JPH04112029A - Transparent thin-walled container - Google Patents
Transparent thin-walled containerInfo
- Publication number
- JPH04112029A JPH04112029A JP22972090A JP22972090A JPH04112029A JP H04112029 A JPH04112029 A JP H04112029A JP 22972090 A JP22972090 A JP 22972090A JP 22972090 A JP22972090 A JP 22972090A JP H04112029 A JPH04112029 A JP H04112029A
- Authority
- JP
- Japan
- Prior art keywords
- container
- polybutylene terephthalate
- heat resistance
- crystallization
- 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
- 238000002425 crystallisation Methods 0.000 claims abstract description 23
- 230000008025 crystallization Effects 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 11
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- -1 polybutylene terephthalate Polymers 0.000 abstract description 35
- 229920005989 resin Polymers 0.000 abstract description 32
- 239000011347 resin Substances 0.000 abstract description 32
- 229920001707 polybutylene terephthalate Polymers 0.000 abstract description 31
- 238000001746 injection moulding Methods 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 13
- 229920001577 copolymer Polymers 0.000 abstract description 9
- 235000013305 food Nutrition 0.000 abstract description 6
- 239000000155 melt Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000003205 fragrance Substances 0.000 abstract 1
- 229920006026 co-polymeric resin Polymers 0.000 description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229920005990 polystyrene resin Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 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
- 230000017525 heat dissipation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 2
- 229920000306 polymethylpentene Polymers 0.000 description 2
- 239000011116 polymethylpentene Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- POIUXCGIAGOITD-UHFFFAOYSA-N 2-[4-[2-[4-(2-hydroxyethyl)phenyl]propan-2-yl]phenyl]ethanol Chemical compound C=1C=C(CCO)C=CC=1C(C)(C)C1=CC=C(CCO)C=C1 POIUXCGIAGOITD-UHFFFAOYSA-N 0.000 description 1
- ZUHPIMDQNAGSOV-UHFFFAOYSA-N 2-benzyl-2-phenylpropanedioic acid Chemical compound C=1C=CC=CC=1C(C(=O)O)(C(O)=O)CC1=CC=CC=C1 ZUHPIMDQNAGSOV-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920006127 amorphous resin Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 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
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Injection Moulding Of Plastics Or The Like (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ポリブチレンテレフタレート共重合樹脂製の
透明薄肉容器に関する。更に詳しくは、特定の融点、結
晶化開始温度、結晶化熱量を有するポリブチレンテレフ
タレート共重合樹脂を射出成形してなる透明薄肉容器に
関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a transparent thin-walled container made of polybutylene terephthalate copolymer resin. More specifically, the present invention relates to a transparent thin-walled container made by injection molding a polybutylene terephthalate copolymer resin having a specific melting point, crystallization initiation temperature, and crystallization heat amount.
従来、プラスチック製の透明容器にお、）で、その用途
に応じ使用される樹脂はポリプロピレン樹脂、ポリエチ
レン樹脂に代表されるポリオレフィン樹脂をはじめポリ
スチレン樹脂、ポリ塩化ビニル樹脂、ポリカーボネート
樹脂及びポリエチレンテレフタレートｐ脂など多岐にわ
たっている。又、これらの成形方法としても射出成形を
はじめ真空成形、ブロー成形、圧縮成形と種々の方法が
あり、それぞれ長所、短所があり、容器の用途、目的に
応じて使い分けされているのが現状である。Traditionally, transparent containers made of plastic have been made of resins such as polyolefin resins such as polypropylene resins and polyethylene resins, as well as polystyrene resins, polyvinyl chloride resins, polycarbonate resins, and polyethylene terephthalate resins. There is a wide range of such things. In addition, there are various molding methods such as injection molding, vacuum molding, blow molding, and compression molding, each of which has advantages and disadvantages, and currently they are used depending on the purpose and purpose of the container. be.
射出成形法は他の成形法に比べ、容器形状の自由度が大
きく、例えば容器に把手を付けたり−、糸じりを付けた
りするのが簡単である事から、広く利用されている成形
法である。射出成形してなる透明容器としては、ポリス
チレン樹脂、ポリプロピレン樹脂、ポリメチルペンテン
樹脂、ポリカーボネート樹脂、ポリアクリロニトリル樹
脂などがあるが、これらは、耐熱性、耐薬品性、寸法安
定性が必ずしも優れているものではない。又、ポリプロ
ピレン樹脂、ポリメチルペンテン樹脂、ポリスチレン樹
脂はオレフィン臭と呼ばれる悪臭又はワックス臭が強く
特に食品用の容器として満足し得るものではない。又、
ポリカーボネート樹脂やポリアクリロニトリル樹脂等の
非晶性樹脂は、耐薬品性が悪く工業用途には不向きであ
り、成形時の固化速度が遅く、成形コストが高いという
欠点もある。即ち、射出成形してなる透明容器用の前述
の樹脂では用途が限定される問題がある。Compared to other molding methods, injection molding has a greater degree of freedom in the shape of the container.For example, it is easy to attach handles and strings to the container, making it a widely used molding method. It is. Transparent containers made by injection molding include polystyrene resin, polypropylene resin, polymethylpentene resin, polycarbonate resin, and polyacrylonitrile resin, but these do not necessarily have superior heat resistance, chemical resistance, and dimensional stability. It's not a thing. Further, polypropylene resin, polymethylpentene resin, and polystyrene resin have a strong odor called olefin odor or a strong wax odor, and are not particularly satisfactory as food containers. or,
Amorphous resins such as polycarbonate resins and polyacrylonitrile resins have poor chemical resistance and are unsuitable for industrial use, and also have the drawbacks of slow solidification speed during molding and high molding costs. That is, the above-mentioned resin for use in transparent containers formed by injection molding has a problem in that its uses are limited.
他方、耐熱性、耐薬品性、寸法安定性及び易成形性に優
れた樹脂としては、ポリブチレンテレフタレートｌ脂が
ある。ポリブチレンテレフタレート樹脂はこのような優
れた特性を生かし、電気部品、自動車部品等の工業用分
野に多く使用されている。ポリブチレンテレフタレート
樹脂製の容器は工業分野や食品用途にも使用されており
、その優れた耐熱性、耐薬品性、寸法安定性は周知の通
りである。しかしながら、ポリブチレンテレフタレート
樹脂は結晶化速度が早く、射出成形法等によっては透明
の成形品が得られないという欠点があった。それ故、耐
熱性、耐薬品性、寸法安定性に優れ、食品の味、香りに
悪影響を及ぼさない透明容器の開発が切望されていた。On the other hand, as a resin excellent in heat resistance, chemical resistance, dimensional stability, and easy moldability, there is polybutylene terephthalate resin. Polybutylene terephthalate resin takes advantage of these excellent properties and is widely used in industrial fields such as electrical parts and automobile parts. Containers made of polybutylene terephthalate resin are used in industrial fields and food applications, and their excellent heat resistance, chemical resistance, and dimensional stability are well known. However, polybutylene terephthalate resin has a fast crystallization rate and has the disadvantage that transparent molded products cannot be obtained by injection molding or the like. Therefore, there has been a strong desire to develop transparent containers that have excellent heat resistance, chemical resistance, and dimensional stability, and do not adversely affect the taste and aroma of foods.
本発明者は、斯かる現状に鑑み、ポリブチレンテレフタ
レート樹脂の優れた特性を生かしたまま、−船釣な射出
成形により透明性を有する薄肉容器を得るべく、鋭意研
究を重ねた結果、特定の融点、結晶化開始温度、結晶化
熱量を持つポリブチレンテレフタレート共重合樹脂を用
いることにより斯かる目的を達成し得ることを見い出し
、本発明に至ったものである。In view of the current situation, the present inventor has conducted intensive research in order to obtain a transparent thin-walled container by simple injection molding while taking advantage of the excellent properties of polybutylene terephthalate resin. The inventors have discovered that this object can be achieved by using a polybutylene terephthalate copolymer resin that has a melting point, a crystallization initiation temperature, and a crystallization heat amount, leading to the present invention.
即ち本発明は、ＡＳＴＭ Ｄ−１２３８により２３５℃
、荷重２１６０ｇの条件で測定したメルトインデックス
が３０〜１５０であり、且つ示差熱量計により測定した
融点、結晶化開始温度、結晶化熱量が（Ｉ）式及び（ｎ
）式の関係で表わされるポリブチレンテレフタレート共
重合樹脂を射出成形してなる透明薄肉容器に関する。That is, the present invention can be applied at 235°C according to ASTM D-1238.
, the melt index measured under the condition of a load of 2160 g is 30 to 150, and the melting point, crystallization start temperature, and crystallization heat amount measured by a differential calorimeter satisfy the formula (I) and (n
This invention relates to a transparent thin-walled container formed by injection molding a polybutylene terephthalate copolymer resin expressed by the following formula.
３０≦Ｔｍ−Ｔｃ≦５０ −（Ｉ）式６．０≦ΔＨ≦
１０．０ ・・・（ＩＩ）式Ｔｍ： １０℃／ｍｉ
ｎで昇温して測定した融点（１）
Ｔｃ： １０℃／ｍｉｎで降温して測定した結晶化開始
温度（１）
ΔＨ：１０℃１０＋ｉｎで降温して測定した結晶化熱量
（ｃａｌ／ｇ）
本発明において使用するポリブチレンテレフタレート樹
脂は、優れた透明性と耐熱性を合わせ持つ事が肝要であ
る。即ち、透明で且つ高度に結晶化させる事が必要であ
る。ホモポリマーでは結晶化速度が早く射出成形では透
明な成形品を得る事はできないため、後記の如く反応性
化合物を１種又は２種以上共重合させ、上記（Ｉ）式及
び（ｎ）式を満足するポリブチレンテレフタレート樹脂
を主体とするコポリマーを射出成形する事により透明で
且つ耐熱性に優れた薄肉容器を得る事が可能となる。30≦Tm-Tc≦50 - Formula (I) 6.0≦ΔH≦
10.0...(II) Formula Tm: 10°C/mi
Melting point (1) measured by increasing the temperature at 10°C/min Tc: Crystallization initiation temperature (1) measured by decreasing the temperature at 10°C/min ΔH: Heat of crystallization (cal/g) measured by decreasing the temperature at 10°C/min It is important that the polybutylene terephthalate resin used in the present invention has both excellent transparency and heat resistance. That is, it needs to be transparent and highly crystallized. Homopolymers have a fast crystallization rate and it is not possible to obtain transparent molded products by injection molding. Therefore, as described below, one or more reactive compounds are copolymerized to form the above formulas (I) and (n). By injection molding a copolymer mainly composed of a satisfactory polybutylene terephthalate resin, it is possible to obtain a thin-walled container that is transparent and has excellent heat resistance.
本発明で使用するポリブチレンテレフタレート共重合樹
脂はＡＳＴＭ Ｄ−１２３８により２３５℃、荷重２１
６０ｇの条件で測定したメルトインデックスが３０〜１
５０のものである。メルトインデックスが３０未満のも
のでは流動性が悪く本発明で必要な薄肉の成形品が得ら
れない。又、メルトインデックスが１５０を越える流動
性の良いものは強度的に不十分なものとなる。特に好ま
しくはメルトインデックスが４０〜１２０のものである
。The polybutylene terephthalate copolymer resin used in the present invention was tested at 235°C under a load of 21% according to ASTM D-1238.
Melt index measured under 60g condition is 30-1
50. If the melt index is less than 30, the fluidity is poor and the thin-walled molded product required in the present invention cannot be obtained. In addition, a material with a melt index exceeding 150 and having good fluidity has insufficient strength. Particularly preferred are those having a melt index of 40 to 120.
（Ｉ）式及び（ｆｆ）式はポリブチレンテレフタレート
共重合樹脂の熱的な性質の内、結晶性の指標となるもの
である。具体的に説明すると、（Ｉ）式は結晶化速度を
、（ｎ）式は結晶化度を規定するものであり、ポリブチ
レンテレフタレート共重合樹脂が（Ｉ）弐及び（ＩＩ）
式を満足することにより透明性、耐熱性、耐薬品性、成
形性に優れた容器を得ることができる。The formulas (I) and (ff) are indicators of crystallinity among the thermal properties of the polybutylene terephthalate copolymer resin. Specifically, the formula (I) defines the crystallization rate, and the formula (n) defines the degree of crystallinity, and the polybutylene terephthalate copolymer resin is
By satisfying the formula, a container with excellent transparency, heat resistance, chemical resistance, and moldability can be obtained.
（Ｉ）式のＴｍ−Ｔｃが３０より小さいと容器の透明性
が悪くなり、５０より大きいと成形性が悪く且つ耐熱性
が低下するので好ましくない。If Tm-Tc of formula (I) is less than 30, the transparency of the container will be poor, and if it is greater than 50, moldability will be poor and heat resistance will be reduced, which is not preferred.
方、（ｎ）式のΔＨが６．０より小さいと耐熱性、耐薬
品性が低下し、１０．０より大きいと透明性が低下する
ため好ましくない。On the other hand, if ΔH in formula (n) is less than 6.0, heat resistance and chemical resistance will decrease, and if it is greater than 10.0, transparency will decrease, which is not preferable.
即ち、優れた透明性、成形性、耐熱性、耐薬品性を持つ
容器を得るためには（Ｉ）式、（ＩＩ）式の両式を満足
するポリブチレンチフタレート共重合樹脂を使用する事
が不可欠となる。That is, in order to obtain a container with excellent transparency, moldability, heat resistance, and chemical resistance, it is necessary to use a polybutylene thiphthalate copolymer resin that satisfies both formulas (I) and (II). becomes essential.
ここで示差熱量計により測定したポリブチレンテレフタ
レート樹脂（ホモポリマー）の融点（Ｔｍ） 、結晶化
開始温度（Ｔｃ）、結晶化熱量（ΔＨ）はポリブチレン
テレフタレート樹脂の重合度（又は分子量）によって異
なることが知られており、重合度の高い（分子量の大き
い）樹脂はどＴｍ 、ＴＣは低くなり、△Ｈは小さくな
る。又、Ｔｍ −ＴｃＯ値はポリブチレンテレフタレー
ト樹脂（ホモポリマー）の重合度が高くなるほど大きく
なるが、Ｔｍ−Ｔｃの値は３０℃以上にはならない。通
常、射出成形に使用されるＭｌが４５のポリブチレンテ
レフタレート樹脂（ホモポリマー）ではＴヨーＴｃが２
１℃、ΔＨが１１．０ｃａｌ／ｇであり、又、Ｍｌが３
のものではＴ。Here, the melting point (Tm), crystallization initiation temperature (Tc), and crystallization heat (ΔH) of the polybutylene terephthalate resin (homopolymer) measured by a differential calorimeter vary depending on the degree of polymerization (or molecular weight) of the polybutylene terephthalate resin. It is known that a resin with a high degree of polymerization (a large molecular weight) has a low Tm, a low TC, and a small ΔH. Further, the Tm-TcO value increases as the degree of polymerization of the polybutylene terephthalate resin (homopolymer) increases, but the Tm-Tc value does not exceed 30°C. Normally, in polybutylene terephthalate resin (homopolymer) with Ml of 45 used for injection molding, T yaw Tc is 2.
1°C, ΔH is 11.0 cal/g, and Ml is 3
T for those.
−Ｔｃが２３℃、ΔＨが１０．２ｃａｌ／ｇである。即
ち、ポリブチレンテレフタレート樹脂のホモポリマーで
は如何に重合度を高くしても射出成形により透明な容器
を得ることが出来ない。-Tc is 23°C and ΔH is 10.2 cal/g. That is, a homopolymer of polybutylene terephthalate resin cannot be used to obtain a transparent container by injection molding, no matter how high the polymerization degree is.
本発明におけるポリブチレンテレフタレート樹脂とは、
上述した特定の融点、結晶化開始温度、結晶化熱量を持
たせるため、ポリブチレンテレフタレートを主体とする
コポリマーである事が必要である。即ち、酸成分として
テレフタル酸又はその低級アルコールエステルとアルコ
ール成分として１，４−ブタンジオールを重縮合して得
られるポリエステルを主体とし、酸成分及び／又はアル
コール成分として他の反応性化合物を共重合させたもの
を言う。他の反応性化合物として、酸成分の例を挙げれ
ばイソフタル酸、フタル酸、アジピン酸、セバシン酸、
コハク酸、シュウ酸等及びこれらの低級アルコールエス
テルや、ナフタレンジカルボン酸、ジフェニルカルボン
酸、ジフェニルエーテルジカルボン酸、ジフェニルエタ
ンジカルボン酸、シクロヘキサンジカルボン酸等のジカ
ルボン酸及びこれらの低級アルコールエステル等が使用
できる。The polybutylene terephthalate resin in the present invention is
In order to have the above-mentioned specific melting point, crystallization initiation temperature, and crystallization heat, it is necessary to use a copolymer mainly composed of polybutylene terephthalate. That is, the polyester obtained by polycondensing terephthalic acid or its lower alcohol ester as the acid component and 1,4-butanediol as the alcohol component is the main component, and other reactive compounds are copolymerized as the acid component and/or alcohol component. Say what you did. Examples of other reactive compounds include isophthalic acid, phthalic acid, adipic acid, sebacic acid,
Succinic acid, oxalic acid, etc. and lower alcohol esters thereof, dicarboxylic acids such as naphthalenedicarboxylic acid, diphenylcarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, cyclohexanedicarboxylic acid, and lower alcohol esters thereof, etc. can be used.
又、多官能性化合物としてトリメシン酸、トリメリット
酸、ピロメリット酸及びこれらのアルコールエステル等
が使用できる。一方、アルコール成分の例としては、エ
チレングリコール、ジエチレングリコール、プロピレン
グリコール、トリメチレングリコール、ヘキサメチレン
グリコール、ネオペンチルグリコール、シクロヘキサン
ジオール、２，２−ビス（４−ヒドロキシエチルフェニ
ル）プロパン、ビスフェノールＳのエチレンオキサイド
付加物（ＥＢＰＳ） 、ビスフェノールＡのエチレンオ
キサイド付加物（ＥＢＰＡ）等の二官能性化合物や、グ
リセリン、トリメチロールエタン、トリメチロールプロ
パン、ペンタエリスリトール等の多官能性化合物が使用
できる。本発明においてはこれら上記の反応性化合物の
１種又は２種以上が使用される。Further, as polyfunctional compounds, trimesic acid, trimellitic acid, pyromellitic acid, alcohol esters thereof, etc. can be used. On the other hand, examples of alcohol components include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexanediol, 2,2-bis(4-hydroxyethylphenyl)propane, and ethylene of bisphenol S. Difunctional compounds such as oxide adduct (EBPS) and ethylene oxide adduct of bisphenol A (EBPA), and polyfunctional compounds such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol can be used. In the present invention, one or more of the above-mentioned reactive compounds are used.
また、ポリブチレンテレフタレート共重合樹脂には本発
明の効果を阻害しない範囲で目的に応じ少量の他の熱可
塑性樹脂や、一般の熱可塑性樹脂に添加される公知の物
質、例えば、酸化防止剤や紫外線吸収剤等の安定剤、可
塑性・帯電防止剤、界面活性剤、顔料、染料、場合によ
っては無機充填剤を目的に応じて補助的に添加したもの
であってもよいが、これらの添加物の配合にあたっては
本発明の目的、効果を阻害しないよう添加剤の種類、配
合量等を考慮する必要がある。In addition, the polybutylene terephthalate copolymer resin may contain small amounts of other thermoplastic resins depending on the purpose as long as they do not impede the effects of the present invention, as well as known substances added to general thermoplastic resins, such as antioxidants, etc. Stabilizers such as ultraviolet absorbers, plasticizers and antistatic agents, surfactants, pigments, dyes, and in some cases inorganic fillers may be added as supplements depending on the purpose, but these additives When blending, it is necessary to consider the type and amount of additives so as not to impede the purpose and effect of the present invention.
次に本発明の容器は、目的とする容器の大きさとも関連
するが厚みとして内表面積の７０％以上に対応する部分
が１ｍｍＪＪ下であることが特徴である。材質として、
メルトインデックスが３０〜１５０で、融点、結晶化開
始温度、結晶化熱量が下記の（Ｉ）式且つ（Ｉ［）式を
満足するポリブチレンテレフタレート共重合樹脂を使用
することによって、かかる薄肉寸法に於いても実用温度
で充分な自立性、形態保持が可能である。Next, the container of the present invention is characterized in that a portion corresponding to 70% or more of the inner surface area has a thickness of 1 mmJJ or less, which is related to the size of the intended container. As a material,
By using a polybutylene terephthalate copolymer resin with a melt index of 30 to 150 and a melting point, crystallization start temperature, and crystallization heat satisfying the following formulas (I) and (I[), it is possible to achieve such thin wall dimensions. Even at practical temperatures, it is possible to maintain sufficient independence and shape.
容器の内表面積の７０に以上の部分で厚みが１ｍｍを越
えると容器の透明度が低下する。又、電子レンジで調理
する場合には電磁波の吸収により内部発熱した熱の蓄積
が多くなるため、かえって変形する場合が出てくるため
好ましくない。If the thickness exceeds 1 mm over 70 mm of the inner surface area of the container, the transparency of the container will decrease. Further, when cooking in a microwave oven, the heat generated internally due to absorption of electromagnetic waves increases, which may cause deformation, which is not preferable.
特に底部は、載置皿等に接触するため放熱が悪くなり、
蓄熱が多くなる傾向があるので側面部より薄くするか或
いは、脚や糸じりを設けて、放熱面積を多くするのが好
ましい。又、目的とする容器が比較的大きい場合には本
願の上記の厚みの規定の範囲に於いて、適宜リブや肉厚
部を設けて補強し、変形、形崩れ防止、その他落下時の
破損強度等を考慮した構造に設計する事も可能であり、
望ましい。In particular, the bottom part comes into contact with the mounting plate, etc., so heat dissipation is poor.
Since heat storage tends to increase, it is preferable to make it thinner than the side portions or to provide legs or threads to increase the heat dissipation area. In addition, if the target container is relatively large, within the range of the thickness stipulated above in this application, ribs or thick parts may be provided as appropriate to strengthen the container to prevent deformation, loss of shape, and other damage resistance in the event of a fall. It is also possible to design a structure that takes into account
desirable.
又、本願でいう優れた透明性をヘイズ値で示せば２０％
以下であり、本発明によれば斯がる透明容器の提供が可
能である。In addition, if the excellent transparency referred to in this application is expressed as a haze value, it is 20%.
According to the present invention, it is possible to provide such a transparent container.
以下実施例により本発明を更に詳しく説明するが、本発
明はこれらに限定されるものではない。The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.
実施例１〜７、比較例１〜４
第１表に示すとおり、各種のポリブチレンテレフタレー
ト樹脂を射出成形して第１図に示す形状の容器を作製し
た（各部の厚さが０．５〜０．８０、上部の直径が７０
ｍｍ、底部の直径が５０ｍｍ、深さが５０ｍｍ）。これ
らの容器について、透明性、耐熱性、耐電子レンジ性、
成形性について試験した。これらの結果を、第１表に示
す。Examples 1 to 7, Comparative Examples 1 to 4 As shown in Table 1, various polybutylene terephthalate resins were injection molded to produce containers having the shape shown in FIG. 0.80, top diameter is 70
mm, bottom diameter 50 mm, depth 50 mm). These containers have transparency, heat resistance, microwave resistance,
The moldability was tested. These results are shown in Table 1.
尚、各種試験方法と評価基準は次の通りである。The various test methods and evaluation criteria are as follows.
透明性 ：ＡＳＴＭ Ｄ−１００３によりヘイズ値を測
定し、下記の評価基準にて表わし
た。Transparency: Haze value was measured according to ASTM D-1003 and expressed using the following evaluation criteria.
○ 良好 ヘイズ値が２０％以下のもの△ やや不
良 〃２ｏ％を越え４０％未満のもの
Ｘ 不良 ” ４０％以上のもの耐熱性Ａ
： １６０℃に設定した空気雰囲気下の熱風乾燥機で
１時間加熱し、容
器の各寸法、上部直径、底部直径、
深さを測定し、保持率を下記の式
で算出し、下記の評価基準にて表
わした。○ Good Haze value is 20% or less △ Slightly poor 〃More than 20% but less than 40%
: Heated in a hot air dryer in an air atmosphere set at 160℃ for 1 hour, measured each dimension of the container, top diameter, bottom diameter, and depth, calculated the retention rate using the following formula, and evaluated according to the following evaluation criteria. It was expressed in
○ 良好 各部の保持率が９９％以上１０１％未満
のもの
△ やや不良 各部の保持率が９８％以上９９％未満又
は１０１％以上１０２％未
満のもの
ｘ 不良 各部の保持率が９８％未満又は１０２％
以上のもの
耐熱性Ｂ：耐熱性Ａの試験と同様、１６０℃に設定した
空気雰囲気下の熱風乾燥
機で１時間加熱し、容器の透明性
としてＡＳＴＭ Ｄ−１００３，によりヘイズ値を測定
し下記の評価基準で表わ
した。○ Good The retention rate of each part is 99% or more and less than 101% △ Slightly poor The retention rate of each part is 98% or more and less than 99% or 101% or more and less than 102% x Poor The retention rate of each part is less than 98% or 102 %
Heat resistance B: Same as the heat resistance A test, the container was heated for 1 hour in a hot air dryer in an air atmosphere set at 160°C, and the haze value was measured according to ASTM D-1003 to measure the transparency of the container. It was expressed using the following evaluation criteria.
Ｏ良好 ヘイズ値の増加が５％以下のもの
△ やや不良 ヘイズ値の増加が５％を越え１０％未満
のもの
Ｘ 不良 ヘイズ値の増加が１０％以上のもの
耐電子レンジ性：容器に局方オリーブ油を５０ｃｃ入れ
、東芝製電子レンジ
発振周波数２４５０ＭＨｚ 、最大
出力５００１１で１０分間加熱した
後、容器の変形、変色につ
いて調べ下記の評価基準で
表わした。O Good Haze value increase is 5% or less △ Slightly poor Haze value increase is more than 5% and less than 10% After adding 50 cc of olive oil and heating the container in a Toshiba microwave oven at an oscillation frequency of 2450 MHz and a maximum output of 50011 for 10 minutes, the container was examined for deformation and discoloration and was evaluated using the following evaluation criteria.
○ 良好 変形、変色ともなし
△ やや不良 若干の変形又は変色有り× 不良
大きな変形又は溶融又は変色有り
比較例５〜７
ポリプロピレン樹脂、アクリロニトリル樹脂及びポリス
チレン樹脂を使用して、実施例１〜７と同様の試験を行
った。評価結果を第１表に示す。○ Good No deformation or discoloration △ Slightly poor Slight deformation or discoloration × Poor
Large deformation, melting, or discoloration Comparative Examples 5 to 7 Tests similar to Examples 1 to 7 were conducted using polypropylene resin, acrylonitrile resin, and polystyrene resin. The evaluation results are shown in Table 1.
（第１表の注）
ＰＢＴコポリマーＡ−Ｄ；酸成分の内、コモノマーとし
てイソフタル酸
成分を１２．５モル％含む
コポリマー（夫々Ｍｌは
異なる）
ＰＢＴコポリマーＥ−Ｆ；酸成分の内、コモノマーとし
てイソフタル酸
成分を２０モル％含むコ
ポリマー（夫々ＭＩは異
なる）
ＰＢＴコポリマーＧ ；ジオール成分の内、コモノマ
ーとしてビス７
エノールＡのエチレン
オキサイド付加物を１５
モル％含むコポリマー
ＰＢＴコポリマーＨ〜■；酸成分の内、コモノマーとし
てイソフタル酸
成分を３０モル％含むコ
ポリマー（夫々Ｍ１は異
なる）
ＰＰ；ポリプロピレン樹脂
ＡＮ；アクリロニトリル樹月旨
ＰＳ；ポリスチレン樹脂
〔発明の効果〕
本発明による透明薄肉容器は、優れた耐熱性、耐薬品性
、耐油性、機械的性質、ガスバリヤ−性を有し、更に無
味、無臭であるので内容物の味、香りを損なわないとい
う、食品包装容器にとって重要な特性も有している。更
に、成形性が優れており、容器を薄肉化する事も容易で
あり、食品包装容器をはじめ、一般容器、工業用途向け
の容器等多岐に渡って好適な容器として使用できる。(Notes to Table 1) PBT copolymers A-D: Copolymers containing 12.5 mol% of isophthalic acid component as a comonomer among the acid components (Ml is different for each) PBT copolymers E-F: As a comonomer among the acid components Copolymer containing 20 mol% of isophthalic acid component (MI is different for each) PBT copolymer G; copolymer containing 15 mol% of ethylene oxide adduct of bis7 enol A as comonomer among diol components PBT copolymer H~■; Among them, a copolymer containing 30 mol% of isophthalic acid component as a comonomer (M1 is different for each) PP: polypropylene resin AN: acrylonitrile resin PS: polystyrene resin [Effects of the Invention] The transparent thin-walled container according to the present invention has excellent heat resistance. It has chemical resistance, oil resistance, mechanical properties, gas barrier properties, and is tasteless and odorless, so it does not impair the taste or aroma of the contents, which are important characteristics for food packaging containers. Furthermore, it has excellent moldability and can be easily made into a thin container, so it can be used as a suitable container for a wide variety of purposes, including food packaging containers, general containers, and containers for industrial use.
第１図（ａ）は本発明の容器の一例の平面略示図、第１
図ら）はその断面略示図である。
１・・・開口部
２・・・底部
３・・・側壁部
４・・・糸じり
５・・・容器本体
第１図
（ａ）FIG. 1(a) is a schematic plan view of an example of the container of the present invention;
Figure 3) is a schematic cross-sectional view thereof. 1... Opening 2... Bottom 3... Side wall 4... String 5... Container body Fig. 1 (a)
Claims (1)
０ｇの条件で測定したメルトインデックスが３０〜１５
０であり、且つ示差熱量計により測定した融点、結晶化
開始温度、結晶化熱量が（ I ）式及び（II）式の関係
で表わされるポリブチレンテレフタレート共重合樹脂を
射出成形してなる透明薄肉容器。 ３０≦Ｔ＿ｍ−Ｔ＿ｃ≦５０・・・（ I ）式６．０≦
ΔＨ≦１０．０・・・（II）式 Ｔ＿ｍ：１０℃／ｍｉｎで昇温して測定した融点（℃） Ｔ＿ｃ：１０℃／ｍｉｎで降温して測定した結晶化開始
温度（℃） ΔＨ：１０℃／ｍｉｎで降温して測定した結晶化熱量（
ｃａｌ／ｇ） ２ 射出成形品の内表面積の７０％以上の部分の厚みが
１ｍｍ以下である請求項１記載の透明薄肉容器。[Claims] 1 According to ASTM D-1238, 235°C, load 216
Melt index measured under 0g condition is 30-15
0, and whose melting point, crystallization start temperature, and crystallization heat as measured by a differential calorimeter are expressed by the relationships of formulas (I) and (II). container. 30≦T_m−T_c≦50...(I) Formula 6.0≦
ΔH≦10.0...(II) Formula T_m: Melting point (°C) measured by increasing temperature at 10°C/min T_c: Crystallization start temperature (°C) measured by decreasing temperature at 10°C/min ΔH: Heat of crystallization measured by lowering the temperature at 10°C/min (
cal/g) 2. The transparent thin-walled container according to claim 1, wherein a thickness of 70% or more of the inner surface area of the injection molded product is 1 mm or less.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22972090A JPH0735059B2 (en) | 1990-08-31 | 1990-08-31 | Transparent thin container |
| KR91015202A KR940009911B1 (en) | 1990-08-31 | 1991-08-31 | Transparent vessel for thin meat |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22972090A JPH0735059B2 (en) | 1990-08-31 | 1990-08-31 | Transparent thin container |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04112029A true JPH04112029A (en) | 1992-04-14 |
| JPH0735059B2 JPH0735059B2 (en) | 1995-04-19 |
Family
ID=16896646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22972090A Expired - Fee Related JPH0735059B2 (en) | 1990-08-31 | 1990-08-31 | Transparent thin container |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0735059B2 (en) |
| KR (1) | KR940009911B1 (en) |
-
1990
- 1990-08-31 JP JP22972090A patent/JPH0735059B2/en not_active Expired - Fee Related
-
1991
- 1991-08-31 KR KR91015202A patent/KR940009911B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR940009911B1 (en) | 1994-10-18 |
| JPH0735059B2 (en) | 1995-04-19 |
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