JPH03239733A - Production of thermoplastic polyester resin foam - Google Patents
Production of thermoplastic polyester resin foamInfo
- Publication number
- JPH03239733A JPH03239733A JP2036768A JP3676890A JPH03239733A JP H03239733 A JPH03239733 A JP H03239733A JP 2036768 A JP2036768 A JP 2036768A JP 3676890 A JP3676890 A JP 3676890A JP H03239733 A JPH03239733 A JP H03239733A
- Authority
- JP
- Japan
- Prior art keywords
- foam
- foaming
- fat
- water
- crystallinity
- 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
- 239000006260 foam Substances 0.000 title claims abstract description 158
- 229920006230 thermoplastic polyester resin Polymers 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 238000005187 foaming Methods 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 230000009477 glass transition Effects 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 18
- 239000004620 low density foam Substances 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000011989 factory acceptance test Methods 0.000 description 59
- 238000012949 factory acceptance testing Methods 0.000 description 59
- 239000003925 fat Substances 0.000 description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 239000007788 liquid Substances 0.000 description 9
- 239000004604 Blowing Agent Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- -1 polyethylene Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 239000004088 foaming agent Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 230000004927 fusion Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- 239000001273 butane Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 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
- 238000002474 experimental method Methods 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011261 inert gas Substances 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
- 239000000155 melt Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- ULUZGMIUTMRARO-UHFFFAOYSA-N (carbamoylamino)urea Chemical compound NC(=O)NNC(N)=O ULUZGMIUTMRARO-UHFFFAOYSA-N 0.000 description 1
- HZNVPDKRGZKQAW-UHFFFAOYSA-N 2-[1,1-bis[4-(2-hydroxyethoxy)phenyl]ethyl]propane-1,3-diol Chemical compound C(O)C(C(C)(C1=CC=C(C=C1)OCCO)C1=CC=C(C=C1)OCCO)CO HZNVPDKRGZKQAW-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- AQBTWPYGBZJMLL-UHFFFAOYSA-N cyclohexane;terephthalic acid Chemical compound C1CCCCC1.OC(=O)C1=CC=C(C(O)=O)C=C1 AQBTWPYGBZJMLL-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 235000004213 low-fat Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、熱可塑性ポリエステル系樹脂発泡体の製造
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a thermoplastic polyester resin foam.
（従来の技術）
熱可塑性ポリエステル系樹脂（以下、これをＰＡＴとい
う）は、ポリスチレンやポリエチレンには見られない優
れた性質を持っている。例えば、ＦＡＴは剛性が大きく
形状安定性がよくて、２００℃に耐えるほどの優れた耐
熱性を持っている。そこで、ＦＡＴを発泡させて、耐熱
性の良好な強靭な断熱材や緩衝材や包装容器などを作ろ
うと企図された。ところがＦＡＴは、ポリスチレンやポ
リエチレンと違ってこれを発泡させることが容易でなか
った。かりに、発泡させ得たとしても、発泡体が低い発
泡倍率を持つに過ぎなかった。(Prior Art) Thermoplastic polyester resin (hereinafter referred to as PAT) has excellent properties not found in polystyrene or polyethylene. For example, FAT has high rigidity, good shape stability, and excellent heat resistance capable of withstanding 200°C. Therefore, attempts were made to foam FAT to create strong heat-resistant insulation materials, cushioning materials, packaging containers, and the like. However, unlike polystyrene and polyethylene, it is not easy to foam FAT. On the other hand, even if foaming could be achieved, the foam only had a low expansion ratio.
ＦＡＴを発泡させるのが困難な理由は、ＦＡＴが結晶性
のものであって、溶融時に発泡に適した粘度を持つよう
に保つことが困難だからである。The reason why it is difficult to foam FAT is that FAT is crystalline and it is difficult to maintain a viscosity suitable for foaming when melted.
詳述すれば、ＦＡＴは、これを加熱して行くと、成る温
度で急激に軟化して粘度の低い液体となるからである。Specifically, when FAT is heated, it rapidly softens at a certain temperature and becomes a liquid with low viscosity.
すなわち、ＦＡＴは、発泡に適した温度を示すのが極め
て狭い温度に限られるので、丁度発泡に適した温度に保
つことが困難だからであり、また粘度の低い液体になる
と発泡剤として働くガスをすぐに放出してしまうからで
ある。従って、ＦＡＴは、発泡させたとしても低い発泡
倍率にとどまり、高倍率に発泡した低密度の発泡体とす
ることが困難であった。In other words, FAT exhibits a temperature suitable for foaming only in an extremely narrow range of temperatures, so it is difficult to maintain the temperature exactly suitable for foaming.Furthermore, when the liquid becomes a low viscosity liquid, the gas that acts as a foaming agent is lost. This is because it will be released immediately. Therefore, even if FAT is foamed, the foaming ratio remains low, and it is difficult to form a low-density foam that is foamed to a high ratio.
この困難を解決するために種々の工夫がなされた。その
多くは、ＦＡＴに種々のものを混合するというものであ
る。例えば、ＦＡＴにエポキシ化合物を混合したり、周
期律表の第１ａ族の金属や第１１ａ族の金属を混合する
という提案であった。Various efforts have been made to solve this difficulty. Most of them involve mixing various things with FAT. For example, there were proposals to mix an epoxy compound with FAT, or to mix metals from group 1a or group 11a of the periodic table.
しかし、これらの提案によっては、高倍率に発泡した大
型発泡体を得ることはできなかった。また、特開昭５９
−１３５２３７号公報は、ＦＡＴ発泡体を作るのに、発
泡剤として高分子量の鎖状芳香族ポリカーボネートを使
用することを奨めている。However, with these proposals, it has not been possible to obtain large foams that expand to a high magnification. Also, JP-A-59
Publication No. 135237 recommends the use of a high molecular weight linear aromatic polycarbonate as a blowing agent to produce a FAT foam.
しかし、これによっても高い発泡倍率に発泡したものは
得られなかった。事実、この公報は、得られた発泡体の
一例として、０．８３ ｆ ／ ｃｃの密度のものを挙
げるに過ぎない。However, even with this method, it was not possible to obtain a product that was foamed to a high expansion ratio. In fact, this publication only cites as an example of the resulting foam a density of 0.83 f/cc.
別の試みとして、特開昭５５−２０４５号公報は、押出
機から押し出した重複の発泡剤含有の高温ＦＡＴを、減
圧された帯域に導いて減圧下で発泡させて、低密度の発
泡体を得る方法を記載している。しかし、発泡剤含有の
高温ＦＡＴは、一般に発泡によって表面に凹凸を生じ、
不規則な外形を持つに至るから、このような高温ＦＡＴ
を連続的に通過させるような減圧帯域を構成することは
、容易でない。とくに、発泡体取出口の減圧シールを充
分なものとすることは困難である。従って、この方法は
実施が容易でないという欠点があった。In another attempt, JP-A-55-2045 discloses that high-temperature FAT containing redundant blowing agents extruded from an extruder is introduced into a vacuum zone and foamed under reduced pressure to produce a low-density foam. It describes how to obtain it. However, high-temperature FAT containing a foaming agent generally causes unevenness on the surface due to foaming.
Such high temperature FAT leads to having an irregular external shape.
It is not easy to construct a depressurized zone that allows continuous passage of . In particular, it is difficult to provide a sufficient vacuum seal at the foam outlet. Therefore, this method has the disadvantage that it is not easy to implement.
（発明が解決しようとする課題）
この発明は、高倍率に発泡したＦＡ’ｌ’発泡体を得よ
うとするものである。さらに詳述すれば、この発明は、
均一微細な気泡を持って発泡した低密度のＦＡＴ発泡体
を、容易に製造できる方法を提供しようとしてなされた
ものである。(Problems to be Solved by the Invention) The present invention aims to obtain an FA'l' foam that is foamed at a high magnification. More specifically, this invention:
This attempt was made to provide a method for easily producing a low-density FAT foam foamed with uniform, fine cells.
（課題解決のための手段）
この発明者は、ＦＡＴの発泡を複数回にわたって行い、
しかも各回ごとに異なった手段を採ると、ＦＡＴを高倍
率に発泡させ得ることを見出した。(Means for solving the problem) The inventor carried out foaming of FAT multiple times,
Moreover, it has been found that FAT can be foamed to a high magnification by employing different means each time.
詳述すれば、初めの発泡すなわち一次発泡は、どのよう
な手段で発泡させてもよいが、ここで得られた発泡体を
急冷して結晶化度を３０％以下に低く抑えた発泡体を得
て、そのあとでこの発泡体に実質的に常圧下で６０℃以
上の水又は水蒸気を直接接触させて加熱すると、この発
泡体はさらに発泡し、その後引き続き又は−旦冷却後に
、この発泡体を水以外の加熱媒体に接触させて１００
’Ｃ以上に加熱すると、ここに高倍率に発泡したＦＡＴ
発泡体の得られることを見出した。この発明は、このよ
うな知見に基づいてなされたものである。To be more specific, the initial foaming, that is, the primary foaming, may be performed by any method, but the foam obtained here is rapidly cooled to suppress the crystallinity to 30% or less. When the foam is heated by direct contact with water or steam at 60° C. or higher under substantially normal pressure, the foam further expands, and then subsequently or once cooled, the foam becomes 100 in contact with a heating medium other than water
When heated above 'C, FAT foams at a high magnification.
It has been found that foams can be obtained. This invention was made based on such knowledge.
この発明は、結晶化度が８０％以下のＦＡＴ発泡体を、
実質的に常圧下で６０℃以上の水又は水蒸気に接触させ
て加熱してさらに発泡させ、次いでこの発泡体を１００
℃以上の温度にある水以外の加熱媒体に接触させて加熱
し、さらに発泡させることを特徴とする、ＰＡ’ｆ’発
泡体の製造方法を提供するものである。This invention uses FAT foam with a crystallinity of 80% or less,
The foam is further foamed by heating it in contact with water or steam at 60°C or higher under substantially normal pressure, and then the foam is heated to a temperature of 100°C.
The present invention provides a method for producing a PA'f' foam, which is characterized by heating the foam by bringing it into contact with a heating medium other than water at a temperature of 0.degree. C. or higher, and further foaming the foam.
（各要件の説明）
この発明において、原料とされるＦＡＴ発泡体は、結晶
化度が３０％以下のものである。このような発泡体を作
るには、ＦＡＴを加熱して軟化させておき、加圧下で発
泡剤を混入し、こうして得た組成物を低圧領域に移して
発泡させ、発泡した直後のＦＡＴ発泡体をＦＡＴのガラ
ス転移点以下に急冷すればよい。(Description of each requirement) In this invention, the FAT foam used as a raw material has a crystallinity of 30% or less. To make such a foam, FAT is heated to soften it, a blowing agent is mixed in under pressure, the composition thus obtained is transferred to a low pressure area and foamed, and the freshly foamed FAT foam is may be rapidly cooled to below the glass transition point of FAT.
この発明で用いられるＦＡＴは、芳香族のジカルボン酸
に二価アルコールを反応させて得られた高分子量の鎖状
エステルである。ジカルボン酸としては、テレフタル酸
が最も多く用いられているカ、イソフタル酸、２．６−
ナフタレンジカルボン酸を用いることもできる。その他
、ジフェニルエテルジカルボン酸、ジフェニルスルホン
ジカルボン酸、ジフェノキシジカルボン酸を用いること
もできる。また、二価アルコールとしては、エチレング
リコールが主として用いられるが、トリメチレングリコ
ール、テトラメチレングリコール、ネオペンチレンゲリ
コール、ヘキサメチレングリコール、シクロヘキサンジ
メチロール、トリシフロチカンジメチロール、２．２−
ビス〜（４−β−ヒドロキシエトキシフェニル）プロパ
ン、４−４’−ビス−（β−ヒドロキシエトキシ）ジフ
ェニルスルホン、ジエチレングリコールを用いることも
できる。このようなＦＡＴは市販されている。この発明
では市販されているＦＡ’Ｉ’を用いることができる。FAT used in this invention is a high molecular weight chain ester obtained by reacting an aromatic dicarboxylic acid with a dihydric alcohol. Terephthalic acid is the most commonly used dicarboxylic acid, isophthalic acid, 2.6-
Naphthalene dicarboxylic acid can also be used. In addition, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid, and diphenoxydicarboxylic acid can also be used. In addition, as the dihydric alcohol, ethylene glycol is mainly used, but trimethylene glycol, tetramethylene glycol, neopentylene gellicol, hexamethylene glycol, cyclohexane dimethylol, tricyflothicane dimethylol, 2.2-
Bis-(4-β-hydroxyethoxyphenyl)propane, 4-4′-bis-(β-hydroxyethoxy)diphenylsulfone, and diethylene glycol can also be used. Such FAT is commercially available. In this invention, commercially available FA'I' can be used.
上述のＦＡＴのうち、この発明で用いるのに適したもの
は、ポリエチレンテレフタレート、ポリブチレンテレフ
タレート、ポリブチレンテレ７タレートエラストマー、
非品性ポリエステル、ポ１１シクロヘキサンテレフタレ
ートなどである。また、上述のＦＡＴは、単独で又は混
合して用いることができる。上述のＦＡＴは、これに他
の樹脂を混合して用いることもできる。他の樹脂を混合
する場合には、他の樹脂はＰＡＴよりも少なくする必要
がある。Among the above-mentioned FATs, those suitable for use in this invention include polyethylene terephthalate, polybutylene terephthalate, polybutylene tere-7-thalerate elastomer,
Non-quality polyester, poly-11 cyclohexane terephthalate, etc. Moreover, the above-mentioned FAT can be used alone or in combination. The above-mentioned FAT can also be used in combination with other resins. When other resins are mixed, the amount of the other resins needs to be less than that of PAT.
ＦＡＴは、一般に、高温で加水分解しやすい樹脂である
から、これを発泡させる場合には、予めこれを乾燥する
ことが望ましい。乾燥には、例えば除湿乾燥機を用いる
のがよい。その場合の乾燥は、例えば露点が一３０℃の
空気を１６０℃に加熱しておき、この空気中にＦＡＴを
約４時間露出するという程度で足りる。Since FAT is generally a resin that is easily hydrolyzed at high temperatures, it is desirable to dry it beforehand when foaming it. For drying, it is preferable to use a dehumidifying dryer, for example. In this case, drying may be carried out by heating air with a dew point of 130° C. to 160° C. and exposing the FAT to this air for about 4 hours.
発泡剤としては、色々なものを用いることができる。大
別すると、ＰＡ’［”の軟化点以上の温度で分解してガ
スを発生する固体化合物や、加熱するとＦＡＴ内で気化
する液体や、加圧下でＦＡＴに溶解させ得る不活性な気
体などに分かれるが、その何れをも用いることができる
。固体化合物は、例えばアゾジカルボンアミド、ジニト
ロソペンタメチレンテトラミン、ヒドラゾカルボンアミ
ド、重炭酸ナトリウムなどである。気化する液体は、例
えばヘキサン、ペンタン、ブタンのような飽和脂肪族炭
化水素、ベンゼン、キシレンのような芳香族炭化水素、
塩化メチレン、フレオン（商標）のようなハロゲン化炭
化水素である。不活性な気体は、例えば二酸化炭素、窒
素などである。その他見泡剤としては、特開昭５９−１
３５２３７号公報が教えるように、高分子量の鎖状芳香
族ボ１１カーボネートを用いることもできる。Various foaming agents can be used. Broadly divided into solid compounds that decompose and generate gas at temperatures above the softening point of PA'['', liquids that vaporize in FAT when heated, and inert gases that can be dissolved in FAT under pressure. Solid compounds include, for example, azodicarbonamide, dinitrosopentamethylenetetramine, hydrazocarbonamide, sodium bicarbonate, etc. Liquids to be vaporized include, for example, hexane, pentane, butane, etc. Saturated aliphatic hydrocarbons such as benzene, aromatic hydrocarbons such as xylene,
Halogenated hydrocarbons such as methylene chloride and Freon™. Examples of the inert gas include carbon dioxide and nitrogen. Other foaming agents include JP-A-59-1
As taught in Japanese Patent No. 35237, high molecular weight linear aromatic bo-11 carbonates can also be used.
ＦＡＴに発泡剤を含ませるには、発泡剤が液状であると
きには、ＦＡＴを常圧下で発泡剤中に浸漬するだけで足
りる場合もあるが、含浸を容易にするためには、発泡剤
の蒸発を防ぎつつ加温して浸漬させることが必要とされ
、従って加温加圧下で浸漬を行わなければならないこと
となる。加温加圧下で含浸させるには、予めＦＡＴを溶
融しておいて、この溶融物中に発泡剤を圧入するのが好
ましい。このためには、押出機を用いてＦＡＴを溶融し
ておき、押出機の途中から発泡剤を圧入するのが有利で
ある。また、押出機を用いると、ＦＡＴに発泡剤を圧入
すると同時に、そのまま押出成形することができ、さら
に同時に発泡させることができるので、便利である。こ
うして行われる発泡が一次発泡であり、ここで得られた
発泡体がこの発明方法の出発原料とされる発泡体である
。To impregnate FAT with a blowing agent, if the blowing agent is in liquid form, it may be sufficient to immerse the FAT in the blowing agent under normal pressure. It is necessary to immerse the material under heating while preventing the immersion from occurring. Therefore, the immersion must be performed under heating and pressure. For impregnation under heating and pressure, it is preferable to melt the FAT in advance and press the blowing agent into the melt. For this purpose, it is advantageous to melt the FAT using an extruder and press the blowing agent into the extruder from the middle of the extruder. Furthermore, when an extruder is used, it is convenient because the foaming agent can be press-fitted into the FAT and extrusion molding can be performed as it is, and foaming can be performed at the same time. The foaming performed in this manner is primary foaming, and the foam obtained here is the foam used as the starting material for the method of this invention.
ＦＡＴは、−次発泡によっては低い倍率にしか発泡しな
い。その発泡倍率は、通常の押出発泡では２倍程度であ
り、特別に高倍率に発泡させたとしても、５倍位にとど
まる。そこで、さらに高倍率に発泡させるために、この
発明では別の手段を用いて発泡させることとするのであ
る。FAT foams only to a low magnification through secondary foaming. The expansion ratio is about 2 times in normal extrusion foaming, and even if it is expanded to a particularly high ratio, it remains around 5 times. Therefore, in order to foam at an even higher magnification, the present invention uses a different means for foaming.
この発明では、−次発泡体におけるＦＡＴの結晶化度が
３０％以下のものを用いる。結晶化度を３０％以下に低
く抑えるには、押出発泡させた直後の高温にある発泡体
をＦＡＴのガラス転移点以下に急冷する。ＦＡＴのガラ
ス転移点は、ＦＡＴを構成している芳香族ジカルボン酸
と、二価アルコールの種類とによって異なるが、おおよ
その範囲を云えば、３０−１００℃である。そこで結晶
化度を３０％以下にするために、３０’Ｃ以下に急冷す
る。In this invention, a secondary foam having a crystallinity of FAT of 30% or less is used. In order to keep the crystallinity low to 30% or less, the foam, which is at a high temperature immediately after extrusion foaming, is rapidly cooled to below the glass transition point of FAT. The glass transition point of FAT varies depending on the type of aromatic dicarboxylic acid and dihydric alcohol constituting FAT, but the approximate range is 30-100°C. Therefore, in order to reduce the crystallinity to 30% or less, it is rapidly cooled to 30'C or less.
一次発泡体は急冷されると、結晶化するいとまがないま
まに固化するから、結晶化度が低いものとなる。結晶化
度は、冷却の程度によって異なり、冷却媒体の種類、冷
却媒体の温度、冷却媒体の接触状況などによって異なる
結果となる。押し出しによって作られた一次発泡体に常
温の水をＷ接接触させて冷却したような場合には、−次
発泡体は結晶化度が数％ないし１０数％となり、通常３
０％以下となる。しかし、押し出しによって作られた一
次発泡体を金型上に導いて形を整えるだけとし、しかも
金型を強制的に冷却しないようなときは、発泡体が急冷
されないから、結晶化度は３０％以上となる。だから、
押し出しによって一次発泡体を作る場合には、−次発泡
体を自然放冷に任せないで、強制冷却した金型に沿って
進行させて、冷却するようにする。When the primary foam is rapidly cooled, it solidifies without having time to crystallize, resulting in a low degree of crystallinity. The degree of crystallinity varies depending on the degree of cooling, and results vary depending on the type of cooling medium, the temperature of the cooling medium, the contact status of the cooling medium, and the like. When a primary foam made by extrusion is cooled by bringing water at room temperature into contact with W, the crystallinity of the primary foam is several percent to several tens of percent, and is usually 3.
It becomes 0% or less. However, when the primary foam made by extrusion is simply guided onto a mold and shaped, and the mold is not forcibly cooled, the crystallinity is 30% because the foam is not rapidly cooled. That's all. that's why,
When the primary foam is made by extrusion, the secondary foam is not allowed to cool naturally, but is cooled by advancing along a forced cooling mold.
一般に、樹脂の結晶化度は、密度、Ｘ線回折像、核磁気
共鳴スペクトルなどによって測定することができるが、
樹脂発泡体はその中に気泡を包蔵しているために、これ
らの方法によって結晶化度を測定することができない。Generally, the crystallinity of a resin can be measured by density, X-ray diffraction pattern, nuclear magnetic resonance spectrum, etc.
Since resin foams contain air bubbles, their crystallinity cannot be measured by these methods.
ところが、好都合にも、ＦＡＴ発泡体は、融解熱を測定
するという熱的方法により、結晶化度を１％のオーダー
までも正確に測定できることが確認された。その原理は
、ＰＡＴ発泡体を定速で加熱して行くと、初めに非結晶
部分が結晶化して発熱し、その後に結晶が融解して融解
熱を吸収するので、この発熱と吸熱とから結晶化度を計
算するのである。具体的には、結晶化に際して発せられ
る冷結晶化熱量と、融解の際に吸収される融解熱量とを
測定し、これを完全結晶の標準品が示す熱量と対比して
結晶化度を算出する。However, it has been conveniently confirmed that the degree of crystallinity of FAT foams can be accurately measured to the order of 1% by a thermal method of measuring the heat of fusion. The principle is that when PAT foam is heated at a constant rate, the amorphous portion first crystallizes and generates heat, and then the crystals melt and absorb the heat of fusion. It calculates the degree of Specifically, the amount of cold crystallization heat emitted during crystallization and the amount of heat of fusion absorbed during melting are measured, and the degree of crystallinity is calculated by comparing this with the amount of heat shown by a fully crystalline standard product. .
実際にＦ Ａ Ｔ発泡体の冷結晶化熱量と融解熱量とを
測定するには、示差走査熱量測定法によることが望まし
い。示差走査熱量測定法では、測定資料と標準品とのヒ
ーターが独立に作動し、定速加熱の過程で両者間に温度
差が生じると、どちらかの熱量の増加又は抑制機構が自
動的に働いてこれを打ち消すので、この熱流速度差が直
接記録されるようになっている。結晶化度は理論的には
次の数式に従って算出される。In order to actually measure the cold crystallization heat and melting heat of FAT foam, it is preferable to use differential scanning calorimetry. In differential scanning calorimetry, the heaters for the measurement sample and the standard sample operate independently, and if a temperature difference occurs between them during the constant-rate heating process, a mechanism to increase or suppress the amount of heat from one of them automatically operates. This cancels out this difference, so this difference in heat flow velocity is recorded directly. The degree of crystallinity is theoretically calculated according to the following formula.
（モル当りの融解熱量−モル当りの冷結晶化熱量）÷（
完全結晶ＦＡＴのモル当りの融解熱量）ＸＩＯＱ−結晶
化度慎）
ここで、完全結晶ＦＡＴのモル当りの融解熱量は、高分
子データハンドブック（培風館発行）によれば、２６．
９ ＫＪとされているので、これを使用することとする
。(heat of fusion per mole – heat of cold crystallization per mole) ÷ (
Heat of fusion per mole of perfectly crystalline FAT)
Since it is said to be 9 KJ, we will use this.
この発明では、結晶化度が３０％以下のＦＡＴ発泡体を
さらに二次発泡させる。二次発泡は、ＰＡＴ発泡体を実
質的に常圧下で６０℃以上の水又は水蒸気に接触させ、
加熱することによって行う。In this invention, the FAT foam having a crystallinity of 30% or less is further subjected to secondary foaming. Secondary foaming involves contacting the PAT foam with water or steam at a temperature of 60°C or higher under substantially normal pressure;
This is done by heating.
水又は水蒸気との接触時間は、得られた二次発泡体が８
０％以下の結晶化度を持つように調節することが好古し
い。それには、一般に水又は水蒸気の温度が高いときに
は接触時間を短くし、逆に温度が低いときには長くする
。なお、二次発泡体の結晶化度は、二次発泡の後１０秒
以内に、発泡体を２０℃の水中に１分間浸漬して急冷し
、その後上述のような方法に従って結晶化度を測定する
。The contact time with water or steam is 8
It is preferable to adjust the crystallinity to 0% or less. For this purpose, the contact time is generally shortened when the temperature of water or steam is high, and conversely lengthened when the temperature is low. The crystallinity of the secondary foam is determined by immersing the foam in 20°C water for 1 minute to rapidly cool it within 10 seconds after secondary foaming, and then measuring the crystallinity according to the method described above. do.
二次発泡に水又は水蒸気を用いる理由は、ＦＡＴ発泡体
の気泡内に水分子を幾分か進入させるためである。実験
によれば、気泡内の水分率が３０００ｐｐｍ以上である
と、その後にＦＡＴ発泡体をさらに高温に加熱したとき
、二次発泡体はさらによく発泡することが確認されてい
るからである。また、二次発泡を６０℃以上に限った理
由は、その温度以上でないとＦＡＴが軟化しないからで
ある。また、二次発泡を実質的に常圧下に限定した理由
は、加圧下の水又は水蒸気を用いると、ＦＡＴの気泡が
周囲の圧力に押されて膨張しにくくなることが確かめら
れたからである。The reason water or steam is used for secondary foaming is to allow some water molecules to enter the cells of the FAT foam. This is because, according to experiments, it has been confirmed that when the moisture content in the cells is 3000 ppm or more, the secondary foam foams even better when the FAT foam is subsequently heated to a higher temperature. Further, the reason why the secondary foaming is limited to 60° C. or higher is that FAT will not soften unless the temperature is higher than that temperature. Further, the reason why the secondary foaming was substantially limited to normal pressure is that it was confirmed that when water or steam under pressure is used, the bubbles of FAT are pushed by the surrounding pressure and become difficult to expand.
気泡内の水分率は色々な方法で測定することができる。Moisture content within bubbles can be measured in various ways.
例えば、加熱減量法、カールフィッシャー法などによっ
て測定することができる。しかし、ここではデュポン９
０３型Ｈ水分計によって測定した。その水分計は、オー
ブンと電解セルとで構成されており、オーブン内に発泡
体を入れて乾燥窒素ガスをキャリヤーとして流し、まず
表面に付着した水分を取り除いてのち、オーブンを加熱
して発泡体を溶融し、その際発生する水分を測定するこ
とを原理としている。そこで発生する水含有の窒素ガス
は、これを電解セルに導いて水分を五酸化燐に吸収させ
、その後この水分を水素と酸素とに電気分解して、水の
量が測定される。For example, it can be measured by a heating loss method, a Karl Fischer method, or the like. But here Dupont 9
Measured using a 03 model H moisture meter. The moisture analyzer consists of an oven and an electrolytic cell.The foam is placed in the oven and dry nitrogen gas is passed through it as a carrier.The moisture attached to the surface is first removed, and then the oven is heated to remove the foam. The principle is to melt the liquid and measure the moisture generated during that process. The water-containing nitrogen gas generated therein is led to an electrolytic cell where the water is absorbed by phosphorus pentoxide, which is then electrolyzed into hydrogen and oxygen, and the amount of water is measured.
この発明では、水又は水蒸気により二次発泡させると同
時に発泡体内に水分を含ませ、こうして得たシートをさ
らに三次発泡させる。三次発泡は、二次発泡に引き続き
行ってもよく、または二次発泡後に一旦冷却しその後に
行ってもよい。また、三次発泡を型内で行い、発泡と同
時に底形することもできる。三次発泡は水以外の加熱媒
体を用いて行い、しかもその加熱媒体を１００℃以上に
加熱して行う。加熱媒体としては、固体、液体、気体の
各種のものを用いることができる。固体としては、アル
ミ、銅、鉄などの各種金属製の板を用いることができ、
液体としてはシリコンオイル、低融点合金の溶融物など
、沸点が１００℃以上のものを用いることができ、気体
としては窒素、炭酸ガス、空気などを用いることができ
る。これらのうちでは金属製の板を用いることが好まし
い。In this invention, the foamed material is subjected to secondary foaming using water or water vapor, and at the same time moisture is impregnated into the foam, and the sheet thus obtained is further foamed tertiarily. The tertiary foaming may be performed subsequent to the secondary foaming, or may be performed after the secondary foaming is once cooled. It is also possible to carry out tertiary foaming in a mold and shape the bottom at the same time as foaming. The tertiary foaming is performed using a heating medium other than water, and the heating medium is heated to 100° C. or higher. As the heating medium, various types of solid, liquid, and gas can be used. As the solid, plates made of various metals such as aluminum, copper, and iron can be used.
As the liquid, one having a boiling point of 100° C. or higher, such as silicone oil or a melt of a low melting point alloy, can be used, and as the gas, nitrogen, carbon dioxide, air, etc. can be used. Among these, it is preferable to use a metal plate.
その理由は、金属製の板を用いると、発泡体の表面を平
滑にしまた発泡体の厚みを均一にしやすいからである。The reason for this is that when a metal plate is used, the surface of the foam can be made smooth and the thickness of the foam can be easily made uniform.
三次発泡では、加熱媒体の温度を１００℃以上とする。In the tertiary foaming, the temperature of the heating medium is set to 100° C. or higher.
１００℃以上とする理由は、実験の結果から来ている。The reason for setting the temperature to 100°C or higher comes from the results of experiments.
すなわち、１００℃以上にしないと、現実によく発泡し
ないからである。それには、前述のように、二次発泡の
除用いた水又は水蒸気が関与しているように見える。す
なわち、二次発泡の除水又は水蒸気でＦＡＴを加熱する
ので、水又は水蒸気が気泡内に入っており、これが１０
０℃以上に加熱されると気泡内で再び気化して気泡を増
大させ、これによって発泡がさらに行われる結果となる
ように見える。That is, unless the temperature is 100°C or higher, foaming does not actually occur well. As mentioned above, it appears that water or steam removed from secondary foaming is involved. In other words, since water is removed from the secondary foaming or the FAT is heated with steam, water or steam enters the bubbles, and this
Heating above 0° C. re-vaporizes within the bubbles, increasing the size of the bubbles, which appears to result in further foaming.
三次発泡は、ＦＡＴ発泡体の結晶化度が３０％に到達す
るまでは、何回も重ねて行うことができる。このように
して得られた発泡体は、少なくとも１０倍以上に発泡し
たものとなり、よく発泡した場合には３０倍以上に発泡
することとなる。しかも、こうして得られた発泡体の気
泡は一般に小さく、また均一に揃っている。また、この
ようにすれば、大きな発泡体を容易に得ることができる
。Tertiary foaming can be repeated many times until the crystallinity of the FAT foam reaches 30%. The foam thus obtained will be at least 10 times more foamed, and if well foamed it will be 30 times more foamed. Moreover, the cells in the foam thus obtained are generally small and uniformly arranged. Moreover, in this way, a large foam can be easily obtained.
この発明の実施にあたっては、ＰＡＴ中に種々の添加剤
を入れることができる。例えば、気泡調整剤として少量
のタルク粉末を加えたり、ＦＡＴの溶融特性を改善する
ために、無水ピロメリット酸のような一分子中に酸無水
物基を二個以上含んでいる化合物や、炭酸す） ＩＪウ
ムのような周期律表中のＩ、■、■族の金属化合物や、
着色剤、帯電防止剤、難燃剤などを加えることができる
。Various additives may be included in the PAT in the practice of this invention. For example, a small amount of talc powder may be added as a bubble control agent, or a compound containing two or more acid anhydride groups in one molecule, such as pyromellitic anhydride, or carbonic acid may be added to improve the melting properties of FAT. ) Metal compounds of groups I, ■, and ■ in the periodic table, such as IJum,
Colorants, antistatic agents, flame retardants, etc. can be added.
また、この発明方法を実施したあとで、得られた発泡体
を高温例えば２００℃以上に保持して、ＦＡＴの結晶化
度を高め、これによって高発泡の耐熱性ＦＡＴ発泡体を
得ることもできる。Further, after carrying out the method of the present invention, the obtained foam can be maintained at a high temperature, for example, 200° C. or higher to increase the degree of crystallinity of FAT, thereby obtaining a highly foamed and heat-resistant FAT foam. .
（発明の効果）
この発明方法によれば初めの材料として、既に普通の方
法により一次発泡させて得られたＦＡＴの一次発泡体を
用い、これに三次発泡と三次発泡とを行わせるので、大
きく発泡した低密度の発泡体を得ることができる。しか
も、−次発泡体は、結晶化度が３０％以下のものを用い
るから、ＦＡＴが低い温度で発泡しやすくなっており、
従って二次発泡では６０℃というような低い温度でも一
次発泡体を発泡させることができる。また、二次発泡で
は水又は水蒸気を実質的に常圧下でＦＡＴに接触させる
こととしたから、−次発泡体は気泡を外圧によって押し
潰されることなく円滑によく発泡するに至る。さらに、
二次発泡では水又は水蒸気を一次発泡体に接触させるこ
ととしたから、二次発泡体の気泡内には水分が進入して
いる。三次発泡では、１００℃以上の温度にある水以外
の加熱媒体に二次発泡体を抜触させて加熱するから、気
泡内に進入している水分が気化又は膨張して気泡を膨ら
ませ、従って二次発泡体をさらによく発泡させることが
できる。また、こうして得られたＦＡＴ発泡体は、均一
微細な気泡を持ったものとなる。従って、この発明方法
によれば、均一微細に発泡した低密度の発泡体を得るこ
とができる。しかも、この発泡体は、ＦＡＴで作られて
いるから、ＦＡＴ自体が強靭で耐熱性の大きい樹脂であ
るために、得られた発泡体は、強靭で耐熱性と断熱性に
すぐれ、しかも軽量であるなどすぐれた性質を持つので
、板又は容器として各方面に利用できるものである。(Effects of the Invention) According to the method of the invention, a primary foam of FAT, which has already been obtained by primary foaming by an ordinary method, is used as the initial material, and this is subjected to tertiary foaming and tertiary foaming. A foamed low density foam can be obtained. Moreover, since the secondary foam uses a material with a crystallinity of 30% or less, it is easy to foam at a low FAT temperature.
Therefore, in secondary foaming, the primary foam can be foamed even at a temperature as low as 60°C. Further, in the secondary foaming, water or steam is brought into contact with the FAT under substantially normal pressure, so that the secondary foaming foams smoothly and well without the bubbles being crushed by external pressure. moreover,
In the secondary foaming, since water or water vapor is brought into contact with the primary foam, water enters into the cells of the secondary foam. In tertiary foaming, the secondary foam is exposed to and heated by a heating medium other than water at a temperature of 100°C or higher, so the moisture that has entered the bubbles evaporates or expands, causing the bubbles to expand. The subsequent foam can be foamed even better. Furthermore, the FAT foam thus obtained has uniform, fine cells. Therefore, according to the method of the present invention, it is possible to obtain a low-density foam that is uniformly and finely foamed. Moreover, since this foam is made of FAT, which itself is a strong and heat-resistant resin, the resulting foam is strong, has excellent heat resistance and heat insulation, and is lightweight. Because of its excellent properties, it can be used in various ways as a board or container.
また、この発明方法によれば、実質的に常圧下で６０℃
以上の水又は水蒸気に一次発泡体を接触させることによ
り二次発泡を行い、１００℃以上の温度にある水以外の
加熱媒体に二次発泡体を接触させることにより三次発泡
を行うので、−次発泡に続けて二次発泡と三次発泡とを
行うことができることとなり、従って連続的に実施でき
る点で工業的に実施容易である。これらの点で、この発
明方法は大きな利益をもたらす。Further, according to the method of this invention, 60°C under substantially normal pressure.
Secondary foaming is performed by bringing the primary foam into contact with the water or steam above, and tertiary foaming is performed by bringing the secondary foam into contact with a heating medium other than water at a temperature of 100°C or higher. This means that secondary foaming and tertiary foaming can be performed subsequent to foaming, and therefore, it is industrially easy to implement in that it can be performed continuously. In these respects, the inventive method provides significant benefits.
次に実施例と比較例とを挙げて、この発明の優れている
所以を具体的に説明する。以下で単に部というのは重量
部の意味である。Next, examples and comparative examples will be given to specifically explain why the present invention is superior. In the following, parts simply mean parts by weight.
実施例１
（−次発泡体の製造）
ＦＡＴとしてポリエチレンテレフタレート（余人社製、
商品名ＴＲ８５８０）を用い、下記の組成物を作った。Example 1 (-Manufacture of secondary foam) Polyethylene terephthalate (manufactured by Yojinsha,
The following composition was prepared using TR8580 (trade name).
ＰＡＴ １００部タルク
０．６部無水ピロメリット
酸 ０．３５部炭酸ナトリウム
０．１部上記の組成物を６５ｗψの押出機
に入れ、押出機の供給部温度を２８０℃、圧縮部の温度
を２８５℃、溶融部の温度を２７０℃１ヘツド部の＆度
を２７５℃、口金の温度を２７０℃として、スクリュー
回転数２５ｒｐｍとした。また、押出機の途中から発泡
剤としてブタンを１３重量部の割合で圧入しで押し出し
た。口金は円環状のものを用い、口径６０朋φでスリッ
ト幅を０．４ ｒｕｎとした。また、口金の先には、直
径２０５Ｗ！Ｒφで長さが７４０朋のプラグを設け、こ
れを２５℃の水で急冷した。PAT 100 parts talc
0.6 part pyromellitic anhydride 0.35 part sodium carbonate
0.1 part of the above composition was put into a 65wψ extruder, and the temperature of the feed section of the extruder was 280℃, the temperature of the compression section was 285℃, and the temperature of the melting section was 270℃. The temperature of the cap was 270° C., and the screw rotation speed was 25 rpm. In addition, butane was injected as a foaming agent at a rate of 13 parts by weight from the middle of the extruder and extruded. The cap used was an annular one with a diameter of 60 mm and a slit width of 0.4 run. Also, the tip of the cap has a diameter of 205W! A plug with an Rφ of 740 mm in length was provided, and this was rapidly cooled with water at 25°C.
こうして得た発泡シートを切り開いて平坦なシトとし、
これを−旦ロール状に巻き取り、これを−次発泡体とし
た。−次発泡体は、厚みが１３ｗ、密度が０．２７９／
ｃｃであった。また、結晶化度は８％であった。−次発
泡体の水分率は２４００ｐｐｍであった。The foam sheet obtained in this way was cut open to form a flat sheet.
This was wound up into a roll, and this was made into a second foam. -The next foam has a thickness of 13W and a density of 0.279/
It was cc. Further, the crystallinity was 8%. - The moisture content of the secondary foam was 2400 ppm.
（二次発泡体の製造）
その後、−次発泡体を１００℃の水蒸気に３分間接触さ
せて更に発泡させて二次発泡体を得た。(Manufacture of secondary foam) Thereafter, the secondary foam was brought into contact with steam at 100° C. for 3 minutes to further foam, thereby obtaining a secondary foam.
二次発泡体は、厚みが４４關、密度が０．０７９り／
ｃｃ、結晶化度は２２％であった。The secondary foam has a thickness of 44 mm and a density of 0.079 mm.
cc, crystallinity was 22%.
（三次発泡体の製造）
二次発泡体の製造５分後に、二次発泡体を１８０℃の鉄
板２枚でプレス圧力２１．ｆ／ｃｉで３０秒間はさみ三
次発泡体を得た。三次発泡シートは、幅が６００ｍ、長
さが１０００ｍｍ、厚みが７．３ ｍｍ 。(Manufacture of tertiary foam) After 5 minutes of manufacturing the secondary foam, press the secondary foam with two iron plates at 180° C. under a pressure of 21. A tertiary foam was obtained by scissoring at f/ci for 30 seconds. The tertiary foam sheet has a width of 600 m, a length of 1000 mm, and a thickness of 7.3 mm.
密度が０．０４８ ｐ ／ｃｃ、発泡倍率は２８倍であ
った。なお、三次発泡を行なった時の発泡体の水分率は
、８７００ ｐｐｍであった。The density was 0.048 p/cc, and the expansion ratio was 28 times. In addition, the moisture content of the foam at the time of tertiary foaming was 8700 ppm.
実施例２
一次発泡体及び二次発泡体の製造については、実施例１
と同じである。Example 2 For the production of primary foam and secondary foam, Example 1
is the same as
（三次発泡体の製造）
鉄板の加熱温度を１２０℃とした以外は実施例１と同じ
条件で三次発泡体を作った。得られた三次発泡体は、幅
が６００ｎ、長さが１０００ｒｘｍ、厚みが５．９闘、
密度が０．０５９９ ／ｃｃ、発泡倍率は２３倍であっ
た。(Manufacture of tertiary foam) A tertiary foam was produced under the same conditions as in Example 1 except that the heating temperature of the iron plate was 120°C. The obtained tertiary foam has a width of 600n, a length of 1000rxm, a thickness of 5.9m,
The density was 0.0599/cc, and the expansion ratio was 23 times.
実施例３ 一次発泡体については、実施例１と同じである。Example 3 The primary foam is the same as in Example 1.
（二次発泡体の製造）
二次発泡体の製造は、水蒸気に５分間接触させることと
した以外は実施例１と同様に処理した。(Manufacture of secondary foam) The secondary foam was manufactured in the same manner as in Example 1 except that it was brought into contact with water vapor for 5 minutes.
得られた二次発泡体は、厚みが４．１謂、密度が０．０
７０ｙ／ｃｃ、結晶化度は２６％であった。The obtained secondary foam has a thickness of 4.1 mm and a density of 0.0 mm.
70y/cc, crystallinity was 26%.
（三次発泡体の製造） 三次発泡体の製造は、実施例１と同じである。(Manufacture of tertiary foam) The production of the tertiary foam is the same as in Example 1.
得られた三次発泡体は、幅が６００ｍｍ、長さが１００
０調、厚みが７．９ ｒｉｍ 、密度が０．０４１’／
ｃｃ、発泡倍率は３１倍であった。なお、水分率は９０
００ｐｐｍであった。The obtained tertiary foam has a width of 600 mm and a length of 100 mm.
0 tone, thickness 7.9 rim, density 0.041'/
cc, and the foaming ratio was 31 times. In addition, the moisture content is 90
It was 00 ppm.
実施例４
一次発泡体及び二次発泡体の製造については、実施例１
と同じである。Example 4 For the production of primary foam and secondary foam, Example 1
is the same as
（三次発泡体の製造）
三次発泡体の製造は、鉄板の接触時間を１０秒とした以
外は実施例１と同様に処理した。得られた三次発泡体は
、幅が６００ｍ＋、長さが１０００前、厚みがａ８ｍ、
密度が０．０５２７ ／ｃｃ、発泡倍率は２６倍であっ
た。(Manufacture of tertiary foam) The tertiary foam was manufactured in the same manner as in Example 1 except that the contact time with the iron plate was 10 seconds. The obtained tertiary foam has a width of 600 m+, a length of 1000 m+, a thickness of A8 m,
The density was 0.0527/cc and the expansion ratio was 26 times.
実施例５
一次発泡体及び二次発泡体の製造については、実施例１
と同じである。Example 5 For the production of primary foam and secondary foam, Example 1
is the same as
（三次発泡体の製造）
三次発泡体の製造は、鉄板のかわりに空気を２００℃に
加熱したオーブンを使用することとした以外は実施例１
と同様に処理した。得られた三次発泡体は、幅が６００
ｍ、長さが１０００ｍｍ。(Production of tertiary foam) The production of the tertiary foam was the same as in Example 1 except that an oven heated to 200°C was used instead of an iron plate.
processed in the same way. The resulting tertiary foam has a width of 600 mm.
m, length is 1000mm.
厚みが５，９顕、密度が０．０６０ Ｙ／ＣＣ，発泡倍
率は２３倍であった。The thickness was 5.9 mm, the density was 0.060 Y/CC, and the expansion ratio was 23 times.
実施例６ 一次発泡体の製造については、実施例１と同じである。Example 6 The production of the primary foam was the same as in Example 1.
（二次発泡体の製造）
一次発泡体を８０℃の温水に３０分間接触させてさらに
発泡させ、二次発泡体を得た。二次発泡体は厚みが２．
７・曲、密度がＯ，１３ｐ／ｃｃ、結晶化度が１０％で
あった。(Manufacture of secondary foam) The primary foam was brought into contact with warm water at 80° C. for 30 minutes to further foam, thereby obtaining a secondary foam. The thickness of the secondary foam is 2.
7. The density was O, 13 p/cc, and the crystallinity was 10%.
（三次発泡体の製造）
二次発泡体の製造５分後に、三次発泡体を１４０℃の鉄
板２枚の間に挾み、２１２／−の圧力で６秒間加圧し、
その１秒あとに１８０℃の容器状の凹凸を持った鉄板２
枚の間に挾み、２１ ’；ｌ／ｃｄの圧力で１６秒間加
圧して、容器状の三次発泡体を得た。この容器は、幅が
１２０ｒｕｎ、長さが１５５ｎ、深さが３ｎであって、
底の厚みが５．６ｆｌ、密度が０． Ｏ６３７／ ｃｃ
、発泡倍率が２２倍であった。(Manufacture of tertiary foam) After 5 minutes of manufacturing the secondary foam, the tertiary foam was sandwiched between two iron plates at 140°C and pressurized at a pressure of 212/- for 6 seconds.
One second later, an iron plate 2 with a container-shaped unevenness at 180℃
It was sandwiched between the sheets and pressurized for 16 seconds at a pressure of 21' l/cd to obtain a container-shaped tertiary foam. This container has a width of 120run, a length of 155n, a depth of 3n,
The thickness of the bottom is 5.6 fl, and the density is 0. O637/cc
, the foaming ratio was 22 times.
なお、三次発泡を行った時の発泡体の水分率は、９２０
０ ｐＩ）ｍであった。The moisture content of the foam after tertiary foaming was 920.
It was 0 pI)m.
比較例１
実施例１と同じ条件で一次発泡体、二次発泡体を作った
が、三次発泡は行なわなかった。得られた発泡体の発泡
倍率は１７倍であった。Comparative Example 1 A primary foam and a secondary foam were made under the same conditions as in Example 1, but tertiary foaming was not performed. The foaming ratio of the obtained foam was 17 times.
比較例２ 一次発泡体の製造については、実施例１と同じである。Comparative example 2 The production of the primary foam was the same as in Example 1.
（二次発泡体の製造）
二次発泡体の製造は水蒸気に７分間接触させることとし
た以外は、実施例１と同様に処理した。(Manufacture of secondary foam) The secondary foam was manufactured in the same manner as in Example 1, except that it was brought into contact with water vapor for 7 minutes.
得られた二次発泡体は、厚みが５．４ ｔｒｔｒ 、密
度が０、 Ｏ６５ｐ ／ｃｃ、発泡倍率が２１倍、結晶
化度は３２％であった。The obtained secondary foam had a thickness of 5.4 trtr, a density of 0, O65p/cc, an expansion ratio of 21 times, and a crystallinity of 32%.
比較例３
一次発泡体の製造については実施例１と同じであり、二
次発泡体の製造については比較例２と同じである。Comparative Example 3 The production of the primary foam was the same as in Example 1, and the production of the secondary foam was the same as in Comparative Example 2.
（三次発泡体の製造） 三次発泡体の製造は、実施例１と同じである。(Manufacture of tertiary foam) The production of the tertiary foam is the same as in Example 1.
得られた三次発泡体は、幅が６００ｆｉ、長さが１００
０ｍｍ、厚みが５．４Ｔ！ｒＭ、密度が０．０６５Ｐ／
ＣＣ，発泡倍率は２１倍で三次発泡はしなかった。The resulting tertiary foam has a width of 600 fi and a length of 100 fi.
0mm, thickness is 5.4T! rM, density is 0.065P/
CC, the foaming ratio was 21 times and no tertiary foaming occurred.
比較例４
一次発泡体の製造については実施例１と同じであり、二
次発泡体の製造については実施例３と同じである。Comparative Example 4 The production of the primary foam was the same as in Example 1, and the production of the secondary foam was the same as in Example 3.
（三次発泡体の製造）
鉄板の加熱温度を９０℃とした以外は、実施例１と同じ
条件で三次発泡体を作った。得られた三次発泡体は、幅
が６００ａ＋、長さが１０００ｍ。(Manufacture of tertiary foam) A tertiary foam was produced under the same conditions as in Example 1, except that the heating temperature of the iron plate was 90°C. The resulting tertiary foam has a width of 600a+ and a length of 1000m.
厚みが４．１ ｔｔｒｍ、密度が０．０７０ ｙ／ＣＣ
，発泡倍率は１９倍で三次発泡はしなかった。Thickness is 4.1 ttrm, density is 0.070 y/CC
The foaming ratio was 19 times, and no tertiary foaming occurred.
Claims (1)
脂発泡体を、実質的に常圧下で６０℃以上の水又は水蒸
気に接触させることにより加熱して発泡させ、次いでこ
の発泡体を１００℃以上の温度にある水以外の加熱媒体
に接触させて加熱し、さらに発泡させることを特徴とす
る、熱可塑性ポリエステル系樹脂発泡体の製造方法。 ２、発泡した直後の軟化している熱可塑性ポリエステル
系樹脂発泡体を、そのガラス転移点以下に急冷して、結
晶化度が３０％以下の熱可塑性ポリエステル系樹脂発泡
体を作り、この発泡体を実質的に常圧下で６０℃以上の
水又は水蒸気に接触させることにより加熱して発泡させ
、次いでこの発泡体を１００℃以上の温度にある水以外
の加熱媒体に接触させて加熱し、さらに発泡させること
を特徴とする、熱可塑性ポリエステル系樹脂発泡体の製
造方法。[Claims] 1. A thermoplastic polyester resin foam having a crystallinity of 30% or less is heated and foamed by contacting it with water or steam at 60° C. or higher under substantially normal pressure, and then A method for producing a thermoplastic polyester resin foam, which comprises heating the foam by contacting it with a heating medium other than water at a temperature of 100° C. or higher, and further foaming the foam. 2. The softened thermoplastic polyester resin foam immediately after foaming is rapidly cooled to below its glass transition point to produce a thermoplastic polyester resin foam with a degree of crystallinity of 30% or less. is heated and foamed by contacting it with water or steam at a temperature of 60°C or higher under substantially normal pressure, then this foam is heated by contacting with a heating medium other than water at a temperature of 100°C or higher, and A method for producing a thermoplastic polyester resin foam, the method comprising foaming.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2036768A JPH0768395B2 (en) | 1990-02-16 | 1990-02-16 | Method for producing thermoplastic polyester resin foam |
| ZA911114A ZA911114B (en) | 1990-02-16 | 1991-02-14 | Process of producing thermoplastic polyester series resin foamed material |
| US07/655,691 US5234640A (en) | 1990-02-16 | 1991-02-15 | Process of producing thermoplastic polyester series resin foamed |
| AU71109/91A AU642962B2 (en) | 1990-02-16 | 1991-02-15 | Process of producing thermoplastic polyester series resin foamed material |
| DE69111636T DE69111636T2 (en) | 1990-02-16 | 1991-02-18 | Process for the production of foamed material from the series of thermoplastic polyester. |
| CA002036548A CA2036548C (en) | 1990-02-16 | 1991-02-18 | Process of producing thermoplastic polyester series resin foamed material |
| EP91301250A EP0442759B1 (en) | 1990-02-16 | 1991-02-18 | Process of producing thermoplastic polyester series resin foamed material |
| US07/792,577 US5128383A (en) | 1990-02-16 | 1991-11-15 | Process of producing thermoplastic polyester series resin foamed material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2036768A JPH0768395B2 (en) | 1990-02-16 | 1990-02-16 | Method for producing thermoplastic polyester resin foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03239733A true JPH03239733A (en) | 1991-10-25 |
| JPH0768395B2 JPH0768395B2 (en) | 1995-07-26 |
Family
ID=12478942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2036768A Expired - Lifetime JPH0768395B2 (en) | 1990-02-16 | 1990-02-16 | Method for producing thermoplastic polyester resin foam |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0768395B2 (en) |
| ZA (1) | ZA911114B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010208091A (en) * | 2009-03-09 | 2010-09-24 | Sekisui Plastics Co Ltd | Method of manufacturing polylactic acid-based resin foamed molding |
| JP2014080022A (en) * | 2012-09-28 | 2014-05-08 | Sekisui Plastics Co Ltd | Foamed body for composite body, composite body and member for composing transportation equipment |
-
1990
- 1990-02-16 JP JP2036768A patent/JPH0768395B2/en not_active Expired - Lifetime
-
1991
- 1991-02-14 ZA ZA911114A patent/ZA911114B/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010208091A (en) * | 2009-03-09 | 2010-09-24 | Sekisui Plastics Co Ltd | Method of manufacturing polylactic acid-based resin foamed molding |
| JP2014080022A (en) * | 2012-09-28 | 2014-05-08 | Sekisui Plastics Co Ltd | Foamed body for composite body, composite body and member for composing transportation equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA911114B (en) | 1991-11-27 |
| JPH0768395B2 (en) | 1995-07-26 |
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