JPH04212829A - Heat-resistant vessel - Google Patents
Heat-resistant vesselInfo
- Publication number
- JPH04212829A JPH04212829A JP2280260A JP28026090A JPH04212829A JP H04212829 A JPH04212829 A JP H04212829A JP 2280260 A JP2280260 A JP 2280260A JP 28026090 A JP28026090 A JP 28026090A JP H04212829 A JPH04212829 A JP H04212829A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- temperature
- sheet
- container
- polyester resin
- 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.)
- Granted
Links
- 229920001225 polyester resin Polymers 0.000 claims abstract description 18
- 239000004645 polyester resin Substances 0.000 claims abstract description 18
- 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 14
- 238000000465 moulding Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000003856 thermoforming Methods 0.000 claims description 12
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical group CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 150000002148 esters Chemical group 0.000 abstract description 10
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 abstract description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 abstract description 6
- 229920000166 polytrimethylene carbonate Polymers 0.000 abstract description 6
- 229920000728 polyester Polymers 0.000 description 18
- -1 polyethylene terephthalate Polymers 0.000 description 18
- 238000002425 crystallisation Methods 0.000 description 17
- 230000008025 crystallization Effects 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229920001707 polybutylene terephthalate Polymers 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000007666 vacuum forming Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- SFHBJXIEBWOOFA-UHFFFAOYSA-N 5-methyl-3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OC(C)COC(=O)C2=CC=C1C=C2 SFHBJXIEBWOOFA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000010411 cooking Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004455 differential thermal analysis Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000001771 impaired effect Effects 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
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- MJHNUUNSCNRGJE-UHFFFAOYSA-N trimethyl benzene-1,2,4-tricarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C(C(=O)OC)=C1 MJHNUUNSCNRGJE-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical class OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- GIXXQTYGFOHYPT-UHFFFAOYSA-N Bisphenol P Chemical compound C=1C=C(C(C)(C)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 GIXXQTYGFOHYPT-UHFFFAOYSA-N 0.000 description 1
- DKPJBSHGFSWHRQ-QDNHWIQGSA-N FOC(C([2H])(F)F)(C(F)(F)F)[2H] Chemical compound FOC(C([2H])(F)F)(C(F)(F)F)[2H] DKPJBSHGFSWHRQ-QDNHWIQGSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- RGCHNYAILFZUPL-UHFFFAOYSA-N trimethyl benzene-1,3,5-tricarboxylate Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(C(=O)OC)=C1 RGCHNYAILFZUPL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
Landscapes
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Polyesters Or Polycarbonates (AREA)
- Package Specialized In Special Use (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Packages (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は耐熱容器の製造法に関し、更に詳しくは高結晶
性でなお且つ高温加熱雰囲気下で耐熱変形性に優れたポ
リエステル樹脂製耐熱容器に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for manufacturing a heat-resistant container, and more particularly to a heat-resistant container made of polyester resin that is highly crystalline and has excellent heat deformation resistance in a high-temperature heating atmosphere. It is something.
ポリエチレンテレフタレート（ＰＥＴ）に代表される芳
香族ポリエステルは、その樹脂シートから射出成形法や
真空成形、圧空成形等の熱成形法により容器を製造する
ことができ、耐薬品性や耐ガス透過性、耐熱性を生かし
た分野で近年、その用途が増えている。Aromatic polyesters, represented by polyethylene terephthalate (PET), can be used to manufacture containers from resin sheets using thermoforming methods such as injection molding, vacuum forming, and pressure forming. In recent years, its use has been increasing in fields that take advantage of its heat resistance.
しかしながら、無配向、非晶質のＰＥＴのシートは結晶
化が進まない温度で熱成形すれば一応透明性に優れた容
器に成形しうるが、斯かるＰＥＴより得た容器は耐熱性
に欠点があり、約８０℃以上の加熱雰囲気下では変形し
、又その結晶性に由来して、加熱雰囲気下で使用する場
合は結晶化が進み、著しく熱収縮や透明性低下が起こる
ため、その用途が制限されている。一方、二軸延伸して
結晶化した透明ＰＥＴシートは、その配向性のために熱
成形が容易でない。又、ＰＥＴ容器の耐熱性、機械的強
度を向上させるべく、容器の成形温度を高くした場合は
、結晶化が進行するため著しく白化し、透明度が極めて
低くなる。ここで共重合等により結晶性を無視すれば透
明性の向上した容器を得ることは可能であるが、この場
合は機械的特性、特に耐熱性が低下して高温使用に耐え
得ないものとなる。However, although sheets of non-oriented, amorphous PET can be formed into containers with excellent transparency if they are thermoformed at a temperature that prevents crystallization, containers made from such PET have shortcomings in heat resistance. However, it deforms in a heated atmosphere of about 80℃ or higher, and due to its crystallinity, when used in a heated atmosphere, crystallization progresses, resulting in significant thermal shrinkage and a decrease in transparency. Limited. On the other hand, transparent PET sheets crystallized by biaxial stretching are not easy to thermoform due to their orientation. Furthermore, if the molding temperature of the PET container is increased in order to improve its heat resistance and mechanical strength, crystallization progresses, resulting in significant whitening and extremely low transparency. If crystallinity is ignored through copolymerization, it is possible to obtain a container with improved transparency, but in this case, the mechanical properties, especially the heat resistance, will deteriorate and the container will not be able to withstand high-temperature use. .
又、ポリブチレンテレフタレート（ＰＢＴ）は更にその
高い結晶性のため、一般に透明の急冷シートを調製する
のが困難であり、熱成形における賦形性が著しく劣るた
め熱成形により透明性に優れた容器を得ることはできな
い。一方、ＰＢＴもポリマー自体に他の構成単位を導入
し、共重合体としてその結晶性を緩和することにより透
明性を高めることは可能であるが、該手法により得られ
た透明容器は加熱により結晶化が進んで透明度が極めて
低く、又、全く非晶性のものはＰＢＴ本来の特性が失わ
れ、特に強度と耐熱性が著しく劣るものとなる。Furthermore, due to its high crystallinity, it is generally difficult to prepare transparent quenched sheets of polybutylene terephthalate (PBT), and its formability in thermoforming is extremely poor, so it is difficult to prepare containers with excellent transparency through thermoforming. cannot be obtained. On the other hand, it is possible to improve the transparency of PBT by introducing other structural units into the polymer itself and relaxing its crystallinity as a copolymer, but the transparent container obtained by this method does not crystallize when heated. If the PBT becomes completely amorphous, the original properties of PBT are lost, and in particular, the strength and heat resistance become extremely poor.
このように芳香族ポリエステルは、一般に結晶性に基づ
く機械的性質や耐熱性と、透明性とを兼備することは至
難であり、その両立が切望されていた。As described above, it is generally difficult for aromatic polyesters to combine mechanical properties and heat resistance based on crystallinity with transparency, and there has been a strong desire to achieve both.
〔課題を解決するための手段〕
以上の課題を解決すべく本発明者らは鋭意検討を重ねた
結果、原料ポリエステルとしてポリプロピレンテレフタ
レート重合体（ＰＰＴ）もしくはこれを主体とする共重
合体を使用し、特にこれより得たシートを特定条件で処
理し、成形加工することにより、透明性と高結晶性を兼
備し、加熱雰囲気下でもその透明性と耐熱性を保持した
容器を提供し得ることを見出し、本発明を完成するに至
ったものである。[Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have made extensive studies and have found that polypropylene terephthalate polymer (PPT) or a copolymer mainly composed of this is used as the raw material polyester. In particular, by treating and molding the sheet obtained from this under specific conditions, it is possible to provide a container that has both transparency and high crystallinity and maintains its transparency and heat resistance even in a heated atmosphere. This is the heading that led to the completion of the present invention.
即ち本発明は、繰り返し単位の８０モル％以上が１，３
−プロパンジオールとテレフタル酸若しくはそのエステ
ル形成性誘導体とのエステル単位からなるポリエステル
樹脂を成形してなる耐熱容器に関するものである。That is, in the present invention, 80 mol% or more of the repeating units are 1,3
- It relates to a heat-resistant container formed by molding a polyester resin comprising ester units of propanediol and terephthalic acid or its ester-forming derivative.
本発明に用いるポリエステル樹脂は、繰り返し単位の８
０モル％以上が１，３−プロパンジオール若しくはその
エステル形成性誘導体とテレフタル酸とのエステル単位
からなるものである。The polyester resin used in the present invention has a repeating unit of 8
At least 0 mol % is composed of ester units of 1,3-propanediol or its ester-forming derivative and terephthalic acid.
本発明に用いるポリエステル樹脂を形成するために必要
な原料化合物を順を追って説明すると、まずテレフタロ
イル基を形成するために必要な原料化合物はテレフタル
酸又はそのエステル形成性誘導体であり、該誘導体とし
ては例えばジアルキルエステル又はジアシル化物より選
ばれるものがあげられる。これらの内で好ましいものは
テレフタル酸又はそのジアルキルエステルであり、特に
好ましいものはテレフタル酸ジメチルである。To explain the raw material compounds necessary for forming the polyester resin used in the present invention step by step, first, the raw material compound necessary for forming the terephthaloyl group is terephthalic acid or its ester-forming derivative. Examples include those selected from dialkyl esters and diacylated products. Among these, preferred is terephthalic acid or its dialkyl ester, and particularly preferred is dimethyl terephthalate.
又、該ポリエステル樹脂のプロピレンテレフタレートユ
ニットを形成するジオールは、１，３−プロパンジオー
ルをモノマー原料として用いることで導入される。Further, the diol forming the propylene terephthalate unit of the polyester resin is introduced by using 1,3-propanediol as a monomer raw material.
本発明に使用されるポリエステル樹脂は、上記の必須原
料化合物を用いて製造されるポリプロピレンテレフタレ
ート（ＰＰＴ）のホモポリマーは勿論のこと、繰り返し
単位の８０モル％以上がプロピレンテレフタレート単位
であるポリプロピレンテレフタレートのコポリマーを包
含する。The polyester resin used in the present invention is not only a homopolymer of polypropylene terephthalate (PPT) produced using the above-mentioned essential raw material compounds, but also a homopolymer of polypropylene terephthalate (PPT) in which 80 mol% or more of the repeating units are propylene terephthalate units. Including copolymers.
斯かるコポリマーを構成するための上記必須原料化合物
以外のコモノマーの原料としては、一価又は多価カルボ
ン酸類とその誘導体、ヒドロキシカルボン酸類とその誘
導体、一価又は多価フェノール類とその誘導体、一価又
は多価脂肪族（脂環族を含む）アルコール類とその誘導
体、一価又は多価アミン類とその誘導体、ヒドロキシア
ミン類とその誘導体、一価又は多価アミド類とその誘導
体、イソシアネート類とその誘導体、イソシアヌレート
類とその誘導体等の一種又は二種以上が挙げられる。Raw materials for comonomers other than the above-mentioned essential raw material compounds for constituting such a copolymer include monovalent or polyvalent carboxylic acids and their derivatives, hydroxycarboxylic acids and their derivatives, monovalent or polyvalent phenols and their derivatives, and monovalent or polyvalent carboxylic acids and their derivatives. Monovalent or polyvalent aliphatic (including alicyclic) alcohols and their derivatives, monovalent or polyvalent amines and their derivatives, hydroxyamines and their derivatives, monovalent or polyvalent amides and their derivatives, isocyanates and derivatives thereof, isocyanurates and derivatives thereof, and the like.
特に一価又は多価カルボン酸類とその誘導体、一価又は
多価フェノール類とその誘導体、一価又は多価脂肪族（
脂環族を含む）アルコール類とその誘導体が好ましく、
その中でも二価カルボン酸類とその誘導体、二価フェノ
ール類とその誘導体、二価脂肪族（脂環族を含む）アル
コール類とその誘導体が好ましい。In particular, monovalent or polyvalent carboxylic acids and their derivatives, monovalent or polyvalent phenols and their derivatives, monovalent or polyvalent aliphatic (
Alcohols (including alicyclic groups) and their derivatives are preferred;
Among these, dihydric carboxylic acids and their derivatives, dihydric phenols and their derivatives, and dihydric aliphatic (including alicyclic) alcohols and their derivatives are preferred.
二価カルボン酸類の例としては、イソフタル酸、オルソ
フタル酸、ジフェン酸、２，６−ナフタレンジカルボン
酸などの芳香族ジカルボン酸、アジピン酸、セバシン酸
などの脂肪族ジカルボン酸、１，４−シクロヘキサンジ
カルボン酸などの脂環族ジカルボン酸等が挙げられる。Examples of dicarboxylic acids include aromatic dicarboxylic acids such as isophthalic acid, orthophthalic acid, diphenic acid, and 2,6-naphthalene dicarboxylic acid; aliphatic dicarboxylic acids such as adipic acid and sebacic acid; and 1,4-cyclohexane dicarboxylic acids. Examples include alicyclic dicarboxylic acids such as acids.
二価カルボン酸の誘導体の例としては、ジアルキルエス
テル又はジアシル化物より選ばれる一種又は二種以上が
挙げられるが、これらの内で好ましいものはジアルキル
エステルであり、特にジメチルエステルが好ましい。Examples of divalent carboxylic acid derivatives include one or more selected from dialkyl esters and diacylated products, and among these, dialkyl esters are preferred, and dimethyl esters are particularly preferred.
二価フェノールの例としては、ハイドロキノン、２，２
−ビス（４−ヒドロキシフェニル）プロパン、ビス（４
−ヒドロキシフェニル）スルホン、４，４−ジフェノー
ル、４，４′−〔１，４−フェニレンビス（１−メチル
エチリデン）〕ビスフェノール、ビス（４−ヒドロキシ
フェニル）エーテル、２，６−ジヒドロキシナフタレン
などの芳香族二価フェノールが挙げられる。二価フェノ
ールの誘導体の例としては、エチレンオキシド２〜４モ
ル付加体、プロピレンオキシド２付加体等が挙げられる
が、特にエチレンオキシド２モル付加体が好ましい。Examples of dihydric phenols include hydroquinone, 2,2
-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)propane,
-hydroxyphenyl) sulfone, 4,4-diphenol, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisphenol, bis(4-hydroxyphenyl)ether, 2,6-dihydroxynaphthalene, etc. aromatic dihydric phenols. Examples of dihydric phenol derivatives include ethylene oxide 2 to 4 mol adducts, propylene oxide 2 adducts, and ethylene oxide 2 mol adducts are particularly preferred.
二価アルコールの例としては、エチレングリコール、１
，４−ブタンジオール、１，５−ペンタンジオール、ネ
オペンチルグリコール、１，６−ヘキサンジオール、１
，１０−デカンジオールなどの脂肪族ジオール、１，４
−シクロヘキサンジオール、１，４−シクロヘキサンジ
メタノール、トリシクロデカンジメタノールなどの脂環
族ジオール等が挙げられる。Examples of dihydric alcohols include ethylene glycol, 1
, 4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1
, aliphatic diols such as 10-decanediol, 1,4
Examples include alicyclic diols such as -cyclohexanediol, 1,4-cyclohexanedimethanol, and tricyclodecane dimethanol.
又、更に該ポリエステルを製造するに際し、トリメシン
酸トリメチル、トリメリット酸トリメチル、トリメチロ
ールプロパン、ペンタエリスリトールの如き三官能以上
の多官能化合物、或いはステアリルアルコール、０−ベ
ンゾイル安息香酸メチルの如き単官能化合物の一種又は
二種以上を、実質的に共重合体が線状である程度に用い
ることもできる。又、ポリブチレングリコール等のポリ
アルキレングリコールを少量用いてポリエステル樹脂に
弾性を付与することも可能である。Furthermore, when producing the polyester, trimethyl or higher functional compounds such as trimethyl trimesate, trimethyl trimellitate, trimethylolpropane, and pentaerythritol, or monofunctional compounds such as stearyl alcohol and methyl 0-benzoylbenzoate may be used. One or more of these may be used to the extent that the copolymer is substantially linear. It is also possible to impart elasticity to the polyester resin by using a small amount of polyalkylene glycol such as polybutylene glycol.
本発明の共重合ポリエステルは、コモノマーとして少な
くとも上記の群より選ばれる一種又は二種以上を原料化
合物とすることが可能であり、これらのコモノマーの全
構成単位に対するモル分率は２０モル％以下であること
が必要である。特に好ましくは１５モル％以下である。The copolymerized polyester of the present invention can use at least one or two or more selected from the above group as a comonomer, and the molar fraction of these comonomers to the total constitutional units is 20 mol% or less. It is necessary that there be. Particularly preferably, it is 15 mol% or less.
上記モル分率が２０モル％よりも大きいと得られた容器
の相対結晶化度が低下するため容器の機械的強度や耐熱
変形性の低下が顕著となる。When the mole fraction is greater than 20 mol%, the relative crystallinity of the resulting container decreases, resulting in a significant decrease in the mechanical strength and heat deformation resistance of the container.
これらのポリエステル樹脂は従来公知の縮合反応や、エ
ステル交換反応を利用して界面重縮合や溶融重合、溶液
重合等により製造することができる。また得られた樹脂
を好ましくは融点から１０℃乃至５０℃低い温度で、減
圧又は不活性ガス存在下で加熱処理を行う固相重合法を
用いることでさらに高重合度製品とすることも可能であ
る。These polyester resins can be produced by interfacial polycondensation, melt polymerization, solution polymerization, etc. using conventionally known condensation reactions and transesterification reactions. Furthermore, it is also possible to obtain a product with an even higher degree of polymerization by using a solid phase polymerization method in which the obtained resin is heat-treated at a temperature preferably 10°C to 50°C lower than its melting point under reduced pressure or in the presence of an inert gas. be.
又、本発明に用いる共重合ポリエステル樹脂には本発明
の効果を阻害しない範囲で目的に応じ、他の熱可塑性樹
脂を補助的に少量併用したり、一般に熱可塑性樹脂に添
加される公知の物質、すなわち、紫外線吸収剤等の安定
剤、帯電防止剤、難燃剤、難燃助剤、染料や顔料等の着
色剤、潤滑剤、可塑剤及び結晶化促進剤、結晶核剤、無
機充填剤等を配合することも勿論可能である。In addition, depending on the purpose, the copolymerized polyester resin used in the present invention may be supplemented with a small amount of other thermoplastic resins, or may contain known substances that are generally added to thermoplastic resins, depending on the purpose, to the extent that the effects of the present invention are not impaired. That is, stabilizers such as ultraviolet absorbers, antistatic agents, flame retardants, flame retardant aids, colorants such as dyes and pigments, lubricants, plasticizers and crystallization promoters, crystal nucleating agents, inorganic fillers, etc. Of course, it is also possible to mix.
斯かる製造方法によって得られたポリエステル樹脂は、
乾燥させたのち、通常の成形方法、例えば射出成形によ
り所望の形状の容器とすることができるが、一旦シート
状に整えたのち、該シートを熱成形することにより容器
とするのが望ましい。シートを調製するには、例えばＴ
−ダイを備えた押出機にてシート状に押出し、これを低
温に設定されたキャスティングドラム上に接触させ急冷
すればよく、これにより低結晶化度、透明、且つ無配向
性のシートを得ることができる。又、該ポリエステル樹
脂からは、この他にもインフレーション法、プレス法等
によりシートとすることができるが、特に上記の如きＴ
−ダイによる押出し法が好ましい。The polyester resin obtained by such a manufacturing method is
After drying, a container of a desired shape can be formed by a conventional molding method such as injection molding, but it is preferable to form a container by forming the sheet into a sheet and then thermoforming the sheet. To prepare a sheet, e.g. T
- It is sufficient to extrude it into a sheet using an extruder equipped with a die, and then bring it into contact with a casting drum set at a low temperature to rapidly cool it, thereby obtaining a sheet with low crystallinity, transparency, and non-orientation. I can do it. In addition, sheets can be made from the polyester resin by other methods such as an inflation method and a press method, but in particular, sheets can be made from the above-mentioned T.
- The extrusion method using a die is preferred.
シートの好ましい厚みについて言及するならば、シート
の厚みが厚い場合にはその表面部分のみが急冷により透
明化し、内部は徐冷状態となり白化しやすい傾向があり
、又該シートを熱成形した場合、賦形性が悪く成形加工
性を著しく損なうことになる。シートの厚みが薄すぎる
場合には、シート自体の機械的強度が発揮されず実用上
の優れた効果が薄れてしまう。従ってシートの好ましい
厚みの範囲を数値をもって特定すれば、０．０５〜２．
００ｍｍであり、より好ましくは０．１０〜１．００ｍ
ｍである。また、急冷によりシートを製造した後に所定
の厚みになるように低延伸比の一軸もしくは二軸延伸を
行ってもかまわないが、好ましくは無延伸が良い。Regarding the preferred thickness of the sheet, if the sheet is thick, only the surface portion becomes transparent due to rapid cooling, while the inside becomes slowly cooled and tends to whiten, and when the sheet is thermoformed, The shapeability is poor and moldability is significantly impaired. If the thickness of the sheet is too thin, the mechanical strength of the sheet itself will not be exhibited and the excellent practical effects will be diminished. Therefore, if the preferable thickness range of the sheet is specified numerically, it is 0.05 to 2.
00mm, more preferably 0.10-1.00m
It is m. Further, after producing a sheet by rapid cooling, uniaxial or biaxial stretching at a low stretching ratio may be performed to obtain a predetermined thickness, but non-stretching is preferable.
本発明においてはシート押出後、直ちに熱成形に移行し
てもよいが、熱成形前のシートに特定の熱履歴を与える
ことで熱成形後の成形体の透明性を一段と向上させるこ
とが可能である。In the present invention, thermoforming may be performed immediately after sheet extrusion, but it is possible to further improve the transparency of the molded product after thermoforming by imparting a specific thermal history to the sheet before thermoforming. be.
熱処理は温水等、所定温度の熱媒中にシートを浸漬する
方法や、所定温度の乾燥機中で加熱する方法、温風を吹
きつける方法、赤外線等の輻射熱による方法などにより
行われる。The heat treatment is performed by immersing the sheet in a heating medium at a predetermined temperature such as hot water, heating the sheet in a dryer at a predetermined temperature, blowing hot air, or using radiant heat such as infrared rays.
又、シートの熱処理温度は下記式（１）を満足させるよ
うな範囲が好ましい。Further, the heat treatment temperature of the sheet is preferably within a range that satisfies the following formula (1).
式（１）Ｔａ≦Ｔｃｃ（℃）
（但し、Ｔａ：熱処理温度（℃）
Ｔｃｃ；ＪＩＳＫ７１２１に基づく示差熱分析法により
昇温速度１０℃／ｍｉｎ
で測定した樹脂の冷結晶化温
度（℃））
熱処理温度がＴｃｃ（℃）よりも高温であると急激な結
晶化によりシートが白濁し、好ましくない。又、熱処理
温度が低いと極めて長時間を要し、生産性等の点で好ま
しくなく、熱処理温度は３０℃以上であることが好まし
い。Formula (1) Ta≦Tcc (°C) (where, Ta: heat treatment temperature (°C); Tcc: cold crystallization temperature of the resin measured at a heating rate of 10°C/min by differential thermal analysis method based on JIS K7121 (°C)) If the heat treatment temperature is higher than Tcc (° C.), the sheet becomes cloudy due to rapid crystallization, which is not preferable. In addition, if the heat treatment temperature is low, it will take a very long time, which is unfavorable in terms of productivity, etc., so the heat treatment temperature is preferably 30° C. or higher.
熱処理のために必要な時間は該ポリエステル樹脂のガラ
ス転移温度、冷結晶化温度、及びガラス転移温度と冷結
晶化温度の間の温度幅、又、熱処理温度とシートの厚さ
により異なる。上記温度幅が大きい程、熱処理温度が低
い程、シートの厚さが厚い程、長い熱処理時間を要する
。The time required for heat treatment varies depending on the glass transition temperature of the polyester resin, the cold crystallization temperature, the temperature range between the glass transition temperature and the cold crystallization temperature, the heat treatment temperature and the thickness of the sheet. The larger the temperature range, the lower the heat treatment temperature, and the thicker the sheet, the longer the heat treatment time is required.
又、熱処理は上記の条件を満たす範囲であれば、一定温
度で保持しても、２段階以上の温度を選んでも、或いは
温度を連続的に変化させても良い。Further, the heat treatment may be carried out at a constant temperature, at two or more stages, or at a continuous temperature change, as long as the above conditions are met.
該シートは一旦熱処理後又はシート押出後、更に常法の
熱成形によって所望する形状の容器に成形される。本発
明でいう熱成形とは、真空成形、圧空成形等の公知の成
形法を総称し、使用される成形機としては、真空成形機
、圧空成形機、又は真空と圧空を併用した万能成形機等
が挙げられる。The sheet is once heat-treated or extruded and then further molded into a container of a desired shape by thermoforming in a conventional manner. Thermoforming in the present invention is a general term for known forming methods such as vacuum forming and pressure forming, and the forming machine used is a vacuum forming machine, a pressure forming machine, or a universal forming machine that uses a combination of vacuum and pressure forming. etc.
熱成形における該シートは、ガラス転移点（Ｔｇ）以上
の温度で加熱軟化せしめられ、続いて速やかに真空下又
は加圧下で金型に密着させられ賦形が行われる。シート
を軟らかくするための予熱温度が冷結晶化温度（Ｔｃｃ
）より高い場合、シートの結晶化が著しく生起するため
、賦形性の不良や肉厚のバラツキが生じる。従って、好
ましくは予熱温度はＴｃｃ以下に選ぶのが良い。成形時
のキャビティー金型の温度範囲は特に限定されないが、
キャビティー金型温度がＴｃｃ＋２（℃）よりも低いと
高結晶化度の容器を得難く、又、加熱時間が長くなり過
ぎるため好ましくない。逆に高温にすると処理時間は短
縮できるが融点に近づき過ぎると賦形性が著しく低下し
、不均一な熱処理による部分的な溶融が生じる場合があ
り、Ｔｍ−５（℃）以下、好ましくはＴｍ−１０（℃）
以下にとどめるのが望ましい。ここでＴｇ、Ｔｃｃ及び
Ｔｍは夫々ＪＩＳＫ７１２１に基づく示差熱分析法によ
り昇温速度１０℃／ｍｉｎで測定した樹脂のガラス転移
温度（℃）、冷結晶化温度（℃）及び融点（℃）である
。In thermoforming, the sheet is softened by heating at a temperature above the glass transition point (Tg), and then immediately brought into close contact with a mold under vacuum or pressure to form the sheet. The preheating temperature to soften the sheet is the cold crystallization temperature (Tcc
), the crystallization of the sheet will occur significantly, resulting in poor formability and variations in wall thickness. Therefore, the preheating temperature is preferably selected to be below Tcc. The temperature range of the cavity mold during molding is not particularly limited, but
If the cavity mold temperature is lower than Tcc+2 (° C.), it is difficult to obtain a container with a high degree of crystallinity, and the heating time becomes too long, which is not preferable. On the other hand, if the temperature is set to a high temperature, the processing time can be shortened, but if the temperature is too close to the melting point, the shapeability will be significantly reduced, and partial melting may occur due to uneven heat treatment. -10(℃)
It is preferable to keep it below. Here, Tg, Tcc, and Tm are the glass transition temperature (°C), cold crystallization temperature (°C), and melting point (°C) of the resin, respectively, as measured by differential thermal analysis based on JIS K7121 at a heating rate of 10°C/min. .
斯かる条件で成形を行うことによって、透明性を保った
まま結晶化が促進されるため、該容器は透明且つ高結晶
性を有し、更に高温加熱雰囲気下でも透明性を維持する
ことができるのである。By performing molding under such conditions, crystallization is promoted while maintaining transparency, so the container is transparent and has high crystallinity, and can maintain transparency even in a high-temperature heating atmosphere. It is.
熱成形後の透明高結晶性容器の好ましい相対結晶化度（
ＣＲ）を特定するならばＣＲが５０％以上である。ここ
で相対結晶化度とは後記するＤＳＣ測定法により求めた
値である。容器の相対結晶化度が５０％未満であると、
高温付近での耐熱性が著しく低下するため、最終製品の
相対結晶化度が５０％以上で、且つ１５０℃で加熱処理
しても相対結晶化度の変化の少ない、充分結晶化の施さ
れたものが実用上好ましく、本発明によれば斯かる容器
の提供が可能となった。Preferred relative crystallinity of transparent highly crystalline containers after thermoforming (
CR) is 50% or more. Here, the relative crystallinity is a value determined by the DSC measurement method described later. The relative crystallinity of the container is less than 50%;
Since the heat resistance at high temperatures decreases significantly, the final product should have a relative crystallinity of 50% or more, and should be sufficiently crystallized with little change in relative crystallinity even after heat treatment at 150°C. It is preferable for practical use, and the present invention has made it possible to provide such a container.
又、容器の透明性を規定する尺度としてはヘイズ値があ
るが、該容器の好ましいヘイズ値を規定すると２５％以
下であり、１５０℃で加熱処理してもヘイズ値２５％以
下を保持するものが実用上望ましく、本発明によれば斯
かる容器の提供が可能となった。In addition, the haze value is a measure that defines the transparency of a container, and the preferred haze value for the container is 25% or less, and the haze value is maintained at 25% or less even after heat treatment at 150 ° C. This is practically desirable, and the present invention has made it possible to provide such a container.
以上の如く、本発明の容器は、以下のような優れた効果
を有する。As described above, the container of the present invention has the following excellent effects.
１）結晶化度５０％以上の高結晶性であるため耐熱性が
高く、１５０℃程度の加熱雰囲気下においても耐熱変形
性を有し、且つヘイズ値２５％以下を保持し、電子レン
ジ調理用食品の調理容器（オーブナブルトレイ）、耐熱
カップ等として、特に内容物を外部から確認できる調理
容器として有利に利用できる。又、熱殺菌を要するもの
、高温の状態で内容物を注入させる容器に適している。1) It has high heat resistance due to its high crystallinity with a degree of crystallinity of 50% or more, and has heat deformation resistance even in a heated atmosphere of about 150°C, and maintains a haze value of 25% or less, making it suitable for microwave cooking. It can be advantageously used as a food cooking container (ovenable tray), heat-resistant cup, etc., especially as a cooking container whose contents can be checked from the outside. It is also suitable for containers that require heat sterilization and containers into which the contents are poured at high temperatures.
２）機械的特性を損なわずに透明性を付与したことから
、内容物を外部から確認できる保護用容器として使用で
きる。2) Since transparency is imparted without impairing mechanical properties, it can be used as a protective container that allows the contents to be confirmed from the outside.
以下、実施例により本発明を更に具体的に説明するが、
本発明はこれらに限定されるものではない。Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these.
尚、主な特性値の測定条件は次の通りである。The conditions for measuring the main characteristic values are as follows.
（１）プロピレンテレフタレート単位置ヘキサフルオロ
イソプロパノール−ｄ２を溶媒とした１Ｈ−ＮＭＲ測定
から求めた。(1) Propylene terephthalate monoposition determined from 1H-NMR measurement using hexafluoroisopropanol-d2 as a solvent.
（２）固有粘度 オルソクロロフェノール中で２５℃で測定した。(2) Intrinsic viscosity Measurements were made in orthochlorophenol at 25°C.
（３）融点、冷結晶化温度、ガラス転移温度ＪＩＳＫ７
１２１に基づき示差熱分析法（ＤＳＣ）により昇温温度
１０℃／ｍｉｎで測定した。(3) Melting point, cold crystallization temperature, glass transition temperature JISK7
Measurement was carried out by differential thermal analysis (DSC) based on 121 at a heating temperature of 10° C./min.
（４）相対結晶化度
シートをＤＳＣ測定用試料に切出し、ＤＳＣ装置を用い
て行った。相対結晶化度（ＣＲ）の算出は下式による。(4) Relative crystallinity The sheet was cut into a sample for DSC measurement, and the measurement was performed using a DSC device. Calculation of relative crystallinity (CR) is based on the following formula.
〔但し、ΔＨｍ；１０℃／ｍｉｎで昇温測定による結晶
融解熱（Ｊ／ｇ）
ΔＨｃｃ；１０℃／ｍｉｎで昇温測定による冷結晶化熱
（Ｊ／ｇ）
（ΔＨｃ）ＨＯＭＯ；改質していないポリプロピレンテ
レフタレートホモポリマー
の溶融状態から１０℃／ｍｉｎで降
温測定による結晶化熱（Ｊ／ｇ）〕
昇温測定時に冷結晶化が進行した後に結晶が融解するた
めに、試料本来の相対結晶化度を求めるには、結晶融解
熱（ΔＨｍ）から冷結晶化ピークの転移熱（ΔＨｃｃ）
の絶対値を差し引くことになる。[However, ΔHm; heat of crystal fusion (J/g) measured by heating at 10°C/min; ΔHcc; heat of cold crystallization (J/g) measured by heating at 10°C/min (ΔHc) HOMO; Heat of crystallization (J/g) measured by cooling the polypropylene terephthalate homopolymer at a rate of 10°C/min from the molten state. To determine the degree of crystallization, calculate the heat of transition of the cold crystallization peak (ΔHcc) from the heat of crystal fusion (ΔHm).
The absolute value of is subtracted.
（５）ヘイズ値
急冷及び熟成後のシートのヘイズ値はＪＩＳＫ７１０５
に基づき積分球式ＨＴＲメーターにより測定した。又、
成形体のヘイズ値は、容器側面部の一部を切り出し、同
様に測定した。(5) Haze value The haze value of the sheet after quenching and aging is JISK7105.
Measured using an integrating sphere HTR meter. or,
The haze value of the molded product was measured in the same manner by cutting out a part of the side surface of the container.
尚、透明性は下記の評価基準にて表した。Note that transparency was expressed using the following evaluation criteria.
◎；極めて良好 ヘイズ値が５％未満
〇；良好 ヘイズ値が５〜１５％
Δ；やや良好 ヘイズ値が１５〜２５％×；不良 ヘイ
ズ値が２５％を越える
（６）成形収縮率
次式により成形収縮率（Ｘ１）を算出した。◎: Very good Haze value is less than 5% 〇: Good Haze value is 5-15% Δ: Fairly good Haze value is 15-25% The molding shrinkage rate (X1) was calculated.
Ｘ１＝〔（ＶＭ−Ｖｃ）／ＶＭ〕×１００（％）（但し
、Ｖｃ；カップ状成形体の内容量ＶＭ；キャビティー金
型の内容量）
尚、成形性は下記の評価基準にて表した。X1=[(VM-Vc)/VM]×100(%) (However, Vc: Inner volume of cup-shaped molded body VM; Inner volume of cavity mold) The moldability is expressed using the following evaluation criteria. did.
◎；極めて良好 ０≦Ｘ１＜２．５（％）〇；良好 ２
．５≦Ｘ１＜５．０（％）Δ；やや良好 ５．０≦Ｘ１
＜７．５（％）×；不良 ７．５≦Ｘ１（％）
（７）耐熱収縮率
次式により耐熱収縮率（Ｘ２）を算出した。◎; Extremely good 0≦X1<2.5(%)〇; Good 2
．． 5≦X1<5.0(%)Δ; Fairly good 5.0≦X1
<7.5 (%) ×; Defective 7.5≦X1 (%) (7) Heat shrinkage resistance The heat shrinkage resistance (X2) was calculated using the following formula.
（但し、Ｖｃ；カツプ状成形体の内容量ＶＨ；１５０℃
の温度の送風乾燥機中に１０分間投入した後のカップ状
成
形体の内容量）
尚、耐熱収縮性は下記の評価基準にて表した。(However, Vc; internal capacity of cup-shaped molded body VH; 150°C
The content of the cup-shaped molded product after being placed in a blow dryer for 10 minutes at a temperature of
◎；極めて良好 ０≦Ｘ２＜２．５（％）〇；良好 ２
．５≦Ｘ２＜５．０（％）△；やや良好 ５．０≦Ｘ２
＜７．５（％）×；不良 ７．５≦Ｘ２（％）
（８）容器加熱後のヘイズ値及び相対結晶化度１５０℃
の温度の送風乾燥機中に１０分間投入した後のカップ状
成形体の一部を切り出し、ＪＩＳＫ７１０５に基づきヘ
イズ値を、また上記（４）の条件より相対結晶化度を求
めた。尚、透明性の評価基準は上記（５）に準じて表し
た。◎; Extremely good 0≦X2<2.5(%)〇; Good 2
．． 5≦X2<5.0(%)△; Fairly good 5.0≦X2
<7.5 (%) ×; Defective 7.5≦X2 (%) (8) Haze value and relative crystallinity after heating the container 150°C
A part of the cup-shaped molded body was cut out after being placed in a blow dryer at a temperature of 10 minutes, and the haze value was determined based on JIS K7105, and the relative crystallinity was determined based on the conditions in (4) above. The evaluation criteria for transparency were expressed in accordance with (5) above.
製造例１（ポリエステルＡの合成）
テレフタル酸ジメチル３２９．６重量部、１，３−プロ
パンジオール２５８．０重量部を所定量の触媒（チタニ
ウムテトラプトキシド）と共にダブルヘリカル攪拌機及
び留出管を備えた反応器に仕込み、十分に窒素置換した
後、常圧下で１６０℃まで温度を上げ、撹拌を開始した
。さらに、徐々に温度を上昇させ副生するメタノールを
留去した。温度が２５０℃に達したところで、徐々に反
応器中を減圧させ、０．１ｔｏｒｒの圧力で３．０時間
撹拌を続け、固有粘度０．７８のポリプロピレンテレフ
タレート樹脂（ＰＰＴ）を得た。得られた該ポリエステ
ルについて、上記したような特性の測定を行った。結果
を表−１に示す。Production Example 1 (Synthesis of Polyester A) 329.6 parts by weight of dimethyl terephthalate and 258.0 parts by weight of 1,3-propanediol were prepared together with a predetermined amount of catalyst (titanium tetraptoxide) equipped with a double helical stirrer and a distillation tube. After the reactor was fully purged with nitrogen, the temperature was raised to 160° C. under normal pressure, and stirring was started. Furthermore, the temperature was gradually raised to distill off methanol as a by-product. When the temperature reached 250° C., the pressure in the reactor was gradually reduced and stirring was continued for 3.0 hours at a pressure of 0.1 torr to obtain polypropylene terephthalate resin (PPT) with an intrinsic viscosity of 0.78. The properties of the obtained polyester were measured as described above. The results are shown in Table-1.
製造例２（ポリエステルＢの合成）
ポリエステルＡをペレット化し、窒素気流下、１９５℃
で固相重合を行い、固有粘度１．３５の高重合度ポリエ
ステルを得た。得られた該ポリエステルについて、上記
したような特性の測定を行った。結果を表−１に示す。Production Example 2 (Synthesis of Polyester B) Polyester A was pelletized and heated at 195°C under a nitrogen stream.
Solid phase polymerization was carried out to obtain a high degree of polymerization polyester having an intrinsic viscosity of 1.35. The properties of the obtained polyester were measured as described above. The results are shown in Table-1.
製造例３〜７（ポリエステルＣ〜Ｇの合成）表−１に示
す添加量の種々のモノマーを、テレフタル酸ジメチル、
１，３−プロパンジオールと共に仕込み、製造例１で用
いたのと同様の製造装置によりポリプロピレンテレフタ
レート共重合体を得た。続いて製造例２と同様に該ポリ
エステル樹脂の固相重合を行い、特性の測定を行った。Production Examples 3 to 7 (Synthesis of Polyesters C to G) Various monomers in the amounts shown in Table 1 were added to dimethyl terephthalate,
A polypropylene terephthalate copolymer was obtained by charging the same with 1,3-propanediol and using the same production apparatus as that used in Production Example 1. Subsequently, the polyester resin was subjected to solid phase polymerization in the same manner as in Production Example 2, and its properties were measured.
結果を表−１に示す。The results are shown in Table-1.
比較製造例１、２（ポリエステルＨ、Ｉの合成）表−１
に示す添加量の種々のモノマーを、テレフタル酸ジメチ
ル、１，３−プロパンジオールと共に仕込み、製造例１
と用いたのと同様の製造装置によりポリプロピレンテレ
フタレート共重合体を得た。続いて製造例２と同様に該
ポリエステル樹脂の固相重合を行い、特性の測定を行っ
た。結果を表−１に示す。Comparative production examples 1 and 2 (synthesis of polyesters H and I) Table 1
Production Example 1
A polypropylene terephthalate copolymer was obtained using the same production equipment as used in the above. Subsequently, the polyester resin was subjected to solid phase polymerization in the same manner as in Production Example 2, and its properties were measured. The results are shown in Table-1.
比較製造例３（ポリエステルＪの合成）１，４−ブタン
ジオール及びテレフタル酸ジメチルを所定量用いて製造
例１と同様の装置によりポリブチレンテレフタレート樹
脂（ＰＢＴ）を製造した。該樹脂は製造例２と同様の固
相重合により固有粘度が１．３６となった。特性の測定
を行った結果を表−１に示す。Comparative Production Example 3 (Synthesis of Polyester J) A polybutylene terephthalate resin (PBT) was produced using the same equipment as in Production Example 1 using predetermined amounts of 1,4-butanediol and dimethyl terephthalate. The resin had an intrinsic viscosity of 1.36 by solid phase polymerization in the same manner as in Production Example 2. Table 1 shows the results of measuring the characteristics.
実施例１〜２、比較例１〜２
原料ポリエステルＢ、Ｃ、Ｈ、Ｉを９０℃で６時間、送
風乾燥機中で乾燥後、８００ｍｍ幅のＴ−ダイより水冷
方式の２５℃の冷却ロール上に押し出した。得られたシ
ートは厚み０．４ｍｍであり、シートの一部を切り出し
、ヘイズ値を求めた。続いて真空成形機を用い、プラグ
金型温度８０℃、キャビティー金型温度１００℃（但し
比較例１は１３０℃）、成形時間１０秒で真空成形を行
い、深さ４５ｍｍ、直径９０ｍｍのカップを成形した。Examples 1-2, Comparative Examples 1-2 Raw material polyesters B, C, H, and I were dried at 90°C for 6 hours in a blow dryer, and then cooled at 25°C using a water-cooled T-die with an 800 mm width. pushed it upwards. The obtained sheet had a thickness of 0.4 mm, and a part of the sheet was cut out to determine the haze value. Next, using a vacuum forming machine, vacuum forming was performed at a plug mold temperature of 80°C, a cavity mold temperature of 100°C (130°C in Comparative Example 1), and a molding time of 10 seconds to form a cup with a depth of 45 mm and a diameter of 90 mm. was molded.
各容器について、容器側面部の一部を切り出しヘイズ値
を求め、又、上記方法により成形体の評価を行った。結
果を表−２に示す。For each container, a part of the side surface of the container was cut out to determine the haze value, and the molded product was evaluated using the above method. The results are shown in Table-2.
比較例３
ポリエステルＪから実施例１と同様の方法によりシート
（厚み０．４ｍｍ）を得たが、シートは著しく白化して
おり、成形材として不適であった。Comparative Example 3 A sheet (thickness 0.4 mm) was obtained from Polyester J in the same manner as in Example 1, but the sheet was significantly whitened and was unsuitable as a molding material.
実施例３
原料ポリエステルＡを９０℃で５時間、送風乾燥機中で
乾燥後、シリンダー温度２５５℃、成形温度（金型温度
）５５℃及びサイクル時間４０秒の条件で射出成形によ
って、深さ４０ｍｍ、直径８５ｍｍ肉厚０．５ｍｍのカ
ップを成形した。成形容器から側面部の一部を切り出し
ヘイズ値を求めたところ、２４．０（％）であり、１５
０℃における耐熱収縮率は６．０（％）であった。Example 3 After drying raw material polyester A at 90°C for 5 hours in a blow dryer, it was injection molded to a depth of 40mm under the conditions of a cylinder temperature of 255°C, a molding temperature (mold temperature) of 55°C, and a cycle time of 40 seconds. A cup with a diameter of 85 mm and a wall thickness of 0.5 mm was molded. When a part of the side surface was cut out from the molded container and the haze value was determined, it was 24.0 (%) and 15
The heat shrinkage rate at 0°C was 6.0 (%).
実施例４〜９
実施例１と同様に原料ポリエステルＢ〜Ｇから厚み０．
４ｍｍのシートを得た後に、シートを表−３に種々の温
度と時間で恒温槽中で熱処理し、続いて実施例１と同様
に真空成形し容器を得た。Examples 4 to 9 As in Example 1, raw material polyesters B to G were made to a thickness of 0.
After obtaining a 4 mm sheet, the sheet was heat treated in a constant temperature bath at various temperatures and times as shown in Table 3, and then vacuum formed in the same manner as in Example 1 to obtain a container.
各容器について、容器側面部の一部を切り出しヘイズ値
を求め、又、上記方法により成形体の評価を行った。結
果を表−３に示す。For each container, a part of the side surface of the container was cut out to determine the haze value, and the molded product was evaluated using the above method. The results are shown in Table-3.
Claims (3)
プロパンジオールとテレフタル酸若しくはそのエステル
形成性誘導体とのエステル単位からなるポリエステル樹
脂を成形してなる耐熱容器。Claim 1: 80 mol% or more of the repeating units are 1,3-
A heat-resistant container formed by molding a polyester resin comprising ester units of propanediol and terephthalic acid or its ester-forming derivative.
載の耐熱容器。2. The heat-resistant container according to claim 1, wherein the shaping is performed by thermoforming.
加熱雰囲気下で耐熱変形性を有し且つヘイズ値が２５％
以下である請求項１又は２記載の耐熱容器。Claim 3: The relative crystallinity is 50% or more, has heat deformation resistance in a heating atmosphere of 150°C, and has a haze value of 25%.
The heat-resistant container according to claim 1 or 2, which is as follows.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28026090A JP3012307B2 (en) | 1990-10-17 | 1990-10-17 | Heat-resistant container |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28026090A JP3012307B2 (en) | 1990-10-17 | 1990-10-17 | Heat-resistant container |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04212829A true JPH04212829A (en) | 1992-08-04 |
| JP3012307B2 JP3012307B2 (en) | 2000-02-21 |
Family
ID=17622517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28026090A Expired - Fee Related JP3012307B2 (en) | 1990-10-17 | 1990-10-17 | Heat-resistant container |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3012307B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT411687B (en) * | 1998-12-07 | 2004-04-26 | Tigerwerk Lack U Farbenfabrik | Carboxy-functional polyester resin used in powder lacquer formulation is based on dicarboxylic acids and diols including pentan-1,5-diol, diethylene glycol and/or derivatives with alkyl side chains |
-
1990
- 1990-10-17 JP JP28026090A patent/JP3012307B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT411687B (en) * | 1998-12-07 | 2004-04-26 | Tigerwerk Lack U Farbenfabrik | Carboxy-functional polyester resin used in powder lacquer formulation is based on dicarboxylic acids and diols including pentan-1,5-diol, diethylene glycol and/or derivatives with alkyl side chains |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3012307B2 (en) | 2000-02-21 |
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