JP2018062119A - Carbon fiber-reinforced plastic laminate and method for producing the same - Google Patents
Carbon fiber-reinforced plastic laminate and method for producing the same Download PDFInfo
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- 239000004918 carbon fiber reinforced polymer Substances 0.000 title 1
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Landscapes
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Moulding By Coating Moulds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、耐熱性を有する繊維強化プラスチック積層体およびその製造方法に関する。 The present invention relates to a fiber-reinforced plastic laminate having heat resistance and a method for producing the same.
航空機部材、自動車部材、風力発電用風車部材、スポーツ用具等の様々な分野において、シート状の繊維強化プラスチックをスタンピング成形により賦形した構造材が広く用いられている。該繊維強化プラスチックは、例えば、強化繊維に熱可塑性樹脂を含浸したプリプレグ基材が複数枚積層されて一体化されることで形成される。 In various fields such as aircraft members, automobile members, wind turbine members for wind power generation, and sports equipment, structural materials formed by stamping molding sheet-like fiber reinforced plastics are widely used. The fiber reinforced plastic is formed, for example, by stacking and integrating a plurality of prepreg base materials in which a reinforced fiber is impregnated with a thermoplastic resin.
プリプレグ基材としては、例えば、連続した繊維長の長い強化繊維を一方向に引き揃えたものに、熱可塑性樹脂を含浸してシート状にしたもの知られている。このような連続した長い強化繊維を用いたプリプレグ基材で形成した繊維強化プラスチックでは、優れた機械物性を有する構造材を製造できる。 As a prepreg base material, for example, a sheet in which continuous reinforcing fibers having a long fiber length are aligned in one direction and impregnated with a thermoplastic resin is known. With a fiber reinforced plastic formed with a prepreg base material using such continuous long reinforcing fibers, a structural material having excellent mechanical properties can be produced.
しかし、該繊維強化プラスチックでは、連続した強化繊維であるがゆえに賦形時の流動性が低く、３次元形状等の複雑な形状に賦形することが難しい。そのため、該繊維強化プラスチックを用いる場合、製造する構造材は主として平面形状に近いものに限られる。 However, since the fiber reinforced plastic is a continuous reinforcing fiber, the fluidity at the time of shaping is low, and it is difficult to form into a complicated shape such as a three-dimensional shape. Therefore, when using this fiber reinforced plastic, the structural material to manufacture is mainly limited to the thing close | similar to a planar shape.
繊維強化プラスチックを３次元形状等の複雑な形状に賦形して構造材を製造する場合には、賦形時の流動性を確保するために、一般に繊維長が１００ｍｍ以下の比較的短い強化繊維が用いられる。しかし、強化繊維の繊維長が短くなると、賦形後の構造材の機械物性が低下しやすい。そのため繊維長が短い強化繊維を用いつつ、機械物性の高い構造材が得られるプリプレグ基材が提案されている（特許文献１）。 When manufacturing a structural material by shaping a fiber reinforced plastic into a complicated shape such as a three-dimensional shape, a relatively short reinforcing fiber generally having a fiber length of 100 mm or less is required to ensure fluidity during shaping. Is used. However, when the fiber length of the reinforcing fiber is shortened, the mechanical properties of the structural material after shaping tend to be lowered. Therefore, a prepreg base material has been proposed in which a structural material having high mechanical properties is obtained while using reinforcing fibers having a short fiber length (Patent Document 1).
このような熱可塑性繊維強化プラスチックを自動車部材の塗装工程などの高い温度に一定時間さらされる部材に用いる場合には、マトリックス樹脂に耐熱性の高いものが用いられる。例えば特許文献２には高耐熱樹脂をマトリックスとすることで塗装の耐熱性を持つ熱可塑性繊維強化プラスチックが示されている。 When such a thermoplastic fiber reinforced plastic is used for a member exposed to a high temperature for a certain period of time, such as a coating process of an automobile member, a matrix resin having high heat resistance is used. For example, Patent Document 2 discloses a thermoplastic fiber reinforced plastic having heat resistance of coating by using a high heat resistant resin as a matrix.
しかしながら、繊維強化プラスチックの耐熱性を向上のために、耐熱性の高いマトリックス樹脂を用いるためには、プリプレグ基材を製造する温度を高く設定する必要がある。強化繊維中に樹脂を含浸させることは、一般的に難易度が高く、さらに高温化が必要な場合には、加熱用の設備コストが増加するだけでなく、高温による樹脂の分解が生じやすく、逆に分解を抑制すべく温度上昇を抑制した場合には加熱不足による含浸不良が生じる。 However, in order to use a highly heat-resistant matrix resin in order to improve the heat resistance of the fiber reinforced plastic, it is necessary to set a high temperature for producing the prepreg base material. It is generally difficult to impregnate the resin in the reinforcing fiber, and when a higher temperature is required, not only the heating equipment cost is increased, but the resin is easily decomposed due to the high temperature, Conversely, when the temperature rise is suppressed to suppress decomposition, impregnation failure occurs due to insufficient heating.
本発明は、上記のプリプレグ基材の製造時の問題を生じることなく、耐熱性を持つ熱可塑性繊維強化プラスチックを提供することを目的とする。 An object of this invention is to provide the thermoplastic fiber reinforced plastic which has heat resistance, without producing the problem at the time of manufacture of said prepreg base material.
本発明者等は、上記課題を解決すべく鋭意検討した結果、本発明を完成するに至った。即ち本発明の要旨は、下記の［１］〜［９］に存する。 As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the gist of the present invention resides in the following [1] to [9].
［１］ 少なくとも２層構造を有する積層体であって、下記Ａ層と下記Ｂ層を有し、Ｂ層の軟化点がＡ層より高く、かつＢ層の軟化点が２３０℃以上、３００℃以下である、繊維強化プラスチック積層体。
Ａ層：強化繊維と熱可塑性樹脂とを含む繊維強化プラスチックあって、前記強化繊維の平均繊維長が１０ｍｍ以上である。
Ｂ層：熱可塑性樹脂、もしくはフィラー含有物と熱可塑性樹脂とを含む強化プラスチックである。
軟化点：層を構成する熱可塑性樹脂が結晶性樹脂の場合は、当該熱可塑性樹脂の融点が当該層の軟化点であり、層を構成する熱可塑性樹脂が非晶性樹脂の場合は、当該熱可塑性樹脂のガラス転移点が当該層の軟化点である。
[1] A laminate having at least a two-layer structure, comprising the following A layer and the following B layer, the softening point of the B layer being higher than that of the A layer, and the softening point of the B layer being 230 ° C. or higher and 300 ° C. A fiber reinforced plastic laminate which is the following.
Layer A: a fiber-reinforced plastic containing reinforcing fibers and a thermoplastic resin, wherein the average fiber length of the reinforcing fibers is 10 mm or more.
B layer: a thermoplastic resin, or a reinforced plastic containing a filler-containing material and a thermoplastic resin.
Softening point: When the thermoplastic resin constituting the layer is a crystalline resin, the melting point of the thermoplastic resin is the softening point of the layer, and when the thermoplastic resin constituting the layer is an amorphous resin, The glass transition point of the thermoplastic resin is the softening point of the layer.
［２］ 繊維強化プラスチック積層体の全厚みに対して、Ｂ層の厚みの割合が０．５以上、０．９以下である、上記［１］に記載の繊維強化プラスチック積層体。
［３］ Ａ層における強化繊維の繊維体積含有率が１０〜６０体積％である、上記［１］または［２］に記載の繊維強化プラスチック積層体。
［４］ Ａ層中の強化繊維の平均繊維長が１０〜５０ｍｍであり、繊維がランダム配向をしている、上記［１］〜［３］のいずれかに記載の繊維強化プラスチック積層体。
［５］ Ａ層が、一方向連続繊維プリプレグ複数枚の積層体である、上記［１］〜［３］のいずれかに記載の繊維強化プラスチック積層体。
[2] The fiber-reinforced plastic laminate according to the above [1], wherein the ratio of the thickness of the B layer is 0.5 or more and 0.9 or less with respect to the total thickness of the fiber-reinforced plastic laminate.
[3] The fiber-reinforced plastic laminate according to the above [1] or [2], wherein the fiber volume content of the reinforcing fibers in the A layer is 10 to 60% by volume.
[4] The fiber-reinforced plastic laminate according to any one of [1] to [3], wherein the average fiber length of the reinforcing fibers in the A layer is 10 to 50 mm, and the fibers are randomly oriented.
[5] The fiber-reinforced plastic laminate according to any one of [1] to [3], wherein the A layer is a laminate of a plurality of unidirectional continuous fiber prepregs.
［６］ Ｂ層のフィラーが、平均繊維長１０ｍｍ以下の繊維状である、上記［１］〜［５］のいずれかに記載の繊維強化プラスチック積層体。
［７］ 少なくとも３層構造を有する積層体であって、両表面層にＡ層を有し、両表面層の間に下記Ｂ層を有する、上記［１］〜［６］のいずれかに記載の繊維強化プラスチック積層体。
［８］ Ａ層とＢ層を、プレス成形で一体化する、上記［１］〜［７］のいずれかに記載の繊維強化プラスチック積層体の製造方法。
［９］ Ａ層とＢ層を、射出成形で一体化する、上記［１］〜〔７〕のいずれかに記載の繊維強化プラスチック積層体の製造方法。
[6] The fiber-reinforced plastic laminate according to any one of the above [1] to [5], wherein the filler of the B layer is a fiber having an average fiber length of 10 mm or less.
[7] The laminate according to any one of the above [1] to [6], which is a laminate having at least a three-layer structure, having A layers on both surface layers, and having the following B layers between both surface layers. Fiber reinforced plastic laminate.
[8] The method for producing a fiber-reinforced plastic laminate according to any one of [1] to [7], wherein the A layer and the B layer are integrated by press molding.
[9] The method for producing a fiber-reinforced plastic laminate according to any one of [1] to [7], wherein the A layer and the B layer are integrated by injection molding.
熱分解や含浸不良などの製造時の問題を生じることなく優れた耐熱性もつ繊維強化プラスチック積層体を提供することができる。 It is possible to provide a fiber-reinforced plastic laminate having excellent heat resistance without causing problems during production such as thermal decomposition and impregnation failure.
本発明の繊維強化プラスチック積層体は、少なくとも２層構造を有する積層体であって、下記Ａ層と下記Ｂ層を有し、Ｂ層の軟化点がＡ層より高く、かつＢ層の軟化点が２３０℃以上、３００℃以下である、繊維強化プラスチック積層体である。 The fiber reinforced plastic laminate of the present invention is a laminate having at least a two-layer structure, and includes the following A layer and the following B layer, the softening point of the B layer being higher than that of the A layer, and the softening point of the B layer. Is a fiber reinforced plastic laminate having a temperature of 230 ° C. or higher and 300 ° C. or lower.
Ｂ層の軟化点がＡ層よりも高いことにより、生産性を維持しつつ低コストで耐熱性をもつ繊維強化繊維強化プラスチック積層体を得ることができる。 When the softening point of the B layer is higher than that of the A layer, it is possible to obtain a fiber reinforced fiber reinforced plastic laminate having heat resistance at low cost while maintaining productivity.
また、成形後の塗装時の焼付温度に耐えるためには、軟化点は２３０℃以上が好ましく、かつ優れた成形加工性を維持するために軟化点は３００℃以下が好ましい。さらにはこの軟化点は２３０℃以上２８０℃以下が好ましい。
＜Ａ層＞
強化繊維と熱可塑性樹脂とを含む繊維強化プラスチックあって、前記強化繊維の平均繊維長が１０ｍｍ以上である。
＜Ｂ層＞
熱可塑性樹脂、もしくはフィラー含有物と熱可塑性樹脂とを含む強化プラスチックである。
Moreover, in order to endure the baking temperature at the time of coating after molding, the softening point is preferably 230 ° C. or higher, and the softening point is preferably 300 ° C. or lower in order to maintain excellent molding processability. Further, the softening point is preferably 230 ° C. or higher and 280 ° C. or lower.
<A layer>
A fiber reinforced plastic including reinforced fibers and a thermoplastic resin, wherein the average fiber length of the reinforced fibers is 10 mm or more.
<B layer>
It is a reinforced plastic containing a thermoplastic resin or a filler-containing material and a thermoplastic resin.
なお、本発明における層の軟化点とは、層を構成する熱可塑性樹脂が結晶性樹脂の場合は、当該熱可塑性樹脂の融点が当該層の軟化点であり、層を構成する熱可塑性樹脂が非晶性樹脂の場合は、当該熱可塑性樹脂のガラス転移点が当該層の軟化点である。 In the present invention, the softening point of the layer means that when the thermoplastic resin constituting the layer is a crystalline resin, the melting point of the thermoplastic resin is the softening point of the layer, and the thermoplastic resin constituting the layer is In the case of an amorphous resin, the glass transition point of the thermoplastic resin is the softening point of the layer.
本発明の繊維強化プラスチック積層体は２層以上の層構造を有するものであれば良いが、強度の観点から、３層以上の層構造を有することが好ましい。また、３層以上の層構造を有する場合は、強度の観点から、両表面層にＡ層を有し、当該両表面の間にＢ層を有することが好ましい。また、強度や耐熱性の関連から、繊維強化プラスチック積層体の全厚みに対して、Ｂ層の厚みの割合が０．５以上、０．９以下であることが好ましい。 The fiber reinforced plastic laminate of the present invention may have any layer structure of two or more layers, but preferably has a layer structure of three or more layers from the viewpoint of strength. Moreover, when it has a layer structure of three or more layers, it is preferable from a viewpoint of intensity | strength to have A layer in both surface layers, and to have B layer between the said both surfaces. Moreover, it is preferable that the ratio of the thickness of B layer is 0.5 or more and 0.9 or less with respect to the total thickness of a fiber reinforced plastic laminated body from a relation of strength or heat resistance.
（強化繊維）
Ａ層に用いられる強化繊維としては、特に限定されず、例えば、無機繊維、有機繊維、金属繊維、又はこれらを組み合わせたハイブリッド構成の強化繊維が使用できる。無機繊維としては、炭素繊維、黒鉛繊維、炭化珪素繊維、アルミナ繊維、タングステンカーバイド繊維、ボロン繊維、ガラス繊維等が挙げられる。有機繊維としては、アラミド繊維、高密度ポリエチレン繊維、その他一般のナイロン繊維、ポリエステル繊維等が挙げられる。金属繊維としては、ステンレス、鉄等の繊維が挙げられ、また金属を被覆した炭素繊維でもよい。これらの中では、最終成形物である構造材の強度等の機械物性を考慮すると、炭素繊維が好ましい。
(Reinforced fiber)
The reinforcing fibers used in the A layer are not particularly limited, and for example, reinforcing fibers having inorganic fibers, organic fibers, metal fibers, or a hybrid structure in which these are combined can be used. Examples of the inorganic fiber include carbon fiber, graphite fiber, silicon carbide fiber, alumina fiber, tungsten carbide fiber, boron fiber, and glass fiber. Examples of the organic fibers include aramid fibers, high density polyethylene fibers, other general nylon fibers, and polyester fibers. Examples of metal fibers include fibers such as stainless steel and iron, and carbon fibers coated with metal may be used. Among these, carbon fibers are preferable in view of mechanical properties such as strength of the structural material that is the final molded product.
炭素繊維としては、特に限定されず、ポリアクリロニトリル（ＰＡＮ）系炭素繊維、ＰＩＣＨ系炭素繊維等が挙げられる。好ましい炭素繊維は、ＪＩＳ Ｒ７６０１（１９８６）に準じて測定したストランド引張強度が１．０ＧＰａ以上９．０ＧＰａ以下で、かつストランド引張弾性率が１５０ＧＰａ以上１０００ＧＰａ以下の炭素繊維である。より好ましい炭素繊維は、ＪＩＳ Ｒ７６０１（１９８６）に準じて測定したストランド引張強度が１．５ＧＰａ以上９．０ＧＰａ以下で、かつストランド引張弾性率が２００ＧＰａ以上１０００ＧＰａ以下の炭素繊維である。 The carbon fiber is not particularly limited, and examples thereof include polyacrylonitrile (PAN) -based carbon fiber and PICH-based carbon fiber. A preferred carbon fiber is a carbon fiber having a strand tensile strength measured in accordance with JIS R7601 (1986) of 1.0 GPa or more and 9.0 GPa or less and a strand tensile elastic modulus of 150 GPa or more and 1000 GPa or less. More preferred carbon fibers are carbon fibers having a strand tensile strength of 1.5 GPa or more and 9.0 GPa or less measured according to JIS R7601 (1986) and a strand tensile modulus of 200 GPa or more and 1000 GPa or less.
Ａ層に用いられる強化繊維の平均繊維長は、１０ｍｍ以上が好ましい。スタンピング成形に用いられる場合には１０〜１００ｍｍが好ましく、１０〜５０ｍｍがさらに好ましく、２０〜５０ｍｍが特に好ましい。一般に強化繊維が長いほど機械物性に優れた構造材が得られるが、特にスタンピング成形時において、流動性が低下するために複雑な３次元形状の構造材が得られにくくなる。強化繊維の平均繊維長が上限値以下であれば、賦形時に優れた流動性が得られ、強化繊維とマトリックス樹脂が流動しやすい。そのため、リブやボス等の複雑な３次元形状の構造材を得ることが容易である。また、強化繊維の平均繊維長が下限値以上であれば、機械物性に優れた構造材を製造できる。 The average fiber length of the reinforcing fibers used in the A layer is preferably 10 mm or more. When used for stamping molding, 10 to 100 mm is preferable, 10 to 50 mm is more preferable, and 20 to 50 mm is particularly preferable. In general, the longer the reinforcing fiber, the more structural material excellent in mechanical properties can be obtained. However, the fluidity is lowered particularly during stamping molding, so that it becomes difficult to obtain a structural material having a complicated three-dimensional shape. When the average fiber length of the reinforcing fibers is not more than the upper limit value, excellent fluidity can be obtained at the time of shaping, and the reinforcing fibers and the matrix resin can easily flow. Therefore, it is easy to obtain a complicated three-dimensional structural material such as a rib or a boss. Moreover, if the average fiber length of the reinforcing fibers is not less than the lower limit value, a structural material having excellent mechanical properties can be produced.
繊維強化プラスチック中に強化繊維の平均繊維長は、以下の方法で測定できる。繊維強化プラスチック中のマトリックス樹脂を焼き飛ばして、強化繊維のみを取り出し、該強化繊維の繊維長をノギス等で測定する。測定は無作為に選択した１００本の強化繊維について行い、平均繊維長はそれらの質量平均として算出する。
強化繊維の平均繊維直径は、１〜５０μｍが好ましく、５〜２０μｍがより好ましい。
The average fiber length of the reinforcing fiber in the fiber reinforced plastic can be measured by the following method. The matrix resin in the fiber reinforced plastic is burned off, and only the reinforcing fiber is taken out, and the fiber length of the reinforcing fiber is measured with a caliper or the like. The measurement is performed on 100 randomly selected reinforcing fibers, and the average fiber length is calculated as the mass average of them.
1-50 micrometers is preferable and, as for the average fiber diameter of a reinforced fiber, 5-20 micrometers is more preferable.
（Ａ層中の強化繊維の繊維体積含有率）
本発明の繊維強化プラスチック中の強化繊維の繊維体積含有率（Ｖｆ）は、１０〜６０体積％が好ましく、１５〜５５体積％がより好ましく、２０〜５０体積％がさらに好ましい。強化繊維のＶｆが上限値以下であれば、靭性低下による界面強度の低下が生じにくく、また賦型時の流動性も低下しにくい。強化繊維のＶｆが下限値以上であれば、繊維強化プラスチックとして必要とされる機械物性が得られやすい。
(Fiber volume content of reinforcing fibers in layer A)
10-60 volume% is preferable, as for the fiber volume content (Vf) of the reinforced fiber in the fiber reinforced plastics of this invention, 15-55 volume% is more preferable, and 20-50 volume% is further more preferable. If the Vf of the reinforcing fiber is not more than the upper limit value, the interface strength is not easily lowered due to a decrease in toughness, and the fluidity at the time of molding is hardly lowered. If Vf of the reinforcing fiber is equal to or higher than the lower limit value, mechanical properties required as a fiber reinforced plastic are easily obtained.
なお、繊維強化プラスチックのＶｆ値は、繊維強化プラスチックにおける強化繊維、マトリックス樹脂、及びボイド（気体）を除く添加剤等のその他の成分の合計体積に対する強化繊維の割合を意味する。ＪＩＳ Ｋ７０７５に基づいて測定されたＶｆ値は繊維強化プラスチック中のボイドの存在量により変動する値であるため、本発明においてはボイドの存在量に依存しない繊維体積含有率を採用する。 The Vf value of the fiber reinforced plastic means the ratio of the reinforced fiber to the total volume of the reinforced fiber, the matrix resin, and other components such as additives excluding voids (gas) in the fiber reinforced plastic. Since the Vf value measured based on JIS K7075 varies depending on the amount of voids present in the fiber reinforced plastic, the present invention employs a fiber volume content that does not depend on the amount of voids present.
（Ａ層のマトリックス樹脂）
Ａ層に用いられるマトリックス樹脂は、１種を単独で使用してもよく、２種以上を併用してもよい。マトリックス樹脂としては、熱可塑性樹脂が好ましい。熱可塑性樹脂は一般的に熱硬化性樹脂よりも靱性値が高いため、マトリックス樹脂として熱可塑性樹脂を用いることで、強度、特に耐衝撃性に優れた構造材が得られやすくなる。また、熱可塑性樹脂は化学反応を伴うことなく冷却固化により形状が定まる。そのため、熱可塑性樹脂を用いる場合は短時間成形が可能となり、繊維強化プラスチックや構造材の生産性に優れる。
(Matrix resin for layer A)
The matrix resin used for the A layer may be used alone or in combination of two or more. As the matrix resin, a thermoplastic resin is preferable. Since a thermoplastic resin generally has a higher toughness value than a thermosetting resin, it is easy to obtain a structural material having excellent strength, particularly impact resistance, by using a thermoplastic resin as a matrix resin. In addition, the shape of the thermoplastic resin is determined by cooling and solidification without chemical reaction. Therefore, when a thermoplastic resin is used, molding can be performed in a short time, and the productivity of fiber reinforced plastic and structural material is excellent.
熱可塑性樹脂としては、特に限定されず、ポリアミド樹脂（ナイロン６、ナイロン６６、ナイロン１２、ナイロンＭＸＤ６等）、ポリオレフィン樹脂（低密度ポリエチレン、高密度ポリエチレン、ポリプロピレン等）、変性ポリオレフィン樹脂（変性ポリプロピレン樹脂等）、ポリエステル樹脂（ポリエチレンテレフタレート、ポリブチレンテレフタレート等）、ポリカーボネート樹脂、ポリアミドイミド樹脂、ポリフェニレンオキシド樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリエーテルエーテルケトン樹脂、ポリエーテルイミド樹脂、ポリスチレン樹脂、ＡＢＳ樹脂、ポリフェニレンサルファイド樹脂、液晶ポリエステル樹脂、アクリロニトリルとスチレンの共重合体、ナイロン６とナイロン６６の共重合体等が挙げられる。変性ポリオレフィン樹脂としては、例えば、マレイン酸等の酸によりポリオレフィン樹脂を変性した樹脂等が挙げられる。熱可塑性樹脂は、１種を単独で使用してもよく、２種以上を併用してもよい。 The thermoplastic resin is not particularly limited, and polyamide resin (nylon 6, nylon 66, nylon 12, nylon MXD6, etc.), polyolefin resin (low density polyethylene, high density polyethylene, polypropylene, etc.), modified polyolefin resin (modified polypropylene resin) Etc.), polyester resin (polyethylene terephthalate, polybutylene terephthalate, etc.), polycarbonate resin, polyamideimide resin, polyphenylene oxide resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyetherimide resin, polystyrene resin, ABS resin , Polyphenylene sulfide resin, liquid crystal polyester resin, copolymer of acrylonitrile and styrene, copolymer of nylon 6 and nylon 66, and the like. . Examples of the modified polyolefin resin include a resin obtained by modifying a polyolefin resin with an acid such as maleic acid. A thermoplastic resin may be used individually by 1 type, and may use 2 or more types together.
Ａ層に用いられる熱可塑性樹脂としては、強化繊維との接着性、強化繊維への含浸性及び熱可塑性樹脂の原料コストの各々のバランスの点から、ポリオレフィン樹脂、変性ポリプロピレン樹脂、ポリアミド樹脂、ポリエステル樹脂及びポリカーボネート樹脂からなる群から選ばれる少なくとも１種を含むことが好ましい。 The thermoplastic resin used for the A layer is a polyolefin resin, a modified polypropylene resin, a polyamide resin, a polyester from the viewpoint of the balance between the adhesion to the reinforcing fiber, the impregnation into the reinforcing fiber, and the raw material cost of the thermoplastic resin. It is preferable to include at least one selected from the group consisting of a resin and a polycarbonate resin.
（Ａ層）
Ａ層の具体例としては、Ａ層中の強化繊維の平均繊維長が１０〜５０ｍｍであり、繊維がランダム配向をしているランダム材や、一方向連続繊維プリプレグ複数枚の積層体等が挙げられる。
(A layer)
Specific examples of the A layer include a random material in which the average fiber length of the reinforcing fibers in the A layer is 10 to 50 mm and the fibers are randomly oriented, a laminate of a plurality of unidirectional continuous fiber prepregs, and the like. It is done.
（Ｂ層の熱可塑性樹脂）
Ｂ層に用いられる熱可塑性樹脂としては、Ａ層より耐熱性に優れることが好ましい。結晶性樹脂の場合は、塗装時の焼付温度に耐えるためには軟化点は２３０℃以上が好ましく、かつ優れた成形加工性を維持するために軟化点は３００℃以下が好ましい。さらにはこの軟化点は２３０℃以上２８０℃以下が好ましい。このような軟化点を持つ熱可塑性樹脂としては、ポリアミド樹脂、ポリエステル樹脂及びポリフェニレンサルファイド樹脂からなる群から選ばれる少なくとも１種を含むことが好ましい。
(B layer thermoplastic resin)
The thermoplastic resin used for the B layer is preferably superior in heat resistance to the A layer. In the case of a crystalline resin, the softening point is preferably 230 ° C. or higher in order to withstand the baking temperature during coating, and the softening point is preferably 300 ° C. or lower in order to maintain excellent moldability. Further, the softening point is preferably 230 ° C. or higher and 280 ° C. or lower. The thermoplastic resin having such a softening point preferably includes at least one selected from the group consisting of polyamide resin, polyester resin, and polyphenylene sulfide resin.
（Ｂ層に含有されるフィラー）
Ｂ層はフィラーを含有していなくてもよいが、強度や耐熱性の観点から、フィラーを含有してもよい。
Ｂ層に含有されるフィラーとしては、ガラス繊維や炭素繊維等を挙げることができる。製造が容易であるとの観点から、Ｂ層に含有されるフィラーは、平均繊維長が１０ｍｍ以下の繊維状であることが好ましく、平均繊維長が０．０１〜５．０ｍｍの繊維状であることがより好ましい。
(Filler contained in layer B)
The layer B may not contain a filler, but may contain a filler from the viewpoint of strength and heat resistance.
Examples of the filler contained in the B layer include glass fiber and carbon fiber. From the viewpoint of easy production, the filler contained in the B layer is preferably fibrous with an average fiber length of 10 mm or less, and is fibrous with an average fiber length of 0.01 to 5.0 mm. It is more preferable.
（他の成分）
本発明のＢ層には、目的の構造材の要求特性に応じて、難燃剤、耐候性改良剤、酸化防止剤、熱安定剤、紫外線吸収剤、可塑剤、滑剤、着色剤、相溶化剤、非繊維状フィラー、導電性フィラー、離型剤、界面活性剤等の添加剤が配合されていてもよい。なおこれらは、Ａ層に配合されていてもよい。
(Other ingredients)
In the B layer of the present invention, a flame retardant, a weather resistance improver, an antioxidant, a heat stabilizer, an ultraviolet absorber, a plasticizer, a lubricant, a colorant, a compatibilizer depending on the required characteristics of the target structural material In addition, additives such as non-fibrous fillers, conductive fillers, mold release agents, and surfactants may be blended. In addition, these may be mix | blended with A layer.
（一方向配向繊維強化プラスチックの製造方法）
本発明の一方向配向繊維強化プラスチックの製造方法としては、下記工程（ｉ）〜（iii）を有する方法が好ましい。
工程（ｉ）：一方向に引き揃えた強化繊維を開繊し、均一目付のシート状の強化繊維束を形成する工程。
工程（ｉｉ）：フィルム状のマトリックス樹脂でこのシート状の強化繊維束を両側から挟み込み、加熱加圧ロールを通して、マトリックス樹脂を含浸する工程。
工程（ｉｉｉ）：前記マトリックス樹脂を含浸した繊維強化束を冷却固化することにより、一方向配向繊維強化プラスチックを得る工程。
(Method for producing unidirectionally oriented fiber reinforced plastic)
As a manufacturing method of the unidirectionally oriented fiber reinforced plastic of the present invention, a method having the following steps (i) to (iii) is preferable.
Step (i): A step of opening the reinforcing fibers aligned in one direction to form a sheet-like reinforcing fiber bundle having a uniform basis weight.
Step (ii): A step of sandwiching the sheet-like reinforcing fiber bundle from both sides with a film-like matrix resin and impregnating the matrix resin through a heating and pressing roll.
Step (iii): A step of obtaining a unidirectionally oriented fiber reinforced plastic by cooling and solidifying the fiber reinforced bundle impregnated with the matrix resin.
（ランダム配向繊維強化プラスチックの製造方法）
本発明のランダム配向繊維強化プラスチックの製造方法としては、下記工程（ｉｖ）〜（ｖｉ）を有する方法が好ましい。
工程（ｉｖ）：前記工程（ｉ）〜（ｉｉｉ）で得られた一方向配向繊維強化プラスチックの繊維軸に交差するように切込みが形成されたプリプレグ基材を含む材料を得る工程。
工程（ｖ）：前記材料の走行方向に対する直交方向に略均一に加圧する加圧装置を用い、前記強化繊維の繊維軸の方向が前記走行方向と交差するようにして、前記材料を一方向に走行させつつ、前記マトリックス樹脂の融点以上、又は融点を有しないときはガラス転移温度以上の温度Ｔに加熱した状態で加圧する工程。
工程（ｖｉ）：前記加圧装置で加圧された前記材料を冷却してランダム配向繊維強化プラスチックを得る工程。
(Production method of randomly oriented fiber reinforced plastic)
As a method for producing the randomly oriented fiber-reinforced plastic of the present invention, a method having the following steps (iv) to (vi) is preferable.
Step (iv): A step of obtaining a material including a prepreg base material in which cuts are formed so as to intersect the fiber axis of the unidirectionally oriented fiber reinforced plastic obtained in the steps (i) to (iii).
Step (v): Using a pressurizing device that presses substantially uniformly in a direction orthogonal to the traveling direction of the material, the direction of the fiber axis of the reinforcing fiber intersects the traveling direction, and the material is unidirectional The process of pressurizing in the state heated to the temperature T more than a glass transition temperature, when not having melting | fusing point or more of the said matrix resin, making it run.
Step (vi): A step of cooling the material pressed by the pressing device to obtain a randomly oriented fiber reinforced plastic.
（繊維強化プラスチック積層体の製造方法）
上記により得られた繊維強化プラスチック（Ａ層）と耐熱樹脂（Ｂ層）を積層することにより繊維強化プラスチック積層体を得るが、その製造方法としては下記のいずれかの方法で行うことが好ましい。いずれの場合もＡ層の前記繊維強化プラスチックは１枚で利用しても良いし、適当な厚みになるように積層して用いても良い。
（１）耐熱樹脂（Ｂ層）をあらかじめシート状に加工しておき、前記繊維強化プラスチック（Ａ層）と積層したものを加熱プレスにより積層する方法。
（２）前記繊維強化プラスチック（Ａ層）を金型内に仕込み、射出成形により残りの空間に耐熱樹脂（Ｂ層）を充填させることにより積層体得る方法。
繊維強化プラスチック積層体を評価する方法としては、以下の方法が挙げられる。
(Manufacturing method of fiber reinforced plastic laminate)
A fiber reinforced plastic laminate is obtained by laminating the fiber reinforced plastic (A layer) and heat-resistant resin (B layer) obtained as described above, and the production method is preferably any of the following methods. In any case, the fiber reinforced plastic of the A layer may be used alone or may be used by being laminated so as to have an appropriate thickness.
(1) A method in which a heat-resistant resin (B layer) is processed into a sheet shape in advance and laminated with the fiber reinforced plastic (A layer) by a hot press.
(2) A method of obtaining a laminate by charging the fiber reinforced plastic (A layer) into a mold and filling the remaining space with a heat resistant resin (B layer) by injection molding.
Examples of methods for evaluating the fiber reinforced plastic laminate include the following methods.
（軟化点の測定方法）
結晶性樹脂の場合、軟化点とは融点と同義であり、ＪＩＳＫ７１２１に記載の融解ピーク温度（Ｔｐｍ）とする。また非晶性樹脂の場合には、軟化点とはガラス転移温度と同義であり、ＪＩＳＫ７１２１に記載の中間点ガラス転移温度（Ｔｍｇ）とする。
(Measurement method of softening point)
In the case of a crystalline resin, the softening point is synonymous with the melting point, and is the melting peak temperature (Tpm) described in JIS K7121. In the case of an amorphous resin, the softening point is synonymous with the glass transition temperature, and is defined as the intermediate point glass transition temperature (Tmg) described in JIS K7121.
（荷重たわみ温度の測定方法）
ＪＩＳＫ７１９１−２に記載の方法のうち、フラットワイズでの試験とする。試験片サイズは、長さ８０ｍｍ、幅１０ｍｍ、厚さ４ｍｍとし、荷重はＢ法である０．４５ＭＰａ、規定たわみ量０．３４ｍｍに到達する温度を、荷重たわみ温度と定義する。
(Measurement method of deflection temperature under load)
Among the methods described in JISK7191-2, a flat-wise test is used. The test piece size is 80 mm in length, 10 mm in width, and 4 mm in thickness. The temperature at which the load reaches 0.45 MPa as defined by the B method and the specified deflection amount is 0.34 mm is defined as the deflection temperature under load.
（耐熱性の評価）
前記荷重たわみ温度が２００℃以上であるものを耐熱性がある繊維強化プラスチック積層体と判断する。
(Evaluation of heat resistance)
Those having a deflection temperature under load of 200 ° C. or higher are judged to be heat-resistant fiber-reinforced plastic laminates.
以下、実施例により本発明をさらに具体的に説明するが、本発明は、実施例に記載の発明に限定されるものではない。
［実施例１］
（Ａ層）
一方向に炭素繊維（三菱レイヨン社製、製品名：パイロフィル（登録商標）ＴＲ−５０Ｓ１５Ｌ）を平面状に引き揃えて目付が７２．０ｇ／ｍ２となる強化繊維シートとし、強化繊維シートの両面を、ポリアミド６樹脂（宇部興産社製、製品名：１０１３Ｂ）からなる目付が４５．６ｇ／ｍ２のフィルムで挟み、２８０℃に加熱したカレンダロールを通して、熱可塑性樹脂を繊維シートに含浸し、繊維体積含有率（Ｖｆ）が３３％、厚さが、０．１２ｍｍの一方向繊維強化プラスチックを得た。得られた一方向繊維強化プラスチックを３００ｍｍ角に切り出し、８層を疑似等方（［０／４５／９０／−４５］ｓ）に重ねた。
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to the invention as described in an Example.
[Example 1]
(A layer)
Carbon fiber (product name: Pyrofil (registered trademark) TR-50S15L manufactured by Mitsubishi Rayon Co., Ltd.) is aligned in one direction to form a reinforcing fiber sheet having a basis weight of 72.0 g / m 2, and both sides of the reinforcing fiber sheet Is sandwiched between films of polyamide 6 resin (manufactured by Ube Industries, product name: 1013B) having a basis weight of 45.6 g / m 2 , and a fiber sheet is impregnated with a thermoplastic sheet through a calender roll heated to 280 ° C., A unidirectional fiber reinforced plastic having a fiber volume content (Vf) of 33% and a thickness of 0.12 mm was obtained. The obtained unidirectional fiber reinforced plastic was cut into a 300 mm square, and 8 layers were stacked in a pseudo isotropic manner ([0/45/90 / −45] s).
（Ｂ層）
次いでポリアミド６６樹脂（デュポン社製、製品名：ザイデル１０１Ｆ）のペレット２５０ｇを３００ｍｍ角で深さ５．０ｍｍの印籠型内に配置して加熱し圧縮成形機（神藤金属工業所製、製品名：ＳＦＡ−５０ＨＨ０）を用いて、高温側プレスにて２８０℃、油圧指示０ＭＰａの条件で７分間保持し、次いで同一温度にて油圧指示２ＭＰａ（プレス圧０．５５ＭＰａ）の条件で７分間保持後、型を冷却プレスに移動させ、８０℃，油圧指示５ＭＰａ（プレス圧１．３８ＭＰａ）にて３分間保持することで約２ｍｍ厚みのシート状成形品を得た。
(B layer)
Next, 250 g of pellets of polyamide 66 resin (manufactured by DuPont, product name: Seidel 101F) are placed in a 300 mm square and 5.0 mm deep stamping mold and heated to form a compression molding machine (manufactured by Shinto Metal Industry, product name: SFA-50HH0), held at high temperature side press at 280 ° C. and hydraulic pressure instruction of 0 MPa for 7 minutes, then held at the same temperature for hydraulic pressure instruction of 2 MPa (press pressure 0.55 MPa) for 7 minutes, The mold was moved to a cooling press and held for 3 minutes at 80 ° C. and a hydraulic pressure instruction of 5 MPa (press pressure 1.38 MPa) to obtain a sheet-like molded product having a thickness of about 2 mm.
このようにして得たＡ層とＢ層をＡ層／Ｂ層／Ａ層の順に重ね、前記型内に配置して加熱し前記圧縮成形機を用いて、高温側プレスにて２８０℃、油圧指示０ＭＰａの条件で７分間保持し、次いで同一温度にて油圧指示２ＭＰａ（プレス圧０．５５ＭＰａ）の条件で７分間保持後、型を冷却プレスに移動させ、８０℃，油圧指示５ＭＰａ（プレス圧１．３８ＭＰａ）にて３分間保持することで、厚み４ｍｍの繊維強化プラスチック積層体を得た。 The A layer and the B layer thus obtained were stacked in the order of A layer / B layer / A layer, placed in the mold, heated, and heated at 280 ° C. with a high temperature side press using the compression molding machine. Hold for 7 minutes under the condition of 0MPa, then hold at the same temperature for 7 minutes under the condition of hydraulic pressure indication 2MPa (press pressure 0.55MPa), then move the mold to the cooling press, 80 ℃, hydraulic pressure indication 5MPa (press pressure 1.38 MPa) for 3 minutes to obtain a fiber reinforced plastic laminate having a thickness of 4 mm.
［評価結果］
Ａ層の軟化温度は２２０℃、Ｂ層の軟化温度は２６３℃、またＡ層とＢ層を積層した繊維強化プラスチック積層体の荷重たわみ温度は２００℃と十分に高いものであった。
[Evaluation results]
The softening temperature of the A layer was 220 ° C., the softening temperature of the B layer was 263 ° C., and the deflection temperature under load of the fiber reinforced plastic laminate in which the A layer and the B layer were laminated was sufficiently high at 200 ° C.
［実施例２］
（Ａ層）
実施例１に記載の方法で得られた一方向繊維強化プラスチックを、３００ｍｍ（繊維軸に対して０゜方向）×９００ｍｍ（繊維軸に対して９０゜方向）の矩形に切り出し、その後カッティングプロッター（レザック製Ｌ−２５００カッティングプロッター）を用いて、切込みと強化繊維の繊維軸となす角度φの絶対値が４５゜、強化繊維の繊維長Ｌが２５ｍｍになるように、一方向繊維強化プラスチックに強化繊維を切断する深さの切込みを入れ、切込入り一方向繊維強化プラスチックを得た。該切込入りプリプレグ基材を強化繊維の繊維軸が同一方向となるように４枚積層してプリプレグ積層体を得た。該プリプレグ積層体を、上下のベルトが１．０ｍ／分で駆動する図２で例示したダブルベルト式加熱加圧機に、プレスロールの軸線方向に対してプリプレグ積層体における強化繊維の繊維軸の方向がなす角度θが０°となるように、投入した。該ダブルベルト式加熱加圧機では、ロール温度３１０℃、ロール直下のベルト間クリアランス３００μｍの条件の２段式のプレスロールにより、プリプレグ積層体を加熱して熱可塑性樹脂を溶融させた状態で加圧した。その後、ロール温度３０℃、ロール直下のベルト間クリアランス３００μｍの条件の１段式の温水ロールを備えた１．５ｍの冷却区間を通過させ、熱可塑性樹脂を固化させて繊維強化プラスチックを得た。
[Example 2]
(A layer)
The unidirectional fiber reinforced plastic obtained by the method described in Example 1 was cut into a rectangle of 300 mm (0 ° direction with respect to the fiber axis) × 900 mm (90 ° direction with respect to the fiber axis), and then a cutting plotter ( Rezac L-2500 cutting plotter) is used to reinforce the unidirectional fiber reinforced plastic so that the absolute value of the angle φ between the cut and the fiber axis of the reinforcing fiber is 45 ° and the fiber length L of the reinforcing fiber is 25 mm. A notch having a depth for cutting the fiber was made to obtain a notched unidirectional fiber-reinforced plastic. Four sheets of the prepreg base material with cuts were laminated so that the fiber axes of the reinforcing fibers were in the same direction to obtain a prepreg laminate. The direction of the fiber axis of the reinforcing fiber in the prepreg laminate with respect to the axial direction of the press roll is applied to the double belt type heating and pressing machine illustrated in FIG. 2 in which the upper and lower belts are driven at 1.0 m / min. Was added so that the angle θ formed by In the double belt type heating and pressurizing machine, the prepreg laminate is heated by a two-stage press roll having a roll temperature of 310 ° C. and a belt clearance of 300 μm immediately below the roll to melt the thermoplastic resin. did. After that, a 1.5 m cooling section provided with a one-stage hot water roll having a roll temperature of 30 ° C. and a clearance between belts of 300 μm immediately below the roll was passed, and the thermoplastic resin was solidified to obtain a fiber reinforced plastic.
（Ｂ層）
実施例と同様の方法にて２ｍｍ厚みのシート状成形品を得た。
このようにして得たＡ層とＢ層を、実施例１と同一の方法で積層、加熱プレスして、厚み４ｍｍの繊維強化プラスチック積層体を得た。
(B layer)
A sheet-like molded product having a thickness of 2 mm was obtained in the same manner as in the example.
The A layer and B layer thus obtained were laminated and heated and pressed in the same manner as in Example 1 to obtain a fiber reinforced plastic laminate having a thickness of 4 mm.
［評価結果］
Ａ層の軟化温度は２２０℃、Ｂ層の軟化温度は２６３℃、Ａ層とＢ層を積層した繊維強化プラスチック積層体の荷重たわみ温度は２００℃と十分に高いものであった。
[Evaluation results]
The softening temperature of the A layer was 220 ° C., the softening temperature of the B layer was 263 ° C., and the deflection temperature under load of the fiber reinforced plastic laminate in which the A layer and the B layer were laminated was sufficiently high, 200 ° C.
［比較例１］
実施例１と同一の方法でＡ層を得た後、実施例１と同一方法でポリアミド６樹脂（宇部興産社製，製品名：１０１３Ｂ）を用いて２ｍｍ厚みのシートを作成した。次いで実施例１と同一の方法で積層、加熱プレスを行い４ｍｍ厚みの繊維強化プラスチック積層体を得た。
その結果、Ａ層の軟化温度は２２０℃、Ｂ層の軟化温度は２２０℃、Ａ層とＢ層を積層した繊維強化プラスチック積層体の荷重たわみ温度は１５５℃と不十分であった。
[Comparative Example 1]
After obtaining A layer by the same method as Example 1, the sheet | seat of 2 mm thickness was created using the polyamide 6 resin (the Ube Industries, product name: 1013B) by the same method as Example 1. FIG. Next, lamination and heating press were performed in the same manner as in Example 1 to obtain a fiber reinforced plastic laminate having a thickness of 4 mm.
As a result, the softening temperature of the A layer was 220 ° C., the softening temperature of the B layer was 220 ° C., and the deflection temperature under load of the fiber reinforced plastic laminate in which the A layer and the B layer were laminated was 155 ° C., which was insufficient.
［実施例３］
Ａ層のフィルムにポリカーボネート樹脂（三菱エンジニアリング社製，製品名：ユーピロンＨ−４０００）とポリブチレンテレフタレート樹脂（三菱エンジニアリング社製，製品名：ノバデュラン５０１０Ｒ５）を８０：２０のブレンド比で混ぜた樹脂を用いた以外は実施例１と全く同一の方法で、Ａ層とＢ層を得、ついでそれらを積層して加熱プレスを行い、４ｍｍ厚みの繊維強化プラスチック積層体を得た。
その結果、Ａ層の軟化温度は２２２℃、Ｂ層の軟化温度は２６３℃、Ａ層とＢ層を積層した繊維強化プラスチック積層体の荷重たわみ温度は２００℃と十分高いものであった。
[Example 3]
A resin in which polycarbonate resin (product name: Iupilon H-4000, manufactured by Mitsubishi Engineering Co., Ltd.) and polybutylene terephthalate resin (product name: manufactured by Mitsubishi Engineering Corp., product name: NOVADURAN 5010R5) is mixed with the A layer film at a blend ratio of 80:20. Except for the use, the A and B layers were obtained in exactly the same manner as in Example 1, and then they were laminated and heated and pressed to obtain a 4 mm thick fiber reinforced plastic laminate.
As a result, the softening temperature of the A layer was 222 ° C., the softening temperature of the B layer was 263 ° C., and the deflection temperature under load of the fiber reinforced plastic laminate in which the A layer and the B layer were laminated was sufficiently high, 200 ° C.
［比較例２］
Ａ層のフィルムにポリカーボネート樹脂（三菱エンジニアリング社製，製品名：ユーピロンＨ−４０００）とポリブチレンテレフタレート樹脂（三菱エンジニアリング社製，製品名：ノバデュラン５０１０Ｒ５）を８０：２０のブレンド比で混ぜた樹脂を用いた以外は実施例２と全く同一の方法で、Ａ層とＢ層を得、ついでそれらを積層して加熱プレスを行い、４ｍｍ厚みの繊維強化プラスチック積層体を得た。
その結果Ａ層の軟化温度は２２２℃、Ｂ層の軟化温度は２２０℃、Ａ層とＢ層を積層した繊維強化プラスチック積層体の荷重たわみ温度は１５５℃と不十分であった。
[Comparative Example 2]
A resin in which polycarbonate resin (product name: Iupilon H-4000, manufactured by Mitsubishi Engineering Co., Ltd.) and polybutylene terephthalate resin (product name: manufactured by Mitsubishi Engineering Corp., product name: NOVADURAN 5010R5) is mixed with the A layer film at a blend ratio of 80:20. Except for the use, the A layer and the B layer were obtained in exactly the same manner as in Example 2, and then they were laminated and heated and pressed to obtain a 4 mm thick fiber reinforced plastic laminate.
As a result, the softening temperature of the A layer was 222 ° C., the softening temperature of the B layer was 220 ° C., and the deflection temperature under load of the fiber reinforced plastic laminate in which the A layer and the B layer were laminated was 155 ° C., which was insufficient.
［実施例４］
一方向に炭素繊維（三菱レイヨン社製、製品名：パイロフィル（登録商標）ＴＲ−５０Ｓ１５Ｌ）を平面状に引き揃えて目付が７２．０ｇ／ｍ２となる強化繊維シートとし、強化繊維シートの両面を、変性ポリプロピレン樹脂（三菱化学社製、製品名：モディックＰ９５８）からなる目付が３６．４ｇ／ｍ２のフィルムで挟み、２５０℃に加熱したカレンダロールを通して、熱可塑性樹脂を繊維シートに含浸し、繊維体積含有率（Ｖｆ）が３３％、厚さが、０．１２ｍｍの一方向繊維強化プラスチックを得た。得られた一方向繊維強化プラスチックを３００ｍｍ角に切り出し、４層を疑似等方（［０／４５／９０／−４５］）に重ねた（Ａ層）。
[Example 4]
Carbon fiber (product name: Pyrofil (registered trademark) TR-50S15L manufactured by Mitsubishi Rayon Co., Ltd.) is aligned in one direction to form a reinforcing fiber sheet having a basis weight of 72.0 g / m 2, and both sides of the reinforcing fiber sheet Is impregnated with a film made of a modified polypropylene resin (product name: Modic P958, manufactured by Mitsubishi Chemical Corporation) with a basis weight of 36.4 g / m 2 , and the fiber sheet is impregnated with a thermoplastic sheet through a calender roll heated to 250 ° C. A fiber volume content (Vf) of 33% and a thickness of 0.12 mm were obtained. The obtained unidirectional fiber-reinforced plastic was cut into a 300 mm square, and four layers were stacked in a pseudo isotropic manner ([0/45/90 / -45]) (A layer).
ついで実施例１と同一の方法ポリアミド６６のペレット３７５ｇを加熱プレスして、厚み３ｍｍのＢ層を得た後、実施例１と全く同一の方法でＡ層／Ｂ層／Ａ層の順に積層し、加熱プレスを行い、４ｍｍ厚みの繊維強化プラスチック積層体を得た。
その結果Ａ層の軟化温度は１６５℃、Ｂ層の軟化温度は２６３℃、Ａ層とＢ層を積層した繊維強化プラスチック積層体の荷重たわみ温度は２００℃と十分であった。
Next, the same method as in Example 1 375 g of polyamide 66 pellets were hot-pressed to obtain a B layer having a thickness of 3 mm, and then layered in the order of A layer / B layer / A layer in the same manner as in Example 1. Then, a hot press was performed to obtain a fiber reinforced plastic laminate having a thickness of 4 mm.
As a result, the softening temperature of the A layer was 165 ° C., the softening temperature of the B layer was 263 ° C., and the deflection temperature under load of the fiber reinforced plastic laminate in which the A layer and the B layer were laminated was 200 ° C.
［比較例３］
Ｂ層にポリアミド６を用いたいた以外は、実施例４と全く同一の方法で４ｍｍ厚みの繊維強化プラスチック積層体を得た。
その結果Ａ層の軟化温度は１６５℃、Ｂ層の軟化温度は２２０℃、Ａ層とＢ層を積層した繊維強化プラスチック積層体の荷重たわみ温度は１５５℃と不十分であった。
[Comparative Example 3]
A fiber-reinforced plastic laminate having a thickness of 4 mm was obtained in the same manner as in Example 4 except that polyamide 6 was used for layer B.
As a result, the softening temperature of the A layer was 165 ° C., the softening temperature of the B layer was 220 ° C., and the deflection temperature under load of the fiber reinforced plastic laminate in which the A layer and the B layer were laminated was 155 ° C., which was insufficient.
［実施例５］
実施例１と同様の方法で一方向配向繊維強化プラスチックを得た後に、加熱プレスを行って１ｍｍ厚みの疑似等方積層の繊維強化プラスチックを得た（Ａ層）。その後、その繊維強化プラスチックを１００ｍｍ×１００ｍｍに切り出し、キャビティサイズが１００ｍｍ×１００ｍｍ、厚み４ｍｍの射出成形用金型に挿入した。その後、インサートしたＡ層の片側に樹脂が充填するように、シリンダ温度３３０℃、金型温度１１０℃にてＰＰＳ樹脂（東レ社製、製品名：トレリナＡ５０４Ｘ９０）を射出成形した。
その結果Ａ層の軟化温度は２２０℃、Ｂ層の軟化温度は２７８℃、Ａ層とＢ層を積層した繊維強化プラスチック積層体の荷重たわみ温度は２５０℃以上で十分に高いものであった。
[Example 5]
After obtaining a unidirectionally oriented fiber reinforced plastic in the same manner as in Example 1, heat pressing was performed to obtain a 1 mm thick pseudo-isotropic laminated fiber reinforced plastic (layer A). Thereafter, the fiber reinforced plastic was cut into 100 mm × 100 mm, and inserted into an injection mold having a cavity size of 100 mm × 100 mm and a thickness of 4 mm. Thereafter, PPS resin (product name: Torelina A504X90, manufactured by Toray Industries, Inc.) was injection molded at a cylinder temperature of 330 ° C. and a mold temperature of 110 ° C. so that the resin was filled on one side of the inserted A layer.
As a result, the softening temperature of the A layer was 220 ° C., the softening temperature of the B layer was 278 ° C., and the deflection temperature under load of the fiber reinforced plastic laminate in which the A layer and the B layer were laminated was 250 ° C. or higher.
［比較例４］
Ｂ層の射出樹脂をＰＥＥＫ樹脂（ＶＩＣＴＲＥＸ社製、製品名：４５０Ｇ）、シリンダ温度３８０℃、金型温度１５０℃に設定した以外は、実施例５と同一の方法で繊維強化プラスチック積層体を得た。しかしながら射出成形の際にＰＥＥＫ樹脂が高温のために、界面に存在するＡ層が分解し、評価を行うことができなかった。
[Comparative Example 4]
A fiber reinforced plastic laminate is obtained in the same manner as in Example 5 except that the injection resin of layer B is set to PEEK resin (product name: 450G manufactured by VICTREX), cylinder temperature 380 ° C., mold temperature 150 ° C. It was. However, since the PEEK resin was at a high temperature during injection molding, the A layer existing at the interface was decomposed and evaluation could not be performed.
［比較例５］
（Ａ層）
一方向に炭素繊維（三菱レイヨン社製、製品名：パイロフィル（登録商標）ＴＲ−５０Ｓ１５Ｌ）を平面状に引き揃えて目付が７２．０ｇ／ｍ２となる強化繊維シートとし、強化繊維シートの両面を、ポリアミド６６樹脂（デュポン社製、製品名：ザイデル１０１Ｆ）からなる目付が４５．６ｇ／ｍ２のフィルムで挟み、２８０℃に加熱したカレンダロールを通したが、繊維束中に樹脂を十分に含浸することはできなかった。
[Comparative Example 5]
(A layer)
Carbon fiber (product name: Pyrofil (registered trademark) TR-50S15L manufactured by Mitsubishi Rayon Co., Ltd.) is aligned in one direction to form a reinforcing fiber sheet having a basis weight of 72.0 g / m 2, and both sides of the reinforcing fiber sheet Is sandwiched between films of polyamide 66 resin (manufactured by DuPont, product name: Seidel 101F) with a basis weight of 45.6 g / m 2 and passed through a calender roll heated to 280 ° C., but the resin is sufficiently contained in the fiber bundle. Could not be impregnated.
１ ダブルベルト式加熱加圧機
１０ プレスロール
１２ ベルト
１４ ＩＲヒータ
１６ 温水ロール
１８ 巻取りロール
２０ 駆動ロール
２２ 従動ロール
２４ ガイドロール
１００ 一方向繊維強化プラスチック
１１０ 強化繊維
１２０ 繊維強化プラスチック（Ａ層）
DESCRIPTION OF SYMBOLS 1 Double belt type heat press machine 10 Press roll 12 Belt 14 IR heater 16 Hot water roll 18 Winding roll 20 Drive roll 22 Driven roll 24 Guide roll 100 Unidirectional fiber reinforced plastic 110 Reinforced fiber 120 Fiber reinforced plastic (A layer)
Claims (9)
Ａ層：強化繊維と熱可塑性樹脂とを含む繊維強化プラスチックあって、前記強化繊維の平均繊維長が１０ｍｍ以上である。
Ｂ層：熱可塑性樹脂、もしくはフィラー含有物と熱可塑性樹脂とを含む強化プラスチックである。
軟化点：層を構成する熱可塑性樹脂が結晶性樹脂の場合は、当該熱可塑性樹脂の融点が当該層の軟化点であり、層を構成する熱可塑性樹脂が非晶性樹脂の場合は、当該熱可塑性樹脂のガラス転移点が当該層の軟化点である。 A laminate having at least a two-layer structure, comprising the following A layer and B layer, the softening point of the B layer being higher than that of the A layer, and the softening point of the B layer being 230 ° C. or higher and 300 ° C. or lower. , Fiber reinforced plastic laminate.
Layer A: a fiber-reinforced plastic containing reinforcing fibers and a thermoplastic resin, wherein the average fiber length of the reinforcing fibers is 10 mm or more.
B layer: a thermoplastic resin, or a reinforced plastic containing a filler-containing material and a thermoplastic resin.
Softening point: When the thermoplastic resin constituting the layer is a crystalline resin, the melting point of the thermoplastic resin is the softening point of the layer, and when the thermoplastic resin constituting the layer is an amorphous resin, The glass transition point of the thermoplastic resin is the softening point of the layer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7395923B2 (en) | 2019-10-03 | 2023-12-12 | Ｕｂｅ株式会社 | Polyamide resin film and laminate for bonding with prepreg |
| JP7453840B2 (en) | 2020-04-22 | 2024-03-21 | 積水化学工業株式会社 | multilayer pipe |
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| JP7453840B2 (en) | 2020-04-22 | 2024-03-21 | 積水化学工業株式会社 | multilayer pipe |
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