JP2020050802A - Fiber-reinforced composite material and manufacturing method thereof - Google Patents
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Abstract
Description
本発明は繊維強化複合材料およびその製造方法に関する。 The present invention relates to a fiber-reinforced composite material and a method for producing the same.
繊維強化複合材料として、従来より、ウレタン樹脂液を長繊維に含浸させて、発泡させるとともに硬化させた長繊維強化ウレタン樹脂発泡体が知られている（特許文献１）。
非特許文献１には、硬質ウレタン樹脂発泡体をガラス長繊維で強化し、木材と同程度の比重および強度を実現した繊維強化複合材料が開示されている。この複合材料は吸水しにくいため、水中に設置される木製の建築資材の代替品として好適であり、例えば角落しに用いられる。
2. Description of the Related Art As a fiber-reinforced composite material, a long-fiber-reinforced urethane resin foam in which a long fiber is impregnated with a urethane resin liquid, foamed and cured is conventionally known (Patent Document 1).
Non-Patent Document 1 discloses a fiber-reinforced composite material in which a hard urethane resin foam is reinforced with long glass fibers to achieve specific gravity and strength comparable to wood. Since this composite material does not easily absorb water, it is suitable as a substitute for wooden building materials installed in water, and is used, for example, for dropping corners.
角落しは、水路の堰き止めに用いられる板状の部材であり、次の２種類に大別される。（１）水路に水が無い状態で設置される角落し。（２）水路に水が満たされている状態で設置される角落し。（１）としては、比重０．５または０．７４の合成木材からなる角落しが上市されている。（２）は水に浮きにくいことが要求されるため、比重０．７４の合成木材の外面にステンレス製の比重調整板を一体的に取り付けて総比重を１．００に調整した角落しが上市されている（非特許文献１）。 The angle drop is a plate-shaped member used for blocking a water channel, and is roughly classified into the following two types. (1) Drops that are installed without water in the waterways. (2) Corner drop installed when the waterway is full of water. As (1), a corner drop made of synthetic wood having a specific gravity of 0.5 or 0.74 is on the market. Since (2) is required to be difficult to float on water, a square drop with a specific gravity adjustment plate made of stainless steel integrally attached to the outer surface of synthetic wood with a specific gravity of 0.74 to adjust the total specific gravity to 1.00 is launched on the market. (Non-Patent Document 1).
前記（２）の角落しは、ステンレス製の比重調整板が露出しているため、錆が発生する可能性がある。
本発明は、水に浮きにくく、錆の発生を防止できる繊維強化複合材料の提供を目的とする。
Since the stainless steel specific gravity adjusting plate is exposed in the corner drop of the above (2), rust may be generated.
An object of the present invention is to provide a fiber-reinforced composite material that is less likely to float on water and can prevent rust.
本発明は以下の態様を有する。
［１］ 硬質ウレタン樹脂組成物の硬化物を含むマトリックスと、比重が２〜３のガラス長繊維とからなり、繊維体積含有率が１５〜３５体積％、比重が１〜２である、繊維強化複合材料。
［２］ 前記マトリックスが発泡体である、［１］の繊維強化複合材料。
［３］ 空隙率が０〜５０％である、［２］の繊維強化複合材料。
［４］ 水中に設置される建築資材用である、［１］〜［３］のいずれかの繊維強化複合材料。
［５］ 角落し用である、［１］〜［３］のいずれかの繊維強化複合材料。
［６］ ［１］の繊維強化複合材料を製造する方法であって、一方向に引きそろえたガラス長繊維に、硬質ウレタン樹脂組成物を含むマトリックス組成物を含浸させた未硬化物を、加熱して、前記硬質ウレタン樹脂組成物を硬化させる硬化工程を有する、繊維強化複合材料の製造方法。
［７］ ［２］の繊維強化複合材料を製造する方法であって、一方向に引きそろえたガラス長繊維に、硬質ウレタン樹脂組成物及び発泡剤を含むマトリックス組成物を含浸させた未硬化物を、加熱して、前記硬質ウレタン樹脂組成物中で発泡させるとともに前記硬質ウレタン樹脂組成物を硬化させる硬化工程を有する、繊維強化複合材料の製造方法。
［８］ 前記繊維強化複合材料の発泡倍率が２以下である、［７］の繊維強化複合材料の製造方法。
The present invention has the following aspects.
[1] A fiber reinforced material comprising a matrix containing a cured product of a hard urethane resin composition and glass long fibers having a specific gravity of 2 to 3, having a fiber volume content of 15 to 35% by volume and a specific gravity of 1 to 2. Composite materials.
[2] The fiber-reinforced composite material according to [1], wherein the matrix is a foam.
[3] The fiber-reinforced composite material according to [2], wherein the porosity is 0 to 50%.
[4] The fiber-reinforced composite material according to any one of [1] to [3], which is used for building materials installed in water.
[5] The fiber-reinforced composite material according to any one of [1] to [3], which is used for corner dropping.
[6] The method for producing a fiber-reinforced composite material according to [1], wherein an uncured material obtained by impregnating a uniaxially aligned glass long fiber with a matrix composition including a hard urethane resin composition is heated. And a curing step of curing the hard urethane resin composition.
[7] The method for producing a fiber-reinforced composite material according to [2], wherein an uncured product is obtained by impregnating a uniaxially aligned glass long fiber with a matrix composition containing a hard urethane resin composition and a foaming agent. Is heated to foam in the hard urethane resin composition and to cure the hard urethane resin composition, the method for producing a fiber-reinforced composite material.
[8] The method for producing a fiber-reinforced composite material according to [7], wherein the expansion ratio of the fiber-reinforced composite material is 2 or less.
本発明によれば、水に浮きにくく、錆の発生を防止できる繊維強化複合材料が得られる。 ADVANTAGE OF THE INVENTION According to this invention, it is hard to float in water and the fiber reinforced composite material which can prevent generation | occurrence | production of rust is obtained.
＜繊維強化複合材料＞
本実施形態の繊維強化複合材料は、ガラス長繊維とマトリックスとからなる複合材料である。
マトリックスは、繊維強化複合材料を構成するガラス長繊維以外の部分である。マトリックスは、硬質ウレタン樹脂組成物の硬化物を含む。マトリックスは硬質ウレタン樹脂組成物の硬化物と、発泡剤に由来する空隙とからなる発泡体が好ましい。マトリックスが、空隙を含まず、硬質ウレタン樹脂組成物の硬化物のみからなっていてもよい。
<Fiber reinforced composite material>
The fiber reinforced composite material of the present embodiment is a composite material composed of long glass fibers and a matrix.
The matrix is a portion other than the long glass fibers constituting the fiber-reinforced composite material. The matrix contains a cured product of the hard urethane resin composition. The matrix is preferably a foam comprising a cured product of the hard urethane resin composition and voids derived from a foaming agent. The matrix may be composed of only a cured product of the hard urethane resin composition without containing voids.
ガラス長繊維は、特に限定されず、繊維強化複合材料の分野で公知のガラス長繊維を使用できる。例えばガラスロービングが好適である。
ガラス長繊維の比重は２〜３が好ましく、２．５〜２．７がより好ましい。ガラス長繊維の比重の測定方法は後述する。
The long glass fiber is not particularly limited, and a long glass fiber known in the field of a fiber reinforced composite material can be used. For example, glass roving is suitable.
The specific gravity of the glass long fiber is preferably from 2 to 3, more preferably from 2.5 to 2.7. The measuring method of the specific gravity of the glass long fiber will be described later.
硬質ウレタン樹脂組成物は、特に限定されず、繊維強化複合材料の分野で公知の硬質ウレタン樹脂組成物を使用できる。
硬質ウレタン樹脂組成物は、ポリオール、触媒、ポリイソシアネート、整泡剤を少なくとも含む。その他の添加剤を含んでもよい。
硬質ウレタン樹脂組成物の比重は１．０〜１．３が好ましく、１．１５〜１．２がより好ましい。
The hard urethane resin composition is not particularly limited, and a known hard urethane resin composition in the field of a fiber-reinforced composite material can be used.
The hard urethane resin composition contains at least a polyol, a catalyst, a polyisocyanate, and a foam stabilizer. Other additives may be included.
The specific gravity of the hard urethane resin composition is preferably from 1.0 to 1.3, and more preferably from 1.15 to 1.2.
発泡剤は、特に限定されず、繊維強化複合材料の分野で公知のものを使用できる。
例えば水を用いることができる。
The foaming agent is not particularly limited, and those known in the field of fiber-reinforced composite materials can be used.
For example, water can be used.
繊維強化複合材料の比重は１以上であり、１．１以上が好ましい。繊維強化複合材料の比重が大きいほど水に沈みやすい。
マトリックスが空隙を含まないときに、繊維強化複合材料の比重は最大となる。したがって、繊維強化複合材料の比重の上限値は材料の比重によるが、現実的には、２以下が好ましく、１．６以下がより好ましい。繊維強化複合材料の比重の測定方法は後述する。
The specific gravity of the fiber reinforced composite material is 1 or more, preferably 1.1 or more. The higher the specific gravity of the fiber-reinforced composite material, the more easily it sinks in water.
When the matrix does not contain voids, the specific gravity of the fiber reinforced composite is maximized. Therefore, the upper limit of the specific gravity of the fiber-reinforced composite material depends on the specific gravity of the material, but is practically preferably 2 or less, more preferably 1.6 or less. The method for measuring the specific gravity of the fiber-reinforced composite material will be described later.
繊維強化複合材料の繊維体積含有率は１５〜３５体積％であり、２０〜３０体積％が好ましい。
繊維強化複合材料の繊維体積含有率が上記範囲内であると、空隙率が低く、比重が高く、曲げ強度および曲げ弾性率に優れた繊維強化複合材料が得られやすい。繊維強化複合材料の繊維体積含有率の測定方法は後述する。
The fiber volume content of the fiber-reinforced composite material is 15 to 35% by volume, preferably 20 to 30% by volume.
When the fiber volume content of the fiber reinforced composite material is within the above range, a porosity is low, the specific gravity is high, and the fiber reinforced composite material excellent in bending strength and flexural modulus is easily obtained. The method for measuring the fiber volume content of the fiber-reinforced composite material will be described later.
繊維強化複合材料の空隙率は０〜４０％が好ましく、０〜３０％がより好ましい。
繊維強化複合材料の空隙率が小さいほど水に沈みやすい。
繊維強化複合材料の空隙率の測定方法は後述する。
The porosity of the fiber-reinforced composite material is preferably from 0 to 40%, more preferably from 0 to 30%.
The smaller the porosity of the fiber-reinforced composite material is, the easier it is to sink in water.
The method for measuring the porosity of the fiber-reinforced composite material will be described later.
本実施形態の繊維強化複合材料は、比重が１〜２、好ましくは１．１〜１．６であり水に浮きにくいため、水中に設置される建築資材用の材料として好適である。
水中に設置される建築資材としては、水路に水が満たされている状態で設置される角落し等が挙げられる。
本実施形態の繊維強化複合材料は、水路に水が無い状態で設置される角落し用の材料としても使用できる。
本実施形態の繊維強化複合材料を用いた建築資材は、所望の形状に成形された繊維強化複合材料そのものであってもよく、さらに表面材、塗膜、把手等の任意の付属部材を設けたものでもよい。
The fiber reinforced composite material of the present embodiment has a specific gravity of 1 to 2, preferably 1.1 to 1.6 and is hard to float in water, and thus is suitable as a material for building materials to be installed in water.
Examples of the building material installed underwater include a corner drop installed when the waterway is filled with water.
The fiber reinforced composite material of the present embodiment can also be used as a corner dropping material that is installed without water in the water channel.
The building material using the fiber-reinforced composite material of the present embodiment may be the fiber-reinforced composite material itself formed into a desired shape, and further provided with a surface material, a coating film, an optional accessory such as a handle. It may be something.
＜繊維強化複合材料の製造方法＞
本実施形態の繊維強化複合材料は、一方向に引きそろえたガラス長繊維に、硬質ウレタン樹脂組成物を含むマトリックス組成物を含浸させた未硬化物を、加熱して硬質ウレタン樹脂組成物を硬化させる硬化工程を有する方法で製造できる。
マトリックスが発泡体である繊維強化複合材料は、マトリックス組成物に、硬質ウレタン樹脂組成物と発泡剤を含有させ、前記硬化工程において、硬質ウレタン樹脂組成物中で発泡させるとともに硬質ウレタン樹脂組成物を硬化させる方法で製造できる。
<Production method of fiber reinforced composite material>
The fiber-reinforced composite material of the present embodiment is obtained by heating an uncured material obtained by impregnating a matrix composition containing a hard urethane resin composition into glass long fibers aligned in one direction, and curing the hard urethane resin composition. It can be manufactured by a method having a curing step of
The fiber-reinforced composite material in which the matrix is a foam, the matrix composition contains a hard urethane resin composition and a foaming agent, and in the curing step, the hard urethane resin composition is foamed in the hard urethane resin composition. It can be manufactured by a curing method.
マトリックス組成物は、硬質ウレタン樹脂組成物の原料と、必要に応じて発泡剤を混合して調製できる。
ガラス長繊維にマトリックス組成物を含浸させる方法は、公知の方法で実施できる。例えば、ガラス長繊維にマトリックス組成物をふりかけ、２枚の板の間で揉んで含浸させる方法を用いることができる。
硬化工程は公知の方法で実施できる。例えば、加熱手段を備えた成形用通路に、ガラス長繊維にマトリックス組成物を含浸させた未硬化物を連続的に導入し、成形用通路内で加熱して硬化させる方法が好ましい。成形用通路において、加熱手段の後段に冷却手段を設けてもよい。成形用通路は筒状であり、成形用通路内の空間は、得ようとする繊維強化複合材料の断面形状に対応する形状の内面で囲まれている。成形用通路内に導入された未硬化物は、成形用通路の内面に沿う形状に賦形され、硬化物となって成形用通路の出口から連続的に排出される。得られた硬化物を所定の長さに切断して、繊維強化複合材料を得る。
The matrix composition can be prepared by mixing the raw material of the hard urethane resin composition and, if necessary, a blowing agent.
The method of impregnating the glass composition into the glass long fibers can be performed by a known method. For example, it is possible to use a method in which a matrix composition is sprinkled on long glass fibers and rubbed and impregnated between two plates.
The curing step can be performed by a known method. For example, a method in which an uncured material obtained by impregnating a matrix composition into long glass fibers is continuously introduced into a molding passage provided with a heating means, and the mixture is heated and cured in the molding passage is preferable. In the molding passage, a cooling means may be provided after the heating means. The molding passage is cylindrical, and the space in the molding passage is surrounded by an inner surface having a shape corresponding to the cross-sectional shape of the fiber-reinforced composite material to be obtained. The uncured material introduced into the molding passage is shaped into a shape along the inner surface of the molding passage, becomes a cured product, and is continuously discharged from the exit of the molding passage. The obtained cured product is cut into a predetermined length to obtain a fiber-reinforced composite material.
未硬化物に配合するガラス長繊維の量は、得ようとする繊維強化複合材料の繊維体積含有率が前記範囲となるように設計する。繊維強化複合材料の体積は、前記成形用通路の内面の形状と、前記硬化物を切断する長さによって決まる。 The amount of the long glass fiber to be added to the uncured product is designed so that the fiber volume content of the fiber-reinforced composite material to be obtained falls within the above range. The volume of the fiber-reinforced composite material is determined by the shape of the inner surface of the molding passage and the length of cutting the cured product.
未硬化物において、マトリックス組成物／ガラス長繊維の体積比は６０／４０〜８０／２０が好ましく、６５／３５〜７５／２５がより好ましい。マトリックス組成物の体積の比率が上記範囲の下限値以上であるとガラス繊維への樹脂の含浸性が良好となやすく、上限値以下であると繊維強化複合材料の繊維体積含有率を高めやすい。 In the uncured material, the volume ratio of the matrix composition / glass long fiber is preferably from 60/40 to 80/20, and more preferably from 65/35 to 75/25. When the volume ratio of the matrix composition is at least the lower limit of the above range, the impregnating property of the resin into the glass fiber is likely to be good, and when it is at most the upper limit, the fiber volume content of the fiber reinforced composite material is likely to be increased.
発泡剤の使用量は、少なすぎるとガラス繊維への樹脂の含浸性が不充分となりやすく、多すぎると空隙率が高くなり維強化複合材料の高比重化が不充分となる。発泡剤の含有量は、かかる不都合が生じない範囲に設定するのが好ましい。例えば、マトリックス組成物の総質量に対して、発泡剤の含有量は０．１〜０．５質量％が好ましく、０．１〜０．３質量％がより好ましい。 If the amount of the foaming agent is too small, the impregnating property of the resin into the glass fiber tends to be insufficient. If the amount is too large, the porosity increases and the specific gravity of the fiber-reinforced composite material becomes insufficient. The content of the foaming agent is preferably set in a range where such inconvenience does not occur. For example, the content of the foaming agent is preferably 0.1 to 0.5% by mass, more preferably 0.1 to 0.3% by mass, based on the total mass of the matrix composition.
繊維強化複合材料の発泡倍率は、２以下が好ましく、１．８以下がより好ましく、１．５９以下がさらに好ましい。発泡倍率の下限は１である。上記範囲の上限値以下であると、比重が１以上である繊維強化複合材料が得られやすい。
発泡倍率は未硬化物の組成によって調整できる。例えば、未硬化物中の発泡剤の含有量が少ないほど発泡倍率は低くなる。また発泡剤の含有量が同じであっても、繊維強化複合材料の単位体積当たりの、未硬化物の使用量（マトリックス組成物とガラス長繊維の合計量）を多くすれば、発泡剤に由来する空隙（気泡）が圧縮されて発泡倍率は低くなる。
発泡倍率の測定方法は後述する。
The expansion ratio of the fiber-reinforced composite material is preferably 2 or less, more preferably 1.8 or less, and still more preferably 1.59 or less. The lower limit of the expansion ratio is 1. When the specific gravity is not more than the upper limit of the above range, a fiber-reinforced composite material having a specific gravity of 1 or more is easily obtained.
The expansion ratio can be adjusted by the composition of the uncured product. For example, the lower the content of the blowing agent in the uncured product, the lower the expansion ratio. Even if the content of the foaming agent is the same, if the amount of the uncured material per unit volume of the fiber-reinforced composite material (the total amount of the matrix composition and the long glass fiber) increases, the The resulting voids (bubbles) are compressed and the expansion ratio decreases.
The method for measuring the expansion ratio will be described later.
本実施形態によれば、後述する実施例に示すように、繊維強化複合材料中のガラス長繊維及び硬質ウレタン樹脂組成物を増量し、発泡倍率を抑えることによって、繊維強化複合材料を高比重化できる。本実施形態の繊維強化複合材料を、水中に設置される建築資材に適用すれば、ステンレス製の比重調整板を取り付けなくても、総比重１．００以上を達成できるため、水に浮きにくく、錆の発生を防止できる。 According to the present embodiment, as shown in Examples described later, by increasing the amount of glass long fibers and the hard urethane resin composition in the fiber-reinforced composite material and suppressing the expansion ratio, the specific gravity of the fiber-reinforced composite material is increased. it can. If the fiber-reinforced composite material of the present embodiment is applied to a building material installed in water, a total specific gravity of 1.00 or more can be achieved without attaching a stainless steel specific gravity adjusting plate, so that it is difficult to float in water, Rust can be prevented.
また、繊維強化複合材料中のガラス長繊維を増量することで、繊維強化複合材料が高比重化するとともに、曲げ強度及び曲げ弾性率も向上する。水中に設置される建築資材の厚さは、耐水圧のために要求される曲げ応力及びたわみ率を満たすように設計するが、曲げ強度及び曲げ弾性率が向上すれば薄肉化を図ることができる。 Further, by increasing the amount of long glass fibers in the fiber-reinforced composite material, the specific gravity of the fiber-reinforced composite material is increased, and the bending strength and the bending elastic modulus are also improved. The thickness of building materials installed in water is designed to satisfy the bending stress and deflection required for water pressure resistance, but if the bending strength and the bending elastic modulus are improved, the thickness can be reduced. .
また、繊維強化複合材料の発泡倍率を抑えることで、繊維強化複合材料が高比重化するとともに、繊維強化複合材料の表面の巣穴を抑制できる。前記巣穴は、発泡によって生じた気体が表面から外部へ抜ける際に形成される穴を意味する。水中に設置される建築資材においては、表面に巣穴があると、泥、汚れ、水中生物(コケなど）等が付着しやすいため、目止めをして巣穴を埋める作業が必要となる。本実施形態によれば、後述する実施例に示されるように、繊維強化複合材料の巣穴が抑制されるため、目止め作業が軽減される、または不要となる。外観も向上する。 Further, by suppressing the expansion ratio of the fiber-reinforced composite material, the specific gravity of the fiber-reinforced composite material can be increased, and burrows on the surface of the fiber-reinforced composite material can be suppressed. The burrow means a hole formed when gas generated by foaming escapes from the surface to the outside. In the case of building materials installed in water, if there are burrows on the surface, mud, dirt, underwater creatures (moss, etc.) and the like are likely to adhere, and thus it is necessary to perform a work to seal and fill the burrows. According to the present embodiment, as shown in Examples described later, burrows of the fiber-reinforced composite material are suppressed, so that the filling operation is reduced or becomes unnecessary. The appearance also improves.
以下に実施例を用いて本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。
＜測定方法・評価方法＞
繊維強化複合材料の物性は以下の方法で測定した。
［発泡倍率］
測定対象の繊維強化複合材料の比重をｘ、非発泡の繊維強化複合材料の比重をｙとし、発泡倍率＝ｙ／ｘで求めた。
非発泡の繊維強化複合材料は、発泡剤を含まない以外は、測定対象の繊維強化複合材料と同じ条件で製造した繊維強化複合材料である。非発泡の繊維強化複合材料の比重は、測定対象の繊維強化複合材料を溶融したものからも測定できる。
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
<Measurement method / Evaluation method>
The physical properties of the fiber reinforced composite material were measured by the following methods.
[Expansion ratio]
The specific gravity of the fiber-reinforced composite material to be measured was x, the specific gravity of the non-foamed fiber-reinforced composite material was y, and the expansion ratio was determined as y / x.
The non-foamed fiber reinforced composite material is a fiber reinforced composite material manufactured under the same conditions as the fiber reinforced composite material to be measured, except that it does not contain a foaming agent. The specific gravity of the non-foamed fiber reinforced composite material can also be measured from the melted fiber reinforced composite material to be measured.
［空隙率］ 繊維強化複合材料の空隙率は、下記の計算式により算出した。
空隙率（単位：％）＝｛（発泡後の繊維強化複合材料の体積−発泡前の繊維強化複合材料の体積）／繊維強化複合材料の体積｝×１００
［繊維体積含有率］ 繊維強化複合材料の繊維体積含有率は下記の計算式により算出した。
繊維体積含有率（単位：体積％）＝（単位体積あたりの繊維体積／単位体積あたりの繊維強化複合材料の体積）×１００
［比重］ 繊維強化複合材料の比重はＪＩＳ Ｚ ２１０１（２００９年）に準じて測定した。
［曲げ強度］ 繊維強化複合材料の曲げ強度はＪＩＳ Ｚ ２１０１（２００９年）に準じて測定した。
［曲げ弾性率］ 繊維強化複合材料の曲げ弾性率はＪＩＳ Ｋ ７０１７（１９９９年）に準じて測定した。
[Porosity] The porosity of the fiber-reinforced composite material was calculated by the following formula.
Porosity (unit:%) = {(volume of fiber-reinforced composite material after foaming−volume of fiber-reinforced composite material before foaming) / volume of fiber-reinforced composite material} × 100
[Fiber volume content] The fiber volume content of the fiber reinforced composite material was calculated by the following formula.
Fiber volume content (unit: volume%) = (fiber volume per unit volume / volume of fiber reinforced composite material per unit volume) × 100
[Specific gravity] The specific gravity of the fiber-reinforced composite material was measured according to JIS Z 2101 (2009).
[Bending strength] The bending strength of the fiber-reinforced composite material was measured according to JIS Z 2101 (2009).
[Flexural Modulus] The flexural modulus of the fiber reinforced composite material was measured according to JIS K 7017 (1999).
［外観（巣穴）の評価］
繊維強化複合材料の外観は以下の方法で評価した。
繊維強化複合材料の表面を目視で観察し、任意の領域（縦、横いずれも１０ｃｍの領域）に存在する孔の数を計測し、以下の基準で評価した。
×：直径５ｍｍ以上の孔が５個以上存在する。
△：直径５ｍｍ以上の孔が１個以上５個未満存在する。
〇：直径５ｍｍ以上の孔は存在しない。直径５ｍｍ未満の孔が１個以上存在する。
◎：直径５ｍｍ以上の孔、直径５ｍｍ未満の孔のいずれも存在しない。
[Evaluation of appearance (burrow)]
The appearance of the fiber reinforced composite material was evaluated by the following method.
The surface of the fiber-reinforced composite material was visually observed, and the number of holes existing in an arbitrary region (a region of 10 cm in both length and width) was measured and evaluated according to the following criteria.
×: Five or more holes having a diameter of 5 mm or more are present.
Δ: One or more and less than 5 holes with a diameter of 5 mm or more are present.
〇: There is no hole having a diameter of 5 mm or more. There is one or more holes having a diameter of less than 5 mm.
A: Neither a hole having a diameter of 5 mm or more nor a hole having a diameter of less than 5 mm is present.
＜マトリックス組成物の原料＞
ポリオール（比重１．１００）、触媒（比重１．０５０）、整泡剤（比重１．０５２）、ポリイソシアネート（比重１．２３０）、発泡剤（水、比重１．０００）。
＜ガラス長繊維＞
ガラスロービング（比重２．６００）。
<Raw materials for matrix composition>
Polyol (specific gravity 1.100), catalyst (specific gravity 1.050), foam stabilizer (specific gravity 1.052), polyisocyanate (specific gravity 1.230), foaming agent (water, specific gravity 1.000).
<Glass long fiber>
Glass roving (specific gravity 2.600).
＜角落し（繊維強化複合材料）の製造方法＞
所定量のガラス長繊維に、所定量のマトリックス組成物を含浸させた未硬化物を、加熱および冷却して角落しを製造した。角落しの、繊維の長さ方向に垂直な断面形状は幅が２４０ｍｍの矩形とし、厚みは３０ｍｍ、４０ｍｍ、５０ｍｍの３通りとした。
具体的には、一方向に引きそろえたガラス長繊維にマトリックス組成物をふりかけ、２枚の板の間で揉んで含浸させて未硬化物を得た。未硬化物を成形用通路に連続的に導入し、成形用通路内で加熱して、マトリックス組成物中の発泡剤を発泡させるともに硬質ウレタン樹脂組成物を硬化させた。その後冷却して長尺の硬化物を得た。成形用通路の内面形状は、目的の角落しの断面形状に対応させた。成形用通路の出口から排出される長尺の硬化物を、所定の長さに切断して角落しを得た。
<Manufacturing method of angle drop (fiber reinforced composite material)>
An uncured product obtained by impregnating a predetermined amount of a long glass fiber with a predetermined amount of a matrix composition was heated and cooled to produce a corner drop. The cross section of the cut corners perpendicular to the fiber length direction was a rectangle having a width of 240 mm and three thicknesses of 30 mm, 40 mm, and 50 mm.
Specifically, the matrix composition was sprinkled on the glass long fibers aligned in one direction, rubbed and impregnated between two plates to obtain an uncured product. The uncured product was continuously introduced into the molding passage, and heated in the molding passage to foam the foaming agent in the matrix composition and to cure the hard urethane resin composition. Thereafter, the mixture was cooled to obtain a long cured product. The shape of the inner surface of the molding passage was made to correspond to the cross-sectional shape of the desired angle drop. The long cured product discharged from the outlet of the molding passage was cut into a predetermined length to obtain a square drop.
（実施例１〜６、比較例１）
表１に示す原料を混合してマトリックス組成物を得た。
表２に示す条件で未硬化物を作製し、上記の方法で角落しを製造した。
製造した角落しのうち、断面形状が４０ｍｍ×２４０ｍｍである角落しについて、表２に示す項目を上記の方法で測定又は評価した。結果を表２に示す（以下、同様）。
(Examples 1 to 6, Comparative Example 1)
The raw materials shown in Table 1 were mixed to obtain a matrix composition.
An uncured product was prepared under the conditions shown in Table 2, and a square drop was manufactured by the above method.
Among the manufactured corner cuts, for the corner cut having a cross-sectional shape of 40 mm × 240 mm, the items shown in Table 2 were measured or evaluated by the above method. The results are shown in Table 2 (the same applies hereinafter).
表２の結果に示されるように、実施例１〜６の角落しは、従来品に相当する比較例１よりも発泡倍率が低く、空隙率が低く、繊維体積含有率が高く、比重が高い。
実施例１〜６の角落しは、ステンレス製の比重調整板を取り付けなくても、総比重１．００以上を達成できるため、水に浮きにくく、錆の発生を防止できる。
また、実施例１〜６の角落しは、比較例１に比べて曲げ強度、曲げ弾性率、及び外観（巣穴抑制）が向上した。
As shown in the results of Table 2, the squares of Examples 1 to 6 have lower expansion ratio, lower porosity, higher fiber volume content, and higher specific gravity than Comparative Example 1 corresponding to the conventional product. .
The corner drop of Examples 1 to 6 can achieve a total specific gravity of 1.00 or more without attaching a specific gravity adjusting plate made of stainless steel, so that it is difficult to float on water, and generation of rust can be prevented.
Moreover, the corner drop of Examples 1-6 improved the bending strength, the bending elastic modulus, and the appearance (burrow suppression) as compared with Comparative Example 1.
Claims (8)
一方向に引きそろえたガラス長繊維に、硬質ウレタン樹脂組成物を含むマトリックス組成物を含浸させた未硬化物を、加熱して、前記硬質ウレタン樹脂組成物を硬化させる硬化工程を有する、繊維強化複合材料の製造方法。 A method for producing the fiber-reinforced composite material according to claim 1,
A fiber-reinforced fiber comprising a hardening step of heating an uncured material obtained by impregnating a matrix composition containing a hard urethane resin composition into glass long fibers aligned in one direction and heating the hard urethane resin composition. Manufacturing method of composite material.
一方向に引きそろえたガラス長繊維に、硬質ウレタン樹脂組成物及び発泡剤を含むマトリックス組成物を含浸させた未硬化物を、加熱して、前記硬質ウレタン樹脂組成物中で発泡させるとともに前記硬質ウレタン樹脂組成物を硬化させる硬化工程を有する、繊維強化複合材料の製造方法。 A method for producing a fiber-reinforced composite material according to claim 2, wherein
An uncured product obtained by impregnating a matrix composition containing a hard urethane resin composition and a foaming agent into glass long fibers aligned in one direction is heated to foam the hard urethane resin composition in the hard urethane resin composition, and A method for producing a fiber-reinforced composite material, comprising a curing step of curing a urethane resin composition.
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|---|---|---|---|---|
| JPS5784826A (en) * | 1980-11-17 | 1982-05-27 | Nisshinbo Ind Inc | Light frp and manufacture thereof |
| JPH09328738A (en) * | 1996-06-11 | 1997-12-22 | Sekisui Chem Co Ltd | Water channel shut-off and close plate |
| JPH10296863A (en) * | 1997-04-22 | 1998-11-10 | Sekisui Chem Co Ltd | Fiber-reinforced resin molded item |
| JP2003041013A (en) * | 2001-07-25 | 2003-02-13 | Sekisui Chem Co Ltd | Fiber-reinforced resin molded article and method for producing the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5784826A (en) * | 1980-11-17 | 1982-05-27 | Nisshinbo Ind Inc | Light frp and manufacture thereof |
| JPH09328738A (en) * | 1996-06-11 | 1997-12-22 | Sekisui Chem Co Ltd | Water channel shut-off and close plate |
| JPH10296863A (en) * | 1997-04-22 | 1998-11-10 | Sekisui Chem Co Ltd | Fiber-reinforced resin molded item |
| JP2003041013A (en) * | 2001-07-25 | 2003-02-13 | Sekisui Chem Co Ltd | Fiber-reinforced resin molded article and method for producing the same |
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