KR950015127B1 - Polyester and use of thereof - Google Patents
Polyester and use of thereof Download PDFInfo
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- KR950015127B1 KR950015127B1 KR1019920006415A KR920006415A KR950015127B1 KR 950015127 B1 KR950015127 B1 KR 950015127B1 KR 1019920006415 A KR1019920006415 A KR 1019920006415A KR 920006415 A KR920006415 A KR 920006415A KR 950015127 B1 KR950015127 B1 KR 950015127B1
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- South Korea
- Prior art keywords
- mol
- polyester
- heat
- bottle
- preform
- Prior art date
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- 229920000728 polyester Polymers 0.000 title claims abstract description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 3
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- 238000000071 blow moulding Methods 0.000 claims abstract 2
- 238000000465 moulding Methods 0.000 claims description 12
- 150000001463 antimony compounds Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- DMCTVRQBJMBEDT-UHFFFAOYSA-N phenol;1,1,1,2-tetrachloroethane Chemical compound ClCC(Cl)(Cl)Cl.OC1=CC=CC=C1 DMCTVRQBJMBEDT-UHFFFAOYSA-N 0.000 claims 1
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract 1
- 239000012046 mixed solvent Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 22
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000008187 granular material Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000009998 heat setting Methods 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 235000013361 beverage Nutrition 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WYOFTXWVYIGTCT-UHFFFAOYSA-K [OH-].[Sb+3].OCC([O-])=O.OCC([O-])=O Chemical compound [OH-].[Sb+3].OCC([O-])=O.OCC([O-])=O WYOFTXWVYIGTCT-UHFFFAOYSA-K 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- KFGCQOLKVDHXJP-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.OC(=O)C1=CC=CC(C(O)=O)=C1 KFGCQOLKVDHXJP-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013518 molded foam Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/003—PET, i.e. poylethylene terephthalate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2390/00—Containers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
Abstract
Description
본 발명은 내열성 및 투명성이 우수한 폴리에스터제 내열보틀 제조에 적합한 폴리에스터에 관한 것이다. 또한 본 발명은 이 폴리에스터로 제조한 보틀성형용 프리폼 및 투명성과 핫필링성이 우수한 폴리에스터제 내열보틀에 관한 것이다.The present invention relates to a polyester suitable for producing a heat-resistant bottle made of polyester having excellent heat resistance and transparency. The present invention also relates to a bottle-forming preform made of this polyester and a heat-resistant bottle made of polyester having excellent transparency and hot peeling properties.
종래에는 각종 용기의 소재로 유리가 널리 사용되고 있었는데, 이 유리용기는 원가가 높기 때문에 통상 사용후의 빈용기를 회수하여 재사용하는 방법이 채용되고 있었다. 또한 유리용기는 자체 중량이 무겁기 때문에 운송경비가 많이 들게되고, 파손되기 쉽다는 치명적인 결함을 가지고 있음으로 인하여 취급이 불편하고 고속충전이 곤란한 등의 문제점이 있었다.Background Art Conventionally, glass has been widely used as a material for various containers, and since the glass container has a high cost, a method of recovering and reusing empty containers after normal use has been adopted. In addition, because the glass container is heavy in its own weight, it costs a lot of transportation expenses, and has a fatal defect that is easy to be damaged, resulting in inconvenience in handling and difficulty in fast charging.
이러한 유리용기의 결점을 개선하기 위하여, 유리용기로부터 여러가지 플라스틱 용기로의 전환이 급속하게 진행되어 왔다. 플라스틱 용기의 소재로는 내용물의 종류에 따라 여러가지 플라스틱이 사용되고 있지만, 그중에서도 폴리에스터는 기계적 강도, 투명성, 가스차단성, 식품위생성, 내용제성 등이 우수하기 때문에 각광받고 있는 소재이며, 특히 음료용기로서의 거의 독점적인 위치를 차지하고 있다.In order to improve the drawback of such a glass container, the conversion from glass container to various plastic containers has progressed rapidly. Various plastics are used for the material of the plastic container according to the kind of contents, but polyester is a material that is in the spotlight because of its excellent mechanical strength, transparency, gas barrier properties, food hygiene, solvent resistance, and the like. Occupies an exclusive position.
이와같은 폴리에스터 보틀의 용도 중에는 과일쥬스와 이온음료 등과 같이 열살균이 필요한 것이 있으며, 이러한 경우에는 뜨거운 액체를 핫필링하는 방법이 사용되고 있고, 따라서 열살균이 필요한 음료의 용기로 사용하기 위해서는 폴리에스터 보틀이 투명성 뿐만아니라, 핫필링에 견딜 수 있는 내열성을 가지고 있어야 한다.Some uses of such polyester bottles require heat sterilization, such as fruit juices and ionic beverages. In this case, a method of hot peeling hot liquids is used. The bottle must have transparency as well as heat resistance to withstand hot peeling.
투명성과 내열성에 대한 요구를 동시에 만족시키기 위한 폴리에스터제 내열보틀을 제조하는 방법으로는 폴리아릴레이트와 같은 고내열성 수지와의 다층 보틀로 성형하는 방법과 성형후에 열고정하는 방법이 공지되어 있는데, 대량생산이 가능한 후자가 일반적으로 사용되고 있다.As a method of manufacturing a polyester heat resistant bottle for satisfying the demand for transparency and heat resistance simultaneously, a method of forming into a multilayer bottle with a high heat resistant resin such as polyarylate and a method of heat setting after molding are known. The latter, which can be produced, is generally used.
대량생산이 가능한, 성형후에 열고정시키는 방법을 상세히 설명하면, 사출된 프리폼의 입구부를 가열하여 결정화시키고 몸통부는 이축연신과 동시에 뜨거운 몰드에 밀착상태로 유지하며 열고정하여 내열성을 부여하는 방법이다.The method of heat-setting after molding, which can be mass-produced, will be described in detail. The method of heating and crystallizing the inlet portion of the injected preform is a method of providing heat resistance by biaxially stretching and keeping the body in close contact with the hot mold and heat-setting.
그러나 이러한 공법을 사용하는 경우, 폴리에스터 자체의 결정화 속도가 느린데다 배향도가 낮은 입구부의 결정화에는 장시간이 소요되므로 생산공정의 병목으로 된다. 따라서 열고정하여 내열성을 부여하는 공정을 사용하면서 높은 생산성을 내기 위해서는 생산공정의 병목이 되는 입구부 결정화 단계에서의 소요시간을 단축하여야 하며, 이를 위하여 보틀성형에 사용되는 폴리에스터 수지의 결정화 속도를 빠르게 조절해야 하지만, 이러한 조작은 보틀 몸통부의 투명성과는 역행하는 것이며, 이렇게 조절된 폴리에스터 수지를 사용하는 경우에는 프리폼 사출공정의 사이클 타임이 길어지게 되는 등의 문제점이 발생된다.However, when such a method is used, it is a bottleneck of the production process because the crystallization rate of the polyester itself and the crystallization of the inlet having a low degree of orientation take a long time. Therefore, in order to produce high productivity while using heat-setting process to give heat resistance, it is necessary to shorten the time required at the inlet crystallization stage, which is a bottleneck of the production process, and to speed up the crystallization rate of the polyester resin used for bottle molding for this purpose. However, this operation is inversely related to the transparency of the bottle body, and when the adjusted polyester resin is used, problems such as a long cycle time of the preform injection process occur.
따라서 본 발명자들은 보틀몸통부의 투명성을 해치지 않으며, 입구부 결정화 시간을 단축하여 보틀성형 생산성을 향상시킬 수 있는 방법을 고안하기 위하여 계속적인 연구를 거듭한 결과 본 발명을 완성하게 된 것이다.Therefore, the present inventors have completed the present invention as a result of repeated studies to devise a method that can improve the bottle molding productivity by reducing the inlet crystallization time without harming the transparency of the bottle body.
즉 본 발명은 전산성분의 적어도 97몰%가 테레프탈산이고, 전글리콜 성분의 적어도 97몰%가 에틸렌글리콜로 구성된 폴리에스터에 있어서, (1) 이소프탈산 성분(A)과 디에틸렌글리콜 성분(B)이 다음의 관계식을 만족하는 양으로 랜덤 공중합 되어 있고,That is, in the present invention, at least 97 mol% of the total acid component is terephthalic acid, and at least 97 mol% of the total glycol component is composed of ethylene glycol, wherein (1) isophthalic acid component (A) and diethylene glycol component (B) Is randomly copolymerized in an amount satisfying the following relational expression,
0.5몰%≤A≤3.0몰%0.5 mol% ≤ A ≤ 3.0 mol%
0.7몰%≤B≤3.0몰%0.7 mol% ≤ B ≤ 3.0 mol%
2.0몰%≤A+B≤5.0몰%2.0 mol% ≤ A + B ≤ 5.0 mol%
(2) 촉매로 사용한 안티몬 화합물이 Sb원자로 하여 폴리에스터에 대하여 250~400ppm 존재하며,(2) 250 to 400 ppm of antimony compound used as a catalyst is present with respect to polyester as Sb atom,
(3) 페놀.테트라클로로에탄(3/2 중량비) 혼합물을 용매로 하여 25℃에서 측정한 극한점도 [η]가 0.70~0.9dl/g의 범위에 있는 것으로 특징지워지는 신규한 내열보틀 성형용 폴리에스터를 제공코자 하는 것이다.(3) For forming a new heat-resistant bottle characterized by having an intrinsic viscosity [η] measured at 25 ° C. using a mixture of phenol and tetrachloroethane (3/2 weight ratio) as a solvent, in the range of 0.70 to 0.9 dl / g. To provide a polyester.
또한 폴리에스터로 성형된 내열보를 성형용 프리폼 및 내열보틀을 제공코자 하는 것이다.In addition, to provide a preform and a heat-resistant bottle for forming a heat-resistant beam molded of polyester.
본 발명의 내열보를 성형용 폴리에스터에 있어서, 랜덤 공중합 성분의 양이 상기의 범위보다 적은 경우에는, 동일한 사출 사이클 타임을 유지하기 위하여 사출온도를 높게 해주어야 할 뿐만아니라, 보틀의 투명성을 높이기 위해서는 사출공정에서의 프리폼 냉각시간을 길게 해주어야 하기 때문에 생산성이 약화되고, 상기의 범위보다 많은 경우에는 사출공정에서의 프리폼 냉각시간을 길게 해주어야 하기 때문에 생산성이 약화되고, 상기의 범위보다 많은 경우에는 사출공정의 생산성과 얻어진 보틀의 투명성은 좋아지지만, 입구부의 결정화가 어렵게 되어버리기 때문에 바람직하지 않다. 그리고 랜덤 공중합 성분의 첨가시기로는, 폴리에스터의 용융 중합반응이 종료되기 이전의 시점이면, 언제라도 가능하지만, 적절한 반응성 및 물성관리를 감안하여 에스테르 교환반응 또는 에스테르화 반응이 실질적으로 종료되기 이전의 단계에서 첨가하는 것이 바람직하다.In the polyester for forming the heat-resistant beam of the present invention, when the amount of the random copolymerization component is less than the above range, not only the injection temperature should be increased in order to maintain the same injection cycle time, but also the injection molding is required to increase the transparency of the bottle. Productivity is weakened because the preform cooling time in the process has to be lengthened, and in the case of more than the above range, productivity is weakened because the preform cooling time in the injection process has to be lengthened. Although productivity and transparency of the obtained bottle are improved, it is not preferable because crystallization of an inlet part becomes difficult. The addition time of the random copolymerization component can be used at any time before the melt polymerization reaction of the polyester is completed, but before the transesterification reaction or the esterification reaction is substantially terminated in consideration of proper reactivity and physical property management. It is preferred to add at the stage of.
또한, 촉매로 사용하는 안티몬 화합물은 폴리에스터의 중합반응에 대한 촉매 활성을 가진 것이며 제한되지 않으며, 삼산화 안티몬, 오산화안티몬, 초산화안티몬, 안티몬글리콜레이트 등을 예시할 수 있는 바, 첨가시기로는 폴리에스터의 용융중합법에 있어서, 중축합반응이 종료되기 이전의 시점이면, 언제라도 좋지만, 반응성 및 물성관리를 감안하여, 에스테르 교환반응 또는 에스테르화 반응이 실질적으로 종료되기 이전의 시점의 단계에서 첨가하는 것이 바람직하다. 그러나 사용량은 Sb 원자로하여 폴리에스터에 대하여 250~400ppm이 되도록 할 필요가 있는데, 이 범위이하로 되는 경우에는 본 발명에 적합한 랜덤 공중합체를 사용하여 성형한 프리폼의 입구부 결정화가 어려워지기 때문에 공업적으로 적당한 생산성을 얻기가 곤란하며, 이범위 이상으로 되는 경우에는 폴리에스터 및 성형폼의 색상이 거무틱틱하게 되어 품위가 저하되기 때문에 바람직하지 않게 된다.In addition, the antimony compound used as a catalyst has a catalytic activity for the polymerization of polyester and is not limited, and can be exemplified by antimony trioxide, antimony pentoxide, antimony acetate, antimony glycolate, etc. In the melt polymerization method of the polyester, any time may be used before the end of the polycondensation reaction, but in consideration of the reactivity and physical property management, at the point before the end of the transesterification or esterification reaction is substantially terminated. It is preferable to add. However, it is necessary to use the amount of Sb to 250 to 400ppm with respect to the polyester, if it is less than this range, it is difficult to crystallize the inlet crystallization of the preform formed by using a random copolymer suitable for the present invention It is difficult to obtain adequate productivity, and when it is in this range or more, the color of the polyester and the molded foam becomes dark and the quality is lowered, which is not preferable.
그리고 폴리에스터의 극한점도가 0.7dl/g 이하인 경우에는 프리폼 및 보틀의 투명성 및 기계적 강도 등의 저하가 야기되는 등의 문제가 있고, 0.90dl/g 이상인 경우에는 폴리에스터의 흐름성이 나빠지므로 프리폼 사출성형성이 떨어지고, 게이트(입구부) 부위의 백탁이 심하게 발생되는 등의 문제점이 생겨 바람직하지 않다.In addition, if the intrinsic viscosity of the polyester is 0.7dl / g or less, there is a problem such as deterioration of the transparency and mechanical strength of the preform and the bottle, and if it is 0.90dl / g or more, the flowability of the polyester is worsened. It is not preferable because problems such as poor injection molding and poor clouding of the gate (inlet) portion occur.
본 발명의 폴리에스터를 제조하는 방법으로는 공지되어 있는 에스테르 교환법(DMT법) 및 직접 에스테르화법(TPA법)의 어느 경우라도 관계없으며, 통상적으로 사용되는 폴리에스터의 용융중합법 및 고상중합법을 사용하면 되며, 폴리에스터의 중합반응 속도 및 물성계량을 위하여, 공지되어 있는 촉매와 안정제와 같은 각종의 첨가제가 적당하게 배합되어 있는 것이라도 좋다.The method for producing the polyester of the present invention may be any of the known transesterification method (DMT method) and direct esterification method (TPA method), and the melt polymerization method and the solid phase polymerization method of polyesters commonly used are What is necessary is just to mix | blend suitably the various additives, such as a well-known catalyst and a stabilizer, for the polymerization rate and physical property measurement of polyester.
본 발명의 내열보틀 성형용 프리폼은 본 발명의 내열보틀성형용 폴리에스터를 원료로하여 이루어지는 것으로, 종래부터 공지되어 있는 사출성형법에 의해 성형할 수 있다.The preform for heat-resistant bottle molding of this invention consists of the polyester for heat-resistant bottle molding of this invention as a raw material, and can be shape | molded by the injection molding method conventionally known.
또한 내열보틀은 상기 내열보틀 성형용 프리폼의 입구부를 결정화시키고, 몸통부는 이축연신과 동시에 열고정시키는 종래부터 잘 알려져 있는 방법으로 성형하면 된다.The heat-resistant bottle may be molded by a conventionally well-known method of crystallizing the inlet portion of the heat-resistant bottle forming preform, and the trunk portion being biaxially stretched and heat-set simultaneously.
이와 같은 본 발명에 의하면, 내열보틀의 제조공정인 프리폼의 사출, 프리폼 입구부의 결정화 및 이축연신 열고정에 의한 내열보틀의 성형의 각 단계에서는 조건설정 폭이 넓어지고, 생산성도 크게 향상될 뿐만 아니라, 쥬스와 이온음료 등과 같이 열살균이 필요한 음료를 핫필링하는 경우에 요구되는 내열성이 우수하며, 투명성이 우수한 고품질의 폴리에스터제 내열보틀을 성형할 수 있게 된다.According to the present invention, at each step of forming the heat resistant bottle by injection of the preform which is a manufacturing process of the heat resistant bottle, crystallization of the preform inlet, and biaxially stretched heat setting, not only the condition setting width is widened, but also the productivity is greatly improved. In the case of hot-filling beverages requiring heat sterilization, such as juices and ionic beverages, the heat resistance required for excellent heat resistance and excellent transparency can be formed in a high quality polyester heat resistant bottle.
이하 실시예를 들어 본 발명을 더욱 상세하게 설명하고자 한다.Hereinafter, the present invention will be described in more detail with reference to the following examples.
[실시예]EXAMPLE
[폴리에스터 입상체제조][Production of polyester granules]
직접 에스테르화법을 사용하고, 이소프탈산 디에틸렌글리콜 및 삼산화 안티몬을 표 1과 같이 첨가하여 에스테르화 반응은 대기압하, 255℃에서 수행하고, 충축한 반응은 1㎜Hg의 진공하, 285℃에서 수행한 후 수중에 토출하여 냉각하고 세단하여 비결정질의 폴리에스터 입상체를 얻었다. 그리고 이것을 0.2㎜Hg의 진공 및 160℃에서 5시간 건조한 후 0.2㎜Hg의 진공 및 215℃에서 고상중합하여 결정질의 폴리에스터 입상체를 얻었다.Using the direct esterification method, isophthalic acid diethylene glycol and antimony trioxide were added as shown in Table 1, and the esterification reaction was carried out at 255 ° C under atmospheric pressure, and the packed reaction was carried out at 285 ° C under vacuum of 1 mmHg. After discharging in water, cooling, and sintering, an amorphous polyester granule was obtained. This was dried for 5 hours at a vacuum of 0.2 mmHg and 160 ° C., followed by solid phase polymerization at a vacuum of 0.2 mmHg and 215 ° C. to obtain crystalline polyester granules.
[표 1]TABLE 1
[프로폼 성형][Proform Molding]
다음에 이 고상중합된 폴리에스터 입상체를 질소분위기하 175℃에서 7시간 건조하고 Husky사제ㆍ사출기 300XL형을 사용하여 배럴온도 285℃로 용융시키고, 10℃로 냉각한 프리폼 금형에 사출하여 외경 38㎜, 두께 3.7㎜의 프리폼을 성형하였다.Next, the solid-phase polymerized polyester granules were dried at 175 ° C. for 7 hours under a nitrogen atmosphere, melted at a barrel temperature of 285 ° C. using an injection machine 300XL manufactured by Husky, and injected into a preform mold cooled to 10 ° C. to an outer diameter of 38. Mm and a thickness of 3.7 mm preform were molded.
[내열보틀 성형][Heat Resistant Bottle Molding]
이 프리폼의 입구부를 Sidel 사제 SBO-10/10 블로우머신에 부착 되어있는 크리스탈라이저에서 결정화시키고, 동 블로우머신을 사용하여 프리폼온도 96℃의 조건하에서 종연신비 약 2.5, 횡연신비 약 2.8로 이축연신 성형함과 동시에 150℃의 표면온도를 갖는 금형내에서 약 8초간 유지한 후 보틀을 취출하는 방법으로 내용적이 1.5이며, 동부에 6개의 감압판넬을 갖고, 바닥부위가 올라간 폴리에스터제 내열보틀로 성형하였다.The inlet of this preform was crystallized in a crystallizer attached to SBO-10 / 10 blow machine manufactured by Sidel, and biaxially stretched with a longitudinal draw ratio of about 2.5 and a transverse draw ratio of about 2.8 under conditions of a preform temperature of 96 ° C using the blow machine. At the same time, the bottle is taken out in a mold having a surface temperature of 150 ° C. for about 8 seconds, and then the bottle is taken out. It was.
표 1에 나타낸 각 폴리에스터 입상체별의 프리폼 사출, 입구부의 결정화, 성형된 내열보틀의 내열성 및 투명성은 다음의 표 2에 나타내었다.Preform injection, crystallization of the inlet portion, and heat resistance and transparency of the molded heat-resistant bottle for each polyester granule shown in Table 1 are shown in Table 2 below.
[비교예][Comparative Example]
표 1의 함량비로 실시예와 동일하게 차례로 폴리에스터 입상체제조, 프리폼 성형, 및 내열보틀 성형하여, 폴리에스터 입상체별의 프리즘 사출, 입구부의 결정화, 성형된 내열보틀의 내열성 및 투명성은 표 2에 나타내었다.Polyester granulation, preform molding, and heat-resistant bottle molding were sequentially performed in the same manner as in the embodiment in the content ratios of Table 1, and the prism injection, crystallization of the inlet portion, and heat resistance and transparency of the molded heat-resistant bottle according to polyester granules were shown in Table 2. Shown in
[표 2]TABLE 2
* 보틀 내열성 : 90℃의 열수를 핫필링하였을 때 수축 및 변형이 없어야 함* Bottle heat resistance: There should be no shrinkage or deformation when hot water at 90 ℃
* 입구부 결정화 조건 : 160℃, 1.4분* Inlet crystallization condition: 160 ℃, 1.4 minutes
이상의 실시예 및 비교예에 나타난 바와 같이, 본 발명의 폴리에스터를 사용하면, 종래에 내열보를 성형용으로 사용되고 있던 폴리에스터 수지를 사용한 경우와 동등한 내열성을 갖는 동시에 투명성이 현저하게 개선된 폴리에스터제 내열보틀을 높은 생산성으로 성형할 수 있게 한다.As shown in the above Examples and Comparative Examples, using the polyester of the present invention, a polyester agent having the same heat resistance as in the case of using a polyester resin that has been used for molding a heat-resistant beam in the past and remarkably improved transparency It is possible to mold heat-resistant bottles with high productivity.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019920006415A KR950015127B1 (en) | 1992-04-17 | 1992-04-17 | Polyester and use of thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019920006415A KR950015127B1 (en) | 1992-04-17 | 1992-04-17 | Polyester and use of thereof |
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| Publication Number | Publication Date |
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| KR930021681A KR930021681A (en) | 1993-11-22 |
| KR950015127B1 true KR950015127B1 (en) | 1995-12-22 |
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| KR100467651B1 (en) * | 1996-12-30 | 2005-04-13 | 에스케이케미칼주식회사 | Injection molding method of polyethylene terephthalate preform |
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