.
이렇게 처리한 시편들에 대하여 일정시간 경과후에 유리병 내에 잔존하는 산소함량을 측정함으로써 산소흡수율을 계산하였다. Oxygen absorbance was calculated by measuring the oxygen content remaining in the glass bottle after a certain time for the treated specimens.
상기와 같이 처리한 용기 내의 산소 농도는 가스크로마토그래피(GC)를 이용하여 측정되었다. GC 측정 조건은 다음과 같았다.The oxygen concentration in the vessel treated as above was measured using gas chromatography (GC). GC measurement conditions were as follows.
- 사용기기명: Agilent 6890 (제작사: Agilent)-Name of device: Agilent 6890 (Manufacturer: Agilent)
- GC 분석 조건-GC analysis conditions
* 인젝터 온도: 210℃  * Injector temperature: 210 ℃
* 인젝션 부피: 0.1 ml  Injection volume: 0.1 ml
* 오븐: 40℃ 항온  * Oven: 40 ℃ constant temperature
* 디텍터: TCD (온도: 240℃)  * Detector: TCD (Temperature: 240 ℃)
* 컬럼: Pack Column (Carboxen 1004)  Column: Pack Column (Carboxen 1004)
* 이동상: He (헬륨)  Mobile phase: He (Helium)
* 유량: 24 ml/min으로 전처리된 시료 분석  * Flow rate: Sample analysis pretreated at 24 ml / min
블랭크(Blank) 용기(시편이 없는 유리병) 내의 산소량과 시편이 투입된 용기 내의 산소량의 차이를 측정함으로써 산소흡수율을 다음식에 의하여 계산하였다. The oxygen absorption rate was calculated by the following equation by measuring the difference between the amount of oxygen in the blank vessel (glass bottle without specimen) and the amount of oxygen in the vessel into which the specimen was placed.
산소흡수율 = (A - B) x 100 / A Oxygen Absorption Rate = (A-B) x 100 / A
여기에서 A는 블랭크 용기 내의 산소량이고, B는 시편투입 용기내의 산소량이다. Where A is the amount of oxygen in the blank vessel and B is the amount of oxygen in the specimen injection vessel.
산소흡수율의 결과를 표 2에 나타내었다.The results of the oxygen absorption rate are shown in Table 2.
표 2
구분 산소함량(%)
12시간후 1일후 3일후 7일후 15일후 30일후
시편없는 병 20.20 20.10 20.20 20.10 20.10 20.10
공지제품 시편 19.20 18.70 17.50 15.80 14.90 14.50
실시예 1 제품 17.30 16.50 16.10 14.90 14.70 14.50
실시예 2 제품 18.10 17.50 16.80 15.10 14.80 14.50
실시예 3 제품 16.10 15.30 14.70 14.50 14.50 14.50
TABLE 2
division Oxygen content (%)
12 hours later 1 day later 3 days later 7 days later 15 days later 30 days later
A specimen without a disease 20.20 20.10 20.20 20.10 20.10 20.10
Notice Product Specimen 19.20 18.70 17.50 15.80 14.90 14.50
Example 1 Product 17.30 16.50 16.10 14.90 14.70 14.50
Example 2 Products 18.10 17.50 16.80 15.10 14.80 14.50
Example 3 Products 16.10 15.30 14.70 14.50 14.50 14.50
상기 표2에서 보는 바와 같이, 본 발명에 따른 실시예 제품은 공지제품에 비하여 빠른 속도로 산소를 흡수할 수 있음을 확인하였다. 본 발명의 실시예 제품 중에서는 발포제에 의하여 발포됨으로써 기공을 가지면서 또한 다공성 실리카를 포함하는 실시예 3 제품이 가장 빠른 속도의 산소흡수율을 보임을 확인하였다. 이것은 발포 기공에 의한 효과와 다공성 실리카에 의한 효과가 중첩적으로 나타난 결과이다. As shown in Table 2, it was confirmed that the example product according to the present invention can absorb oxygen at a faster rate than the known product. Among Example products of the present invention, it was confirmed that the Example 3 product having pores by being foamed by a blowing agent and also including porous silica showed the fastest oxygen absorption rate. This is a result of overlapping the effect by the foamed pores and the effect by the porous silica.
한편, 산소흡수율에 대한 발포 기공에 의한 효과(실시예 1)가 다공성 실리카에 의한 효과(실시예 2)보다 우수함을 확인하였다. On the other hand, it was confirmed that the effect by the foamed pores on the oxygen absorption rate (Example 1) is superior to the effect by the porous silica (Example 2).

Claims (12)

  1. 열가소성 수지로 된 베이스 수지 60~98 중량%; 수분흡수제 수지 0.1~20 중량%; 산소흡수제 1~20 중량%; 및 발포제 0.1~5 중량%를 포함하는 산소흡수 수지 조성물.60 to 98% by weight of the base resin of the thermoplastic resin; 0.1-20% by weight of a water absorbent resin; 1-20% by weight of an oxygen absorbent; And 0.1 to 5 wt% of a blowing agent.
  2. 열가소성 수지로 된 베이스 수지 60~98 중량%; 수분흡수제 수지 0.1~20 중량%; 산소흡수제 1~20 중량%; 및 다공성 물질 0.1~20 중량%를 포함하는 산소흡수 수지 조성물.60 to 98% by weight of the base resin of the thermoplastic resin; 0.1-20% by weight of a water absorbent resin; 1-20% by weight of an oxygen absorbent; And 0.1-20% by weight of a porous material.
  3. 제1항에 있어서,The method of claim 1,
    상기 산소흡수 수지 조성물은 다공성 물질 0.1~20 중량%를 더 포함하는 것을 특징으로 하는 산소흡수 수지 조성물.The oxygen absorbing resin composition is an oxygen absorbing resin composition, characterized in that it further comprises 0.1 to 20% by weight of a porous material.
  4. 제1항 내지 제3항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 3,
    상기 산소흡수제는 환원성을 갖는 화합물인 것을 특징으로 하는 산소흡수 수지 조성물.The oxygen absorbent is an oxygen absorbing resin composition, characterized in that the compound having a reducing property.
  5. 제4항에 있어서,The method of claim 4, wherein
    상기 산소흡수제는 아황산나트륨 또는 아황산칼륨인 것을 특징으로 하는 산소흡수 수지 조성물.The oxygen absorbing resin composition, characterized in that the sodium sulfite or potassium sulfite.
  6. 제4항 및 제5항 중 어느 한 항에 있어서,The method according to any one of claims 4 and 5,
    상기 산소흡수제의 입자크기는 1~900 nm인 것을 특징으로 하는 산소흡수 수지 조성물.Particle size of the oxygen absorbent is an oxygen absorbing resin composition, characterized in that 1 ~ 900 nm.
  7. 제1항 내지 제3항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 3,
    상기 수분흡수제 수지는 에틸렌 비닐 알콜 공중합체(Ethylene Vinyl Alcohol Copolymer; EVOH)인 것을 특징으로 하는 산소흡수 수지 조성물.The water absorbent resin is an oxygen absorbent resin composition, characterized in that the ethylene vinyl alcohol copolymer (Ethylene Vinyl Alcohol Copolymer; EVOH).
  8. 제2항 및 제3항 중 어느 한 항에 있어서,The method according to any one of claims 2 and 3, wherein
    상기 다공성 물질은 실리카인 것을 특징으로 하는 산소흡수 수지 조성물.The porous material is an oxygen absorbing resin composition, characterized in that the silica.
  9. 제1항 내지 제3항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 3,
    상기 베이스 수지는 폴리올레핀 수지와 고무 성분으로 이루어지고, 상기 폴리올레핀 수지와 상기 고무 성분의 중량비는 2:1~1:2인 것을 특징으로 하는 산소흡수 수지 조성물.The base resin is composed of a polyolefin resin and a rubber component, the weight ratio of the polyolefin resin and the rubber component is 2: 1 to 1: 2, the oxygen absorption resin composition.
  10. 제9항에 있어서,The method of claim 9,
    상기 고무 성분은 알파올레핀 고무와 스티렌부타디엔 고무의 혼합물이고, 상기 알파올레핀 고무와 상기 스테렌부타디엔 고무의 중량비는 2:1~1:2인 것을 특징으로 하는 산소흡수 수지 조성물. The rubber component is a mixture of an alpha olefin rubber and a styrene butadiene rubber, and the weight ratio of the alpha olefin rubber and the styrene butadiene rubber is 2: 1 to 1: 2.
  11. 제1항 내지 제10항 중 어느 한 항에 따른 산소흡수 수지 조성물에 의하여 제조되는 산소흡수 제품.An oxygen absorption product produced by the oxygen absorption resin composition according to any one of claims 1 to 10.
  12. 제11항에 있어서,The method of claim 11,
    상기 제품은 상기 산소흡수 수지 조성물에 의하여 제조되는 가스켓이 마련된 병마개인 것을 특징으로 하는 산소흡수 제품.The product is oxygen absorbing product, characterized in that the bottle is provided with a gasket manufactured by the oxygen absorbing resin composition.
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