JP2018103490A - Thermosetting sheet-like molding material and method for producing fiber-reinforced plastic - Google Patents
Thermosetting sheet-like molding material and method for producing fiber-reinforced plastic Download PDFInfo
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- JP2018103490A JP2018103490A JP2016253061A JP2016253061A JP2018103490A JP 2018103490 A JP2018103490 A JP 2018103490A JP 2016253061 A JP2016253061 A JP 2016253061A JP 2016253061 A JP2016253061 A JP 2016253061A JP 2018103490 A JP2018103490 A JP 2018103490A
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- Prior art keywords
- sheet
- thermosetting
- layer
- molding material
- carbon fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 146
- 239000012778 molding material Substances 0.000 title claims abstract description 71
- 229920002430 Fibre-reinforced plastic Polymers 0.000 title claims abstract description 33
- 239000011151 fibre-reinforced plastic Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 70
- 239000004917 carbon fiber Substances 0.000 claims abstract description 70
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- 239000011342 resin composition Substances 0.000 claims abstract description 57
- 239000000835 fiber Substances 0.000 claims abstract description 48
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- 239000011347 resin Substances 0.000 claims description 37
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Abstract
Description
本発明は、熱硬化性シート状成形材料及び繊維強化プラスチックの製造方法に関する。詳しくは、本発明は、成形時に良好な流動性及び複雑形状への追従性を確保し、作業性に優れると共に、優れた強度特性を発現する繊維強化プラスチックを製造することのできる熱硬化性シート状成形材料並びにそれを用いた繊維強化プラスチックの製造方法に関する。 The present invention relates to a thermosetting sheet-shaped molding material and a method for producing a fiber-reinforced plastic. Specifically, the present invention is a thermosetting sheet capable of producing a fiber-reinforced plastic that ensures excellent fluidity and followability to complex shapes during molding, has excellent workability, and exhibits excellent strength characteristics. The present invention relates to a molding material and a method for producing a fiber reinforced plastic using the same.
補強材として炭素繊維を用いた炭素繊維強化プラスチック（以下、ＣＦＲＰと略すことがある）は、低比重、高強度、高弾性率などの優れた特性があることから、航空機、自動車、スポーツ用品など多くの産業用途において注目され、その需要は年々高まりつつある。 Carbon fiber reinforced plastic using carbon fiber as a reinforcing material (hereinafter abbreviated as CFRP) has excellent properties such as low specific gravity, high strength, and high modulus of elasticity. It attracts attention in many industrial applications, and its demand is increasing year by year.
ＣＦＲＰの製造方法としては、連続炭素繊維束にマトリックス樹脂を含浸せしめた半硬化状態の中間基材（プリプレグ）を用いたオートクレーブ成形法や、予め型内で成形部材の形状に賦形した未含浸の連続炭素繊維束基材にマトリックス樹脂を注入して含浸させた後、硬化させるＲＴＭ（レジントランスファーモールディング）成形法が一般的である。これらの成形法により得られた炭素繊維強化プラスチックは、繊維束が連続した炭素繊維であるために優れた強度特性を有すると共に、そのバラつきが少ないという利点がある。 The CFRP can be produced by an autoclave molding method using a semi-cured intermediate base material (prepreg) in which a continuous carbon fiber bundle is impregnated with a matrix resin, or a non-impregnated shape preliminarily shaped into a molded member in a mold. An RTM (resin transfer molding) molding method is generally used in which a matrix resin is injected and impregnated into a continuous carbon fiber bundle base material, followed by curing. The carbon fiber reinforced plastics obtained by these molding methods have the advantage that they have excellent strength characteristics because the fiber bundles are continuous carbon fibers and have little variation.
しかしながら、これらのプリプレグを用いたオートクレーブ成形法やＲＴＭ成形法のように連続炭素繊維を用いた場合、全ての繊維束が連続した炭素繊維であるが故に基材の流動性が乏しく、三次元形状などの複雑形状を有する繊維強化プラスチックを成形することは難しい。そのため、これらの成形法は、製品形状が平面に近い部材に限定される。 However, when continuous carbon fibers are used as in the autoclave molding method and RTM molding method using these prepregs, the fluidity of the substrate is poor because all fiber bundles are continuous carbon fibers, and the three-dimensional shape It is difficult to mold a fiber reinforced plastic having a complicated shape such as. Therefore, these molding methods are limited to members whose product shape is close to a flat surface.
三次元形状などの複雑形状を有する部材に適した成形方法として、熱硬化性シート状成形材料を用いるシートモールディングコンパウンド（以下、ＳＭＣと略することがある）成形法がある。ＳＭＣ成形法は、通常、１２〜２５ｍｍ程度の長さに機械的に切断された短繊維束に熱硬化性樹脂を含浸させ半硬化状態とした熱硬化性シート状成形材料を金型内に配置し、加熱・圧縮成形することにより所定の製品形状に成形を行うものである。ＳＭＣは、短繊維束を使用しているため、金型内での流動性に優れ、三次元形状などの複雑形状にも追従が可能である。 As a molding method suitable for a member having a complicated shape such as a three-dimensional shape, there is a sheet molding compound (hereinafter sometimes abbreviated as SMC) molding method using a thermosetting sheet-shaped molding material. In the SMC molding method, a thermosetting sheet-shaped molding material, which is usually semi-cured by impregnating a thermosetting resin into a short fiber bundle mechanically cut to a length of about 12 to 25 mm, is placed in a mold. Then, it is molded into a predetermined product shape by heating and compression molding. Since SMC uses short fiber bundles, it has excellent fluidity in the mold and can follow complicated shapes such as a three-dimensional shape.
しかしながら、ＳＭＣは、そのシート化工程において切断された繊維束を分散する際に、その繊維束の分布量ムラや配向ムラが生じてしまうため、連続繊維を用いた繊維強化プラスチックと比べて、得られる繊維強化プラスチックの強度特性が低下すると共にそのバラつきが大きくなる欠点があった。 However, SMC produces unevenness in distribution amount and orientation unevenness of the fiber bundle when dispersing the fiber bundle cut in the sheet forming step, so that it can be obtained compared to fiber reinforced plastic using continuous fibers. There is a drawback that the strength characteristics of the fiber reinforced plastic to be produced are lowered and the variation is increased.
複雑形状への追従性を有し、かつ優れた力学特性を発現する繊維強化プラスチックを得る方法として、連続した炭素繊維の繊維方向を横切る方向に断続的に有限長の切り込みを入れたプリプレグ基材を複数層積層してなるプリプレグ基材積層体と、その最表層の少なくとも片側に配設された切り込みを入れていないプリプレグ基材とで構成されたシート状プリプレグを用いることが開示されている（例えば、特許文献１を参照）。また、高強度でかつ意匠性に優れた繊維強化プラスチックを圧縮成形法を用いて短時間に製造するために、実質的に連続した強化繊維に熱硬化性樹脂を含浸させたものと、その少なくとも片側表面にあり、短繊維状の強化繊維に熱硬化性樹脂を含浸させたもの（ＳＭＣ）とを重ね合せた成形材料を用いることが開示されている（例えば、特許文献２を参照）。 A prepreg base material with a finite length cut intermittently in the direction crossing the fiber direction of continuous carbon fibers as a method to obtain fiber reinforced plastics that can follow complex shapes and exhibit excellent mechanical properties It is disclosed that a sheet-like prepreg composed of a prepreg base material laminate formed by laminating a plurality of layers and a prepreg base material provided with at least one side of the outermost layer and having no cuts is used ( For example, see Patent Document 1). Also, in order to produce a high-strength and high-strength fiber-reinforced plastic using a compression molding method in a short time, a substantially continuous reinforcing fiber impregnated with a thermosetting resin, and at least It is disclosed that a molding material is used which is superposed on a surface of one side and a short fiber-like reinforcing fiber impregnated with a thermosetting resin (SMC) (see, for example, Patent Document 2).
しかしながら、一般的にプリプレグは非常に薄い基材であるため、特許文献１に開示される技術では肉厚の成形体を成形する際には多くの積層工程を要すると共に、切り込みを入れたプリプレグ基材を積層する際には切り込みの方向を考慮した複雑な積層パターンが必要であり、作業性の観点からＳＭＣに劣るという問題がある。 However, in general, since the prepreg is a very thin base material, the technique disclosed in Patent Document 1 requires a large number of laminating steps when forming a thick molded body, and a prepreg base with cuts. When laminating materials, a complicated laminating pattern in consideration of the cutting direction is required, which is inferior to SMC from the viewpoint of workability.
また、特許文献２に開示される技術は、ＳＭＣを使用しているので、特許文献１に開示される技術と比較すると肉厚部品を成形する際の積層工程における作業性の改善が期待できる。しかしながら、実際の成形作業現場においてプリプレグ及びＳＭＣという異なる２種類の基材を用いることは作業スペースや作業工数の観点からは更なる改善の余地があった。また、硬化物の強度特性にも改善の余地があった。 Moreover, since the technique disclosed in Patent Document 2 uses SMC, improvement in workability in the stacking process when forming a thick part can be expected as compared with the technique disclosed in Patent Document 1. However, the use of two different types of base materials, prepreg and SMC, in the actual molding work site has room for further improvement from the viewpoint of work space and work man-hours. There was also room for improvement in the strength properties of the cured product.
従って、本発明は、かかる従来技術の課題を解消し、成形時に良好な流動性及び複雑形状への追従性を確保し、作業性に優れると共に、優れた強度特性を発現する繊維強化プラスチックを製造することのできる熱硬化性シート状成形材料並びにそれを用いた繊維強化プラスチックの製造方法を提供することを目的とする。 Therefore, the present invention eliminates the problems of the prior art, ensures good fluidity and followability to complex shapes during molding, and produces a fiber reinforced plastic that exhibits excellent workability and excellent strength characteristics. It is an object of the present invention to provide a thermosetting sheet-like molding material that can be used and a method for producing a fiber-reinforced plastic using the same.
本発明は、以下［１］〜［８］で示される。
［１］一方向炭素繊維シート（Ａ１）に熱硬化性樹脂組成物（Ｂ）が含浸された層（以下、「Ａ１Ｂ層」と記載することもある）とランダムに配向した短繊維束（Ａ２）に熱硬化性樹脂組成物（Ｂ）が含浸された層（以下、「Ａ２Ｂ層」と記載することもある）とがＡ１Ｂ層、Ａ２Ｂ層及びＡ１Ｂの順に積層されたものであって、２つのＡ１Ｂ層の一方向炭素繊維シート（Ａ１）の繊維の方向が同一である熱硬化性シート状成形材料。
［２］前記一方向炭素繊維シート（Ａ１）の目付重量が５０〜２００ｇ／ｍ２である［１］に記載の熱硬化性シート状成形材料。
［３］前記熱硬化性樹脂組成物（Ｂ）が、エポキシ樹脂、ビニルエステル樹脂及び不飽和ポリエステル樹脂から選ばれる少なくとも１種の熱硬化性樹脂（Ｂ１）を含む［１］又は［２］に記載の熱硬化性シート状成形材料。
［４］前記熱硬化性樹脂（Ｂ１）が、ビニルエステル樹脂である［３］に記載の熱硬化性シート状成形材料。
［５］前記熱硬化性樹脂組成物（Ｂ）が、ポリイソシアネート（Ｂ３）を含む［１］〜［４］のいずれかに記載の熱硬化性シート状成形材料。
［６］前記熱硬化性シート状成形材料１００質量部に対して、前記一方向炭素繊維シート（Ａ１）及び前記短繊維束（Ａ２）の合計量が、３０〜６０質量部である［１］〜［５］のいずれかに記載の熱硬化性シート状成形材料。
［７］前記熱硬化性シート状成形材料１００質量部に対して、前記一方向炭素繊維シート（Ａ１）が、３〜１３質量部含まれる［１］〜［６］のいずれかに記載の熱硬化性シート状成形材料。
［８］［１］〜［７］のいずれかに記載の熱硬化性シート状成形材料を加熱、加圧することを含む繊維強化プラスチックの製造方法。
The present invention is shown by [1] to [8] below.
[1] A layer in which the thermosetting resin composition (B) is impregnated in the unidirectional carbon fiber sheet (A1) (hereinafter sometimes referred to as “A1B layer”) and a randomly oriented short fiber bundle (A2) ) In which the thermosetting resin composition (B) is impregnated (hereinafter also referred to as “A2B layer”) are laminated in the order of A1B layer, A2B layer, and A1B. A thermosetting sheet-shaped molding material in which the directions of the fibers of the unidirectional carbon fiber sheet (A1) of the two A1B layers are the same.
[2] The thermosetting sheet-shaped molding material according to [1], wherein the basis weight of the unidirectional carbon fiber sheet (A1) is 50 to 200 g / m 2 .
[3] In [1] or [2], the thermosetting resin composition (B) includes at least one thermosetting resin (B1) selected from an epoxy resin, a vinyl ester resin, and an unsaturated polyester resin. The thermosetting sheet-like molding material as described.
[4] The thermosetting sheet-shaped molding material according to [3], wherein the thermosetting resin (B1) is a vinyl ester resin.
[5] The thermosetting sheet-shaped molding material according to any one of [1] to [4], wherein the thermosetting resin composition (B) includes a polyisocyanate (B3).
[6] The total amount of the unidirectional carbon fiber sheet (A1) and the short fiber bundle (A2) is 30 to 60 parts by mass with respect to 100 parts by mass of the thermosetting sheet-shaped molding material [1]. -The thermosetting sheet-like molding material in any one of [5].
[7] The heat according to any one of [1] to [6], wherein 3 to 13 parts by mass of the unidirectional carbon fiber sheet (A1) is included with respect to 100 parts by mass of the thermosetting sheet-shaped molding material. Curable sheet-shaped molding material.
[8] A method for producing a fiber-reinforced plastic, comprising heating and pressurizing the thermosetting sheet-shaped molding material according to any one of [1] to [7].
本発明によれば、成形時に良好な流動性及び複雑形状への追従性を確保し、作業性に優れると共に、優れた強度特性を発現する繊維強化プラスチックを製造することのできる熱硬化性シート状成形材料並びに方法を提供することができる。 According to the present invention, a thermosetting sheet that can produce a fiber-reinforced plastic that ensures good fluidity and conformability to a complex shape during molding, has excellent workability, and exhibits excellent strength characteristics. Molding materials as well as methods can be provided.
［熱硬化性シート状成形材料の積層形態］
本発明に係る熱硬化性シート状成形材料は、一方向炭素繊維シート（Ａ１）に熱硬化性樹脂組成物（Ｂ）が含浸された層（Ａ１Ｂ層）とランダムに配向した短繊維束（Ａ２）に熱硬化性樹脂組成物（Ｂ）が含浸された層（Ａ２Ｂ層）とがＡ１Ｂ層、Ａ２Ｂ層及びＡ１Ｂ層の順に積層され、２つのＡ１Ｂ層の一方向炭素繊維シート（Ａ１）の繊維の方向が略同一であるものである。
[Laminated form of thermosetting sheet-shaped molding material]
The thermosetting sheet-shaped molding material according to the present invention comprises a layer (A1B layer) in which a unidirectional carbon fiber sheet (A1) is impregnated with a thermosetting resin composition (B) and a randomly oriented short fiber bundle (A2). ) And the layer (A2B layer) impregnated with the thermosetting resin composition (B) are laminated in the order of A1B layer, A2B layer and A1B layer, and the fibers of the unidirectional carbon fiber sheet (A1) of the two A1B layers Are substantially the same.
本発明に係る熱硬化性シート状成形材料の具体的な積層形態としては、例えば、図１に示されるＡ１Ｂ層／Ａ２Ｂ層／Ａ１Ｂ層、図２に示されるＡ１Ｂ層／Ａ２Ｂ層／Ａ２Ｂ層／Ａ１Ｂ層、Ａ１Ｂ層／Ａ１Ｂ層／Ａ２Ｂ層／Ａ２Ｂ層／Ａ１Ｂ層／Ａ１Ｂ層、Ａ１Ｂ層／Ａ２Ｂ層／Ａ１Ｂ層／Ａ１Ｂ層／Ａ２Ｂ層／Ａ１Ｂ層などが挙げられる。即ち、Ａ１Ｂ層が積層方向の両側の最外に位置する積層形態であれば、Ａ１Ｂ層１０及びＡ２Ｂ層１１をそれぞれ単層としてもよいし、複層としてもよい。複層とする場合、含浸される熱硬化性樹脂組成物（Ｂ）の組成は同じであってもよいし、異なってもよい。また、Ａ１Ｂ層とＡ２Ｂ層との間には、熱硬化性樹脂組成物（Ｂ）を硬化させてなる樹脂層が存在してもよい。この樹脂層を構成する熱硬化性樹脂組成物（Ｂ）は、一方向炭素繊維シート（Ａ１）及び短繊維束（Ａ２）に含浸させた熱硬化性樹脂組成物の組成と同じであってもよいし、異なってもよい。
Specific examples of the laminated form of the thermosetting sheet-like molding material according to the present invention include, for example, A1B layer / A2B layer / A1B layer shown in FIG. 1, A1B layer / A2B layer / A2B layer shown in FIG. Examples include A1B layer, A1B layer / A1B layer / A2B layer / A2B layer / A1B layer / A1B layer, A1B layer / A2B layer / A1B layer / A1B layer / A2B layer / A1B layer. That is, as long as the A1B layer is a laminated form in which the A1B layer is positioned on the outermost sides on both sides in the lamination direction, the
［熱硬化性シート状成形材料の製造方法］
本発明の熱硬化性シート状成形材料は、一般的なＳＭＣ製造装置を用いて製造することができる。後述の原材料を混合して熱硬化性樹脂組成物（Ｂ）を得た後、その熱硬化性樹脂組成物（Ｂ）を一方向炭素繊維シート（Ａ１）及び／又は短繊維束（Ａ２）に含浸してシート化し、それをＡ１Ｂ層、Ａ２Ｂ層及びＡ１Ｂ層の順に積層することで製造することができる。例えば、Ａ１Ｂ層からなるシートとＡ２Ｂ層からなるシートとをそれぞれ製造し、それらをＡ１Ｂ層、Ａ２Ｂ層及びＡ１Ｂ層の順に積層することで本発明の熱硬化性シート状成形材料を得ることができる。また、一方向炭素繊維シート（Ａ１）、短繊維束（Ａ２）及び一方向炭素繊維シート（Ａ１）の順に積層したところに熱硬化性樹脂組成物（Ｂ）を一度に含浸させることで本発明の熱硬化性シート状成形材料を得ることもできる。Ａ１Ｂ層のみ、及びＡ２Ｂ層のみを先にシート化してから積層する方法で図１の熱硬化性シート状成形材料を得る方法を例に、以下に、本発明の熱硬化性シート状成形材料を製造する具体的な方法を説明する。
[Method for producing thermosetting sheet-shaped molding material]
The thermosetting sheet-shaped molding material of the present invention can be manufactured using a general SMC manufacturing apparatus. After the raw materials described below are mixed to obtain a thermosetting resin composition (B), the thermosetting resin composition (B) is formed into a unidirectional carbon fiber sheet (A1) and / or a short fiber bundle (A2). It can be manufactured by impregnating into a sheet and laminating it in the order of A1B layer, A2B layer and A1B layer. For example, the thermosetting sheet-shaped molding material of the present invention can be obtained by producing a sheet composed of an A1B layer and a sheet composed of an A2B layer and laminating them in the order of an A1B layer, an A2B layer, and an A1B layer. . In addition, the present invention can be achieved by impregnating the thermosetting resin composition (B) at a time into a place where the unidirectional carbon fiber sheet (A1), the short fiber bundle (A2), and the unidirectional carbon fiber sheet (A1) are laminated in this order. The thermosetting sheet-shaped molding material can also be obtained. As an example of the method of obtaining the thermosetting sheet-like molding material of FIG. 1 by the method of laminating only the A1B layer and the A2B layer first, the thermosetting sheet-like molding material of the present invention will be described below. A specific method for manufacturing will be described.
まず、熱硬化性樹脂組成物（Ｂ）の各原材料をミキサーなどで混合する。材料を混合する順番や攪拌機に特に制限は無いが、混合時の温度は２０〜４５℃であることが好ましい。次に、この混合した熱硬化性樹脂組成物（Ｂ）をＳＭＣ製造装置の上下に設置されたキャリアフィルムに均一な厚さになるように塗布する。キャリアフィルムとしては、一般に用いられているものであれば特に制限は無いが、ポリエチレンフィルム、ポリプロピレンフィルムなどを用いることができる。続いて、熱硬化性樹脂組成物（Ｂ）を塗布した上下キャリアフィルムの片方又は両方に一方向炭素繊維シート（Ａ１）を配置する。この時、一方向炭素繊維シート（Ａ１）の繊維の方向はキャリアフィルムの繰出し方向と同一方向である。その後、上下のキャリアフィルムを挟み込み、全体に圧力を加えながら含浸ロールの間を通し、一方向炭素繊維シート（Ａ１）に熱硬化性樹脂組成物（Ｂ）を含浸してシート化する。同様の方法で、短繊維束（Ａ２）に熱硬化性樹脂組成物（Ｂ）を含浸してシート化したものも作製する。 First, each raw material of a thermosetting resin composition (B) is mixed with a mixer etc. Although there is no restriction | limiting in particular in the order and stirrer which mix a material, It is preferable that the temperature at the time of mixing is 20-45 degreeC. Next, the mixed thermosetting resin composition (B) is applied to a carrier film installed at the top and bottom of the SMC manufacturing apparatus so as to have a uniform thickness. The carrier film is not particularly limited as long as it is generally used, but a polyethylene film, a polypropylene film and the like can be used. Subsequently, the unidirectional carbon fiber sheet (A1) is disposed on one or both of the upper and lower carrier films to which the thermosetting resin composition (B) is applied. At this time, the direction of the fibers of the unidirectional carbon fiber sheet (A1) is the same as the feeding direction of the carrier film. Thereafter, the upper and lower carrier films are sandwiched between the impregnating rolls while applying pressure to the whole, and the unidirectional carbon fiber sheet (A1) is impregnated with the thermosetting resin composition (B) to form a sheet. In the same manner, a sheet formed by impregnating the short fiber bundle (A2) with the thermosetting resin composition (B) is also produced.
得られたシートは、室温〜６０℃の温度で１〜２４０時間加温して熟成することが好ましい。室温〜６０℃で１〜２４０時間熟成させることで、キャリアフィルムの剥離が容易となるとともに、キャリアフィルムを剥がした際にベタツキの少ないシートを得ることができる。 The obtained sheet is preferably aged by heating at room temperature to 60 ° C. for 1 to 240 hours. By aging at room temperature to 60 ° C. for 1 to 240 hours, the carrier film can be easily peeled off, and a sheet with little stickiness when the carrier film is peeled off can be obtained.
得られたシートをＡ１Ｂ層、Ａ２Ｂ層及びＡ１Ｂ層の順に積層することで、図１に示される熱硬化性シート状成形材料を得ることができる。 By laminating the obtained sheet in the order of the A1B layer, the A2B layer, and the A1B layer, the thermosetting sheet-like molding material shown in FIG. 1 can be obtained.
［（Ａ１）一方向炭素繊維シート］
一方向炭素繊維シート（Ａ１）は、緯糸を含まない形態であり、例えば、予め炭素繊維を一方向に引き揃えてシート状にした一方向炭素繊維基材や、シート状にした一方向炭素繊維基材をマトリックス樹脂や集束剤で含浸し固定したプリプレグ状シートを用いることができる。
[(A1) Unidirectional carbon fiber sheet]
A unidirectional carbon fiber sheet (A1) is a form which does not contain a weft. For example, a unidirectional carbon fiber substrate in which carbon fibers are preliminarily aligned in one direction to form a sheet, or a unidirectional carbon fiber formed in a sheet form. A prepreg-like sheet in which a base material is impregnated with a matrix resin or a sizing agent and fixed can be used.
一方向炭素繊維シート（Ａ１）の目付重量は、熱硬化性シート状成形材料の成形時に良好な流動性を有し、繊維強化プラスチックが優れた強度を発現するために、５０〜２００ｇ／ｍ２であることが好ましく、７５〜２００ｇ／ｍ２であることがより好ましく、１００〜２００ｇ／ｍ２であることが最も好ましい。 The weight per unit area of the unidirectional carbon fiber sheet (A1) is 50 to 200 g / m 2 in order to have good fluidity when the thermosetting sheet-shaped molding material is molded and the fiber reinforced plastic exhibits excellent strength. it is preferably, more preferably 75~200g / m 2, and most preferably 100 to 200 g / m 2.
一方向炭素繊維シート（Ａ１）は、熱硬化性シート状成形材料１００質量部に対して、３〜１３質量部含まれることが好ましく、４〜１２質量部含まれることがより好ましく、５〜１０質量部含まれることが最も好ましい。一方向炭素繊維シート（Ａ１）の含有量が３質量部以上であると、短繊維束（Ａ２）のみを用いた従来のＳＭＣと比較して良好な強度特性が発現する。一方、一方向炭素繊維シート（Ａ１）の含有量が１３質量部以下であると、成形時の流動性が良好となる。 The unidirectional carbon fiber sheet (A1) is preferably contained in an amount of 3 to 13 parts by mass, more preferably 4 to 12 parts by mass, with respect to 100 parts by mass of the thermosetting sheet-shaped molding material. Most preferably, parts by weight are included. When the content of the unidirectional carbon fiber sheet (A1) is 3 parts by mass or more, good strength characteristics are exhibited as compared with the conventional SMC using only the short fiber bundle (A2). On the other hand, when the content of the unidirectional carbon fiber sheet (A1) is 13 parts by mass or less, the fluidity at the time of molding becomes good.
［（Ａ２）ランダムに配向した短繊維束］
短繊維束（Ａ２）に用いる繊維の種類には特に制限は無く、炭素繊維、アラミド繊維、ボロン繊維、ガラス繊維などが例示できる。これらの繊維束は、単独で用いてもよいし、又は二種類以上を用いてもよい。これらの中でも、炭素繊維は比強度及び比弾性に優れるので好ましく、ガラス繊維はこれらの繊維束の中で比較的安価で強度も優れるので好ましい。短繊維束（Ａ２）の繊維長は、ＳＭＣにおいて通常用いられる長さであればよく、具体的には１２〜２５ｍｍである。
[(A2) Randomly oriented short fiber bundle]
There is no restriction | limiting in particular in the kind of fiber used for a short fiber bundle (A2), A carbon fiber, an aramid fiber, a boron fiber, a glass fiber etc. can be illustrated. These fiber bundles may be used alone or in combination of two or more. Among these, carbon fiber is preferable because it is excellent in specific strength and specific elasticity, and glass fiber is preferable because it is relatively inexpensive and excellent in strength among these fiber bundles. The fiber length of a short fiber bundle (A2) should just be the length normally used in SMC, and is specifically 12-25 mm.
一方向炭素繊維シート（Ａ１）及び短繊維束（Ａ２）の合計量は、繊維強化プラスチックに要求される強度によって異なるが、熱硬化性シート状成形材料１００質量部（一方向炭素繊維シート（Ａ１）、短繊維束（Ａ２）及び熱硬化性樹脂組成物（Ｂ）の合計１００質量部）に対して、３０〜６０質量部であることが好ましく、３５〜５５質量部であることがより好ましく、４０〜５０質量部であることが最も好ましい。一方向炭素繊維シート（Ａ１）及び短繊維束（Ａ２）の合計量が３０質量部以上であれば繊維強化プラスチックの強度が十分に高くなる。一方、一方向炭素繊維シート（Ａ１）及び短繊維束（Ａ２）の合計量が６０質量部以下であれば成形時の流動性が良好となる。 The total amount of the unidirectional carbon fiber sheet (A1) and the short fiber bundle (A2) varies depending on the strength required for the fiber reinforced plastic, but 100 parts by mass of the thermosetting sheet-shaped molding material (unidirectional carbon fiber sheet (A1)). ), The short fiber bundle (A2) and the thermosetting resin composition (B) in a total of 100 parts by mass), preferably 30 to 60 parts by mass, and more preferably 35 to 55 parts by mass. 40 to 50 parts by mass is most preferable. If the total amount of the unidirectional carbon fiber sheet (A1) and the short fiber bundle (A2) is 30 parts by mass or more, the strength of the fiber reinforced plastic is sufficiently high. On the other hand, if the total amount of the unidirectional carbon fiber sheet (A1) and the short fiber bundle (A2) is 60 parts by mass or less, the fluidity during molding is good.
［（Ｂ）熱硬化性樹脂組成物］
本発明で用いる熱硬化性樹脂組成物（Ｂ）は、加熱により硬化可能であり、一方向炭素繊維シート（Ａ１）及び短繊維束（Ａ２）に含浸できるものであれば特に制限は無い。
[(B) Thermosetting resin composition]
The thermosetting resin composition (B) used in the present invention is not particularly limited as long as it can be cured by heating and can be impregnated into the unidirectional carbon fiber sheet (A1) and the short fiber bundle (A2).
［（Ｂ１）熱硬化性樹脂］
熱硬化性樹脂組成物（Ｂ）は、主成分として、エポキシ樹脂、ビニルエステル樹脂及び不飽和ポリエステル樹脂から選ばれる少なくとも１種の熱硬化性樹脂（Ｂ１）を含むことが好ましい。
[(B1) Thermosetting resin]
The thermosetting resin composition (B) preferably contains at least one thermosetting resin (B1) selected from an epoxy resin, a vinyl ester resin, and an unsaturated polyester resin as a main component.
エポキシ樹脂としては、例えば、ビスフェノールタイプのエポキシ樹脂、ノボラックタイプのエポキシ樹脂又はこれらの混合物が挙げられる。 Examples of the epoxy resin include a bisphenol type epoxy resin, a novolac type epoxy resin, or a mixture thereof.
不飽和ポリエステル樹脂は、例えば多価アルコールと多塩基酸を重縮合（エステル化）させることで得られる。多価アルコールとしては、例えば、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、ペンタンジオール、ヘキサンジオール、ネオペンタンジオール、水素化ビスフェノールＡ、ビスフェノールＡ及びグリセリンなどが挙げられる。多塩基酸としては、無水マレイン酸、フマル酸、シトラコン酸、イタコン酸、無水フタル酸、イソフタル酸、テレフタル酸、ヘット酸、コハク酸、アジピン酸、セバシン酸、テトラクロロ無水フタル酸、テトラブロモ無水フタル酸、エンドメチレンテトラヒドロ無水フタル酸などの飽和又は不飽和多塩基酸が挙げられる。 The unsaturated polyester resin can be obtained, for example, by polycondensation (esterification) of a polyhydric alcohol and a polybasic acid. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, pentanediol, hexanediol, neopentanediol, hydrogenated bisphenol A, bisphenol A, and glycerin. . Polybasic acids include maleic anhydride, fumaric acid, citraconic acid, itaconic acid, phthalic anhydride, isophthalic acid, terephthalic acid, het acid, succinic acid, adipic acid, sebacic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride Examples thereof include saturated or unsaturated polybasic acids such as acid and endomethylenetetrahydrophthalic anhydride.
ビニルエステル樹脂は、例えば、エポキシ樹脂と不飽和一塩基酸とをエステル化触媒の存在下で反応することで得られたものである。エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、１，６−ヘキサンジオールグリシジルエーテルなどのエポキシ樹脂又はそれらのエポキシ樹脂を併用した混合樹脂が挙げられる。 The vinyl ester resin is obtained, for example, by reacting an epoxy resin and an unsaturated monobasic acid in the presence of an esterification catalyst. Examples of the epoxy resin include bisphenol A type epoxy resins, phenol novolac type epoxy resins, epoxy resins such as 1,6-hexanediol glycidyl ether, and mixed resins using these epoxy resins in combination.
不飽和一塩基酸としては、例えば、アクリル酸、メタアクリル酸、桂皮酸、クロトン酸、マレイン酸モノメチル、マレイン酸モノプロピル、マレイン酸モノ（２ーエチルヘキシル）、ソルビン酸などが挙げられる。 Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, mono (2-ethylhexyl) maleate, and sorbic acid.
中でも、ビニルエステル樹脂は、成形時に短時間で硬化できるため成形サイクルに優れると共に、室温での保存安定性及び繊維強化プラスチックの強度も比較的良好であることから、好適に用いることができる。熱硬化性樹脂（Ｂ１）は、熱硬化性樹脂組成物（Ｂ）１００質量部に対して、１５〜９０質量部含まれることが好ましく、３５〜８５質量部含まれることがより好ましく、５０〜８０質量部含まれることが最も好ましい。熱硬化性樹脂（Ｂ１）の含有量が上記範囲内であると、成形時の流動性及び繊維強化プラスチックの強度の両立が容易である。 Among these, vinyl ester resins can be suitably used because they can be cured in a short time at the time of molding and are excellent in the molding cycle, and also have storage stability at room temperature and relatively good strength of fiber-reinforced plastic. The thermosetting resin (B1) is preferably contained in an amount of 15 to 90 parts by mass, more preferably 35 to 85 parts by mass with respect to 100 parts by mass of the thermosetting resin composition (B). Most preferably, 80 parts by mass is contained. When the content of the thermosetting resin (B1) is within the above range, it is easy to achieve both the fluidity during molding and the strength of the fiber-reinforced plastic.
［（Ｂ２）重合性モノマー］
熱硬化性樹脂組成物（Ｂ）は、重合性モノマー（Ｂ２）を含むことが好ましい。特に、熱硬化性樹脂（Ｂ１）としてビニルエステル樹脂又は不飽和ポリエステル樹脂を用いた場合、重合性モノマー（Ｂ２）を熱硬化性樹脂（Ｂ１）の適切な希釈溶媒として用いることができる。重合性モノマー（Ｂ２）は、熱硬化性樹脂（Ｂ１）と重合可能なエチレン性不飽和結合を有しているものであれば適宜なものを用いることができる。重合性モノマー（Ｂ２）としては、例えば、スチレン、ビニルトルエン、α−メチルトルエン、ジアリルフタレート、トリアリルイソシアヌレート、ジアリルフタレートプレポリマー、（メタ）アクリル酸エチル、（メタ）アクリル酸メチルなどが挙げられる。
[(B2) polymerizable monomer]
The thermosetting resin composition (B) preferably contains a polymerizable monomer (B2). In particular, when a vinyl ester resin or an unsaturated polyester resin is used as the thermosetting resin (B1), the polymerizable monomer (B2) can be used as an appropriate dilution solvent for the thermosetting resin (B1). As the polymerizable monomer (B2), any suitable monomer can be used as long as it has an ethylenically unsaturated bond polymerizable with the thermosetting resin (B1). Examples of the polymerizable monomer (B2) include styrene, vinyl toluene, α-methyl toluene, diallyl phthalate, triallyl isocyanurate, diallyl phthalate prepolymer, ethyl (meth) acrylate, methyl (meth) acrylate, and the like. It is done.
重合性モノマー（Ｂ２）は、熱硬化性樹脂（Ｂ１）１００質量部に対して、５〜８０質量部含まれることが好ましく、２５〜７５質量部含まれることがより好ましく、３５〜７０質量部含まれることが最も好ましい。重合性モノマー（Ｂ２）の含有量が上記範囲内であると、成形時の流動性及び繊維強化プラスチックの強度の両立が容易である。 The polymerizable monomer (B2) is preferably contained in an amount of 5 to 80 parts by mass, more preferably 25 to 75 parts by mass, with respect to 100 parts by mass of the thermosetting resin (B1). Most preferably it is included. When the content of the polymerizable monomer (B2) is within the above range, it is easy to achieve both the fluidity during molding and the strength of the fiber-reinforced plastic.
［（Ｂ３）ポリイソシアネート］
熱硬化性樹脂組成物（Ｂ）は、ポリイソシアネート（Ｂ３）を含むことが好ましい。ポリイソシアネート（Ｂ３）は、一分子中に少なくとも二つのイソシアナト基を有するものであれば特に限定されない。ポリイソシアネート（Ｂ３）としては、トリレンジイソシアネート（ＴＤＩ）、４，４’−ジフェニルメタンジイソシアネート（ＭＤＩ）、水素添加キシリレンジイソシアネート（Ｈ６ＸＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、シクロヘキサンジイソシアネート（ＣＨＤＩ）、水素添加４，４’−ジフェニルメタンジイソシアネート（Ｈ１２ＭＤＩ）、キシリレンジイソシアネート（ＸＤＩ）、テトラメチルキシリエンジイソシアネート（ＴＭＸＤＩ）、１，６−ヘキサメチレンジイソシアネート（ＨＤＩ）などが挙げられる。これらのポリイソシアネート（Ｂ３）は、単独で用いてもよいし、二種以上を併用してもよい。
[(B3) Polyisocyanate]
The thermosetting resin composition (B) preferably contains polyisocyanate (B3). The polyisocyanate (B3) is not particularly limited as long as it has at least two isocyanato groups in one molecule. As polyisocyanate (B3), tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), hydrogenated xylylene diisocyanate (H6XDI), isophorone diisocyanate (IPDI), cyclohexane diisocyanate (CHDI), hydrogenated 4 4,4'-diphenylmethane diisocyanate (H12MDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 1,6-hexamethylene diisocyanate (HDI), and the like. These polyisocyanates (B3) may be used alone or in combination of two or more.
ポリイソシアネート（Ｂ３）は、熱硬化性樹脂組成物（Ｂ）に対して、３〜１５質量％含まれることが好ましく、４〜１２質量％含まれることがより好ましく、５〜１０質量％含まれることが最も好ましい。ポリイソシアネート（Ｂ３）の含有量が上記範囲内であると、増粘が好適に進行しシートの取扱い性が良好となると共に、増粘が進行し過ぎることがなく、成形時の流動性が確保される。 The polyisocyanate (B3) is preferably contained in an amount of 3 to 15% by mass, more preferably 4 to 12% by mass, and more preferably 5 to 10% by mass with respect to the thermosetting resin composition (B). Most preferred. When the content of the polyisocyanate (B3) is within the above range, the thickening suitably proceeds and the handleability of the sheet is improved, and the thickening does not proceed excessively, and the fluidity during molding is ensured. Is done.
［（Ｂ４）硬化剤］
熱硬化性樹脂組成物（Ｂ）を加熱硬化させるための硬化剤には特に制限はなく、選定した熱硬化性樹脂（Ｂ１）及び重合性モノマー（Ｂ２）に適した公知のものを使用することができる。熱硬化性樹脂（Ｂ１）としてエポキシ樹脂を使用する場合の硬化剤としては、例えば、アミン、酸無水物、フェノール樹脂、メルカプタン、ルイス酸アミン錯体、オニウム塩、イミダゾールなどが挙げられる。エポキシ樹脂の硬化剤は、熱硬化性樹脂組成物（Ｂ）１００質量部に対して、３〜１０質量部の範囲で添加することが好ましい。
[(B4) Curing Agent]
There is no particular limitation on the curing agent for heat-curing the thermosetting resin composition (B), and a known one suitable for the selected thermosetting resin (B1) and polymerizable monomer (B2) should be used. Can do. Examples of the curing agent when an epoxy resin is used as the thermosetting resin (B1) include amines, acid anhydrides, phenol resins, mercaptans, Lewis acid amine complexes, onium salts, and imidazoles. The epoxy resin curing agent is preferably added in an amount of 3 to 10 parts by mass with respect to 100 parts by mass of the thermosetting resin composition (B).
熱硬化性樹脂（Ｂ１）としてビニルエステル樹脂又は不飽和ポリエステル樹脂を使用する場合の硬化剤としては、例えば、ｔ−ブチルパーオキシオクトエート、ベンゾイルパーオキサイド、１，１，ジ−ｔ−ブチルパーオキシ３，３，５，トリメチルシクロヘキサン、ｔ−ブチルパーオキシイソプロピルカーボネート、ｔ−ブチルパーオキシベンゾエート、ジクミルパーオキサイド、ジ−ｔ−ブチルパーオキサイドなどの過酸化物が挙げられる。これらの硬化剤は、単独で使用してもよいし、又は二種類以上を用いてもよい。ビニルエステル樹脂又は不飽和ポリエステル樹脂の硬化剤は、熱硬化性樹脂組成物（Ｂ）１００質量部に対して、５質量部以下の範囲で添加することが好ましい。 Examples of the curing agent when a vinyl ester resin or an unsaturated polyester resin is used as the thermosetting resin (B1) include t-butyl peroxy octoate, benzoyl peroxide, 1,1, di-t-butyl per Examples thereof include peroxides such as oxy 3,3,5, trimethylcyclohexane, t-butyl peroxyisopropyl carbonate, t-butyl peroxybenzoate, dicumyl peroxide, and di-t-butyl peroxide. These curing agents may be used alone or in combination of two or more. It is preferable to add the hardening | curing agent of vinyl ester resin or unsaturated polyester resin in 5 mass parts or less with respect to 100 mass parts of thermosetting resin compositions (B).
上記した（Ｂ１）〜（Ｂ４）成分は、熱硬化性樹脂組成物（Ｂ）に対して、合計で６０〜１００質量％含まれることが好ましく、６５〜１００質量％含まれることがより好ましく、７０〜１００質量％含まれることが最も好ましい。（Ｂ１）〜（Ｂ４）成分の含有量が上記範囲内であると、一方向炭素繊維シート（Ａ１）及び短繊維束（Ａ２）への含浸性を確保することができると共に、成形時の流動性及び繊維強化プラスチックの強度の両立が容易である。 The above components (B1) to (B4) are preferably contained in a total amount of 60 to 100% by mass, more preferably 65 to 100% by mass, with respect to the thermosetting resin composition (B). It is most preferable that 70-100 mass% is contained. When the content of the components (B1) to (B4) is within the above range, the impregnation property to the unidirectional carbon fiber sheet (A1) and the short fiber bundle (A2) can be secured, and the flow during molding It is easy to achieve both compatibility and strength of fiber reinforced plastic.
［（Ｂ５）添加剤］
本発明で用いる熱硬化性樹脂組成物（Ｂ）には、本発明の効果を損なわない範囲で、内部離型剤、無機充填材、低収縮化剤、重合禁止剤、着色剤などの添加剤を添加してもよい。
[(B5) Additive]
In the thermosetting resin composition (B) used in the present invention, additives such as an internal mold release agent, an inorganic filler, a low shrinkage agent, a polymerization inhibitor, and a colorant are added within the range not impairing the effects of the present invention. May be added.
内部離型剤としては、例えば、ステアリン酸亜鉛、ステアリン酸、ステアリン酸カルシウム、ステアリン酸アルミニウム、ステアリン酸マグネシウム、カルナバワックスなどが挙げられる。これらの内部離型剤は、単独で用いてもよいし、又は二種類以上を用いてもよい。内部離型剤は、熱硬化性樹脂組成物（Ｂ）１００質量部に対して、１５質量部以下の範囲で添加することができる。 Examples of the internal mold release agent include zinc stearate, stearic acid, calcium stearate, aluminum stearate, magnesium stearate, carnauba wax and the like. These internal mold release agents may be used alone or in combination of two or more. An internal mold release agent can be added in 15 mass parts or less with respect to 100 mass parts of thermosetting resin compositions (B).
無機充填材としては、例えば、シリカ、アルミナ、マイカ、水酸化アルミニウム、炭酸カルシウム、石こう、硫酸バリウム、クレー、タルクなどの無機粉末が挙げられる。これらの無機充填材は、単独で用いてもよいし、又は二種類以上を用いてもよい。無機充填材は、熱硬化性樹脂組成物（Ｂ）１００質量部に対して、４５質量部以下の範囲で添加することができる。 Examples of the inorganic filler include inorganic powders such as silica, alumina, mica, aluminum hydroxide, calcium carbonate, gypsum, barium sulfate, clay, and talc. These inorganic fillers may be used alone or in combination of two or more. An inorganic filler can be added in 45 mass parts or less with respect to 100 mass parts of thermosetting resin compositions (B).
低収縮化剤としては、既存のシートモールディングコンパウンドにおいて一般に使用されているものを使用することができ、例えば、ポリスチレン、ポリエチレン、ポリメチルメタクリレート、ポリ酢酸ビニル、飽和ポリエステル、ポリカプロラクトンなどが挙げられる。これらの低収縮化剤は、単独で用いてもよいし、又は二種類以上を用いてもよい。低収縮化剤は、熱硬化性樹脂組成物（Ｂ）１００質量部に対して、２０質量部以下の範囲で添加することができる。 As the low shrinkage agent, those generally used in existing sheet molding compounds can be used, and examples thereof include polystyrene, polyethylene, polymethyl methacrylate, polyvinyl acetate, saturated polyester, and polycaprolactone. These low shrinkage agents may be used alone or in combination of two or more. The low shrinkage agent can be added in a range of 20 parts by mass or less with respect to 100 parts by mass of the thermosetting resin composition (B).
重合禁止剤としては、例えば、ハイドロキノン、トリメチルハイドロキノン、ｐ−ベンゾキノン、ナフトキノン、ｔ−ブチルハイドロキノン、カテコール、ｐ−ｔ−ブチルカテコール、２，６−ジ−ｔ−ブチル−４−メチルフェノールなどが挙げられる。これらの重合禁止剤は、単独で使用してもよいし、又は二種以上を併用してもよい。重合禁止剤は、熱硬化性樹脂組成物（Ｂ）１００質量部に対して、０．３質量部以下の範囲で添加することができる。重合禁止剤は、スチレン、ビニルトルエン、α−メチルトルエン、ジアリルフタレート、トリアリルイソシアヌレート、ジアリルフタレートプレポリマー、（メタ）アクリル酸エチル、（メタ）アクリル酸メチルなどの重合性モノマーに、溶解させて用いることができる。 Examples of the polymerization inhibitor include hydroquinone, trimethylhydroquinone, p-benzoquinone, naphthoquinone, t-butylhydroquinone, catechol, pt-butylcatechol, 2,6-di-t-butyl-4-methylphenol. It is done. These polymerization inhibitors may be used alone or in combination of two or more. A polymerization inhibitor can be added in 0.3 mass parts or less with respect to 100 mass parts of thermosetting resin compositions (B). Polymerization inhibitors are dissolved in polymerizable monomers such as styrene, vinyltoluene, α-methyltoluene, diallyl phthalate, triallyl isocyanurate, diallyl phthalate prepolymer, ethyl (meth) acrylate, methyl (meth) acrylate, etc. Can be used.
着色剤は、成形品を着色する必要のある場合に用いるものであり、シートモールディングコンパウンドにおいて通常使用されている各種の無機顔料や有機顔料を使用することができる。着色剤は、熱硬化性樹脂組成物（Ｂ）１００質量部に対して、１０質量部以下の範囲で添加することができる。 The colorant is used when it is necessary to color a molded article, and various inorganic pigments and organic pigments that are usually used in sheet molding compounds can be used. A coloring agent can be added in 10 mass parts or less with respect to 100 mass parts of thermosetting resin compositions (B).
［繊維強化プラスチック］
本発明に係る繊維強化プラスチックは、上述した熱硬化性シート状成形材料を加熱・加圧により硬化させたものである。
[Fiber reinforced plastic]
The fiber-reinforced plastic according to the present invention is obtained by curing the above-described thermosetting sheet-shaped molding material by heating and pressing.
本発明において、熱硬化性シート状成形材料の成形方法は、熱硬化性シート状成形材料を加熱・加圧して硬化できるものであればよく、例えば、オートクレーブ成形法、真空バック成形法、圧縮成形法などの成形方法を挙げることができる。中でも、圧縮成形法は、他の成形方法と比較して高圧で成形することができるため、複雑形状の繊維強化プラスチックを短時間で製造することができ、生産性にも優れているため好ましい。具体的には、図１及び２に示されるように、下金型１４上に熱硬化性シート状成形材料１２を配置した後、熱硬化性シート状成形材料１２を上金型１３と下金型１４とで加熱、加圧すればよい。こうして得られる繊維強化プラスチックの両表面には、一方向炭素繊維シート（Ａ１）に熱硬化性樹脂組成物（Ｂ）が含浸硬化された層が配置されているので、所望の方向に対して優れた強度特性を発現することができる。圧縮成形法における好ましい硬化条件はシートや金型の形状によるが、例えば金型温度１００〜１８０℃、成形圧力５〜２０ＭＰａ、成形時間６０〜６００秒とすることができる。
In the present invention, the thermosetting sheet-shaped molding material may be molded by any method as long as it can be cured by heating and pressurizing the thermosetting sheet-shaped molding material. For example, an autoclave molding method, a vacuum back molding method, a compression molding method. Examples of the forming method include a method. Among them, the compression molding method is preferable because it can be molded at a higher pressure than other molding methods, and thus a complex-shaped fiber-reinforced plastic can be produced in a short time and has excellent productivity. Specifically, as shown in FIGS. 1 and 2, after the thermosetting sheet-shaped
本発明の製造方法に従って得られる繊維強化プラスチックは、広範囲に使用することができ、特に強度、剛性、軽量化が要求される自動車部品や機械部品に好適である。 The fiber reinforced plastic obtained according to the production method of the present invention can be used in a wide range, and is particularly suitable for automobile parts and machine parts that require strength, rigidity and light weight.
以下、実施例及び比較例により本発明を具体的に説明するが、本発明は、特にこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not specifically limited to these.
＜一方向炭素繊維シート（Ａ１）の作製＞
連続した炭素繊維トウ（東レ株式会社製トレカ（登録商標）Ｔ７００−１２Ｋ）から、長さ１ｍの炭素繊維トウを複数本切出し、それらを一方向に引き揃えて目付重量が１００ｇ／ｍ２となるように並べ、その長さ方向の両端部を粘着テープで固定することで、一方向炭素繊維シートを得た。
<Production of Unidirectional Carbon Fiber Sheet (A1)>
A plurality of carbon fiber tows having a length of 1 m are cut out from a continuous carbon fiber tow (Torayca (registered trademark) T700-12K manufactured by Toray Industries, Inc.), and they are aligned in one direction so that the basis weight is 100 g / m 2. A unidirectional carbon fiber sheet was obtained by aligning both ends in the length direction with an adhesive tape.
＜熱硬化性樹脂組成物（Ｂ）の作製＞
下記表１に示す組成となるように以下の材料（Ｂ１）〜（Ｂ５）を２５℃で混合し、熱硬化性樹脂組成物Ｂａを得た。
（Ｂ１）ビニルエステル樹脂、（Ｂ２）重合性モノマー（スチレン）
昭和電工株式会社製リポキシ（登録商標）Ｒ−８０４。ビスフェノールＡ型ビニルエステル樹脂のスチレン溶解品。スチレン含有率４０質量％。
（Ｂ３）ポリイソシアネート
日本ポリウレタン工業株式会社製、４，４’−ジフェニルメタンジイソシアネート。
（Ｂ４）硬化剤
日油株式会社製、ｔ−ブチルパーオキシベンゾエート
（Ｂ５）内部離型剤
日油株式会社製、ステアリン酸亜鉛。
（Ｂ５）無機充填材
昭和電工株式会製ハイジライト（登録商標）Ｈ−４２、水酸化アルミニウム。
（Ｂ５）重合禁止剤
精工化学株式会社製ｐ−ベンゾキノンを三井化学株式会社製メチルメタアクリレートに５質量％の濃度で溶解したもの。
<Preparation of thermosetting resin composition (B)>
The following materials (B1) to (B5) were mixed at 25 ° C. so as to have the composition shown in Table 1 below to obtain a thermosetting resin composition Ba.
(B1) vinyl ester resin, (B2) polymerizable monomer (styrene)
Lipoxy (registered trademark) R-804 manufactured by Showa Denko KK A styrene-dissolved product of bisphenol A type vinyl ester resin. Styrene content 40% by mass.
(B3) Polyisocyanate 4,4'-diphenylmethane diisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd.
(B4) Curing agent manufactured by NOF Corporation, t-butyl peroxybenzoate (B5) Internal mold release agent manufactured by NOF Corporation, zinc stearate.
(B5) Inorganic filler Hygielite (registered trademark) H-42, aluminum hydroxide manufactured by Showa Denko KK
(B5) Polymerization inhibitor What dissolved p-benzoquinone by Seiko Chemical Co., Ltd. in methyl methacrylate by Mitsui Chemicals Co., Ltd. at a concentration of 5% by mass.
＜熱硬化性シート状成形材料の作製−１＞
〔実施例１−１〕
ＳＭＣ製造装置を用いて、熱硬化性樹脂組成物Ｂａを上下キャリアフィルム（ポリプロピレン）に厚さが均一になるよう塗布した。
次いで、下側のキャリアフィルムにのみ一方向炭素繊維シート（目付重量１００ｇ／ｍ２）１枚を配置した。その一方向炭素繊維シート上に短繊維束（Ａ２）として２５ｍｍの長さに機械的に切断された炭素繊維トウを散布し、上側のキャリアフィルムで挟み込んで熱硬化性樹脂組成物を含浸させた。４０℃で２４時間熟成させた後、２８０×２８０ｍｍの大きさに２枚切り出し、２枚の一方向炭素繊維シートの繊維の配向方向が同一になるようにＡ２Ｂ層同士を対向させて重ね合せて、図２に示されるような熱硬化性シート状成形材料（Ａ１Ｂ層が積層方向の両側の最外に位置する）として実施例１−１の熱硬化性シート状成形材料を得た。実施例１−１の熱硬化性シート状成形材料は、一方向炭素繊維シート（Ａ１）、短繊維束（Ａ２）及び熱硬化性樹脂組成物Ｂａの含有量が、熱硬化性シート状成形材料１００質量部に対して、それぞれ５質量部、４５質量部及び５０質量部となるような条件で作製した。また、単位面積当たりのシート重量は約４ｋｇ／ｍ２であった。
<Preparation of thermosetting sheet-shaped molding material-1>
[Example 1-1]
Using the SMC manufacturing apparatus, the thermosetting resin composition Ba was applied to the upper and lower carrier films (polypropylene) so as to have a uniform thickness.
Next, one unidirectional carbon fiber sheet (weight per unit area: 100 g / m 2 ) was disposed only on the lower carrier film. On the unidirectional carbon fiber sheet, carbon fiber tow mechanically cut to a length of 25 mm as a short fiber bundle (A2) was sprayed and sandwiched between upper carrier films to impregnate the thermosetting resin composition. . After aging at 40 ° C. for 24 hours, two sheets are cut into a size of 280 × 280 mm, and the A2B layers are opposed to each other so that the orientation directions of the fibers of the two unidirectional carbon fiber sheets are the same. The thermosetting sheet-like molding material of Example 1-1 was obtained as a thermosetting sheet-like molding material as shown in FIG. 2 (the A1B layer is located on the outermost side on both sides in the stacking direction). The thermosetting sheet-like molding material of Example 1-1 has a content of the unidirectional carbon fiber sheet (A1), the short fiber bundle (A2), and the thermosetting resin composition Ba. It produced on the conditions which became 5 mass parts, 45 mass parts, and 50 mass parts with respect to 100 mass parts, respectively. The sheet weight per unit area was about 4 kg / m 2 .
〔実施例２−１〕
一方向炭素繊維シート（目付重量１００ｇ／ｍ２）２枚を同一方向に重ねて目付重量を２００ｇ／ｍ２とした一方向炭素繊維シートを下側のキャリアフィルムにのみ配置したこと以外は、実施例１−１と同様にして、実施例２−１の熱硬化性シート状成形材料を得た。実施例２−１の熱硬化性シート状成形材料は、一方向炭素繊維シート（Ａ１）、短繊維束（Ａ２）及び熱硬化性樹脂組成物Ｂａの含有量が、熱硬化性シート状成形材料１００質量部に対して、それぞれ１０質量部、４０質量部及び５０質量部となるような条件で作製した。
[Example 2-1]
Except that two unidirectional carbon fiber sheets (weight per unit weight 100 g / m 2 ) were stacked in the same direction and the unidirectional carbon fiber sheet having a basis weight of 200 g / m 2 was arranged only on the lower carrier film. The thermosetting sheet-shaped molding material of Example 2-1 was obtained in the same manner as Example 1-1. In the thermosetting sheet-like molding material of Example 2-1, the contents of the unidirectional carbon fiber sheet (A1), the short fiber bundle (A2), and the thermosetting resin composition Ba are the thermosetting sheet-like molding materials. It produced on the conditions which became 10 mass parts, 40 mass parts, and 50 mass parts with respect to 100 mass parts, respectively.
〔比較例１−１〕
一方向炭素繊維シート（Ａ１）を使用せず、短繊維束（Ａ２）及び熱硬化性樹脂組成物Ｂａの含有量を、熱硬化性シート状成形材料１００質量部に対して、それぞれ５０質量部及び５０質量部とした以外は、実施例１−１と同様にして、比較例１−１の熱硬化性シート状成形材料（Ａ２Ｂ層のみからなる）を得た。
[Comparative Example 1-1]
Without using the unidirectional carbon fiber sheet (A1), the content of the short fiber bundle (A2) and the thermosetting resin composition Ba is 50 parts by mass with respect to 100 parts by mass of the thermosetting sheet-shaped molding material. And except having set it as 50 mass parts, it carried out similarly to Example 1-1, and obtained the thermosetting sheet-like molding material (it consists only of A2B layer) of the comparative example 1-1.
〔比較例２−１〕
Ａ２Ｂ層ではなくＡ１Ｂ層を対向させて重ね合せたこと以外は、実施例１−１と同様にして、比較例２−１の熱硬化性シート状成形材料（Ａ２Ｂ層が積層方向の両側の最外に位置する）を得た。
[Comparative Example 2-1]
The thermosetting sheet-shaped molding material of Comparative Example 2-1 (the A2B layer was the most on both sides in the stacking direction) was the same as Example 1-1 except that the A1B layer was opposed to each other instead of the A2B layer. Located outside).
＜繊維強化プラスチックの製造及び機械的強度の評価＞
実施例１−１、２−１及び比較例１−１、２−１で得られた熱硬化性シート状成形材料を成形品寸法が３００ｍｍ×３００ｍｍとなる金型に置き、金型温度１４０℃、成形圧力１５ＭＰａ及び成形時間１８０秒の条件で加熱・加圧して硬化させ、それぞれ厚さ２ｍｍ×３００ｍｍ×３００ｍｍの平板形状の繊維強化プラスチックを得た。
<Manufacture of fiber reinforced plastic and evaluation of mechanical strength>
The thermosetting sheet-like molding materials obtained in Examples 1-1 and 2-1 and Comparative Examples 1-1 and 2-1 were placed in a mold having a molded product size of 300 mm × 300 mm, and the mold temperature was 140 ° C. Then, it was cured by heating and pressing under conditions of a molding pressure of 15 MPa and a molding time of 180 seconds to obtain flat fiber-reinforced plastics each having a thickness of 2 mm × 300 mm × 300 mm.
得られた平板形状の繊維強化プラスチックから長さ１００ｍｍ及び幅１５ｍｍの試験片を切出した。ここでは、試験片の長さ方向と、一方向炭素繊維シートの繊維の配向方向とが同一になるように試験片を切出した。得られた試験片を、オートグラフＡＧ−Ｘｐｌｕｓ（株式会社島津製作所製）を用いてＪＩＳ Ｋ ７０７４に準じ、試験速度５ｍｍ／分、支点間距離８０ｍｍの条件で、２３℃の温度条件下で試験を実施した。試験片の数はｎ＝１０とし、曲げ強さ及び曲げ弾性率の平均値を算出した。実施例及び比較例それぞれの結果を表２に示す。 A test piece having a length of 100 mm and a width of 15 mm was cut out from the obtained flat fiber reinforced plastic. Here, the test piece was cut out so that the length direction of the test piece and the orientation direction of the fibers of the unidirectional carbon fiber sheet were the same. The obtained test piece was tested under a temperature condition of 23 ° C. using an autograph AG-Xplus (manufactured by Shimadzu Corporation) according to JIS K 7074 at a test speed of 5 mm / min and a fulcrum distance of 80 mm. Carried out. The number of test pieces was n = 10, and the average values of bending strength and bending elastic modulus were calculated. Table 2 shows the results of the examples and comparative examples.
＜熱硬化性シート状成形材料の作製−２＞
〔実施例１−２〕
ＳＭＣ製造装置を用いて、熱硬化性樹脂組成物Ｂａを上下キャリアフィルム（ポリプロピレン）に厚さが均一になるよう塗布した。
次いで、下側のキャリアフィルムにのみ一方向炭素繊維シート（目付重量１００ｇ／ｍ２）１枚を配置した。その一方向炭素繊維シート上に短繊維束（Ａ２）として２５ｍｍの長さに機械的に切断された炭素繊維トウを散布し、上側のキャリアフィルムで挟み込んで熱硬化性樹脂組成物を含浸させた。４０℃で２４時間熟成させた後、１６０×１４０ｍｍの大きさの成形材料を２枚切り出し、２枚の熱硬化性シート状成形材料の一方向炭素繊維シートの繊維の配向方向が同一になるようにＡ２Ｂ層同士を対向させて重ね合せて、図２に示されるような熱硬化性シート状成形材料（Ａ１Ｂ層が積層方向の両側の最外に位置する）として実施例１−２の熱硬化性シート状成形材料を得た。
<Preparation-2 of thermosetting sheet-like molding material>
[Example 1-2]
Using the SMC manufacturing apparatus, the thermosetting resin composition Ba was applied to the upper and lower carrier films (polypropylene) so as to have a uniform thickness.
Next, one unidirectional carbon fiber sheet (weight per unit area: 100 g / m 2 ) was disposed only on the lower carrier film. On the unidirectional carbon fiber sheet, carbon fiber tow mechanically cut to a length of 25 mm as a short fiber bundle (A2) was sprayed and sandwiched between upper carrier films to impregnate the thermosetting resin composition. . After aging at 40 ° C. for 24 hours, two 160 × 140 mm molding materials are cut out so that the orientation directions of the two unidirectional carbon fiber sheets of the two thermosetting sheet-like molding materials are the same. The A2B layers are laminated to face each other, and the thermosetting sheet-like molding material as shown in FIG. 2 (the A1B layer is located on the outermost side on both sides in the stacking direction) is thermoset of Example 1-2. Sheet-like molding material was obtained.
〔実施例２−２〕
一方向炭素繊維シート（目付重量１００ｇ／ｍ２）２枚を同一方向に重ねて目付重量を２００ｇ／ｍ２とした一方向炭素繊維シートを下側のキャリアフィルムにのみ配置したこと以外は、実施例１−２と同様にして、実施例２−２の熱硬化性シート状成形材料を得た。実施例２−１の熱硬化性シート状成形材料は、一方向炭素繊維シート（Ａ１）、短繊維束（Ａ２）及び熱硬化性樹脂組成物Ｂａの含有量が、熱硬化性シート状成形材料１００質量部に対して、それぞれ１０質量部、４０質量部及び５０質量部となるような条件で作製した。
[Example 2-2]
Except that two unidirectional carbon fiber sheets (weight per unit weight 100 g / m 2 ) were stacked in the same direction and the unidirectional carbon fiber sheet having a basis weight of 200 g / m 2 was arranged only on the lower carrier film. The thermosetting sheet-shaped molding material of Example 2-2 was obtained in the same manner as Example 1-2. In the thermosetting sheet-like molding material of Example 2-1, the contents of the unidirectional carbon fiber sheet (A1), the short fiber bundle (A2), and the thermosetting resin composition Ba are the thermosetting sheet-like molding materials. It produced on the conditions which became 10 mass parts, 40 mass parts, and 50 mass parts with respect to 100 mass parts, respectively.
〔比較例１−２〕
一方向炭素繊維シート（Ａ１）を使用せず、短繊維束（Ａ２）及び熱硬化性樹脂組成物Ｂａの含有量を、熱硬化性シート状成形材料１００質量部に対して、それぞれ５０質量部及び５０質量部とした以外は、実施例１−２と同様にして、比較例１−２の熱硬化性シート状成形材料（Ａ２Ｂ層のみからなる）を得た。
[Comparative Example 1-2]
Without using the unidirectional carbon fiber sheet (A1), the content of the short fiber bundle (A2) and the thermosetting resin composition Ba is 50 parts by mass with respect to 100 parts by mass of the thermosetting sheet-shaped molding material. And except having set it as 50 mass parts, it carried out similarly to Example 1-2, and obtained the thermosetting sheet-like molding material (it consists only of A2B layer) of the comparative example 1-2.
〔比較例２−２〕
Ａ２Ｂ層ではなくＡ１Ｂ層を対向させて重ね合せたこと以外は、実施例１−２と同様にして、比較例２−２の熱硬化性シート状成形材料（Ａ２Ｂ層が積層方向の両側の最外に位置する）を得た。
[Comparative Example 2-2]
The thermosetting sheet-shaped molding material of Comparative Example 2-2 (the A2B layer is the most on both sides in the stacking direction), as in Example 1-2, except that the A1B layer was opposed to each other instead of the A2B layer. Located outside).
＜繊維強化プラスチックの製造及び成形性の評価＞
実施例１−２、２−２及び比較例１−２、２−２で得られた熱硬化性シート状成形材料を、成形品形状が１７０×１５０ｍｍの曲面板形状にリブ及びボスが設けられたものとなる金型に置き、金型温度１４０℃、成形圧力１５ＭＰａ及び成形時間１８０秒の条件で加熱・加圧して硬化させ、それぞれ繊維強化プラスチックを得た。
<Manufacture of fiber-reinforced plastic and evaluation of formability>
The thermosetting sheet-like molding materials obtained in Examples 1-2 and 2-2 and Comparative Examples 1-2 and 2-2 are provided with ribs and bosses in a curved plate shape having a molded product shape of 170 × 150 mm. It was placed in a mold, and cured by heating and pressing under conditions of a mold temperature of 140 ° C., a molding pressure of 15 MPa, and a molding time of 180 seconds to obtain fiber reinforced plastics.
得られた繊維強化プラスチックのリブ及びボスに欠肉が無い場合を成形性良好（○）とし、欠肉がある場合を不良（×）とした。ここで、リブの形状は、長さ８０ｍｍ、最大高さ１７ｍｍ、リブ根本の幅３ｍｍ、リブ先端の幅２ｍｍであり、ボスの形状は、ボス根本の直径１２ｍｍ、ボス先端の直径８ｍｍ、高さ７ｍｍである。実施例及び比較例それぞれの結果を表２に示す。 The case where the obtained fiber reinforced plastic ribs and bosses did not have a lacking thickness was defined as good moldability (◯), and the case where there was a lacking thickness was judged as poor (x). Here, the rib has a length of 80 mm, a maximum height of 17 mm, a rib root width of 3 mm, and a rib tip width of 2 mm. A boss shape has a boss root diameter of 12 mm, a boss tip diameter of 8 mm, and a height. 7 mm. Table 2 shows the results of the examples and comparative examples.
上記表２から、実施例１及び２は、比較例１及び２と比較して、曲げ強さ及び曲げ弾性率が大幅に向上しており、また、リブやボスなどの三次元構造を有する複雑形状にも対応していることがわかる。 From Table 2 above, Examples 1 and 2 have significantly improved bending strength and bending elastic modulus compared to Comparative Examples 1 and 2, and have a complicated three-dimensional structure such as ribs and bosses. It turns out that it corresponds also to a shape.
１０ 一方向炭素繊維シートに熱硬化性樹脂組成物が含浸された層（Ａ１Ｂ層）、１１ 短繊維束に熱硬化性樹脂組成物が含浸された層（Ａ２Ｂ層）、１２ 熱硬化性シート状成形材料、１３ 上金型、１４ 下金型。 10 Layer (A1B layer) impregnated with thermosetting resin composition in unidirectional carbon fiber sheet, 11 Layer (A2B layer) impregnated thermosetting resin composition in short fiber bundle, 12 Thermosetting sheet Molding material, 13 upper mold, 14 lower mold.
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