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KR20000040988A - Method for the preparation of polyethylene terephthalate bottle - Google Patents

Method for the preparation of polyethylene terephthalate bottle Download PDF

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Publication number
KR20000040988A
KR20000040988A KR1019980056755A KR19980056755A KR20000040988A KR 20000040988 A KR20000040988 A KR 20000040988A KR 1019980056755 A KR1019980056755 A KR 1019980056755A KR 19980056755 A KR19980056755 A KR 19980056755A KR 20000040988 A KR20000040988 A KR 20000040988A
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KR
South Korea
Prior art keywords
preform
polyethylene terephthalate
pet
container
infrared
Prior art date
Application number
KR1019980056755A
Other languages
Korean (ko)
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KR100616179B1 (en
Inventor
김태영
신철원
이영록
곽규대
Original Assignee
조민호
에스케이케미칼 주식회사
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Priority to KR1019980056755A priority Critical patent/KR100616179B1/en
Publication of KR20000040988A publication Critical patent/KR20000040988A/en
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Publication of KR100616179B1 publication Critical patent/KR100616179B1/en

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Classifications

    • 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
    • B29C49/42—Component parts, details or accessories; Auxiliary operations
    • B29C49/64—Heating or cooling preforms, parisons or blown articles
    • B29C49/6409—Thermal conditioning of preforms
    • 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
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/06—Injection blow-moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D22/00—Producing hollow articles
    • B29D22/003—Containers for packaging, storing or transporting, e.g. bottles, jars, cans, barrels, tanks
    • 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
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • 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
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C2049/023—Combined blow-moulding and manufacture of the preform or the parison using inherent heat of the preform, i.e. 1 step blow moulding
    • 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

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

PURPOSE: A method for the preparation of polyethylene terephthalate (abbreviated as PET) bottle is provided which improves productivity of the PET bottle without side reactions such as lowering of transparency and darkening of colors. CONSTITUTION: A method for the preparation of PET bottle comprises an injection process of injecting a PET resin to produce a preform, intermediate product; and a blow process of reheating the preform up to a glass transition temperature of the raw material or higher using an infrared light heater, putting the heated preform into a forming mold and blowing it under high pressure to form a bottle, characterized by reheating the preform using the infrared light heater, under a condition that an opaque insert is inserted within the preform.

Description

폴리에틸렌테레프탈레이트 용기의 제조법Manufacturing method of polyethylene terephthalate container

본 발명은 폴리에틸렌테레프탈레이트(이하 'PET'라 한다.) 용기(bottle)의 제조방법에 관한 것으로, 보다 상세하게는 투명한 PET용기를 성형할 때 프리폼(소위 '패리슨')의 재가열성을 향상시켜 생산성을 증대시키는 방법에 관한 것이다.The present invention relates to a method for producing a polyethylene terephthalate (hereinafter referred to as 'PET') bottle, and more particularly to reheating of preform (so-called 'parison') when molding a transparent PET container. To increase productivity.

현재 PET는 그 용도의 다양성과 탄산음료 및 기타 음료 시장의 성장, 그리고 유리용기의 대체나 재활용 측면의 유해성 플라스틱에 대한 대체 플라스틱으로 사용되므로 그 수요가 매년 10% 이상의 성장을 거듭하고 있다. 주요 용도는 탄산음료, 생수, 과즙음료 등의 용기, 블리스터 패키징 및 쉬트 등이며, 제품 성형성이 향상되고 용융가공시 부반응이 덜 일어나는 수지에 대한 요구가 증대되고 있다.Currently, PET is used as a substitute plastic for hazardous plastics in terms of its variety of uses, the growth of carbonated drinks and other beverage markets, and the replacement or recycling of glass containers. The main uses are carbonated beverages, bottled water, juiced beverage containers, blister packaging and sheets, and the like, and the demand for resins having improved product formability and less side reactions during melt processing is increasing.

PET의 제조과정을 살펴보면, 원료인 테레프탈산과 에틸렌 글리콜을 고온 고압의 반응기에 투입하고 여기서 만들어진 저분자량의 올리고머를 고온의 진공상태에서 반응촉매, 정색제 및 안정제 등의 존재하에 중합하여 고분자량의 PET로 합성한다. 이렇게 생성된 PET는 용기로 사용하기에는 물성이 부족하므로 결정화공정 및 고상중합을 거쳐 원하는 물성을 갖게 한다.In the manufacturing process of PET, terephthalic acid and ethylene glycol as raw materials are introduced into a reactor of high temperature and high pressure, and the low molecular weight oligomer produced therein is polymerized in the presence of a reaction catalyst, a colorant, and a stabilizer under a high temperature vacuum to obtain a high molecular weight PET. To synthesize. The PET thus produced lacks physical properties to be used as a container, and thus has a desired physical property through a crystallization process and a solid phase polymerization.

일반적으로 PET용기는 사출-블로우(injection blow) 공정으로 성형된다. 종전에는 한 기계에서 사출과 블로우의 두 공정을 모두 거쳤으나, 수요가 급성장하면서 사출과 블로우를 분리하여 생산하는 2단계방식으로 제조하는 추세이다.In general, PET containers are molded by an injection blow process. Previously, a single machine went through both injection and blow processes, but as the demand grows rapidly, it is manufactured in a two-stage process in which injection and blow are separately produced.

2단계 방식의 PET용기의 제조방법은 일반적으로 PET수지를 사출하여 중간제품인 프리폼을 만들고, 블로우 공정에서는 이 프리폼을 원료물질의 유리전이온도(glass transition temperature, Tg) 이상까지 적외선 히터를 사용하여 재가열한 후 가열된 프리폼을 성형 몰드에 넣고 고압으로 블로우하여 용기로 성형한다.In general, the two-step PET container is manufactured by injecting PET resin into an intermediate product preform, and in the blow process, the preform is reheated using an infrared heater up to the glass transition temperature (Tg) of the raw material. Then, the heated preform is placed in a molding mold and blown at a high pressure to be molded into a container.

이러한 방법에서 프리폼이 얼마나 빨리 적외선 히터의 열을 흡수하는가에 따라 PET 용기의 생산성이 크게 좌우된다. 환언하면, 프리폼을 적외선 히터로 재가열하여 용기를 성형할 때, 용기의 생산량은 프리폼이 적외선을 얼마나 빨리 흡수하느냐가 중요한 인자로 작용한다.In this way, the productivity of the PET container depends largely on how quickly the preform absorbs the heat of the infrared heater. In other words, when the container is molded by reheating the preform with an infrared heater, the yield of the container is an important factor in how quickly the preform absorbs infrared rays.

종래, 프리폼이 적외선 히터에서 열을 단시간내에 흡수하도록 하기 위하여 다양한 방법이 제안되어 왔다. 예를 들어 미국특허 제4,250,078호에서는 산화철을 함유시켜 적외선 흡수시간을 단축시키고 안트라퀴논 염료를 사용하는 것이 기술되어 있고, 미국특허 제 3,951,905호 및 제3,795,639호 등에서는 프리폼이 적외선을 효과적으로 흡수하게 하는 방법으로 안티모니 등과 같은 촉매와 안정제의 조합을 이용하는 방법이 기술되어 있다.Conventionally, various methods have been proposed to allow the preform to absorb heat in an infrared heater in a short time. For example, U.S. Patent No. 4,250,078 describes the use of anthraquinone dyes by containing iron oxide to shorten the infrared absorption time, while U.S. Patent Nos. 3,951,905 and 3,795,639 describe methods for allowing preforms to effectively absorb infrared radiation. A method of using a combination of a catalyst and a stabilizer such as antimony is described.

그러나 상기한 종래의 방법들은 첨가제의 배합에 주의를 요하고 또한 첨가제의 배합에 따른 유해성 여부가 논란의 여지를 안고 있었다.However, the above-described conventional methods require attention to the formulation of the additives, and there is a controversy over the hazards caused by the formulation of the additives.

한편, 프리폼 내에 적외선을 산란시킬 수 있는 입자들의 수나 크기에 따라 적외선의 흡수 속도가 변할 수 있으며 프리폼의 색에 따라 적외선 흡수속도가 좌우되기도 한다. 특히 프리폼이 검은색을 띨 경우 적외선 흡수에 유리한 것으로 알려져 있다. 이러한 원리를 도입한 종래기술로서, 미국특허 제 4,535,118호 및 제 4,476,272호에는 카본 블랙을 첨가하여 프리폼이 검은 색을 띠게 함으로써 프리폼의 재가열성을 향상시키는 방법이 기술되어 있다. 그러나 이 방법은 카본 블랙이 극성이 없기 때문에 PET에서 분산이 어렵다는 단점이 있었다.Meanwhile, the absorption rate of infrared rays may vary depending on the number or size of particles that may scatter infrared rays in the preform, and the absorption rate of infrared rays may also depend on the color of the preform. In particular, when the preform is black, it is known to be advantageous for infrared absorption. As a prior art incorporating this principle, US Pat. Nos. 4,535,118 and 4,476,272 describe methods for improving the reheatability of a preform by adding carbon black to make the preform black. However, this method has a disadvantage in that dispersion is difficult in PET because carbon black has no polarity.

또한 이와 같이 원료측면에서 적외선 재가열성을 향상시키는 방법은 프리폼 및 용기의 투명도가 떨어지고 색이 어두워지는 부작용이 불가피하다.In addition, the method of improving the infrared reheatability in terms of the raw material side is inevitable side effects that the transparency of the preform and the container and the color becomes dark.

따라서 본 발명은 상기한 바와 같은 선행기술의 문제점이 없이 프리폼이 적외선을 효과적으로 흡수하도록 하는 것을 기술적 과제로 한다.Therefore, a technical object of the present invention is to allow the preform to effectively absorb infrared rays without the problems of the prior art as described above.

상기한 과제를 해결하기 위한 연구에서 본 발명자는 원료물질 측면으로 접근하지 않고 성형기 측면으로 접근하여 PET용기의 2단계 성형중 블로우 성형시의 적외선 재가열성을 향상시킬수 있다는 사실을 발견하였다.In the study for solving the above problems, the present inventors found that the infrared reheatability during the blow molding during the two-stage molding of the PET container can be improved by approaching the molding machine side rather than approaching the raw material side.

도 1은 본 발명에 따라 패리슨의 적외선 재가열공정에서 패리슨 내부에 불투명 인서어트를 삽입한 상태에서 적외선램프로 이루어진 히터로 가열하는 것을 설명하기 위한 도면이다.1 is a view for explaining the heating with a heater made of an infrared lamp in the state of inserting an opaque insert in the parison in the infrared reheating process of the parison according to the present invention.

*도면중 주요부분에 대한 부호의 설명** Description of the symbols for the main parts of the drawings *

1: 프리폼(preform) 또는 패리슨(parison)1: preform or parison

2: 인서어트(insert)2: insert

3: 적외선 램프(IR lamp)3: IR lamp

4: 반사경4: reflector

상기한 발견에 기초한 본 발명에 의하면, 폴리에틸렌테레프탈레이트 수지를 사출하여 중간제품인 프리폼을 만들고, 블로우 공정에서는 이 프리폼을 원료물질의 유리전이온도 이상까지 적외선 히터를 사용하여 재가열한 후 가열된 프리폼을 성형 몰드에 넣고 고압으로 블로우하여 용기로 성형시키는 폴리에틸렌테레프탈레이트 용기의 제조방법에 있어서, 프리폼의 적외선 히터에 의한 재가열을 프리폼의 내부에 불투명 재질의 인서어트를 삽입한 상태에서 수행하는 것을 특징으로 하는 폴리에틸렌테레프탈레이트 용기의 제조방법이 제공된다.According to the present invention based on the above findings, polyethylene terephthalate resin is injected to make an intermediate product preform, and in the blow process, the preform is reheated using an infrared heater up to the glass transition temperature of the raw material and then the heated preform is formed. A method for producing a polyethylene terephthalate container which is put into a mold and blown into a container by high pressure, wherein the reheating by an infrared heater of the preform is performed while inserts of an opaque material are inserted into the inside of the preform. A method of making a terephthalate container is provided.

이하, 본 발명을 보다 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in more detail.

일반적으로 2단계 블로우 공정에서 프리폼이 블로우 가능한 온도 범위까지 적외선으로 가열할 경우 일정시간 동안 프리폼이 회전하며 적외선을 쬐는데, 본 발명에서는 이 때 프리폼 내부에 일정한 색을 띈 불투명한 인서어트를 설치하여 프리폼의 승온온도를 크게 향상시킬 수 있었다. 이러한 본 발명에 의하면 프리폼과 용기의 투명도 및 색의 손상없이 용기의 생산성을 향상시킬 수 있게 된다.In general, when the preform is heated in the infrared to the blowable temperature range in the two-stage blow process, the preform rotates for a predetermined time and emits infrared rays. In the present invention, an opaque insert having a predetermined color is installed inside the preform. The temperature rising temperature of the preform could be greatly improved. According to the present invention it is possible to improve the productivity of the container without damaging the transparency and color of the preform and the container.

이때 불투명 인서어트의 재질은 통상적인 PET용기의 가공온도에서 변형이 일어나지 않는 것이면 특별히 제한되지 않으나, 경제적인 측면을 고려할 때 종이, 합성수지가 바람직하다.At this time, the material of the opaque insert is not particularly limited as long as the deformation does not occur at the processing temperature of a conventional PET container, paper and synthetic resin is preferable in consideration of economic aspects.

이하 본 발명을 실시예에 의거하여 설명하면 아래와 같으며 본 발명이 실시예에 의해 제한되는 것은 아니다.Hereinafter, the present invention will be described based on the following examples, and the present invention is not limited by the examples.

실시예 중의 극한점도는 오르토-클로로페놀을 이용하여 35℃에서 측정하였으며, 칼라-엘(col-L)은 클수록 흰색을, 작을수록 검은색을 나타내며, 칼라-비(col-b)는 클수록 노란색을, 작을수록 파란색에 가까움을 의미한다.Intrinsic viscosity was measured at 35 ℃ using ortho-chlorophenol, color-L (col-L) is white, the smaller is black, the larger the color-ratio (col-b) is yellow The smaller, means closer to blue.

[실시예 1]Example 1

도 1에 나타낸 바와 같이 프리폼(1)의 일측에 IR 램프들(3)이 설치되고, 대향측에 반사경(4)이 설치되며 프리폼(1)이 회전가능한 크루프[(Krupp):독일]사에서 제작한 적외선 블로우기에서 프리폼을 재가열하였다. 이때 프리폼은 극한점도 0.75㎗/g, col-L 81의 투명한 프리폼을 사용하고 그 내부에 10㎝×10㎝의 흰색 종이를 둥글게 말아서 만든 인서어트(2)를 삽입한 상태로 재가열하였다.As shown in FIG. 1, the IR lamps 3 are installed at one side of the preform 1, the reflector 4 is installed at the opposite side, and the preform 1 is rotatable. The preform was reheated in the manufactured infrared blower. At this time, the preform was reheated using an insert (2) made of a transparent preform having an intrinsic viscosity of 0.75-/ g and a col-L 81 and by rolling a white paper of 10 cm × 10 cm in a round shape.

적외선 가열조건은 열량 95%, 가열시간 26.5초, 평형시간 8초, 1차 블로우압 18㎏/㎠, 2차 블로우압 34㎏/㎠이었다. 적외선 가열후 프리폼의 온도를 측정한 결과 117℃이었다.Infrared heating conditions were 95% of heat, 26.5 seconds of heating time, 8 seconds of equilibrium time, 18 kg / cm 2 of primary blow pressure, and 34 kg / cm 2 of secondary blow pressure. It was 117 degreeC when the temperature of the preform after infrared heating was measured.

[실시예 2]Example 2

인서어트(2)로서 10㎝×10㎝의 흰색 종이에 5㎜의 간격으로 검은 선을 그은 것을 둥글게 말아서 만든 것을 사용한 것을 제외하고는 실시예 1과 동일한 절차를 반복, 프리폼을 적외선으로 재가열하였다. 적외선 가열후 프리폼의 온도를 측정한 결과 119℃이었다.The same procedure as in Example 1 was repeated except that white inserts of 10 cm × 10 cm were made by rolling black lines at intervals of 5 mm as the insert 2, and the preform was reheated with infrared rays. It was 119 degreeC when the temperature of the preform after infrared heating was measured.

[실시예 3]Example 3

인서어트(2)로서 10㎝×10㎝의 검은 종이를 둥글게 말아서 만든 것을 사용한 것을 제외하고는 실시예 1과 동일한 절차를 반복, 프리폼을 적외선으로 재가열하였다. 적외선 가열후 프리폼의 온도를 측정한 결과 123℃이었다.The same procedure as in Example 1 was repeated except that the insert 2 was made of a roll of 10 cm x 10 cm black paper, and the preform was reheated in infrared light. It was 123 degreeC when the temperature of the preform after infrared heating was measured.

[비교예 1]Comparative Example 1

인서어트(2)를 사용하지 않은 것을 제외하고는 실시예 1과 동일한 절차를 반복하여 프리폼을 적외선으로 재가열하였다. 적외선 가열후 프리폼의 온도를 측정한 결과 115℃이었다.The preform was reheated to infrared with the same procedure as in Example 1 except that the insert 2 was not used. It was 115 degreeC when the temperature of the preform after infrared heating was measured.

상기한 실시예와 비교예를 대비하면 알 수 있는 바와 같이, 프리폼의 내부에 불투명 재질의 인서어트를 삽입하여 프리폼을 적외선으로 재가열하면 적외선 히터의 열을 훨씬 빨리 흡수하게 되므로 용기의 투명도가 떨어지고 색이 어두워지는 부작용이 없이 PET 용기의 생산성을 크게 향상시킬 수 있게 된다.As can be seen from the above examples and comparative examples, inserting an opaque material insert into the inside of the preform and reheating the preform to infrared absorbs heat from the infrared heater much faster, resulting in poor transparency and color of the container. The productivity of the PET container can be greatly improved without this darkening side effect.

Claims (3)

폴리에틸렌테레프탈레이트 수지를 사출하여 중간제품인 프리폼을 만들고, 블로우 공정에서는 이 프리폼을 원료물질의 유리전이온도 이상까지 적외선 히터를 사용하여 재가열한 후 가열된 프리폼을 성형 몰드에 넣고 고압으로 블로우하여 용기로 성형시키는 폴리에틸렌테레프탈레이트 용기의 제조방법에 있어서,Polyethylene terephthalate resin is injected to make an intermediate product preform, and in the blow process, the preform is reheated using an infrared heater up to the glass transition temperature of the raw material, and then the heated preform is put into a molding mold and blown at high pressure into a container. In the method for producing a polyethylene terephthalate container to 프리폼의 적외선 히터에 의한 재가열을 프리폼의 내부에 불투명 재질의 인서어트를 삽입한 상태에서 수행하는 것을 특징으로 하는 폴리에틸렌테레프탈레이트 용기의 제조방법.A method of manufacturing a polyethylene terephthalate container, wherein reheating by an infrared heater of a preform is performed while an insert of an opaque material is inserted into the preform. 제 1 항에 있어서, 상기 불투명 인서어트의 소재가 통상적인 폴리에틸렌테레프탈레이트 용기의 가공온도에서 변형이 일어나지 않는 것임을 특징으로 하는 폴리에틸렌테레프탈레이트 용기의 제조방법.The method of manufacturing a polyethylene terephthalate container according to claim 1, wherein the material of the opaque insert is not deformed at a processing temperature of a conventional polyethylene terephthalate container. 제 2 항에 있어서, 상기 불투명 인서어트의 소재가 종이 또는 합성수지인 것을 특징으로 하는 폴리에틸렌테레프탈레이트 용기의 제조방법.The method of manufacturing a polyethylene terephthalate container according to claim 2, wherein the opaque insert is made of paper or synthetic resin.
KR1019980056755A 1998-12-21 1998-12-21 Manufacturing method of polyethylene terephthalate container _ KR100616179B1 (en)

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KR20040085791A (en) * 2003-04-01 2004-10-08 (주)옥야 The pitcher and Manufacture method of pitcher draft beer
WO2014032730A1 (en) * 2012-08-31 2014-03-06 Sa Des Eaux Minerales D'evian Saeme Bottle, method of making the same and use of fdca and diol monomers in such bottle
WO2014032731A1 (en) * 2012-08-31 2014-03-06 Sa Des Eaux Minerales D'evian Saeme Method of making a bottle made of fdca and diol monomers and apparatus for implementing such method

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KR101038376B1 (en) 2003-12-30 2011-06-01 에스케이케미칼주식회사 The manufacturing method of the bottles made from plastics, including polyethylene terephthalate and other materials

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JPS5611232A (en) * 1979-07-10 1981-02-04 Yoshino Kogyosho Co Ltd Jig for stretch blow molding piece
DE3888929T2 (en) * 1987-06-09 1994-07-21 Toyo Seikan Kaisha Ltd METHOD FOR HEATING A BOTTLE OR PRE-FORM MADE OF THERMOPLASTIC PLASTIC AND METHOD FOR CONTROLLING THE TEMPERATURE OF A HEATING DEVICE.
KR960012848B1 (en) * 1994-06-15 1996-09-24 삼성전자 주식회사 Disk driver interface unit
KR970033745A (en) * 1995-12-21 1997-07-22 김준웅 Injection-Blow Molding Method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040085791A (en) * 2003-04-01 2004-10-08 (주)옥야 The pitcher and Manufacture method of pitcher draft beer
WO2014032730A1 (en) * 2012-08-31 2014-03-06 Sa Des Eaux Minerales D'evian Saeme Bottle, method of making the same and use of fdca and diol monomers in such bottle
WO2014032731A1 (en) * 2012-08-31 2014-03-06 Sa Des Eaux Minerales D'evian Saeme Method of making a bottle made of fdca and diol monomers and apparatus for implementing such method
US10737426B2 (en) 2012-08-31 2020-08-11 SOCIETE ANONYME DES EAUX MINERALES D'EVIAN et en abrege, “S.A.E.M.E” Method of making a bottle made of FDCA and diol monomers and apparatus for implementing such method

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