JP2015039842A - Fiber-reinforced resin sheet, integrated molding, and method for producing them - Google Patents
Fiber-reinforced resin sheet, integrated molding, and method for producing them Download PDFInfo
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Landscapes
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Abstract
Description
本発明は強化繊維からなるマットに熱可塑性樹脂が含浸してなる繊維強化樹脂シート、該繊維強化樹脂シートを含んでなる一体成形品、およびそれらの製造方法に関する。 The present invention relates to a fiber reinforced resin sheet obtained by impregnating a mat made of reinforcing fibers with a thermoplastic resin, an integrally formed article including the fiber reinforced resin sheet, and a method for producing the same.
強化繊維とマトリックス樹脂からなる繊維強化プラスチック（ＦＲＰ）は、軽量性や力学特性に優れることから、各種産業用途に幅広く利用されている。中でも、熱可塑性樹脂を用いたＦＲＰは、高速成形による大量生産が可能であり、リサイクル性にも優れることから、近年、特に注目を集めている。特に運輸部門では軽量化が燃費に直結する事から、自動車部材等への熱可塑性樹脂を用いたＦＲＰの適用検討が活発に進められている。 Fiber reinforced plastic (FRP) composed of reinforced fibers and matrix resin is widely used in various industrial applications because of its excellent light weight and mechanical properties. Among these, FRP using a thermoplastic resin has attracted particular attention in recent years because it can be mass-produced by high-speed molding and has excellent recyclability. In particular, in the transportation sector, since weight reduction is directly linked to fuel consumption, studies on application of FRP using thermoplastic resin to automobile members and the like are being actively promoted.
軽量化を実現するには、スキンに高剛性材料、コアに低比重材を用いたサンドイッチ構造体がしばしば用いられる。低比重のコアで厚みを増やすことで、均一な材料よりも優れた比曲げ剛性を得ることができる。コア材としては発泡性の熱可塑性樹脂やハニカム構造体等が使用されるが、加工性の観点から、繊維状のコア材料を用いたサンドイッチ構造体が注目されている。 In order to achieve weight reduction, a sandwich structure using a highly rigid material for the skin and a low specific gravity material for the core is often used. By increasing the thickness with a core having a low specific gravity, it is possible to obtain a specific bending rigidity superior to that of a uniform material. As the core material, a foamable thermoplastic resin, a honeycomb structure, or the like is used. From the viewpoint of workability, a sandwich structure using a fibrous core material has attracted attention.
特許文献１には、不連続強化繊維をスプリングバックさせた発泡層に、別途成形された表層を接合してなる多孔質成形品が開示されている。発泡層を中間におき、表層に別途成形した材料を配置することで、優れた軽量化を達成できるとしている。また、特許文献２には、ＦＲＰの発泡シート同士を無機フィラー含有熱可塑性樹脂にて接着させることで、所望の厚みとした均質な多孔質成形品とその製造方法が開示されている。これによれば、スプリングバックにより形成した空隙へ無機フィラー含有熱可塑性樹脂が含浸することで、発泡シート同士が良く接着した軽量構造体を製造できる。しかしながら、これらの技術では発泡層と表層、あるいは発泡層同士に十分な接着性が得られない場合がある。特に、異なる樹脂を用いた層間を強固に接着させる技術については、開示も示唆もない。さらに軽量構造体中において、無機フィラー含有熱可塑性樹脂による接着層を配置することで、繊維による強化がなされない部分が生じ、接着性・全体強度に不均質性が生じる場合がある。 Patent Document 1 discloses a porous molded product obtained by joining a separately formed surface layer to a foamed layer in which discontinuous reinforcing fibers are spring-backed. It is said that an excellent weight reduction can be achieved by placing a foam layer in the middle and placing a separately molded material on the surface layer. Patent Document 2 discloses a homogeneous porous molded article having a desired thickness by bonding FRP foam sheets with thermoplastic resin containing an inorganic filler, and a method for producing the same. According to this, the lightweight structure which the foamed sheets adhered well can be manufactured by impregnating the inorganic filler containing thermoplastic resin to the space | gap formed by the springback. However, these techniques may not provide sufficient adhesion between the foam layer and the surface layer or between the foam layers. In particular, there is no disclosure or suggestion of a technique for firmly bonding layers using different resins. Furthermore, in the lightweight structure, by arranging an adhesive layer made of an inorganic filler-containing thermoplastic resin, a portion that is not reinforced by fibers is generated, and inhomogeneity may occur in adhesion and overall strength.
本発明は、上記の課題を鑑み、特に異なる熱可塑性樹脂をマトリックスとした材料であっても強固に接合可能な繊維強化樹脂シート、およびそれを用いた一体成形品、ならびにそれらの製造方法を提供する。 In view of the above-mentioned problems, the present invention provides a fiber-reinforced resin sheet that can be strongly bonded even with a material that uses a different thermoplastic resin as a matrix, an integrally molded product using the same, and a method for producing the same. To do.
前記課題を解決するために、本発明は以下の構成を採用する。
（１）不連続強化繊維からなるマットに熱可塑性樹脂が含浸されてなる繊維強化樹脂シートであって、前記シートは空隙を有する空隙層と実質的に空隙を有しない含浸層を有し、空隙層は含浸層の少なくとも片側に配置され、更に空隙層と含浸層の境界面にて強化繊維を共有している、繊維強化樹脂シート。
（２）空隙率が６５〜９０体積％である、（１）に記載の繊維強化樹脂シート。
（３）前記空隙層が強化繊維の起毛力により形成される（１）または（２）に記載の繊維強化樹脂シート。
（４）前記マットは、不連続強化繊維がモノフィラメント状に分散してなる、（１）〜（３）のいずれかに記載の繊維強化樹脂シート。
（５）前記マットは、不連続強化繊維がランダムに分散してなる、（１）〜（４）のいずれかに記載の繊維強化樹脂シート。
（６）前記マットを構成する強化繊維の面外角度θｚが５°以上である、（１）〜（５）のいずれかに記載の繊維強化樹脂シート。
（７）前記マットを構成する強化繊維が炭素繊維である、（１）〜（６）のいずれかに記載の繊維強化樹脂シート。
（８）前記熱可塑性樹脂が、ポリオレフィン樹脂、ポリアミド樹脂、ポリフェニレンサルファイド樹脂、ポリエステル系樹脂、ポリエーテルイミド樹脂から選択される少なくとも１種である、（１）〜（７）のいずれかに記載の繊維強化樹脂シート。
（９）少なくとも下記工程［１］，［２］および［３］を有する、（１）〜（８）のいずれかに記載の繊維強化樹脂シートの製造方法。
工程［１］：熱可塑性樹脂を溶融もしくは軟化する温度以上に加熱された状態で圧力を付与し、前記マットに熱可塑性樹脂を含浸せしめて繊維樹脂シートとする工程
工程［２］：次いで、繊維樹脂シートを冷却し、そこに含まれる熱可塑性樹脂を全体的に固化せしめる工程
工程［３］：次いで、熱可塑性樹脂が全体的に固化した繊維樹脂シートの少なくとも片表面を熱可塑性樹脂の溶融または軟化する温度以上に加熱し、強化繊維の起毛力により空隙層を形成する工程
（１０）少なくとも下記工程［１］，［２’］および［３’］を有する、（１）〜（８）のいずれかに記載の繊維強化樹脂シートの製造方法。
工程［１］：熱可塑性樹脂を溶融もしくは軟化する温度以上に加熱された状態で圧力を付与し、前記マットに熱可塑性樹脂を含浸せしめて繊維樹脂シートとする工程
工程［２’］：次いで、熱可塑性樹脂が溶融もしくは軟化した繊維樹脂シートに圧力を保持した状態で、その片表面を冷却して、冷却側の熱可塑性樹脂を固化せしめる工程
工程［３’］：次いで、もう片表面の熱可塑性樹脂が固化するより前に圧力を開放して、強化繊維の起毛力により空隙層を形成する工程
（１１）（１）〜（８）のいずれかに記載の繊維強化樹脂シートからなる第１の部材の空隙層に、熱可塑性樹脂から構成される別の成形体からなる第２の部材の熱可塑性樹脂が含浸してなる、一体成形品。
（１２）前記第１の部材を構成する熱可塑性樹脂と第２の部材を構成する熱可塑性樹脂が互いに相溶しないものである、（１１）に記載の一体成形品。
（１３）一体成形品中において第１の部材と第２の部材とが最大高さＲｙ５０μｍ以上、平均粗さＲｚ３０μｍ以上の凹凸形状を有して境界層を形成してなる、（１１）または（１２）に記載の一体成形品。
（１４）（１１）〜（１３）のいずれかに記載の一体成形品を製造する方法であって、前記第２の部材が射出成形による成形体であり、第２の部材をインサート射出成形ないしアウトサート射出成形により第１の部材に接合する、一体成形品の製造方法。
（１５）（１１）〜（１３）のいずれかに記載の一体成形品を製造する方法であって、前記第２の部材がプレス成形による成形体であり、第２の部材をプレス成形により第１の部材に接合してなる、一体成形品の製造方法。
（１６）（１１）〜（１３）のいずれかに記載の一体成形品が、自動車内外装、電気・電子機器筐体、自転車、スポーツ用品用構造用材料、輸送用箱体として用いられる、実装部材。
In order to solve the above problems, the present invention adopts the following configuration.
(1) A fiber-reinforced resin sheet obtained by impregnating a thermoplastic resin with a mat composed of discontinuous reinforcing fibers, the sheet having a void layer having voids and an impregnation layer having substantially no voids, The fiber reinforced resin sheet, wherein the layer is disposed on at least one side of the impregnated layer, and further shares the reinforcing fiber at the interface between the void layer and the impregnated layer.
(2) The fiber-reinforced resin sheet according to (1), wherein the porosity is 65 to 90% by volume.
(3) The fiber reinforced resin sheet according to (1) or (2), wherein the void layer is formed by raising force of reinforcing fibers.
(4) The mat is a fiber-reinforced resin sheet according to any one of (1) to (3), in which discontinuous reinforcing fibers are dispersed in a monofilament shape.
(5) The fiber-reinforced resin sheet according to any one of (1) to (4), wherein the mat is formed by discontinuously discontinuous reinforcing fibers.
(6) The fiber-reinforced resin sheet according to any one of (1) to (5), wherein an out-of-plane angle θz of the reinforcing fibers constituting the mat is 5 ° or more.
(7) The fiber-reinforced resin sheet according to any one of (1) to (6), wherein the reinforcing fibers constituting the mat are carbon fibers.
(8) The thermoplastic resin according to any one of (1) to (7), wherein the thermoplastic resin is at least one selected from polyolefin resins, polyamide resins, polyphenylene sulfide resins, polyester resins, and polyetherimide resins. Fiber reinforced resin sheet.
(9) The manufacturing method of the fiber reinforced resin sheet in any one of (1)-(8) which has at least following process [1], [2] and [3].
Step [1]: Step [2] in which a pressure is applied in a state heated to a temperature higher than the temperature at which the thermoplastic resin is melted or softened and the mat is impregnated with the thermoplastic resin to obtain a fiber resin sheet [2]: Next, the fiber Step [3] of cooling the resin sheet and totally solidifying the thermoplastic resin contained therein [3]: Next, at least one surface of the fiber resin sheet on which the thermoplastic resin is totally solidified is melted of the thermoplastic resin or Heating above the softening temperature and forming a void layer by the raising force of the reinforcing fibers (10) At least the following steps [1], [2 ′] and [3 ′], (1) to (8) The manufacturing method of the fiber reinforced resin sheet in any one.
Step [1]: Applying pressure in a state heated above the temperature at which the thermoplastic resin is melted or softened, and impregnating the mat with the thermoplastic resin to obtain a fiber resin sheet [2 ′]: Step [3 ′] of cooling the one surface of the fiber resin sheet in which the thermoplastic resin is melted or softened while maintaining the pressure to solidify the thermoplastic resin on the cooling side: Next, the heat of the other surface Step (11) in which the pressure is released before the plastic resin is solidified and the void layer is formed by the raising force of the reinforcing fibers (11) The first fiber-reinforced resin sheet according to any one of (1) to (8) An integrally molded product obtained by impregnating the void layer of the member with the thermoplastic resin of the second member made of another molded body made of a thermoplastic resin.
(12) The integrally molded product according to (11), wherein the thermoplastic resin constituting the first member and the thermoplastic resin constituting the second member are incompatible with each other.
(13) In the integrally molded product, the first member and the second member have a concavo-convex shape having a maximum height Ry of 50 μm or more and an average roughness Rz of 30 μm or more to form a boundary layer (11) or ( The integrally molded product according to 12).
(14) A method for producing an integrally molded product according to any one of (11) to (13), wherein the second member is a molded body by injection molding, and the second member is inserted by injection molding. A method for manufacturing an integrally molded article, wherein the first member is joined by outsert injection molding.
(15) A method for producing an integrally molded product according to any one of (11) to (13), wherein the second member is a molded body by press molding, and the second member is formed by press molding. A method for producing an integrally molded product, which is formed by joining to one member.
(16) The mounting in which the integrally molded product according to any one of (11) to (13) is used as an automobile interior / exterior, a housing for electric / electronic devices, a bicycle, a structural material for sports equipment, and a transport box Element.
本発明の繊維強化樹脂シートは、空隙を有する空隙層を有することで、異なる樹脂材料が一体成形時に空隙に入り込み、当該シートの強化繊維を共有するとともに樹脂境界面に複雑なアンカリング構造を形成する。このため、得られる一体成形品は新たな接着剤塗布工程や、新たな接合工程を踏む必要なく強固に接合できる。さらに、互いに相溶しない樹脂同士でも強固に接着した一体成形品を得ることができる。 The fiber-reinforced resin sheet of the present invention has a void layer having voids, so that different resin materials enter the voids during integral molding, share the reinforcing fibers of the sheet, and form a complex anchoring structure on the resin interface To do. For this reason, the integrally molded product obtained can be joined firmly without having to go through a new adhesive application process or a new joining process. Furthermore, an integrally molded product can be obtained in which even resins that are not compatible with each other are firmly bonded.
加えて、本発明の繊維強化樹脂シートは、上記のアンカリング構造による強固な接合が容易に形成するため、異なる熱可塑性樹脂材料を用いたハイブリッド成形を容易に実施でき、生産性および軽量性に優れるハイブリッド成形品を得ることができる。 In addition, since the fiber-reinforced resin sheet of the present invention is easily formed by the above-described anchoring structure, it is easy to perform hybrid molding using different thermoplastic resin materials, resulting in high productivity and light weight. An excellent hybrid molded product can be obtained.
以下、本発明について詳しく説明する。 The present invention will be described in detail below.
本発明の繊維強化樹脂シートは、強化繊維からなるマットに熱可塑性樹脂が含浸されてなる繊維強化樹脂シートであって、前記シートは空隙を有する空隙層と実質的に空隙を有しない含浸層を有し、空隙層は含浸層の少なくとも片側に配置され、さらに空隙層と含浸層の境界面で強化繊維を共有している。 The fiber-reinforced resin sheet of the present invention is a fiber-reinforced resin sheet obtained by impregnating a thermoplastic resin with a mat made of reinforcing fibers, and the sheet includes a void layer having voids and an impregnation layer substantially free of voids. The void layer is disposed on at least one side of the impregnation layer, and further shares the reinforcing fiber at the boundary surface between the void layer and the impregnation layer.
ここで、本発明の繊維強化樹脂シートについて、図１を用いてより詳細に説明する。繊維強化樹脂シート１は強化繊維と熱可塑性樹脂からなり、空隙４（他の空隙については符号を省略している）を有する空隙層２と、熱可塑性樹脂により実質的に空隙を有しない含浸層３により構成される。かかる繊維強化樹脂シートは、空隙層と該空隙層以外の含浸層が実質的に同一のシートから構成される
本発明において、不連続強化繊維からなるマットとは、不連続の強化繊維から構成される面状体である。マットには、強化繊維以外に粉末形状や繊維形状の樹脂成分を含んでもよい。
Here, the fiber-reinforced resin sheet of the present invention will be described in more detail with reference to FIG. The fiber reinforced resin sheet 1 is composed of a reinforced fiber and a thermoplastic resin, and has a void layer 2 having voids 4 (reference numerals are omitted for other voids) and an impregnation layer substantially free of voids due to the thermoplastic resin. 3. In such a fiber reinforced resin sheet, a gap layer and an impregnation layer other than the gap layer are composed of substantially the same sheet. In the present invention, the mat composed of discontinuous reinforcing fibers is composed of discontinuous reinforcing fibers. It is a planar body. The mat may contain a resin component having a powder shape or a fiber shape in addition to the reinforcing fiber.
本発明の繊維強化樹脂シートは実質的に空隙を有さない含浸層の少なくとも一方に、空隙を有する空隙層を有する。この空隙４に、後述するように、一体成形品の製造時に第２の部材を構成する熱可塑性樹脂が流れ込み、境界面に複雑なアンカリング構造が形成され、優れた接合強度を発現する。また、第２の部材を構成する熱可塑性樹脂の含浸度合いを制御することで、一体成形品の中央に空隙を残したサンドイッチ構造を形成する事ができ、このようなサンドイッチ構造体は優れた軽量化効果を有する。 The fiber-reinforced resin sheet of the present invention has a void layer having voids in at least one of the impregnated layers having substantially no voids. As will be described later, the thermoplastic resin constituting the second member flows into the gap 4 during the manufacture of the integrally molded product, and a complex anchoring structure is formed on the boundary surface, thereby exhibiting excellent bonding strength. Further, by controlling the degree of impregnation of the thermoplastic resin constituting the second member, it is possible to form a sandwich structure in which a gap is left in the center of the integrally molded product, and such a sandwich structure is excellent in light weight. It has an effect.
本発明の繊維強化樹脂シートにおいて、空隙層の空隙率は、通常６５〜９０体積％が好ましく、７０〜９０体積％であることが更に好ましい。この範囲とすることで、アンカリング構造による接合強度をより強固にすることができる。なお、実質的に空隙を有しない含浸層とは、通常空隙率が５体積％未満である含浸層であることを現す。 In the fiber reinforced resin sheet of the present invention, the porosity of the void layer is usually preferably from 65 to 90% by volume, and more preferably from 70 to 90% by volume. By setting it as this range, the joint strength by an anchoring structure can be strengthened more. In addition, the impregnated layer having substantially no voids means an impregnated layer having a porosity of usually less than 5% by volume.
本発明において、空隙層における空隙率は、例えば以下の方法により測定できる。ここで、空隙層と含浸層を有する繊維強化樹脂シートの拡大断面図を示した図２を用いて説明する。 In the present invention, the porosity in the void layer can be measured, for example, by the following method. Here, it demonstrates using FIG. 2 which showed the expanded sectional view of the fiber reinforced resin sheet which has a space | gap layer and an impregnation layer.
空隙層における空隙率は、研磨、またはスライスにより切り出された空隙層から、ＪＩＳ Ｋ７０７５（１９９１）に規定される「炭素繊維強化プラスチックの繊維含有率及び空洞率試験方法」の燃焼法を参考にして算出される。また、研磨に際してはＪＩＳ Ｒ６２５３に準拠した耐水研磨紙を用いることができる。なお、空隙層とは、例えば図２における空隙層と含浸層との境界面５から空隙層最外面６までの層を指す。 The void ratio in the void layer is determined by referring to the combustion method of “Fiber content rate and void ratio test method of carbon fiber reinforced plastic” defined in JIS K7075 (1991) from the void layer cut by polishing or slicing. Calculated. In polishing, water-resistant abrasive paper according to JIS R6253 can be used. The void layer refers to a layer from the boundary surface 5 between the void layer and the impregnated layer in FIG. 2 to the outermost surface 6 of the void layer.
ここで、空隙層と含浸層の境界面とは、含浸層の厚みから規定される空隙層と含浸層の実質的な層の区別点である。該含浸層の厚み算出の方法として、繊維強化樹脂シートの厚み方向における重量分率の変化より算出する方法が例示できる。該繊維強化樹脂シートを厚み方向にｎ等分し、１区間厚み分をスライス、または研磨により除去した残りのｎ―１区間分の重量Ｗ１を測定し、繊維強化樹脂シートの全重量Ｗ０に対する残留した区間の重量分率ｗ１を算出する。続いて、同様に残留したｎ−１区間から、前除去区間に隣接する１区間分をスライス、または研磨により除去し、ｎ−２区間重量Ｗ２を測定しさらに重量分率ｗ２を算出する。以上の操作をｎ―１回繰り返し、各区間除去後の残留区分重量分率ｗｉを算出する。以上の測定により、除去した厚みＴ＝Σｔｉ（ｉ＝１、２、・・・、ｎ−１）と、残留した繊維強化樹脂シート重量分率の相関関係を整理することで、図３に例示されるような相関図が得られる。得られた相関図において傾きは、除去厚みにおける見掛け密度を意味しており、該傾きが変化する変曲点までの厚みが含浸層の厚みとなり、含浸層から空隙層へ遷移する面といえる。故に、図３における、除去した厚みから含浸層厚みが特定され、すなわち境界面を特定することができる。なお、分割数ｎは１０とすることで、精度よく所定厚みを除去することが可能で、かつ変曲点を十分見出すことができ、境界面を特定することができる。 Here, the interface between the void layer and the impregnated layer is a substantial distinction between the void layer and the impregnated layer defined by the thickness of the impregnated layer. Examples of the method for calculating the thickness of the impregnated layer include a method of calculating from a change in weight fraction in the thickness direction of the fiber reinforced resin sheet. The fiber reinforced resin sheet is divided into n equal parts in the thickness direction, and the weight W1 of the remaining n-1 section removed by slicing or polishing one section thickness is measured, and the residual to the total weight W0 of the fiber reinforced resin sheet is measured. The weight fraction w1 of the obtained section is calculated. Subsequently, from the remaining n-1 section, one section adjacent to the previous removal section is removed by slicing or polishing, the n-2 section weight W2 is measured, and the weight fraction w2 is calculated. The above operation is repeated n-1 times to calculate the residual section weight fraction wi after each section is removed. FIG. 3 illustrates the correlation between the removed thickness T = Σti (i = 1, 2,..., N−1) and the remaining fiber reinforced resin sheet weight fraction by the above measurement. Correlation diagram is obtained. In the obtained correlation diagram, the slope means the apparent density in the removal thickness, and the thickness up to the inflection point at which the slope changes becomes the thickness of the impregnated layer, and can be said to be a surface that transitions from the impregnated layer to the void layer. Therefore, the thickness of the impregnation layer is specified from the removed thickness in FIG. 3, that is, the boundary surface can be specified. When the division number n is 10, the predetermined thickness can be accurately removed, inflection points can be found sufficiently, and the boundary surface can be specified.
ここで、境界面の特定方法について図３を用いてより詳細に説明する。図３に本発明の繊維強化樹脂シートを１０等分した場合の、除去した厚みと、除去後に残留した繊維強化樹脂シートの重量分率の関係の一例を示す。境界面とは、含浸層から空隙層へと遷移する面を指す。すなわち、線形領域（Ａ）―（Ａ’）の外挿線９と、線形領域（Ｂ）―（Ｂ’）の外挿線１０の交点１１が示す除去厚みが含浸層厚み１２を意味し、つまり境界面までの距離として規定される。故に、境界面は含浸層と空隙層の見かけ密度変化を基に求められる。 Here, a method for specifying the boundary surface will be described in more detail with reference to FIG. FIG. 3 shows an example of the relationship between the removed thickness and the weight fraction of the fiber-reinforced resin sheet remaining after the removal when the fiber-reinforced resin sheet of the present invention is divided into 10 equal parts. The boundary surface refers to a surface that transitions from the impregnated layer to the void layer. That is, the removal thickness indicated by the intersection 11 of the extrapolation line 9 of the linear region (A)-(A ′) and the extrapolation line 10 of the linear region (B)-(B ′) means the impregnated layer thickness 12, That is, it is defined as the distance to the boundary surface. Therefore, the boundary surface is obtained based on the apparent density change of the impregnated layer and the void layer.
本発明において、通常、前記空隙層は強化繊維の起毛力により、連続した空隙として形成される。連続した空隙とは、繊維樹脂シートを樹脂の軟化点以上の温度に加熱させたときに、強化繊維の弾性率に起因した起毛力に伴うマットの膨張により生成した、互いに連結した空孔部分をいう。該空孔部分は図１に例示されるように、強化繊維由来の空隙が生じ、熱可塑性樹脂が強化繊維を被覆するように付着した態様を示し、該空隙層と含浸層は、強化繊維が共有された状態となる。強化繊維が共有された状態とは、空隙層と含浸層の両層において、強化繊維からなる同一のマットから構成されている状態を指す。すなわち、空隙層と含浸層とを構成し共有している強化繊維と熱可塑性樹脂の関係は、いずれの層においても同等の強化繊維の体積割合で構成される状態をとる。なお、ここで、強化繊維の体積割合とは、強化繊維の体積と熱可塑性樹脂の体積の総計に対する強化繊維の体積の割合を意味している。これにより、繊維強化樹脂シートの空隙を保持することができる。また、一体成型品とした時に強固な接合性を発現することができる。 In the present invention, the void layer is usually formed as a continuous void by the raising force of the reinforcing fibers. The continuous voids are pores connected to each other generated by the expansion of the mat caused by the raising force caused by the elastic modulus of the reinforcing fiber when the fiber resin sheet is heated to a temperature equal to or higher than the softening point of the resin. Say. As illustrated in FIG. 1, the void portion shows a mode in which voids derived from reinforcing fibers are generated and the thermoplastic resin is adhered so as to cover the reinforcing fibers. It becomes a shared state. The state in which the reinforcing fibers are shared refers to a state in which both the void layer and the impregnated layer are formed of the same mat made of the reinforcing fibers. That is, the relationship between the reinforcing fiber and the thermoplastic resin constituting and sharing the void layer and the impregnated layer is in a state constituted by the volume ratio of the same reinforcing fiber in any layer. Here, the volume ratio of the reinforcing fiber means the ratio of the volume of the reinforcing fiber to the total volume of the reinforcing fiber and the thermoplastic resin. Thereby, the space | gap of a fiber reinforced resin sheet can be hold | maintained. Moreover, strong joining property can be expressed when it is set as an integrally molded product.
本発明における強化繊維からなるマットは、互いに連結した空隙層を形成する観点から、不織布状形態を取ることが好ましい。ここで、不織布形態とは、強化繊維のストランドおよび／またはモノフィラメントが面状に分散した形態を指し、チョップドストランドマット、コンティニュアンスストランドマット、抄紙マット、カーディングマット、エアレイドマット、などが例示できる。ストランドとは、複数本の単繊維が並行配列して集合したもので、繊維束とも言われる。不織布形態のマットとすることで、起毛力が増加して適切な空隙率が確保される。 The mat made of reinforcing fibers in the present invention preferably takes a non-woven fabric form from the viewpoint of forming void layers connected to each other. Here, the non-woven fabric form refers to a form in which strands and / or monofilaments of reinforcing fibers are dispersed in a planar shape, and examples thereof include a chopped strand mat, a continuous strand mat, a papermaking mat, a carding mat, and an airlaid mat. A strand is a collection of a plurality of single fibers arranged in parallel and is also called a fiber bundle. By setting it as the mat | matte of a nonwoven fabric form, raising force increases and appropriate porosity is ensured.
前記不織布形態において、強化繊維が略モノフィラメント状に分散していることが、より好ましい。略モノフィラメント状に分散するとは、強化繊維からなるマットを構成する不連続強化繊維のうち、フィラメント数１００本未満のストランドが５０重量％以上含まれることを指す。強化繊維が略モノフィラメント状に分散することで、繊維強化樹脂シート中に複雑かつ緻密なネットワーク構造が形成され、より複雑な空隙を形成できる。これにより、一体成型品とした際に、第２の成形材料との境界層に緻密なアンカリング構造を形成し、一体成形品の境界層をより強固に接合できる。 In the nonwoven fabric form, it is more preferable that the reinforcing fibers are dispersed in a substantially monofilament form. Dispersing in a substantially monofilament form means that 50% by weight or more of strands having less than 100 filaments are included in discontinuous reinforcing fibers constituting a mat composed of reinforcing fibers. By dispersing the reinforcing fibers in a substantially monofilament shape, a complicated and dense network structure is formed in the fiber reinforced resin sheet, and more complicated voids can be formed. Thereby, when it is set as an integrally molded product, a dense anchoring structure is formed in the boundary layer with the second molding material, and the boundary layer of the integrally molded product can be joined more firmly.
ここで、フィラメント数１００本以上のストランド重量割合は、以下に例示する方法により測定される。繊維強化樹脂シートから樹脂の焼き飛ばし等により強化繊維から成るマットを取り出し、マットの重量（Ｗｍ）を測定する。視認されるストランドをピンセットにより全て抽出し、抽出されたストランドの長さＬｓを１／１００ｍｍの精度で、重量Ｗｓを１／１００ｍｇの精度で測定する。経験上、視認により抽出できるストランドはフィラメント数１００本以上であり、抽出後の残分のフィラメント数は１００本未満である。また、のちに算出されるフィラメント数の結果において、フィラメント数が１００本未満となる場合、これについてはＷｓの積算対象から除外する。ｉ番目（ｉ＝１〜ｎ）に抽出されたストランドの長さＬｓｉおよび重量Ｗｓｉから、次式によりストランドにおけるフィラメント数Ｆｉを算出する。ここで、式中におけるＤはフィラメントの繊度（ｍｇ／ｍｍ）である。
・ Ｆｉ（本）＝Ｗｓｉ／（Ｄ×Ｌｓｉ）
Here, the strand weight ratio of 100 or more filaments is measured by the method exemplified below. A mat made of reinforcing fibers is taken out from the fiber reinforced resin sheet by burning out the resin, and the weight (Wm) of the mat is measured. All visible strands are extracted with tweezers, and the length Ls of the extracted strand is measured with an accuracy of 1/100 mm and the weight Ws is measured with an accuracy of 1/100 mg. From experience, strands that can be extracted by visual recognition have 100 or more filaments, and the number of filaments remaining after extraction is less than 100. Moreover, in the result of the filament number calculated later, when the number of filaments is less than 100, this is excluded from Ws accumulation targets. From the length Lsi and the weight Wsi of the strand extracted i-th (i = 1 to n), the number of filaments Fi in the strand is calculated by the following equation. Here, D in the formula is the fineness (mg / mm) of the filament.
-Fi (book) = Wsi / (D x Lsi)
上記にて算出されるＦｉをもとに、ストランドの選別をおこなう。図４は、本発明の繊維強化樹脂シートのフィラメント数５０本毎の階級別で見た、各階級に占める重量分率の内訳を示す。図４において、フィラメント数の小さい側から２階級（フィラメント０〜１００本）の棒グラフと、全ての棒グラフの総和との比率が、フィラメント数１００本未満のストランドの重量分率Ｒｗ（ｗｔ％）に相当する。これは、上記にて実測された数値を用いて、次式により算出できる。
・ Ｒｗ（重量％）＝｛Ｗｍ−Σ（Ｗｓｉ）｝／Ｗｍ×１００
Based on the Fi calculated above, the strands are selected. FIG. 4 shows a breakdown of the weight fraction in each class as seen by class for every 50 filaments of the fiber-reinforced resin sheet of the present invention. In FIG. 4, the ratio of the bar graph of the second class (from 0 to 100 filaments) from the side with the smallest number of filaments to the sum of all the bar graphs is the weight fraction Rw (wt%) of the strands with less than 100 filaments. Equivalent to. This can be calculated by the following equation using the numerical values actually measured above.
Rw (% by weight) = {Wm−Σ (Wsi)} / Wm × 100
前記不織布形態において、強化繊維がモノフィラメント状に分散しているものが、さらに好ましい。ここで、モノフィラメント状に分散しているとは、繊維強化樹脂シート中にて任意に選択した強化繊維について、その二次元接触角が１度以上である単繊維の割合（以下、繊維分散率とも称す）が８０％以上であることを指す。従って図４において、強化繊維からなるマットにおけるフィラメント数１００本以下のストランドの重量分率Ｒｗが１００％に該当する繊維強化樹脂シートのみを対象とする。 In the nonwoven fabric form, it is more preferable that the reinforcing fibers are dispersed in a monofilament form. Here, “dispersed in a monofilament shape” means a ratio of single fibers having a two-dimensional contact angle of 1 degree or more with respect to the reinforcing fibers arbitrarily selected in the fiber reinforced resin sheet (hereinafter also referred to as fiber dispersion ratio). Refers to 80% or more. Therefore, in FIG. 4, only the fiber reinforced resin sheet in which the weight fraction Rw of the strands having 100 or less filaments in the mat made of reinforcing fibers corresponds to 100% is targeted.
二次元接触角とは、不連続の強化繊維の単繊維と該単繊維と接触する単繊維とで形成される角度のことであり、接触する単繊維同士が形成する角度のうち、０度以上９０度以下の鋭角側の角度と定義する。この二次元接触角について、図面を用いてさらに説明する。図５（ａ）、（ｂ）は本発明における一実施態様であって、繊維強化樹脂シートの不連続強化繊維を面方向（ａ）および厚み方向（ｂ）から観察した場合の模式図である。単繊維１３を基準とすると、単繊維１３は図５（ａ）で単繊維１４〜１８と交わって観察されるが、図５（ｂ）では単繊維１３は単繊維１７および１８とは接触していない。この場合、基準となる単繊維１３について、二次元接触角度の評価対象となるのは単繊維１４〜１６であり、接触する２つの単繊維が形成する２つの角度のうち、０度以上９０度以下の鋭角側の角度１９である。 The two-dimensional contact angle is an angle formed by a single fiber of discontinuous reinforcing fibers and a single fiber that comes into contact with the single fiber. Of the angles formed by the single fibers that come into contact with each other, 0 degrees or more It is defined as an acute angle of 90 degrees or less. This two-dimensional contact angle will be further described with reference to the drawings. FIGS. 5 (a) and 5 (b) are one embodiment of the present invention, and are schematic views when discontinuous reinforcing fibers of a fiber reinforced resin sheet are observed from the surface direction (a) and the thickness direction (b). . When the single fiber 13 is used as a reference, the single fiber 13 is observed to intersect with the single fibers 14 to 18 in FIG. 5A, but the single fiber 13 is in contact with the single fibers 17 and 18 in FIG. Not. In this case, the evaluation target of the two-dimensional contact angle of the reference single fiber 13 is the single fibers 14 to 16, and of the two angles formed by the two single fibers that are in contact with each other, 0 degrees or more and 90 degrees The following acute angle 19 is set.
繊維強化樹脂シートから二次元接触角を測定する方法としては、特に制限はないが、例えば、繊維強化樹脂シートの表面から強化繊維の配向を観察する方法が例示できる。この場合、繊維強化樹脂シートの表面を研磨して強化繊維を露出させることで、より強化繊維を観察しやすくなる。また、透過光を利用して強化繊維の配向を観察する方法が例示できる。この場合、繊維強化樹脂シートを薄くスライスすることで、強化繊維を観察しやすくなる。さらに、繊維強化樹脂シートをＸ線ＣＴにより透過観察して強化繊維の配向画像を撮影する方法も例示できる。Ｘ線透過性の高い強化繊維の場合には、強化繊維にトレーサ用の繊維を混合しておく、あるいは強化繊維にトレーサ用の薬剤を塗布しておくと、強化繊維を観察しやすくなるため好ましい。また、上記方法で測定が困難な場合には、光学顕微鏡または電子顕微鏡を用いて、強化繊維の配向を直接、観察する方法が例示できる。前記観察方法に基づき、繊維分散率は次の手順で測定する。無作為に選択した単繊維（図５における単繊維１３）に対して接触している全ての単繊維（図５における単繊維１４〜１８）との二次元接触角を測定する。これを１００本の単繊維についておこない、二次元接触角を測定した全ての単繊維の総本数と、二次元接触角が１度以上である単繊維の本数との比率から、割合を算出する。 Although there is no restriction | limiting in particular as a method of measuring a two-dimensional contact angle from a fiber reinforced resin sheet, For example, the method of observing the orientation of a reinforced fiber from the surface of a fiber reinforced resin sheet can be illustrated. In this case, it becomes easier to observe the reinforcing fibers by polishing the surface of the fiber-reinforced resin sheet to expose the reinforcing fibers. Moreover, the method of observing the orientation of the reinforcing fiber using transmitted light can be exemplified. In this case, it becomes easy to observe the reinforcing fiber by thinly slicing the fiber-reinforced resin sheet. Furthermore, a method of transmitting a fiber reinforced resin sheet through X-ray CT and photographing an orientation image of the reinforced fiber can also be exemplified. In the case of a reinforcing fiber having a high X-ray permeability, it is preferable to mix a tracer fiber with the reinforcing fiber or to apply a tracer agent to the reinforcing fiber because the reinforcing fiber can be easily observed. . Moreover, when it is difficult to measure by the above method, a method of directly observing the orientation of the reinforcing fiber using an optical microscope or an electron microscope can be exemplified. Based on the observation method, the fiber dispersion rate is measured by the following procedure. Two-dimensional contact angles with all single fibers (single fibers 14 to 18 in FIG. 5) in contact with randomly selected single fibers (single fibers 13 in FIG. 5) are measured. This is performed for 100 single fibers, and the ratio is calculated from the ratio between the total number of all single fibers whose two-dimensional contact angle is measured and the number of single fibers whose two-dimensional contact angle is 1 degree or more.
前記不織布形態において、強化繊維がランダムに分散していることが、より好ましい。ここで、強化繊維がランダムに分散しているとは、繊維強化樹脂シート中にて任意に選択した強化繊維の二次元配向角の平均値が３０〜６０度であることをいう。より好ましくは、４０〜５０度である。二次元配向角とは、強化繊維の単繊維と、該単繊維と交差する単繊維とで形成される角度のことであり、交差する単繊維同士が形成する角度のうち、０度以上９０度以下の鋭角側の角度と定義する。この二次元配向角について、図面を用いてさらに説明する。ここで、図５にてマットからランダムに抽出した強化繊維分散状態の一例（ａ）、（ｂ）を示す。図５（ａ）、（ｂ）において、単繊維１３を基準とすると、単繊維１３は他の単繊維１４〜１８と交差している。ここで交差とは、観察する二次元平面において、基準とする単繊維が他の単繊維と交わって観察される状態のことを意味し、単繊維１３と単繊維１４〜１８が必ずしも接触している必要はなく、投影して見た場合に交わって観察される状態についても例外ではない。つまり、基準となる単繊維１３について見た場合、単繊維１４〜１８の全てが二次元配向角の評価対象であり、図５（ａ）中において二次元配向角は交差する２つの単繊維が形成する２つの角度のうち、０度以上９０度以下の鋭角側の角度１９である。 In the nonwoven fabric form, it is more preferable that the reinforcing fibers are randomly dispersed. Here, that the reinforcing fibers are randomly dispersed means that the average value of the two-dimensional orientation angles of the reinforcing fibers arbitrarily selected in the fiber-reinforced resin sheet is 30 to 60 degrees. More preferably, it is 40 to 50 degrees. The two-dimensional orientation angle is an angle formed by a single fiber of the reinforcing fiber and a single fiber that intersects with the single fiber, and the angle formed by the intersecting single fibers is 0 degree or more and 90 degrees. It is defined as the following angle on the acute angle side. This two-dimensional orientation angle will be further described with reference to the drawings. Here, examples (a) and (b) of the reinforcing fiber dispersion state randomly extracted from the mat in FIG. 5 are shown. 5A and 5B, when the single fiber 13 is used as a reference, the single fiber 13 intersects with the other single fibers 14-18. Crossing here means a state in which a single fiber as a reference is observed crossing another single fiber in a two-dimensional plane to be observed, and the single fiber 13 and the single fibers 14 to 18 are not necessarily in contact with each other. It is not necessary to be present, and it is no exception for the state observed when they are projected. That is, when the single fiber 13 serving as a reference is viewed, all of the single fibers 14 to 18 are evaluation targets of the two-dimensional orientation angle, and two single fibers whose two-dimensional orientation angles intersect in FIG. Among the two angles to be formed, the angle 19 is an acute angle side of 0 degree or more and 90 degrees or less.
繊維強化樹脂シートから二次元配向角を測定する方法としては、特に制限はないが、例えば、構成要素の表面から強化繊維の配向を観察する方法が例示でき、上述した二次元接触角の測定方法と同様の手段を取ることができる。二次元配向角の平均値は、次の手順で測定する。無作為に選択した単繊維（図５における単繊維１３）に対して交差している全ての単繊維（図５における単繊維１４〜１８）との二次元配向角の平均値を測定する。例えば、ある単繊維に交差する別の単繊維が多数の場合には、交差する別の単繊維を無作為に２０本選び測定した平均値を代用してもよい。前記測定について別の単繊維を基準として合計５回繰り返し、その平均値を二次元配向角の平均値として算出する。強化繊維がランダムに分散することで、強化繊維の起毛により形成される空隙が、より複雑な空孔部分が形成される。 The method for measuring the two-dimensional orientation angle from the fiber reinforced resin sheet is not particularly limited. For example, the method for observing the orientation of the reinforcing fiber from the surface of the component can be exemplified, and the above-described method for measuring the two-dimensional contact angle. You can take similar measures. The average value of the two-dimensional orientation angle is measured by the following procedure. The average value of the two-dimensional orientation angles with all the single fibers (single fibers 14 to 18 in FIG. 5) intersecting with the randomly selected single fibers (single fibers 13 in FIG. 5) is measured. For example, when there are many other single fibers that cross a certain single fiber, an average value obtained by randomly selecting and measuring 20 other single fibers that intersect may be used instead. The measurement is repeated a total of 5 times based on another single fiber, and the average value is calculated as the average value of the two-dimensional orientation angle. As the reinforcing fibers are randomly dispersed, voids formed by raising the reinforcing fibers form more complicated hole portions.
前記不織布形態において、強化繊維がモノフィラメント状かつランダムに分散していることが、最も好ましい。 In the nonwoven fabric form, it is most preferable that the reinforcing fibers are monofilament-like and randomly dispersed.
また、繊維強化樹脂シート中における強化繊維の面外角度θｚが５°以上であることが、繊維の起毛による最適な空隙に形成させる観点から好ましい。ここで、強化繊維の面外角度θｚとは、繊維強化樹脂シートの厚さ方向に対する強化繊維の傾き度合いであって、値が大きいほど厚み方向に立つ、すなわち起毛していることを示す。θｚは、０〜９０°の範囲で与えられる。θｚを５°以上とすることで、上述した空隙をより効果的に発生できる。θｚの上限値は特に制限ないが、起毛力の限界や一体成形品とした際の繊維体積含有率を鑑みて、１５°以下であることが好ましい。 In addition, it is preferable that the out-of-plane angle θz of the reinforcing fiber in the fiber-reinforced resin sheet is 5 ° or more from the viewpoint of forming an optimal void by raising the fibers. Here, the out-of-plane angle θz of the reinforcing fiber is the degree of inclination of the reinforcing fiber with respect to the thickness direction of the fiber-reinforced resin sheet, and indicates that the larger the value is, the higher the fiber is standing in the thickness direction. θz is given in the range of 0 to 90 °. By setting θz to 5 ° or more, the above-described gap can be generated more effectively. The upper limit of θz is not particularly limited, but is preferably 15 ° or less in view of the limit of raising force and the fiber volume content when an integrally molded product is obtained.
強化繊維の面外角度θｚは、図６に示す繊維強化樹脂シート２０の面方向に対する垂直断面の観察に基づき測定する方法が、例示できる。図６は、繊維強化樹脂シートの面方向に対する垂直断面（ａ）とその奥行き方向（ｂ）を示すものである。図６（ａ）において、強化繊維２１、２２の断面は、測定を簡便にするため、楕円形状に近似されている。ここで、強化繊維２１の断面は、楕円アスペクト比（＝楕円長軸／楕円短軸）が小さく見られ、対して強化繊維２２の断面は、楕円アスペクト比が大きく見られる。一方、図６（ｂ）によると、強化繊維２１は、奥行き方向Ｙに対してほぼ平行な傾きを持ち、強化繊維２１は、奥行き方向Ｙに対して一定量の傾きを持っている。この場合、図６（ａ）における断面２２の強化繊維については、繊維強化樹脂シートの面方向Ｘと繊維主軸（楕円における長軸方向）αとがなす角度θｘが、強化繊維の面外角度θｚとほぼ等しくなる。一方、強化繊維２１については、角度θｘと面外角度θｚの示す角度に大きな乖離があり、角度θｘが面外角度θｚを反映しているとはいえない。したがって、繊維強化樹脂シートの面方向に対する垂直断面から面外角度θｚを読み取る場合、繊維断面の楕円アスペクト比が一定以上のものについて、抽出することで面外角度θｚの検出精度を高めることができる。 A method of measuring the out-of-plane angle θz of the reinforcing fiber based on observation of a vertical cross section with respect to the surface direction of the fiber reinforced resin sheet 20 illustrated in FIG. 6 can be exemplified. FIG. 6 shows a vertical section (a) and a depth direction (b) with respect to the surface direction of the fiber reinforced resin sheet. In FIG. 6A, the cross-sections of the reinforcing fibers 21 and 22 are approximated to an elliptical shape for easy measurement. Here, the cross section of the reinforcing fiber 21 has a small elliptical aspect ratio (= ellipse long axis / short elliptical axis), whereas the cross section of the reinforcing fiber 22 has a large elliptical aspect ratio. On the other hand, according to FIG. 6B, the reinforcing fiber 21 has a substantially parallel inclination with respect to the depth direction Y, and the reinforcing fiber 21 has a certain amount of inclination with respect to the depth direction Y. In this case, for the reinforcing fiber of the cross section 22 in FIG. 6A, the angle θx formed by the surface direction X of the fiber reinforced resin sheet and the fiber principal axis (major axis direction in the ellipse) α is the out-of-plane angle θz of the reinforcing fiber. Is almost equal to On the other hand, the reinforcing fiber 21 has a large difference between the angle θx and the angle indicated by the out-of-plane angle θz, and it cannot be said that the angle θx reflects the out-of-plane angle θz. Therefore, when the out-of-plane angle θz is read from the vertical cross section with respect to the surface direction of the fiber reinforced resin sheet, the detection accuracy of the out-of-plane angle θz can be increased by extracting the out-of-plane angle θz of the fiber cross section with a certain elliptic aspect ratio .
ここで、抽出対象となる楕円アスペクト比の指標としては、単繊維の断面形状が真円に近い、すなわち強化繊維の長尺方向に垂直な断面における繊維アスペクト比が１．１以下である場合、楕円アスペクト比が２０以上の強化繊維についてＸ方向と繊維主軸αの為す角度を測定し、これを面外角度θｚとして採用する方法を利用できる。一方、単繊維の断面形状が楕円形や繭形等であり、繊維アスペクト比が１．１より大きい場合には、より大きな楕円アスペクト比を持つ強化繊維に注目し、面外角度を測定した方がよく、繊維アスペクト比が１．１以上１．８未満の場合には楕円アスペクト比が３０以上、繊維アスペクト比が１．８以上２．５未満の場合には楕円アスペクト比が４０以上、繊維アスペクト比が２．５以上の場合には楕円アスペクト比が５０以上の強化繊維を選び、面外角度θｚを測定するとよい。 Here, as an index of the elliptical aspect ratio to be extracted, the cross-sectional shape of the single fiber is close to a perfect circle, that is, when the fiber aspect ratio in the cross section perpendicular to the longitudinal direction of the reinforcing fiber is 1.1 or less, For a reinforcing fiber having an elliptical aspect ratio of 20 or more, a method of measuring the angle formed by the X direction and the fiber principal axis α and adopting this as the out-of-plane angle θz can be used. On the other hand, if the cross-sectional shape of the single fiber is an ellipse or a saddle, etc., and the fiber aspect ratio is greater than 1.1, pay attention to the reinforcing fiber having a larger elliptical aspect ratio and measure the out-of-plane angle When the fiber aspect ratio is 1.1 or more and less than 1.8, the elliptical aspect ratio is 30 or more. When the fiber aspect ratio is 1.8 or more and less than 2.5, the elliptical aspect ratio is 40 or more. When the aspect ratio is 2.5 or more, it is preferable to select a reinforcing fiber having an elliptical aspect ratio of 50 or more and measure the out-of-plane angle θz.
本発明において、強化繊維からなるマットを構成する強化繊維としては、例えば、ポリアクリロニトリル（ＰＡＮ）系、レーヨン系、リグニン系、ピッチ系の炭素繊維、黒鉛繊維、ガラスなどの絶縁性繊維、アラミド、ＰＢＯ、ポリフェニレンスルフィド、ポリエステル、アクリル、ナイロン、ポリエチレンなどの有機繊維、シリコンカーバイト、シリコンナイトライドなどの無機繊維が挙げられる。軽量化効果の観点から炭素繊維が好ましく、ＰＡＮ系炭素繊維がより好ましい。これらの繊維は表面処理が施されていてもよい。表面処理としては、導電体として金属の被着処理のほかに、カップリング剤による処理、サイジング剤による処理、結束剤による処理、添加剤の付着処理などがある。また、これらの強化繊維は１種類を単独で用いてもよいし、２種類以上を併用してもよい。また、得られる成形品の導電性を高める観点からは、ニッケルや銅やイッテルビウムなどの金属を被覆した強化繊維を用いることもできる。 In the present invention, the reinforcing fibers constituting the mat made of reinforcing fibers include, for example, polyacrylonitrile (PAN) -based, rayon-based, lignin-based, pitch-based carbon fibers, graphite fibers, insulating fibers such as glass, aramid, Examples thereof include organic fibers such as PBO, polyphenylene sulfide, polyester, acrylic, nylon, and polyethylene, and inorganic fibers such as silicon carbide and silicon nitride. From the viewpoint of lightening effect, carbon fiber is preferable, and PAN-based carbon fiber is more preferable. These fibers may be subjected to a surface treatment. Examples of the surface treatment include a treatment with a coupling agent, a treatment with a sizing agent, a treatment with a binding agent, and an adhesion treatment of an additive in addition to a process for depositing a metal as a conductor. Moreover, these reinforcing fibers may be used individually by 1 type, and may use 2 or more types together. Further, from the viewpoint of improving the conductivity of the obtained molded product, reinforcing fibers coated with a metal such as nickel, copper, ytterbium, etc. can also be used.
本発明において、強化繊維から成るマットの製造方法としては、強化繊維を空気流にて分散シート化するエアレイド法や強化繊維を機械的にくし削りながら成形してシート化するカーディング法などの乾式プロセス、強化繊維を水中にて攪拌して抄紙するラドライト法による湿式プロセスを公知技術として挙げることができる。強化繊維をよりモノフィラメント状に近づける手段としては、乾式プロセスにおいては、開繊バーを設ける方法やさらに開繊バーを振動させる方法、さらにカードの目をファインにする方法や、カードの回転速度を調整する方法などが例示できる。湿式プロセスにおいては、強化繊維の攪拌条件を調整する方法、分散液の強化繊維濃度を希薄化する方法、分散液の粘度を調整する方法、分散液を移送させる際に渦流を抑制する方法などが例示できる。特に、湿式法で製造することが好ましく、投入繊維の濃度を増やしたり、分散液の流速（流量）とメッシュコンベアの速度を調整したり、することで強化繊維からなるマットの強化繊維の割合Ｖｆｍを容易に調整することができる。例えば、分散液の流速に対して、メッシュコンベアの速度を遅くすることで、得られる強化繊維からなるマット中の繊維の配向が引き取り方向に向き難くなり、嵩高い強化繊維からなるマットを製造可能である。強化繊維からなるマットとしては、強化繊維単体から構成されていてもよく、強化繊維が粉末形状や繊維形状のマトリックス樹脂成分と混合されていたり、強化繊維が有機化合物や無機化合物と混合されていたり、強化繊維同士が樹脂成分で目留めされていてもよい。 In the present invention, as a method for producing a mat composed of reinforcing fibers, a dry method such as an airlaid method in which reinforcing fibers are dispersed into a sheet of air by an air flow or a carding method in which reinforcing fibers are molded while being mechanically scraped to form a sheet. As a known technique, a wet process by a radrite method in which paper is made by stirring the process and reinforcing fibers in water can be cited. As a means of bringing the reinforcing fibers closer to a monofilament shape, in the dry process, a method of providing a fiber opening bar, a method of vibrating the fiber opening bar, a method of further finening the card eye, and adjusting the rotation speed of the card The method of doing etc. can be illustrated. In the wet process, there are a method of adjusting the stirring condition of the reinforcing fiber, a method of diluting the reinforcing fiber concentration of the dispersion, a method of adjusting the viscosity of the dispersion, and a method of suppressing the vortex when the dispersion is transferred. It can be illustrated. In particular, it is preferably produced by a wet method, and the ratio Vfm of the reinforcing fibers of the mat made of reinforcing fibers can be obtained by increasing the concentration of the input fibers or adjusting the flow rate (flow rate) of the dispersion and the speed of the mesh conveyor. Can be adjusted easily. For example, by slowing down the mesh conveyor with respect to the flow rate of the dispersion, it becomes difficult to orient the fibers in the resulting mat made of reinforcing fibers in the take-off direction, making it possible to produce mats made of bulky reinforcing fibers It is. The mat made of reinforcing fibers may be composed of reinforcing fibers alone, and the reinforcing fibers are mixed with a matrix resin component in a powder form or fiber shape, or the reinforcing fibers are mixed with an organic compound or an inorganic compound. Further, the reinforcing fibers may be sealed with a resin component.
本発明の繊維強化樹脂シートを構成する熱可塑性樹脂としては、例えば、「ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリトリメチレンテレフタレート（ＰＴＴ）、ポリエチレンナフタレート（ＰＥＮ）、液晶ポリエステル等のポリエステルや、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、ポリブチレン等のポリオレフィンや、ポリオキシメチレン（ＰＯＭ）、ポリアミド（ＰＡ）、ポリフェニレンスルフィド（ＰＰＳ）などのポリアリーレンスルフィド、ポリケトン（ＰＫ）、ポリエーテルケトン（ＰＥＫ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリエーテルケトンケトン（ＰＥＫＫ）、ポリエーテルニトリル（ＰＥＮ）、ポリテトラフルオロエチレンなどのフッ素系樹脂、液晶ポリマー（ＬＣＰ）」などの結晶性樹脂、「スチレン系樹脂の他、ポリカーボネート（ＰＣ）、ポリメチルメタクリレート（ＰＭＭＡ）、ポリ塩化ビニル（ＰＶＣ）、ポリフェニレンエーテル（ＰＰＥ）、ポリイミド（ＰＩ）、ポリアミドイミド（ＰＡＩ）、ポリエーテルイミド（ＰＥＩ）、ポリサルホン（ＰＳＵ）、ポリエーテルサルホン、ポリアリレート（ＰＡＲ）」などの非晶性樹脂、その他、フェノール系樹脂、フェノキシ樹脂、更にポリスチレン系、ポリオレフィン系、ポリウレタン系、ポリエステル系、ポリアミド系、ポリブタジエン系、ポリイソプレン系、フッ素系樹脂、およびアクリロニトリル系等の熱可塑エラストマー等や、これらの共重合体および変性体等から選ばれる熱可塑性樹脂が挙げられる。中でも、得られる成形品の軽量性の観点からはポリオレフィンが好ましく、強度の観点からはポリアミドが好ましく、表面外観の観点からポリカーボネートやスチレン系樹脂のような非晶性樹脂が好ましく、耐熱性の観点からポリアリーレンスルフィドが好ましく、連続使用温度の観点からポリエーテルエーテルケトンが好ましく用いられる。 Examples of the thermoplastic resin constituting the fiber-reinforced resin sheet of the present invention include “polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), liquid crystal polyester, and the like. Polyesters, polyolefins such as polyethylene (PE), polypropylene (PP) and polybutylene, polyarylene sulfides such as polyoxymethylene (POM), polyamide (PA) and polyphenylene sulfide (PPS), polyketones (PK) and polyethers Fluorine resins such as ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether nitrile (PEN), polytetrafluoroethylene, liquid crystal Crystalline resins such as MER (LCP), “Styrene resins, polycarbonate (PC), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyphenylene ether (PPE), polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone (PSU), polyethersulfone, polyarylate (PAR) "and other amorphous resins, phenolic resins, phenoxy resins, polystyrenes, polyolefins, Examples thereof include thermoplastic elastomers such as polyurethane-based, polyester-based, polyamide-based, polybutadiene-based, polyisoprene-based, fluorine-based resins, and acrylonitrile-based resins, and copolymers and modified products thereof. Among them, polyolefin is preferable from the viewpoint of light weight of the obtained molded product, polyamide is preferable from the viewpoint of strength, amorphous resin such as polycarbonate and styrene resin is preferable from the viewpoint of surface appearance, and heat resistance is preferable. From the viewpoint of continuous use temperature, polyether ether ketone is preferably used.
前記群に例示された熱可塑性樹脂は、本発明の目的を損なわない範囲で、エラストマーあるいはゴム成分などの耐衝撃性向上剤、他の充填材や添加剤を含有しても良い。これらの例としては、無機充填材、難燃剤、導電性付与剤、結晶核剤、紫外線吸収剤、酸化防止剤、制振剤、抗菌剤、防虫剤、防臭剤、着色防止剤、熱安定剤、離型剤、帯電防止剤、可塑剤、滑剤、着色剤、顔料、染料、発泡剤、制泡剤、あるいは、カップリング剤が挙げられる。 The thermoplastic resins exemplified in the above group may contain an impact resistance improver such as an elastomer or a rubber component, and other fillers and additives as long as the object of the present invention is not impaired. Examples of these include inorganic fillers, flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, anti-coloring agents, heat stabilizers. , Release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, or coupling agents.
本発明の繊維強化樹脂シートは、強化繊維からなるマットに、融点もしくは軟化点以上に加熱された熱可塑性樹脂に圧力を付与して含浸させ、その後空隙層を形成させることで得ることができる。 The fiber-reinforced resin sheet of the present invention can be obtained by impregnating a mat composed of reinforcing fibers with a thermoplastic resin heated to a melting point or a softening point or higher so as to impregnate, and then forming a void layer.
具体的には、本発明の繊維強化樹脂シートの製造方法として、少なくとも下記工程［１］，［２］および［３］を有する製造方法が好ましく例示される。
工程［１］：熱可塑性樹脂を溶融もしくは軟化する温度以上に加熱された状態で圧力を付与し、前記マットに熱可塑性樹脂を含浸せしめて繊維樹脂シートとする工程
工程［２］：次いで、繊維樹脂シートを冷却し、そこに含まれる熱可塑性樹脂を全体的に固化せしめる工程
工程［３］：次いで、熱可塑性樹脂が全体的に固化した繊維樹脂シートの少なくとも片表面を熱可塑性樹脂の溶融または軟化する温度以上に加熱し、強化繊維の起毛力により空隙層を形成する工程
Specifically, as a method for producing the fiber-reinforced resin sheet of the present invention, a production method having at least the following steps [1], [2] and [3] is preferably exemplified.
Step [1]: Step [2] in which a pressure is applied in a state heated to a temperature higher than the temperature at which the thermoplastic resin is melted or softened and the mat is impregnated with the thermoplastic resin to obtain a fiber resin sheet [2]: Next, the fiber Step [3] of cooling the resin sheet and totally solidifying the thermoplastic resin contained therein [3]: Next, at least one surface of the fiber resin sheet on which the thermoplastic resin is totally solidified is melted of the thermoplastic resin or Heating above the softening temperature and forming a void layer by the raising force of the reinforcing fiber
上記各工程について具体的に説明する。工程［１］では、熱可塑性樹脂と強化繊維マットが同一のキャビティ内へ投入される。熱可塑性樹脂並びに強化繊維マットは、予め所定のサイズにカットされ、積層された状態、連続体の状態、いずれであっても良い。熱可塑性樹脂を溶融もしくは軟化する温度以上に加熱された状態で圧力を付与することで、熱可塑性樹脂が強化繊維マットへ実質的に含浸される。なお、圧力の付与は強化繊維マットの隅々まで、熱可塑性樹脂を実質的に完全に含浸させる必要があることから、一定の圧力付与時間を設けることが好ましい。また、キャビティ温度は用いる熱可塑性樹脂の溶融もしくは軟化する温度以上であることが必須である。 Each of the above steps will be specifically described. In step [1], the thermoplastic resin and the reinforcing fiber mat are put into the same cavity. The thermoplastic resin and the reinforcing fiber mat may be cut into a predetermined size in advance and laminated, or in a continuous state. By applying pressure in a state where the thermoplastic resin is heated to a temperature higher than the temperature at which the thermoplastic resin is melted or softened, the thermoplastic fiber is substantially impregnated into the reinforcing fiber mat. In addition, since it is necessary to impregnate the thermoplastic resin substantially completely to every corner of the reinforcing fiber mat, it is preferable to provide a certain pressure application time. Further, it is essential that the cavity temperature is equal to or higher than the temperature at which the thermoplastic resin used melts or softens.
次いで工程［２］にて、熱可塑性樹脂と強化繊維マットの含浸体が、熱可塑性樹脂の固化温度以下まで冷却されることで、空隙層を有さない実質的に含浸された繊維樹脂シートが得られる。なお、本工程では繊維樹脂シートの熱可塑性樹脂が固化するまでは、冷却中においても工程［１］と同じ圧力が付与されることが望ましい。加圧冷却とすることで、起毛力による不要な空隙を抑えることができる。 Next, in step [2], the impregnated body of the thermoplastic resin and the reinforcing fiber mat is cooled to a temperature equal to or lower than the solidification temperature of the thermoplastic resin, whereby a substantially impregnated fiber resin sheet having no void layer is obtained. can get. In this step, it is desirable that the same pressure as in step [1] is applied even during cooling until the thermoplastic resin of the fiber resin sheet is solidified. By setting it as pressure cooling, the unnecessary space | gap by raising force can be suppressed.
次いで工程［３］では、空隙層を有さない繊維樹脂シートの少なくとも片表面を、加熱設備にて繊維樹脂シートを構成する熱可塑性樹脂が軟化または溶融する温度まで加熱する。該熱可塑性樹脂が軟化または溶融することで強化繊維が開放され、強化繊維の起毛力により、空隙層が形成される。工程［３］は通常、工程［１］、［２］とは別の設備で行われる。工程［３］は、空隙層を形成する重要な工程であるため、温度が精密に制御されることが求められる。 Next, in step [3], at least one surface of the fiber resin sheet having no void layer is heated to a temperature at which the thermoplastic resin constituting the fiber resin sheet is softened or melted by a heating facility. The thermoplastic resin is softened or melted to release the reinforcing fibers, and a void layer is formed by the raising force of the reinforcing fibers. Step [3] is usually performed in a facility separate from steps [1] and [2]. Step [3] is an important step for forming a void layer, and therefore, the temperature is required to be precisely controlled.
上記工程［１］、［２］を実現するための設備としては、圧縮成形機、ダブルベルトプレス、カレンダーロールを好適に用いることができる。バッチ式の場合は前者であり、加熱用と冷却用の２機を並列した間欠プレスシステムとすることで生産性の向上が図れる。連続式の場合は後者であって、ロールからロールへの加工を容易におこなうことができ、連続生産性に優れる。また、空隙層を形成する工程［３］の加熱設備としては、ＩＲヒーターやヒートプラテンが例示できる。空隙層をより大きく形成したい場合は、均質に加熱でき、短時間で深い部分まで空隙層を形成できることから、非接触加熱方式の前者が好ましい。また、極表層だけを空隙層とする場合は後者であり、接触型加熱を用いることで極表層の熱可塑性樹脂だけを軟化または溶融させることができ、空隙層の成形性に優れる。 As equipment for realizing the above steps [1] and [2], a compression molding machine, a double belt press, and a calendar roll can be suitably used. In the case of a batch type, the former, the productivity can be improved by using an intermittent press system in which two machines for heating and cooling are arranged in parallel. In the case of a continuous type, the latter, which can be easily processed from roll to roll, and is excellent in continuous productivity. Moreover, IR heater and a heat platen can be illustrated as a heating installation of the process [3] which forms a space | gap layer. When it is desired to form the gap layer larger, the former of the non-contact heating method is preferable because it can be heated uniformly and the gap layer can be formed in a deep portion in a short time. Further, when only the extreme surface layer is used as the void layer, the latter is used, and by using contact heating, only the thermoplastic resin of the extreme surface layer can be softened or melted, and the moldability of the void layer is excellent.
また、本発明の繊維強化樹脂シートの製造方法として、少なくとも以下の［１］，［２’］および［３’］を有する別の製造方法も例示できる。
工程［１］：熱可塑性樹脂を溶融もしくは軟化する温度以上に加熱された状態で圧力を付与し、前記マットに熱可塑性樹脂を含浸せしめて繊維樹脂シートとする工程
工程［２’］：次いで、熱可塑性樹脂が溶融もしくは軟化した繊維樹脂シートに圧力を保持した状態で、その片表面を冷却して、冷却側の熱可塑性樹脂を固化せしめる工程
工程［３’］：次いで、もう片表面の熱可塑性樹脂が固化するより前に圧力を開放して、強化繊維の起毛力により空隙層を形成する工程
Moreover, another manufacturing method which has at least the following [1], [2 '], and [3'] can also be illustrated as a manufacturing method of the fiber reinforced resin sheet of this invention.
Step [1]: Applying pressure in a state heated above the temperature at which the thermoplastic resin is melted or softened, and impregnating the mat with the thermoplastic resin to obtain a fiber resin sheet [2 ′]: Step [3 ′] of cooling the one surface of the fiber resin sheet in which the thermoplastic resin is melted or softened while maintaining the pressure to solidify the thermoplastic resin on the cooling side: Next, the heat of the other surface The step of releasing the pressure before the plastic resin solidifies and forming the void layer by the raising force of the reinforcing fibers
上記方法を採用することにより、熱可塑性樹脂の含浸工程と空隙層の形成工程を単一のキャビティ内で完結する事が可能となる。工程［２’］は、工程［１］と同様の加圧状態で、繊維強化樹脂シートの一部分を冷却する工程であり、キャビティの片側を樹脂固化温度以下の温度にまで冷却し、片表面のみの熱可塑性樹脂を固化させる工程である。工程［３’］は加圧加熱、加圧冷却を行ったキャビティ内で、繊維樹脂シートの冷却面とは異なる面を起毛させ空隙層を形成する工程である。工程［２’］にて繊維強化樹脂シートの全域が固化温度以下に到達する前に、キャビティを開放することが重要である。空隙層を形成する表面側のキャビティは熱可塑性樹脂の軟化または溶融温度以上であることが好ましい。これにより、繊維樹脂シート全域が固化してしまうことを防ぐ事ができる。 By adopting the above method, it is possible to complete the step of impregnating the thermoplastic resin and the step of forming the void layer in a single cavity. Step [2 ′] is a step of cooling a part of the fiber-reinforced resin sheet in the same pressure state as in step [1]. One side of the cavity is cooled to a temperature equal to or lower than the resin solidification temperature, and only one surface is cooled. This is a step of solidifying the thermoplastic resin. Step [3 '] is a step of forming a void layer by raising a surface different from the cooling surface of the fiber resin sheet in the cavity subjected to pressure heating and pressure cooling. In step [2 '], it is important to open the cavity before the entire area of the fiber reinforced resin sheet reaches the solidification temperature or lower. The cavity on the surface side forming the void layer is preferably at or above the softening or melting temperature of the thermoplastic resin. Thereby, it can prevent that the whole fiber resin sheet solidifies.
上記工程［１］，［２’］および［３’］を実現するための設備としては、圧縮成形機、ダブルベルトプレス、カレンダーロールを挙げることができる。バッチ式の場合は圧縮成形機を用いることができ、加熱用と冷却用の２機を並列した間欠プレスシステムとすることで生産性の向上が図れる。連続式の場合はダブルベルトプレス、カレンダーロールであって、ロールからロールへの加工を容易におこなうことができ、連続生産性に優れる。 As equipment for realizing the above steps [1], [2 '] and [3'], a compression molding machine, a double belt press, and a calender roll can be exemplified. In the case of the batch type, a compression molding machine can be used, and productivity can be improved by using an intermittent press system in which two machines for heating and cooling are arranged in parallel. In the case of a continuous type, it is a double belt press or a calender roll, which can be easily processed from roll to roll, and is excellent in continuous productivity.
本発明の繊維強化樹脂シートは、それを第１の部材として用いて、その空隙層に、熱可塑性樹脂から構成される別の成形体からなる第２の部材の熱可塑性樹脂を含浸せしめて一体成形品とすると、かかる繊維強化樹脂シートと第２の部材が強固に接合した一体成形品を得ることができる。 The fiber-reinforced resin sheet of the present invention is used as a first member, and the void layer is impregnated with a thermoplastic resin of a second member made of another molded body made of a thermoplastic resin. When a molded product is obtained, an integrally molded product in which the fiber-reinforced resin sheet and the second member are firmly bonded can be obtained.
かかる一体成型品は、前記繊維強化樹脂シートを含んでなる成形体であって、前記繊維強化樹脂シートを少なくとも一層含んだ積層体と第２の部材とを成形してなる、一体成形品である。一体成形品において優れた接合性を得る観点から、第２の部材を構成する成分は、本発明の繊維強化樹脂シートにおける空隙に含浸する必要があるため、熱可塑性樹脂をマトリックスとする材料である。具体的には、プレス成形向けシート、射出成形体が例示できる。マトリックス樹脂の種類は、繊維強化樹脂シートと第２の部材で、同じでも異なっていてもよい。繊維強化樹脂シートを構成する強化繊維が第２の部材と共有され、かつ樹脂同士が複雑なアンカリング構造を形成することで、従来一体化しても接合が困難であった素材同士を強固に接合することができる。 Such an integrally molded product is a molded body including the fiber reinforced resin sheet, and is an integrally molded product formed by molding a laminate including at least one layer of the fiber reinforced resin sheet and a second member. . From the viewpoint of obtaining excellent bondability in the integrally molded product, the component constituting the second member is a material using a thermoplastic resin as a matrix because it is necessary to impregnate the voids in the fiber-reinforced resin sheet of the present invention. . Specifically, a sheet for press molding and an injection molded body can be exemplified. The type of the matrix resin may be the same or different between the fiber reinforced resin sheet and the second member. Reinforcing fibers composing the fiber reinforced resin sheet are shared with the second member, and the resin forms a complex anchoring structure, so that materials that were difficult to join even if integrated together are firmly joined together can do.
第２の部材には強化繊維を含んでいても良い。第２の部材に用いられる強化繊維、マトリックス樹脂は、前述の繊維強化樹脂シートを構成する材料群から適宜選択でき、同一であっても異なっていてもよい。なお、本発明では、第１の部材を構成する熱可塑性樹脂と第２の部材を構成する熱可塑性樹脂が互いに相溶しないものとしても、第１の部材と第２の部材を強固に接合できるという、より際立った効果を奏する。 The second member may contain reinforcing fibers. The reinforcing fiber and matrix resin used for the second member can be appropriately selected from the material group constituting the above-described fiber-reinforced resin sheet, and may be the same or different. In the present invention, even if the thermoplastic resin constituting the first member and the thermoplastic resin constituting the second member are not compatible with each other, the first member and the second member can be firmly joined. It has a more prominent effect.
本発明の一体成形品において、繊維強化樹脂シートを構成する熱可塑性樹脂と上記第２の部材を構成する熱可塑性樹脂は、最大高さＲｙ５０μｍ以上、平均粗さＲｚ３０μｍ以上の凹凸形状を有する境界層を形成することが、より強固な接合のために好ましい。ここで、本発明の一体成形品における、維強化樹脂シートを構成する熱可塑性樹脂と、第２の部材を構成する熱可塑性樹脂とが形成する境界層について、図７を用いて詳細に説明する。図７は、一体成形品２３における繊維強化樹脂シートと第２の部材との境界層の断面図である。Ｘは一体成形品の面方向、Ｚは厚み方向を表す。繊維強化樹脂シートのマトリックス樹脂２４と第２の部材を構成する熱可塑性樹脂２５とが、強化繊維からなるマット（図示せず）に含浸されており、凹凸形状を有する境界面２６が形成されている。かかる境界面は、厚み方向Ｚにおいて、複数の凹部と凸部を有しており、そのうち、最も窪みの大きい凹部２７と最も突出した凸部２８とのＺ方向における差をｄｍａｘとして定義する。なお、凹部２７は図上において独立した島状に見られるが、これも含めて、最も侵入量の深い部分を凹凸部それぞれの端部と解釈する。一方、境界層における凹凸形状のうち、最も窪みの小さい凹部２９と最も突出の小さい凸部３０とのＺ方向における落差をｄｍｉｎとして定義する。ここで、ｄｍａｘが本発明で言うところの最大高さＲｙとなり、ｄｍａｘとｄｍｉｎの平均値が本発明で言うところの平均粗さＲｚとして定義される。 In the integrally molded article of the present invention, the thermoplastic resin constituting the fiber reinforced resin sheet and the thermoplastic resin constituting the second member have a concavo-convex shape having a maximum height Ry of 50 μm or more and an average roughness Rz of 30 μm or more. Is preferable for stronger bonding. Here, the boundary layer formed by the thermoplastic resin constituting the fiber reinforced resin sheet and the thermoplastic resin constituting the second member in the integrally molded product of the present invention will be described in detail with reference to FIG. . FIG. 7 is a cross-sectional view of the boundary layer between the fiber reinforced resin sheet and the second member in the integrally molded product 23. X represents the surface direction of the integrally molded product, and Z represents the thickness direction. The matrix resin 24 of the fiber reinforced resin sheet and the thermoplastic resin 25 constituting the second member are impregnated in a mat (not shown) made of reinforced fibers, and a boundary surface 26 having an uneven shape is formed. Yes. Such a boundary surface has a plurality of concave portions and convex portions in the thickness direction Z, and of these, the difference in the Z direction between the concave portion 27 having the largest depression and the protruding portion 28 having the largest protrusion is defined as dmax. In addition, although the recessed part 27 is seen as an independent island shape in the drawing, including this, the part with the deepest penetration amount is interpreted as the end part of each uneven part. On the other hand, of the concavo-convex shape in the boundary layer, a drop in the Z direction between the concave portion 29 having the smallest depression and the convex portion 30 having the smallest protrusion is defined as dmin. Here, dmax is the maximum height Ry referred to in the present invention, and the average value of dmax and dmin is defined as the average roughness Rz referred to in the present invention.
かかる境界層は、最大高さＲｙ５０μｍ以上、平均粗さＲｚ３０μｍ以上の凹凸形状を有して形成されていることが好ましい。かかる態様をとることにより、繊維強化樹脂シートと第２の部材を構成する熱可塑性樹脂との強固な接合を有する一体成形品が与えられる。より好ましくは、Ｒｙ３００μｍ、Ｒｚ１００μｍ以上である。なお、ＲｙとＲｚは繊維強化樹脂シートを構成する強化繊維マットの起毛力と関連しており、前述したように、モノフィラメントかつランダム分散のマットを用いることで、複雑かつ連結した空孔を形成し、空孔が含浸媒体となることで、ＲｙおよびＲｚの値をより大きくすることができる。 Such a boundary layer is preferably formed to have a concavo-convex shape having a maximum height Ry of 50 μm or more and an average roughness Rz of 30 μm or more. By taking this aspect, an integrally molded product having a strong bond between the fiber reinforced resin sheet and the thermoplastic resin constituting the second member is provided. More preferably, Ry is 300 μm and Rz is 100 μm or more. Ry and Rz are related to the raising force of the reinforcing fiber mat constituting the fiber reinforced resin sheet. As described above, by using a monofilament and randomly dispersed mat, complex and connected pores are formed. Since the pores become the impregnation medium, the values of Ry and Rz can be further increased.
かかる境界層における最大高さＲｙおよび平均粗さＲｚの測定法としては、一体成形品の断面観察による方法が例示できる。一体成形品の厚み方向の垂直断面が観察面となるように研磨された試料を用意する。前記試料を顕微鏡にて観察することで、視野中において図７に相当する像が確認できる。ここから、上記にて定義される、凹凸界面のうち、最も窪みの大きい凹部と最も突出の大きい凸部との差ｄｍａｘ、最も窪みの小さい凹部と最も突出の小さい凸部との差ｄｍｉｎをそれぞれ測定する。この操作を異なる像について１０回おこない、測定されるｄｍａｘのうち、最も大きい値を境界層における凹凸形状の最大高さＲｙ（μｍ）とする。また、測定されるｄｍａｘおよびｄｍｉｎの総和をＮ数で除した値を、境界層における凹凸形状の平均粗さＲｚとする。 Examples of the method for measuring the maximum height Ry and the average roughness Rz in the boundary layer include a method by observing a cross section of the integrally molded product. A sample that is polished so that a vertical cross section in the thickness direction of the integrally molded product becomes an observation surface is prepared. By observing the sample with a microscope, an image corresponding to FIG. 7 can be confirmed in the visual field. From here, the difference dmax between the concave part with the largest depression and the convex part with the largest protrusion, and the difference dmin between the concave part with the smallest depression and the convex part with the smallest protrusion, respectively, of the uneven surface defined above. taking measurement. This operation is performed 10 times for different images, and the largest value among the measured dmax is defined as the maximum height Ry (μm) of the uneven shape in the boundary layer. Further, a value obtained by dividing the total sum of dmax and dmin measured by N number is defined as an average roughness Rz of the uneven shape in the boundary layer.
前記一体成形品において、アンカリング構造を有する境界層では、本発明の繊維強化樹脂シートを構成する熱可塑性樹脂により皮膜された強化繊維の一部が、前記第２の部材を構成する熱可塑性樹脂と共有されている。強化繊維を共有する様態は、強化繊維樹脂シートの厚み方向の垂直断面が観察面となるように研磨された試料を用意することで、観察できる。一体成形品の境界層を構成する強化繊維と熱可塑性樹脂の態様の一例を図８に例示する。図８は、一体成形品の境界面の厚さ方向の断面図であり、繊維強化樹脂シートを構成する熱可塑性樹脂３２と、第２の部材を構成する熱可塑性樹脂３３との境界面において、強化繊維が共有されている。共有される態様は具体的には、図８における３４の様に、強化繊維が、繊維強化樹脂シートを構成する熱可塑性樹脂および／または、第２の部材を構成する熱可塑性樹脂に皮膜されている態様が挙げられる。また、図８における３５のように、繊維強化樹脂シートを構成する熱可塑性樹脂と、第２の部材を構成する熱可塑性樹脂を貫通した態様も例示できる。いずれの態様においても、異樹脂間の境界層の形成と、その強固な接合に重要な役割を持つ。共有する強化繊維はモノフィラメント状、および／または数本からなるストランドであり、本発明の繊維強化樹脂シートを構成する強化繊維が本態様をとっても良いし、第２の部材が強化繊維を含む場合は、第２の部材を構成する強化繊維が本態様をとっても良く、第１、第２の部材を構成するそれぞれの強化繊維がどちらもが本態様をとっても良い。 In the integrally molded product, in the boundary layer having an anchoring structure, a part of the reinforcing fibers coated with the thermoplastic resin constituting the fiber reinforced resin sheet of the present invention is part of the thermoplastic resin constituting the second member. Shared with. The mode of sharing the reinforcing fiber can be observed by preparing a sample that is polished so that the vertical cross section in the thickness direction of the reinforcing fiber resin sheet becomes the observation surface. An example of the embodiment of the reinforcing fiber and the thermoplastic resin constituting the boundary layer of the integrally molded product is illustrated in FIG. FIG. 8 is a cross-sectional view in the thickness direction of the boundary surface of the integrally molded product, and at the boundary surface between the thermoplastic resin 32 constituting the fiber reinforced resin sheet and the thermoplastic resin 33 constituting the second member, Reinforcing fiber is shared. Specifically, as shown in 34 in FIG. 8, the shared mode is formed by coating the reinforcing fiber with the thermoplastic resin constituting the fiber-reinforced resin sheet and / or the thermoplastic resin constituting the second member. The aspect which is mentioned is mentioned. Moreover, the aspect penetrated through the thermoplastic resin which comprises a fiber reinforced resin sheet and the thermoplastic resin which comprises a 2nd member like 35 in FIG. 8 can also be illustrated. In any embodiment, it plays an important role in the formation of a boundary layer between different resins and its strong bonding. The reinforcing fiber to be shared is a monofilament and / or several strands, and the reinforcing fiber constituting the fiber-reinforced resin sheet of the present invention may take this mode, or when the second member includes the reinforcing fiber. The reinforcing fiber constituting the second member may take this aspect, and each of the reinforcing fibers constituting the first and second members may take this aspect.
上述した一体成形品は、本発明の繊維強化樹脂シートと第２の部材とを、加熱および加圧、さらに冷却工程を有する手段にて成形することにより与えることができる。ここで、一体成形品を得るにあたり、部材同士を予め積層して積層体としていてもよい。積層単位については特に制限はないが、少なくとも空隙層部分を接合面に配置することで強固な接合を得ることができる。前記積層体には、本発明の繊維強化樹脂シートに加え、他の積層単位を含むことができる。かかる積層単位の構成は特には制限されないが、例えば、連続繊維で補強された熱可塑性樹脂をマトリックスとするＵＤテープ、不連続強化繊維で補強された、ＧＭＴ、ＳＭＣ、などの繊維強化基材、あるいは、樹脂シート、発泡体、などの非繊維強化成形基材、が挙げられる。なかでも、得られる成形体の力学特性の観点からは、繊維強化成形基材であることが好ましく用いることができる。 The integrally molded product described above can be provided by molding the fiber-reinforced resin sheet of the present invention and the second member by means having heating and pressurizing and cooling processes. Here, in obtaining an integrally molded product, the members may be laminated in advance to form a laminated body. Although there is no restriction | limiting in particular about a lamination | stacking unit, Strong joining can be obtained by arrange | positioning at least a space | gap layer part to a joining surface. In addition to the fiber reinforced resin sheet of this invention, the said laminated body can contain another lamination unit. The structure of such a laminated unit is not particularly limited, but, for example, a UD tape using a thermoplastic resin reinforced with continuous fibers as a matrix, a fiber reinforced base material such as GMT or SMC reinforced with discontinuous reinforcing fibers, Alternatively, non-fiber reinforced molded base materials such as resin sheets and foams can be used. Among these, a fiber reinforced molded base material can be preferably used from the viewpoint of the mechanical properties of the obtained molded body.
かかる一体成形品を得るための加熱および加圧を有する一般的な手段としては、プレス成形法が例示できる。プレス成形法としては、予め成形型を中間基材ないし積層体の成形温度以上に昇温しておき、加熱された成形型内に中間基材ないし積層体を配置し、型締めして加圧し、次いでその状態を維持しながら成形型を冷却し成形品を得る方法、いわゆるホットプレス成形がある。また、成形温度以上に加熱された中間基材ないし積層体を、中間基材ないし積層体の固化温度未満に保持された成形型に配置し、型締めして加圧し、次いでその状態を維持しながら中間基材ないし積層体を冷却し成形品を得る方法、いわゆるスタンピング成形やヒートアンドクール成形等がある。これらプレス成形方法のうち、成形サイクルを早めて生産性を高める観点からは、スタンピング成形ないしヒートアンドクール成形が好ましい。 As a general means having heating and pressurization for obtaining such an integrally molded product, a press molding method can be exemplified. As the press molding method, the mold is heated in advance to the molding temperature of the intermediate substrate or laminate, the intermediate substrate or laminate is placed in the heated mold, and the mold is clamped and pressurized. Then, there is a method of obtaining a molded product by cooling the mold while maintaining the state, so-called hot press molding. In addition, the intermediate substrate or laminate heated above the molding temperature is placed in a mold held below the solidification temperature of the intermediate substrate or laminate, clamped and pressurized, and then maintained in that state. However, there are methods for obtaining a molded product by cooling the intermediate substrate or laminate, so-called stamping molding, heat and cool molding, and the like. Among these press molding methods, stamping molding or heat and cool molding is preferable from the viewpoint of increasing the productivity by increasing the molding cycle.
前記第１の部材と第２の部材とを接合させる手段は、特に限定されない。例えば、（ｉ）第１の部材と第２の部材とを別々に予め成形しておき、両者を接合する方法、（ｉｉ）第１の部材を予め成形しておき、第２の部材を成形すると同時に両者を接合する方法、がある。前記（ｉ）の具体例としては、第１の部材をプレス成形し、第２の部材をプレス成形ないし射出成形にて作製する。作製したそれぞれの部材を、熱板溶着、振動溶着、超音波溶着、レーザー溶着、抵抗溶着、誘導加熱溶着、などの公知の溶着手段により接合する方法がある。一方、前記（ｉｉ）の具体例としては、第１の部材をプレス成形し、次いで射出成形金型にインサートし、第２の部材を形成する材料を金型に射出成形し、溶融ないし軟化状態にある材料の熱量で第１の部材の被着面を溶融ないし軟化させて接合する方法がある。また、前記（ｉｉ）の別の具体例としては、第１の部材をプレス成形し、次いでプレス成形金型内に配置し、第２の部材を形成する材料をプレス成形金型内にチャージし、プレス成形することで、前記と同様の原理で接合する方法がある。一体成形品の量産性の観点からは、好ましくは（ｉｉ）の方法であって、射出成形としてインサート射出成形やアウトサート射出成形、および、プレス成形としてスタンピング成形やヒートアンドクール成形が好ましく使用される。すなわち、第２の部材が射出成形による成形体であり、第２の部材をインサート射出成形またはアウトサート射出成形により第１の部材に接合するか、第２の部材がプレス成形による成形体であり、第２の部材をプレス成形により第１の部材に接合するのが、本発明の一体成形品を製造するのに特に好ましく用いられる。 The means for joining the first member and the second member is not particularly limited. For example, (i) a method in which the first member and the second member are separately molded in advance, and the two are joined together. (Ii) the first member is molded in advance, and the second member is molded. At the same time, there is a method of joining the two. As a specific example of (i), the first member is press-molded, and the second member is produced by press molding or injection molding. There is a method of joining the produced members by known welding means such as hot plate welding, vibration welding, ultrasonic welding, laser welding, resistance welding, induction heating welding and the like. On the other hand, as a specific example of the above (ii), the first member is press-molded, then inserted into an injection mold, and the material for forming the second member is injection-molded into the mold to be melted or softened. There is a method in which the adherend surface of the first member is melted or softened by the amount of heat of the material. As another specific example of the above (ii), the first member is press-molded and then placed in the press-molding die, and the material for forming the second member is charged into the press-molding die. There is a method of joining on the same principle as described above by press molding. From the viewpoint of mass productivity of the integrally molded product, the method (ii) is preferable, and insert injection molding or outsert injection molding is preferably used as injection molding, and stamping molding or heat and cool molding is preferably used as press molding. The That is, the second member is a molded body by injection molding, and the second member is joined to the first member by insert injection molding or outsert injection molding, or the second member is a molded body by press molding. The joining of the second member to the first member by press molding is particularly preferably used for producing the integrally molded product of the present invention.
本発明の一体成形品により与えられる実装部材の用途としては、例えば、「パソコン、ディスプレイ、ＯＡ機器、携帯電話、携帯情報端末、ファクシミリ、コンパクトディスク、ポータブルＭＤ、携帯用ラジオカセット、ＰＤＡ（電子手帳などの携帯情報端末）、ビデオカメラ、デジタルビデオカメラ、光学機器、オーディオ、エアコン、照明機器、娯楽用品、玩具用品、その他家電製品などの筐体、トレイ、シャーシ、内装部材、またはそのケース」などの電気、電子機器部品、「支柱、パネル、補強材」などの土木、建材用部品、「各種メンバ、各種フレーム、各種ヒンジ、各種アーム、各種車軸、各種車輪用軸受、各種ビーム、プロペラシャフト、ホイール、ギアボックスなどの、サスペンション、アクセル、またはステアリング部品」、「フード、ルーフ、ドア、フェンダ、トランクリッド、サイドパネル、リアエンドパネル、アッパーバックパネル、フロントボディー、アンダーボディー、各種ピラー、各種メンバ、各種フレーム、各種ビーム、各種サポート、各種レール、各種ヒンジなどの、外板、またはボディー部品」、「バンパー、バンパービーム、モール、アンダーカバー、エンジンカバー、整流板、スポイラー、カウルルーバー、エアロパーツなど外装部品」、「インストルメントパネル、シートフレーム、ドアトリム、ピラートリム、ハンドル、各種モジュールなどの内装部品」、または「モーター部品、ＣＮＧタンク、ガソリンタンク、燃料ポンプ、エアーインテーク、インテークマニホールド、キャブレターメインボディー、キャブレタースペーサー、各種配管、各種バルブなどの燃料系、排気系、または吸気系部品」などの自動車、二輪車用構造部品、「その他、オルタネーターターミナル、オルタネーターコネクター、ＩＣレギュレーター、ライトディヤー用ポテンショメーターベース、エンジン冷却水ジョイント、エアコン用サーモスタットベース、暖房温風フローコントロールバルブ、ラジエーターモーター用ブラッシュホルダー、タービンべイン、ワイパーモーター関係部品、ディストリビュター、スタータースィッチ、スターターリレー、ウィンドウオッシャーノズル、エアコンパネルスィッチ基板、燃料関係電磁気弁用コイル、バッテリートレイ、ＡＴブラケット、ヘッドランプサポート、ペダルハウジング、プロテクター、ホーンターミナル、ステップモーターローター、ランプソケット、ランプリフレクター、ランプハウジング、ブレーキピストン、ノイズシールド、スペアタイヤカバー、ソレノイドボビン、エンジンオイルフィルター、点火装置ケース、スカッフプレート、フェイシャー」、などの自動車、二輪車用部品、「ランディングギアポッド、ウィングレット、スポイラー、エッジ、ラダー、エレベーター、フェイリング、リブ」などの航空機用部品が挙げられる。力学特性の観点からは、自動車内外装、電気・電子機器筐体、自転車、スポーツ用品用構造材、航空機内装材、輸送用箱体に好ましく用いられる。なかでも、とりわけ複数の部品から構成されるモジュール部材に好適である。 Examples of the use of the mounting member provided by the integrally molded product of the present invention include “PC, display, OA equipment, mobile phone, personal digital assistant, facsimile, compact disk, portable MD, portable radio cassette, PDA (electronic notebook). Such as portable information terminals), video cameras, digital video cameras, optical equipment, audio, air conditioners, lighting equipment, entertainment equipment, toy products, other household appliances, etc., trays, chassis, interior members, or their cases Electrical and electronic equipment parts, civil engineering and construction material parts such as `` posts, panels, reinforcements '', `` various members, various frames, various hinges, various arms, various axles, various wheel bearings, various beams, propeller shafts, Suspension, accelerator, or steering components such as wheels and gearboxes , "Hood, roof, door, fender, trunk lid, side panel, rear end panel, upper back panel, front body, underbody, various pillars, various members, various frames, various beams, various supports, various rails, various hinges, etc. Outer panel or body parts "," Bumper, bumper beam, molding, under cover, engine cover, current plate, spoiler, cowl louver, aero parts, exterior parts "," instrument panel, seat frame, door trim, pillar trim " , Interior parts such as handles, various modules ", or" motor parts, CNG tank, gasoline tank, fuel pump, air intake, intake manifold, carburetor main body, carburetor spacer, Automobiles such as seed piping, various fuel systems such as valves, exhaust systems, or intake system parts ", structural parts for motorcycles," others, alternator terminals, alternator connectors, IC regulators, potentiometer bases for light steering, engine coolant joints , Thermostat base for air conditioner, Heating hot air flow control valve, Brush holder for radiator motor, Turbine vane, Wiper motor related parts, Distributor, Starter switch, Starter relay, Window washer nozzle, Air conditioner panel switch board, Fuel related electromagnetic Coil for valve, battery tray, AT bracket, headlamp support, pedal housing, protector, horn terminal, step motor rotor, run , Socket parts, lamp reflectors, lamp housings, brake pistons, noise shields, spare tire covers, solenoid bobbins, engine oil filters, ignition device cases, scuff plates, fascias, etc., automobile parts, landing gear pods, winglets , Spoilers, edges, ladders, elevators, failings, ribs, etc. From the viewpoint of mechanical properties, it is preferably used for automobile interior and exterior, electrical / electronic equipment housings, bicycles, sports equipment structural materials, aircraft interior materials, and transport boxes. Especially, it is suitable for the module member comprised from a some component especially.
以下、実施例により本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
（１）境界面の特定方法
繊維強化樹脂シートから幅２５ｍｍ、長さ５０ｍｍの小片を切り出し、質量Ｗ０を１／１００ｇの精度で測定し、また厚みを１／１００ｍｍの精度で測定した。続いて、測定された厚みを１０等分に分割した際の１区間分の厚みｔを算出した。算出された厚みｔを研磨により除去した。本研磨は、ＪＩＳ Ｂ７５１３（１９９２）に準拠した精密定盤の上で、ＪＩＳ Ｒ６２５３（２００６）に規定される粒度Ｐ１５００の耐水研磨紙を用いて所定厚みを湿式研磨した。この時、研磨と残留した厚みの測定を交互に繰り返して、削り過ぎが無いように注意深く研磨した。次いで残留した繊維強化樹脂シートの質量Ｗ１を１／１００ｇまで測定し、研磨前の全繊維強化樹脂シートの質量Ｗ０に対する重量分率ｗ１を次式を用いて算出した。
・ｗｉ＝（Ｗｉ／Ｗ０）×１００
Ｗｉ：ｉ区間目を除去した後に残留した繊維強化樹脂シートの質量（ｇ）
ｗｉ：研磨前の全繊維強化樹脂シートの質量Ｗ０に対する、ｉ区間目を除去した後に残留した繊維強化樹脂シートの重量分率（重量％）
(1) Identification method of boundary surface A small piece having a width of 25 mm and a length of 50 mm was cut out from the fiber-reinforced resin sheet, the mass W0 was measured with an accuracy of 1/100 g, and the thickness was measured with an accuracy of 1/100 mm. Subsequently, the thickness t for one section when the measured thickness was divided into 10 equal parts was calculated. The calculated thickness t was removed by polishing. In this polishing, a predetermined thickness was wet-polished using a water-resistant abrasive paper having a particle size P1500 defined in JIS R6253 (2006) on a precision surface plate conforming to JIS B7513 (1992). At this time, the polishing and the measurement of the remaining thickness were repeated alternately to carefully polish so that there was no excessive shaving. Next, the mass W1 of the remaining fiber reinforced resin sheet was measured up to 1/100 g, and the weight fraction w1 with respect to the mass W0 of the entire fiber reinforced resin sheet before polishing was calculated using the following formula.
・ Wi = (Wi / W0) × 100
Wi: Mass (g) of the fiber-reinforced resin sheet remaining after removing the i-th section
wi: Weight fraction (% by weight) of the fiber-reinforced resin sheet remaining after removing the i-th section with respect to the mass W0 of the entire fiber-reinforced resin sheet before polishing.
次いで、残留した繊維強化樹脂シートの研磨面側を、同様にしてｔだけ研磨し、残留した繊維強化樹脂シートの質量Ｗ２を測定した。以上の作業を９回繰り返し、ｘ軸に除去した厚みＴ＝ｉ×ｔ、ｙ軸に残留した繊維強化樹脂シートの重量分率ｗｉ（ｉ＝０、１、２、・・・、９）をプロットし、図３に例示される相関図を作成した。得られた相関図より、Ｗ０からＷ３を繋ぐ外挿線（図３における９）と、Ｗ７からＷ９を繋ぐ外挿線（図３における１０）を作成し、２直線の交点における除去厚み、つまり含浸層厚み、すなわち研磨前の底面から境界面までの距離を相関図上にて求めた。 Subsequently, the polishing surface side of the remaining fiber reinforced resin sheet was similarly polished by t, and the mass W2 of the remaining fiber reinforced resin sheet was measured. The above operation is repeated nine times, and the thickness T = i × t removed on the x axis and the weight fraction wi (i = 0, 1, 2,..., 9) of the fiber reinforced resin sheet remaining on the y axis. Plotting was performed and the correlation diagram illustrated in FIG. 3 was created. From the obtained correlation diagram, an extrapolation line (9 in FIG. 3) connecting W0 to W3 and an extrapolation line (10 in FIG. 3) connecting W7 to W9 are created, and the removal thickness at the intersection of two straight lines, that is, The thickness of the impregnated layer, that is, the distance from the bottom surface to the boundary surface before polishing was determined on the correlation diagram.
（２）空隙層の空隙率測定方法
繊維強化樹脂シートから幅５０ｍｍ、長さ５０ｍｍの小片を切り出し、（１）にて特定した境界面を基に、繊維強化樹脂シートの空隙層部分を研磨により丁寧に削り出して単離した。本研磨についても（１）の境界面の特定方法と同様の方法を用いて研磨した。単離した空隙層を、試験片として、２枚のステンレス製メッシュ（２．５ｃｍ当たり５０個のメッシュを有する平織形状）に挟み、繊維強化樹脂シートが動かないようにネジを調整して固定した。これを空気中５００℃で３０分間加熱し、樹脂成分を焼き飛ばした(焼き飛ばし法)。焼き飛ばした後に残る強化繊維について質量の測定を行い、得られた質量より、ＪＩＳ Ｋ７０７５（１９９１）に規定される「炭素繊維強化プラスチックの繊維含有率及び空洞率試験方法」を参考にして、次式を用いて空隙率を算出した。
・Ｖｖ＝１００−（Ｖｆ＋Ｖｒ）
・Ｖｆ＝（Ｗｆ×ρｃ）／ρｆ
・Ｖｒ＝（（１００−Ｗｆ）×ρｃ）／ρｒ
・Ｗｆ＝（Ｗ’／Ｗ）×１００
Ｗ：試験片の質量（ｇ）
Ｗ’：焼き飛ばした後に残る強化繊維の質量（ｇ）
Ｗｆ：試験片の繊維質量含有率（％）
Ｖｆ：試験片の繊維体積含有率（体積％）
Ｖｖ：空隙率（体積％）
Ｖｒ：試験片の樹脂体積含有率（体積％）
ρｃ：試験片の密度（ｇ／ｃｍ３）
ρｆ：試験片に用いられている炭素繊維の密度（ｇ／ｃｍ３）
(2) Method for measuring porosity of void layer A small piece having a width of 50 mm and a length of 50 mm is cut out from the fiber reinforced resin sheet, and the void layer portion of the fiber reinforced resin sheet is polished by polishing based on the boundary surface specified in (1). Carefully carved out and isolated. Also for this polishing, polishing was performed using the same method as the method for specifying the boundary surface in (1). The isolated void layer was sandwiched between two stainless steel meshes (plain weave shape having 50 meshes per 2.5 cm) as test pieces, and fixed by adjusting the screws so that the fiber-reinforced resin sheet did not move. . This was heated in air at 500 ° C. for 30 minutes to burn off the resin component (baking off method). Measure the mass of the reinforcing fiber remaining after burning off, and from the obtained mass, referring to “Fiber content rate and void ratio test method of carbon fiber reinforced plastic” defined in JIS K7075 (1991), The porosity was calculated using the formula.
・ Vv = 100− (Vf + Vr)
Vf = (Wf × ρc) / ρf
Vr = ((100−Wf) × ρc) / ρr
・ Wf = (W ′ / W) × 100
W: Mass of test piece (g)
W ': Mass of reinforcing fiber remaining after burning (g)
Wf: Fiber mass content of test specimen (%)
Vf: Fiber volume content of test specimen (volume%)
Vv: porosity (volume%)
Vr: Resin volume content of test specimen (volume%)
ρc: Test piece density (g / cm 3 )
ρf: density of carbon fiber used in the test piece (g / cm 3 )
（３）強化繊維からなるマットにおける細繊度ストランドの重量分率（Ｒｗ）
繊維強化樹脂シートから幅２５ｍｍ、長さ２５ｍｍの小片を切り出し、それを試験片として、上記（２）と同様の焼き飛ばし法にて樹脂成分を焼き飛ばして、強化繊維からなるマットを取り出し、重量Ｗｍを測定した。次いで、強化繊維からなるマットから、視認されるストランドをピンセットにより抽出し、１／１００ｍｍの精度でストランドの長さＬｓ、１／１００ｍｇの精度でストランドの重量Ｗｓを測定した。これを強化繊維からなるマット中に存在する全てのストランド（ｎ個）について繰り返した。得られたストランドの長さＬｓおよび重量Ｗｓから、次式によりストランドにおけるフィラメント数Ｆを算出した。
・Ｆｉ（本）＝Ｗｓｉ／（Ｄ×Ｌｓｉ）
Ｆｉ：ストランドにおけるフィラメント数の個別値（本）（ｉ＝１〜ｎ）
Ｗｓｉ：ストランドの重量（ｍｇ）
Ｌｓｉ：ストランドの長さ（ｍｍ）
Ｄ：フィラメント１本当たりの繊度（ｍｇ／ｍｍ）
(3) Weight fraction (Rw) of fineness strands in the mat made of reinforcing fibers
A 25 mm wide and 25 mm long piece is cut out from the fiber reinforced resin sheet, and the test piece is used as a test piece to burn out the resin component by the same burning method as in (2) above. Wm was measured. Next, the visible strand was extracted with tweezers from the mat made of reinforcing fibers, and the strand length Ls was measured with an accuracy of 1/100 mm, and the weight Ws of the strand was measured with an accuracy of 1/100 mg. This was repeated for all the strands (n) present in the mat made of reinforcing fibers. From the length Ls and weight Ws of the obtained strand, the number of filaments F in the strand was calculated by the following formula.
・ Fi (book) = Wsi / (D × Lsi)
Fi: Individual value (number) of filament number in the strand (i = 1 to n)
Wsi: Strand weight (mg)
Lsi: Strand length (mm)
D: Fineness per filament (mg / mm)
前記にて算出されたＦｉをもとに、フィラメント数が１００本以上のストランドを選別した。選別したストランドの重量Ｗｉから次式にて、フィラメント数が１００本未満の重量分率Ｒｗを算出した。
・Ｒｗ（重量％）＝｛Ｗｍ−Σ（Ｗｓｉ）｝／Ｗｍ×１００
Ｗｍ：強化繊維からなるマットの重量（ｍｇ）
Based on the Fi calculated above, strands having 100 or more filaments were selected. From the weight Wi of the selected strand, the weight fraction Rw having the number of filaments of less than 100 was calculated by the following formula.
Rw (% by weight) = {Wm−Σ (Wsi)} / Wm × 100
Wm: Weight of mat made of reinforcing fibers (mg)
（４）強化繊維からなるマットの繊維分散率
上記（３）と同様の方法にて、繊維強化樹脂シートから強化繊維からなるマットを取り出した。得られた強化繊維からなるマットを電子顕微鏡（キーエンス（株）製、ＶＨＸ−５００）を用いて観察し、無作為に単繊維を１本選定し、該単繊維に接触する別の単繊維との二次元接触角を測定した。二次元接触角は接触する２つの単繊維とのなす２つの角度のうち、０°以上９０°以下の角度（鋭角側）を採用した。二次元接触角の測定は、選定した単繊維に接触する全ての単繊維を対象とし、これを１００本の単繊維について実施した。得られた結果から、二次元接触角を測定した全ての単繊維の総本数と、二次元接触角度が１度以上である単繊維の本数とからその比率を算出し、繊維分散率を求めた。
(4) Fiber Dispersion Rate of Mat Made of Reinforced Fiber A mat made of reinforcing fiber was taken out from the fiber reinforced resin sheet by the same method as (3) above. The mat made of the obtained reinforcing fibers is observed with an electron microscope (VHX-500, manufactured by Keyence Corporation), one single fiber is randomly selected, and another single fiber in contact with the single fiber The two-dimensional contact angle was measured. As the two-dimensional contact angle, an angle (acute angle side) of 0 ° or more and 90 ° or less among two angles formed by two single fibers in contact with each other was adopted. The measurement of the two-dimensional contact angle was performed on 100 single fibers, targeting all single fibers that contact the selected single fibers. From the obtained results, the ratio was calculated from the total number of all single fibers whose two-dimensional contact angle was measured and the number of single fibers whose two-dimensional contact angle was 1 degree or more, and the fiber dispersion rate was obtained. .
（５）強化繊維からなるマットの二次元配向角
上記（３）と同様の方法にて、繊維強化樹脂シートから強化繊維からなるマットを取り出した。得られた強化繊維からなるマットを電子顕微鏡（キーエンス（株）製、ＶＨＸ−５００）を用いて観察し、無作為に単繊維を１本選定し、該単繊維に交差する別の単繊維との二次元配向角を画像観察より測定した。配向角は交差する２つの単繊維とのなす２つの角度のうち、０°以上９０°以下の角度（鋭角側）を採用した。選定した単繊維１本あたりの二次元配向角の測定数はｎ＝２０とした。同様の測定を合計５本の単繊維を選定しておこない、その平均値をもって二次元配向角とした。
(5) Two-dimensional orientation angle of mat made of reinforcing fibers A mat made of reinforcing fibers was taken out of the fiber-reinforced resin sheet by the same method as in (3) above. The mat made of the obtained reinforcing fibers was observed with an electron microscope (VHX-500, manufactured by Keyence Corporation), one single fiber was randomly selected, and another single fiber intersecting with the single fiber The two-dimensional orientation angle was measured by image observation. Of the two angles formed by the two intersecting single fibers, the angle between 0 ° and 90 ° (acute angle side) was adopted as the orientation angle. The number of measured two-dimensional orientation angles per selected single fiber was n = 20. The same measurement was performed by selecting a total of 5 single fibers, and the average value was taken as the two-dimensional orientation angle.
（６）繊維強化樹脂シート中における強化繊維の面外角度θｚ
繊維強化樹脂シートから幅２５ｍｍ、長さ２５ｍｍの小片を切り出し、エポキシ樹脂に包埋した上で、シート厚み方向の垂直断面が観察面となるように研磨して試料を作製した。前記試料をレーザー顕微鏡（キーエンス（株）製、ＶＫ−９５１０）で４００倍に拡大し、繊維断面形状の観察をおこなった。観察画像を汎用画像解析ソフト上に展開し、ソフトに組み込まれたプログラムを利用して観察画像中に見える個々の繊維断面を抽出し、該繊維断面を内接する楕円を設け、形状を近似した（以降、繊維楕円と呼ぶ）。さらに、繊維楕円の長軸長さα／短軸長さβで表されるアスペクト比が２０以上の繊維楕円に対し、Ｘ軸方向と繊維楕円の長軸方向の為す角を求めた。繊維強化樹脂シートの異なる部位から抽出した観察試料について上記操作を繰り返すことにより、計６００本の強化繊維について面外角度を測定し、その平均値を繊維強化樹脂シートの面外角度θｚとして求めた。
(6) Out-of-plane angle θz of reinforcing fiber in fiber-reinforced resin sheet
A small piece having a width of 25 mm and a length of 25 mm was cut out from the fiber-reinforced resin sheet, embedded in an epoxy resin, and then polished so that a vertical cross section in the sheet thickness direction was an observation surface to prepare a sample. The sample was magnified 400 times with a laser microscope (manufactured by Keyence Corporation, VK-9510), and the fiber cross-sectional shape was observed. The observation image is developed on general-purpose image analysis software, and individual fiber cross sections that are visible in the observation image are extracted using a program incorporated in the software, and an ellipse that inscribes the fiber cross section is provided to approximate the shape ( Hereinafter referred to as a fiber ellipse). Further, for the fiber ellipse having an aspect ratio of 20 or more represented by the major axis length α / minor axis length β of the fiber ellipse, the angle formed by the X axis direction and the major axis direction of the fiber ellipse was determined. By repeating the above operation for observation samples extracted from different parts of the fiber reinforced resin sheet, the out-of-plane angle was measured for a total of 600 reinforced fibers, and the average value was obtained as the out-of-plane angle θz of the fiber reinforced resin sheet. .
（７）一体成型品の境界層における凹凸形状（Ｒｙ、Ｒｚ）
繊維強化樹脂シートから幅２５ｍｍ、長さ２５ｍｍの小片を切り出し、エポキシ樹脂に包埋したうえで、シート厚み方向の垂直断面が観察面となるように研磨して試料を作製した。前記試料をレーザー顕微鏡（キーエンス（株）製、ＶＫ−９５１０）で２００倍に拡大し、無作為に選定した１０ヶ所（互いの視野は重複しない）について、撮影をおこなった。撮影した画像から、第１の部材を構成する熱可塑性樹脂と、第２の部材を構成する熱可塑性樹脂とが形成する境界層を、樹脂のコントラストにより確認した。コントラストが不鮮明な場合は、画像処理により濃淡を明確化した。上記にて撮影した１０視野について、それぞれの視野中における凹凸界面のうち、最も窪みの大きい凹部と最も突出の大きい凸部との垂直落差ｄｍａｘ、最も窪みの小さい凹部と最も突出の小さい凸部との垂直落差ｄｍｉｎをそれぞれ測定した。これら各視野による１０点のｄｍａｘのうち、最も大きい値を境界層における凹凸形状の最大高さＲｙ（μｍ）とした。また、上記にて得られたｄｍａｘおよびｄｍｉｎから、境界層における凹凸形状の平均粗さＲｚを、次式により算出した。
・Ｒｚ（μｍ）＝Σ（ｄｉｍａｘ＋ｄｉｍｉｎ）／２ｎ
ｄｉｍａｘ：各視野における最大垂直落差（ｉ＝１、２、・・・１０）（μｍ）
ｄｉｍｉｎ：各視野における最小垂直落差（ｉ＝１、２、・・・１０）（μｍ）
ｎ：測定視野数
(7) Uneven shape (Ry, Rz) in the boundary layer of the integrally molded product
A small piece having a width of 25 mm and a length of 25 mm was cut out from the fiber reinforced resin sheet, embedded in an epoxy resin, and then polished so that a vertical cross section in the sheet thickness direction was an observation surface to prepare a sample. The sample was magnified 200 times with a laser microscope (manufactured by Keyence Corporation, VK-9510), and photographed at 10 randomly selected locations (the fields of view did not overlap each other). From the photographed image, the boundary layer formed by the thermoplastic resin constituting the first member and the thermoplastic resin constituting the second member was confirmed by the contrast of the resin. When the contrast was unclear, the shading was clarified by image processing. Of the ten fields captured above, of the uneven interfaces in each field of view, the vertical drop dmax between the concave part with the largest depression and the convex part with the largest protrusion, the concave part with the smallest depression and the convex part with the smallest protrusion. The vertical drop dmin was measured. Of the 10 dmax values in each field of view, the largest value was taken as the maximum height Ry (μm) of the irregular shape in the boundary layer. Further, from the dmax and dmin obtained above, the average roughness Rz of the uneven shape in the boundary layer was calculated by the following equation.
Rz (μm) = Σ (dimax + dimin) / 2n
dimax: Maximum vertical drop in each field of view (i = 1, 2,... 10) (μm)
dimin: Minimum vertical drop in each field of view (i = 1, 2,... 10) (μm)
n: Number of viewing fields
（８）一体成形品における接合部のせん断強度τ２
ＪＩＳ Ｋ６８５０（１９９９）に規定される「接着剤−剛性被着材の引張せん断接着強さ試験法」を参考して、一体成形品における接合部のせん断強度τ２の評価をおこなった。本試験における試験片は、実施例で得られる一体成形品の平面部分を切り出して使用した。試験片を図９に示す。試験片３６は長さｌの異なる位置にて、試験片両表面から厚さｈの中間深さｈ１／２に到達する幅ｗの切欠き３７が挿入された形状であって、前記中間深さｈ１／２の位置にて第１の部材と第２の部材との接合部が形成されている。前記試験片を５本用意し、万能試験機（インストロン社製、万能試験機４２０１型）にて引張試験をおこなった。試験により得られた全てのデータ（ｎ＝５）の平均値を、一体成形品における接合部のせん断強度τ２（ＭＰａ）とした。
(8) Shear strength τ2 of the joint in the integrally molded product
With reference to the “Adhesive-Rigid Adhering Material Tensile Shear Bond Strength Test Method” defined in JIS K6850 (1999), the shear strength τ2 of the joint in the integrally molded product was evaluated. The test piece in this test was cut out from the flat part of the integrally molded product obtained in the example. A test piece is shown in FIG. The test piece 36 has a shape in which a notch 37 having a width w reaching the intermediate depth h1 / 2 of the thickness h is inserted from both surfaces of the test piece at different positions of the length l. A joint portion between the first member and the second member is formed at a position of h 1/2 . Five test pieces were prepared, and a tensile test was performed using a universal testing machine (manufactured by Instron, universal testing machine 4201). The average value of all data (n = 5) obtained by the test was defined as the shear strength τ2 (MPa) of the joint in the integrally molded product.
［強化繊維１］
ポリアクリロニトリルを主成分とする重合体から紡糸、焼成処理を行い、総フィラメント数１２０００本の連続炭素繊維を得た。さらに該連続炭素繊維を電解表面処理し、１２０℃の加熱空気中で乾燥して強化繊維１を得た。この強化繊維１の特性は次に示す通りであった。
密度：１．８０ｇ／ｃｍ３
単繊維径：７μｍ
引張強度：４．９ＧＰａ
引張弾性率：２３０ＧＰａ
[Reinforcing fiber 1]
Spinning and firing were performed from a polymer containing polyacrylonitrile as a main component to obtain continuous carbon fibers having a total filament number of 12,000. Further, the continuous carbon fiber was subjected to electrolytic surface treatment and dried in heated air at 120 ° C. to obtain reinforcing fiber 1. The properties of the reinforcing fiber 1 were as shown below.
Density: 1.80 g / cm 3
Single fiber diameter: 7μm
Tensile strength: 4.9 GPa
Tensile modulus: 230 GPa
［樹脂シート１］
未変性ポリプロピレン樹脂（プライムポリマー（株）製、“プライムポリプロ”（登録商標）Ｊ１０６ＭＧ）９０質量％と、酸変性ポリプロピレン樹脂（三井化学（株）製、“アドマー”（登録商標）ＱＥ８００）１０質量％とからなるマスターバッチを用いて、目付１００ｇ／ｍ２のシートを作製した。得られた樹脂シートの特性を表１に示す。
[Resin sheet 1]
90% by mass of unmodified polypropylene resin (manufactured by Prime Polymer Co., Ltd., “Prime Polypro” (registered trademark) J106MG) and 10 mass of acid-modified polypropylene resin (manufactured by Mitsui Chemicals, Inc., “Admer” (registered trademark) QE800) A sheet having a basis weight of 100 g / m 2 was prepared using a master batch consisting of%. The properties of the obtained resin sheet are shown in Table 1.
［樹脂シート２］
ポリアミド６樹脂（東レ（株）製“アミラン”（登録商標）ＣＭ１０２１Ｔ）からなる目付１２４ｇ／ｍ２の樹脂フィルムを作製した。得られた樹脂シートの特性を表１に示す。
[Resin sheet 2]
A resin film having a basis weight of 124 g / m 2 made of polyamide 6 resin (“Amilan” (registered trademark) CM1021T manufactured by Toray Industries, Inc.) was produced. The properties of the obtained resin sheet are shown in Table 1.
［樹脂シート３］
ナイロン６６樹脂（東レ（株）製“アミラン”（登録商標）ＣＭ３００６）からなる目付１２６ｇ／ｍ２の樹脂フィルムを作製した。得られた樹脂シートの特性を表１に示す。
[Resin sheet 3]
A resin film having a basis weight of 126 g / m 2 made of nylon 66 resin (“Amilan” (registered trademark) CM3006 manufactured by Toray Industries, Inc.) was produced. The properties of the obtained resin sheet are shown in Table 1.
［樹脂シート４］
ポリカーボネート樹脂（三菱エンジニアリングプラスチック（株）製“ユーピロン”（登録商標）Ｈ−４０００）からなる目付１３２ｇ／ｍ２の樹脂フィルムを作製した。得られた樹脂シートの特性を表１に示す。
[Resin sheet 4]
A resin film having a basis weight of 132 g / m 2 made of polycarbonate resin (“Iupilon” (registered trademark) H-4000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.) was produced. The properties of the obtained resin sheet are shown in Table 1.
［樹脂シート５］
ポリフェニレンサルファイド樹脂（東レ（株）製“トレリナ”（登録商標）Ｍ２８８８）からなる目付６７ｇ／ｍ２の樹脂マットを作製した。得られた樹脂シートの特性を表１に示す。
[Resin sheet 5]
A resin mat having a basis weight of 67 g / m 2 made of polyphenylene sulfide resin (“Torelina” (registered trademark) M2888 manufactured by Toray Industries, Inc.) was produced. The properties of the obtained resin sheet are shown in Table 1.
［樹脂シート６］
変性ポリフェニレンエーテル樹脂（ＳＡＢＩＣ（株）製“ＮＯＲＹＬ”（登録商標）ＰＰＸ７１１０）からなる目付１００ｇ／ｍ２のシートを作製した。得られた樹脂シートの特性を表１に示す。
[Resin sheet 6]
A sheet having a basis weight of 100 g / m 2 made of a modified polyphenylene ether resin (“NORYL” (registered trademark) PPX7110 manufactured by SABIC Co., Ltd.) was produced. The properties of the obtained resin sheet are shown in Table 1.
［強化繊維マット１］
強化繊維１をカートリッジカッターで６ｍｍにカットし、チョップド強化繊維を得た。水と界面活性剤（ナカライテスク（株）製、ポリオキシエチレンラウリルエーテル（商品名））からなる濃度０．１重量％の分散媒を４０リットル作製し、かかる分散媒を抄造装置に投入した。抄造装置は、回転翼付き攪拌機を備えた上部の抄造槽（容量３０リットル）と、下部の貯水槽（容量１０リットル）からなり、抄造槽と貯水槽の間には多孔支持体を設けてある。まず、かかる分散媒を攪拌機にて空気の微小気泡が発生するまで撹拌した。その後、所望の目付となるように、重量を調整したチョップド強化繊維を、空気の微小気泡が分散した分散媒中に投入して攪拌することにより、強化繊維が分散したスラリーを得た。次いで、貯水層からスラリーを吸引し、多孔支持体を介して脱水して強化繊維抄造体とした。前記抄造体を熱風乾燥機にて１５０℃、２時間の条件下で乾燥させ、目付け１００ｇ／ｍ２の強化繊維マット１を得た。得られた強化繊維マットの特性を表２に示す。
[Reinforcing fiber mat 1]
Reinforcing fiber 1 was cut to 6 mm with a cartridge cutter to obtain chopped reinforcing fiber. 40 liters of a dispersion medium having a concentration of 0.1% by weight made of water and a surfactant (manufactured by Nacalai Tesque Co., Ltd., polyoxyethylene lauryl ether (trade name)) was prepared, and the dispersion medium was put into a papermaking apparatus. The papermaking apparatus is composed of an upper papermaking tank (capacity 30 liters) equipped with a stirrer with rotating blades and a lower water storage tank (capacity 10 liters), and a porous support is provided between the papermaking tank and the water storage tank. . First, the dispersion medium was stirred with a stirrer until air microbubbles were generated. Thereafter, the chopped reinforcing fibers adjusted in weight so as to have a desired basis weight were put into a dispersion medium in which fine air bubbles were dispersed and stirred to obtain a slurry in which the reinforcing fibers were dispersed. Next, the slurry was sucked from the water storage layer and dehydrated through a porous support to obtain a reinforced fiber sheet. The papermaking product was dried in a hot air dryer at 150 ° C. for 2 hours to obtain a reinforcing fiber mat 1 having a basis weight of 100 g / m 2 . The properties of the obtained reinforcing fiber mat are shown in Table 2.
［強化繊維マット２］
強化繊維マットの目付けを２００ｇ／ｍ２とした以外は、強化繊維マット１と同様の方法によって、強化繊維マット２を得た。得られた強化繊維マットの特性を表２に示す。
[Reinforcing fiber mat 2]
A reinforcing fiber mat 2 was obtained in the same manner as the reinforcing fiber mat 1 except that the basis weight of the reinforcing fiber mat was 200 g / m 2 . The properties of the obtained reinforcing fiber mat are shown in Table 2.
［強化繊維マット３］
強化繊維マットの目付けを５０ｇ／ｍ２とした以外は、強化繊維マット１と同様の方法によって、強化繊維マット２を得た。得られた強化繊維マットの特性を表２に示す。
[Reinforcing fiber mat 3]
A reinforcing fiber mat 2 was obtained in the same manner as the reinforcing fiber mat 1 except that the basis weight of the reinforcing fiber mat was 50 g / m 2 . The properties of the obtained reinforcing fiber mat are shown in Table 2.
［強化繊維マット４］
強化繊維１を並行に引き揃え、１．２本／ｃｍの密度で一方向に配列してシート状の強化繊維群を形成した。強化繊維１を、１．２本／ｃｍの密度で、前記強化繊維群と直交する方向に配列し、強化繊維１同士を交錯させ、織機を用いて平織組織の二方向性織物を形成した。前記二方向性織物を強化繊維マット４として取り扱った。強化繊維マットの特性を表２に示す。
[Reinforcing fiber mat 4]
The reinforcing fibers 1 were aligned in parallel and arranged in one direction at a density of 1.2 fibers / cm to form a sheet-like reinforcing fiber group. The reinforcing fibers 1 were arranged at a density of 1.2 fibers / cm in a direction perpendicular to the reinforcing fiber group, the reinforcing fibers 1 were interlaced, and a bi-directional woven fabric having a plain weave structure was formed using a loom. The bidirectional fabric was handled as a reinforcing fiber mat 4. Table 2 shows the properties of the reinforcing fiber mat.
［ＧＭＴ］
ガラス繊維強化ポリプロピレン樹脂成形材料（ＧＭＴ）（Ｑｕａｄｒａｎｔ社製、“ユニシート”（登録商標）Ｐ４０３８−ＢＫ３１）を実施例１と同様の方法にて成形し、１．６ｍｍの厚みに形成されたＧＭＴを得た。
[GMT]
Glass fiber reinforced polypropylene resin molding material (GMT) (manufactured by Quadrant, “Uni Sheet” (registered trademark) P4038-BK31) was molded in the same manner as in Example 1, and GMT formed to a thickness of 1.6 mm was formed. Obtained.
［ＰＰコンパウンド］
強化繊維１と樹脂シート１を作製した際に用いたマスターバッチとを、２軸押出機（日本製鋼所（株）製、ＴＥＸ−３０α）を用いてコンパウンドし、繊維含有量３０重量％の射出成形用ペレット（ＰＰコンパウンド）を製造した。
[PP compound]
The reinforcing fiber 1 and the master batch used when the resin sheet 1 was produced were compounded using a twin-screw extruder (manufactured by Nippon Steel Works, Ltd., TEX-30α) and injected with a fiber content of 30% by weight. Pellet for molding (PP compound) was produced.
（実施例１）
不連続強化繊維のマットとして強化繊維マット１と、熱可塑性樹脂として樹脂シート１を［樹脂シート１／強化繊維マット１／樹脂シート１／強化繊維マット１／樹脂シート１／強化繊維マット１／樹脂シート１］の順番に配置し、積層体を作製した。前記積層体を２２０℃の金型温度に予熱したプレス成形金型に配置し、１２０秒間保持した後、４ＭＰａの圧力を付与してさらに１２０秒間保持した。圧力を保持した状態でキャビティ温度を５０℃まで冷却し、金型を開いて熱可塑性樹脂が完全含浸された繊維樹脂シートを得た。得られた繊維樹脂シートの片側表面を２００℃に設定したヒートプラテン上にて３分間加熱し、強化繊維の起毛力によってスプリングバックさせ、繊維強化樹脂シートを得た。得られた繊維強化樹脂シートを第１の部材として用い、予め強化繊維マット１に樹脂シート２を含浸させた繊維強化熱可塑性樹脂を第２の部材として用いて、繊維強化樹脂シートの空隙層面が第２の部材との接合面となるように、第１の部材である繊維強化樹脂シートと第２の部材との積層体を作成した。このとき、前記積層体のうち、第２の部材は予めＩＲヒータにて予熱温度２７０℃に加熱しておいた。プレス成形用金型を下型が２２０℃、上型が２７０℃の温度で保持された状態として、前記積層体を下側に第１の部材、上側に第２の部材になるようプレス成形金型に配置して金型を閉じ、３ＭＰａの圧力を付与して６０秒間保持した後、圧力を保持した状態でキャビティ温度を５０℃まで冷却し、金型を開いて一体成形品を得た。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表３に示す。
Example 1
A reinforcing fiber mat 1 as a discontinuous reinforcing fiber mat and a resin sheet 1 as a thermoplastic resin [resin sheet 1 / reinforced fiber mat 1 / resin sheet 1 / reinforced fiber mat 1 / resin sheet 1 / reinforced fiber mat 1 / resin Sheet 1] was arranged in this order to produce a laminate. The laminate was placed in a press mold preheated to a mold temperature of 220 ° C. and held for 120 seconds, and then a pressure of 4 MPa was applied and further held for 120 seconds. While maintaining the pressure, the cavity temperature was cooled to 50 ° C., the mold was opened, and a fiber resin sheet completely impregnated with the thermoplastic resin was obtained. One side surface of the obtained fiber resin sheet was heated on a heat platen set at 200 ° C. for 3 minutes, and was spring-backed by the raising force of the reinforcing fibers to obtain a fiber reinforced resin sheet. Using the obtained fiber reinforced resin sheet as the first member, and using the fiber reinforced thermoplastic resin obtained by impregnating the reinforced fiber mat 1 with the resin sheet 2 as the second member, the void layer surface of the fiber reinforced resin sheet is The laminated body of the fiber reinforced resin sheet which is a 1st member, and the 2nd member was created so that it might become a joint surface with a 2nd member. At this time, the second member of the laminate was previously heated to a preheating temperature of 270 ° C. with an IR heater. The press mold is such that the lower mold is held at a temperature of 220 ° C. and the upper mold is maintained at a temperature of 270 ° C., and the laminate is the first member on the lower side and the second member on the upper side. The mold was closed by placing it in the mold, and after applying a pressure of 3 MPa and holding for 60 seconds, the cavity temperature was cooled to 50 ° C. while the pressure was held, and the mold was opened to obtain an integrally molded product. Table 3 shows the characteristics of the obtained fiber reinforced resin sheet (first member) and the integrally molded product.
（実施例２）
繊維樹脂シートのヒートプラテン上での加熱時間を３分から１分に変更した以外は実施例１と同様にして繊維強化樹脂シートおよび一体成形品を得た。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表３に示す。
(Example 2)
A fiber reinforced resin sheet and an integrally molded product were obtained in the same manner as in Example 1 except that the heating time of the fiber resin sheet on the heat platen was changed from 3 minutes to 1 minute. Table 3 shows the characteristics of the obtained fiber reinforced resin sheet (first member) and the integrally molded product.
（実施例３）
繊維樹脂シートのヒートプラテン上での加熱時間を３分から２分に変更した以外は実施例１と同様にして繊維強化樹脂シートおよび一体成形品を得た。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表３に示す。
Example 3
A fiber reinforced resin sheet and an integrally molded product were obtained in the same manner as in Example 1 except that the heating time of the fiber resin sheet on the heat platen was changed from 3 minutes to 2 minutes. Table 3 shows the characteristics of the obtained fiber reinforced resin sheet (first member) and the integrally molded product.
（実施例４）
繊維樹脂シートのヒートプラテン上での加熱時間を３分から３０秒に変更した以外は実施例１と同様にして繊維強化樹脂シートおよび一体成形品を得た。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表３に示す。
Example 4
A fiber reinforced resin sheet and an integrally molded product were obtained in the same manner as in Example 1 except that the heating time of the fiber resin sheet on the heat platen was changed from 3 minutes to 30 seconds. Table 3 shows the characteristics of the obtained fiber reinforced resin sheet (first member) and the integrally molded product.
（実施例５）
第２の部材に用いる樹脂シートを、樹脂シート２から樹脂シート３に変更し、一体成形品を得る工程におけるＩＲヒータの予熱温度、ならびにプレス金型の上型温度をともに２７０℃から２８０℃に変更した以外は、実施例１と同様にして繊維強化樹脂シートおよび一体成形品を得た。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表３に示す。
(Example 5)
The resin sheet used for the second member is changed from the resin sheet 2 to the resin sheet 3, and both the preheating temperature of the IR heater and the upper mold temperature of the press die are changed from 270 ° C. to 280 ° C. in the process of obtaining an integrally molded product. A fiber reinforced resin sheet and an integrally molded product were obtained in the same manner as in Example 1 except for the change. Table 3 shows the characteristics of the obtained fiber reinforced resin sheet (first member) and the integrally molded product.
（実施例６）
第２の部材に用いる樹脂シートを、樹脂シート２から樹脂シート４に変更し、一体成形品を得る工程におけるＩＲヒータの予熱温度、ならびにプレス金型の上型温度をともに２７０℃から２８０℃に変更した以外は、実施例１と同様にして繊維強化樹脂シートおよび一体成形品を得た。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表３に示す。
(Example 6)
The resin sheet used for the second member is changed from the resin sheet 2 to the resin sheet 4, and both the preheating temperature of the IR heater and the upper mold temperature of the press die are changed from 270 ° C. to 280 ° C. in the process of obtaining an integrally molded product. A fiber reinforced resin sheet and an integrally molded product were obtained in the same manner as in Example 1 except for the change. Table 3 shows the characteristics of the obtained fiber reinforced resin sheet (first member) and the integrally molded product.
（実施例７）
第２の部材に用いる樹脂シートを、樹脂シート２から樹脂シート５に変更し、一体成形品を得る工程におけるＩＲヒータの予熱温度、ならびにプレス金型の上型温度をともに２７０℃から３００℃に変更した以外は、実施例１と同様にして繊維強化樹脂シートおよび一体成形品を得た。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表３に示す。
(Example 7)
The resin sheet used for the second member is changed from the resin sheet 2 to the resin sheet 5, and the preheating temperature of the IR heater and the upper mold temperature of the press mold are both changed from 270 ° C. to 300 ° C. in the process of obtaining an integrally molded product. A fiber reinforced resin sheet and an integrally molded product were obtained in the same manner as in Example 1 except for the change. Table 3 shows the characteristics of the obtained fiber reinforced resin sheet (first member) and the integrally molded product.
（実施例８）
第２の部材に用いる樹脂シートを、樹脂シート２から樹脂シート６に変更し、一体成形品を得る工程におけるＩＲヒータの予熱温度、ならびにプレス金型の上型温度をともに２７０℃から２８０℃に変更した以外は、実施例１と同様にして繊維強化樹脂シートおよび一体成形品を得た。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表３に示す。
(Example 8)
The resin sheet used for the second member is changed from the resin sheet 2 to the resin sheet 6, and both the preheating temperature of the IR heater and the upper mold temperature of the press die are changed from 270 ° C. to 280 ° C. in the process of obtaining an integrally molded product. A fiber reinforced resin sheet and an integrally molded product were obtained in the same manner as in Example 1 except for the change. Table 3 shows the characteristics of the obtained fiber reinforced resin sheet (first member) and the integrally molded product.
（実施例９）
第１の部材に用いる強化繊維マットを、強化繊維マット１から強化繊維マット２に変更した以外は、実施例１と同様にして繊維強化樹脂シートおよび一体成形品を得た。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表３に示す。
（実施例１０）
第１の部材に用いる強化繊維マットを、強化繊維マット１から強化繊維マット３に変更した以外は、実施例１と同様にして第１の部材である繊維強化樹脂シートを得た。一方、第２の部材として、ＧＭＴを２３０℃に保持されたヒートプラテンに配置して、０．１ＭＰａの圧力を付与しながら１分間予熱した。次いで、得られた繊維強化樹脂シートの空隙層面を接合面となるように、上下共に１２０℃に予熱されたプレス成形用金型内に配置し、その上に予熱が完了したＧＭＴを重ねて配置して金型を閉じ、１５ＭＰａの圧力を付与した状態で１２０秒間保持して、５０℃まで金型冷却し、一体成形品を得た。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表３に示す。
（実施例１１）
第１の部材に用いる樹脂シートを、樹脂シート１から樹脂シート２に変更し、繊維樹脂シートを得る際の金型温度と、繊維樹脂シートに空隙層を形成する際のヒートプラテンの設定温度を２００℃から２７０℃に変更した以外は、実施例１と同様にして、第１の部材である繊維強化樹脂シートを得た。得られた繊維強化樹脂シートを第１の部材として、該繊維強化樹脂シートの空隙層を有する面を接合面となるように射出成形用金型にインサートして、ＰＰコンパウンドを用いて、第２の部材を射出成形し、図７に示すような一体成形品３８を得た。この時、射出成形機のシリンダー温度は２００℃、金型温度は６０℃であった。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表４に示す。
（実施例１２）
第１の部材に用いる樹脂シートを、樹脂シート１から樹脂シート３に変更し、繊維樹脂シートを得る際の金型温度と、繊維樹脂シートに空隙層を形成する際のヒートプラテンの設定温度を２００℃から２８０℃に変更した以外は、実施例１と同様にして第１の部材である繊維強化樹脂シートを得た。さらに、得られた繊維強化樹脂シートを第１の部材として、実施例１１と同様の方法にて一体成形品を得た。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表４に示す。
（実施例１３）
第１の部材に用いる樹脂シートを、樹脂シート１から樹脂シート４に変更し、繊維樹脂シートを得る際の金型温度と、繊維樹脂シートに空隙層を形成する際のヒートプラテンの設定温度を２００℃から２８０℃に変更した以外は、実施例１と同様にして第１の部材である繊維強化樹脂シートを得た。さらに、得られた繊維強化樹脂シートを第１の部材として、実施例１１と同様の方法にて一体成形品を得た。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表４に示す。
（実施例１４）
第１の部材に用いる樹脂シートを、樹脂シート１から樹脂シート５に変更し、繊維樹脂シートを得る際の金型温度と、繊維樹脂シートに空隙層を形成する際のヒートプラテンの設定温度を２００℃から３００℃に変更した以外は、実施例１と同様にして第１の部材である繊維強化樹脂シートを得た。さらに、得られた繊維強化樹脂シートを第１の部材として、実施例１１と同様の方法にて一体成形品を得た。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表４に示す。
（実施例１５）
第１の部材に用いる樹脂シートを、樹脂シート１から樹脂シート６に変更し、繊維樹脂シートを得る際の金型温度と、繊維樹脂シートに空隙層を形成する際のヒートプラテンの設定温度を２００℃から２８０℃に変更した以外は、実施例１と同様にして第１の部材である繊維強化樹脂シートを得た。さらに、得られた繊維強化樹脂シートを第１の部材として、実施例１１と同様の方法にて一体成形品を得た。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表４に示す。
(比較例１)
実施例１で得られた繊維樹脂シートを、スプリングバックを生じる工程を経ず、つまり空隙率が０体積％の繊維強化樹脂シートとした。第１の部材をその空隙率が０体積％の繊維強化樹脂シートに変更した以外は、実施例１と同様にして一体成形品を得た。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表５に示す。
（比較例２）
不連続強化繊維のマットとして強化繊維マット１に代えて、強化繊維マット４を用いた以外は比較例１と同様にして繊維強化樹脂シートおよび一体成形品を得た。得られた繊維強化樹脂シート（第１の部材）および一体成形品の特性をまとめて表５に示す
Example 9
A fiber reinforced resin sheet and an integrally molded product were obtained in the same manner as in Example 1 except that the reinforcing fiber mat used for the first member was changed from the reinforcing fiber mat 1 to the reinforcing fiber mat 2. Table 3 shows the characteristics of the obtained fiber reinforced resin sheet (first member) and the integrally molded product.
(Example 10)
A fiber reinforced resin sheet as a first member was obtained in the same manner as in Example 1 except that the reinforcing fiber mat used for the first member was changed from the reinforcing fiber mat 1 to the reinforcing fiber mat 3. On the other hand, as a second member, GMT was placed on a heat platen maintained at 230 ° C., and preheated for 1 minute while applying a pressure of 0.1 MPa. Next, the gap layer surface of the obtained fiber reinforced resin sheet is placed in a press mold that is preheated to 120 ° C. both on the top and bottom, and the preheated GMT is placed on top of it so that it becomes the joint surface. Then, the mold was closed and held for 120 seconds under a pressure of 15 MPa, and the mold was cooled to 50 ° C. to obtain an integrally molded product. Table 3 shows the characteristics of the obtained fiber reinforced resin sheet (first member) and the integrally molded product.
(Example 11)
The resin sheet used for the first member is changed from the resin sheet 1 to the resin sheet 2, and the mold temperature when obtaining the fiber resin sheet and the set temperature of the heat platen when forming the void layer in the fiber resin sheet are set. A fiber reinforced resin sheet as a first member was obtained in the same manner as in Example 1 except that the temperature was changed from 200 ° C to 270 ° C. Using the obtained fiber reinforced resin sheet as a first member, the surface having the void layer of the fiber reinforced resin sheet is inserted into an injection mold so as to be a bonding surface, and a second compound is formed using a PP compound. These members were injection-molded to obtain an integrally molded product 38 as shown in FIG. At this time, the cylinder temperature of the injection molding machine was 200 ° C., and the mold temperature was 60 ° C. Table 4 summarizes the properties of the obtained fiber-reinforced resin sheet (first member) and the integrally molded product.
(Example 12)
The resin sheet used for the first member is changed from the resin sheet 1 to the resin sheet 3, and the mold temperature when obtaining the fiber resin sheet and the set temperature of the heat platen when forming the void layer in the fiber resin sheet A fiber reinforced resin sheet as a first member was obtained in the same manner as in Example 1 except that the temperature was changed from 200 ° C to 280 ° C. Further, an integrally molded product was obtained in the same manner as in Example 11 using the obtained fiber-reinforced resin sheet as the first member. Table 4 summarizes the properties of the obtained fiber-reinforced resin sheet (first member) and the integrally molded product.
(Example 13)
The resin sheet used for the first member is changed from the resin sheet 1 to the resin sheet 4, and the mold temperature when obtaining the fiber resin sheet and the set temperature of the heat platen when forming the void layer in the fiber resin sheet are set. A fiber reinforced resin sheet as a first member was obtained in the same manner as in Example 1 except that the temperature was changed from 200 ° C to 280 ° C. Further, an integrally molded product was obtained in the same manner as in Example 11 using the obtained fiber-reinforced resin sheet as the first member. Table 4 summarizes the properties of the obtained fiber-reinforced resin sheet (first member) and the integrally molded product.
(Example 14)
The resin sheet used for the first member is changed from the resin sheet 1 to the resin sheet 5, and the mold temperature when obtaining the fiber resin sheet and the set temperature of the heat platen when forming the void layer in the fiber resin sheet are set. A fiber reinforced resin sheet as a first member was obtained in the same manner as in Example 1 except that the temperature was changed from 200 ° C to 300 ° C. Further, an integrally molded product was obtained in the same manner as in Example 11 using the obtained fiber-reinforced resin sheet as the first member. Table 4 summarizes the properties of the obtained fiber-reinforced resin sheet (first member) and the integrally molded product.
(Example 15)
The resin sheet used for the first member is changed from the resin sheet 1 to the resin sheet 6, and the mold temperature when obtaining the fiber resin sheet and the set temperature of the heat platen when forming the void layer in the fiber resin sheet are set. A fiber reinforced resin sheet as a first member was obtained in the same manner as in Example 1 except that the temperature was changed from 200 ° C to 280 ° C. Further, an integrally molded product was obtained in the same manner as in Example 11 using the obtained fiber-reinforced resin sheet as the first member. Table 4 summarizes the properties of the obtained fiber-reinforced resin sheet (first member) and the integrally molded product.
(Comparative Example 1)
The fiber resin sheet obtained in Example 1 was not subjected to a step of generating a springback, that is, a fiber reinforced resin sheet having a porosity of 0% by volume. An integrally molded product was obtained in the same manner as in Example 1 except that the first member was changed to a fiber reinforced resin sheet having a porosity of 0% by volume. Table 5 summarizes the properties of the obtained fiber-reinforced resin sheet (first member) and the integrally molded product.
(Comparative Example 2)
A fiber-reinforced resin sheet and an integrally molded product were obtained in the same manner as in Comparative Example 1 except that the reinforcing fiber mat 4 was used in place of the reinforcing fiber mat 1 as a discontinuous reinforcing fiber mat. Table 5 summarizes the properties of the obtained fiber-reinforced resin sheet (first member) and the integrally molded product.
実施例１〜４において、ヒートプラテン上で加熱する時間を変化させたが、いずれも空隙層と含浸層を共有した繊維強化樹脂シートが得られていることから、第２の材料と一体化した際、異樹脂の複雑な含浸を促進させることができた為、一体成形品として十分な接合がなされた。加えて、強化繊維の面外角度θｚも好適な態様にあったため、第２の部材中の熱可塑性樹脂と良好な境界層を形成し、実用に耐えうる十分な接合強度が得られた。特に実施例１〜３では、空隙率がより好ましい範囲で形成したことにより、境界層における最大高さＲｙ、平均粗さＲｚが十分なサイズにまで成長し、より理想的な境界層が形成されていることで格段に高い接合強度を示した。一方で実施例２や実施例４の様に、空隙率が小さい場合は、境界層における最大高さＲｙ、平均粗さＲｚも小さくなるが、この場合においても同一シートに空隙層と含浸層とが形成されたことで、一体成形品の境界層において強化繊維を共有した為、十分な接合強度が得られている。 In Examples 1 to 4, the heating time on the heat platen was changed, but since fiber reinforced resin sheets that shared the void layer and the impregnation layer were obtained, they were integrated with the second material. At this time, since the complicated impregnation of the different resin could be promoted, sufficient joining as an integrally molded product was achieved. In addition, since the out-of-plane angle θz of the reinforcing fibers was also in a suitable mode, a sufficient boundary layer was formed with the thermoplastic resin in the second member, and sufficient bonding strength that could withstand practical use was obtained. Particularly in Examples 1 to 3, by forming the porosity in a more preferable range, the maximum height Ry and average roughness Rz in the boundary layer grow to a sufficient size, and a more ideal boundary layer is formed. As a result, the joint strength was remarkably high. On the other hand, as in Example 2 and Example 4, when the porosity is small, the maximum height Ry and average roughness Rz in the boundary layer are also small. In this case as well, the void layer and the impregnated layer are formed on the same sheet. Since the reinforcing fibers are shared in the boundary layer of the integrally molded product, sufficient bonding strength is obtained.
また、実施例５〜１０において、いずれにおいても、空隙率がより好ましい範囲にあたる繊維強化樹脂シートを得ることができた。さらに該繊維強化樹脂シートから得た一体成形品は、第１の部材のスプリングバックに基づく空隙により、融点または軟化点の異なる異樹脂で構成される部材においても、適切なアンカリング構造を形成し強化繊維を共有したことで、十分な接合強度を有しており実用に問題のない一体成形品を得ることができた。これは強化繊維からなる繊維強化樹脂シート中の空隙部が異樹脂の複雑な含浸を促進して、境界層における最大高さＲｙ、平均粗さＲｚを十分なサイズにまで成長させたことにより理想的な境界層が形成されていることに加え、強化繊維の面外角度θｚも好適な態様にあったため、第２の部材中の熱可塑性樹脂と良好な境界層を形成しているためである。プレス成形法による一体成型品として、例えば図１０に記載の一体成形品が例示できる。 Moreover, in Examples 5-10, the fiber reinforced resin sheet which has a porosity in a more preferable range could be obtained. Further, the integrally molded product obtained from the fiber reinforced resin sheet forms an appropriate anchoring structure even in a member made of a different resin having a different melting point or softening point due to a gap based on the spring back of the first member. By sharing the reinforcing fiber, it was possible to obtain an integrally molded product having sufficient bonding strength and no problem in practical use. This is ideal because the voids in the fiber-reinforced resin sheet made of reinforcing fibers promoted complex impregnation of different resins, and the maximum height Ry and average roughness Rz in the boundary layer were grown to a sufficient size. In addition to the fact that the boundary layer is formed, the out-of-plane angle θz of the reinforcing fiber is also in a suitable mode, and therefore, a good boundary layer is formed with the thermoplastic resin in the second member. . As an integrally molded product by the press molding method, for example, an integrally molded product shown in FIG. 10 can be exemplified.
また、実施例１１〜１５においても、空隙層と含浸層とを共有した各種樹脂シートを得ることができ、さらに該繊維強化樹脂シートから得た一体成形品は、第１の部材のスプリングバックに基づく空隙に、第２の材料がインサートされ、適切なアンカリング構造を形成し強化繊維を共有したことにより、十分な接合強度を有しており実用に問題のない一体成形品を得ることができた。 In Examples 11 to 15 as well, various resin sheets sharing the void layer and the impregnated layer can be obtained, and the integrally molded product obtained from the fiber-reinforced resin sheet is used as the spring back of the first member. Since the second material is inserted into the gap based on this, an appropriate anchoring structure is formed, and the reinforcing fiber is shared, it is possible to obtain an integrally molded product having sufficient bonding strength and having no practical problems. It was.
しかし、比較例１においては強化繊維マットを使用したが、繊維強化樹脂シートが強化繊維マットに基づくスプリングバックによる空隙を有さないため、接合部における熱可塑性樹脂のアンカリング構造、または強化繊維の共有が不十分であり一体成形品の接合強度が不十分であった。比較例２では強化繊維が束状かつ連続した状態で存在しているため、第２の材料を構成する熱可塑性樹脂が境界層にて十分な含浸が得られず、また強化繊維の共有状態が得られなかった為、接合強度が不十分であった。 However, although the reinforcing fiber mat was used in Comparative Example 1, since the fiber reinforced resin sheet does not have a gap due to the spring back based on the reinforcing fiber mat, the anchoring structure of the thermoplastic resin in the joint portion or the reinforcing fiber Sharing was insufficient and the joint strength of the integrally molded product was insufficient. In Comparative Example 2, the reinforcing fibers exist in a bundled and continuous state, so that the thermoplastic resin constituting the second material cannot be sufficiently impregnated in the boundary layer, and the shared state of the reinforcing fibers is not present. Since it was not obtained, the bonding strength was insufficient.
さらに、特許文献１、２における多孔質一体成型品は接合性について検討されておらず、また強化繊維の共有についての明記もない。比較例１と同様に強化繊維が共有されていない態様であることから、接合性は必ずしも高いものではなく、本発明における実施例１〜１４に対し接合性は劣る。 Furthermore, the porous integrally molded article in Patent Documents 1 and 2 has not been examined for bondability, and there is no description about sharing of reinforcing fibers. Since the reinforcing fiber is not shared as in Comparative Example 1, the bondability is not necessarily high, and the bondability is inferior to Examples 1-14 in the present invention.
本発明によれば、強化繊維によるスプリングバックの空隙形成に由来するアンカリング効果により、接合部分の境界層において強固な接合を有するため、適用する熱可塑性樹脂の組合せに特段の制限なく、異なる樹脂のハイブリッド体を容易に得ることが出来る。よって、自動車内外装、電気・電子機器筐体、自転車、スポーツ用品用構造材、航空機内装材、輸送用箱体、などの幅広い用途に好適に用いることができる。 According to the present invention, the anchoring effect derived from the formation of the springback voids by the reinforcing fibers has a strong bond in the boundary layer of the bonded portion, so that there is no particular limitation on the combination of thermoplastic resins to be applied, and different resins The hybrid body can be easily obtained. Therefore, it can be suitably used for a wide range of applications such as automobile interior and exterior, electrical / electronic equipment casings, bicycles, structural materials for sporting goods, aircraft interior materials, and transport boxes.
１、２０ 繊維強化樹脂シート
２ 空隙層
３ 実質的に空隙を有さない含浸層
４ 連続した空孔形状を有する空隙
５ 境界面
６ 空隙層最外面
７ 線形領域（Ａ）―（Ａ’）
８ 線形領域（Ｂ）―（Ｂ’）
９ 線形領域（Ａ）―（Ａ’）の外挿線
１０ 線形領域（Ｂ）―（Ｂ’）の外挿線
１１ 外挿線交点
１２ 含浸層厚み
１３、１４、１５、１６、１７、１８、２１、２２、３４、３５ 強化繊維（単繊維）
１９ 二次元接触角、二次元配向角
２３、３１、３８ 一体成形品
２４、３２ 第１の部材（繊維強化樹脂シート）における熱可塑性樹脂
２５、３３ 第２の部材（繊維強化樹脂シート）における熱可塑性樹脂
２６ 繊維強化樹脂シートと第２の部材の境界層
２７ 境界層における最も窪みの大きい凹部
２８ 境界層における最も突出の大きい凸部
２９ 境界層における最も窪みの小さい凹部
３０ 境界層における最も突出の小さい凸部
３６ せん断強度τ２の評価に供する試験片
３７ 切欠き
３９ 第１の部材
４０ 第２の部材
DESCRIPTION OF SYMBOLS 1,20 Fiber reinforced resin sheet 2 Gap layer 3 Impregnated layer 4 having substantially no void Gap 5 having continuous pore shape Boundary surface 6 Gap layer outermost surface 7 Linear region (A)-(A ′)
8 Linear region (B)-(B ')
9 Extrapolation line 10 of linear region (A)-(A ′) Extrapolation line 11 of linear region (B)-(B ′) Extrapolation line intersection 12 Impregnation layer thickness 13, 14, 15, 16, 17, 18 , 21, 22, 34, 35 Reinforcing fibers (single fibers)
19 Two-dimensional contact angle, two-dimensional orientation angle 23, 31, 38 Integrated molded product 24, 32 Thermoplastic resin 25, 33 in first member (fiber reinforced resin sheet) Heat in second member (fiber reinforced resin sheet) Plastic resin 26 Boundary layer 27 between fiber reinforced resin sheet and second member Recessed portion 28 having the largest depression in the boundary layer Convex portion having the largest protrusion in the boundary layer 29 Recessed portion having the smallest depression in the boundary layer 30 The most protruding portion in the boundary layer Small convex portion 36 Test piece 37 used for evaluation of shear strength τ2 Notch 39 First member 40 Second member
Claims (16)
工程［１］：熱可塑性樹脂を溶融もしくは軟化する温度以上に加熱された状態で圧力を付与し、前記マットに熱可塑性樹脂を含浸せしめて繊維樹脂シートとする工程
工程［２］：次いで、繊維樹脂シートを冷却し、そこに含まれる熱可塑性樹脂を全体的に固化せしめる工程
工程［３］：次いで、熱可塑性樹脂が全体的に固化した繊維樹脂シートの少なくとも片表面を熱可塑性樹脂の溶融または軟化する温度以上に加熱し、強化繊維の起毛力により空隙層を形成する工程 The manufacturing method of the fiber reinforced resin sheet in any one of Claims 1-8 which has following process [1], [2], and [3] at least.
Step [1]: Step [2] in which a pressure is applied in a state heated to a temperature higher than the temperature at which the thermoplastic resin is melted or softened and the mat is impregnated with the thermoplastic resin to obtain a fiber resin sheet [2]: Next, the fiber Step [3] of cooling the resin sheet and totally solidifying the thermoplastic resin contained therein [3]: Next, at least one surface of the fiber resin sheet on which the thermoplastic resin is totally solidified is melted of the thermoplastic resin or Heating above the softening temperature and forming a void layer by the raising force of the reinforcing fiber
工程［１］：熱可塑性樹脂を溶融もしくは軟化する温度以上に加熱された状態で圧力を付与し、前記マットに熱可塑性樹脂を含浸せしめて繊維樹脂シートとする工程
工程［２’］：次いで、熱可塑性樹脂が溶融もしくは軟化した繊維樹脂シートに圧力を保持した状態で、その片表面を冷却して、冷却側の熱可塑性樹脂を固化せしめる工程
工程［３’］：次いで、もう片表面の熱可塑性樹脂が固化するより前に圧力を開放して、強化繊維の起毛力により空隙層を形成する工程 The manufacturing method of the fiber reinforced resin sheet in any one of Claims 1-8 which has at least following process [1], [2 '] and [3'].
Step [1]: Applying pressure in a state heated above the temperature at which the thermoplastic resin is melted or softened, and impregnating the mat with the thermoplastic resin to obtain a fiber resin sheet [2 ′]: Step [3 ′] of cooling the one surface of the fiber resin sheet in which the thermoplastic resin is melted or softened while maintaining the pressure to solidify the thermoplastic resin on the cooling side: Next, the heat of the other surface The step of releasing the pressure before the plastic resin solidifies and forming the void layer by the raising force of the reinforcing fibers
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