JPH04342739A - Production of resin molding having heat resistance and impact resistance - Google Patents
Production of resin molding having heat resistance and impact resistanceInfo
- Publication number
- JPH04342739A JPH04342739A JP11629691A JP11629691A JPH04342739A JP H04342739 A JPH04342739 A JP H04342739A JP 11629691 A JP11629691 A JP 11629691A JP 11629691 A JP11629691 A JP 11629691A JP H04342739 A JPH04342739 A JP H04342739A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- radiation
- heat resistance
- aromatic polyether
- impact resistance
- 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.)
- Withdrawn
Links
- 239000011347 resin Substances 0.000 title claims abstract description 19
- 229920005989 resin Polymers 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000000465 moulding Methods 0.000 title abstract description 7
- 230000005855 radiation Effects 0.000 claims abstract description 26
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 230000001678 irradiating effect Effects 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 229920000728 polyester Polymers 0.000 claims 1
- 229920000570 polyether Polymers 0.000 abstract description 19
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 18
- 230000009477 glass transition Effects 0.000 abstract description 5
- 238000011033 desalting Methods 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 238000005452 bending Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 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
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal bicarbonate Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/04—After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0844—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using X-ray
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/085—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using gamma-ray
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
- B29C2035/0872—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using ion-radiation, e.g. alpha-rays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
- B29C2035/0877—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
- B29C2035/0883—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using neutron radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Polyethers (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、芳香族ポリエーテル系
共重合体からなり、耐熱性および耐衝撃性を有する樹脂
成形体の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a resin molded article made of an aromatic polyether copolymer and having heat resistance and impact resistance.
【０００２】0002
【従来の技術】近年、高い耐熱性と機械的強度を有する
いわゆるエンジニアリングプラスチックスが、金属など
の代替材料として広い分野で用いられるようになった。
このようなエンジニアリングプラスチックスとして種々
の化学構造を有するものが開発されているが、耐熱性が
増大するにともなって、一般的に脆くなる傾向が強く、
耐衝撃性が低下するという欠点がある。例えば特開平２
−２５５８３３号公報に記載された芳香族ポリエーテル
系共重合体は耐熱性が良好であるが、耐衝撃性について
は、必ずしも十分であるとは言えない。2. Description of the Related Art In recent years, so-called engineering plastics, which have high heat resistance and mechanical strength, have come to be used in a wide range of fields as substitute materials for metals and the like. Such engineering plastics with various chemical structures have been developed, but as their heat resistance increases, they generally tend to become brittle.
It has the disadvantage of reduced impact resistance. For example, JP-A-2
Although the aromatic polyether copolymer described in JP-255833 has good heat resistance, it cannot be said that its impact resistance is necessarily sufficient.
【０００３】ところで、プラスチック材料に放射線を照
射してプラスチック材料を改質することは古くから行な
われている。例えば、不飽和結合を有する樹脂に放射線
を照射することにより、樹脂を架橋化してその特性を改
善することは一般に行なわれているが、不飽和結合を持
たない樹脂に放射線を照射すると、樹脂が分解して劣化
して脆くなり、耐衝撃性が低下するという欠点があった
。By the way, modifying plastic materials by irradiating them with radiation has been practiced for a long time. For example, it is common practice to crosslink resins and improve their properties by irradiating a resin with unsaturated bonds with radiation, but if a resin without unsaturated bonds is irradiated with radiation, the resin will It has the disadvantage that it decomposes and deteriorates, becoming brittle and having reduced impact resistance.
【０００４】0004
【発明の目的】従って本発明は、上述の不飽和結合を持
たない樹脂に属する芳香族ポリエーテル系共重合体が本
来有する高い耐熱性を維持しつつ、その欠点である耐衝
撃性が不十分である点を改善することにより、耐熱性お
よび耐衝撃性を有する樹脂成形体を提供することを目的
とする。OBJECTS OF THE INVENTION Therefore, the present invention aims to maintain the high heat resistance inherent to the above-mentioned aromatic polyether copolymers, which belong to the resins without unsaturated bonds, while solving the drawback of insufficient impact resistance. An object of the present invention is to provide a resin molded article having heat resistance and impact resistance by improving certain points.
【０００５】[0005]
【目的を達成するための手段】本発明者らは、この目的
達成のために検討を加えた結果、不飽和結合を持たない
樹脂に放射線を照射する従来方法において樹脂が分解、
劣化するのは、照射する放射線の線量について配慮がな
く、多量の放射線を照射していたからであることを見い
出し、この知見に基づき更に検討を加えた結果、芳香族
ポリエーテル系共重合体成形物に所定量の放射線を照射
することにより、ポリエーテル系共重合体が本来有する
耐熱性を維持しつつ、耐衝撃性の向上した樹脂成形体が
得られることを見い出した。[Means for Achieving the Object] As a result of studies to achieve this object, the present inventors have found that in the conventional method of irradiating radiation to a resin that does not have unsaturated bonds, the resin decomposes.
We discovered that the reason for the deterioration was that large amounts of radiation were being irradiated without consideration for the dose of radiation. Based on this knowledge, we conducted further studies and found that aromatic polyether copolymer molded products It has been found that by irradiating a predetermined amount of radiation, a resin molded article with improved impact resistance can be obtained while maintaining the heat resistance inherent to the polyether copolymer.
【０００６】従って本発明は、式Therefore, the present invention provides the formula
【０００７】[0007]
【化３】[C3]
【０００８】で表わされる繰り返し単位および式Repeating unit and formula represented by
【００
０９】00
09]
【化４】[C4]
【００１０】（式中ｎは１または２である）で表わされ
る繰り返し単位からなり、式［Ｉ］の繰り返し単位と式
［ＩＩ］の繰り返し単位の合計量に対する式［Ｉ］の繰
り返し単位の含有割合〔［Ｉ］／（［Ｉ］＋［ＩＩ］）
〕がモル基準で０．１〜０．５である芳香族ポリエーテ
ル系共重合体からなる成形物に、放射線を１０５ 〜１
０７ グレイの放射線量で照射することを特徴とする樹
脂成形体の製造方法を要旨とするものである。(where n is 1 or 2), the content of the repeating unit of formula [I] relative to the total amount of the repeating unit of formula [I] and the repeating unit of formula [II] Ratio [[I]/([I]+[II])
] is 0.1 to 0.5 on a molar basis.
07 The gist of the present invention is a method for producing a resin molded body characterized by irradiation with a gray radiation dose.
【００１１】以下、本発明を詳説する。本発明の樹脂成
形体の製造方法は、上述のように式［Ｉ］の繰り返し単
位と式［ＩＩ］の繰り返し単位からなり、式［Ｉ］の繰
り返し単位と式［ＩＩ］の繰り返し単位の合計量に対す
る式［Ｉ］の繰り返し単位の含有割合〔［Ｉ］／（［Ｉ
］＋［ＩＩ］）〕がモル基準で０．１〜０．５である芳
香族ポリエーテル系共重合体を出発材料として用いる。
この芳香族ポリエーテル系重合体は、式The present invention will be explained in detail below. As described above, the method for producing a resin molded article of the present invention consists of a repeating unit of formula [I] and a repeating unit of formula [II], and a total of repeating units of formula [I] and repeating units of formula [II]. The content ratio of the repeating unit of formula [I] to the amount [[I]/([I
]+[II])] is 0.1 to 0.5 on a molar basis, an aromatic polyether copolymer is used as a starting material. This aromatic polyether polymer has the formula
【００１２】0012
【化５】[C5]
【００１３】で示される４，４′−ビフェノールと、式
4,4'-biphenol represented by the formula
【００１４】[0014]
【化６】[C6]
【００１５】で示されるジハロゲノベンゾニトリルと、
式A dihalogenobenzonitrile represented by
formula
【００１６】[0016]
【化７】[C7]
【００１７】で示される４，４′−ジハロゲノベンゾフ
ェノン（ｎ＝１）および／または１，４−ビス（４′−
ハロゲノベンゾイル）ベンゼン（ｎ＝２）とを、アルカ
リ金属炭酸塩やアルカリ金属炭酸水素塩などのアルカリ
金属化合物の存在下に、Ｎ−メチルピロリドン（ＮＭＰ
）、Ｎ，Ｎ−ジメチルイミダゾリジノン（ＤＭＩ）、ジ
メチルアセトアミド（ＤＭＡｃ）、ジメチルホルムアミ
ド（ＤＭＦ）、ジフェニルスルホンなどの溶媒中で脱塩
重縮合反応させることにより得られたものであり、繰り
返し単位［Ｉ］と繰り返し単位［ＩＩ］の合計量に対す
る繰り返し単位［Ｉ］の含有割合を０．１〜０．５限定
した理由は、０．１未満では、ポリエーテル系共重合体
のガラス転移温度が低くなって耐熱性が低下したり、融
点が高くなって成形性の劣化を招き、一方０．５を超え
ると、ポリエーテル系共重合体の結晶性が失われて、耐
熱性、耐溶剤性が低下するからである。4,4'-dihalogenobenzophenone (n=1) and/or 1,4-bis(4'-
halogenobenzoyl)benzene (n=2) in the presence of an alkali metal compound such as an alkali metal carbonate or alkali metal bicarbonate
), N,N-dimethylimidazolidinone (DMI), dimethylacetamide (DMAc), dimethylformamide (DMF), diphenylsulfone, etc., and is obtained by desalting polycondensation reaction in a solvent such as The reason why the content ratio of repeating unit [I] to the total amount of [I] and repeating unit [II] is limited to 0.1 to 0.5 is that if it is less than 0.1, the glass transition temperature of the polyether copolymer will decrease. If it exceeds 0.5, the crystallinity of the polyether copolymer will be lost, resulting in poor heat resistance and solvent resistance. This is because the quality decreases.
【００１８】このポリエーテル系共重合体は、４００℃
で測定した溶融粘度が３，０００ポイズ以上で、ガラス
転移点が１３０〜２５０℃であるものが好ましい。[0018] This polyether copolymer is heated at 400°C.
It is preferable to have a melt viscosity of 3,000 poise or more and a glass transition point of 130 to 250°C.
【００１９】本発明においては、上述のポリエーテル系
共重合体からなる成形物に、所定量の放射線を照射する
。放射線が照射される成形物は、押出成形、射出成形、
圧縮成形等の成形手段を用いてポリエーテル系共重合体
を成形することにより得られ、その形状は問わず、目的
に応じて任意の形状をとり得る。In the present invention, a molded article made of the above polyether copolymer is irradiated with a predetermined amount of radiation. Molded products that are irradiated with radiation include extrusion molding, injection molding,
It is obtained by molding a polyether copolymer using a molding means such as compression molding, and can take any shape depending on the purpose.
【００２０】この成形物に照射される放射線としては、
α線、β線、γ線、Ｘ線、中性子線、加速電子線、重陽
子線またはこれらの組み合せが挙げられる。照射雰囲気
は、空気中あるいは真空中、アルゴン、ヘリウム、窒素
などの不活性ガス中のいずれでも良く、照射時温度は室
温から２５０℃までとするのが好ましい。The radiation irradiated to this molded product is as follows:
Examples include alpha rays, beta rays, gamma rays, X-rays, neutron beams, accelerated electron beams, deuteron beams, or combinations thereof. The irradiation atmosphere may be air, vacuum, or an inert gas such as argon, helium, or nitrogen, and the temperature during irradiation is preferably from room temperature to 250°C.
【００２１】本発明によれば、照射される放射線の線量
を１０５ 〜１０７ グレイに限定することにより、芳
香族ポリエーテル系共重合体の分解を過度に惹き起すこ
となく、架橋化を促進し、その結果、耐熱性を維持しつ
つ耐衝撃性に優れた樹脂成形体が得られる。一方、放射
線の線量が１０５ グレイ未満では、芳香族ポリエーテ
ル系共重合体の架橋化が十分でなく、耐衝撃性が向上せ
ず、１０７ グレイを超えると、芳香族ポリエーテル系
共重合体の分解による耐衝撃性などの物性の低下を招く
ことになる。According to the present invention, by limiting the dose of radiation to 105 to 107 gray, crosslinking is promoted without excessively causing decomposition of the aromatic polyether copolymer, As a result, a resin molded article having excellent impact resistance while maintaining heat resistance can be obtained. On the other hand, if the radiation dose is less than 105 Gy, the aromatic polyether copolymer will not be sufficiently crosslinked and its impact resistance will not improve, and if the radiation dose exceeds 107 Gy, the aromatic polyether copolymer will not be sufficiently crosslinked. Decomposition will lead to a decline in physical properties such as impact resistance.
【００２２】[0022]
【実施例】以下、実施例により本発明を詳細に説明する
。
（１）芳香族ポリエーテル系共重合体の製造例トルエン
を満たしたディーンスタルクトラップ、撹拌装置及びア
ルゴンガス吹き込み管を備えた内容積２００リットルの
反応器に２，６−ジクロロベンゾニトリル１５４８ｇ（
９モル）、４，４′−ビフェノール５５８０ｇ（３０モ
ル）、炭酸カリウム４５６１ｇ（３３モル）及びＮ−メ
チルピロリドン５０リットルを加え、アルゴンガスを吹
き込みながら１時間かけて１９５℃まで昇温した。[Examples] The present invention will be explained in detail below with reference to Examples. (1) Production example of aromatic polyether copolymer 1548 g of 2,6-dichlorobenzonitrile (1548 g of 2,6-dichlorobenzonitrile (
9 mol), 5580 g (30 mol) of 4,4'-biphenol, 4561 g (33 mol) of potassium carbonate, and 50 liters of N-methylpyrrolidone were added, and the temperature was raised to 195° C. over 1 hour while blowing argon gas.
【００２３】昇温後少量のトルエンを加えて生成する水
を共沸により除去した。ついで温度１９５℃にて３０分
間反応を行なった後、４，４′−ジフルオロベンゾフェ
ノン４５８２ｇ（２１モル）をＮ−メチルピロリドン７
０リットルに溶解させた溶液を加えて、さらに１時間反
応を行なった。After raising the temperature, a small amount of toluene was added and the produced water was removed by azeotropy. Then, after carrying out a reaction at a temperature of 195°C for 30 minutes, 4,582 g (21 mol) of 4,4'-difluorobenzophenone was added to 7 mol of N-methylpyrrolidone.
A solution dissolved in 0 liters was added and the reaction was further carried out for 1 hour.
【００２４】反応終了後生成物をブレンダーで粉砕し、
水、メタノールの順に洗浄を行ない乾燥し、白色状の共
重合体１０．０ｋｇ（収率９８％）を得た。この共重合
体の特性について測定したところ、温度４００℃にて測
定した溶融粘度（ゼロせん断粘度）は１３，０００ポイ
ズ、ガラス転移温度は１８２℃、結晶融点は３７９℃、
熱分解開始温度は５６２℃（空気中５％重量減）であっ
た。この共重合体は下記の繰り返し単位［Ｉａ］および
［ＩＩａ］からなるものである。After the reaction is completed, the product is pulverized with a blender,
The copolymer was washed with water and methanol in this order and dried to obtain 10.0 kg (yield: 98%) of a white copolymer. When the properties of this copolymer were measured, the melt viscosity (zero shear viscosity) measured at a temperature of 400°C was 13,000 poise, the glass transition temperature was 182°C, the crystal melting point was 379°C,
The starting temperature of thermal decomposition was 562°C (5% weight loss in air). This copolymer consists of the following repeating units [Ia] and [IIa].
【００２５】[0025]
【化８】[Chemical formula 8]
【００２６】（２）樹脂成形体の製造例（１）で得られ
た芳香族ポリエーテル系共重合体を池貝鉄工社製２軸押
出機にて３９０℃で溶融混練してペレット化を行なった
。その後３９０℃にて東芝製ＩＳ４５Ｐ射出成形機で曲
げ・アイゾット衝撃用試料片を作成した。各試料片を電
子線照射装置で２ＭｅＶ（メガエレクトロンボルト）、
１ｍＡの加速電子線ビームを所定の時間照射後、ＡＳＴ
Ｍ Ｄ−７９０及びＤ−２５６に準処して曲げ試験お
よびアイゾット衝撃試験を行なった。結果を表１に示し
た。(2) Production example of resin molded article The aromatic polyether copolymer obtained in (1) was melt-kneaded at 390°C in a twin-screw extruder manufactured by Ikegai Tekko Co., Ltd. and pelletized. . Thereafter, specimens for bending and Izod impact were prepared using a Toshiba IS45P injection molding machine at 390°C. Each sample piece was irradiated with an electron beam at 2MeV (megaelectron volt).
After irradiating a 1 mA accelerated electron beam for a predetermined time, AST
A bending test and an Izod impact test were conducted in accordance with MD-790 and D-256. The results are shown in Table 1.
【００２７】[0027]
【表１】[Table 1]
【００２８】表１より、放射線照射を行なわない比較例
１の場合、曲げ強度が１７６０ｋｇ／ｃｍ２ 、アイゾ
ット衝撃強度が１０．４ｋｇ・ｃｍ／ｃｍと低い値を示
した。また放射線照射を行なったが、その線量が０．７
７×１０４ グレイ（１０５ グレイ未満）である比較
例２の場合、比較例１に比べ曲げ強度およびアイゾット
衝撃強度が上昇したが、未だ不十分であった。これに対
して放射線線量が４．５×１０５グレイ（１０５ グレ
イ以上）である実施例１の場合、比較例２に比べて曲げ
強度およびアイゾット衝撃強度の急激な上昇が認められ
た。このことから、本発明において放射線線量の下限を
１０５ グレイに限定したことによる臨界的意義が明ら
かとなった。From Table 1, in the case of Comparative Example 1 in which radiation irradiation was not performed, the bending strength was 1760 kg/cm 2 and the Izod impact strength was as low as 10.4 kg·cm/cm. Also, radiation irradiation was performed, but the dose was 0.7
In the case of Comparative Example 2, which was 7×10 4 Gray (less than 10 5 Gray), the bending strength and Izod impact strength were increased compared to Comparative Example 1, but were still insufficient. On the other hand, in the case of Example 1 in which the radiation dose was 4.5×10 5 Gy (10 5 Gy or more), a rapid increase in bending strength and Izod impact strength was observed compared to Comparative Example 2. From this, the critical significance of limiting the lower limit of the radiation dose to 105 Gy in the present invention has become clear.
【００２９】また放射線線量を、１０５ 〜１０７ グ
レイの範囲で実施例１よりも上昇させた実施例２（２．
１×１０６ グレイ）および実施例３（６．９×１０６
グレイ）の場合、実施例１よりも曲げ強度およびアイ
ゾット衝撃強度がさらに向上した。Furthermore, Example 2 (2.
1×106 gray) and Example 3 (6.9×106
Gray), the bending strength and Izod impact strength were further improved compared to Example 1.
【００３０】ところが放射線線量を１０７ グレイを超
える２．１×１０７ グレイした比較例３の場合は、放
射線線量が６．９×１０６ グレイである実施例３に比
べて、曲げ強度およびアイゾット衝撃強度が急激に低下
している。このことから、本発明において放射線線量の
上限を１０７ グレイに限定したことによる臨界的意義
が明らかとなった。However, in the case of Comparative Example 3, in which the radiation dose was 2.1×10 7 Gray exceeding 10 7 Gray, the bending strength and Izod impact strength were lower than in Example 3, in which the radiation dose was 6.9×10 6 Gray. It is rapidly declining. From this, the critical significance of limiting the upper limit of the radiation dose to 107 Gy in the present invention has become clear.
【００３１】また放射線照射後の共重合体のガラス転移
温度は、照射線量の増大に伴なって上昇し、耐熱性が徐
々に改善されている。Furthermore, the glass transition temperature of the copolymer after radiation irradiation increases as the irradiation dose increases, and the heat resistance gradually improves.
【００３２】[0032]
【発明の効果】以上のように本発明によれば、芳香族ポ
リエーテル系共重合体が本来有する高い耐熱性を維持し
つつ、その欠点である耐衝撃性が不十分である点を改善
することにより、耐熱性および耐衝撃性を有する樹脂成
形体が得られた。As described above, according to the present invention, while maintaining the high heat resistance inherent to aromatic polyether copolymers, the drawback of insufficient impact resistance can be improved. As a result, a resin molded article having heat resistance and impact resistance was obtained.
Claims (1)
位からなり、式［Ｉ］の繰り返し単位と式［ＩＩ］の繰
り返し単位の合計量に対する式［Ｉ］の繰り返し単位の
含有割合〔［Ｉ］／（［Ｉ］＋［ＩＩ］）〕がモル基準
で０．１〜０．５である芳香族ポリエーテル系共重合体
からなる成形物に、放射線を１０５ 〜１０７ グレイ
の放射線量で照射することを特徴とする樹脂成形体の製
造方法。Claim 1: Consists of a repeating unit represented by the formula [I] and a repeating unit represented by the formula [Chemical 2] (wherein n is 1 or 2), comprising a repeating unit of the formula [I] and a repeating unit of the formula [I] An aromatic polyester whose content ratio [[I]/([I]+[II])] of repeating units of formula [I] to the total amount of repeating units of formula [II] is 0.1 to 0.5 on a molar basis. A method for producing a resin molded article, which comprises irradiating a molded article made of an ether copolymer with radiation at a radiation dose of 105 to 107 Gy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11629691A JPH04342739A (en) | 1991-05-21 | 1991-05-21 | Production of resin molding having heat resistance and impact resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11629691A JPH04342739A (en) | 1991-05-21 | 1991-05-21 | Production of resin molding having heat resistance and impact resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04342739A true JPH04342739A (en) | 1992-11-30 |
Family
ID=14683517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11629691A Withdrawn JPH04342739A (en) | 1991-05-21 | 1991-05-21 | Production of resin molding having heat resistance and impact resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04342739A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997021537A1 (en) * | 1995-12-11 | 1997-06-19 | Shell Internationale Research Maatschappij B.V. | Cross-linked polyketones |
| US5705539A (en) * | 1995-12-11 | 1998-01-06 | Shell Oil Company | Curing polyketones with high energy radiation |
-
1991
- 1991-05-21 JP JP11629691A patent/JPH04342739A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997021537A1 (en) * | 1995-12-11 | 1997-06-19 | Shell Internationale Research Maatschappij B.V. | Cross-linked polyketones |
| US5705539A (en) * | 1995-12-11 | 1998-01-06 | Shell Oil Company | Curing polyketones with high energy radiation |
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