JP2022047258A - Method for producing pressure container, thermoplastic resin composition and prepreg - Google Patents
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- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
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- 238000006243 chemical reaction Methods 0.000 description 4
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- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
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- VIYWVRIBDZTTMH-UHFFFAOYSA-N 2-[4-[2-[4-[2-(2-methylprop-2-enoyloxy)ethoxy]phenyl]propan-2-yl]phenoxy]ethyl 2-methylprop-2-enoate Chemical compound C1=CC(OCCOC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCCOC(=O)C(C)=C)C=C1 VIYWVRIBDZTTMH-UHFFFAOYSA-N 0.000 description 1
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- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
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- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- Pressure Vessels And Lids Thereof (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Description
本発明は、圧力容器の製造方法、熱可塑性樹脂組成物およびプリプレグに関する。 The present invention relates to a method for manufacturing a pressure vessel, a thermoplastic resin composition and a prepreg.
航空宇宙分野において、地球環境への影響を少なくするという観点から、ロケット等の燃料タンクとして用いられる圧力容器の軽量化が要望されている。例えば、プラスチック製の容器本体(ライナー)に、樹脂を炭素繊維等の強化繊維に含浸させてなる繊維強化樹脂材料(プリプレグ)を外殻として巻き付けた圧力容器の製造が知られている(例えば特許文献1参照)。 In the aerospace field, there is a demand for weight reduction of pressure vessels used as fuel tanks for rockets and the like from the viewpoint of reducing the impact on the global environment. For example, it is known to manufacture a pressure vessel in which a fiber-reinforced resin material (prepreg) made by impregnating a reinforcing fiber such as carbon fiber with a plastic container body (liner) is wound as an outer shell (for example, a patent). See Document 1).
強化繊維に含浸させる樹脂として、耐熱性、耐薬品性、耐久性に優れていることから、スーパーエンジニアリングプラスチックと称されている高性能熱可塑性樹脂を採用するのが望ましいとされている。しかしながら、この熱可塑性樹脂は溶融温度が高く、溶融粘度が高いので、例えば自動繊維積層(Automated Fiber Placement:AFP)によってプリプレグを積層する場合には、完璧な含浸や層間接着が困難であった。そのため、高性能熱可塑性樹脂が強化繊維中に良好に含浸し、かつ層間での接着性が良好である圧力容器を高い生産性で製造できる技術が望まれている。 As the resin to be impregnated into the reinforcing fibers, it is desirable to use a high-performance thermoplastic resin called a super engineering plastic because it has excellent heat resistance, chemical resistance, and durability. However, since this thermoplastic resin has a high melting temperature and a high melting viscosity, it is difficult to completely impregnate or bond the prepregs, for example, by laminating prepregs by automated fiber placement (AFP). Therefore, there is a demand for a technique capable of producing a pressure vessel in which a high-performance thermoplastic resin is satisfactorily impregnated into the reinforcing fiber and the adhesiveness between layers is good with high productivity.
したがって、本発明の目的は、高性能熱可塑性樹脂が強化繊維中に良好に含浸し、かつ層間での接着性が良好である圧力容器を高い生産性で製造できる技術を提供することにある。 Therefore, an object of the present invention is to provide a technique capable of producing a pressure vessel in which a high-performance thermoplastic resin is satisfactorily impregnated into a reinforcing fiber and the adhesiveness between layers is good with high productivity.
本発明のある態様は、圧力容器の製造方法である。該方法は、(A)ポリエーテルスルホン、ポリスルホン、ポリアリレートからなる群より選択される熱可塑性樹脂と、
(B)電子線照射により重合し得る官能基を少なくとも1個有するモノマー、または
(B’)電子線照射によりラジカルを発生する化合物と、ラジカルと付加反応することができる官能基を分子中に少なくとも1個以上有する化合物との混合物と、
を含み、
成分(A)のハンセン溶解度パラメータ(HSP)からの成分(B)のHSPの距離が6.5以下であり、成分(A):成分(B)または(B’)の質量比が90:10~50:50である熱可塑性樹脂組成物を用いる圧力容器の製造方法であって、
前記熱可塑性樹脂を溶融させ、溶融した熱可塑性樹脂組成物を強化繊維に含浸させてプリプレグを得る工程と、
前記熱可塑性樹脂組成物が溶融した状態で前記プリプレグをライナーの外周に巻回して積層する工程と、
積層したプリプレグに電子線を照射する工程と、
を含む。
One aspect of the present invention is a method of manufacturing a pressure vessel. The method comprises (A) a thermoplastic resin selected from the group consisting of polyethersulfone, polysulfone, and polyarylate.
(B) A monomer having at least one functional group that can be polymerized by electron beam irradiation, or (B') a compound that generates radicals by electron beam irradiation, and at least a functional group capable of an addition reaction with a radical in the molecule. A mixture with one or more compounds and
Including
The distance of HSP of component (B) from the Hansen solubility parameter (HSP) of component (A) is 6.5 or less, and the mass ratio of component (A): component (B) or (B') is 90:10. A method for producing a pressure vessel using a thermoplastic resin composition of ~ 50: 50.
A step of melting the thermoplastic resin and impregnating the reinforcing fibers with the melted thermoplastic resin composition to obtain a prepreg.
A step of winding the prepreg around the outer circumference of the liner and laminating the thermoplastic resin composition in a molten state.
The process of irradiating the laminated prepreg with an electron beam,
including.
本発明の他の態様は、熱可塑性樹脂組成物である。該熱可塑性樹脂組成物は、(A)ポリエーテルスルホン、ポリスルホン、ポリアリレートからなる群より選択される熱可塑性樹脂と、
(B)電子線照射により重合し得る官能基を少なくとも1個有するモノマー、または
(B’)電子線照射によりラジカルを発生する化合物と、ラジカルと付加反応することができる官能基を分子中に少なくとも1個以上有する化合物との混合物と、を含み、
成分(A)のハンセン溶解度パラメータ(HSP)からの成分(B)のHSPの距離が6.5以下であり、成分(A):成分(B)または(B’)の質量比が90:10~50:50である。
Another aspect of the present invention is a thermoplastic resin composition. The thermoplastic resin composition comprises (A) a thermoplastic resin selected from the group consisting of polyethersulfone, polysulfone, and polyarylate.
(B) A monomer having at least one functional group that can be polymerized by electron beam irradiation, or (B') a compound that generates radicals by electron beam irradiation, and at least a functional group capable of an addition reaction with a radical in the molecule. Containing a mixture with one or more compounds
The distance of HSP of component (B) from the Hansen solubility parameter (HSP) of component (A) is 6.5 or less, and the mass ratio of component (A): component (B) or (B') is 90:10. ~ 50:50.
本発明のさらに他の態様は、プリプレグである。該プリプレグは、上記熱可塑性樹脂組成物を強化繊維に含浸させてなる。 Yet another aspect of the invention is a prepreg. The prepreg is made by impregnating reinforcing fibers with the above-mentioned thermoplastic resin composition.
本発明によれば、高性能熱可塑性樹脂が強化繊維中に良好に含浸し、かつ層間での接着性が良好である圧力容器を高い生産性で製造できる。 According to the present invention, a pressure vessel in which a high-performance thermoplastic resin is satisfactorily impregnated into a reinforcing fiber and the adhesiveness between layers is good can be produced with high productivity.
(熱可塑性樹脂組成物)
以下、圧力容器の製造に好適に用いられる本発明の熱可塑性樹脂組成物について説明する。熱可塑性樹脂組成物は、(A)ポリエーテルスルホン、ポリスルホン、ポリアリレートからなる群より選択される熱可塑性樹脂と、(B)電子線照射により重合し得る官能基を少なくとも1個有するモノマー、または(B’)電子線照射によりラジカルを発生する化合物と、ラジカルと付加反応することができる官能基を分子中に少なくとも1個以上有する化合物との混合物と、
を含み、
成分(A)のハンセン溶解度パラメータ(HSP)からの成分(B)のHSPの距離が6.5以下であり、成分(A):成分(B)または(B’)の質量比が90:10~50:50である。成分(A)の熱可塑性樹脂に、それとHSP値が近いモノマー(B)または混合物(B’)を混合することによって、得られた熱可塑性樹脂組成物の溶融温度が熱可塑性樹脂(A)のものより低くなり、溶融粘度も低くなる。このことから、熱可塑性樹脂組成物を強化繊維中に良好に含浸させることができる。ここで、熱可塑性樹脂組成物は、熱可塑性樹脂(A)よりも強度が劣化しているが、熱可塑性樹脂組成物に電子線を照射して、モノマー(B)または混合物(B’)を重合させることによって、強度を回復させることができる。
(Thermoplastic resin composition)
Hereinafter, the thermoplastic resin composition of the present invention, which is suitably used for manufacturing a pressure vessel, will be described. The thermoplastic resin composition is a thermoplastic resin selected from the group consisting of (A) polyethersulfone, polysulfone, and polyarylate, and (B) a monomer having at least one functional group that can be polymerized by electron beam irradiation, or (B') A mixture of a compound that generates a radical by irradiation with an electron beam and a compound having at least one functional group in the molecule capable of performing an addition reaction with the radical.
Including
The distance of HSP of component (B) from the Hansen solubility parameter (HSP) of component (A) is 6.5 or less, and the mass ratio of component (A): component (B) or (B') is 90:10. ~ 50:50. By mixing the thermoplastic resin of the component (A) with the monomer (B) or the mixture (B') having a similar HSP value, the melting temperature of the obtained thermoplastic resin composition is that of the thermoplastic resin (A). It will be lower than the one and the melt viscosity will be lower. From this, the thermoplastic resin composition can be satisfactorily impregnated into the reinforcing fibers. Here, the thermoplastic resin composition has a lower strength than that of the thermoplastic resin (A), but the thermoplastic resin composition is irradiated with an electron beam to obtain the monomer (B) or the mixture (B'). By polymerizing, the strength can be restored.
成分(A)のハンセン溶解度パラメータ(HSP)からの成分(B)のHSPの距離が6.5以下である。成分(A)と成分(B)の相溶性を高めるという観点から、このHSPの距離が5.5以下であることが好ましく、4.5以下であることがより好ましい。 The distance of the HSP of the component (B) from the Hansen solubility parameter (HSP) of the component (A) is 6.5 or less. From the viewpoint of enhancing the compatibility between the component (A) and the component (B), the distance of this HSP is preferably 5.5 or less, and more preferably 4.5 or less.
本実施の形態にかかる熱可塑性樹脂組成物において、成分(A):成分(B)または(B’)の質量比が90:10~50:50である。熱可塑性樹脂組成物の低粘度化効果と電子線照射後の物性回復効果の両立の観点から、この質量比が85:15~60:40であることが好ましく、80:20~70:30であることがより好ましい。 In the thermoplastic resin composition according to the present embodiment, the mass ratio of the component (A): the component (B) or (B') is 90:10 to 50:50. From the viewpoint of achieving both the effect of reducing the viscosity of the thermoplastic resin composition and the effect of recovering the physical properties after irradiation with an electron beam, the mass ratio is preferably 85:15 to 60:40, preferably 80:20 to 70:30. It is more preferable to have.
モノマー(B)の官能基としては、例えば、メタクリル基、アクリル基が挙げられる。成分(A)との溶融混錬プロセスにおける熱的安定性の観点から、成分(B)の官能基はメタクリル基であることが好ましい。 Examples of the functional group of the monomer (B) include a methacrylic group and an acrylic group. From the viewpoint of thermal stability in the melt-kneading process with the component (A), the functional group of the component (B) is preferably a methacrylic group.
混合物(B’)において、電子線照射によりラジカルを発生する化合物としては、例えば、ポリアミド6、ポリアミド66、ポリプロピレン、ポリエチレン等の飽和炭化水素連鎖を有する化合物が挙げられる。成分(A)との相溶性と経済性の両立の観点から、該化合物はポリアミド6であることが好ましい。 Examples of the compound that generates a radical by electron beam irradiation in the mixture (B') include compounds having a saturated hydrocarbon chain such as polyamide 6, polyamide 66, polypropylene, and polyethylene. From the viewpoint of achieving both compatibility with the component (A) and economic efficiency, the compound is preferably polyamide 6.
混合物(B’)において、ラジカルと付加反応することができる官能基を分子中に少なくとも1個以上有する化合物としては、例えば、トリアリルイソシアヌレート(TAIC)、トリアリルシアヌレート(TAC)、ジアリルフタレート(DAP)が挙げられる。耐熱性と経済性の両立の観点から、該化合物はトリアリルイソシアヌレート(TAIC)であることが好ましい。 In the mixture (B'), examples of the compound having at least one functional group capable of addition reaction with a radical in the molecule include triallyl isocyanurate (TAC), triallyl cyanurate (TAC), and diallyl phthalate. (DAP) can be mentioned. From the viewpoint of achieving both heat resistance and economy, the compound is preferably triallyl isocyanurate (TAIC).
(圧力容器の製造方法)
本実施の形態にかかる圧力容器の製造方法は、上記の実施の形態にかかる熱可塑性樹脂組成物を用いる。該方法は、熱可塑性樹脂組成物を溶融させ、溶融した熱可塑性樹脂組成物を強化繊維に含浸させてプリプレグを得る工程と、熱可塑性樹脂組成物が溶融した状態でプリプレグをライナーの外周に巻回して積層する工程と、積層したプリプレグに電子線を照射する工程と、を含む。
(Manufacturing method of pressure vessel)
The method for manufacturing a pressure vessel according to the present embodiment uses the thermoplastic resin composition according to the above embodiment. The method comprises a step of melting a thermoplastic resin composition and impregnating a reinforcing fiber with the melted thermoplastic resin composition to obtain a prepreg, and winding the prepreg around the outer periphery of the liner in a state where the thermoplastic resin composition is melted. It includes a step of turning and laminating, and a step of irradiating the laminated prepreg with an electron beam.
プリプレグを得る工程において、上記の熱可塑性樹脂組成物を溶融させ、溶融した熱可塑性樹脂組成物を強化繊維に含浸させる。上記の熱可塑性樹脂組成物は、比較的溶融温度が低く、溶融粘度も低いことから、強化繊維に良好に含浸することができる。 In the step of obtaining the prepreg, the above-mentioned thermoplastic resin composition is melted, and the molten thermoplastic resin composition is impregnated into the reinforcing fibers. Since the above-mentioned thermoplastic resin composition has a relatively low melting temperature and a low melting viscosity, it can be satisfactorily impregnated into reinforcing fibers.
プリプレグを構成する強化繊維としては、例えば、炭素繊維、ガラス繊維、バサルト繊維等が挙げられる。これらの強化繊維は1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。軽量かつ高強度であることから、強化繊維は炭素繊維であることが好ましい。 Examples of the reinforcing fiber constituting the prepreg include carbon fiber, glass fiber, basalt fiber and the like. One of these reinforcing fibers may be used alone, or two or more thereof may be used in combination. Since it is lightweight and has high strength, the reinforcing fiber is preferably carbon fiber.
プリプレグは、ライナー外周に巻回することから、好ましくはテープ状もしくはシート状に成形される。テープ状のプリプレグの厚みは、例えば200μm以下であり、好ましくは150~30μmであり、より好ましくは100~30μmである。 Since the prepreg is wound around the outer periphery of the liner, it is preferably formed into a tape shape or a sheet shape. The thickness of the tape-shaped prepreg is, for example, 200 μm or less, preferably 150 to 30 μm, and more preferably 100 to 30 μm.
次に、プリプレグを、例えばフィラメントワインディングによって、ライナー外周に巻回する。図1は、圧力容器のライナーへのプリプレグの積層工程および電子線照射によるプリプレグのモノマー成分の重合工程を説明するための模式図である。図1に示すように、固定軸10には、ライナー(図示せず)が固定されており、固定軸10を矢印Aの方向に回転させることによって、ライナーの外周にプリプレグ12を巻回している。プリプレグ12を巻回する際には、加熱ロール14によって、プリプレグ12を加熱しながら矢印Bで示すようにプレスしている。この加熱によって、プリプレグ12に含浸されている熱可塑性樹脂組成物は溶融した状態となり、積層したプリプレグ12の層同士が接着できるようになる。したがって、積層時のプリプレグ12の加熱温度は、熱可塑性樹脂組成物の溶融温度以上であることが望ましい。具体的には、加熱温度は、130~200℃であることが好ましく、150~180℃であることがより好ましい。
The prepreg is then wound around the liner perimeter, for example by filament winding. FIG. 1 is a schematic diagram for explaining a step of laminating a prepreg on a liner of a pressure vessel and a step of polymerizing a monomer component of the prepreg by irradiation with an electron beam. As shown in FIG. 1, a liner (not shown) is fixed to the fixed
ライナーの材料としては、圧力容器に充填される燃料を漏洩させない材料が用いられ、圧力容器のライナー材料として公知のものを用いることができる。ライナー材料の具体例としては、例えば、アルミニウム、ポリアミド6等が挙げられる。ライナー材料は、1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。 As the material of the liner, a material that does not leak the fuel filled in the pressure vessel is used, and a known liner material of the pressure vessel can be used. Specific examples of the liner material include aluminum, polyamide 6, and the like. As the liner material, one type may be used alone, or two or more types may be used in combination.
次に、電子線照射装置16によって、ライナーに巻かれたプリプレグ12へ順次電子線Cを照射する。これによって、プリプレグの熱可塑性樹脂組成物に成分(B)のモノマーまたは成分(B’)の混合物を重合させる。成分(B)のモノマーおよび成分(B’)の混合物は、空気中ではその重合が酸素阻害を受けるため、巻かれたプリプレグ12の最上面では、電子線が照射されても直ちに熱可塑性樹脂組成物の重合は起こらない。最上面より下の層では、酸素阻害を受けず、最上面から透過した電子線によって、重合が起きる。これによって、プリプレグの層間の接着をより強固にすることができる。また、プリプレグの熱可塑性樹脂組成物は、成分(B)のモノマーまたは成分(B’)の混合物が成分(A)の樹脂と共存しているため、成分(A)の樹脂の性能(強度)と比較して、熱可塑性樹脂組成物自体の性能が低下しているが、成分(B)のモノマーまたは成分(B’)の混合物を電子線によって重合させることによって、熱可塑性樹脂組成物の性能を回復させることができる。
Next, the
電子線の照射量は、プリプレグの厚みや熱可塑性樹脂組成物に含まれる成分の種類に応じて適宜調整できる。実現可能性という観点から、電子線の照射量が10kGy~500kGyであり、加速電圧が50Kev~500Kevであることが好ましい。 The irradiation amount of the electron beam can be appropriately adjusted according to the thickness of the prepreg and the type of the component contained in the thermoplastic resin composition. From the viewpoint of feasibility, it is preferable that the irradiation amount of the electron beam is 10 kGy to 500 kGy and the acceleration voltage is 50 Kev to 500 Kev.
以下、本発明を実施例によってさらに詳細に説明するが、これらの実施例は本発明を何ら限定するものではない。 Hereinafter, the present invention will be described in more detail by way of examples, but these examples do not limit the present invention in any way.
(材料)
実施例および比較例で使用した材料の詳細は下記の通りである。
PES5003P(標準グレード):ポリエーテルスルホン,住友化学社製「スミカエクセルPES5003P」
PES3500P(低分子量グレード):ポリエーテルスルホン,住友化学社製「スミカエクセルPES3500P」
TAIC:トリアリルイソシアヌレート,三菱ケミカル社製「TAIC」
BPE-80N:2,2-ビス(4-(メタクリロキシ-エトキシ)フェニル)プロパン(エチレンオキシド2.3モル),新中村化学社製「NKエステルBPE-80N」
3000MK:ビスフェノールAジグリシジルエーテルメタクリル酸付加物,共栄社化学社製「エポキシエステル3000MK」
ポリアミド6 CM1001:東レ社製「アミランCM1001」
(material)
Details of the materials used in the examples and comparative examples are as follows.
PES5003P (standard grade): Polyether sulfone, "Sumika Excel PES5003P" manufactured by Sumitomo Chemical Co., Ltd.
PES3500P (Low molecular weight grade): Polyether sulfone, "Sumika Excel PES3500P" manufactured by Sumitomo Chemical Co., Ltd.
TAIC: Triallyl Isocyanurate, "TAIC" manufactured by Mitsubishi Chemical Corporation
BPE-80N: 2,2-bis (4- (methacryloxy-ethoxy) phenyl) propane (2.3 mol of ethylene oxide), "NK ester BPE-80N" manufactured by Shin-Nakamura Chemical Co., Ltd.
3000MK: Bisphenol A diglycidyl ether methacrylic acid adduct, "Epoxy ester 3000MK" manufactured by Kyoeisha Chemical Co., Ltd.
Polyamide 6 CM1001: "Amiran CM1001" manufactured by Toray Industries, Inc.
[合成例1:メタクリロイルオキシエチル-p-トルエンスルホネート(HEMA-Ts)の合成]
13.0gの2-ヒドロキシエチルメタクリレート、20.2gのトリエチルアミンおよび0.9gのトリメチルアミン塩酸塩を50mLのトルエンに溶解させ、1Lのセパラブルフラスコに仕込んだ。フラスコ内を窒素置換した後0℃まで冷却し、フラスコに取り付けた滴下ロートから、28.6gの塩化p-トルエンスルホニルを50mLのトルエンに溶解させた溶液を滴下した。0℃で1時間撹拌して反応させた後、8.8gのN,N-ジメチルエチレンジアミンを加えて15分撹拌した。トルエンを留去した後、酢酸エチルおよび純水を加えて、溶媒抽出を行ない、有機相を飽和食塩水で数回洗浄した。有機相の溶媒を留去した後、カラムクロマトグラフィー(移動相は酢酸エチル)にて精製し、目的物を得た。
[Synthesis Example 1: Synthesis of methacryloyloxyethyl-p-toluenesulfonate (HEMA-Ts)]
13.0 g of 2-hydroxyethyl methacrylate, 20.2 g of triethylamine and 0.9 g of trimethylamine hydrochloride were dissolved in 50 mL of toluene and placed in a 1 L separable flask. The inside of the flask was replaced with nitrogen and then cooled to 0 ° C., and a solution of 28.6 g of p-toluenesulfonyl chloride dissolved in 50 mL of toluene was added dropwise from the dropping funnel attached to the flask. After stirring and reacting at 0 ° C. for 1 hour, 8.8 g of N, N-dimethylethylenediamine was added and the mixture was stirred for 15 minutes. After distilling off toluene, ethyl acetate and pure water were added, solvent extraction was performed, and the organic phase was washed with saturated brine several times. After distilling off the solvent of the organic phase, it was purified by column chromatography (the mobile phase was ethyl acetate) to obtain the desired product.
[合成例2:ビス[4-(2-ヒドロキシエトキシ)フェニル]スルホン・モノメタクリレート(BHEPS-mMA)の合成]
33.8gのビス[4-(2-ヒドロキシエトキシ)フェニル]スルホンおよび45.5gのトリエチルアミンを100mLの脱水ジメチルホルムアミドに溶解させ、1Lのセパラブルフラスコに仕込んだ。フラスコ内を窒素置換した後0℃まで冷却し、フラスコに取り付けた滴下ロートから、41.8gの塩化メタクリロイルを50mLの脱水ジメチルホルムアミドに溶解させた溶液を滴下した。0℃で一晩撹拌して反応させた後、クロロホルムで希釈し、純水を加えて反応をクエンチするとともに飽和食塩水で数回洗浄した。有機相の溶媒を留去した後、カラムクロマトグラフィー(移動相はクロロホルム:メタノール=20:1)にて精製し、メタノールからの再結晶により目的物を得た。
[Synthesis Example 2: Synthesis of bis [4- (2-hydroxyethoxy) phenyl] sulfone monomethacrylate (BHEPS-mMA)]
33.8 g of bis [4- (2-hydroxyethoxy) phenyl] sulfone and 45.5 g of triethylamine were dissolved in 100 mL of dehydrated dimethylformamide and placed in a 1 L separable flask. The inside of the flask was replaced with nitrogen and then cooled to 0 ° C., and a solution of 41.8 g of methacryloyl chloride dissolved in 50 mL of dehydrated dimethylformamide was added dropwise from the dropping funnel attached to the flask. After stirring and reacting overnight at 0 ° C., the mixture was diluted with chloroform, pure water was added to quench the reaction, and the reaction was washed several times with saturated brine. After distilling off the solvent of the organic phase, it was purified by column chromatography (mobile phase was chloroform: methanol = 20: 1), and the desired product was obtained by recrystallization from methanol.
[合成例3:ビス[4-(2-ヒドロキシエトキシ)フェニル]スルホン・ジメタクリレート(BHEPS-dMA)の合成]
33.8gのビス[4-(2-ヒドロキシエトキシ)フェニル]スルホンおよび10.1gのトリエチルアミンを100mLの脱水ジメチルホルムアミドに溶解させ、1Lのセパラブルフラスコに仕込んだ。フラスコ内を窒素置換した後0℃まで冷却し、フラスコに取り付けた滴下ロートから、10.5gの塩化メタクリロイルを50mLの脱水ジメチルホルムアミドに溶解させた溶液を滴下した。0℃で一晩撹拌して反応させた後、クロロホルムで希釈し、純水を加えて反応をクエンチするとともに飽和食塩水で数回洗浄した。有機相の溶媒を留去した後、カラムクロマトグラフィー(移動相は酢酸エチル:ヘキサン=7:3)にて精製し、目的物を得た。
[Synthesis Example 3: Synthesis of bis [4- (2-hydroxyethoxy) phenyl] sulfone dimethacrylate (BHEPS-dMA)]
33.8 g of bis [4- (2-hydroxyethoxy) phenyl] sulfone and 10.1 g of triethylamine were dissolved in 100 mL of dehydrated dimethylformamide and placed in a 1 L separable flask. The inside of the flask was replaced with nitrogen and then cooled to 0 ° C., and a solution prepared by dissolving 10.5 g of methacryloyl chloride in 50 mL of dehydrated dimethylformamide was added dropwise from the dropping funnel attached to the flask. After stirring and reacting overnight at 0 ° C., the mixture was diluted with chloroform, pure water was added to quench the reaction, and the reaction was washed several times with saturated brine. After distilling off the solvent of the organic phase, the product was purified by column chromatography (the mobile phase was ethyl acetate: hexane = 7: 3) to obtain the desired product.
下記表1に示す処方に従い、実施例および比較例の樹脂組成物を作製した。これらの樹脂組成物の相溶性および流動開始温度を以下のようにして測定した。 The resin compositions of Examples and Comparative Examples were prepared according to the formulations shown in Table 1 below. The compatibility and flow start temperature of these resin compositions were measured as follows.
(樹脂組成物の相溶性)
実施例および比較例の樹脂組成物それぞれを観察し、以下の基準で相溶性を評価した。結果を表1に示す。
◎:透明で且つブリード無し
〇:白濁するがブリード無し
△:白濁し、ブリード有り
×:分離が激しく使用不可能
(Compatibility of resin composition)
The resin compositions of Examples and Comparative Examples were observed, and the compatibility was evaluated according to the following criteria. The results are shown in Table 1.
◎: Transparent and no bleed 〇: Cloudy but no bleed △: Cloudy, with bleed ×: Separation is severe and unusable
(樹脂組成物の流動開始温度の測定)
実施例および比較例の樹脂組成物それぞれの流動開始温度を、定試験力押出形細管式レオメータフローテスタCFT(島津製作所社製)にて測定した。測定条件は、50kg負荷、昇温速度3℃/分、ダイ穴径1mm、ダイ厚み1mmである。結果を表1に示す。
(Measurement of flow start temperature of resin composition)
The flow start temperature of each of the resin compositions of Examples and Comparative Examples was measured with a constant test force extrusion type thin tube rheometer flow tester CFT (manufactured by Shimadzu Corporation). The measurement conditions are a load of 50 kg, a heating rate of 3 ° C./min, a die hole diameter of 1 mm, and a die thickness of 1 mm. The results are shown in Table 1.
実施例および比較例の樹脂組成物それぞれを用いてサイズ120~130μm厚のフィルムを作製した。得られたフィルムに、NHVコーポレーション社製EBC-300装置を用いて下記表1に示す条件で電子線を照射することによって、硬化したフィルムを作製した。硬化フィルムの引張強度を、JIS K7161-1に準拠して求めた。結果を表1に示す。 Films having a size of 120 to 130 μm were prepared using the resin compositions of Examples and Comparative Examples, respectively. A cured film was produced by irradiating the obtained film with an electron beam under the conditions shown in Table 1 below using an EBC-300 device manufactured by NHV Corporation. The tensile strength of the cured film was determined according to JIS K7161-1. The results are shown in Table 1.
表1に示すように、ポリエーテルスルホン(PES)のHSPからのHSPの距離が6.5以下であるモノマー1種が混合されている実施例2、3の熱可塑性樹脂組成物は透明かつブリードがなく、PESとモノマーとの相溶性が優れていた。実施例2、3の熱可塑性樹脂組成物は、PESのみの比較例1と比較して、流動開始温度が低下していた。また、実施例2、3の熱可塑性樹脂組成物を用いて作製したフィルムでは、電子線の照射によって、引張強度の回復が見られた。ポリアミド6およびトリアリルイソシアヌレート(TAIC)の二種のモノマーが混合されている実施例1の熱可塑性樹脂組成物でも、同様の結果が得られた。 As shown in Table 1, the thermoplastic resin compositions of Examples 2 and 3 in which one monomer having an HSP distance of 6.5 or less from the HSP of the polyether sulfone (PES) are mixed are transparent and bleed. The compatibility between PES and the monomer was excellent. In the thermoplastic resin compositions of Examples 2 and 3, the flow start temperature was lower than that of Comparative Example 1 containing only PES. Further, in the films prepared using the thermoplastic resin compositions of Examples 2 and 3, the tensile strength was recovered by irradiation with an electron beam. Similar results were obtained with the thermoplastic resin composition of Example 1 in which two types of monomers, polyamide 6 and triallyl isocyanurate (TAIC), were mixed.
PESのHSPからのHSPの距離が6.5を超えるモノマーが混合されている比較例1の熱可塑性樹脂組成物は分離が激しく、その後の使用が不可能であった。同様のモノマーが混合されている比較例2の熱可塑性樹脂組成物は白濁し、ブリードがあった。これらの比較例の熱可塑性樹脂組成物では、流動開始温度はPESより低下していたが、実施例1~3ほど温度は低下しなかった。 The thermoplastic resin composition of Comparative Example 1 in which a monomer having an HSP distance of more than 6.5 from the HSP of PES was mixed was severely separated and could not be used thereafter. The thermoplastic resin composition of Comparative Example 2 in which the same monomer was mixed was cloudy and had bleeding. In the thermoplastic resin compositions of these comparative examples, the flow start temperature was lower than that of PES, but the temperature was not as low as that of Examples 1 to 3.
本発明は、ロケット等の燃料タンクとして用いられる圧力容器の製造に利用できる。 INDUSTRIAL APPLICABILITY The present invention can be used for manufacturing a pressure vessel used as a fuel tank for a rocket or the like.
12 プリプレグ。 12 prepreg.
Claims (10)
(B)電子線照射により重合し得る官能基を少なくとも1個有するモノマー、または
(B’)電子線照射によりラジカルを発生する化合物と、ラジカルと付加反応することができる官能基を分子中に少なくとも1個以上有する化合物との混合物と、
を含み、
成分(A)のハンセン溶解度パラメータ(HSP)からの成分(B)のHSPの距離が6.5以下であり、成分(A):成分(B)または(B’)の質量比が90:10~50:50である熱可塑性樹脂組成物を用いる圧力容器の製造方法であって、
前記熱可塑性樹脂組成物を溶融させ、溶融した熱可塑性樹脂組成物を強化繊維に含浸させてプリプレグを得る工程と、
前記熱可塑性樹脂組成物が溶融した状態で前記プリプレグをライナーの外周に巻回して積層する工程と、
積層したプリプレグに電子線を照射する工程と、
を有することを特徴とする圧力容器の製造方法。 (A) A thermoplastic resin selected from the group consisting of polyethersulfone, polysulfone, and polyarylate, and
(B) A monomer having at least one functional group that can be polymerized by electron beam irradiation, or (B') a compound that generates radicals by electron beam irradiation, and at least a functional group capable of an addition reaction with a radical in the molecule. A mixture with one or more compounds and
Including
The distance of HSP of component (B) from the Hansen solubility parameter (HSP) of component (A) is 6.5 or less, and the mass ratio of component (A): component (B) or (B') is 90:10. A method for producing a pressure vessel using a thermoplastic resin composition of ~ 50: 50.
A step of melting the thermoplastic resin composition and impregnating the reinforcing fibers with the melted thermoplastic resin composition to obtain a prepreg.
A step of winding the prepreg around the outer circumference of the liner and laminating the thermoplastic resin composition in a molten state.
The process of irradiating the laminated prepreg with an electron beam,
A method for manufacturing a pressure vessel.
(B)電子線照射により重合し得る官能基を少なくとも1個有するモノマー、または
(B’)電子線照射によりラジカルを発生する化合物と、ラジカルと付加反応することができる官能基を分子中に少なくとも1個以上有する化合物との混合物と、を含み、
成分(A)のハンセン溶解度パラメータ(HSP)からの成分(B)のHSPの距離が6.5以下であり、成分(A):成分(B)または(B’)の質量比が90:10~50:50であることを特徴とする熱可塑性樹脂組成物。 (A) A thermoplastic resin selected from the group consisting of polyethersulfone, polysulfone, and polyarylate, and
(B) A monomer having at least one functional group that can be polymerized by electron beam irradiation, or (B') a compound that generates radicals by electron beam irradiation, and at least a functional group capable of an addition reaction with a radical in the molecule. Containing a mixture with one or more compounds
The distance of HSP of component (B) from the Hansen solubility parameter (HSP) of component (A) is 6.5 or less, and the mass ratio of component (A): component (B) or (B') is 90:10. A thermoplastic resin composition characterized by being ~ 50:50.
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