JP6866713B2 - Composite material molding method and molded product - Google Patents
Composite material molding method and molded product Download PDFInfo
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Description
本発明は、複合材料の成形方法および成形品に関する。 The present invention relates to a method for molding a composite material and a molded product.
炭素繊維及び炭素繊維複合材料は、引張強度・引張弾性率が高く、耐熱性、耐薬品性、疲労特性、耐摩耗性に優れる、線膨張係数が小さく寸法安定性に優れる、電磁波シールド性、Ｘ線透過性に富むなどの優れた特長を有していることから、スポーツ・レジャー、航空・宇宙、一般産業用途に幅広く適用されている。従来は、エポキシ樹脂などの熱硬化性樹脂を複合材料のマトリックスとすることが多かったが、最近、リサイクル性・高速成型性の観点から熱可塑性樹脂が注目されている。 Carbon fibers and carbon fiber composite materials have high tensile strength and tensile elastic modulus, are excellent in heat resistance, chemical resistance, fatigue characteristics, and abrasion resistance, have a small linear expansion coefficient and are excellent in dimensional stability, electromagnetic wave shielding property, X. Since it has excellent features such as high line transparency, it is widely applied to sports / leisure, aerospace, and general industrial applications. Conventionally, thermosetting resins such as epoxy resins have often been used as a matrix of composite materials, but recently, thermoplastic resins have been attracting attention from the viewpoint of recyclability and high-speed moldability.
特許文献１〜３には、熱可塑性樹脂と炭素繊維からなる複合材料が開示されている。
特許文献１では、ポリプロピレンと炭素繊維からなる複合材料が開示されており、流動成形性の評価として、２３０℃で複合材料を予熱したスタンピング成形を行なっている。一般的にポリプロピレンのガラス転移温度は０℃、融点は１８０℃と言われており、融点以上の温度へ予熱した後に成形されている。
また特許文献２では、６ナイロンと炭素繊維からなる複合材料が開示されており、２８０℃で複合材料を予熱したスタンピング成形を行なっている。一般的に６ナイロンのガラス転移温度は５０℃、融点は２２５℃と言われており、融点以上の温度へ予熱した後に成形されている。
特許文献３では、ポリカーボネートと炭素繊維を含む炭素長繊維含有樹脂材料が開示されており、シリンダー温度３００℃で可塑化して射出成形を行なっている。一般的にポリカーボネートのガラス転移温度は１４５℃と言われており、ガラス転移温度より１５０℃以上高温で可塑化した後に成形されている。
Patent Documents 1 to 3 disclose a composite material composed of a thermoplastic resin and carbon fibers.
Patent Document 1 discloses a composite material composed of polypropylene and carbon fiber, and stamping molding is performed by preheating the composite material at 230 ° C. as an evaluation of flow moldability. It is generally said that polypropylene has a glass transition temperature of 0 ° C. and a melting point of 180 ° C., and is molded after being preheated to a temperature equal to or higher than the melting point.
Further, Patent Document 2 discloses a composite material composed of 6 nylon and carbon fiber, and stamping molding is performed by preheating the composite material at 280 ° C. It is generally said that 6 nylon has a glass transition temperature of 50 ° C. and a melting point of 225 ° C., and is molded after being preheated to a temperature equal to or higher than the melting point.
Patent Document 3 discloses a carbon filament-containing resin material containing polycarbonate and carbon fibers, which is plasticized at a cylinder temperature of 300 ° C. to perform injection molding. Generally, the glass transition temperature of polycarbonate is said to be 145 ° C., and the polycarbonate is molded after being plasticized at a temperature higher than the glass transition temperature by 150 ° C. or higher.
このように、熱可塑性樹脂と炭素繊維を含む複合材料を成形する場合に、ガラス転移温度より１５０℃以上高温への予熱や、融点以上への予熱の後に成形する事は一般的であり、広く実施されている。
しかしながらこれらの方法では、高温まで予熱するため、熱可塑性樹脂が熱劣化する恐れや、著しく軟化する事で取扱いが困難になる恐れがあった。
In this way, when molding a composite material containing a thermoplastic resin and carbon fibers, it is common and widely molded after preheating to a temperature higher than the glass transition temperature of 150 ° C. or higher or to a temperature higher than the melting point. It has been implemented.
However, in these methods, since the thermoplastic resin is preheated to a high temperature, there is a risk that the thermoplastic resin is thermally deteriorated and that the thermoplastic resin is remarkably softened, which makes it difficult to handle.
また炭素繊維複合材料は、従来板金などの金属を使っていた部品を代替するために、例えば２．５ｍｍ以下の薄肉での活用が検討される場合がある。
特許文献１の実施例では、厚さ４ｍｍの複合材料を融点以上に予熱した後に金型内に運搬してプレス成形しているが、流動させるためには高いプレス圧力が必要であり、例えば１０００ｃｍ２以上といった大きな投影面積で、薄肉まで流動させる事は困難となる場合がある。
特許文献２の実施例１では、厚さ１．１ｍｍの複合材料を予熱した後に金型内に運搬してプレス成形しているが、融点以上の高温では複合材料が十分に軟化すると考えられるため、運搬が困難になる場合がある。
特許文献３の実施例では、ガラス転移温度より１５０℃以上の高温で可塑化した後に金型内に射出成形しているが、例えば１０００ｃｍ２以上といった大きな投影面積で、薄肉成形品を射出成形する場合には、高い型締め圧が必要となり、困難となる場合がある。
Further, the carbon fiber composite material may be considered for use in a thin wall of, for example, 2.5 mm or less in order to replace parts that have conventionally used a metal such as sheet metal.
In the embodiment of Patent Document 1, a composite material having a thickness of 4 mm is preheated to a melting point or higher and then transported into a mold for press molding. However, a high press pressure is required for the flow, for example, 1000 cm. With a large projected area of 2 or more, it may be difficult to flow even a thin wall.
In Example 1 of Patent Document 2, a composite material having a thickness of 1.1 mm is preheated and then transported into a mold for press molding. However, it is considered that the composite material is sufficiently softened at a high temperature equal to or higher than the melting point. , May be difficult to transport.
In the example of Patent Document 3, after plasticizing at a high temperature of 150 ° C. or higher than the glass transition temperature, injection molding is performed in the mold, but a thin-walled molded product is injection-molded in a large projected area such as 1000 cm 2 or more. In some cases, a high mold clamping pressure is required, which may be difficult.
このような状況から、熱可塑性樹脂と炭素繊維を含む複合材料の成形方法として、より薄肉に対応し易い方法が求められていた。 Under these circumstances, as a method for molding a composite material containing a thermoplastic resin and carbon fibers, a method that is easier to handle with a thinner wall has been required.
本発明は、熱可塑性樹脂と炭素繊維を含む複合材料から、熱劣化の恐れが少なく、かつ薄肉の成形品を得やすい成形方法を提供する。 The present invention provides a molding method from a composite material containing a thermoplastic resin and carbon fibers, which has less risk of thermal deterioration and makes it easy to obtain a thin-walled molded product.
本発明者らは、特定の温度範囲で塑性加工する事で、薄肉でも成形し易い事を見出し、また特定の組成で特に成形し易い事を見出し、本発明を完成するに至った。即ち本発明の要旨は、以下の［１］〜［７］に存する。
〔１〕 熱可塑性樹脂（Ａ）と炭素繊維（Ｂ）を含む複合材料を、ガラス転移点（Ｔｇ）以上、Ｔｇ＋１２０℃以下の温度で塑性加工する成形方法。
〔２〕 前記塑性樹脂（Ａ）が、晶性樹脂（Ａ−１）を含む複合材料を融点以下の温度で塑性加工したものである上記〔１〕記載の成形方法。
〔３〕 熱可塑性樹脂（Ａ）の５０％以上が非晶性樹脂（Ａ−２）である複合材料を塑性加工する、上記〔１〕または〔２〕に記載の成形方法。
〔４〕 塑性加工が、絞り加工または曲げ加工の何れかである上記〔１〕〜〔３〕のいずれかに記載の成形方法。
〔５〕 塑性加工した後に、ガラス転移点以下の温度で金型から取り出す、上記〔１〕〜〔４〕のいずれかに記載の成形方法。
〔６〕 複合材料の厚さが、０．４ｍｍ以上２．５ｍｍ以下である、上記〔１〕〜〔５〕のいずれかに記載の成形方法。
〔７〕 上記〔１〕〜〔６〕のいずれかに成形方法によって得られた成形品。
The present inventors have found that it is easy to mold even a thin wall by plastic working in a specific temperature range, and that it is particularly easy to mold with a specific composition, and have completed the present invention. That is, the gist of the present invention lies in the following [1] to [7].
[1] A molding method for plastic working a composite material containing a thermoplastic resin (A) and carbon fibers (B) at a temperature of Tg + 120 ° C. or higher at a glass transition point (Tg) or higher.
[2] The molding method according to the above [1], wherein the plastic resin (A) is a composite material containing a crystalline resin (A-1) plastically processed at a temperature equal to or lower than the melting point.
[3] The molding method according to the above [1] or [2], wherein a composite material in which 50% or more of the thermoplastic resin (A) is an amorphous resin (A-2) is plastically processed.
[4] The molding method according to any one of the above [1] to [3], wherein the plastic working is either drawing or bending.
[5] The molding method according to any one of [1] to [4] above, wherein after plastic working, the product is taken out from the mold at a temperature equal to or lower than the glass transition point.
[6] The molding method according to any one of [1] to [5] above, wherein the thickness of the composite material is 0.4 mm or more and 2.5 mm or less.
[7] A molded product obtained by the molding method according to any one of the above [1] to [6].
本発明により、熱可塑性樹脂と炭素繊維を含む複合材料から、熱劣化の恐れが少なく、かつ薄肉の成形品を得やすい成形方法を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a molding method from a composite material containing a thermoplastic resin and carbon fibers, which has less risk of thermal deterioration and makes it easy to obtain a thin-walled molded product.
（熱可塑性樹脂（Ａ））
本発明で用いられる複合材料は、熱可塑性樹脂（Ａ）を含む。樹脂成分の主成分が熱可塑性樹脂（Ａ）であり、樹脂成分の９５％以上が熱可塑性樹脂（Ａ）である事が好ましく、樹脂成分が熱可塑性樹脂（Ａ）からなる事がさらに好ましい。熱可塑性である事で、本発明の成形方法で成形し易い。
熱可塑性樹脂（Ａ）としては、例えば、ポリプロピレン、６ナイロン、６６ナイロン、６１０ナイロン、６１２ナイロン、１２ナイロン、ＭＸＤ６ナイロン、ＸＤ１０ナイロン、９Ｔナイロン、１０Ｔナイロン、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリフェニレンサルファイド等の結晶性樹脂；ポリカーボネート、ＡＢＳ、アクリル等の非晶性樹脂等が挙げられる。これらの熱可塑性樹脂（Ａ）は、１種を単独で用いてもよく、２種以上を併用してもよい。
複合材料中の熱可塑性樹脂（Ａ）の含有率は、複合材料１００質量％中、３０質量％以上８０質量％以下が好ましく、４０質量％以上７０質量％以下がより好ましく、５０質量％以上６５質量％以下が更に好ましい。
複合材料中の熱可塑性樹脂（Ａ）の含有率が３０質量％以上であると、複合材料の成形性に優れる。また、熱可塑性樹脂組成物中の熱可塑性樹脂（Ａ）の含有率が８０質量％以下であると、炭素繊維（Ｂ）を十分配合できるため、成形品の機械特性に優れる。
(Thermoplastic resin (A))
The composite material used in the present invention contains a thermoplastic resin (A). The main component of the resin component is the thermoplastic resin (A), 95% or more of the resin component is preferably the thermoplastic resin (A), and the resin component is more preferably composed of the thermoplastic resin (A). Since it is thermoplastic, it is easy to mold by the molding method of the present invention.
Examples of the thermoplastic resin (A) include polypropylene, 6 nylon, 66 nylon, 610 nylon, 612 nylon, 12 nylon, MXD6 nylon, XD10 nylon, 9T nylon, 10T nylon, polybutylene terephthalate, polyethylene terephthalate, and polyphenylene sulfide. Crystalline resin; Examples thereof include amorphous resins such as polycarbonate, ABS, and acrylic. One of these thermoplastic resins (A) may be used alone, or two or more thereof may be used in combination.
The content of the thermoplastic resin (A) in the composite material is preferably 30% by mass or more and 80% by mass or less, more preferably 40% by mass or more and 70% by mass or less, and 50% by mass or more and 65% by mass or more, based on 100% by mass of the composite material. More preferably, it is by mass or less.
When the content of the thermoplastic resin (A) in the composite material is 30% by mass or more, the moldability of the composite material is excellent. Further, when the content of the thermoplastic resin (A) in the thermoplastic resin composition is 80% by mass or less, the carbon fibers (B) can be sufficiently blended, so that the mechanical properties of the molded product are excellent.
（結晶性樹脂（Ａ−１））
熱可塑性樹脂（Ａ）は、結晶性樹脂（Ａ−１）を含むことが好ましい。
結晶性樹脂（Ａ−１）としては、ポリプロピレン、６ナイロン、６６ナイロン、６１０ナイロン、６１２ナイロン、１２ナイロン、ＭＸＤ６ナイロン、ＸＤ１０ナイロン、９Ｔナイロン、１０Ｔナイロン、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリフェニレンサルファイド等が挙げられる。耐熱性、成形性のバランスから、６ナイロン、６６ナイロン、６１０ナイロン、６１２ナイロン、１２ナイロン、ＭＸＤ６ナイロン、ポリブチレンテレフタレート、ポリエチレンテレフタレート、が好ましく、吸湿による物性低下が少なく比較的安価な事から、ポリブチレンテレフタレート、ポリエチレンテレフタレートが好ましい。
熱可塑性樹脂（Ａ）中の結晶性樹脂（Ａ−１）の配合量は、５０％以下が好ましく、５％以上４０％以下がさらに好ましく、１５％以上３０％以下が最も好ましい。
結晶性樹脂（Ａ−１）を含むことで、ガラス転移点以上であっても、べたつきが少なく、ハンドリングし易い。
(Crystalline resin (A-1))
The thermoplastic resin (A) preferably contains a crystalline resin (A-1).
Examples of the crystalline resin (A-1) include polypropylene, 6 nylon, 66 nylon, 610 nylon, 612 nylon, 12 nylon, MXD6 nylon, XD10 nylon, 9T nylon, 10T nylon, polybutylene terephthalate, polyethylene terephthalate, and polyphenylene sulfide. Can be mentioned. From the balance of heat resistance and moldability, 6 nylon, 66 nylon, 610 nylon, 612 nylon, 12 nylon, MXD6 nylon, polybutylene terephthalate, and polyethylene terephthalate are preferable. Polybutylene terephthalate and polyethylene terephthalate are preferable.
The blending amount of the crystalline resin (A-1) in the thermoplastic resin (A) is preferably 50% or less, more preferably 5% or more and 40% or less, and most preferably 15% or more and 30% or less.
By containing the crystalline resin (A-1), even if it is above the glass transition point, there is little stickiness and it is easy to handle.
（非晶性樹脂（Ａ−２））
熱可塑性樹脂（Ａ）は、非晶性樹脂（Ａ−２）を含むことが好ましい。
非晶性樹脂（Ａ−２）としては、ポリカーボネート、ＡＢＳ、アクリル、ポリスチレン、ポリフェニレンエーテル等が挙げられる。ガラス転移温度が高く耐熱性が高い点から、ポリカーボネートが好ましい。
非晶性樹脂（Ａ−２）は、熱可塑性樹脂（Ａ）の５０％以上である事が好ましい。さらに好ましくは６０％以上９５％以下であり、もっとも好ましくは７０％以上８５％以下である。非晶性樹脂（Ａ−２）がこの範囲であると、塑性加工し易い。
また熱可塑性樹脂（Ａ）は、成形性に優れる事から、結晶性樹脂（Ａ−１）と非晶性樹脂（Ａ−２）を含むポリマーアロイが好ましい。また、成形性と機械特性のバランスに優れる事から、ポリカーボネート／ポリブチレンテレフタレートアロイ、ポリカーボネート／ポリエチレンテレフタレートアロイがさらに好ましい。
(Amorphous resin (A-2))
The thermoplastic resin (A) preferably contains an amorphous resin (A-2).
Examples of the amorphous resin (A-2) include polycarbonate, ABS, acrylic, polystyrene, polyphenylene ether and the like. Polycarbonate is preferable because it has a high glass transition temperature and high heat resistance.
The amorphous resin (A-2) is preferably 50% or more of the thermoplastic resin (A). More preferably, it is 60% or more and 95% or less, and most preferably 70% or more and 85% or less. When the amorphous resin (A-2) is in this range, plastic working is easy.
Further, the thermoplastic resin (A) is preferably a polymer alloy containing a crystalline resin (A-1) and an amorphous resin (A-2) because it is excellent in moldability. Further, polycarbonate / polybutylene terephthalate alloy and polycarbonate / polyethylene terephthalate alloy are more preferable because they have an excellent balance between moldability and mechanical properties.
（炭素繊維（Ｂ））
本発明に用いられる複合材料は、炭素繊維（Ｂ）を含む。炭素繊維としては、ＰＡＮ系炭素繊維や、ピッチ系炭素繊維が挙げられるが、ＰＡＮ系炭素繊維が好ましい。
ここでＰＡＮ系炭素繊維とは、「アクリロニトリルを主成分として重合させたポリアクリルニトリル系樹脂からなる繊維を、不融化させて、さらに炭化させて生成した実質的に炭素のみからなるフィラメント繊維」を主たる成分として構成される繊維の集合体であることを意味する。ＰＡＮ系炭素繊維は、低密度及び高比強度といった利点がある。
ＰＡＮ系炭素繊維を構成するフィラメント繊維の最大フェレ径をＰＡＮ系炭素繊維の直径とした場合、ＰＡＮ系炭素繊維の直径は１μｍ以上２０μｍ以下が好ましく、４μｍ以上１５μｍ以下がさらに好ましく、特に好ましくは５μｍ以上８μｍ以下である。
ＰＡＮ系炭素繊維は、長繊維、チョップドファイバー、ミルドファイバーを用いる事ができるが、所望の機械特性や加工性を得るために、質量平均長さを制御する観点から、長繊維や、チョップドファイバーが好ましい。
以上のような性質を有するＰＡＮ系炭素繊維として好適に用いられている市販品としては、パイロフィル（登録商標）チョップドファイバー ＴＲ０６Ｕ、ＴＲ０６ＵＬ，ＴＲ０６ＮＥ、ＴＲ０６ＮＬ、ＭＲ０６ＮＥ、ＭＲ０３ＮＥ、長繊維 ＴＲ５０Ｓ １５Ｌ、ＴＲＨ５０ １８Ｍ、ＴＲＨ５０ ６０Ｍ、ＴＲＷ４０ ５０Ｌ、ＭＲ６０Ｈ ２４Ｐ、ＨＲ４０ １２Ｍ（以上、商品名、三菱レイヨン社製）などが挙げられる。
複合材料中の炭素繊維（Ｂ）の含有率は、複合材料１００質量％中、２０質量％以上７０質量％以下が好ましく、３０質量％以上６０質量％以下がより好ましく、３５質量％以上５０質量％以下が更に好ましい。
複合材料中の炭素繊維（Ｂ）の含有率が２０質量％以上であると、成形品の機械特性に優れる。また、熱可塑性樹脂組成物中の炭素繊維（Ｂ）の含有率が７０質量％以下であると、熱可塑性樹脂（Ａ）を十分配合できるため、成形性に優れる。
複合材料中の炭素繊維（Ｂ）の質量平均繊維長に特に制限は無いが、機械特性の観点から０．１ｍｍ以上が好ましく、１０ｍｍ以上がさらに好ましい。また成形性の観点から、５０ｍｍ以下が好ましく。３０ｍｍ以下がさらに好ましい。
(Carbon fiber (B))
The composite material used in the present invention contains carbon fiber (B). Examples of the carbon fiber include PAN-based carbon fiber and pitch-based carbon fiber, but PAN-based carbon fiber is preferable.
Here, the PAN-based carbon fiber is a "filament fiber made of substantially only carbon produced by insolubilizing and further carbonizing a fiber made of a polyacrylonitrile-based resin polymerized with acrylonitrile as a main component". It means that it is an aggregate of fibers composed as a main component. PAN-based carbon fibers have advantages such as low density and high specific strength.
When the maximum ferret diameter of the filament fiber constituting the PAN-based carbon fiber is the diameter of the PAN-based carbon fiber, the diameter of the PAN-based carbon fiber is preferably 1 μm or more and 20 μm or less, more preferably 4 μm or more and 15 μm or less, and particularly preferably 5 μm. It is 8 μm or less.
Long fibers, chopped fibers, and milled fibers can be used as the PAN-based carbon fibers, but long fibers and chopped fibers are used from the viewpoint of controlling the mass average length in order to obtain desired mechanical properties and workability. preferable.
Commercially available products preferably used as PAN-based carbon fibers having the above properties include Pyrofil (registered trademark) chopped fibers TR06U, TR06UL, TR06NE, TR06NL, MR06NE, MR03NE, long fibers TR50S 15L, TRH50 18M, Examples thereof include TRH50 60M, TRW40 50L, MR60H 24P, and HR40 12M (above, trade name, manufactured by Mitsubishi Rayon Co., Ltd.).
The content of carbon fiber (B) in the composite material is preferably 20% by mass or more and 70% by mass or less, more preferably 30% by mass or more and 60% by mass or less, and 35% by mass or more and 50% by mass in 100% by mass of the composite material. % Or less is more preferable.
When the content of the carbon fiber (B) in the composite material is 20% by mass or more, the mechanical properties of the molded product are excellent. Further, when the content of the carbon fibers (B) in the thermoplastic resin composition is 70% by mass or less, the thermoplastic resin (A) can be sufficiently blended, so that the moldability is excellent.
The mass average fiber length of the carbon fiber (B) in the composite material is not particularly limited, but is preferably 0.1 mm or more, and more preferably 10 mm or more from the viewpoint of mechanical properties. Further, from the viewpoint of moldability, 50 mm or less is preferable. 30 mm or less is more preferable.
（複合材料）
本発明に用いられる複合材料は、熱可塑性樹脂（Ａ）と炭素繊維（Ｂ）以外に、必要に応じて他の添加剤を含んでも良い。他の添加剤としては、例えば、着色剤、酸化防止剤、金属不活性材、カーボンブラック、造核剤、離型剤、滑剤、帯電防止剤、光安定剤、紫外線吸収剤、ガラス繊維、無機フィラー、耐衝撃性改質剤、溶融張力向上剤、難燃剤、可塑剤等が挙げられる。これらの他の添加剤は、１種を単独で用いても良く、２種以上を併用しても良い。
複合材料中の他の添加剤の含有率は、複合材料や成形品の本来の性能を損なわないことから、複合材料１００質量％中、０質量％以上１０質量％以下が好ましく、０質量％以上５質量％以下がより好ましく、０質量％以上３質量％以下が更に好ましい。
複合材料の厚さは、０．４ｍｍ以上２．５ｍｍ以下が好ましく、０．５ｍｍ以上１．７ｍｍ以下がさらに好ましい。０．４ｍｍ以上である事で、複合材料の優れた機械特性を活かす事ができる。また、２．５ｍｍ以下であれば、より薄肉軽量な成形品を得る事ができる。
複合材料の製造方法に特に制限はないが、熱可塑性樹脂（Ａ）と炭素繊維（Ｂ）からなるプリプレグを積層する方法や、熱可塑性樹脂（Ａ）と炭素繊維（Ｂ）からなるペレットを射出成形する方法、熱可塑性樹脂（Ａ）と炭素繊維（Ｂ）からなるペレットを押出成形する方法等が挙げられる。ペレットを用いる場合に、より大きな面積の複合材料を効率的に得るためには、押出成形が好ましい。
(Composite material)
The composite material used in the present invention may contain other additives, if necessary, in addition to the thermoplastic resin (A) and the carbon fiber (B). Other additives include, for example, colorants, antioxidants, metal inerts, carbon black, nucleating agents, mold release agents, lubricants, antistatic agents, light stabilizers, UV absorbers, glass fiber, inorganics. Examples thereof include fillers, impact resistance modifiers, melt tension improvers, flame retardants, and plasticizers. These other additives may be used alone or in combination of two or more.
The content of other additives in the composite material is preferably 0% by mass or more and 10% by mass or less, preferably 0% by mass or more, in 100% by mass of the composite material, because the original performance of the composite material or the molded product is not impaired. 5% by mass or less is more preferable, and 0% by mass or more and 3% by mass or less is further preferable.
The thickness of the composite material is preferably 0.4 mm or more and 2.5 mm or less, and more preferably 0.5 mm or more and 1.7 mm or less. When it is 0.4 mm or more, the excellent mechanical properties of the composite material can be utilized. Further, if it is 2.5 mm or less, a thinner and lighter molded product can be obtained.
The method for producing the composite material is not particularly limited, but a method of laminating a prepreg composed of a thermoplastic resin (A) and a carbon fiber (B) or an injection of pellets composed of a thermoplastic resin (A) and a carbon fiber (B). Examples thereof include a molding method, a method of extrusion molding pellets composed of a thermoplastic resin (A) and a carbon fiber (B), and the like. When pellets are used, extrusion molding is preferred in order to efficiently obtain a composite material with a larger area.
（塑性加工）
本発明の成形方法は、塑性加工である。
ここで塑性加工とは、延伸、鍛造、絞り、曲げ加工であり、これらを組み合わせた方法も含む。好ましくは、曲げ加工、絞り加工であり、さらに好ましくは曲げ加工である。
本発明の塑性加工では、曲げ加工機等の従来板金加工で用いられている加工機を用いる事が可能であるが、より複雑な成形品を効率的に生産する観点から、金型を用いたプレス加工が好ましい。
金型を用いる場合、複合材料をＴｇ以上Ｔｇ＋１２０℃以下の温度に予熱した後に、金型内に運搬し、金型を閉じる事で所望の塑性加工を行う方法が好ましい。金型の温度に特に制限はないが、高い生産性を求める場合には、Ｔｇ以下の温度が好ましい。また、少量の加工であれば、Ｔｇ以上の温度の金型を用いて塑性加工した後に、金型をＴｇ以下に冷やしてから取り出す方法が容易である。
(Plastic working)
The molding method of the present invention is plastic working.
Here, the plastic working is drawing, forging, drawing, and bending, and includes a method combining these. Bending processing and drawing processing are preferable, and bending processing is more preferable.
In the plastic working of the present invention, it is possible to use a processing machine such as a bending machine which is conventionally used for sheet metal processing, but from the viewpoint of efficiently producing a more complicated molded product, a mold is used. Press working is preferred.
When a die is used, a method is preferable in which the composite material is preheated to a temperature of Tg or more and Tg + 120 ° C. or less, then transported into the die, and the desired plastic working is performed by closing the die. The temperature of the mold is not particularly limited, but when high productivity is required, a temperature of Tg or less is preferable. Further, in the case of a small amount of processing, it is easy to perform plastic working using a mold having a temperature of Tg or higher, cool the mold to Tg or lower, and then take out the mold.
（加工温度）
本発明の成形方法では、ガラス転移点（Ｔｇ）以上、Ｔｇ＋１２０℃以下で塑性加工する。Ｔｇ＋２０℃以上が好ましく、Ｔｇ＋３０℃以上がさらに好ましい。また、Ｔｇ＋８０℃以下が好ましく、Ｔｇ＋７０℃以下がさらに好ましい。
また、熱可塑性樹脂（Ａ）が結晶性樹脂（Ａ−１）を含む場合には、融点（Ｔｍ）以下が好ましく、Ｔｍ−４０℃以下がさらに好ましい。
この範囲では、より加工性に優れる。
ここでガラス転移点（Ｔｇ）、融点（Ｔｍ）は、複合材料の一部を切出し、示差走査熱量計（ＤＳＣ）により、１０℃／分の速度で昇温しながら測定した値である。
本発明の成形方法で金型を用いる場合、Ｔｇ以上であっても、Ｔｇに近い温度であれば変形が少なく金型から取り出す事が可能であるが、安定した成形のためには、成形品の表面の温度がＴｇ以下になってから金型から取り出す事が好ましい。Ｔｇ以上で取出した場合には、金型から取り出した後に変形が生じ、所望の寸法精度が得られない場合がある。取り出し時の金型の温度は、Ｔｇ以下が好ましく、Ｔｇ−５℃以下がさらに好ましい。
(Processing temperature)
In the molding method of the present invention, plastic working is performed at a glass transition point (Tg) or higher and Tg + 120 ° C. or lower. Tg + 20 ° C. or higher is preferable, and Tg + 30 ° C. or higher is even more preferable. Further, Tg + 80 ° C. or lower is preferable, and Tg + 70 ° C. or lower is more preferable.
When the thermoplastic resin (A) contains a crystalline resin (A-1), the melting point (Tm) or lower is preferable, and Tm-40 ° C. or lower is even more preferable.
In this range, the workability is more excellent.
Here, the glass transition point (Tg) and the melting point (Tm) are values measured by cutting out a part of the composite material and raising the temperature with a differential scanning calorimeter (DSC) at a rate of 10 ° C./min.
When a mold is used in the molding method of the present invention, even if it is Tg or more, it can be taken out from the mold with little deformation if the temperature is close to Tg. It is preferable to remove the product from the mold after the temperature of the surface of the product becomes Tg or less. If it is taken out at Tg or more, deformation may occur after it is taken out from the mold, and the desired dimensional accuracy may not be obtained. The temperature of the mold at the time of taking out is preferably Tg or less, and more preferably Tg-5 ° C. or less.
（成形品）
本発明の成形品は、複合材料を塑性加工する事によって得られるが、その５０％以上の面積において、複合材料の厚さの９０％以上の厚さが好ましく、複合材料の厚さと等しい事が好ましい。本発明の成形方法では、厚さの変化を伴う加工も可能であるが、より高い加圧力が必要となるため、加工費用が高くなる恐れがある。
成形品の平均厚さは、０．４ｍｍ以上２ｍｍ以下が好ましく、０．５ｍｍ以上１．７ｍｍ以下がさらに好ましい。
(Molding)
The molded product of the present invention is obtained by plastic working a composite material, and in an area of 50% or more thereof, a thickness of 90% or more of the thickness of the composite material is preferable, and it is equal to the thickness of the composite material. preferable. In the molding method of the present invention, processing accompanied by a change in thickness is possible, but since a higher pressing force is required, the processing cost may increase.
The average thickness of the molded product is preferably 0.4 mm or more and 2 mm or less, and more preferably 0.5 mm or more and 1.7 mm or less.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
（ガラス転移点、融点の測定）
複合材料をニッパーで切断し、約１０ｍｇをアルミニウム容器に精秤し、示差走査熱量計（機種名「ＤＳＣ７０２０」、ＳＩＩ社製）を用いて測定した。２８０℃に加熱した後に−４０℃まで急冷し、その後に−４０℃から２８０℃まで１０℃／分の昇温条件で測定する事で、ガラス転移点、融点を測定した。
(Measurement of glass transition point and melting point)
The composite material was cut with nippers, about 10 mg was precisely weighed in an aluminum container, and measured using a differential scanning calorimeter (model name "DSC7020", manufactured by SII). The glass transition point and melting point were measured by heating to 280 ° C., rapidly cooling to −40 ° C., and then measuring from −40 ° C. to 280 ° C. under a temperature rising condition of 10 ° C./min.
（取扱い性）
ステンレス板上で加工温度となった複合材料を軍手で運ぶ際の取扱い性を、以下の基準で評価した。
○：容易に運ぶ事ができる。
△：表面がざらつき、やや運び難い。
×：軟らかすぎて運び難い。
(Handling)
The handleability when transporting a composite material that has reached the processing temperature on a stainless steel plate by work gloves was evaluated according to the following criteria.
◯: Can be easily carried.
Δ: The surface is rough and it is a little difficult to carry.
×: It is too soft to carry.
（加工性）
加工性を以下の基準で評価した。
○：成形品に割れやヒビ等が無く良好である。
△：成形品にヒビが発生するが、割れない。
×：成形品が割れる。
(Workability)
The workability was evaluated according to the following criteria.
◯: The molded product is good with no cracks or cracks.
Δ: The molded product is cracked but does not crack.
X: The molded product cracks.
（外観）
成形品外観を以下の基準で評価した。
○：形状や表面外観に異常が無く、良好。
△：概略形状は良好だが、表面に凹凸が発生。
×：形状不良。
(appearance)
The appearance of the molded product was evaluated according to the following criteria.
◯: Good with no abnormality in shape or surface appearance.
Δ: The approximate shape is good, but the surface is uneven.
X: Poor shape.
（原料）
熱可塑性ポリエステル樹脂（Ａ−１）：ポリブチレンテレフタレート樹脂（商品名「ノバデュラン５００８」、三菱エンジニアリングプラスチック（株）製）
ポリカーボネート樹脂（Ａ−２−１）：ポリカーボネート樹脂（商品名「ユーピロンＨ−４０００」、三菱エンジニアリングプラスチック（株）製）
ポリカーボネート樹脂（Ａ−２−２）：ポリカーボネート樹脂（商品名「ノバレックス７０２０ＩＲ」、三菱エンジニアリングプラスチック（株）製）
炭素繊維（Ｂ−１）：ＰＡＮ系炭素繊維（商品名「パイロフィル ＴＲ５０Ｓ」、三菱レイヨン（株）製）
炭素繊維（Ｂ−２）：ＰＡＮ系炭素繊維（商品名「パイロフィル ＴＲ０６ＵＬ」、三菱レイヨン（株）製、繊維長６ｍｍ、チョップドファイバー）
耐衝撃性改良剤：シリコーン−アクリル複合ゴム系耐衝撃性改良剤（商品名「メタブレン Ｓ−２００６」、三菱レイヨン（株）製）
(material)
Thermoplastic polyester resin (A-1): Polybutylene terephthalate resin (trade name "Novaduran 5008", manufactured by Mitsubishi Engineering Plastics Co., Ltd.)
Polycarbonate resin (A-2-1): Polycarbonate resin (trade name "Iupilon H-4000", manufactured by Mitsubishi Engineering Plastics Co., Ltd.)
Polycarbonate resin (A-2-2): Polycarbonate resin (trade name "Novalex 7020IR", manufactured by Mitsubishi Engineering Plastics Co., Ltd.)
Carbon fiber (B-1): PAN-based carbon fiber (trade name "Pyrofil TR50S", manufactured by Mitsubishi Rayon Co., Ltd.)
Carbon fiber (B-2): PAN-based carbon fiber (trade name "Pyrofil TR06UL", manufactured by Mitsubishi Rayon Co., Ltd., fiber length 6 mm, chopped fiber)
Impact resistance improver: Silicone-acrylic composite rubber type impact resistance improver (trade name "Metabren S-2006", manufactured by Mitsubishi Rayon Co., Ltd.)
（参考例１）０．５ｍｍ厚の複合材料（Ｘ−１）の製造
ポリカーボネート樹脂（Ａ−２−１）８０質量部、熱可塑性ポリエステル樹脂（Ａ−１）２０質量部、耐衝撃性改良剤 ５質量部、安定剤 ０．９質量部を二軸押出機で混練してＰＣ／ＰＢＴアロイのペレットを得た。
(Reference Example 1) Manufacture of 0.5 mm-thick composite material (X-1) 80 parts by mass of polycarbonate resin (A-2-1), 20 parts by mass of thermoplastic polyester resin (A-1), impact resistance improver 5 parts by mass and 0.9 parts by mass of the stabilizer were kneaded with a twin-screw extruder to obtain pellets of PC / PBT alloy.
このペレットと炭素繊維（Ｂ−１）を特許文献１記載の方法に従って複合化し、炭素繊維を４４％含む、厚さ０．５ｍｍの複合材料（Ｘ−１）を得た。ガラス転移点 ９７℃、融点 ２１０℃であった。 The pellet and carbon fiber (B-1) were composited according to the method described in Patent Document 1 to obtain a composite material (X-1) having a thickness of 0.5 mm and containing 44% of carbon fiber. The glass transition point was 97 ° C. and the melting point was 210 ° C.
（参考例２）０．６ｍｍ厚の複合材料（Ｘ−２）の製造
ポリカーボネート樹脂（Ａ−２−２）７６質量部、熱可塑性ポリエステル樹脂（Ａ−１）１９質量部、耐衝撃性改良剤 ５質量部、安定剤 ０．４質量部を二軸押出機のメインフィーダーから供給し、炭素繊維（Ｂ−２）６７質量部をサイドフィーダーから供給し、ダイスから出たストランドを水冷した後にストランドカッターでカットし、ペレット状の熱可塑性樹脂組成物（Ｙ）を得た。
ここで得られた熱可塑性樹脂組成物（Ｙ）を、シリンダー温度２７０℃、金型温度１００℃で射出成形した後に、２枚のステンレス板に挟んで、２７０℃に設定したプレス成形機で厚さ０．６ｍｍになるように圧縮し、その後８０℃に設定したプレス成形機で冷却した後にステンレス板の間から取り出して、炭素繊維を４０％含む、厚さ０．６ｍｍの複合材料（Ｘ−２）を得た。ガラス転移点 １０４℃、融点 ２１０℃であった。
(Reference Example 2) Manufacture of 0.6 mm-thick composite material (X-2) 76 parts by mass of polycarbonate resin (A-2-2), 19 parts by mass of thermoplastic polyester resin (A-1), impact resistance improver 5 parts by mass and 0.4 parts by mass of stabilizer are supplied from the main feeder of the twin-screw extruder, 67 parts by mass of carbon fiber (B-2) is supplied from the side feeder, and the strands from the die are water-cooled and then strands. It was cut with a cutter to obtain a pellet-shaped thermoplastic resin composition (Y).
The thermoplastic resin composition (Y) obtained here was injection-molded at a cylinder temperature of 270 ° C. and a mold temperature of 100 ° C., sandwiched between two stainless steel plates, and thickened by a press molding machine set at 270 ° C. A 0.6 mm thick composite material (X-2) containing 40% carbon fiber, which was compressed to a size of 0.6 mm, then cooled in a press molding machine set at 80 ° C., and then taken out from between the stainless steel plates. Got The glass transition point was 104 ° C. and the melting point was 210 ° C.
（参考例３）２ｍｍ厚の複合材料（Ｘ−３）の製造
（参考例２）のペレット状で得られた熱可塑性樹脂組成物（Ｙ）を、シリンダー温度２７０℃、金型温度１００℃の条件で、１００ｍｍ×１００ｍｍ×２ｍｍのキャビティを有する金型を用いて射出成形する事で、炭素繊維を４０％含む、厚さ２ｍｍの複合材料（Ｘ−３）を得た。ガラス転移点 １０４℃、融点 ２１０℃であった。
(Reference Example 3) Production of a 2 mm-Thick Composite Material (X-3) A thermoplastic resin composition (Y) obtained in the form of pellets of (Reference Example 2) is subjected to a cylinder temperature of 270 ° C. and a mold temperature of 100 ° C. Under the conditions, a composite material (X-3) having a thickness of 2 mm containing 40% of carbon fibers was obtained by injection molding using a mold having a cavity of 100 mm × 100 mm × 2 mm. The glass transition point was 104 ° C. and the melting point was 210 ° C.
（実施例１）複合材料（Ｘ−１）のプレス機を使った曲げ加工
図１に記載の概略断面を有する金型を１５０℃に加熱し、その一方で７０ｍｍ（下型の凸部は６０ｍｍ）に切断した複合材料（Ｘ−１）を１５０℃の金属板上で予熱した。金型の上型（キャビティ側）を外し、複合材料（Ｘ−１）を下型（コア側）の上に置き、手で軽く押しつけた後に、その上に上型を置き、プレス成形した。金型が閉じきってすぐに、８０℃に設定したプレス機に金型ごと移動し、加圧したまま１００℃以下になるまで冷却した。その後に金型を開き、成形品を得た。天面の厚さは０．５ｍｍであり、端部は曲げ加工されており、外観は平滑であった。
(Example 1) Bending process of composite material (X-1) using a press machine A mold having a schematic cross section shown in FIG. 1 is heated to 150 ° C., while 70 mm (the convex portion of the lower mold is 60 mm). The composite material (X-1) cut into () was preheated on a metal plate at 150 ° C. The upper mold (cavity side) of the mold was removed, the composite material (X-1) was placed on the lower mold (core side), lightly pressed by hand, and then the upper mold was placed on it and press-molded. Immediately after the dies were completely closed, the dies were moved to a press machine set at 80 ° C. and cooled to 100 ° C. or lower while being pressurized. After that, the mold was opened to obtain a molded product. The thickness of the top surface was 0.5 mm, the end was bent, and the appearance was smooth.
（実施例２）複合材料（Ｘ−２）のプレス機を使った曲げ加工
複合材料（Ｘ−１）の代わりに複合材料（Ｘ−２）を用いる点を除いては、実施例１と同様に実施し、成形品を得た。天面の厚さは１ｍｍであり、端部は曲げ加工されており、外観は平滑であった。
(Example 2) Bending process of composite material (X-2) using a press machine Same as in Example 1 except that the composite material (X-2) is used instead of the composite material (X-1). To obtain a molded product. The thickness of the top surface was 1 mm, the end was bent, and the appearance was smooth.
（実施例３）複合材料（Ｘ−１）の曲げ加工
複合材料（Ｘ−２）を７０×２５ｍｍに切断し、１４０℃の金属板上で予熱した。これを軍手で掴んで、曲げ加工機（ミニシャーベンダー ＭＳＢ−８（株式会社東洋アソシエイツ製））にセットし、直ちに曲げ加工を実施し、成型品を得た。
(Example 3) Bending process of composite material (X-1) The composite material (X-2) was cut into 70 × 25 mm and preheated on a metal plate at 140 ° C. This was grasped by a work gloves, set in a bending machine (Mini Sherbender MSB-8 (manufactured by Toyo Associates Co., Ltd.)), and immediately bent, and a molded product was obtained.
（実施例４〜１１）複合材料の曲げ加工
複合材料の種類と加工温度を表１に記載の通りに変更する点を除いては、実施例３と同様に実施し、成型品を得た。
(Examples 4 to 11) Bending processing of composite material A molded product was obtained in the same manner as in Example 3 except that the type and processing temperature of the composite material were changed as shown in Table 1.
（比較例１〜２）複合材料の低温での曲げ加工
複合材料の種類と加工温度を表１に記載の通りに変更する点を除いては、実施例３と同様に実施したが、曲げ加工の際に複合材料が割れてしまい、成型品が得られなかった。
(Comparative Examples 1 and 2) Bending of Composite Material at Low Temperature The same procedure as in Example 3 was carried out except that the type and processing temperature of the composite material were changed as shown in Table 1, but bending was performed. At that time, the composite material was cracked and a molded product could not be obtained.
（比較例３〜４）複合材料の高温での曲げ加工
複合材料の種類と加工温度を表１に記載の通りに変更する点を除いては、実施例３と同様に実施したが、複合材料が軟らかいため、曲げ加工機に運ぶ際に掴んだ部分の周辺が大きく変形してしまった。曲げ加工は可能なものの、加工部分以外が大きく変形した。
(Comparative Examples 3 to 4) Bending of Composite Material at High Temperature The same procedure as in Example 3 was carried out except that the type and processing temperature of the composite material were changed as shown in Table 1, but the composite material was used. Because it is soft, the area around the part that was gripped when it was carried to the bending machine was greatly deformed. Although it can be bent, the parts other than the processed part are greatly deformed.
以上から明らかなように、実施例１〜１１は、曲げ加工可能であった。特に実施例１〜７は好ましい範囲内のため、加工性や外観が特に優れていた。比較例１〜２は、加工温度が低すぎるために、複合材料の軟化が不十分であり、曲げ加工できずに割れてしまった。比較例３〜４は、加工温度が高すぎるために複合材料が軟らかくなりすぎ取扱い辛かった。 As is clear from the above, Examples 1 to 11 were bendable. In particular, since Examples 1 to 7 were within a preferable range, the workability and appearance were particularly excellent. In Comparative Examples 1 and 2, since the processing temperature was too low, the composite material was not sufficiently softened and could not be bent and cracked. In Comparative Examples 3 and 4, the composite material became too soft and difficult to handle because the processing temperature was too high.
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