JPS6226286B2 - - Google Patents
Info
- Publication number
- JPS6226286B2 JPS6226286B2 JP55051791A JP5179180A JPS6226286B2 JP S6226286 B2 JPS6226286 B2 JP S6226286B2 JP 55051791 A JP55051791 A JP 55051791A JP 5179180 A JP5179180 A JP 5179180A JP S6226286 B2 JPS6226286 B2 JP S6226286B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- polyethylene terephthalate
- heat treatment
- acetaldehyde
- containers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 72
- -1 polyethylene terephthalate Polymers 0.000 claims description 41
- 229920001225 polyester resin Polymers 0.000 claims description 40
- 239000004645 polyester resin Substances 0.000 claims description 40
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 37
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 description 29
- 239000008188 pellet Substances 0.000 description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- 235000014171 carbonated beverage Nutrition 0.000 description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000007664 blowing Methods 0.000 description 8
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- 239000008157 edible vegetable oil Substances 0.000 description 7
- 235000013334 alcoholic beverage Nutrition 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 3
- 239000008162 cooking oil Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- RQXXCWHCUOJQGR-UHFFFAOYSA-N 1,1-dichlorohexane Chemical compound CCCCCC(Cl)Cl RQXXCWHCUOJQGR-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- UTNSTOOXQPHXJQ-UHFFFAOYSA-N 2-[4-[4-(2-hydroxyethoxy)phenyl]sulfonylphenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1S(=O)(=O)C1=CC=C(OCCO)C=C1 UTNSTOOXQPHXJQ-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- QLIQIXIBZLTPGQ-UHFFFAOYSA-N 4-(2-hydroxyethoxy)benzoic acid Chemical compound OCCOC1=CC=C(C(O)=O)C=C1 QLIQIXIBZLTPGQ-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
-
- 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
- C08G63/88—Post-polymerisation treatment
- C08G63/90—Purification; Drying
-
- 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
-
- 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
-
- 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
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/25—Solid
- B29K2105/251—Particles, powder or granules
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Description
【発明の詳細な説明】
本発明はポリエステル樹脂製中空成形品の製造
法に関する。更に詳しくは、本発明はポリエステ
ル樹脂中のアセトアルデヒド含量が極めて少く、
充填した内容物の異臭のないポリエステル樹脂製
中空成形品の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a blow molded article made of polyester resin. More specifically, the present invention has extremely low acetaldehyde content in the polyester resin,
This invention relates to a method for manufacturing a polyester resin hollow molded product that does not cause any unpleasant odor from the filled contents.
従来から、ポリエステル樹脂特にポリエチレン
テレフタレートはその優れた透明性、耐薬品性、
寸法安定性及び機械的性能を有する故に、種々の
用途例えば繊維、フイルムあるいはガラス繊維を
混入した成形品等に広く使用されている。近年、
このようなポリエステル樹脂から成る透明な延伸
高配向容器は、ポリエステル樹脂特にポリエチレ
ンテレフタレートの持つている優れた特性即ち透
明性、耐水蒸気透過性、耐気体透過性、衛生性、
安全性及びバランスのとれた機械的性能と相俟つ
て、炭酸飲料、食油、ソース、しよう油、調味
料、化粧品、医薬品、アルコール飲料等の容器ま
たは瓶の分野において目覚しい用途展開がなされ
ている。 Traditionally, polyester resins, especially polyethylene terephthalate, have been known for their excellent transparency, chemical resistance,
Because of its dimensional stability and mechanical performance, it is widely used in various applications such as fibers, films, and molded products containing glass fibers. recent years,
Such a transparent stretched highly oriented container made of polyester resin takes advantage of the excellent properties of polyester resin, particularly polyethylene terephthalate, namely transparency, water vapor permeability, gas permeability, hygiene,
Coupled with its safety and well-balanced mechanical performance, it has found remarkable application in the fields of containers and bottles for carbonated beverages, cooking oil, sauces, soybean oil, seasonings, cosmetics, pharmaceuticals, alcoholic beverages, etc.
しかしながら、ポリエステル樹脂からなる容器
または瓶を炭酸飲料、あるいは食油、ジユース、
アルコール等の容器または瓶として使用する場
合、充填した内容物に異臭の認められることが特
に問題となり、それ故内容物の異臭のない容器ま
たは瓶の開発が所望されている。ポリエステル樹
脂から成る容器または瓶における内容物の異臭の
原因については、未だ完全には明らかになつてい
ないが、樹脂中のアセトアルデヒドが、内容物に
移ることが異臭の主な原因の一つである事が確認
されており、例えば上記の如き炭酸飲料、食油、
ジユース、アルコール飲料等の容器としてポリエ
ステル樹脂製容器を使用する場合、樹脂中のアセ
トアルデヒド量を極力減少させておくことが必要
である。 However, containers or bottles made of polyester resin cannot be used for carbonated beverages, cooking oil, youth, etc.
When used as a container or bottle for alcohol, etc., it is particularly problematic that the contents filled therein have an off-odor, and therefore it is desired to develop a container or bottle that does not have an off-odor on the contents. The cause of off-odor in the contents of containers or bottles made of polyester resin is not yet completely clear, but one of the main causes of off-odor is that acetaldehyde in the resin transfers to the contents. For example, carbonated drinks such as those mentioned above, cooking oil,
When using polyester resin containers as containers for youth drinks, alcoholic beverages, etc., it is necessary to reduce the amount of acetaldehyde in the resin as much as possible.
ポリエチレンテレフタレートは通常エチレング
リコールとテレフタール酸のエステル化反応によ
つて又はジメチルテレフタレートをエチレングリ
コールでエステル交換した後、三酸化アンチモン
の様な重合触媒の存在下で、280及至290℃の温度
及び１mmHg以下の圧力のもとで重縮合させ、次
いで押出してプレツト化される。しかし、このよ
うにして製造されたポリエチレンテレフタレート
のペレツトはその中に多くの量のアセトアルデヒ
ドが含有されているので、そのまゝの状態では上
記の如き炭酸飲料等の容器の製造には、使用でき
ない。 Polyethylene terephthalate is usually produced by an esterification reaction of ethylene glycol and terephthalic acid or after transesterification of dimethyl terephthalate with ethylene glycol in the presence of a polymerization catalyst such as antimony trioxide at a temperature of 280 to 290°C and below 1 mmHg. Polycondensation is carried out under a pressure of 300 mL, followed by extrusion into pellets. However, the polyethylene terephthalate pellets produced in this way contain a large amount of acetaldehyde, so they cannot be used as is for producing containers for carbonated drinks, etc. as described above. .
従つて、ポリエステル樹脂特にポリエチレンテ
レフタレートを用いて、上記の如き炭酸飲料等の
容器を製造する場合、樹脂中のアセトアルデヒド
の量を何らかの方法により極力少くする必要があ
る。 Therefore, when producing containers for carbonated beverages as described above using polyester resin, particularly polyethylene terephthalate, it is necessary to reduce the amount of acetaldehyde in the resin as much as possible by some method.
かかるポリエステル樹脂中のアセトアルデヒド
含量を減少させる方法として、米国特許第
4064112号明細書に記載されている様に、ポリマ
ーを固相重合で製造する方法が一般に採用されて
いるが、この固相重合法は不活性ガス雰囲気下あ
るいは減圧下で重合操作を行なう必要がある事、
更に特別の装置を必要とするなど経済性を考慮す
れば望ましい方法とは言いがたい。また、ポリエ
ステル樹脂を130〜200℃の温度で加熱処理する事
によりアセトアルデヒドを飛散させる方法も提案
されているが、この方法は長時間の加熱処理を要
するにもかかわらずアセトアルデヒドの減少効果
が十分でなく、更に加熱処理時の雰囲気が空気の
場合、ポリマーの大幅な分子量低下をきたす等の
欠点を有している。 As a method for reducing the acetaldehyde content in such polyester resins, US Pat.
As described in the specification of No. 4064112, a method for producing polymers by solid phase polymerization is generally adopted, but this solid phase polymerization method requires the polymerization operation to be carried out under an inert gas atmosphere or under reduced pressure. There is something
Furthermore, it is difficult to say that this is a desirable method from an economical point of view, as it requires special equipment. In addition, a method has been proposed in which acetaldehyde is dispersed by heat-treating polyester resin at a temperature of 130 to 200°C, but this method does not have a sufficient effect of reducing acetaldehyde, although it requires a long heat treatment. Furthermore, when the atmosphere during the heat treatment is air, there are drawbacks such as a significant decrease in the molecular weight of the polymer.
本発明者らは、かかる欠点が改良され、かつポ
リエステル樹脂中のアセトアルデヒド含量を著し
く減少させる方法について鋭意検討を行つた結
果、ポリエステル樹脂を特定の条件下で加熱処理
する事により、ポリエステル樹脂のアセトアルデ
ヒド含量を著しく減少させる事ができ、しかも該
ポリエステル樹脂より製造した容器はこれに内容
物を充填したとき内容物に異臭が認められない事
を見い出し、本発明に到達した。 The inventors of the present invention have conducted intensive studies on a method for improving these drawbacks and significantly reducing the acetaldehyde content in polyester resin. As a result, the inventors have found that by heat-treating polyester resin under specific conditions, the acetaldehyde content in polyester resin can be reduced. The present invention was achieved based on the discovery that the content of polyester resin can be significantly reduced, and that when the container is filled with the contents, no off-odor is observed.
すなわち、本発明はポリエステル樹脂を用いて
中空成形品を製造するに当り、該ポリエステル樹
脂として樹脂中のアセトアルデヒド濃度が
10ppm以下となるまで加熱処理したのち一旦50
℃以下の温度まで冷却し、再び100℃以上の温度
で加熱処理したポリエステル樹脂を用いる事を特
徴とするポリエステル樹脂製中空成形品の製造法
である。 That is, in producing a blow molded product using a polyester resin, the present invention provides that the polyester resin has a low acetaldehyde concentration in the resin.
After heat treatment until it becomes 10ppm or less, 50%
This is a method for producing a polyester resin blow molded article, which is characterized by using a polyester resin that has been cooled to a temperature of 100°C or lower and then heat-treated at a temperature of 100°C or higher.
本発明の方法によれば、固相重合の場合の様な
特別の装置も必要でなく、簡単な操作でポリエス
テル樹脂中のアセトアルデヒド含量を大巾に減少
させることが可能である。従つて、本発明の方法
によれば、容器製造業者がおおむね既に所有して
いる樹脂乾燥設備を使用する事によつてもアセト
アルデヒド含量の著しく減少したポリエステル樹
脂を容易に得る事ができ、しかもこのものから優
れた特性の容器を製造しうる事も大きな利点であ
る。本発明の方法によつて得られる中空成形品例
えば容器、瓶等は異臭が特に問題となる炭酸飲料
用、食油用、ジユース用、アルコール飲料用等の
容器または瓶として使用可能である。 According to the method of the present invention, no special equipment is required as in the case of solid phase polymerization, and it is possible to greatly reduce the acetaldehyde content in the polyester resin with simple operations. Therefore, according to the method of the present invention, a polyester resin with significantly reduced acetaldehyde content can be easily obtained even by using resin drying equipment that container manufacturers generally already own. Another great advantage is that containers with excellent properties can be manufactured from raw materials. The hollow molded products, such as containers and bottles, obtained by the method of the present invention can be used as containers or bottles for carbonated beverages, edible oils, juices, alcoholic beverages, etc. in which off-odor is a particular problem.
本発明でいうポリエステル樹脂とはテレフタル
酸またはその低級アルキルエステルとエチレング
リコールの反応によつて得られるポリエチレンテ
レフタレートを主たる対象とするが、テレフタル
酸成分の一部（通常20モル％以下）を、例えばイ
ソフタル酸、ナフタレンジカルボン酸、ジフエニ
ルジカルボン酸、ジフエノキシエタンジカルボン
酸、ジフエニルエーテルジカルボン酸、ジフエニ
ルスルホンジカルボン酸等の如き芳香族ジカルボ
ン酸；ヘキサヒドロテレフタール酸、ヘキサヒド
ロイソフタール酸等の如き脂環族ジカルボン酸；
アジピン酸、セバチン酸、アゼライン酸等の如き
脂肪族ジカルボン酸；ｐ−β−ヒドロキシエトキ
シ安息香酸、ε−オキシカプロン酸等の如きオキ
シ酸等の他の二官能性カルボン酸の一種以上で、
及び／又はエチレングリコール成分の一部（通常
20モル％以下）を例えばトリエチレングリコー
ル、テトラメチレングリコール、ヘキサメチレン
グリコール、デカメチレングリコール、ネオペン
チルグリコール、ジエチレングリコール、トリエ
チレングリコール、１・１−ジクロヘキサンジメ
チロール、１・４−シクロヘキサンジメチロー
ル、２・２−ビス（4′−β−ヒドロキシエトキシ
フエニル）プロパン、ビス（4′−β−ヒドロキシ
エトキシフエニル）スルホン等の如き他のグリコ
ール及びこれらの機能的誘導体の如き多官能化合
物の１種以上で置換し、共重合せしめたものであ
つても良い。 The polyester resin referred to in the present invention mainly refers to polyethylene terephthalate obtained by the reaction of terephthalic acid or its lower alkyl ester with ethylene glycol, and a portion of the terephthalic acid component (usually 20 mol% or less), for example, Aromatic dicarboxylic acids such as isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, etc.; hexahydroterephthalic acid, hexahydroisophthalic acid, etc. Alicyclic dicarboxylic acids such as;
one or more other difunctional carboxylic acids such as aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, etc.; oxyacids such as p-β-hydroxyethoxybenzoic acid, ε-oxycaproic acid, etc.;
and/or part of the ethylene glycol component (usually
20 mol% or less), for example, triethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, 1,1-dichlorohexane dimethylol, 1,4-cyclohexane dimethylol, 2.1 of polyfunctional compounds such as other glycols such as 2-bis(4'-β-hydroxyethoxyphenyl)propane, bis(4'-β-hydroxyethoxyphenyl)sulfone, etc. and their functional derivatives. It may be substituted with more than one species and copolymerized.
かかるポリエステル樹脂のうちポリエチレンテ
レフタレートのホモポリマーが最も好ましいが、
該ポリエチレンテレフタレートは固有粘度が0.6
以上のもの、更には0.65以上のものであることが
好ましい。またポリエチレンテレフタレートの軟
化点は、220℃及至270℃が好ましく、特に250乃
至265℃が好ましい。他のポリエステル樹脂も上
述と同様の物性を有する事が望ましい。またポリ
エステル樹脂は、この分野の普通の知識をもつ者
に知られているいかなる方法によつて製造された
ものであつても良い。例えば、ポリエチレンテレ
フタレートは、エチレングリコールとテレフター
ル酸とのエステル化反応により、或いはジメチル
テレフタレートの様なテレフタール酸のジアルキ
ルエステル類をエチレングリコールとエステル交
換して得られるモノマーを、三酸化アンチモン、
二酸化ゲルマニウム等の様な重合触媒の存在下で
280乃至290℃の温度及び１mmHg以下の圧力のも
とで重縮合させ、次いで生成ポリマーを280乃至
285℃の温度で窒素圧力により水中に押し出して
固化されたものであつても良い。この固化したポ
リエチレンテレフタレートはこの分野の知識ある
者には知られた方法でペレツト化することができ
る。ペレツトの形状はいかなる形状のものでもよ
いが、例えば立方形、球または円筒形粒子などを
とりうる。ポリエチレンテレフタレートペレツト
の大きさは、熱処理及び成形に好適な大きさとす
るのが望ましい。あまり小さすぎると熱処理時に
ペレツト間の融着をおこしやすく、またペレツト
化する際の生産効率が悪くなる熱処理によるアセ
トアルデヒドの飛散は、ペレツト中での拡散と関
係があり、ペレツトが大きすぎるとアセトアルデ
ヒドの減少速度が小さくなるので、あまり大きす
ぎるのは好ましくない。ポリエチレンテレフタレ
ートペレツトとして実質的立方体を使用する場
合、その一辺の最大長さを約６ｍ／ｍ以下とする
のが望ましく、特に一辺２〜４ｍ／ｍの立方体を
とするのが好ましい。 Among such polyester resins, homopolymers of polyethylene terephthalate are most preferred;
The polyethylene terephthalate has an intrinsic viscosity of 0.6
or more, preferably 0.65 or more. Further, the softening point of polyethylene terephthalate is preferably 220°C to 270°C, particularly preferably 250 to 265°C. It is desirable that other polyester resins also have physical properties similar to those described above. The polyester resin may also be produced by any method known to those of ordinary skill in the art. For example, polyethylene terephthalate is produced using antimony trioxide, monomers obtained by esterification reaction of ethylene glycol and terephthalic acid, or transesterification of dialkyl esters of terephthalic acid such as dimethyl terephthalate with ethylene glycol.
In the presence of a polymerization catalyst such as germanium dioxide, etc.
Polycondensation is carried out at a temperature of 280 to 290°C and a pressure of 1 mmHg or less, and then the resulting polymer is
It may be solidified by extrusion into water at a temperature of 285°C under nitrogen pressure. This solidified polyethylene terephthalate can be pelletized by methods known to those skilled in the art. The pellets may have any shape, for example cubic, spherical or cylindrical particles. It is desirable that the size of the polyethylene terephthalate pellets be suitable for heat treatment and molding. If the pellets are too small, fusion between the pellets will easily occur during heat treatment, and production efficiency will be reduced during pelletization.The scattering of acetaldehyde during heat treatment is related to diffusion in the pellets, and if the pellets are too large, the acetaldehyde will It is not preferable to make it too large because the rate of decrease will be slow. When a substantial cube is used as the polyethylene terephthalate pellet, it is desirable that the maximum length of one side thereof be about 6 m/m or less, and it is particularly preferable to use a cube having a side of 2 to 4 m/m.
溶融重合法で製造されたポリエチレンテレフタ
レートは、通常約20ppm以上、代表的には約
35ppm以上のアセトアルデヒドを含有している
が、かかるポリエチレンテレフタレートは容器又
は瓶を製造する前に一般に知られた条件により加
熱処理しても、大巾な分子量の低下をともなうこ
となしに、炭酸飲料用等の容器として使用可能な
レベルのアセトアルデヒド含量まで、アセトアル
デヒドを減らすことは困難である。 Polyethylene terephthalate produced by melt polymerization usually has a concentration of about 20 ppm or more, typically about
Although it contains more than 35 ppm of acetaldehyde, polyethylene terephthalate can be used for carbonated beverages without any significant decrease in molecular weight even if it is heat-treated under generally known conditions before producing containers or bottles. It is difficult to reduce the acetaldehyde content to a level that allows it to be used as containers such as containers.
本発明の方法は、上記の如きアセトアルデヒド
含量のポリエチレンテレフタレートでも、これを
２段階で加熱処理して樹脂中のアセトアルデヒド
を大巾に減少したポリエチレンテレフタレート樹
脂となし、炭酸飲料用等の容器又は瓶として使用
可能な容器又は瓶を製造するものであるが、その
為に第１段階の加熱処理においてアセトアルデヒ
ド含量を10ppm以下、好ましくは8ppm以下にす
る必要がある。第１段階の加熱処理後のアセトア
ルデヒド含量が10ppmより多い場合には、第２
段階の加熱処理において大巾な分子量の低下を伴
なう事なしにアセトアルデヒド含量を炭酸飲料用
等の容器又は瓶として使用可能なレベルまで減少
させるのは困難である。 In the method of the present invention, polyethylene terephthalate having the acetaldehyde content as described above is heat-treated in two steps to form a polyethylene terephthalate resin in which the acetaldehyde in the resin is greatly reduced, and the resin can be used as a container or bottle for carbonated drinks, etc. In order to produce usable containers or bottles, it is necessary to reduce the acetaldehyde content to 10 ppm or less, preferably 8 ppm or less in the first heat treatment. If the acetaldehyde content after the first stage heat treatment is more than 10 ppm, the second stage
It is difficult to reduce the acetaldehyde content to a level that can be used as containers or bottles for carbonated beverages, etc., without causing a significant decrease in molecular weight during step heat treatment.
第１段階の加熱処理はアセトアルデヒド含量を
10ppm以下にできるものであれば任意の条件を
選ぶ事ができる。一般的には、120乃至200℃、好
ましくは150乃至180℃の温度において約30分乃至
10時間、好ましくは、２乃至８時間の加熱処理を
行なう。120℃以下の温度では長時間加熱処理し
てもアセトアルデヒド含量を10ppm以下とする
事は困難となるので注意を要する。 The first stage of heat treatment reduces the acetaldehyde content.
Any conditions can be selected as long as they can reduce the amount to 10ppm or less. Generally, at a temperature of 120 to 200°C, preferably 150 to 180°C, for about 30 minutes to
Heat treatment is carried out for 10 hours, preferably 2 to 8 hours. At temperatures below 120°C, it is difficult to reduce the acetaldehyde content to 10 ppm or less even with long-term heat treatment, so care must be taken.
本発明の方法においては、第１段階の加熱処理
を行なつたのちポリエチレンテレフタレート樹脂
を一旦50℃以下の温度、好ましくは室温まで冷却
する必要がある。冷却の際吸湿防止等の特別な操
作は何ら必要なく、第１段階の加熱処理後例えば
放冷により50℃以下の温度にすれば良い。50℃以
下に冷却する事なく連続で加熱処理を行うと、本
発明の目的は達成されない。 In the method of the present invention, it is necessary to once cool the polyethylene terephthalate resin to a temperature of 50° C. or lower, preferably to room temperature, after the first stage heat treatment. There is no need for any special operation such as prevention of moisture absorption during cooling, and the temperature may be reduced to 50° C. or lower by, for example, cooling after the first stage heat treatment. If the heat treatment is performed continuously without cooling to below 50°C, the object of the present invention will not be achieved.
第２段階の加熱処理は、ポリエチレンテレフタ
レート樹脂の冷却後直ちに行つても良いし、長時
間室温において放置後行つても何らさしつかえな
い。第２段階の加熱処理は100℃以上の温度であ
れば任意の条件を選べ得るが、ポリエチレンテレ
フタレート樹脂より成る容器又は瓶を炭酸飲料用
等の容器又は瓶として使用するにはポリエチレン
テレフタレートペレツト中のアセトアルデヒド濃
度を3ppm以下にする必要がある。このような低
アセトアルデヒド含量のペレツトは通常120乃至
200℃、好ましくは150乃至180℃の温度において
30分乃至10時間、好ましくは２乃至８時間加熱処
理を行う事により得られる。 The second stage heat treatment may be performed immediately after cooling the polyethylene terephthalate resin, or may be performed after being left at room temperature for a long time. The heat treatment in the second stage can be carried out under any conditions as long as the temperature is 100°C or higher, but in order to use containers or bottles made of polyethylene terephthalate resin as containers or bottles for carbonated beverages, etc. It is necessary to reduce the acetaldehyde concentration to 3 ppm or less. These low acetaldehyde content pellets typically have a
At a temperature of 200℃, preferably 150-180℃
It can be obtained by heat treatment for 30 minutes to 10 hours, preferably 2 to 8 hours.
第１段及び第２段階の加熱処理は、いづれも通
常の加熱処理装置を使用すれば良く、特殊な装置
を用いることもない。例えばポリエステル樹脂の
乾燥用設備を使用することができる。又加熱処理
時の雰囲気も任意に選ぶ事ができ、例えば空気、
減湿空気あるいは窒素等の雰囲気下で行なうこと
ができるが、減湿空気の雰囲気が好ましく使用さ
れる。 For the first and second stage heat treatments, a normal heat treatment apparatus may be used, and no special equipment is required. For example, equipment for drying polyester resins can be used. In addition, the atmosphere during heat treatment can be arbitrarily selected, such as air,
This can be carried out under an atmosphere of dehumidified air or nitrogen, but an atmosphere of dehumidified air is preferably used.
本発明の方法により加熱処理されたポリエステ
ル樹脂は中空成形体例えば容器、瓶等に成形され
る。炭酸飲料用、食油用、ジユース用、アルコー
ル飲料用等に使用される容器又は瓶はダイレクト
ブロー、インジエクシヨンブロー、二軸延伸ブロ
ー等のいずれの成形方法によつても成形する事が
できる。 The polyester resin heat-treated by the method of the present invention is molded into hollow molded articles such as containers and bottles. Containers or bottles used for carbonated beverages, edible oil, youth, alcoholic beverages, etc. can be molded by any molding method such as direct blowing, injection blowing, biaxial stretch blowing, etc.
上述の加熱処理したポリエステル樹脂を用いて
ダイレクトブローにより容器または瓶を成形する
場合、先ず加熱溶融したポリエステル樹脂をパイ
プ状に押し出し、次いで該パイプ状押出し物を所
望の長に切断しかつ底をくり切る事により、有底
化したパリソンを作り、更に該パリソンを希望す
る容器又は瓶の形状を有する金型に移し、パリソ
ン内に圧縮流体例えば圧縮空気を吹き込んで容器
または瓶の形状まで膨張させる。ポリエステル樹
脂特にポリエチレンテレフタレートを用いてダイ
レクトブローにより容器又は瓶を成形する場合、
パリソンを押し出し成形する際にいわゆるドロー
ダウン現象が生じやすい。それ故、ポリマーの溶
融粘度を充分に高くすることが好ましく、その為
には重合度の高いポリエステル樹脂例えば固有粘
度が0.8以上、さらには0.9以上のポリエチレンテ
レフタレートを使用するのが好ましい。 When molding a container or bottle by direct blowing using the heat-treated polyester resin described above, first extrude the heated and molten polyester resin into a pipe shape, then cut the pipe-shaped extrudate into a desired length and cut out the bottom. A parison with a bottom is made by cutting, and the parison is transferred to a mold having the shape of a desired container or bottle, and a compressed fluid such as compressed air is blown into the parison to expand it to the shape of the container or bottle. When molding containers or bottles by direct blowing using polyester resin, especially polyethylene terephthalate,
When extruding a parison, a so-called drawdown phenomenon tends to occur. Therefore, it is preferable to sufficiently increase the melt viscosity of the polymer, and for this purpose, it is preferable to use a polyester resin with a high degree of polymerization, such as polyethylene terephthalate with an intrinsic viscosity of 0.8 or more, more preferably 0.9 or more.
また、ポリエステル樹脂を用いて二軸延伸ブロ
ーにより容器又は瓶を成形する場合、まず射出成
形機にて240〜300℃に加熱溶融したポリエステル
樹脂を、プリフオーム金型へ射出・冷却する事に
より有底のパリソンを成形し、次いで該パリソン
をポリエステル樹脂のガラス転位点以上の温度に
再加熱し、希望する容器または瓶の形状を有する
金型内に移した後、延伸ロツドにより軸方向に延
伸するとともに、圧縮流体例えば圧縮空気を吹込
んで容器または瓶の形状まで膨張させる。 In addition, when molding containers or bottles using polyester resin by biaxial stretch blowing, first the polyester resin is heated and melted at 240 to 300°C using an injection molding machine, and then injected into a preform mold and cooled. The parison is then reheated to a temperature above the glass transition point of the polyester resin, transferred into a mold having the shape of a desired container or bottle, and then stretched in the axial direction with a stretching rod. , by blowing a compressed fluid, such as compressed air, into the shape of the container or bottle.
かくして得られた容器又は瓶は内容物充填時に
異臭がなく、特に炭酸飲料用、ジユース用、食油
用、アルコール飲料用等の容器として有用であ
る。 The containers or bottles thus obtained do not have any off-odor when filled with contents, and are particularly useful as containers for carbonated drinks, juices, edible oils, alcoholic beverages, etc.
以下実施例を掲げて本発明を詳述する。なお例
中で測定する主な特性の測定法を以下に示す。 The present invention will be described in detail below with reference to Examples. The methods for measuring the main characteristics measured in the examples are shown below.
固有粘度：ｏ−クロロフエノールを溶媒として35
℃で測定。Intrinsic viscosity: 35 using o-chlorophenol as a solvent
Measured in °C.
軟化点：ビカツト軟化点測定装置により測定
ASTM Ｄ−1525による。Softening point: Measured by Vikatsuto softening point measuring device
According to ASTM D-1525.
アセトアルデヒド含量：液体窒素中で20メツシシ
ユ以下に微粉砕した試料を、150℃のガスクロ
マトグラフのサンプル挿入場所に入れて20分間
保持し、次いで遊離したアセトアルデヒドを室
温のカラムに凝縮させた後該カラムを135℃ま
で急速に昇温する。求められたピーク面積を標
準サンプルのピーク面積と比較する事により、
遊離したアセトアルデヒドの量を求め、この値
から試料中のアセトアルデヒド含量を算出す
る。Acetaldehyde content: A sample pulverized to 20 mesh or less in liquid nitrogen is placed in the sample insertion area of a gas chromatograph at 150°C and held for 20 minutes.Then, the liberated acetaldehyde is condensed on a column at room temperature, and then the column is Rapidly heat up to 135℃. By comparing the obtained peak area with the peak area of the standard sample,
The amount of acetaldehyde released is determined, and the acetaldehyde content in the sample is calculated from this value.
実施例 １
ジメチルテレフタレートに対して５ミリモル％
の酢酸チタンを触媒として用いて、ジメチルテレ
フタレートとエチレングリコールとのエステル交
換反応を行つた後、さらに反応生成物に酸化ゲル
マニウム30ミリモル％及び正リン酸40ミリモル％
を添加して最終温度285℃、真空度0.5mmHgのも
とに重縮合反応を行い、固有粘度0.75のポリエチ
レンテレフタレートを得た。このポリエチレンテ
レフタレートを反応釜から３Kg／cm2Ｇの窒素圧力
下で水中に押し出し、一辺３mmの立方体のペレツ
トを得た。このペレツトの軟化点は259℃、アセ
トアルデヒド含量は41ppmであつた。Example 1 5 mmol% based on dimethyl terephthalate
After carrying out the transesterification reaction between dimethyl terephthalate and ethylene glycol using titanium acetate as a catalyst, the reaction product further contains 30 mmol% germanium oxide and 40 mmol% orthophosphoric acid.
was added to carry out a polycondensation reaction at a final temperature of 285°C and a degree of vacuum of 0.5 mmHg to obtain polyethylene terephthalate with an intrinsic viscosity of 0.75. This polyethylene terephthalate was extruded from the reaction vessel into water under a nitrogen pressure of 3 kg/cm 2 G to obtain cubic pellets with sides of 3 mm. The pellets had a softening point of 259°C and an acetaldehyde content of 41 ppm.
この様にして製造したポリエチレンテレフタレ
ートのペレツトを、まず熱風式乾燥機を使用し、
160℃の温度で４時間加熱処理を行つた後室温ま
で放冷した。このときのポリエチレンテレフタレ
ートペレツトのアセトアルデヒド含量は7ppmで
あつた。この加熱処理後のペレツトを室温で１昼
夜放置した後、再び熱風式乾燥機を使用し、160
℃の温度で４時間加熱処理を行つた。 The polyethylene terephthalate pellets produced in this way were first dried using a hot air dryer.
After performing a heat treatment at a temperature of 160°C for 4 hours, it was allowed to cool to room temperature. The acetaldehyde content of the polyethylene terephthalate pellets at this time was 7 ppm. After this heat-treated pellet was left at room temperature for a day and night, it was dried again using a hot air dryer,
Heat treatment was carried out at a temperature of .degree. C. for 4 hours.
得られたポリエチレンテレフタレートのペレツ
トはアセトアルデヒド含量が2.0ppmのものであ
つた。更にこのペレツトの固有粘度は、0.73であ
り、加熱処理による固有粘度の低下は極く小さい
ものであつた。 The resulting polyethylene terephthalate pellets had an acetaldehyde content of 2.0 ppm. Furthermore, the intrinsic viscosity of this pellet was 0.73, and the decrease in intrinsic viscosity due to heat treatment was extremely small.
上記の２段の加熱処理で得られポリエチレンテ
レフタレートのペレツトを使用し、シリンダー温
度280℃の射出成形機を用い重量50ｇの円筒状有
底パリソンを成形し、次いで該パリソンを内部温
度が90〜105℃になる様に再加熱した後２軸延伸
ブローを行い内容積１のボトルを得た。このボ
トルに炭酸飲料（コーラ）或いは食用油を充填
し、密封状態で室温にて、３ケ月保持後、内容物
の風味・味等をテストしたところ何ら異臭は認め
られなかつた。 Using the polyethylene terephthalate pellets obtained through the above two-stage heat treatment, a cylindrical bottomed parison weighing 50 g was molded using an injection molding machine with a cylinder temperature of 280°C, and then the parison was molded at an internal temperature of 90 to 105°C. After reheating to a temperature of .degree. C., biaxial stretching blowing was performed to obtain a bottle with an inner volume of 1. This bottle was filled with carbonated beverage (cola) or edible oil and kept in a sealed state at room temperature for 3 months, and then the flavor and taste of the contents were tested, and no abnormal odor was observed.
比較例 １
実施例１における溶融重合で製造されたポリエ
チレンテレフタレートのペレツトを、実施例１と
同じ、熱風式乾燥機を使用して160℃で実施例１
の２段加熱処理時間の合計と同じ時間、すなわち
８時間連続的に加熱処理した。得られたポリエチ
レンテレフタレートのペレツトはアセトアルデヒ
ド含量が5ppmのものであり、実施例１の方法に
くらべてペレツト中のアセトアルデヒド含量の大
きなものであつた。このペレツトを用いて、さら
に実施例１と同様の方法により内容積１のボト
ルを作り、このボトルに炭酸飲料（コーラ）或い
は食用油を充填し、密封状態で室温にて３ケ月保
持後内容物の風味・味等をテストしたところ異臭
が感じられた。その結果該容器は炭酸飲料或いは
食用油の容器としては使用できないことが明らか
となつた。Comparative Example 1 Polyethylene terephthalate pellets produced by melt polymerization in Example 1 were heated to 160°C using the same hot air dryer as in Example 1.
The heat treatment was continued for the same time as the total time of the two-stage heat treatment, that is, 8 hours. The polyethylene terephthalate pellets obtained had an acetaldehyde content of 5 ppm, which was higher than that obtained by the method of Example 1. Using these pellets, a bottle with an internal volume of 1 is made in the same manner as in Example 1, filled with carbonated drink (cola) or edible oil, and kept in a sealed state at room temperature for 3 months, after which the contents are When I tested the flavor, taste, etc., I noticed a strange odor. As a result, it became clear that the container could not be used as a container for carbonated drinks or edible oil.
比較例 ２
実施例１における溶融重合で製造されたポリエ
チレンテレフタレートのペレツトを、実施例１と
同じ熱風乾燥機を使用して、185℃で８時間連続
的に加熱処理した。得られたポリエチレンテレフ
タレートのペレツトは、アセトアルデヒド含量が
3.0ppmであり、実施例１とほぼ同等のアセトア
ルデヒド含量を示したが、その固有粘度は0.68で
あり、実施例１のものに比較し、大巾な重合度低
下が認められた。Comparative Example 2 The polyethylene terephthalate pellets produced by melt polymerization in Example 1 were continuously heat-treated at 185° C. for 8 hours using the same hot air dryer as in Example 1. The polyethylene terephthalate pellets obtained have an acetaldehyde content of
The acetaldehyde content was 3.0 ppm, which was almost the same as that of Example 1, but the intrinsic viscosity was 0.68, indicating that the degree of polymerization was significantly lower than that of Example 1.
実施例 ２
実施例１の溶融重合で製造されたポリエチレン
テレフタレートのペレツトを、まず−50℃の露点
をもつ減湿空気を用いて180℃の温度で２時間加
熱処理した後室温まで放冷した。このときのポリ
エチレンテレフタレートペレツトのアセトアルデ
ヒド含量は6.5ppmであつた。この加熱処理ペレ
ツトを室温で１昼夜放置した後、再び−50℃の露
点をもつ減湿空気を用いて180℃の温度で３時間
加熱処理した。Example 2 The polyethylene terephthalate pellets produced by melt polymerization in Example 1 were first heat-treated at 180°C for 2 hours using dehumidified air having a dew point of -50°C, and then allowed to cool to room temperature. The acetaldehyde content of the polyethylene terephthalate pellets at this time was 6.5 ppm. The heat-treated pellets were left at room temperature for a day and night, and then heat-treated again at a temperature of 180°C for 3 hours using dehumidified air having a dew point of -50°C.
得られたポリエチレンテレフタレートのペレツ
トはアセトアルデヒド含量が1.5ppmのものであ
つた。又、この固有粘度は0.73であり、加熱処理
による固有粘度の低下は極く小さいものであつ
た。この２段の加熱処理で得られたポリエチレン
テレフタレートのチツプを用いて、実施例１と同
じ方法により内容積１のボトルを成形した。こ
のボトルに炭酸飲料（コーラ）或いは食用油を充
填し、密封状態で３ケ月間室温保持したのち内容
物の風味・味等をテストしたところ異臭が感じら
れなかつた。 The resulting polyethylene terephthalate pellets had an acetaldehyde content of 1.5 ppm. Further, the intrinsic viscosity was 0.73, and the decrease in the intrinsic viscosity due to heat treatment was extremely small. Using the polyethylene terephthalate chips obtained through this two-stage heat treatment, a bottle having an internal volume of 1 was molded in the same manner as in Example 1. This bottle was filled with carbonated beverage (cola) or edible oil, kept sealed at room temperature for 3 months, and then the flavor and taste of the contents were tested, and no abnormal odor was detected.
Claims (1)
するに当り、該ポリエステル樹脂として樹脂中の
アセトアルデヒド濃度が10ppm以下となるまで
加熱処理したのち一旦50℃以下の温度まで冷却
し、再び100℃以上の温度で加熱処理したポリエ
ステル樹脂を用いることを特徴とするポリエステ
ル樹脂製中空成形品の製造法。 ２ ポリエステル樹脂がポリエチレンテレフタレ
ートであることを特徴とする特許請求の範囲第１
項記載の製造法。[Claims] 1. When producing a blow molded product using a polyester resin, the polyester resin is heat-treated until the acetaldehyde concentration in the resin is 10 ppm or less, and then once cooled to a temperature of 50°C or less, A method for producing a polyester resin blow molded product, characterized by using polyester resin that has been heat-treated at a temperature of 100°C or higher. 2. Claim 1, characterized in that the polyester resin is polyethylene terephthalate.
Manufacturing method described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5179180A JPS56148526A (en) | 1980-04-21 | 1980-04-21 | Manufacture of hollow moldings made of polyester resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5179180A JPS56148526A (en) | 1980-04-21 | 1980-04-21 | Manufacture of hollow moldings made of polyester resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56148526A JPS56148526A (en) | 1981-11-18 |
| JPS6226286B2 true JPS6226286B2 (en) | 1987-06-08 |
Family
ID=12896756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5179180A Granted JPS56148526A (en) | 1980-04-21 | 1980-04-21 | Manufacture of hollow moldings made of polyester resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56148526A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2139061C (en) * | 1993-12-28 | 1998-12-08 | Mitsui Chemicals, Inc. | Process for preparing polyester |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5036461A (en) * | 1973-06-22 | 1975-04-05 | ||
| JPS5048103A (en) * | 1973-08-30 | 1975-04-30 | ||
| JPS5285255A (en) * | 1976-01-09 | 1977-07-15 | Toray Industries | Method of producing hollow formed article of thermoplastic polyester resin |
| JPS5328676A (en) * | 1976-08-31 | 1978-03-17 | Teijin Ltd | Process for manufacturing polyester hollow object or preceding object thereof |
| JPS5364260A (en) * | 1976-11-22 | 1978-06-08 | Unitika Ltd | Process for crystallization of flame-retardant copolyester chips |
| JPS54149793A (en) * | 1978-05-16 | 1979-11-24 | Celanese Corp | Preparation of polyethylene terephthalate suitable for drinking container |
-
1980
- 1980-04-21 JP JP5179180A patent/JPS56148526A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5036461A (en) * | 1973-06-22 | 1975-04-05 | ||
| JPS5048103A (en) * | 1973-08-30 | 1975-04-30 | ||
| JPS5285255A (en) * | 1976-01-09 | 1977-07-15 | Toray Industries | Method of producing hollow formed article of thermoplastic polyester resin |
| JPS5328676A (en) * | 1976-08-31 | 1978-03-17 | Teijin Ltd | Process for manufacturing polyester hollow object or preceding object thereof |
| JPS5364260A (en) * | 1976-11-22 | 1978-06-08 | Unitika Ltd | Process for crystallization of flame-retardant copolyester chips |
| JPS54149793A (en) * | 1978-05-16 | 1979-11-24 | Celanese Corp | Preparation of polyethylene terephthalate suitable for drinking container |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56148526A (en) | 1981-11-18 |
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