KR870002104B1 - Polypropylene resin composition stable to radiation - Google Patents
Polypropylene resin composition stable to radiationDownload PDFInfo
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- KR870002104B1 KR870002104B1KR1019850001613AKR850001613AKR870002104B1KR 870002104 B1KR870002104 B1KR 870002104B1KR 1019850001613 AKR1019850001613 AKR 1019850001613AKR 850001613 AKR850001613 AKR 850001613AKR 870002104 B1KR870002104 B1KR 870002104B1
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Abstract
Translated fromKoreanDescription
Translated fromKorean본 발명은 방사선에 안정한 폴리프로필렌 수지 조성물에 관한 것이다.The present invention relates to a polypropylene resin composition stable to radiation.
폴리프로필렌 수지는 위생적으로 우수하고 또한 그 성형품은 외부로부터 내용물을 투시할 수 있는 정도로 반투명성이므로 식품용기, 의료용기, 의료기구 등에 널리 이용되고 있다.Polypropylene resins are excellent in hygiene and their molded products are translucent enough to see the contents from the outside, so they are widely used in food containers, medical containers, medical devices, and the like.
그러나 식품용기, 의료기구 등의 용도에 있어서 내용물에 분진 및 기타 이물질이 혼입되어 있는지의 여부를 확인하는 것은 매우 중요하다. 또한, 용기를 저해하지 않고 내용물의 본래 색깔을 확인하는 것이 요망된다.However, in the use of food containers, medical devices, etc., it is very important to check whether or not dust and other foreign substances are mixed in the contents. It is also desirable to confirm the original color of the contents without disturbing the container.
상기 이용분야에서 폴리프로필렌수지로 만들어진 용기, 기구 등의 투명성의 향상이 절실히 요망되고 있다.In the field of use, there is an urgent need to improve the transparency of containers, appliances, and the like made of polypropylene resin.
또, 식품용기, 의료기구등은 그 이용분야에서 사용하기 전에 멸균해야 한다. 멸균은 통상 수증기를 이용하거나, 멸균작용이 강한 에틸렌 산화물 및 과산화수소에 의해 실시된다. 방사선에 조사(exposure) 시킴으로 인한 방사선 멸균이 최근 개발되었고 식품용기 또는 의료기구를 멸균하기 위해 이용되는 예가 많아진다. 폴리프로필렌 수지는 수증기 멸균 및 가스 멸균에 안정하다. 그러나 방사선 멸균에 대해서는 안정성이 나쁘므로 황변(yellowing)이나 물성을 저하시키는 단점이 있다.In addition, food containers, medical devices, etc. must be sterilized before use in the field of use. Sterilization is usually carried out by steam or by sterile ethylene oxide and hydrogen peroxide. Radiation sterilization due to exposure to radiation has recently been developed and many examples are used to sterilize food containers or medical devices. Polypropylene resins are stable to steam sterilization and gas sterilization. However, the radiation sterilization is poor in stability, yellowing (yellowing) or has the disadvantage of lowering the physical properties.
특히 물성의 저하에 대해 언급하면, 방사선을 조사함에 의해 내충격성이 방사선을 조사하기 전에 비해 반으로 감소하고, 또 방사선 조사후 오히려 열을 가하면 물성의 저하가 현저하고 폴리프로필로필렌수지의 취화가 촉진되어 취성파쇄도 생긴다.In particular, when deteriorating the physical properties, the impact resistance is reduced by half when irradiated with radiation, and when heat is applied after irradiation, the physical properties are remarkably deteriorated and the embrittlement of the polypropylpropylene resin Promotes brittle fracture.
방사선 조사에 의한 폴리프로필렌 수지에 대한 물성의 저하를 방지하기 위해 폴리프로필렌 수지에 특정 안정제를 첨가하는 방법이 있고, 이를테면 트리아릴포스파이트 단독, 트리아릴포스파이트 및 숨겨진 페놀계 산화방지제의 병용, 또는 트리아릴 포스파이트 및 숨겨진 아민계 내광 및 내후성 안정제를 병용하는 것이 알려져 있다(일본 특허공고 제179,234/1982호 참조).There is a method of adding a specific stabilizer to the polypropylene resin in order to prevent degradation of the physical properties of the polypropylene resin by irradiation, such as the use of triaryl phosphite alone, triaryl phosphite and hidden phenolic antioxidants, or It is known to use triaryl phosphite and hidden amine light and weather resistance stabilizers in combination (see Japanese Patent Publication No. 179,234 / 1982).
그러나 트리스 (2,5-디-t-부틸페닐) 포스파이트 또는 트리스 (2,4-디-t-부틸페닐) 포스파이트 같은 트리아릴 포스파이트만의 첨가는 폴리프로필렌 수지 성형물의 방사선 조사의 안정성은 아직 불충분하다. 그러므로 타의 안정제와의 병용이 요망되고 있지만, 이를테면 2,6-디-t-부틸-p-메틸페놀, 테트라키스 [메틸렌-3-(3,5-디-t-부틸-4-히드록시페닐)-프로피오네이트] 메탄 등의 숨겨진 페놀계 산화방지제와의 병용에는 폴리프로필렌 수지 성형물의 방사선 조사 직후 및 조사 후 더욱 열이력을 가할 때의 안정성을 유지하기에 충분한 첨가량을 사용한다면 성형물의 황변이 문제로 된다.However, the addition of only triaryl phosphites, such as tris (2,5-di-t-butylphenyl) phosphite or tris (2,4-di-t-butylphenyl) phosphite, has been found to stabilize the irradiation of polypropylene resin moldings. Is not enough yet. Therefore, in combination with other stabilizers is desired, such as 2,6-di-t-butyl-p-methylphenol, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl ) -Propionate] In combination with hidden phenolic antioxidants such as methane, the yellowing of the molding may be reduced if the amount of the additive is sufficient to maintain stability immediately after irradiation of the polypropylene resin molding and when the thermal history is applied after irradiation. It becomes a problem.
또, 비스 (2,2,6,6-테트라메틸-4-피페리딜) 세바케이트, N,N'-비스 (2,2,6,6-테트라메틸-4-피페리딜) 헥사메틸렌디아민 중합체 또는 디메틸숙시네이트와 2-(4-히드록시-2,2,6,6-테트라메틸-1-피페리딜) 에탄올의 축합물 등과 같이 숨겨진 아민계 내광, 내후 안정제와 병용할 때 폴리프로필렌 수지 성형물의 방사선 조사 안정성은 만족할만 하고, 황변의 문제도 생기지 않지만 투명성에 대해서는 문제가 있다.In addition, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene When used in combination with hidden amine-based light and weather stabilizers such as condensates of diamine polymers or dimethylsuccinate with 2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) ethanol Irradiation stability of the propylene resin molding is satisfactory, and yellowing does not occur, but transparency is a problem.
그 중에서도, 트리스 (2,4-디-t-부틸페닐) 포스파이트와 N,N'-비스 (2,2,6,6-테트라메틸-4-피페리딜) 헥사메틸렌디아민 중합체의 병용이 특히 내방사선 조사성이 양호하고, 이들의 안정제는 안전하기 때문에, 이들을 병용한 조성물은 투명성에 문제가 있는 점을 제외하고 식품용기 및 의료기구용으로 사용하기에 우수하다.Especially, the combination of tris (2,4-di-t-butylphenyl) phosphite and N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine polymer is easy to use. In particular, since radiation resistance is good and these stabilizers are safe, the composition which uses them together is excellent for use for food containers and medical instruments, except that there is a problem in transparency.
이들 안정제를 병용 첨가한 폴리프로필렌 수지 성형물은 상기한 바와 같이 내방사선성은 양호하지만 투명성이 거의 없고 이 성형물을 식품이나 의료용도의 용기나 주사통 등의 물품이나 약품을 넣은 것으로서 사용한 경우 투명성은 아직 불충분하고, 내용물에 혼입되는 미세한 먼지나 이물질을 확인하기가 곤란할뿐만 아니라 내용물의 정확한 색깔을 확인할 수 없는 중대한 결함이 있다.Polypropylene resin moldings in combination with these stabilizers have good radiation resistance as described above, but have little transparency, and the transparency is still insufficient when the moldings are used as food or medical containers or syringes. In addition, it is difficult to identify the fine dust or foreign matter mixed in the contents, and there is a serious defect that cannot confirm the exact color of the contents.
최근의 원가절감의 필요성에 비추어 볼 때, 보다 얇은 벽을 갖는 성형품 사출성형에 있어서는 다수 생산이 요구되고 있다. 그러므로, 고성형 유동성을 갖는 폴리프로필렌 수지 조성물이 요구되고 있다.In view of the recent need for cost reduction, a large number of productions are required for injection molding of thinner walls. Therefore, there is a need for a polypropylene resin composition having high molding fluidity.
본 발명의 목적은 방사선 조사에 안정하고 황변 및 물성저하를 유발하지 않으며 투명성이 우수한 폴리프로필렌 수지 조성물을 제공하는 데에 있다.An object of the present invention is to provide a polypropylene resin composition that is stable to radiation, does not cause yellowing and deterioration of physical properties, and is excellent in transparency.
본 발명의 또 다른 목적은 방사선 조사에 안정하고 황변 및 물성저하를 일으키지 않으며, 투명성 및 성형 유동성이 우수한 폴리프로필렌 슈지 조성물을 제공하는 데에 있다.It is still another object of the present invention to provide a polypropylene shoe composition which is stable to radiation, does not cause yellowing and deterioration of physical properties, and is excellent in transparency and molding fluidity.
본 발명의 또 다른 목적은 다음 설명으로부터 분명해진다.Another object of the present invention is apparent from the following description.
본 발명에서는 다음의 폴리프로필렌 수지 조성물을 제공한다.In the present invention, the following polypropylene resin composition is provided.
하기 화합물로 구성되고 투명성이 우수한 방사선에 안정한 폴리프로필렌 수지 조성물 :A polypropylene resin composition composed of the following compounds and stable to radiation having excellent transparency:
(a) 폴리프로필렌 수지;(a) polypropylene resins;
(b) 하기 구조식 (I)을 갖는 소르비톨 유도체;(b) sorbitol derivatives having the following structural formula (I);
(c) 하기 구조식(II)을 갖는 포스파이트 화합물;(c) phosphite compounds having the formula (II) below;
(d) 하기 구조식(III)을 갖는 폴리아민 화합물;(d) polyamine compounds having the following structural formula (III);
상기에서,In the above,
R은 수소원자 또는 탄소원자 1-8의 알킬기이고;R is a hydrogen atom or an alkyl group of 1-8 carbon atoms;
R1은 3차 부틸, 1, 1-디메틸프로필, 시클로헥실 또는 페닐기이고;R1 is tertiary butyl, 1, 1-dimethylpropyl, cyclohexyl or phenyl group;
R2는 수소원자 또는 메틸, 3차부틸, 1,1-디메틸프로필, 시클로헥실 또는 페닐기이고;R2 is a hydrogen atom or a methyl, tert-butyl, 1,1-dimethylpropyl, cyclohexyl or phenyl group;
n은 평균 1-40의 정수이고;n is an integer of 1-40 on average;
상기 화합물(b), (c) 및 (d)의 함량은 폴리프로필렌 수지 (a)의 100중량부 기준으로 각각 0.005-8중량부, 0.01-4중량부 및 0.01-4중량부이다.The content of the compounds (b), (c) and (d) is 0.005-8 parts by weight, 0.01-4 parts by weight and 0.01-4 parts by weight based on 100 parts by weight of the polypropylene resin (a), respectively.
상기 수지 조성물의 성형 유동성은 유기 과산화물 (e)의 존재하에 190℃ 내지 270℃에서 가열처리함으로써 증진될 수 있다.Molding fluidity of the resin composition can be enhanced by heat treatment at 190 ° C to 270 ° C in the presence of an organic peroxide (e).
본 발명을 실시하는데 유용한 폴리프로필렌 수지는 프로필렌 단일중합체, 에틸렌함량이 0.1 내지 7중량%인 프로필렌-에틸렌 공중합체, α-올레핀 함량이 0.1 내지 20중량%이고 임의로 에틸렌을 함유할 수 있는 프로필렌-α-올레핀 공중합체 등이 있다. 반면, 폴리프로필렌 수지는 이들 중합체의 혼합물일 수 있다. α-올레핀을 부텐-1, 헥센-1 및 4-메틸펜텐-1과 같이 탄소원자 4-8을 갖는 것이 특히 양호하다.Polypropylene resins useful in the practice of the present invention are propylene homopolymers, propylene-ethylene copolymers having an ethylene content of 0.1 to 7% by weight, propylene-α having an α-olefin content of 0.1 to 20% by weight and optionally containing ethylene. -Olefin copolymers and the like. Polypropylene resins, on the other hand, may be mixtures of these polymers. Particular preference is given to the α-olefins having 4-8 carbon atoms, such as butene-1, hexene-1 and 4-methylpentene-1.
본 발명을 실시하는데 유용한 구조식(I)의 소르비톨 유도체의 예로는 디벤질리덴소르비톨, 1.3,2.4-디(메틸벤질리덴)소르비톨, 1.3,2.4-디(에틸벤질리덴)소르비톨, 1.3,2.4-디(프로필벤질리덴)소르비톨, 1.3,2.4-디(부틸벤릴리덴)소르비톨, 1.3,2.4-디(헥실벤질리덴)소르비톨 등이 있다. 상기 예의 화합물 각각은 3이성체, 즉 구조식(I)의 치환기 R의 위치에 따라 오르토-이성체, 메타-이성체 및 파라-이성체를 갖는다. 실제상은 구입하기 쉬운 파라-이성체가 양호하다.Examples of sorbitol derivatives of formula (I) useful for practicing the present invention include dibenzylidene sorbitol, 1.3,2.4-di (methylbenzylidene) sorbitol, 1.3,2.4-di (ethylbenzylidene) sorbitol, 1.3,2.4-di (Propylbenzylidene) sorbitol, 1.3,2.4-di (butylbenlylidene) sorbitol, 1.3,2.4-di (hexylbenzylidene) sorbitol and the like. Each of the compounds of the above examples has tri-isomers, i.e., ortho-isomers, meta-isomers and para-isomers, depending on the position of substituent R of formula (I). In practice, para-isomers that are easy to purchase are preferred.
소르비톨 유도체는 폴리프로필렌 수지 100중량부에 대해 0.005 내지 8중량부, 양호하기로는 0.01 내지 8중량부 또는 가장 양호하기로는 0.05 내지 1중량부의 양으로 혼합된다. 0.005중량부 미만으로는 투명성이 충분히 개량되지 않고 8중량부를 초과한 경우에는 블리이딩(bleeding)의 문제가 발생한다. 그러므로 상기 제 1 범위 외의 양으로 소르비톨 유도체를 병용하는 것은 양호하지 않다.The sorbitol derivative is mixed in an amount of 0.005 to 8 parts by weight, preferably 0.01 to 8 parts by weight or most preferably 0.05 to 1 part by weight, based on 100 parts by weight of polypropylene resin. If the amount is less than 0.005 parts by weight and the transparency is not sufficiently improved, and more than 8 parts by weight, a bleeding problem occurs. Therefore, it is not good to use sorbitol derivatives together in an amount outside the first range.
본 발명을 실시하는데 유용한 구조식(II)의 포스파이트 화합물의 대표적인 예로는 트리스(2,5-디-t-부틸페닐) 포스파이트, 트리스(2-t-부틸페닐) 포스파이트, 트리스[2-(1,1-디메틸프로필)페닐] 포스파이트, 트리스 (2-페닐페닐) 포스파이트, 트리스(2-시클로헥실페닐) 포스파이트, 트리스(2,4-디-t-부틸페닐) 포스파이트, 트리스(2-t-부틸-4-페닐페닐) 포스파이트 등이 있다.Representative examples of phosphite compounds of formula (II) useful for practicing the present invention include tris (2,5-di-t-butylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, tris [2- (1,1-dimethylpropyl) phenyl] phosphite, tris (2-phenylphenyl) phosphite, tris (2-cyclohexylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, Tris (2-t-butyl-4-phenylphenyl) phosphite and the like.
포스파이트 화합물은 0.01 내지 4중량부, 양호하기로는 0.02 내지 2중량부의 양으로 첨가된다. 0.01중량부 미만으로 첨가되면 방사선에 조사시킨 후 안정성에 큰 영향을 미치지 않는다. 4중량부 이상을 첨가해도 효과에 큰 영향을 미치는 것은 아니지만 가격이 높아지는 문제가 발생한다. 이는 바람직하지 않은 것이다.The phosphite compound is added in an amount of 0.01 to 4 parts by weight, preferably 0.02 to 2 parts by weight. If added below 0.01 part by weight, it does not significantly affect the stability after irradiation. Adding more than 4 parts by weight does not have a significant effect on the effect, but a problem arises in that the price increases. This is undesirable.
본 발명을 실시하는데 유용한 구조식(III)의 폴리아민화합물은 0.001 내지 4중량부, 양호하기로는 0.02 내지 2중량부의 양으로 첨가된다. 0.01중량부 미만으로 첨가하면 방사선 조사 후의 안정성에 대해 현저한 효과가 없고, 또 4중량부를 초과해도 첨가해도 그 효과가 크게 증대되는 것이 아니지만, 가격이 높아지는 문제가 발생한다.The polyamine compound of formula (III) useful for practicing the present invention is added in an amount of 0.001 to 4 parts by weight, preferably 0.02 to 2 parts by weight. When added below 0.01 part by weight, there is no remarkable effect on the stability after irradiation, and even when added above 4 parts by weight, the effect does not significantly increase, but a problem arises in that the price increases.
유기 과산화물의 예로서는 t-부틸 퍼옥시피발레이트, 라우로일 퍼록사이드, 시클로헥사논 퍼록사이드, t-부틸퍼록시이소프로필카보네이트, t-부틸퍼록시벤조에이트, 메틸에틸케톤 퍼록사이드, 디큐밀 퍼록사이드, 2,5-디메틸-2,5-디(t-부틸퍼록시)헥산, 디-t-부틸퍼록사이드, 2,5-디메틸-2,5-디(t-부틸퍼록시)헥신-3등이 있다. 이들은 단독 또는 혼합사용될 수 있다: 첨가될 유기과산화물의 양은 분자량 조절 후 얻어질 목적 용융지수 및 각 폴리프로필렌 수지의 용융지수에 따라 달라진다. 일반적으로는 폴리프로필렌 수지 100중량부에 대해 0.001 내지 0.1중량부의 양으로 유기과산화물을 가하는 것이 적당하다.Examples of organic peroxides include t-butyl peroxypivalate, lauroyl peroxide, cyclohexanone peroxide, t-butylperoxyisopropylcarbonate, t-butylperoxybenzoate, methylethylketone peroxide, dicumyl perlock Said, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne- There is a third place. These may be used alone or in combination: the amount of organic peroxide to be added depends on the desired melt index to be obtained after molecular weight adjustment and the melt index of each polypropylene resin. Generally, it is appropriate to add an organic peroxide in an amount of 0.001 to 0.1 parts by weight based on 100 parts by weight of polypropylene resin.
본 발명의 조성물에는 필요에 따라 다른 첨가제, 이를테면 상기 이외의 산화방지제, 상기 이외의 자외선 방지제, 자외선 안정제, 안료, 분산제, 중화제 등의 각종 첨가제를 첨가할 수 있다.If necessary, various additives, such as other additives such as antioxidants other than those described above, anti-UV agents other than those described above, UV stabilizers, pigments, dispersants, and neutralizing agents, may be added to the composition of the present invention.
본 발명의 조성물에 첨가될 산화방지제의 예로는 2,6-디-t-부틸-p-메틸페놀, n-옥타데실-3-(4-히드록시-3,5-디-t-부틸페닐)프로피오네이트, 테트라키스[메틸렌-3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트]메탄 등이 있다. 그러나 이들 산화방지제는 방사선에 조사될 때 수지의 황변을 일으킨다. 그러므로 본 발명의 조성물에 가할 산화방지제의 양에는 제한이 가해진다.Examples of antioxidants to be added to the compositions of the present invention include 2,6-di-t-butyl-p-methylphenol, n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl ) Propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and the like. However, these antioxidants cause yellowing of the resin when irradiated with radiation. Therefore, a limit is placed on the amount of antioxidant to be added to the composition of the present invention.
또한 펜타에리트리톨 테트라키스(β-라우릴 티오프로피오네이트), 디라우틸 디티오프로피오네이트 등과 같은 황-계 산화방지제를 사용할 수 있다. 그러나 이러한 황계 산화방지제는 용혈성의 문제를 발생시켜 그 사용이 제한된다.Sulfur-based antioxidants such as pentaerythritol tetrakis (β-lauryl thiopropionate), dilautyl dithiopropionate and the like can also be used. However, such sulfur-based antioxidants cause hemolytic problems and their use is limited.
대표적인 자외선 흡수제로서는 2-히드록시-4-n-옥톡시벤조페논, 2-(2-히드록시-3,5-디-t-부틸페닐)-5-클로로벤조트리아졸 등이 있다.Representative ultraviolet absorbers include 2-hydroxy-4-n-octoxybenzophenone, 2- (2-hydroxy-3,5-di-t-butylphenyl) -5-chlorobenzotriazole, and the like.
대표적인 자외선 안정제로서는 비스(2,2,6,6-테트라메틸-4-피페리딜)세바케이트가 있다.Representative ultraviolet stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate.
본 발명의 수시 조성물은 다음 방법에 따라 양호하게 제조될 수 있다. 즉, 폴리프로필렌수지(a), 구조식(I)로 표시되는 소르비톨 유도체(b), 구조식(II)로 표시되는 포스파이트 화합물 (c) 및 구조식(III)으로 표시되는 폴리아민 화합물(d), 필요하다면 유기과산화물(e)뿐만 아니라 본 분야에서 일반적으로 사용되는 중화제(예, 칼슘 스테아레이트), 결정핵제, 산화 방지제, 자외선 흡수제, 자외선 안정제 등과 같은 첨가제를 헨쉘 혼합기 같은 혼합기에서 모두 혼합하여 균일하게 분산시킨다. 그 결과 형성된 혼합물을 응용시킨 후 압출기에 의해 펠릿화한다.The occasional composition of this invention can be manufactured favorably according to the following method. That is, polypropylene resin (a), sorbitol derivative (b) represented by structural formula (I), phosphite compound (c) represented by structural formula (II), and polyamine compound (d) represented by structural formula (III), required If necessary, uniformly disperse all organic additives (e) as well as additives such as neutralizers (e.g., calcium stearate), nucleating agents, antioxidants, UV absorbers, UV stabilizers, etc., which are commonly used in the art, in a mixer such as a Henschel mixer. Let's do it. The resulting mixture is applied and then pelletized by an extruder.
필요하다면, 폴리프로필렌 수지, 소르비톨 유도체, 포스파이트 화합물 및 폴리아민 화합물을 포함하는 본 발명의 조성물은 유기 과산화물 존재하에 190°내지 270°에서 열처리할 수 있다. 상기 펠릿화단계에서 용융-압출 온도를 상기 범위내로 설정하므로써 열처리할 수 있다. 190℃ 미만의 온도에서는 조성물을 용융 및 혼합하기가 불편하다. 한편, 270℃이상의 온도를 사용하면 수지의 착색 및 열노화가 생겨 바람직하지 못하다.If desired, the compositions of the present invention comprising polypropylene resins, sorbitol derivatives, phosphite compounds and polyamine compounds can be heat treated at 190 ° to 270 ° in the presence of organic peroxides. In the pelletizing step, the heat treatment may be performed by setting the melt-extrusion temperature within the above range. At temperatures below 190 ° C. it is inconvenient to melt and mix the composition. On the other hand, the use of a temperature of 270 DEG C or higher causes undesired coloring and thermal aging of the resin.
본 발명의 폴리프로필렌 수지 조성물은 방사선 조사에 대해 매우 안정성이 높고 투명성에서도 우수하기 때문에 이들 성질을 이용해서 식품포장, 의료기구(주사기, 침원, 프로텍터 등), 의료용기 및 기타 용도에 유효하게 사용될 수 있다. 더우기, 열노화된 조성물은 성형 유동성이 우수하다.Since the polypropylene resin composition of the present invention is very stable to radiation and excellent in transparency, it can be effectively used in food packaging, medical equipment (syringe, bedding, protectors, etc.), medical containers and other applications by using these properties. have. Moreover, the heat aged composition is excellent in molding fluidity.
본 발명은 하기 본 발명의 실시예 및 비교예에 의해 특히 상세히 설명된다. 그러나 하기 실시예들은 본 발명을 예증하는데 지나지 않으며 그 한계를 제한하는 것은 아니다.The invention is illustrated in particular by the following examples and comparative examples of the invention. The following examples, however, are merely illustrative of the invention and do not limit its limitation.
[실시예 1]Example 1
135℃의 테트라린 중에서 측정한 고유점도 1.62를 갖고 에틸렌 3.5중량%를 함유하는 에틸렌-프로필렌 임의의 공중합체 100중량부를 1.3,2.4-디(에틸벤질리덴)소르비톨 0.3중량부, 트리스(2,4-디-t-부틸페닐) 포스파이트 0.02중량부, 구조식(III)으로 나타내지고 평균 분자량이 1800 내지 2200인 폴리아민 화합물 0.02중량부, 및 칼슘스테아레이트 0.07중량부를 가한다. 그 결과 형성된 조성물을 혼합한 다음 일반압출기를 통해 약 240℃의 압출온도에서 펠릿화한다. 사출 성형기를 사용하여 사출 성형온도 약 240℃에서 160㎜×80㎜×두께 1㎜의 평판으로 성형하였다.0.3 parts by weight of 1.3,2.4-di (ethylbenzylidene) sorbitol, tris (2,4), 100 parts by weight of any copolymer of ethylene-propylene having an intrinsic viscosity of 1.62 and containing 3.5% by weight of ethylene, measured in tetralin at 135 ° C. 0.02 parts by weight of -di-t-butylphenyl) phosphite, 0.02 parts by weight of a polyamine compound represented by formula (III) and having an average molecular weight of 1800 to 2200, and 0.07 parts by weight of calcium stearate. The resulting composition is mixed and then pelletized through a general extruder at an extrusion temperature of about 240 ° C. The injection molding machine was used to form a flat plate of 160 mm x 80 mm x thickness 1 mm at an injection molding temperature of about 240 캜.
얻어진 평탄에 코발트-60방사선원의 γ-선을 2.5Mrad 조사한 후 평탄을 80℃의 대기하에 2주 동안 방치시킨다.2.5 Mrad of the cobalt-60 radiation source was irradiated to the obtained flat surface, and the flatness was left to stand for 2 weeks in the atmosphere of 80 degreeC.
조사 전후의 내충격성, 투명성 및 황변에 대해 검토하였다.The impact resistance, transparency and yellowing before and after the irradiation were examined.
내충격성은 그 평탄을 내경 50㎜의 파이프에 놓고, 이에 1/2 직경의 충격 코어를 놓은 다음 상부로부터 하중을 낙하시킨다. 내충격성은 플레이트가 파괴되었을 때의 높이에 해당하는 충격 에너지로 표시한다.Impact resistance places the flat in a pipe 50 mm in diameter, places a 1/2 inch impact core and then drops the load from the top. Impact resistance is expressed by the impact energy corresponding to the height when the plate is broken.
투명성은 시판되는 헤이즈(haze) 측정기(ASTM D-1003에 따라)를 사용하여 측정된다.Transparency is measured using a commercially available haze meter (according to ASTM D-1003).
황변은 육안으로 평가하여 다음과 같이 구분한다 :Yellowing is assessed visually and divided into:
⊙ : 황변이 나타나지 않음 ○ : 약간 황변이 있음⊙: No yellowing ○: Slightly yellowing
△ : 황변이 나타남 × : 황변이 심하게 나타남△: yellowing appears ×: yellowing appears severely
그 결과를 표 1에 나타낸다.The results are shown in Table 1.
[실시예 2]Example 2
트리스(2,4-디-t-부틸페닐) 포스파이트와 폴리아민 화합물의 양을 각각 0.05중량부 및 0.05중량부로 증가시키는 것을 제외하고 실시예 1의 과정을 반복한다.The procedure of Example 1 is repeated except that the amounts of tris (2,4-di-t-butylphenyl) phosphite and polyamine compound are increased to 0.05 parts by weight and 0.05 parts by weight, respectively.
그 결과 얻어진 평판의 물리적 성질에 대한 측정치를 표 1에 나타낸다.Table 1 shows the measured values for the physical properties of the resulting flat plate.
[실시예 3]Example 3
트리스(2,4-디-t-부틸페닐) 포스파이트와 폴리아민 화합물의 양을 각각 0.08중량부와 0.08중량부로 증가시키는 것을 제외하고 실시예 1의 과정을 반복한다.The procedure of Example 1 is repeated except that the amounts of tris (2,4-di-t-butylphenyl) phosphite and polyamine compound are increased to 0.08 parts by weight and 0.08 parts by weight, respectively.
그 결과 얻어진 평판의 물리적 성질에 대한 측정치를 표 1에 나타낸다.Table 1 shows the measured values for the physical properties of the resulting flat plate.
[비교예 1]Comparative Example 1
트리스(2,4-디-t-부틸페닐) 포스파이트와 폴리아민 화합물 대신에 테트라키스[메틸렌-3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트] 메탄 0.1중량부를 사용하는 것을 제외하고 실시예 1의 과정을 반복한다.Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane 0.1 instead of tris (2,4-di-t-butylphenyl) phosphite and polyamine compound The procedure of Example 1 is repeated except that parts by weight are used.
그 결과 얻어진 평판의 물리적 성질에 대한 측정치를 표 1에 나타낸다.Table 1 shows the measured values for the physical properties of the resulting flat plate.
내방사선성은 본 발명의 조성물보다 나쁘다.The radiation resistance is worse than the composition of the present invention.
[비교예 2]Comparative Example 2
1.3,2.4-디(에틸벤질리덴)소르비톨이 사용되지 않는 것을 제외하고 실시예 3의 과정을 반복한다.The procedure of Example 3 is repeated except that 1.3,2.4-di (ethylbenzylidene) sorbitol is not used.
그 결과 얻어진 평판의 물리적 성질에 대한 측정치를 표 1에 나타낸다.Table 1 shows the measured values for the physical properties of the resulting flat plate.
내방사선성은 좋지만 투명성은 낮다.Good radiation resistance but low transparency.
[비교예 3]Comparative Example 3
폴리아미드 화합물이 사용되지 않는 것을 제외하고 실시예 3의 과정을 반복한다.The procedure of Example 3 is repeated except that no polyamide compound is used.
그 결과 얻어진 평판의 물리적 성질에 대한 측정치는 표 1에 나타낸다.The measured value about the physical property of the resultant plate is shown in Table 1.
내방사선성은 본 발명의 조성물보다 나쁘다.The radiation resistance is worse than the composition of the present invention.
[비교예 4][Comparative Example 4]
트리스(2,4-디-t-부틸페닐)포스파이트가 사용되지 않는 것을 제외하고 실시예 3의 과정을 반복한다.The procedure of Example 3 is repeated except that no tris (2,4-di-t-butylphenyl) phosphite is used.
그 결과 얻어진 평판의 물리적 성질에 대한 측정치를 표 1에 나타낸다.Table 1 shows the measured values for the physical properties of the resulting flat plate.
내방사선성은 본 발명의 조성물보다 나쁘다.The radiation resistance is worse than the composition of the present invention.
[비교예 5][Comparative Example 5]
폴리아민 화합물 대신에 테트라키스 [메틸렌3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트]메탄 0.1중량부가 사용되는 것을 제외하고 실시예 3과 똑같은 방법으로 평판을 제조한다.Plates were prepared in the same manner as in Example 3 except that 0.1 part by weight of tetrakis [methylene3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane was used instead of the polyamine compound. do.
그 결과 얻어진 평판의 물리적 성질에 대한 측정치를 표 1에 나타낸다.Table 1 shows the measured values for the physical properties of the resulting flat plate.
방사선에 조사 직후 황변이 심하게 나타난다.Yellowing appears severe immediately after irradiation.
[비교예 6]Comparative Example 6
폴리아민 화합물 대신에 비스(2,2,6,6-테트라메틸-4-피페리딜) 세바케이트 0.1중량부가 사용되는 것을 제외하고 실시예 3과 똑같은 방법으로 평판을 제조한다.A flat plate was prepared in the same manner as in Example 3 except that 0.1 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate was used instead of the polyamine compound.
물리적 성질에 대한 측정치를 표 1에 나타낸다.The measurements for the physical properties are shown in Table 1.
내방사선성은 본 발명의 조성물보다 나쁘다.The radiation resistance is worse than the composition of the present invention.
[비교예 7]Comparative Example 7
1.3,2,4-디(에틸벤질리덴)소르비톨과 폴리아민 화합물 대신에 디메틸 숙시네이트/2-(4-히드록시-2,2,6,6-테트라메틸-1-피페리딜)에탄올 축합생성물 0.1중량부가 사용되는 것을 제외하고 실시예 3과 똑같은 방법으로 평판을 제조한다.Dimethyl succinate / 2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) ethanol condensation product instead of 1.3,2,4-di (ethylbenzylidene) sorbitol and polyamine compound A flat plate was prepared in the same manner as in Example 3 except that 0.1 part by weight was used.
물리적 성질에 대한 측정치는 표 1에 나타낸다.Measurements for physical properties are shown in Table 1.
내방사선성은 좋지만 그 투명성은 낮다.Good radiation resistance but low transparency.
[표 1]TABLE 1
* A : 트리스 (2,4-디-t-부틸페닐) 포스파이트* A: Tris (2,4-di-t-butylphenyl) phosphite
B : 폴리아민 화합물(평균분자량 : 1800-2200)B: polyamine compound (average molecular weight: 1800-2200)
C : 1.3,2.4-디(에틸벤질리덴)소르비톨C: 1.3,2.4-di (ethylbenzylidene) sorbitol
D : 테트라키스 메틸렌-3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트 메탄D: tetrakis methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate methane
E : 비스(2.2,6.6-테트라메틸-4-피페리딜)세바케이트E: bis (2.2,6.6- tetramethyl-4-piperidyl) sebacate
F : 디메틸 숙시네이트/2-(4-히드록시-2,2,6,6-테트라메틸-1-피페리딜)에탄올 축합 생성물.F: Dimethyl succinate / 2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) ethanol condensation product.
G : 칼슘 스테아레이트G: calcium stearate
[실시예 4]Example 4
135℃의 테트라린 중에서 1.62의 고유점도를 갖고 에틸렌 3.5중량%를 함유하는 에틸렌-프로필렌 임의의 공중합체 100중량부에 1.3,2.4-디(에틸벤질리덴)소르비톨 0.3중량부, 트리스(2,4-디-t-부틸페닐)포스파이트 0.08중량부, 구조식(III)으로 표시되는 평균분자량이 1800-2200인 폴리아민 화합물 0.08중량부와 2,5-디메틸-2,5-비스(t-부틸퍼록시)헥산 0.02중량부뿐만 아니라 칼슘 스테아레이트 0.07중량부를 가한다. 그 결과 형성된 조성물을 혼합한 후 일반 압출기를 통해 약 240℃의 압출온도에서 펠릿화한다.0.3 parts by weight of 1.3,2.4-di (ethylbenzylidene) sorbitol, 100 parts by weight of any copolymer of ethylene-propylene having an intrinsic viscosity of 1.62 and containing 3.5% by weight of ethylene in tetralin at 135 ° C, tris (2,4 0.08 parts by weight of -di-t-butylphenyl) phosphite, 0.08 parts by weight of a polyamine compound having an average molecular weight of 1800-2200 represented by Structural Formula (III), and 2,5-dimethyl-2,5-bis (t-butylper 0.02 parts by weight of calcium stearate as well as 0.02 parts by weight of oxy) hexane are added. The resulting composition is mixed and pelletized at an extrusion temperature of about 240 ° C. through a conventional extruder.
그 결과 제조된 펠릿은 약 240℃의 사출 성형온도에서 사출성형기에 의해 160㎜×80㎜×두께 1㎜의 평판으로 성형한다.The resulting pellets are molded into flat plates of 160 mm x 80 mm x thickness 1 mm by an injection molding machine at an injection molding temperature of about 240 ° C.
한편, 펠릿은 용용 트롬지수 ASTM D-1238에 따라 측정한다.On the other hand, pellets are measured according to the molten thrombus index ASTM D-1238.
상기에서 얻어진 평판에 코발트-60 방사선원의 2.5Mrad γ-선을 조사한 후, 80℃의 대기에서 평판을 2주 동안 방치한다.After irradiating the 2.5 Mrad γ-ray of the cobalt-60 radiation source to the plate obtained above, the plate is left for 2 weeks in an atmosphere of 80 ℃.
평판의 내충격성, 투명성 및 황변은 실시예 1의 방법대로 조사하기 전후에 측정한다.The impact resistance, transparency and yellowing of the plate were measured before and after irradiation according to the method of Example 1.
그 결과를 표 2에 나타낸다.The results are shown in Table 2.
[실시예 5]Example 5
트리스(2,4-디-t-부틸페닐) 포스파이트와 폴리아민 화합물의 함량이 각각 0.05중량부 및 0.05중량부로 감소되는 것을 제외하고 실시예 4의 과정을 반복한다.The procedure of Example 4 is repeated except that the contents of tris (2,4-di-t-butylphenyl) phosphite and polyamine compound are reduced to 0.05 parts by weight and 0.05 parts by weight, respectively.
그 결과를 표 2에 나타낸다.The results are shown in Table 2.
[실시예 6]Example 6
트리스 (2,4-디-t-부틸페닐) 포스파이트와 폴리아민 화합물의 함량이 각각 0.02중량부와 0.02중량부로 변경되는 것을 제외하고 실시예 4의 과정을 반복한다.The procedure of Example 4 is repeated except that the contents of the tris (2,4-di-t-butylphenyl) phosphite and the polyamine compound are changed to 0.02 parts by weight and 0.02 parts by weight, respectively.
그 결과를 표 2에 나타낸다.The results are shown in Table 2.
[비교예 8]Comparative Example 8
트리스 (2,4-디-t-부틸페닐) 포스파이트 및 폴리아민 화합물 대신 테트라키스 [메틸렌-3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트] 메탄 0.1중량부가 사용되는 것을 제외하고 실시예 4의 과정을 반복한다.0.1 weight of tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] instead of tris (2,4-di-t-butylphenyl) phosphite and polyamine compound The procedure of Example 4 is repeated except that additional is used.
그 결과를 표 1에 나타낸다.The results are shown in Table 1.
그외 내방사선성은 본 발명의 조성물보다 못하다.Other radiation resistance is lower than the composition of the present invention.
[비교예 9]Comparative Example 9
1.3,2.4-디(에틸벤질리덴)소르비톨이 사용되지 않는 것을 제외하고 실시예 4의 과정을 반복한다.The procedure of Example 4 is repeated except that 1.3,2.4-di (ethylbenzylidene) sorbitol is not used.
그 결과를 표 2에 나타낸다.The results are shown in Table 2.
그의 내방사선성은 양호하지만 투명성은 나쁘다.Its radiation resistance is good but its transparency is bad.
[비교예 10]Comparative Example 10
폴리아민 화합물이 사용되지 않는 것을 제외하고 실시예 4의 과정을 반복한다.The procedure of Example 4 is repeated except that no polyamine compound is used.
그 실험결과를 표 2에 나타낸다.The experimental results are shown in Table 2.
그의 내방사선성은 본 발명의 조성물보다 나쁘다.Its radiation resistance is worse than the composition of the present invention.
[비교예 11]Comparative Example 11
트리스(2,4-디-t-부틸페닐)포스파이트가 사용되지 않는 것을 제외하고 실시예 4의 과정을 반복한다.The procedure of Example 4 is repeated except that no tris (2,4-di-t-butylphenyl) phosphite is used.
그 실험결과를 표 2에 나타낸다.The experimental results are shown in Table 2.
그의 내방사선성은 본 발명의 조성물보다 나쁘다.Its radiation resistance is worse than the composition of the present invention.
[비교예 12]Comparative Example 12
폴리아민 화합물 대신 테트라키스[메틸렌-3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트] 메탄 0.1중량부가 사용되는 것을 제외하고 실시예 4의 과정을 반복한다.The procedure of Example 4 is repeated except that 0.1 parts by weight of tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is used instead of the polyamine compound.
실험결과를 표 2에 나타낸다.The experimental results are shown in Table 2.
방사선 조사 직후 황변현상이 심하다.Severe yellowing immediately after irradiation.
[비교예 13]Comparative Example 13
폴리아민 화합물 대신 비스(2,2,6,6-테트라메틸-4-피페리딜) 세바케이트 0.1중량부가 사용되는 것을 제외하고 실시예 4의 과정을 반복한다.The procedure of Example 4 is repeated except that 0.1 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate is used instead of the polyamine compound.
실험결과를 표 2에 나타낸다.The experimental results are shown in Table 2.
그의 내방사선성은 본 발명의 조성물보다 나쁘다.Its radiation resistance is worse than the composition of the present invention.
[비교예 14]Comparative Example 14
1.3,2.4-디(에틸벤질리덴)소르비톨 및 폴리아민 화합물 대신 디메틸숙시네이트/2-(4-히드록시-2,2,6,6-테트라메틸-1-피페리딜) 에탄올 축합생성물 0.1중량부가 사용되는 것을 제외하고 실시예 4의 과정을 반복한다.0.1 parts by weight of dimethylsuccinate / 2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) ethanol condensation product in place of 1.3,2.4-di (ethylbenzylidene) sorbitol and polyamine compound The procedure of Example 4 is repeated except that it is used.
그 실험결과를 표 2에 나타낸다.The experimental results are shown in Table 2.
그의 내방사신상은 양호하지만 투명성은 낮다.His radiation-resistant image is good but its transparency is low.
[실시예 7]Example 7
2,5-디메틸-2,5-비스(5-부틸퍼록시) 핵산의 함량이 0.04중량부로 변경되는 것을 제외하고 실시예 4의 과정을 반복한다.The process of Example 4 is repeated except that the content of 2,5-dimethyl-2,5-bis (5-butylperoxy) nucleic acid is changed to 0.04 parts by weight.
실험결과를 표 3에 나타낸다.The experimental results are shown in Table 3.
[실시예 8]Example 8
2,5-디메틸-2,5-비스(5-부틸퍼록시) 핵산의 함량이 0.06중량부로 변경되는 것을 제외하고 실시예 4의 과정을 반복한다.The procedure of Example 4 is repeated except that the content of 2,5-dimethyl-2,5-bis (5-butylperoxy) nucleic acid is changed to 0.06 parts by weight.
그 실험결과를 표 3에 나타낸다.The experimental results are shown in Table 3.
비교목적을 위해 실시예 3의 조성물에 대한 펠릿의 MI값과 기타 물리적 자료를 표 3에 나타낸다.The MI values and other physical data of the pellets for the composition of Example 3 are shown in Table 3 for comparative purposes.
본 실시예의 조성물에 대한 내방사선은 본 발명의 기타 화합물과 다르지는 않지만, 성형성은 본 발명의 조성물보다 다소 나쁘다.The radiation resistance to the compositions of this example is not different from other compounds of the invention, but the moldability is somewhat worse than the compositions of the invention.
[표 2]TABLE 2
* A : 트리스 (2,4-디-t-부틸페닐) 포스파이트* A: Tris (2,4-di-t-butylphenyl) phosphite
B : 폴리아민 화합물(평균분자량 : 1800-2200)B: polyamine compound (average molecular weight: 1800-2200)
C : 1.3,2.4-디(에틸벤질리덴)소르비톨C: 1.3,2.4-di (ethylbenzylidene) sorbitol
D : 테트라키스 [메틸렌-3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트] 메탄D: tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane
E : 비스(2.2,6.6-테트라메틸-4-피페리딜) 세바케이트E: bis (2.2,6.6-tetramethyl-4-piperidyl) sebacate
F : 디메틸 숙시네이트/2-(4-히드록시-2,2,6,6-테트라메틸-1-피페리딜) 에탄올 축합생성물F: Dimethyl succinate / 2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) ethanol condensation product
G : 칼슘 스테아레이트G: calcium stearate
[표 3]TABLE 3
* 수지 100중량부당 사용된 중량부* Parts by weight used per 100 parts by weight of resin
Claims (11)
Translated fromKorean
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP46522 | 1984-03-13 | ||
| JP4652284AJPS60190443A (en) | 1984-03-13 | 1984-03-13 | Polypropylene resin composition stable to radiation |
| JP46522/83 | 1984-03-13 | ||
| JP59069197AJPS60212442A (en) | 1984-04-09 | 1984-04-09 | Radiation stable polypropylene resin composition |
| JP69197 | 1984-04-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR850006433A KR850006433A (en) | 1985-10-05 |
| KR870002104B1true KR870002104B1 (en) | 1987-12-08 |
Family
ID=26386616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019850001613AExpiredKR870002104B1 (en) | 1984-03-13 | 1985-03-13 | Polypropylene resin composition stable to radiation |
Country Status (9)
| Country | Link |
|---|---|
| KR (1) | KR870002104B1 (en) |
| AU (1) | AU552479B2 (en) |
| CA (1) | CA1254339A (en) |
| DE (1) | DE3508983A1 (en) |
| FR (1) | FR2561247B1 (en) |
| GB (1) | GB2156360B (en) |
| IT (1) | IT1184148B (en) |
| NL (1) | NL8500696A (en) |
| PT (1) | PT80096B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0243319A3 (en)* | 1986-04-25 | 1989-02-15 | Ciba-Geigy Ag | Thermoplastics stabilized against the influence of light |
| EP0303894A3 (en)* | 1987-08-18 | 1991-03-20 | American Cyanamid Company | Radiation sterilizable composition and articles made therefrom |
| JPH032239A (en)* | 1989-05-31 | 1991-01-08 | Mitsubishi Petrochem Co Ltd | Colored food molded products |
| US5219600A (en)* | 1989-05-31 | 1993-06-15 | Mitsubishi Petrochemical Co., Ltd. | Molded product for colored food |
| US4959402A (en)* | 1989-06-08 | 1990-09-25 | Becton, Dickinson And Company | High clarity radiation stable polymeric compostion and articles therefrom |
| GB2261667A (en)* | 1991-11-20 | 1993-05-26 | Sandoz Ltd | Stabilized polymeric compositions |
| US5342978A (en)* | 1993-05-24 | 1994-08-30 | General Electric Company | Organic phosphite ester compositions containing hindered piperdinyl light stabilizers |
| GB0005629D0 (en)* | 2000-03-10 | 2000-05-03 | Clariant Int Ltd | Light stabilizer composition |
| FR2866892B1 (en)* | 2004-02-27 | 2007-09-21 | Arkema | ORGANIC PEROXIDE COMPOSITION AND ALCOHOL FOR CROSSLINKING ELASTOMERS |
| WO2008024154A1 (en)* | 2006-08-22 | 2008-02-28 | Exxonmobil Chemical Patents Inc. | High clarity polymer compositions, methods and articles made therefrom |
| EP3177683B1 (en)* | 2014-08-08 | 2021-02-24 | Braskem America, Inc. | Composition comprising polypropylene and polyol, and method of making the same |
| GB201812145D0 (en) | 2018-07-25 | 2018-09-05 | Addivant Switzerland Gmbh | Composition |
| GB2591482A (en) | 2020-01-29 | 2021-08-04 | Si Group Switzerland Chaa Gmbh | Non-dust blend |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5122740A (en)* | 1974-08-16 | 1976-02-23 | Kenzo Hamada | |
| NO146433C (en)* | 1975-03-21 | 1982-09-29 | Montefibre Spa | STABILIZED POLYOLEFIN MATERIALS CONTAINING A POLYAMINE AS A STABILIZER |
| SE398498B (en)* | 1976-05-03 | 1977-12-27 | Strabruken Ab | REFRACTORY PULP INTENDED FOR USE IN METALLURGIC OVENS AS STAMP OR PREPARATION MASS OR AFTER PRESSING AND / OR VIBRATION AS A BRICK, WHICH MASS CONSISTS OF A MIXTURE INCLUDING FIREFIGHTED FOOD ... |
| IT1165130B (en)* | 1979-06-28 | 1987-04-22 | Montedison Spa | POLYCONDENSATES OF PIPERIDINS REPLACED AND THEIR USE AS POLYMER STABILIZERS |
| JPS5630449A (en)* | 1979-08-21 | 1981-03-27 | Mitsui Toatsu Chem Inc | Polypropylene composition |
| IT1151035B (en)* | 1980-07-31 | 1986-12-17 | Chimosa Chimica Organica Spa | PIPERIDYL-DERIVATIVES OF TRIAZINIC COPOLYMERS, PROCESSES FOR THEIR PREPARATION AND STABILIZED COMPOSITIONS THAT INCLUDE THEM |
| JPS5892660A (en)* | 1981-11-27 | 1983-06-02 | Adeka Argus Chem Co Ltd | Piperidylamine compound |
| JPS58180543A (en)* | 1982-04-19 | 1983-10-22 | Mitsubishi Petrochem Co Ltd | Propylene polymer composition |
| JPS58185632A (en)* | 1982-04-23 | 1983-10-29 | Iic Kagaku Kogyo Kk | Polyolefin resin composition |
- 1985
- 1985-02-22CACA000474969Apatent/CA1254339A/ennot_activeExpired
- 1985-03-04GBGB08505499Apatent/GB2156360B/ennot_activeExpired
- 1985-03-06AUAU39571/85Apatent/AU552479B2/ennot_activeCeased
- 1985-03-11ITIT19844/85Apatent/IT1184148B/enactive
- 1985-03-12NLNL8500696Apatent/NL8500696A/ennot_activeApplication Discontinuation
- 1985-03-12PTPT80096Apatent/PT80096B/ennot_activeIP Right Cessation
- 1985-03-12FRFR8503614Apatent/FR2561247B1/ennot_activeExpired
- 1985-03-13DEDE19853508983patent/DE3508983A1/ennot_activeCeased
- 1985-03-13KRKR1019850001613Apatent/KR870002104B1/ennot_activeExpired
Also Published As
| Publication number | Publication date |
|---|---|
| IT1184148B (en) | 1987-10-22 |
| PT80096B (en) | 1986-11-20 |
| GB2156360A (en) | 1985-10-09 |
| CA1254339A (en) | 1989-05-16 |
| DE3508983A1 (en) | 1985-09-26 |
| IT8519844A0 (en) | 1985-03-11 |
| NL8500696A (en) | 1985-11-01 |
| KR850006433A (en) | 1985-10-05 |
| PT80096A (en) | 1985-04-01 |
| FR2561247A1 (en) | 1985-09-20 |
| AU552479B2 (en) | 1986-06-05 |
| AU3957185A (en) | 1985-09-19 |
| GB8505499D0 (en) | 1985-04-03 |
| GB2156360B (en) | 1987-07-01 |
| FR2561247B1 (en) | 1987-12-11 |
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