JP2021042306A - Fiber-reinforced resin composite molding and its manufacturing method - Google Patents

Fiber-reinforced resin composite molding and its manufacturing method Download PDF

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JP2021042306A
JP2021042306A JP2019165131A JP2019165131A JP2021042306A JP 2021042306 A JP2021042306 A JP 2021042306A JP 2019165131 A JP2019165131 A JP 2019165131A JP 2019165131 A JP2019165131 A JP 2019165131A JP 2021042306 A JP2021042306 A JP 2021042306A
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fiber
compound
reinforced resin
layer
resin
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JP7139296B2 (en
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杉浦 好典
Yoshinori Sugiura
好典 杉浦
尚幸 田辺
Naoyuki Tanabe
尚幸 田辺
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Inoac Corp
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Inoue MTP KK
Inoac Corp
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Priority to CN202080061111.7A priority patent/CN114375252A/en
Priority to PCT/JP2020/031851 priority patent/WO2021039722A1/en
Priority to EP20858902.8A priority patent/EP4023427A4/en
Priority to US17/638,199 priority patent/US20220402238A1/en
Priority to TW109129237A priority patent/TW202116557A/en
Publication of JP2021042306A publication Critical patent/JP2021042306A/en
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00Aeronautics or air transport
    • Y02T50/40Weight reduction

Abstract

To provide a thin fiber-reinforced resin composite molding having rigidity and capable of forming a shape into a complicated shape.SOLUTION: A fiber-reinforced resin composite molding comprises: a rigid layer 11 formed from a fiber-reinforced resin material for rigid layers; a shape-forming layer 21 formed at least on one surface of the rigid layer 11 from a compound for shape-forming layer made of fibers shorter than fibers contained in the fiber-reinforced resin material for rigid layers and a thermo-setting resin; and a resin 31 formed from a liquid resin adhered to a surface of the shape-forming layer 21, in which the fiber-reinforced resin material for rigid layers, the compound for shape-forming layers, and the liquid resin are heated, compressed and cured in a laminate state.SELECTED DRAWING: Figure 1

Description

本発明は、繊維強化樹脂複合成形体とその製造方法に関する。 The present invention relates to a fiber-reinforced resin composite molded product and a method for producing the same.

従来、繊維強化樹脂成形体は、高強度且つ高剛性であるという点から、スポーツ、レジャー、航空機などの幅広い産業分野で使用されている。
繊維強化樹脂成形体の製造方法として、補強繊維に熱硬化性樹脂を含浸したプリプレグや、シートモールディングコンパウンドなどを圧縮成形する方法が、多くの分野で採用されている。
Conventionally, a fiber reinforced resin molded product has been used in a wide range of industrial fields such as sports, leisure, and aircraft because of its high strength and high rigidity.
As a method for producing a fiber-reinforced resin molded product, a method of compression molding a prepreg in which reinforcing fibers are impregnated with a thermosetting resin, a sheet molding compound, or the like is adopted in many fields.

プリプレグは補強繊維として長繊維を用いるため、高強度・高剛性の成形体が得られる反面、複雑な形状に賦形し難い。それに対して、シートモールディングコンパウンドは、補強繊維として短い繊維を用いるため、成形品の強度はプリプレグより低くなるものの、成形時の流動性に優れ、リブやボスなどの複雑な形状にも賦形し易い。 Since the prepreg uses long fibers as reinforcing fibers, a molded product having high strength and high rigidity can be obtained, but it is difficult to shape the prepreg into a complicated shape. On the other hand, since the sheet molding compound uses short fibers as reinforcing fibers, the strength of the molded product is lower than that of the prepreg, but it has excellent fluidity during molding and can be shaped into complicated shapes such as ribs and bosses. easy.

また、プリプレグとシートモールディングコンパウンドの双方の利点を取り入れて剛性を維持しつつ、複雑な形状な賦形を可能にするため、プリプレグとシートモールディングコンパウンドを積層して圧縮成形することが提案されている(特許文献1)。 In addition, it has been proposed that the prepreg and the sheet molding compound are laminated and compression molded in order to take advantage of both the prepreg and the sheet molding compound and maintain the rigidity while enabling the shaping of a complicated shape. (Patent Document 1).

特開2009−083441号公報Japanese Unexamined Patent Publication No. 2009-083441

しかし、プリプレグとシートモールディングコンパウンドを積層して圧縮成形した複合成形体は、シートモールディングコンパウンドから形成された層の厚みを、圧縮成形前のシートモールディングコンパウンドの厚みに対して70%程度にしかできないため、成形品全体の厚みを薄くすることができず、剛性を有し、複雑形状に賦形可能な薄肉な成形体を得ることができなかった。 However, in a composite molded body obtained by laminating a prepreg and a sheet molding compound and compression molding, the thickness of the layer formed from the sheet molding compound can be made only about 70% of the thickness of the sheet molding compound before compression molding. It was not possible to reduce the thickness of the entire molded product, and it was not possible to obtain a thin molded product having rigidity and capable of shaping into a complicated shape.

本発明は、前記の点に鑑みなされたものであり、剛性を有し、複雑形状及び薄肉に賦形可能な繊維強化樹脂複合成形体と、その製造方法の提供を目的とする。 The present invention has been made in view of the above points, and an object of the present invention is to provide a fiber-reinforced resin composite molded product having rigidity and capable of shaping into a complicated shape and a thin wall, and a method for producing the same.

請求項1の発明は、剛性層用繊維強化樹脂材から形成された剛性層と、前記剛性層用繊維強化樹脂材に含まれる繊維よりも短い繊維と熱硬化性樹脂とよりなる賦形層用コンパウンドから、前記剛性層の少なくとも一面に形成された賦形層と、前記賦形層の表面に付着した液状樹脂が硬化した樹脂と、よりなり、前記剛性層用繊維強化樹脂材と前記賦形層用コンパウンドが、積層状態で前記液状樹脂と共に加熱圧縮硬化したものであることを特徴とする繊維強化樹脂複合成形体に係る。 The invention of claim 1 is for a shaping layer composed of a rigid layer formed of a fiber reinforced resin material for a rigid layer, fibers shorter than the fibers contained in the fiber reinforced resin material for a rigid layer, and a thermosetting resin. The compound is composed of a shaping layer formed on at least one surface of the rigid layer and a resin obtained by curing the liquid resin adhering to the surface of the shaping layer, and the fiber reinforced resin material for the rigid layer and the shaping. The present invention relates to a fiber reinforced resin composite molded body, wherein the layer compound is a laminated state obtained by heat compression curing together with the liquid resin.

請求項2の発明は、請求項1において、前記剛性層用繊維強化樹脂材はプリプレグであり、前記賦形層用コンパウンドはシートモールディングコンパウンドであり、前記液状樹脂は熱硬化性樹脂であることを特徴する。 According to the first aspect of the present invention, the fiber-reinforced resin material for the rigid layer is a prepreg, the compound for the shaping layer is a sheet molding compound, and the liquid resin is a thermosetting resin. Characterize.

請求項3の発明は、剛性層用繊維強化樹脂材から形成された剛性層と、前記剛性層用繊維強化樹脂材に含まれる繊維よりも短い繊維と熱硬化性樹脂とよりなる賦形層用コンパウンドから、前記剛性層の少なくとも一面に形成された賦形層と、前記賦形層の表面に付着した液状樹脂が硬化した樹脂とよりなる繊維強化樹脂複合成形体の製造方法であって、前記賦形層用コンパウンドの表面に液状樹脂を塗布し、または該賦形層用コンパウンドの表面を押圧することになる金型の型面に液状樹脂を塗布し、前記剛性層用繊維強化樹脂材と前記賦形層用コンパウンドを、積層状態で前記液状樹脂と共に前記金型で加熱圧縮し、硬化させることを特徴とする。 The invention of claim 3 is for a shaping layer composed of a rigid layer formed of a fiber-reinforced resin material for a rigid layer, fibers shorter than the fibers contained in the fiber-reinforced resin material for a rigid layer, and a thermosetting resin. A method for producing a fiber-reinforced resin composite molded body, which comprises a shaping layer formed on at least one surface of the rigid layer from a compound and a resin obtained by curing a liquid resin adhering to the surface of the shaping layer. A liquid resin is applied to the surface of the shaping layer compound, or the liquid resin is applied to the mold surface of the mold that presses the surface of the shaping layer compound, and the fiber-reinforced resin material for the rigid layer is used. The compound for a shaping layer is heat-compressed together with the liquid resin in the mold in a laminated state and cured.

請求項4の発明は、請求項3において、前記剛性層用繊維強化樹脂材はプリプレグであり、前記賦形層用コンパウンドはシートモールディングコンパウンドであり、前記液状樹脂は熱硬化性樹脂であることを特徴する。 According to the third aspect of the present invention, the fiber-reinforced resin material for the rigid layer is a prepreg, the compound for the shaping layer is a sheet molding compound, and the liquid resin is a thermosetting resin. Characterize.

本発明によれば、繊維強化樹脂複合成形体は、剛性層用繊維強化樹脂材と賦形層用コンパウンドと液状樹脂が、積層状態で液状樹脂と共に加熱圧縮硬化したものであるため、繊維強化樹脂複合成形体を製造する際の金型による加熱圧縮時に、液状樹脂が、賦形層用コンパウンドと金型の型面間で断熱層として作用し、賦形層用コンパウンドの硬化反応が遅れることから、硬化完了までの間における賦形層用コンパウンドの流動量が大になり、賦形層用コンパウンドから形成される賦形層を薄肉にできる。さらに、液状樹脂が、賦形層用コンパウンドと金型の型面間で潤滑剤の作用をして賦形層用コンパウンドの流動性を向上させるため、それによっても賦形層を薄くすることができる。その結果、剛性層による剛性を有し、かつ賦形層によって複雑な形状に賦形でき、さらに薄肉な繊維強化樹脂複合成形体を得ることができる。 According to the present invention, the fiber-reinforced resin composite molded body is a fiber-reinforced resin material in which a fiber-reinforced resin material for a rigid layer, a compound for a shaping layer, and a liquid resin are heat-compressed and cured together with the liquid resin in a laminated state. During heating and compression by the mold when manufacturing the composite molded product, the liquid resin acts as a heat insulating layer between the compound for the shaping layer and the mold surface of the mold, and the curing reaction of the compound for the shaping layer is delayed. The amount of flow of the shaping layer compound until the completion of curing is increased, and the shaping layer formed from the shaping layer compound can be thinned. Furthermore, since the liquid resin acts as a lubricant between the compound for the shaping layer and the mold surface of the mold to improve the fluidity of the compound for the shaping layer, the shaping layer can also be thinned. it can. As a result, it is possible to obtain a fiber-reinforced resin composite molded product having rigidity due to the rigid layer, being able to be shaped into a complicated shape by the shaping layer, and having a thinner wall thickness.

本発明における繊維強化樹脂複合成形体の一実施形態の断面図である。It is sectional drawing of one Embodiment of the fiber-reinforced resin composite molded article in this invention. 金型の一実施形態の断面図である。It is sectional drawing of one Embodiment of a mold. 各実施例と各比較例における塗布樹脂の構成と成形後の厚み等を示す表である。It is a table which shows the composition of the coating resin in each Example and each comparative example, the thickness after molding and the like.

以下、本発明の繊維強化樹脂複合成形体とその製造方法について説明する。
図1に示す繊維強化樹脂複合成形体10は、剛性用繊維強化樹脂材から形成された剛性層11と、賦形層用コンパウンドから形成された賦形層21と、賦形層用コンパウンドの表面に付着した液状樹脂が硬化した樹脂31とよりなる。
Hereinafter, the fiber-reinforced resin composite molded product of the present invention and a method for producing the same will be described.
The fiber-reinforced resin composite molded body 10 shown in FIG. 1 has a rigid layer 11 formed of a rigid fiber-reinforced resin material, a shaping layer 21 formed of a shaping layer compound, and a surface of the shaping layer compound. The liquid resin adhering to is composed of the cured resin 31.

剛性層11は、剛性層用繊維強化樹脂材が加熱圧縮されて硬化したものからなる。
剛性層用繊維強化樹脂材は、繊維シートに熱硬化性樹脂が含浸したものである。繊維シートとしては、炭素繊維、ガラス繊維、アラミド繊維等の繊維から構成されたものを挙げることができる。特に、軽量化と剛性向上の点から炭素繊維が好ましい。繊維シートは、織物、編み物、不織布等であってもよい。織物としては、平織、綾織、朱子織、三軸織等がある。また、繊維シートは、一方向あるいは複数方向に配向した繊維で構成されていてもよい。繊維シートは、剛性向上の点から、繊維織物が好ましい。
The rigid layer 11 is made of a fiber-reinforced resin material for a rigid layer that has been heat-compressed and cured.
The fiber-reinforced resin material for a rigid layer is a fiber sheet impregnated with a thermosetting resin. Examples of the fiber sheet include those composed of fibers such as carbon fiber, glass fiber, and aramid fiber. In particular, carbon fiber is preferable from the viewpoint of weight reduction and rigidity improvement. The fiber sheet may be a woven fabric, a knitted fabric, a non-woven fabric, or the like. As the woven fabric, there are plain weave, twill weave, satin weave, triaxial weave and the like. Further, the fiber sheet may be composed of fibers oriented in one direction or a plurality of directions. As the fiber sheet, a fiber woven fabric is preferable from the viewpoint of improving rigidity.

繊維シートを構成する繊維は、後記の賦形層用コンパウンドに含まれる繊維よりも繊維長が長いものが好ましく、例えば連続繊維あるいは不連続繊維からなるものが挙げられる。 The fibers constituting the fiber sheet preferably have a longer fiber length than the fibers contained in the compound for the shaping layer described later, and examples thereof include continuous fibers and discontinuous fibers.

繊維シートに含浸する熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂、ビニルエステル樹脂、不飽和ポリエステル樹脂、またはこれらの混合樹脂等が挙げられる。繊維シートに熱硬化性樹脂が含浸した剛性層用繊維強化樹脂材としては、プリプレグが好ましい。 Examples of the thermosetting resin impregnated in the fiber sheet include an epoxy resin, a phenol resin, a vinyl ester resin, an unsaturated polyester resin, and a mixed resin thereof. A prepreg is preferable as the fiber reinforced resin material for a rigid layer in which a fiber sheet is impregnated with a thermosetting resin.

賦形層21は、剛性層用繊維強化樹脂材に含まれる繊維よりも短い繊維と熱硬化性樹脂とよりなる賦形層用コンパウンドが加熱圧縮されて硬化したものからなる。賦形層21の表面形状は、繊維強化樹脂複合成形体10の用途等に応じて適宜の凹形状、凸形状、凹凸形状を有するものであってもよい。 The shaping layer 21 is made of a compound for a shaping layer made of a fiber shorter than the fiber contained in the fiber-reinforced resin material for a rigid layer and a thermosetting resin, which is heat-compressed and cured. The surface shape of the shaping layer 21 may have an appropriate concave shape, convex shape, or uneven shape depending on the application of the fiber reinforced resin composite molded body 10.

賦形層用コンパウンドに含まれる繊維の長さは、成形性の点から30mm以下が好ましく、また、剛性向上の点からは5mm以上が好ましい。賦形層用コンパウンドに含まれる繊維としては、炭素繊維、ガラス繊維等の短繊維が挙げられる。特に軽量化と剛性向上の点から炭素繊維が好ましい。 The length of the fiber contained in the compound for the shaping layer is preferably 30 mm or less from the viewpoint of moldability, and is preferably 5 mm or more from the viewpoint of improving rigidity. Examples of the fiber contained in the compound for the shaping layer include short fibers such as carbon fiber and glass fiber. In particular, carbon fiber is preferable from the viewpoint of weight reduction and rigidity improvement.

賦形層用コンパウンドに含まれる熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂、ビニルエステル樹脂、不飽和ポリエステル樹脂、またはこれらの混合樹脂等が挙げられる。
賦形層用コンパウンドとしては、シートモールディングコンパウンド(以下SMCと記す)が好ましい。SMCは、熱硬化性樹脂に充填材や硬化剤などを含んだコンパウンドを、ガラス繊維や炭素繊維などの繊維材に含浸させたシート状の成形材料をいう。
Examples of the thermosetting resin contained in the compound for the shaping layer include an epoxy resin, a phenol resin, a vinyl ester resin, an unsaturated polyester resin, and a mixed resin thereof.
As the compound for the shaping layer, a sheet molding compound (hereinafter referred to as SMC) is preferable. SMC refers to a sheet-shaped molding material obtained by impregnating a fiber material such as glass fiber or carbon fiber with a compound containing a filler or a curing agent in a thermosetting resin.

樹脂31は、液状樹脂が硬化したものからなる。液状樹脂は、熱硬化性樹脂からなる。液状樹脂は、繊維強化樹脂複合成形体10を製造する際、賦形層用コンパウンドと共に加熱圧縮されることにより、賦形層用コンパウンドに含まれる熱硬化性樹脂の硬化剤と混ざり合うため、硬化剤を含まなくても硬化することができる。 The resin 31 is made of a cured liquid resin. The liquid resin is made of a thermosetting resin. When the fiber-reinforced resin composite molded body 10 is manufactured, the liquid resin is heated and compressed together with the shaping layer compound, and is mixed with the thermosetting resin curing agent contained in the shaping layer compound, so that the liquid resin is cured. It can be cured without containing an agent.

液状樹脂を構成する熱硬化性樹脂としては、ビニルエステル樹脂、不飽和ポリエステル樹脂、エポキシ樹脂等のラジカル重合型の熱硬化性樹脂が好ましい。熱硬化性樹脂には、必要に応じて、硬化剤、分散剤、難燃剤、UV吸収剤等を添加してもよい。また、液状樹脂には、熱硬化性樹脂と共に溶媒が配合され、塗布可能な粘度に調製してもよい。 As the thermosetting resin constituting the liquid resin, a radical polymerization type thermosetting resin such as a vinyl ester resin, an unsaturated polyester resin, or an epoxy resin is preferable. If necessary, a curing agent, a dispersant, a flame retardant, a UV absorber, or the like may be added to the thermosetting resin. Further, the liquid resin may be mixed with a solvent together with the thermosetting resin to adjust the viscosity so that it can be applied.

剛性層11と賦形層21と樹脂31は、繊維強化樹脂複合成形体10を製造する際の加熱圧縮によって、剛性層用繊維強化樹脂材と賦形層用コンパウンド、及びその表面の液状樹脂が、積層状態で硬化することにより一体化して形成されている。 The rigid layer 11, the shaping layer 21, and the resin 31 are formed by heating and compressing the fiber-reinforced resin composite molded body 10, so that the fiber-reinforced resin material for the rigid layer, the compound for the shaping layer, and the liquid resin on the surface thereof are formed. , It is integrally formed by curing in a laminated state.

繊維強化樹脂複合成形体10の製造方法について説明する。繊維強化樹脂複合成形体10の製造方法は、塗布工程と、加熱圧縮工程とからなる。 A method for producing the fiber-reinforced resin composite molded body 10 will be described. The method for producing the fiber-reinforced resin composite molded body 10 includes a coating step and a heat compression step.

塗布工程では、賦形層用コンパウンドの一側表面、あるいは金型の型面に、未硬化の液状樹脂を塗布する。図2に示す金型60は、上型61と下型63とからなる。金型の型面に、未硬化の液状樹脂を塗布する場合は、次の加熱圧縮工程で賦形層用コンパウンドを押圧することになる型面、例えば上型61の型面に対して液状樹脂を塗布する。なお、賦形層用コンパウンドの一側表面への液状樹脂の塗布は、金型60の下型63に、剛性層用繊維強化樹脂材と賦形層用コンパウンドを積層配置し、その賦形層用コンパウンドの表面に液状樹脂を塗布してもよい。塗布方法は、刷毛塗り、ローラ塗り、スプレー塗り等を挙げることができ、何れの方法でもよい。また、液状樹脂を塗布する範囲は、賦形層用コンパウンドの表面全体に限られず、その一部であってもよい。 In the coating step, the uncured liquid resin is coated on one side surface of the compound for the shaping layer or the mold surface of the mold. The mold 60 shown in FIG. 2 includes an upper mold 61 and a lower mold 63. When uncured liquid resin is applied to the mold surface of the mold, the liquid resin is applied to the mold surface on which the compound for the shaping layer is pressed in the next heating and compression step, for example, the mold surface of the upper mold 61. Is applied. To apply the liquid resin to one side surface of the shaping layer compound, a fiber reinforced resin material for a rigid layer and a shaping layer compound are laminated and arranged on the lower mold 63 of the mold 60, and the shaping layer thereof. A liquid resin may be applied to the surface of the compound. Examples of the coating method include brush coating, roller coating, spray coating and the like, and any method may be used. Further, the range of applying the liquid resin is not limited to the entire surface of the compound for the shaping layer, and may be a part thereof.

賦形層用コンパウンドは、繊維強化樹脂複合成形体10において説明したとおりである。ここで使用する賦形層用コンパウンドの大きさは、製品(繊維強化樹脂複合成形体10)に対して平面寸法が30〜100%の大きさが好ましい。
また、液状樹脂は、繊維強化樹脂複合成形体10において説明したとおりである。液状樹脂の塗布量は、賦形層用コンパウンドの表面に対して20〜200g/mとなるようにするのが好ましい。
The compound for the shaping layer is as described in the fiber reinforced resin composite molded body 10. The size of the compound for the shaping layer used here is preferably a size having a plane dimension of 30 to 100% with respect to the product (fiber reinforced resin composite molded body 10).
The liquid resin is as described in the fiber reinforced resin composite molded body 10. The amount of the liquid resin applied is preferably 20 to 200 g / m 2 with respect to the surface of the compound for the shaping layer.

加熱圧縮工程では、金型60の上型61の型面と下型63の型面間に、剛性層用繊維強化樹脂材と、賦形層用コンパウンドと、液状樹脂を積層状態で配置し、その状態で上型63の型面と下型61の型面で加熱・圧縮する。下型63には、繊維強化樹脂複合成形体10の賦形用キャビティが形成されている。賦形用キャビティの平面サイズは、繊維強化樹脂複合成形体10の平面サイズと等しくされている。 In the heat compression step, a fiber-reinforced resin material for a rigid layer, a compound for a shaping layer, and a liquid resin are arranged in a laminated state between the mold surface of the upper mold 61 of the mold 60 and the mold surface of the lower mold 63. In that state, the mold surface of the upper mold 63 and the mold surface of the lower mold 61 are heated and compressed. The lower mold 63 is formed with a shaping cavity for the fiber-reinforced resin composite molded body 10. The plane size of the shaping cavity is equal to the plane size of the fiber reinforced resin composite molded body 10.

加熱・圧縮により、剛性層用繊維強化樹脂材が圧縮されると共に賦形層用コンパウンドが圧縮されて金型60内で流動し、剛性層用繊維強化樹脂材と賦形層用コンパウンドがキャビティ形状に賦形されて硬化する。その際、賦形層用コンパウンドと型面間に液状樹脂が存在するため、液状樹脂が賦形層用コンパウンド表面で潤滑剤の作用をし、金型60内で賦形層用コンパウンドの流動性が向上し、賦形層用コンパウンドは薄く賦形される。また、賦形層用コンパウンドと型面間で液状樹脂が断熱層の作用をして、型面からの伝熱による賦形層用コンパウンドの硬化反応を遅らせ、硬化完了するまでの間における賦形層用コンパウンドの流動量を大にするため、これによっても賦形層用コンパウンドは薄く賦形される。 By heating and compressing, the fiber-reinforced resin material for the rigid layer is compressed and the compound for the shaping layer is compressed and flows in the mold 60, and the fiber-reinforced resin material for the rigid layer and the compound for the shaping layer have a cavity shape. It is shaped into and hardens. At that time, since the liquid resin exists between the compound for the shaping layer and the mold surface, the liquid resin acts as a lubricant on the surface of the compound for the shaping layer, and the fluidity of the compound for the shaping layer in the mold 60. Is improved, and the compound for the shaping layer is thinly shaped. In addition, the liquid resin acts as a heat insulating layer between the compound for the shaping layer and the mold surface, delaying the curing reaction of the compound for the shaping layer by heat transfer from the mold surface, and shaping until the curing is completed. This also thinly shapes the shaping layer compound in order to increase the flow of the layering compound.

また、加熱・圧縮時、賦形層用コンパウンドの表面の液状樹脂は、型面で押圧されて、賦形層用コンパウンドの表面及びその付近の熱硬化性樹脂と混ざり合って硬化する。その際、液状樹脂は、硬化剤が含まれていなくても、賦形層用コンパウンドに含まれている硬化剤と混ざり合うことで硬化することができる。 Further, during heating and compression, the liquid resin on the surface of the shaping layer compound is pressed by the mold surface and mixed with the thermosetting resin on the surface of the shaping layer compound and its vicinity to be cured. At that time, the liquid resin can be cured by mixing with the curing agent contained in the compound for the shaping layer even if the curing agent is not contained.

加熱圧縮工程時の加熱は、金型に設けた電熱ヒータ等の加熱手段により、あるいは予め金型を加熱炉等に収容して加熱しておく方法などにより行う。加熱温度は、剛性層用繊維強化樹脂材及び賦形層用コンパウンドに含まれる熱硬化性樹脂及び液状樹脂が硬化する温度とされる。 The heating in the heating and compression step is performed by a heating means such as an electric heater provided in the mold, or by a method in which the mold is previously housed in a heating furnace or the like and heated. The heating temperature is a temperature at which the thermosetting resin and the liquid resin contained in the fiber-reinforced resin material for the rigid layer and the compound for the shaping layer are cured.

加熱圧縮工程により、剛性層用繊維強化樹脂材が圧縮されて硬化した剛性層と、賦形層用コンパウンドが圧縮されて薄く賦形された状態で硬化した賦形層と、その表面で液状樹脂が硬化してなる樹脂とが一体化し、図1に示した剛性層11と賦形層21とその表面の樹脂31とからなる厚みの薄い繊維強化樹脂複合成形体10が得られる。 A rigid layer in which the fiber-reinforced resin material for the rigid layer is compressed and cured by the heat compression step, a shaping layer in which the compound for the shaping layer is compressed and cured in a thinly shaped state, and a liquid resin on the surface thereof. The resin obtained by curing the resin is integrated to obtain a thin fiber reinforced resin composite molded body 10 composed of the rigid layer 11 shown in FIG. 1, the shaping layer 21, and the resin 31 on the surface thereof.

フェノール樹脂溶液(住友ベークライト株式会社製、品名:PR−55791B、樹脂濃度60wt%エタノール溶液)中に、炭素繊維織物(帝人株式会社製、品名:W−3161L、厚み0.22mm)を400×400mmに裁断したものを漬け、取り出した後に、25℃の室温で2時間自然乾燥し、その後、60℃の雰囲気下で1時間乾燥させて剛性層用繊維強化樹脂材(プリプレグ)を形成した。 400 x 400 mm of carbon fiber woven fabric (manufactured by Teijin Co., Ltd., product name: W-3161L, thickness 0.22 mm) in a phenol resin solution (manufactured by Sumitomo Bakelite Co., Ltd., product name: PR-55791B, resin concentration 60 wt% ethanol solution) After being soaked and taken out, it was naturally dried at room temperature of 25 ° C. for 2 hours, and then dried in an atmosphere of 60 ° C. for 1 hour to form a fiber-reinforced resin material (prepreg) for a rigid layer.

金型の下型の成形面に、剛性層用繊維強化樹脂材(プリプレグ)の1枚を配置し、その上に300×300mmのサイズに切り出した賦形層用コンパウンド(SMC、三菱ケミカル株式会社製、品名:STR120N131、厚み2mm、繊維含有率53%)を積層し、その賦形層用コンパウンドの表面に、図3の各実施例に示す液状の未硬化の塗布樹脂(熱硬化性樹脂)を刷毛で塗布し、その後に金型を閉じて150℃×20分間、圧力200kgf/cmで加熱圧縮し、剛性層用繊維強化樹脂材(プリプレグ)と賦形層用コンパウンド及び塗布樹脂を積層圧縮状態で硬化させた。それにより、剛性層用繊維強化樹脂材(プリプレグ)から形成された剛性層と、賦形層用コンパウンドから形成された賦形層と、塗布樹脂から形成された樹脂との積層一体品からなる繊維強化樹脂複合成形体を製造した。金型は下型と上型とよりなり、横460×縦460mmの成形面が形成されている。 A compound for shaping layer (SMC, Mitsubishi Chemical Co., Ltd.) in which one piece of fiber reinforced resin material (prepreg) for rigid layer is placed on the molding surface of the lower mold of the mold and cut out to a size of 300 x 300 mm on it. Manufactured by, product name: STR120N131, thickness 2 mm, fiber content 53%), and the liquid uncured coating resin (thermosetting resin) shown in each example of FIG. 3 is laminated on the surface of the compound for the shaping layer. Is applied with a brush, and then the mold is closed and heated and compressed at a pressure of 200 kgf / cm 2 for 150 ° C. × 20 minutes, and a fiber reinforced resin material (prepreg) for a rigid layer, a compound for a shaping layer, and a coating resin are laminated. It was cured in a compressed state. As a result, a fiber made of a laminated integral product of a rigid layer formed of a fiber reinforced resin material (prepreg) for a rigid layer, a shaping layer formed of a compound for a shaping layer, and a resin formed of a coating resin. A reinforced resin composite molded body was manufactured. The mold is composed of a lower mold and an upper mold, and a molding surface having a width of 460 mm and a length of 460 mm is formed.

また、賦形層用コンパウンドの表面に熱硬化性樹脂を塗布しないで加熱圧縮成形することにより、比較例1〜3の繊維強化樹脂複合成形体を製造した。
各実施例及び各比較例の繊維強化樹脂複合成形体について、成形後の厚みを測定した。その結果を図3に示す。なお、図3のチャージ率[%]は、賦形層用コンパウンドの元厚(2mm)に対する賦形層の厚みの割合である。チャージ率の計算において、賦形層の厚みは、加熱圧縮によって剛性層用繊維強化樹脂材(プリプレグ)の厚み(0.22mm)が変化しないとして、成形後の厚み(繊維強化樹脂複合成形体の厚み)から剛性層用繊維強化樹脂材(プリプレグ)の厚み(0.22mm)を引いて得た値を用いた。
Further, the fiber-reinforced resin composite molded bodies of Comparative Examples 1 to 3 were produced by heat-compression molding without applying a thermosetting resin to the surface of the compound for the shaping layer.
The thickness of the fiber-reinforced resin composite molded product of each Example and each Comparative Example was measured after molding. The result is shown in FIG. The charge rate [%] in FIG. 3 is the ratio of the thickness of the shaping layer to the original thickness (2 mm) of the compound for the shaping layer. In the calculation of the charge rate, the thickness of the shaping layer is the thickness after molding (fiber-reinforced resin composite molded body), assuming that the thickness (0.22 mm) of the fiber-reinforced resin material (prepreg) for the rigid layer does not change due to heating and compression. The value obtained by subtracting the thickness (0.22 mm) of the fiber reinforced resin material (prepreg) for the rigid layer from the thickness) was used.

実施例1は、賦形層用コンパウンドの表面に、塗布樹脂(熱硬化性樹脂)として、ビニルエステル樹脂(昭和電工株式会社社製、品名:リポキシR−806)を、50g/m塗布した例である。実施例1は、成形後の繊維強化樹脂複合成形体の厚みが0.95mm、チャージ率37%であった。なお、賦形層用コンパウンド(厚み2mm)から形成された賦形層の厚みは、繊維強化樹脂複合成形体の厚み(0.95mm)−剛性層用繊維強化樹脂材の厚み(0.22mm)=0.73mmであり、賦形層が薄肉に形成されている。 In Example 1, 50 g / m 2 of vinyl ester resin (manufactured by Showa Denko KK, product name: Lipoxy R-806) was applied as a coating resin (thermosetting resin) to the surface of the compound for the shaping layer. This is an example. In Example 1, the thickness of the fiber-reinforced resin composite molded product after molding was 0.95 mm, and the charge rate was 37%. The thickness of the shaping layer formed from the compound for the shaping layer (thickness 2 mm) is the thickness of the fiber reinforced resin composite molded body (0.95 mm) -the thickness of the fiber reinforced resin material for the rigid layer (0.22 mm). = 0.73 mm, and the shaping layer is formed thinly.

実施例2は、賦形層用コンパウンドの表面に、塗布樹脂(熱硬化性樹脂)として実施例1と同じビニルエステル樹脂(昭和電工株式会社社製、品名:リポキシR−806)を、75g/m塗布した例である。実施例2は、成形後の繊維強化樹脂複合成形体の厚みが0.93mm、チャージ率36%であった。賦形層用コンパウンド(厚み2mm)から形成された賦形層の厚みは、繊維強化樹脂複合成形体の厚み(0.93mm)−剛性層用繊維強化樹脂材の厚み(0.22mm)=0.71mmであり、塗布樹脂の塗布量を実施例1よりも増加させたことにより、賦形層が実施例1よりも薄肉に形成された。 In Example 2, 75 g / g of the same vinyl ester resin (manufactured by Showa Denko KK, product name: Lipoxy R-806) as the coating resin (thermosetting resin) on the surface of the compound for the shaping layer. m 2 is coated with an example. In Example 2, the thickness of the fiber-reinforced resin composite molded product after molding was 0.93 mm, and the charge rate was 36%. The thickness of the shaping layer formed from the compound for the shaping layer (thickness 2 mm) is the thickness of the fiber reinforced resin composite molded body (0.93 mm) -the thickness of the fiber reinforced resin material for the rigid layer (0.22 mm) = 0. It was .71 mm, and the shaping layer was formed thinner than in Example 1 by increasing the coating amount of the coating resin as compared with Example 1.

実施例3は、賦形層用コンパウンドの表面に、塗布樹脂(熱硬化性樹脂)として実施例1及び実施例2と同じビニルエステル樹脂(昭和電工株式会社社製、品名:リポキシR−806)を、100g/m塗布した例である。実施例3は、成形後の繊維強化樹脂複合成形体の厚みが0.91mm、チャージ率35%であった。賦形層用コンパウンド(厚み2mm)から形成された賦形層の厚みは、繊維強化樹脂複合成形体の厚み(0.91mm)−剛性層用繊維強化樹脂材の厚み(0.22mm)=0.69mmであり、塗布樹脂の塗布量を実施例1及び実施例2よりも増加させたことにより、賦形層が実施例1及び実施例2よりもさらに薄肉に形成された。 In Example 3, the same vinyl ester resin as in Examples 1 and 2 as a coating resin (thermosetting resin) on the surface of the compound for the shaping layer (manufactured by Showa Denko KK, product name: Lipoxy R-806). Is an example in which 100 g / m 2 is applied. In Example 3, the thickness of the fiber-reinforced resin composite molded product after molding was 0.91 mm, and the charge rate was 35%. The thickness of the shaping layer formed from the compound for the shaping layer (thickness 2 mm) is the thickness of the fiber reinforced resin composite molded body (0.91 mm) -the thickness of the fiber reinforced resin material for the rigid layer (0.22 mm) = 0. It was .69 mm, and by increasing the coating amount of the coating resin as compared with Examples 1 and 2, the shaping layer was formed to be thinner than those of Examples 1 and 2.

実施例4は、賦形層用コンパウンドの表面に、塗布樹脂(熱硬化性樹脂)として不飽和ポリエステル樹脂(昭和電工株式会社社製、品名:RIGOLAC T−543TPA)を、50g/m塗布した例である。実施例4は、成形後の繊維強化樹脂複合成形体の厚みが1.00mm、チャージ率39%であった。賦形層用コンパウンド(厚み2mm)から形成された賦形層の厚みは、繊維強化樹脂複合成形体の厚み(1.00mm)−剛性層用繊維強化樹脂材の厚み(0.22mm)=0.78mmであり、薄肉に形成された。 In Example 4, 50 g / m 2 of unsaturated polyester resin (manufactured by Showa Denko KK, product name: RIGOLAC T-543TPA) was applied as a coating resin (thermosetting resin) to the surface of the compound for the shaping layer. This is an example. In Example 4, the thickness of the fiber-reinforced resin composite molded product after molding was 1.00 mm, and the charge rate was 39%. The thickness of the shaping layer formed from the compound for the shaping layer (thickness 2 mm) is the thickness of the fiber reinforced resin composite molded body (1.00 mm) -the thickness of the fiber reinforced resin material for the rigid layer (0.22 mm) = 0. It was .78 mm and was formed thin.

このように、実施例1〜4は、剛性層用繊維強化樹脂材(プリプレグ)に積層した賦形層用コンパウンドの表面に液状の熱硬化性樹脂を塗布して加熱圧縮成形したことにより、賦形層用コンパウンドから形成される賦形層の厚みを、0.69〜0.78mmと薄肉に賦形でき、厚み1mm以下の薄い繊維強化樹脂複合成形体を得ることができた。 As described above, in Examples 1 to 4, a liquid thermosetting resin was applied to the surface of the shaping layer compound laminated on the fiber reinforced resin material (prepreg) for the rigid layer, and heat compression molding was performed. The thickness of the shaping layer formed from the compound for the shaping layer could be shaped as thin as 0.69 to 0.78 mm, and a thin fiber-reinforced resin composite molded body having a thickness of 1 mm or less could be obtained.

比較例1は、賦形層用コンパウンドの表面に、液状の熱硬化性樹脂を塗布しなかった例であり、加熱圧縮条件は実施例1〜4と同様である。比較例1は、成形後の繊維強化樹脂複合成形体の厚みが1.12mm、チャージ率45%であった。賦形層用コンパウンド(厚み2mm)から形成された賦形層の厚みは、繊維強化樹脂複合成形体の厚み(1.12mm)−剛性層用繊維強化樹脂材の厚み(0.22mm)=0.90mmであり、賦形層用コンパウンドの表面に液状の熱硬化性樹脂を塗布しなかったことにより、賦形層が実施例1〜4よりも厚肉に形成された。 Comparative Example 1 is an example in which the liquid thermosetting resin was not applied to the surface of the compound for the shaping layer, and the heating and compression conditions were the same as in Examples 1 to 4. In Comparative Example 1, the thickness of the fiber-reinforced resin composite molded product after molding was 1.12 mm, and the charge rate was 45%. The thickness of the shaping layer formed from the compound for the shaping layer (thickness 2 mm) is the thickness of the fiber reinforced resin composite molded body (1.12 mm) -the thickness of the fiber reinforced resin material for the rigid layer (0.22 mm) = 0. The size was 90 mm, and the shaping layer was formed thicker than in Examples 1 to 4 because the liquid thermosetting resin was not applied to the surface of the shaping layer compound.

比較例2は、比較例1における賦形層用コンパウンド面積を10%増加し、液状の熱硬化性樹脂を塗布しなかった例である。比較例2は、成形後の繊維強化樹脂複合成形体の厚みが1.30mm、チャージ率54%であった。賦形層用コンパウンド(厚み2mm)から形成された賦形層の厚みは、繊維強化樹脂複合成形体の厚み(1.30mm)−剛性層用繊維強化樹脂材の厚み(0.22mm)=1.08mmであり、賦形層用コンパウンドの量を増加したことにより、賦形層が比較例1よりも厚肉に形成された。 Comparative Example 2 is an example in which the compound area for the shaping layer in Comparative Example 1 was increased by 10% and the liquid thermosetting resin was not applied. In Comparative Example 2, the thickness of the fiber-reinforced resin composite molded product after molding was 1.30 mm, and the charge rate was 54%. The thickness of the shaping layer formed from the compound for the shaping layer (thickness 2 mm) is the thickness of the fiber reinforced resin composite molded body (1.30 mm) -the thickness of the fiber reinforced resin material for the rigid layer (0.22 mm) = 1. It was .08 mm, and by increasing the amount of the compound for the shaping layer, the shaping layer was formed thicker than that of Comparative Example 1.

比較例3は、比較例1における賦形層用コンパウンド面積を20%増加し、液状の熱硬化性樹脂を塗布しなかった例である。比較例3は、成形後の繊維強化樹脂複合成形体の厚みが1.60mm、チャージ率69%であった。賦形層用コンパウンド(厚み2mm)から形成された賦形層の厚みは、繊維強化樹脂複合成形体の厚み(1.60mm)−剛性層用繊維強化樹脂材の厚み(0.22mm)=1.38mmであり、賦形層用コンパウンドの量を増加したことにより、賦形層が比較例1及び比較例2よりも厚肉に形成された。 Comparative Example 3 is an example in which the compound area for the shaping layer in Comparative Example 1 was increased by 20% and the liquid thermosetting resin was not applied. In Comparative Example 3, the thickness of the fiber-reinforced resin composite molded product after molding was 1.60 mm, and the charge rate was 69%. The thickness of the shaping layer formed from the compound for the shaping layer (thickness 2 mm) is the thickness of the fiber reinforced resin composite molded body (1.60 mm) -the thickness of the fiber reinforced resin material for the rigid layer (0.22 mm) = 1. It was .38 mm, and by increasing the amount of the compound for the shaping layer, the shaping layer was formed thicker than in Comparative Example 1 and Comparative Example 2.

このように、本発明によれば、剛性層による剛性と、賦形層による薄肉で複雑形状に賦形可能との両者を有する線維強化樹脂複合成形体を得ることができる。 As described above, according to the present invention, it is possible to obtain a fiber-reinforced resin composite molded product having both the rigidity of the rigid layer and the thin-walled and complex-shaped shape formed by the shaping layer.

10 繊維強化樹脂複合成形体
11 剛性層
21 賦形層
31 樹脂
60 金型
61 上型
63 下型
10 Fiber reinforced resin composite molded body 11 Rigid layer 21 Shaped layer 31 Resin 60 Mold 61 Upper mold 63 Lower mold

Claims (4)

剛性層用繊維強化樹脂材から形成された剛性層と、
前記剛性層用繊維強化樹脂材に含まれる繊維よりも短い繊維と熱硬化性樹脂とよりなる賦形層用コンパウンドから、前記剛性層の少なくとも一面に形成された賦形層と、
前記賦形層の表面に付着した液状樹脂が硬化した樹脂と、
よりなり、
前記剛性層用繊維強化樹脂材と前記賦形層用コンパウンドが、積層状態で前記液状樹脂と共に加熱圧縮硬化したものであることを特徴とする繊維強化樹脂複合成形体。
Rigid layer formed from fiber reinforced resin material for rigid layer and
A shaping layer formed on at least one surface of the rigid layer from a compound for a shaping layer composed of fibers shorter than the fibers contained in the fiber-reinforced resin material for the rigid layer and a thermosetting resin.
A resin obtained by curing the liquid resin adhering to the surface of the shaping layer and
Consists of
A fiber-reinforced resin composite molded body characterized in that the fiber-reinforced resin material for a rigid layer and the compound for a shaping layer are heat-compressed and cured together with the liquid resin in a laminated state.
前記剛性層用繊維強化樹脂材はプリプレグであり、
前記賦形層用コンパウンドはシートモールディングコンパウンドであり、
前記液状樹脂は熱硬化性樹脂であることを特徴する請求項1に記載の繊維強化樹脂複合成形体。
The fiber-reinforced resin material for the rigid layer is a prepreg.
The compound for the shaping layer is a sheet molding compound.
The fiber-reinforced resin composite molded product according to claim 1, wherein the liquid resin is a thermosetting resin.
剛性層用繊維強化樹脂材から形成された剛性層と、前記剛性層用繊維強化樹脂材に含まれる繊維よりも短い繊維と熱硬化性樹脂とよりなる賦形層用コンパウンドから、前記剛性層の少なくとも一面に形成された賦形層と、前記賦形層の表面に付着した液状樹脂が硬化した樹脂とよりなる繊維強化樹脂複合成形体の製造方法であって、
前記賦形層用コンパウンドの表面に液状樹脂を塗布し、または該賦形層用コンパウンドの表面を押圧することになる金型の型面に液状樹脂を塗布し、
前記剛性層用繊維強化樹脂材と前記賦形層用コンパウンドを、積層状態で前記液状樹脂と共に前記金型で加熱圧縮し、硬化させることを特徴とする繊維強化樹脂複合成形体の製造方法。
From the rigid layer formed from the fiber reinforced resin material for the rigid layer, and the compound for the shaping layer composed of the fibers shorter than the fibers contained in the fiber reinforced resin material for the rigid layer and the thermosetting resin, the rigid layer A method for producing a fiber-reinforced resin composite molded body, which comprises a shaping layer formed on at least one surface and a resin obtained by curing a liquid resin adhering to the surface of the shaping layer.
A liquid resin is applied to the surface of the compound for the shaping layer, or the liquid resin is applied to the mold surface of the mold that presses the surface of the compound for the shaping layer.
A method for producing a fiber-reinforced resin composite molded product, which comprises heating and compressing the fiber-reinforced resin material for a rigid layer and the compound for a shaping layer together with the liquid resin in the mold in a laminated state and curing the compound.
前記剛性層用繊維強化樹脂材はプリプレグであり、
前記賦形層用コンパウンドはシートモールディングコンパウンドであり、
前記液状樹脂は熱硬化性樹脂であることを特徴する請求項3に記載の繊維強化樹脂複合成形体の製造方法。
The fiber-reinforced resin material for the rigid layer is a prepreg.
The compound for the shaping layer is a sheet molding compound.
The method for producing a fiber-reinforced resin composite molded product according to claim 3, wherein the liquid resin is a thermosetting resin.
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