KR20030057797A - Polyester resin composition with excellent uv blocking property and biaxial-oriented polyester bottle prepared by using the same - Google Patents
Polyester resin composition with excellent uv blocking property and biaxial-oriented polyester bottle prepared by using the same Download PDFInfo
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- KR20030057797A KR20030057797A KR1020010087881A KR20010087881A KR20030057797A KR 20030057797 A KR20030057797 A KR 20030057797A KR 1020010087881 A KR1020010087881 A KR 1020010087881A KR 20010087881 A KR20010087881 A KR 20010087881A KR 20030057797 A KR20030057797 A KR 20030057797A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/18—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using several blowing steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2022/00—Hollow articles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
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Abstract
Description
본 발명은 투명성이 우수함과 동시에 자외선 차단성이 우수한 폴리에스테르 수지 조성물 및 그를 이용하여 제조된 병에 관한 것으로, 보다 상세하게는 폴리에틸렌테레프탈레이트와 폴리에틸렌나프탈레이트를 용융혼합하여 제조된 폴리에스테르 수지 조성물 및 상기 수지 조성물을 2축연신 블로우 성형하여 제조된 병에 관한 것이다.The present invention relates to a polyester resin composition having excellent transparency and excellent UV protection and a bottle manufactured using the same, and more particularly, to a polyester resin composition prepared by melt-mixing polyethylene terephthalate and polyethylene naphthalate, and It relates to a bottle produced by biaxially oriented blow molding the resin composition.
종래에는 조미료, 유제품, 쥬스, 탄산음료, 맥주, 청주, 화장품, 세제 등을 충진하는 용기로서 유리 용기가 널리 이용되어 왔다. 그러나, 유리 용기는 제조비가 높아, 통상 사용후의 공용기를 회수하여 내용물을 재충진하는 방식으로 순환 재이용되어 왔다. 하지만, 이와 같이 유리 용기를 순환 재이용하는데에는 용기의 무게가 무거워 높은 운송경비가 소요될 뿐 아니라 파손이 쉬워 취급이 불편한 점등 여러가지 문제점이 있었다.Conventionally, glass containers have been widely used as containers for seasonings, dairy products, juices, carbonated drinks, beer, sake, cosmetics, detergents, and the like. However, glass containers have a high manufacturing cost, and have been recycled in a manner to recover the common air after use and refill the contents. However, in order to recycle the glass container in this way, the weight of the container is heavy and high transportation cost is required, and there are various problems in that it is easy to be damaged and is inconvenient to handle.
따라서, 최근에는 이러한 문제점을 갖는 유리 용기로부터 경량이고 취급이 용이한 각종 플라스틱 용기로의 전환이 급속하게 진행되고 있다. 플라스틱 용기는 충진 내용물의 종류 및 사용 목적에 따라 각종의 플라스틱 재료로 성형된다. 현재로서는 플라스틱 용기 중에서도 특히 폴리에틸렌테레프탈레이트(PET)를 연신 성형하여 얻어진 병이 기계적 강도, 내열성, 투명성 및 가스차단성 등의 측면에서 성능이 우수하여, 쥬스, 청량음료, 조미료, 세제, 화장품 등의 충진 용기로서 널리 이용되고 있다.Therefore, in recent years, the transition from the glass container which has such a problem to the various plastic container which is lightweight and easy to handle is progressing rapidly. Plastic containers are molded from various plastic materials depending on the type of filling contents and the purpose of use. Currently, bottles obtained by stretching and molding polyethylene terephthalate (PET) in plastic containers are excellent in terms of mechanical strength, heat resistance, transparency and gas barrier properties, and thus are filled with juices, soft drinks, seasonings, detergents and cosmetics. It is widely used as a container.
그런데, 주류, 탄산음료 등은 자외선에 의하여 변질되기가 쉬워서, 이들을 충진하는 PET 병에는 우수한 투명성이 필요함과 동시에 우수한 자외선 차단성도 요구된다. 그러나, 종래의 PET 병은 투명성이 우수하지만 자외선도 잘 투과시켜서, 자외선 차단성의 개선이 요구되어 왔다. 이를 위해, 종래에는 주로 녹색계열의 자외선차단 착색제를 첨가하여 PET 병을 성형하였다. 하지만, 녹색 착색제의 사용으로 인하여 PET 병의 재활용에 어려움이 있어 착색제의 사용에는 한계가 있다 하겠다. 따라서, 우수한 투명성을 가짐과 동시에 자외선 차단성이 우수한 새로운 폴리에스테르 병이 요구되고 있는 실정이다.However, liquor, carbonated beverages, and the like are easily deteriorated by ultraviolet rays, and thus, PET bottles filling them require excellent transparency and excellent ultraviolet ray blocking properties. However, the conventional PET bottle is excellent in transparency, but also transmits ultraviolet rays well, and there has been a demand for improvement of UV blocking property. To this end, conventionally, a PET bottle was formed by adding a green sunscreen colorant. However, due to the use of the green colorant, there is a difficulty in recycling the PET bottle, so the use of the colorant will be limited. Therefore, there is a need for a new polyester bottle having excellent transparency and excellent UV protection.
본 발명은 상기와 같은 종래기술의 문제점들을 해결하기 위한 것으로, 투명성이 우수함과 동시에 자외선 차단성이 우수한 폴리에스테르 2축연신 병을 제공함을 목적으로 한다.The present invention is to solve the problems of the prior art as described above, and an object of the present invention is to provide a polyester biaxially-stretched bottle excellent in transparency and excellent UV protection.
즉, 본 발명의 한 측면은 폴리에틸렌테레프탈레이트 99~60중량부와 폴리에틸렌나프탈레이트 1~40중량부를 용융혼련하여 제조된 폴리에스테르 수지 조성물을 제공한다.That is, one aspect of the present invention provides a polyester resin composition prepared by melt kneading 99 to 60 parts by weight of polyethylene terephthalate and 1 to 40 parts by weight of polyethylene naphthalate.
본 발명의 다른 측면은 상기 폴리에스테르 수지 조성물을 사출성형하여 얻은 프리폼을 2축연신 블로우 성형하여 제조된, 연신 배율이 3~10배이고 동부의 두께가 0.2~0.6mm인 폴리에스테르 2축연신 병을 제공한다.Another aspect of the present invention is a polyester biaxial stretching bottle having a draw ratio of 3 to 10 times and an eastern thickness of 0.2 to 0.6 mm prepared by biaxial stretching blow molding the preform obtained by injection molding the polyester resin composition. to provide.
본 발명에 따른 폴리에스테르 2축연신 병은 [A]폴리에틸렌테레프탈레이트 99~60중량부와 [B]폴리에틸렌나프탈레이트 1~40중량부([A]와 [B]의 합계는 100중량부)를 용융혼련하여 제조된 폴리에스테르 수지 조성물을 사용하여 성형된다.The polyester biaxially oriented bottle according to the present invention comprises 99 to 60 parts by weight of [A] polyethylene terephthalate and 1 to 40 parts by weight of [B] polyethylene naphthalate (the total of [A] and [B] is 100 parts by weight). It is shape | molded using the polyester resin composition manufactured by melt-kneading.
이하 본 발명의 폴리에스테르 수지 조성물에 대하여 보다 상세하게 설명한다.Hereinafter, the polyester resin composition of the present invention will be described in more detail.
본 발명에 사용된 폴리에틸렌테레프탈레이트(성분 [A])는 테레프탈산 또는 이의 에스테르 유도체와 에틸렌글리콜 또는 이의 에스테르 유도체로부터 유도된 단위로 구성된다.The polyethylene terephthalate (component [A]) used in the present invention is composed of units derived from terephthalic acid or ester derivatives thereof and ethylene glycol or ester derivatives thereof.
이러한 폴리에틸렌테레프탈레이트는 테레프탈산 이외의 다른 디카르복실산류 및/또는 에틸렌글리콜 이외의 다른 디하이드록시 화합물류로부터 유도된 단위를 10몰% 이하의 양으로 함유할 수도 있다.Such polyethylene terephthalate may contain 10 mole% or less of units derived from dicarboxylic acids other than terephthalic acid and / or dihydroxy compounds other than ethylene glycol.
테레프탈산 이외의 다른 디카르복실산류의 구체적인 예로는 프탈산, 이소프탈산 등의 방향족 디카르복실산, 사이클로헥산디카르복실산 등의 지환족 디카르복실산, 및 이의 에스테르 유도체를 들 수 있다.Specific examples of dicarboxylic acids other than terephthalic acid include aromatic dicarboxylic acids such as phthalic acid and isophthalic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and ester derivatives thereof.
또한, 에틸렌글리콜 이외의 디하이드록시 화합물류의 구체적인 예로는 프로필렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 테트라에틸렌글리콜 등의 지방족 글리콜, 사이클로헥산디메탄올 등의 지환족 글리콜, 비스페놀, 하이드로퀴논 등의 방향족 디올, 및 이의 에스테르 유도체를 들 수 있다.Specific examples of dihydroxy compounds other than ethylene glycol include aliphatic glycols such as propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, alicyclic glycols such as cyclohexanedimethanol, bisphenol, hydroquinone and the like. Aromatic diols, and ester derivatives thereof.
본 발명에 사용되는 폴리에틸렌테레프탈레이트의 극한점도(용매: o-클로로페놀; 온도: 25℃)는 0.7~1.3dl/g, 바람직하게는 0.8~1.2dl/g, 더욱 바람직하게는 0.85~1.0dl/g인 것이 적당하다. 폴리에틸렌테레프탈레이트의 극한점도가 0.7dl/g 미만이면 성형자체가 극히 곤란하며, 1.3dl/g를 초과하면 폴리에틸렌나프탈레이트와의 용융거동이 상이하여 블렌드가 원할하게 이루어지지 않는다.The ultimate viscosity (solvent: o-chlorophenol; temperature: 25 ° C) of the polyethylene terephthalate used in the present invention is 0.7 to 1.3 dl / g, preferably 0.8 to 1.2 dl / g, more preferably 0.85 to 1.0 dl It is appropriate to be / g. If the intrinsic viscosity of the polyethylene terephthalate is less than 0.7dl / g, the molding itself is extremely difficult, and if it exceeds 1.3dl / g, the melt behavior with polyethylene naphthalate is different and the blend is not made smoothly.
본 발명에 사용된 폴리에틸렌테레프탈레이트의 시차주사형열량계(DSC, 승온속도 10℃/min)로 측정한 결정융해온도는 220~265℃, 바람직하게는 240~260℃인 것이 적당하다. 폴리에틸렌테레프탈레이트의 결정융해온도가 220℃ 미만이거나 265℃를 초과하면, 폴리에틸렌나프탈레이트와의 상용성이 저하되어 블렌드 효과가 극히 저조해진다.The crystal melting temperature measured by the differential scanning calorimeter (DSC, temperature rising rate of 10 ℃ / min) of the polyethylene terephthalate used in the present invention is appropriately 220 ~ 265 ℃, preferably 240 ~ 260 ℃. If the crystal melting temperature of polyethylene terephthalate is lower than 220 ° C or higher than 265 ° C, the compatibility with polyethylenenaphthalate is lowered and the blending effect is extremely poor.
또한, 본 발명에 사용된 폴리에틸렌테레프탈레이트의 유리전이온도는 50~120℃, 바람직하게는 70~90℃인 것이 적당하다. 50℃ 미만의 유리전이온도를 갖는폴리에틸렌테레프탈레이트는 고상으로 펠렛화하기 어려운 반면, 유리전이온도가 120℃를 초과하는 경우에는 용융이 어려워 성형이 매우 곤란해진다.In addition, the glass transition temperature of the polyethylene terephthalate used in the present invention is 50 ~ 120 ℃, preferably 70 ~ 90 ℃. While polyethylene terephthalate having a glass transition temperature of less than 50 ° C. is difficult to pelletize into a solid phase, when the glass transition temperature exceeds 120 ° C., melting becomes difficult and molding becomes very difficult.
한편, 본 발명에 사용된 폴리에틸렌나프탈레이트(성분 [B])는 2,6-나프탈렌디카르복실산과 에틸렌글리콜로부터 유도된 에틸렌-2,6-나프탈렌디카르복실레이트 단위를 70~100몰%, 바람직하게는 80~100몰%, 더욱 바람직하게는 90~98몰%의 양으로 함유한다.On the other hand, polyethylene naphthalate (component [B]) used in the present invention is 70-100 mol% of ethylene-2,6-naphthalenedicarboxylate units derived from 2,6-naphthalenedicarboxylic acid and ethylene glycol, Preferably it is contained in the amount of 80-100 mol%, More preferably, it is 90-98 mol%.
이러한 폴리에틸렌나프탈레이트는 2,6-나프탈렌디카르복실산 이외의 다른 디카르복실산류 및/또는 에틸렌글리콜 이외의 다른 디하이드록시 화합물류로부터 유도된 단위를 30몰% 이하의 양으로 함유할 수도 있다.Such polyethylene naphthalate may contain a unit derived from dicarboxylic acids other than 2,6-naphthalenedicarboxylic acid and / or dihydroxy compounds other than ethylene glycol in an amount of 30 mol% or less. .
2,6-나프탈렌디카르복실산 이외의 다른 디카르복실산류의 구체적인 예로는 테레프탈산, 이소프탈산, 2,7-나프탈렌디카르복실산, 2,5-나프탈렌디카르복실산, 1,4-나프탈렌디카르복실산 등의 방향족 디카르복실산, 및 이의 에스테르 유도체를 들 수 있다.Specific examples of dicarboxylic acids other than 2,6-naphthalenedicarboxylic acid include terephthalic acid, isophthalic acid, 2,7-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,4-naphthalene Aromatic dicarboxylic acids, such as dicarboxylic acid, and ester derivatives thereof are mentioned.
또한, 에틸렌글리콜 이외의 다른 디하이드록시 화합물류의 구체적인 예로는 프로필렌글리콜, 테트라메틸렌글리콜, 네오펜틸글리콜, 디에틸렌글리콜, 트리에틸렌글리콜 등의 지방족 글리콜, 사이클로헥산디메탄올 등의 지환족 글리콜, 비스페놀, 하이드로퀴논 등의 방향족 디올, 및 이의 에스테르 유도체를 들 수 있다.Specific examples of dihydroxy compounds other than ethylene glycol include aliphatic glycols such as propylene glycol, tetramethylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, and alicyclic glycols such as cyclohexanedimethanol, and bisphenols. And aromatic diols such as hydroquinone, and ester derivatives thereof.
본 발명에 사용된 폴리에틸렌나프탈레이트의 극한점도(용매: o-클로로페놀; 온도: 25℃)는 0.5~1.0dl/g, 바람직하게는 0.55~0.9dl/g, 더욱 바람직하게는0.6~0.8dl/g인 것이 적당하다. 0.5dl/g 미만의 점도에서는 성형물의 충격강도가 상당히 낮아지며, 1.0dl/g를 초과하는 점도에서는 폴리에틸렌테레프탈레이트와의 용융거동이 상이하여 블렌드가 어렵다.The ultimate viscosity (solvent: o-chlorophenol; temperature: 25 ° C.) of the polyethylene naphthalate used in the present invention is 0.5 to 1.0 dl / g, preferably 0.55 to 0.9 dl / g, more preferably 0.6 to 0.8 dl It is appropriate to be / g. At viscosities less than 0.5 dl / g, the impact strength of the moldings is considerably lowered, and at viscosities greater than 1.0 dl / g, the melt behavior with polyethylene terephthalate is different, making blending difficult.
본 발명에 사용된 폴리에틸렌나프탈레이트의 시차주사형열량계(DSC, 승온속도 10℃/min)로 측정된 승온결정화온도는 150℃ 이상, 바람직하게는 160~230℃, 더욱 바람직하게는 180~220℃인 것이 좋다. 폴리에틸렌나프탈레이트의 승온결정화온도가 150℃ 미만이면 폴리에틸렌나프탈레이트의 연신에 의한 결정화가 지연되어 소정의 내압성이 발현되지 않는 반면, 240℃를 초과하는 경우에는 백화의 원인이 된다.The elevated temperature crystallization temperature measured by differential scanning calorimeter (DSC, heating rate 10 ℃ / min) of the polyethylene naphthalate used in the present invention is 150 ℃ or more, preferably 160 ~ 230 ℃, more preferably 180 ~ 220 ℃ It is good to be. If the elevated temperature crystallization temperature of polyethylene naphthalate is less than 150 ° C., crystallization by stretching of polyethylene naphthalate is delayed so that a predetermined pressure resistance is not expressed, whereas if it exceeds 240 ° C., it causes whitening.
본 발명의 폴리에스테르 수지 조성물은 상기 [A]와 [B] 성분의 합계를 100중량부로 하였을 때, [A] 99~60중량부, 바람직하게는 95~75중량부와 [B] 1~40중량부, 바람직하게는 5~25중량부를 공지의 혼합장치, 예를 들어 리본블렌더 또는 텀블러블렌더 등을 이용하여 균일하게 혼합한 후, 1축 압출기 또는 2축 압출기 등으로 용융 혼련하여 제조된다. 이때 용융 혼련은 통상 270~320℃, 바람직하게는 280~300℃의 온도에서 행하여진다. 270℃ 미만의 온도에서는 [A] 및 [B] 성분의 용융이 매우 어려우며, 320℃를 초과하는 온도에서는 열분해 작용이 우세하여 최종제품의 물성에 불리한 영향을 준다. 이와 같이 제조된 본 발명의 수지 조성물 100 중량부당 상기 [B] 성분의 함량이 40 중량부를 초과할 경우에는, 비결정영역이 과다하여 소정의 병에서 요구되는 연신 결정화가 이루어지지 않으며, 따라서 성형성 및 내압성이 매우 부족하게 된다.The polyester resin composition of the present invention is 99 to 60 parts by weight, preferably 95 to 75 parts by weight and [B] 1 to 40 when the total amount of the components [A] and [B] is 100 parts by weight. By weight, preferably 5 to 25 parts by weight is uniformly mixed using a known mixing device, for example, ribbon blender or tumbler blender, etc., and then melt kneaded with a single screw extruder or a twin screw extruder. Melt-kneading at this time is normally performed at the temperature of 270-320 degreeC, Preferably it is 280-300 degreeC. At temperatures below 270 ° C, melting of [A] and [B] components is very difficult. At temperatures above 320 ° C, pyrolysis predominates and adversely affects the physical properties of the final product. When the content of the component [B] is more than 40 parts by weight per 100 parts by weight of the resin composition of the present invention prepared as described above, the amorphous region is excessive, so that the stretch crystallization required in a given bottle is not achieved, and thus the moldability and The pressure resistance becomes very poor.
이하 본 발명의 폴리에스테르 2축연신 병에 대하여 보다 상세하게 설명한다.Hereinafter, the polyester biaxial stretching bottle of the present invention will be described in more detail.
본 발명에 따르면, 상기와 같은 폴리에스테르 수지 조성물을 사출성형하여 프리폼(preform)을 얻은 다음, 이를 2축연신 블로우 성형함으로써 투명성과 자외선 차단성이 모두 우수한 폴리에스테르 2축연신 병을 용이하게 생산할 수 있다.According to the present invention, injection molding the polyester resin composition as described above to obtain a preform (preform), and then by biaxially blow molding it can easily produce a polyester biaxially drawn bottle excellent in both transparency and UV protection. have.
본 발명의 폴리에스테르 수지 조성물로 된 프리폼을 2축연신 블로우 성형하는 방법은 특별히 제한되지 아니하며 통상의 방법을 따른다. 본 발명에서는 사출성형 후의 프리폼을 일단 냉각시킨 후 냉(冷)프리폼을 연신 블로우 성형할 수도 있고(2-스테이지 방식), 이와 달리 사출성형 후 냉각되지 않은 온(溫)프리폼을 연신 블로우 성형할 수도 있다(1-스테이지 방식). 연신 블로우 성형시에는, 블로우 성형 금형 내에 삽입한 후 수지 조성물의 연신온도(통상 90~140℃)로 가열해둔 프리폼을 종방향으로 이동하는 로드(load)와 가압기체에 의하여 종·횡 2축 방향으로 연신한다. 이 때, 종축방향으로는 통상 1.5~3배, 바람직하게는 2~2.5배, 그리고 횡축방향으로는 통상 2~5배, 바람직하게는 3~4배로 연신하는 것이 좋다. 본 발명에서는 연신배율(종×횡)을 최대 10배 이하로 제한한다. 상기 종·횡 연신비의 하한치(종: 1.5배, 횡: 2배) 미만에서는 연신에 의한 결정화가 부족하여 병의 물성이 저하되는 반면, 종·횡 연신비가 모두 상기 상한치(종: 3.0배, 횡: 4.0배)를 넘을 경우에는 병의 백화가 촉진되어 헤이즈(haze)에 불리한 영향을 미친다.The method of biaxially drawing blow molding the preform made of the polyester resin composition of the present invention is not particularly limited and follows a conventional method. In the present invention, the preform after injection molding is once cooled, and the cold preform may be stretch blow-molded (two-stage method). Alternatively, the on-preform that is not cooled after injection molding may be stretch blow-molded. (One-stage). In the case of stretch blow molding, the longitudinal and transverse biaxial directions are formed by a rod and a pressurized gas which move the preform inserted into the blow molding die and then heated at the stretching temperature of the resin composition (usually 90 to 140 ° C.) in the longitudinal direction. To extend. At this time, it is usually 1.5 to 3 times, preferably 2 to 2.5 times, and 2 to 5 times, preferably 3 to 4 times, in the longitudinal axis direction. In the present invention, the draw ratio (vertical × horizontal) is limited to 10 times or less at maximum. Below the lower limit (length: 1.5 times, width: 2 times) of the longitudinal and lateral stretch ratios, the crystallization due to stretching is insufficient, and the physical properties of the bottle are lowered. 4.0 times), the whitening of the disease is promoted, which adversely affects haze.
상술한 바와 같이 제조된 본 발명의 폴리에스테르 2축연신 병은 병 동부의 두께가 바람직하게는 0.2~0.6mm의 범위 내에 들고, 병 동부의 자외선 투과율이 50%이하, 바람직하게는 40% 이하, 더욱 바람직하게는 30% 이하이다. 본 발명의 폴리에스테르 2축연신 병은 넓은 영역의 자외선을 차단하는데 효과적이며, 특히 종래의 PET 병에서 차단성이 좋지 않았던 320nm 파장의 자외선에 대해서도 차단성이 우수하다. 본 발명의 폴리에스테르 2축연신 병은 이처럼 우수한 자외선 차단성을 가짐과 동시에, 투명성도 매우 뛰어나 병 동부의 헤이즈치가 5% 이하, 바람직하게는 4% 이하이다.The polyester biaxially oriented bottle of the present invention prepared as described above has the thickness of the bottle eastern part preferably in the range of 0.2 to 0.6 mm, the ultraviolet transmittance of the bottle eastern 50% or less, preferably 40% or less, More preferably, it is 30% or less. The polyester biaxially oriented bottle of the present invention is effective in blocking ultraviolet rays in a wide area, and particularly excellent in blocking properties against ultraviolet rays having a wavelength of 320 nm, which is not good in conventional PET bottles. The polyester biaxially oriented bottle of the present invention has such excellent ultraviolet ray blocking property and is also excellent in transparency, and has a haze value of 5% or less, preferably 4% or less in the eastern part of the bottle.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하고자 하나, 이러한 실시예들은 단지 설명의 목적을 위한 것으로 본 발명을 제한하는 것으로 해석되어서는 안된다. 하기 실시예에서 병의 투명성 및 자외선 차단성의 평가방법은 다음과 같다:Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention. In the following examples, the evaluation method of the transparency and the sunscreen of the bottle is as follows:
[투명성][Transparency]
실시예(또는 비교예)에서 제조된 병의 동부를 잘라내어 헤이즈 메타를 사용하여 ASTM D 1003에 의거 동일 시험편의 헤이즈를 3회씩 측정한 후, 그 평균치에 의하여 투명성을 평가하였다.The eastern part of the bottle manufactured in the Example (or the comparative example) was cut out, and the haze of the same test piece was measured 3 times according to ASTM D1003 using haze meta, and transparency was evaluated by the average value.
[자외선 차단성][UV protection]
실시예(또는 비교예)에서 제조된 병 동부를 잘라내어 자외가시광분광광도계를 이용하여 380nm 파장 광선의 투과율을 측정하였다.The eastern part of the bottle prepared in Example (or Comparative Example) was cut out and the transmittance of 380 nm wavelength light was measured using an ultraviolet visible spectrophotometer.
실시예 1Example 1
폴리에틸렌테레프탈레이트(극한점도=1.1 dl/g) 90중량부, 및 2,6-나프탈렌디카르본산과 테레프탈산 및 에틸렌글리콜로부터 얻어진 공중합 폴리에틸렌나프탈레이트(극한점도=0.63 dl/g; 2,6-나프탈렌디카르본산/테레프탈산=92/8) 10중량부를 텀블러 블렌더를 이용하여 혼합한 후, 압출기를 사용하여 300℃, 스크류 회전수 180rpm의 조건으로 용융 혼련하여 폴리에스테르 수지 펠렛을 수득하였다.90 parts by weight of polyethylene terephthalate (intrinsic viscosity = 1.1 dl / g) and copolymerized polyethylene naphthalate (intrinsic viscosity = 0.63 dl / g; 2,6-naphthalene) obtained from 2,6-naphthalenedicarboxylic acid, terephthalic acid and ethylene glycol 10 parts by weight of dicarboxylic acid / terephthalic acid = 92/8) were mixed using a tumbler blender, and then melt kneaded using an extruder under conditions of 300 ° C. and a screw rotation speed of 180 rpm to obtain a polyester resin pellet.
상기 수지 펠렛을 사출성형기로 280~290℃에서 성형하여 프리폼을 얻은 후, 연신 블로우 성형기(Corpoplast사 제품, 모델명 LB-01)로 연신하여 2축연신 폴리에스테르 병을 얻었다. 이 때 연신 온도는 110~130℃로 하였고, 연신 배율은 종방향 2.1배, 횡방향 3.5배로 하였다. 이와 같이 제조된 병의 특성을 하기 표 1에 나타내었다.The resin pellet was molded at an injection molding machine at 280 to 290 ° C to obtain a preform, and then stretched with a stretch blow molding machine (Corpoplast, model name LB-01) to obtain a biaxially stretched polyester bottle. At this time, the stretching temperature was 110 to 130 ° C, and the draw ratio was 2.1 times in the longitudinal direction and 3.5 times in the lateral direction. The properties of the bottles thus prepared are shown in Table 1 below.
실시예 2∼3Examples 2 to 3
폴리에스테르 수지 조성물 제조에 사용되는 폴리에틸렌테레프탈레이트와 폴리에틸렌나프탈레이트의 양을 하기 표 1에 따라 변경한 외에는 상기 실시예 1과 동일한 방법으로 2축연신 폴리에스테르 병을 제조하였다. 이와 같이 제조된 병의 특성을 하기 표 1에 나타내었다.A biaxially stretched polyester bottle was prepared in the same manner as in Example 1 except that the amounts of polyethylene terephthalate and polyethylene naphthalate used for preparing the polyester resin composition were changed according to Table 1 below. The properties of the bottles thus prepared are shown in Table 1 below.
비교예 1Comparative Example 1
폴리에스테르 수지 조성물 대신에 폴리에틸렌테레프탈레이트 단독에 녹색 착색제를 0.2중량% 첨가하여 사용한 것 외에는 상기 실시예 1과 동일한 방법으로 2축연신 폴리에스테르 병을 제조하였다. 이와 같이 제조된 병의 특성을 하기 표 1에 나타내었다.A biaxially stretched polyester bottle was prepared in the same manner as in Example 1, except that 0.2 wt% of a green colorant was added to polyethylene terephthalate alone instead of the polyester resin composition. The properties of the bottles thus prepared are shown in Table 1 below.
비교예 2∼3Comparative Examples 2 to 3
폴리에스테르 수지 조성물 대신에 폴리에틸렌테레프탈레이트 또는 폴리에틸렌나프탈레이트만을 사용한 것 외에는 상기 실시예 1과 동일 방법으로 2축연신 폴리에스테르 병을 제조하였다. 이와 같이 제조된 병의 특성을 하기 표 1에 나타내었다.A biaxially stretched polyester bottle was prepared in the same manner as in Example 1 except that only polyethylene terephthalate or polyethylene naphthalate was used instead of the polyester resin composition. The properties of the bottles thus prepared are shown in Table 1 below.
이상에서 상세히 설명한 바와 같이, 본 발명에 의한 폴리에스테르 2축연신 병은 투명성 및 자외선 차단성이 매우 우수하므로, 주류, 탄산음료 등의 용기로서 매우 유용하다.As described in detail above, the polyester biaxial stretching bottle according to the present invention is very useful as a container for liquor, carbonated beverages, etc. because of its excellent transparency and UV blocking properties.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100615998B1 (en) * | 2003-11-05 | 2006-08-28 | 주식회사 효성 | Manufacturing method of transparent polyester container for excluding UV and the container manufactured by this method |
| EP2072558A2 (en) | 2007-07-31 | 2009-06-24 | Futura Polyesters Limited | A polymeric composition and a PET/PEN copolyester suitable for manufacturing pasteurizable containers |
| KR200453440Y1 (en) * | 2008-04-02 | 2011-05-09 | 조규복 | Dual locking apparatus for personal ornaments |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0847979A (en) * | 1994-08-05 | 1996-02-20 | Mitsui Petrochem Ind Ltd | Polyester bottle possible to re-fill |
| WO1998024844A1 (en) * | 1996-12-06 | 1998-06-11 | Continental Pet Technologies, Inc. | Process for making pen/pet blends and transparent articles therefrom |
| JPH10330607A (en) * | 1997-05-28 | 1998-12-15 | Toyobo Co Ltd | Thermoplastic thermosetting molding product and its production |
| JP2000080256A (en) * | 1998-06-26 | 2000-03-21 | Teijin Ltd | Bottle |
| KR20010029470A (en) * | 1997-07-04 | 2001-04-06 | 미야베 요시까즈 | Polyester resin composition and bottle produced from the resin composition |
-
2001
- 2001-12-29 KR KR1020010087881A patent/KR20030057797A/en not_active Application Discontinuation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0847979A (en) * | 1994-08-05 | 1996-02-20 | Mitsui Petrochem Ind Ltd | Polyester bottle possible to re-fill |
| WO1998024844A1 (en) * | 1996-12-06 | 1998-06-11 | Continental Pet Technologies, Inc. | Process for making pen/pet blends and transparent articles therefrom |
| JPH10330607A (en) * | 1997-05-28 | 1998-12-15 | Toyobo Co Ltd | Thermoplastic thermosetting molding product and its production |
| KR20010029470A (en) * | 1997-07-04 | 2001-04-06 | 미야베 요시까즈 | Polyester resin composition and bottle produced from the resin composition |
| JP2000080256A (en) * | 1998-06-26 | 2000-03-21 | Teijin Ltd | Bottle |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100615998B1 (en) * | 2003-11-05 | 2006-08-28 | 주식회사 효성 | Manufacturing method of transparent polyester container for excluding UV and the container manufactured by this method |
| EP2072558A2 (en) | 2007-07-31 | 2009-06-24 | Futura Polyesters Limited | A polymeric composition and a PET/PEN copolyester suitable for manufacturing pasteurizable containers |
| EP2072558A3 (en) * | 2007-07-31 | 2009-09-16 | Futura Polyesters Limited | A polymeric composition and a PET/PEN copolyester suitable for manufacturing pasteurizable containers |
| KR200453440Y1 (en) * | 2008-04-02 | 2011-05-09 | 조규복 | Dual locking apparatus for personal ornaments |
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