JPH03179040A - Production of foam - Google Patents
Production of foamInfo
- Publication number
- JPH03179040A JPH03179040A JP32011289A JP32011289A JPH03179040A JP H03179040 A JPH03179040 A JP H03179040A JP 32011289 A JP32011289 A JP 32011289A JP 32011289 A JP32011289 A JP 32011289A JP H03179040 A JPH03179040 A JP H03179040A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- crystal polymer
- foam
- phenylenebisoxazoline
- compound
- 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.)
- Pending
Links
- 239000006260 foam Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920000106 Liquid crystal polymer Polymers 0.000 claims abstract description 30
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims abstract description 29
- -1 phenylenebisoxazoline compound Chemical class 0.000 claims abstract description 13
- 238000005187 foaming Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 abstract description 20
- 238000000465 moulding Methods 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- ZDNUPMSZKVCETJ-UHFFFAOYSA-N 2-[4-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=C(C=2OCCN=2)C=C1 ZDNUPMSZKVCETJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000004604 Blowing Agent Substances 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 9
- 239000008188 pellet Substances 0.000 description 8
- 125000005274 4-hydroxybenzoic acid group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229960001019 oxacillin Drugs 0.000 description 5
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XCZKKZXWDBOGPA-UHFFFAOYSA-N 2-phenylbenzene-1,4-diol Chemical group OC1=CC=C(O)C(C=2C=CC=CC=2)=C1 XCZKKZXWDBOGPA-UHFFFAOYSA-N 0.000 description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical class NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- CZGWDPMDAIPURF-UHFFFAOYSA-N (4,6-dihydrazinyl-1,3,5-triazin-2-yl)hydrazine Chemical compound NNC1=NC(NN)=NC(NN)=N1 CZGWDPMDAIPURF-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- VOGDKZZTBPDRBD-UHFFFAOYSA-N 2-[2-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical class O1CCN=C1C1=CC=CC=C1C1=NCCO1 VOGDKZZTBPDRBD-UHFFFAOYSA-N 0.000 description 1
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical group C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 229920006328 Styrofoam Polymers 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008261 styrofoam Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野〉
本発明は、液晶ポリマーからなる発泡成形品の製造方法
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 manufacturing a foam molded article made of a liquid crystal polymer.
（従来の技術）
合成樹脂からなる発泡成形品は、軽量で、廉価であるこ
とから建築、包装等の広い分野で大量に使用されている
。最も代表的なものは発泡スチロール成形品であり、建
物の断熱材やクツション材から生鮮食料品や電気製品の
包装まで、生活に密着して使用されている。(Prior Art) Foamed molded products made of synthetic resin are lightweight and inexpensive, and are therefore used in large quantities in a wide range of fields such as construction and packaging. The most typical product is styrofoam molded products, which are used closely in daily life in everything from insulation and cushioning materials for buildings to packaging for fresh foods and electrical products.
しかし９発泡スチロール底形品で代表される従来の発泡
成形品は、耐熱性が低いとともに、軽量化した分９強力
が低下しており、その用途は断熱材、−クツション材、
包装材のように、あまり耐熱性や強力を必要とされない
分野に限られている。However, conventional foam molded products, such as foamed polystyrene bottom products, have low heat resistance and are less strong due to their reduced weight, and are used as insulation materials, cushioning materials,
It is limited to fields where heat resistance and strength are not required, such as packaging materials.
したがって、耐熱性及び強力に優れた発泡成形品が開発
されれば、自動車、電気・電子機器等の分野にも用途が
広がるものとして期待されている。Therefore, if a foamed molded product with excellent heat resistance and strength is developed, it is expected that its applications will expand to fields such as automobiles and electrical/electronic equipment.
ところで、近年、耐熱性に優れるとともに高強力で、高
弾性率の成形品を与えるエンジニアリングプラスチック
として液晶ポリマー〈サーモトロピック液晶ポリマー〉
が注目されている。By the way, in recent years, liquid crystal polymers (thermotropic liquid crystal polymers) have been used as engineering plastics that provide molded products with excellent heat resistance, high strength, and high modulus of elasticity.
is attracting attention.
この液晶ポリマーを発泡成形すれば、軽量化とコストダ
ウンが図れるとともに、耐熱性と高強力とを有する発泡
成形品が得られることが期待される。また、液晶ポリマ
ーは射出成形すると異方性の強い成形品となり、用途に
よっては使用できないことがあるが１発泡成形すれば生
成する非連続の泡の一つ一つが２軸延伸されたフィルム
と同様になるため異方性が緩和される。If this liquid crystal polymer is foam-molded, it is expected that it will be possible to reduce weight and cost, as well as to obtain a foam-molded product that has heat resistance and high strength. In addition, when liquid crystal polymer is injection molded, it becomes a molded product with strong anisotropy, which may make it unusable depending on the application, but if one foam molding is performed, each discontinuous bubble produced is similar to a biaxially stretched film. Therefore, the anisotropy is relaxed.
しかし、液晶ポリマーから実用的な発泡成形品を製造す
る方法は開発されていない。特開昭５８−１９３３６号
公報には、各種の全芳香族液晶ポリマーからなる発泡成
形品が開示されているが、液晶ポリマーに単に発泡剤を
混合して成形する方法では発泡倍率がせいぜい１．５倍
程度までの発泡成形品しか得られず、その実用的価値は
成形品のひげの防止程度であった。However, no method has been developed for producing practical foam molded products from liquid crystal polymers. JP-A-58-19336 discloses foam molded products made of various wholly aromatic liquid crystal polymers, but in a method in which a blowing agent is simply mixed with the liquid crystal polymer and molded, the foaming ratio is at most 1. A foamed molded product only up to about 5 times larger was obtained, and its practical value was limited to the prevention of whiskers on the molded product.
（発明が解決しようとする課題） 本発明は、液晶ポリマー特有の耐熱性と高強力。(Problem to be solved by the invention) The present invention features the heat resistance and high strength unique to liquid crystal polymers.
高弾性率の成形品を与えるという特性を損なうことなく
、高発泡倍率で、高性能の発泡成形品を得ることのでき
る発泡成形品の製造方法を提供しようとするものである
。The object of the present invention is to provide a method for manufacturing a foamed molded product that can produce a high-performance foamed molded product with a high expansion ratio without impairing the property of providing a molded product with a high modulus of elasticity.
（課題を解決するための手段）
本発明は上記の課題を解決するものであり、その要旨は
、液晶ポリマーに発泡成形して発泡成形品を製造するに
際し、フェニレンビスオキサゾリン化合物を反応させな
がら発泡させることを特徴とする発泡成形品の製造方法
にある。(Means for Solving the Problems) The present invention solves the above problems, and the gist thereof is to foam while reacting a phenylene bisoxazoline compound when manufacturing a foam molded product by foam molding a liquid crystal polymer. A method of manufacturing a foam molded article is provided.
本発明における液晶ポリマーは発泡成形可能なものであ
れば特に限定されないが、優れた耐熱性と機械的特性を
有し１発泡体の泡の冷却固定が容易なことから、 Ａ３
７Ｍロー６４８に基づいて荷重１８．６ｋｇ／ｃｄで測
定した熱変形温度が１５０℃以上のものが好ましい。こ
のような液晶ポリマーの具体例としては、■特公昭５６
−１８０１６号公報及び特開昭６３−２４４２０号公報
に開示されたパラヒドロキシ安息香酸残基単位とエチレ
ンテレフタレート単位とからなる共重合ポリエステルの
うち、パラヒドロキシ安息香酸残基単位が７５モル％以
上のもの、■特開昭５４−７７６９１号公報に開示され
た６−ヒドロキシ−２−ナフトエ酸残基単位とパラヒド
ロキシ安息香酸残基単位とからなる共重合ポリエステル
、■特公昭４７−４７８７０号公報に開示されたパラヒ
ドロキシ安息香酸残基単位とテレフタル酸残基単位及び
２価フェノール残基単位からなる共重合ポリエステル、
■特開昭５３−６５４２１号公報に開示されたフェニル
ハイドロキノン残基単位とテレフタル酸残基単位とから
なる共重合ポリエステル、■米国特許第４６００７６５
号明細書に開示されたフェニルハイドロキノン残基単位
とスタイロハイドロキノン残基単位とからなる共重合ポ
リエステル等が挙げられる。中でも既存の発泡剤がその
まま使用できること、優れた耐熱性を有し、広範な用途
に対応できることから、■及び■の液晶ポリエステルが
好ましく用いられる。最も好ましいものはフェニレンビ
スオキサゾリン化合物が反応する末端カルボキシル基を
多量に含み１反応が容易である点で■の液晶ポリエステ
ルである。The liquid crystal polymer in the present invention is not particularly limited as long as it can be foam-molded, but it has excellent heat resistance and mechanical properties, and it is easy to cool and fix the foam of one foam.
It is preferable that the heat deformation temperature measured at a load of 18.6 kg/cd based on 7M Low 648 is 150° C. or higher. Specific examples of such liquid crystal polymers include:
Among the copolymerized polyesters consisting of parahydroxybenzoic acid residue units and ethylene terephthalate units disclosed in JP-A-18016 and JP-A-63-24420, the parahydroxybenzoic acid residue units contain 75 mol% or more. (1) A copolymerized polyester consisting of a 6-hydroxy-2-naphthoic acid residue unit and a para-hydroxybenzoic acid residue unit disclosed in JP-A-54-77691; A copolymerized polyester comprising a disclosed parahydroxybenzoic acid residue unit, a terephthalic acid residue unit, and a dihydric phenol residue unit,
■Copolymerized polyester consisting of phenylhydroquinone residue units and terephthalic acid residue units disclosed in JP-A No. 53-65421, ■US Patent No. 4600765
Copolymerized polyesters consisting of phenylhydroquinone residue units and stylohydroquinone residue units disclosed in the above specification are included. Among them, liquid crystalline polyesters (1) and (2) are preferably used because existing blowing agents can be used as they are, they have excellent heat resistance, and can be used in a wide range of applications. The most preferred is the liquid crystalline polyester (2) in that it contains a large amount of terminal carboxyl groups with which the phenylenebisoxazoline compound reacts and one reaction is easy.
本発明におけるフェニレンビスオキサゾリン化合物は１
次の一般式で表される。The phenylenebisoxazoline compound in the present invention is 1
It is expressed by the following general formula.
［Ｒ’〜Ｒ１１は水素原子又はアルキル基を表す。〕フ
ェニレンビスオキサゾリン化合物の具体例としては、２
．２’−ｐ−フェニレンビス（２−オキサゾリン）、２
．２’−ｍ−フェニレンビス（２−オキサプリン）、２
．２’−ｐ−フェニレンビス（４−メチル−２−オキサ
シリン）、２．２’−ｐ−フェニレンビス（４，４’−
ジメチル−２−オキサシリン）、２．２’−ｍ−フェニ
レンビス（４−メチル−２−オキサシリン）、２．２’
−ｍ−フェニレンビス（４，４’−ジメチル−２−オキ
サシリン〉等が挙げられる。[R' to R11 represent a hydrogen atom or an alkyl group. ] Specific examples of phenylenebisoxazoline compounds include 2
．． 2'-p-phenylenebis(2-oxazoline), 2
．． 2'-m-phenylenebis(2-oxaprine), 2
．． 2'-p-phenylenebis(4-methyl-2-oxacillin), 2,2'-p-phenylenebis(4,4'-
dimethyl-2-oxacillin), 2.2'-m-phenylenebis(4-methyl-2-oxacillin), 2.2'
-m-phenylenebis(4,4'-dimethyl-2-oxacillin) and the like.
フェニレンビスオキサゾリン化合物は、液晶ポリマー中
に発泡時に存在させる必要があり８通常液晶ポリマーに
混合して成形機に供給する。これらの７工ニレンビスオ
キサゾリン化合物は、液晶ポリマーの末端カポキシル基
と２２０〜３２０℃の温度で速やかに反応し、その粘度
を急激に増加させ。The phenylenebisoxazoline compound must be present in the liquid crystal polymer at the time of foaming, and is usually mixed with the liquid crystal polymer and supplied to the molding machine. These 7-functional nylenebisoxazoline compounds rapidly react with the terminal capoxyl group of the liquid crystal polymer at a temperature of 220 to 320°C, rapidly increasing its viscosity.
高い倍率の発泡を可能にする。フェニレンビスオキサゾ
リン化合物の添加量は、適度な溶融粘度を与えることか
ら０．２〜５重量％、特に０．８〜２．５重量％とする
のが適当である。Enables high foaming ratio. The amount of the phenylenebisoxazoline compound added is suitably 0.2 to 5% by weight, particularly 0.8 to 2.5% by weight in order to provide a suitable melt viscosity.
また１本発明における発泡方法は特に限定されず９分解
性発泡剤を使用する方法、低沸点の溶剤を使用する方法
、気体を圧入して分散させる方法等が採用できるが９分
解性の発泡剤を使用する方法が簡便である。分解性の発
泡剤の具体例としては、アゾジカルボンアミド誘導体、
５−フェニルテトラゾール、トリヒドラジノトリアジン
、ヒドラゾン誘導体等が挙げられる。これらの発泡剤は
約２５０〜３１０℃の範囲で分解する。発泡剤の分解は
温度と時間に依存するが１発泡剤の分解温度をポリマー
の加工温度に合わせることが重要である。Further, the foaming method in the present invention is not particularly limited, and methods such as using a 9-decomposable blowing agent, a method using a low-boiling point solvent, and a method of dispersing gas by pressurizing it can be adopted. The method of using is simple. Specific examples of degradable blowing agents include azodicarbonamide derivatives,
Examples include 5-phenyltetrazole, trihydrazinotriazine, and hydrazone derivatives. These blowing agents decompose in the range of about 250-310°C. Although the decomposition of the blowing agent depends on temperature and time, it is important to match the decomposition temperature of the blowing agent to the processing temperature of the polymer.
ポリマーが十分に融解する前に発泡剤が分解してしまう
と発泡構造が不十分となる。発泡剤の必要量は発泡剤の
ガス発生量及び目的とする成形品の発泡度合いにより異
なるが、一般に０．１〜１０重量％重量％１一常１〜５
である。発泡剤はそのまま液晶ポリマーのペレットに添
加してもよいが、適当な低融点の樹脂に配合してマスタ
ーペレットとして添加するのが好ましい。マスターペレ
ットとして添加する場合、液晶ポリマーの特性を損なわ
ないため、一般に１発泡剥製度ｌＯ〜３０重量％のマス
ターペレットを液晶ポリマーに対して２０重量％以下混
合するのが適当である。If the blowing agent decomposes before the polymer fully melts, the foam structure will be inadequate. The required amount of the blowing agent varies depending on the amount of gas generated by the blowing agent and the degree of foaming of the intended molded product, but is generally 0.1 to 10% by weight, 1 to 5% by weight.
It is. Although the blowing agent may be added to the liquid crystal polymer pellets as it is, it is preferable to mix it with an appropriate low melting point resin and add it as a master pellet. When added as master pellets, in order not to impair the properties of the liquid crystal polymer, it is generally appropriate to mix master pellets with a degree of 1 foam taxidermy of lO to 30% by weight to the liquid crystal polymer in an amount of 20% by weight or less.
本発明において、成形方法は特に限定されず。In the present invention, the molding method is not particularly limited.
押し出し成形、プレス成形、射出成形等何れでもよい。Any method such as extrusion molding, press molding, or injection molding may be used.
本発明の方法は、金型で形状を決めてしまう射出成形法
よりも、押し出し成形法を採用したときに顕著な効果を
奏する。何れの成形方法を採用する場合も、液晶ボｒＪ
マーとフェニレンビスオキサゾリン化合物との反応と発
泡とのタイミングを合わせ１発泡後速やかに冷却するこ
とが優れた発泡成形品を得る上で重要である。成形温度
や圧力は使用する液晶ポリマー及び目的とする発泡成形
品の特性に合わせて適宜選定すればよい。The method of the present invention is more effective when an extrusion molding method is used than an injection molding method in which the shape is determined by a mold. No matter which molding method is used, the liquid crystal
In order to obtain an excellent foamed molded product, it is important to adjust the timing of the reaction between the polymer and the phenylenebisoxazoline compound and the foaming, and to quickly cool the product after one foaming. The molding temperature and pressure may be appropriately selected depending on the liquid crystal polymer used and the characteristics of the intended foamed molded product.
本発明の方法によれば、液晶ポリマーの分子が泡によっ
て配向されるため、優れた発泡成形品が得られるが、必
要に応じて、各種の強化材及び充填剤を添加することに
よって一層改良された性能の発泡成形品を得ることがで
きる。例えば、ガラス繊維のような強化材を６０重量％
以下、好ましくは１０〜４５重量％添加することができ
、顔料、酸化防止剤、成核剤等を０．２〜１０重量％、
好ましくは０．５〜２重量％添加することができる。According to the method of the present invention, the molecules of the liquid crystal polymer are oriented by the bubbles, so an excellent foamed molded product can be obtained, but it can be further improved by adding various reinforcing materials and fillers as necessary. It is possible to obtain a foamed molded product with excellent performance. For example, 60% by weight of reinforcing material such as glass fiber.
Below, preferably 10 to 45% by weight can be added, and pigments, antioxidants, nucleating agents, etc. can be added in 0.2 to 10% by weight,
Preferably, it can be added in an amount of 0.5 to 2% by weight.
なお１本発明の方法で得られる発泡成形品を。Note: 1. Foamed molded products obtained by the method of the present invention.
減圧下に、２４０℃程度の温度で熱処理すると熱的特性
が著しく向上する。Heat treatment at a temperature of about 240° C. under reduced pressure significantly improves thermal properties.
（作 用）
本発明の方法においては、液晶ポリマーとフェニレンオ
キサゾリン化合物とを反応させて液晶ポリマーの溶融粘
度が増大させながら発泡させるため、高い倍率の発泡成
形品が得られる。(Function) In the method of the present invention, a liquid crystal polymer and a phenylene oxazoline compound are caused to react and foamed while increasing the melt viscosity of the liquid crystal polymer, so that a foamed molded article with a high magnification can be obtained.
そして９本発明によれば、優れた機械的特性を有する発
泡成形品が得られる。その理由は、液晶ポリマー分子の
配向が９発泡過程で膨張しつつある泡壁の２軸伸長性の
流れによって引き起こされ。According to the present invention, a foam molded article having excellent mechanical properties can be obtained. The reason is that the orientation of liquid crystal polymer molecules is caused by the biaxial extensional flow of the expanding bubble wall during the foaming process.
液晶ポリマー特有の自己補強構造が形成されるとともに
異方性が緩和されるためと認められる。This is believed to be because a self-reinforcing structure unique to liquid crystal polymers is formed and the anisotropy is relaxed.
（実施例） 次に、実施例により本発明を具体的に説明する。(Example) Next, the present invention will be specifically explained with reference to Examples.
なお、特性値の測定法等は次のとおりである。The method for measuring the characteristic values is as follows.
引張強度 ＡＳＴＭ ０−６３８に準じて測定した。tensile strength Measured according to ASTM 0-638.
曲げ弾性率 ＡＳＴＭローフ９０に準じて測定した。bending modulus Measured according to ASTM Loaf 90.
参考例（マスターペレットの調製）
パラヒドロキシ安息香酸残基単位６０モル％とエチレン
テレフタレート単位４０モル％とからなる液晶ポリエス
テル（ユニチカ社製 ロッドランしＣ−３０００） ８
０重量部と分解温度２５０〜３００℃の発泡剤：アゾジ
カルボンアミド２０重量部とを２軸エクストルーダーに
供給して２２５℃で混練した後、ストランド状に押し出
し、水冷し、コールドペレタイザーでペレット化した。Reference Example (Preparation of Master Pellets) Liquid crystalline polyester consisting of 60 mol% of parahydroxybenzoic acid residue units and 40 mol% of ethylene terephthalate units (Rodrunshi C-3000, manufactured by Unitika) 8
0 parts by weight and 20 parts by weight of azodicarbonamide, a blowing agent with a decomposition temperature of 250 to 300°C, were supplied to a twin-screw extruder and kneaded at 225°C, extruded into strands, cooled with water, and pelletized with a cold pelletizer. did.
実施例１〜７及び比較例１〜４
パラヒドロキシ安息香酸残基単位８０モル％とエチレン
テレフタレート単位２０モル％とからなる液晶ポリエス
テル（ユニチカ社製 ロッドランＬＣ−５０００）のペ
レットに参考例のマスターペレット及び２．２’−ｍ−
フェニレンビス（２−オキサシリン）の粉末（式日製薬
社製）を第１表に示した添加量となるように混合し、
Ｌ／Ｄが２５で、直径が３０ｍｍの車軸エクストルーダ
ーに供給し、厚さ３ｍｍ、幅１２０ ｍｍのＴダイから
、２８５℃で押し出し、ローラに挟んで適当なドラフト
を与えながら引き取り、厚さ２ｍｍの発泡シートを得た
。Examples 1 to 7 and Comparative Examples 1 to 4 Master pellets of reference examples were added to pellets of liquid crystal polyester (Rodlan LC-5000 manufactured by Unitika) consisting of 80 mol% of parahydroxybenzoic acid residue units and 20 mol% of ethylene terephthalate units. and 2.2'-m-
Phenylene bis(2-oxacillin) powder (manufactured by Shikinichi Pharmaceutical Co., Ltd.) was mixed in the amount shown in Table 1,
It is supplied to an axle extruder with an L/D of 25 and a diameter of 30 mm, extruded through a T-die with a thickness of 3 mm and a width of 120 mm at 285°C, and taken out while giving an appropriate draft between rollers to a thickness of 2 mm. A foamed sheet was obtained.
この際、エクストルーダー温度は、入口で２５０℃、圧
縮部で２７０℃、先端で２７０〜３００℃となるように
制御し１発泡は圧縮部以降で急激に起こるようにした。At this time, the extruder temperature was controlled to be 250° C. at the inlet, 270° C. at the compression section, and 270 to 300° C. at the tip, so that one foaming occurred rapidly after the compression section.
得られたシートの中央部を押し出し方向（ＭＯ力方向及
びそれと直角な方向（ＴＯ力方向に幅１２゜７ｍｍで切
り出し、その特性値を測定した結果を第１表に示す。The central part of the obtained sheet was cut out to a width of 12.7 mm in the extrusion direction (MO force direction and the direction perpendicular thereto (TO force direction), and the characteristic values thereof were measured. Table 1 shows the results.
本発明の要件を満足する実施例１〜７では、高い発泡倍
率を示し、断面には非連続の泡が均一に認められ１機械
的特性、耐熱性とも良好であり。In Examples 1 to 7, which satisfy the requirements of the present invention, a high expansion ratio was exhibited, discontinuous bubbles were uniformly observed in the cross section, and both mechanical properties and heat resistance were good.
異方性の緩和された発泡シートが得られた。A foamed sheet with relaxed anisotropy was obtained.
これに対して、比較例２では、押し出された溶融物の粘
度が低く９円滑な引き取りができず、比較例１及び３で
は、シート化はできたが１発泡倍率が低く、シートの断
面には泡が偏在していた。On the other hand, in Comparative Example 2, the viscosity of the extruded melt was low and it was not possible to take it off smoothly.In Comparative Examples 1 and 3, although it was possible to form a sheet, the expansion ratio was low and the cross section of the sheet bubbles were unevenly distributed.
第
表
注： ｐｏｚはフェニレンビスオキサゾリン化合物、Ｍ
Ｐはマスターペレットを示す。Table note: poz is a phenylenebisoxazoline compound, M
P indicates master pellet.
実施例８及び比較例４ 実施例３及び比較例１と同じ組成物を用いて。Example 8 and Comparative Example 4 Using the same composition as Example 3 and Comparative Example 1.
日本製鋼新製Ｊ−１００ｓ型射出成形機により射出成形
して、引張強度及び曲げ弾性率測定用試験片（厚さ１／
８ ＄＞）を成形した。この際、平均滞留時間２分間、
金型温度１２０℃、成形温度（樹脂温度〉２８５℃とし
た。また、射出圧力は約１８０ｋｇ／ｃｄ、射出速度は
約３０ｃｃ／ｓｅｃとした。Test pieces for measuring tensile strength and flexural modulus (thickness 1/2
8 $>) was molded. At this time, the average residence time was 2 minutes,
The mold temperature was 120° C., and the molding temperature (resin temperature) was 285° C. The injection pressure was about 180 kg/cd, and the injection speed was about 30 cc/sec.
発泡成形品（試験片）の特性値を第２表に示す。Table 2 shows the characteristic values of the foamed molded product (test piece).
第２表
（発明の効果〉
本発明によれば、液晶ポリマー特有の耐熱性と高強力、
高弾性率の成形品を与えるという特性を損なうことなく
、高発泡倍率で、高性能の発泡成形品を得ることが可能
となる。Table 2 (Effects of the Invention) According to the present invention, the heat resistance and high strength peculiar to liquid crystal polymers,
It becomes possible to obtain a high-performance foam molded product with a high expansion ratio without impairing the property of providing a molded product with a high elastic modulus.
Claims (1)
るに際し、フェニレンビスオキサゾリン化合物を反応さ
せながら発泡させることを特徴とする発泡成形品の製造
方法。(1) A method for producing a foam molded article, which comprises foaming a liquid crystal polymer while reacting a phenylenebisoxazoline compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32011289A JPH03179040A (en) | 1989-12-07 | 1989-12-07 | Production of foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32011289A JPH03179040A (en) | 1989-12-07 | 1989-12-07 | Production of foam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03179040A true JPH03179040A (en) | 1991-08-05 |
Family
ID=18117834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32011289A Pending JPH03179040A (en) | 1989-12-07 | 1989-12-07 | Production of foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03179040A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0943646A4 (en) * | 1996-09-30 | 2000-01-05 | Sekisui Chemical Co Ltd | Expandable synthetic resin composition, synthetic resin foam, and process for the production of the foam |
| JP2008069217A (en) * | 2006-09-13 | 2008-03-27 | Toray Ind Inc | Polyester film and method for producing the same |
-
1989
- 1989-12-07 JP JP32011289A patent/JPH03179040A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0943646A4 (en) * | 1996-09-30 | 2000-01-05 | Sekisui Chemical Co Ltd | Expandable synthetic resin composition, synthetic resin foam, and process for the production of the foam |
| JP2008069217A (en) * | 2006-09-13 | 2008-03-27 | Toray Ind Inc | Polyester film and method for producing the same |
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