JP2005089706A - Blackish-colored fiber-reinforced resin composition - Google Patents
Blackish-colored fiber-reinforced resin composition Download PDFInfo
- Publication number
- JP2005089706A JP2005089706A JP2003328513A JP2003328513A JP2005089706A JP 2005089706 A JP2005089706 A JP 2005089706A JP 2003328513 A JP2003328513 A JP 2003328513A JP 2003328513 A JP2003328513 A JP 2003328513A JP 2005089706 A JP2005089706 A JP 2005089706A
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- Prior art keywords
- fiber
- resin composition
- component
- reinforced resin
- fiber reinforced
- 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.)
- Granted
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- 150000002978 peroxides Chemical class 0.000 description 1
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- 239000002685 polymerization catalyst Substances 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、維強化樹脂組成物およびそれから得られる成形品、例えば、自動車部品（フロントエンド、ファンシェラウド、クーリングファン、エンジンアンダーカバー、エンジンカバー、ラジエターボックス、サイドドア、バックドアインナー、バックドアアウター、外板、ルーフレール、ドアハンドル、ラゲージボックス、ホイールカバー、ハンドル、クーリングモジュール）、二輪・自転車部品（ラゲージボックス、ハンドル、ホイール）、住宅関連部品（温水洗浄弁座部品、浴室部品、椅子の脚、バルブ類、メーターボックス）、その他（電動工具部品、草刈り機ハンドル、ホースジョイント）に関する。 The present invention relates to a fiber reinforced resin composition and a molded article obtained therefrom, for example, automobile parts (front end, fan sheroud, cooling fan, engine under cover, engine cover, radiator box, side door, back door inner, back door outer. , Outer panels, roof rails, door handles, luggage boxes, wheel covers, handles, cooling modules), motorcycle and bicycle parts (luggage boxes, handles, wheels), housing-related parts (hot water cleaning valve seat parts, bathroom parts, chair legs , Valves, meter boxes) and others (power tool parts, mower handles, hose joints).
特に黒系着色の多い自動車部品（外装の一部であるルーフレール・ラゲージボックス、エンジンルームを開けた際すぐに目に付くフロントエンド・ファンシェラウド・エンジンカバー・クーリングモジュール）、その他、ハンドル類（トラクターハンドル、ドアハンドル・草刈り機ハンドル）に好適な黒系着色されている繊維強化樹脂組成物に関する。 Car parts with a lot of black coloration (roof rails / luggage boxes that are part of the exterior, front end, fan shroud, engine cover, cooling module that can be seen immediately when the engine room is opened), and other handles (tractors) The present invention relates to a fiber-reinforced resin composition colored in black suitable for a handle, a door handle, or a mower handle).
繊維強化樹脂組成物は、金属やエンジニアリングプラスチックの代替製品用の素材として従来から用いられている。また、強度部品、特に自動車部品用途の部品は、耐候性を付与すること、透けて見えなくすること、厚薄により外観が損なわれたり、強化繊維が表面に露出し外観が損なわれたりする見た目の外観異状を低減させることなどの目的で黒、あるいは灰色に着色して使用する場合が多い。 The fiber reinforced resin composition has been conventionally used as a material for an alternative product of metal or engineering plastic. In addition, strength parts, especially parts for automotive parts, have the appearance of imparting weather resistance, making them transparent and invisible, the appearance of the parts being damaged by the thickness, and the appearance of the reinforcing fibers being exposed to the surface. In many cases, it is used by coloring it in black or gray for the purpose of reducing the appearance abnormality.
成形品を着色することを目的として顔料をポリオレフィン樹脂に配合し成形する場合、顔料のモース硬度がガラス繊維のそれより高い場合、繊維強化樹脂の強度が落ちることが特許文献１に開示されている。また、カーボンブラックは比較的モース硬度が小さく、モース硬度の観点からは強度低下しないものと考えられるが、実際はモース硬度の小さいカーボンブラックを使用しても強度低下を起こす。特許文献１には、特定の粒子径を有するカーボンブラックを使用することでガラスの破断を防ぐ例が記載されているが、その有効性は限定されている。 Patent Document 1 discloses that when a pigment is blended with a polyolefin resin for the purpose of coloring a molded article and molded, if the Mohs hardness of the pigment is higher than that of glass fiber, the strength of the fiber reinforced resin decreases. . Carbon black has a relatively small Mohs hardness, and it is considered that the strength does not decrease from the viewpoint of the Mohs hardness. However, even if carbon black having a small Mohs hardness is used, the strength is actually decreased. Patent Document 1 describes an example of preventing glass breakage by using carbon black having a specific particle diameter, but its effectiveness is limited.
通常、着色用に使用されているカーボンブラックは、樹脂に対する親和性、分散性を増大させるために揮発分の多い（通常３％以上）のものが使用されている。その様なカーボンブラックを用いて繊維強化樹脂組成物の着色を行うと着色をしていないものに比較して、強度が低下する傾向があることが知られている（例えば、特許文献２参照）。 Usually, carbon black used for coloring has a high volatile content (usually 3% or more) in order to increase the affinity and dispersibility for the resin. It is known that when such a carbon black is used to color a fiber reinforced resin composition, the strength tends to decrease as compared to a case where the fiber reinforced resin composition is not colored (for example, see Patent Document 2). .
揮発分の少ないカーボンブラックは、カーボンブラック表面に存在している含酸素官能基の数が少ない。含酸素官能基が多い場合、ポリマーとの相互作用が生じ、補強性、カーボンブラックの分散性が増すことが期待でき、通常の着色用には含酸素官能基が多いカーボンブラックが使用させている。しかしがら、この含酸素官能基は強化繊維と樹脂との相互作用を阻害するものと推定され、そのために強化繊維と樹脂との接着強度が低下し、繊維強化樹脂組成物の強度低下を引き起こすものと推定される。 Carbon black with a low volatile content has a small number of oxygen-containing functional groups present on the surface of the carbon black. When there are many oxygen-containing functional groups, interaction with the polymer occurs, and it can be expected that the reinforcing property and the dispersibility of carbon black will increase. Carbon black with many oxygen-containing functional groups is used for normal coloring. . However, it is presumed that this oxygen-containing functional group inhibits the interaction between the reinforcing fiber and the resin, and as a result, the adhesive strength between the reinforcing fiber and the resin is lowered and the strength of the fiber-reinforced resin composition is reduced. It is estimated to be.
本発明は、黒系着色による物性低下が抑えられた、自動車部品などの高い強度が要求される部品などを製造するのに好適な、黒系着色された繊維強化樹脂組成物およびそれからなる成形品を提供することを目的とする。 The present invention relates to a black-colored fiber-reinforced resin composition suitable for producing parts requiring high strength, such as automobile parts, in which deterioration in physical properties due to black-based coloring is suppressed, and a molded article comprising the same The purpose is to provide.
上記目的を達成するため、本発明者らは繊維の破断以外の理由で物性が低下していないかを鋭意検討したところ、揮発物（カーボンブラック表面の官能基量に対応）の影響が極めて重要であり、繊維強化樹脂組成物を黒系着色するために用いるカーボンブラックの揮発分を低く抑えることによって、黒系着色による繊維強化樹脂組成物の物性低下が抑制できることを見出し本発明を完成させた。 In order to achieve the above object, the present inventors diligently examined whether the physical properties have deteriorated for reasons other than fiber breakage, and the influence of volatile matter (corresponding to the amount of functional groups on the carbon black surface) is extremely important. It was found that by suppressing the volatile content of carbon black used for black-coloring the fiber-reinforced resin composition to a low level, it was possible to suppress deterioration in physical properties of the fiber-reinforced resin composition due to black-based coloring. .
本発明の第１の態様は、下記成分
（Ａ）ポリオレフィン樹脂
（Ｂ）酸変性ポリオレフィン樹脂
（Ｃ）強化繊維
（Ｄ）カーボンブラック
を含み、
成分（Ａ）＋（Ｂ）：（Ｃ）＝１０〜９５：９０〜５（質量比）の範囲であり、かつ、
成分（Ｄ）が０．０５〜１０．０質量％の範囲で含まれる繊維強化樹脂組成物であって、
成分（Ｄ）カーボンブラックの、９５０℃、７分間熱したときの揮発分が３質量％以下であることを特徴とする繊維強化樹脂組成物を提供する。
The first aspect of the present invention includes the following component (A) polyolefin resin (B) acid-modified polyolefin resin (C) reinforcing fiber (D) carbon black,
Component (A) + (B) :( C) = 10 to 95:90 to 5 (mass ratio), and
A fiber reinforced resin composition containing component (D) in a range of 0.05 to 10.0% by mass,
Provided is a fiber-reinforced resin composition characterized in that the volatile content of component (D) carbon black when heated at 950 ° C. for 7 minutes is 3% by mass or less.
本発明の第２の態様は、上記第１の態様の繊維強化樹脂組成物からなる成形品を提供する。 The second aspect of the present invention provides a molded article comprising the fiber-reinforced resin composition of the first aspect.
本発明によれば、引張り強度や曲げ強度などの機械強度が改善され、かつそれらの保持率も改善された、黒系着色された繊維強化樹脂組成物およびそれからなる成形品を提供することができる。また、振動疲労強度が飛躍的に改善された。 According to the present invention, it is possible to provide a black-based colored fiber reinforced resin composition having improved mechanical strength such as tensile strength and bending strength, and improved retention thereof, and a molded article comprising the same. . In addition, vibration fatigue strength has been dramatically improved.
以下、本発明を詳細に説明する。
本発明の第１の態様である、繊維強化樹脂組成物（以下、本発明の繊維強化樹脂組成物という）は、下記成分
（Ａ）ポリオレフィン樹脂
（Ｂ）酸変性ポリオレフィン樹脂
（Ｃ）強化繊維
（Ｄ）カーボンブラック
を含み、
成分（Ａ）＋（Ｂ）：（Ｃ）＝１０〜９５：９０〜５（質量比）の範囲であり、かつ、
成分（Ｄ）が０．０５〜１０．０質量％の範囲で含まれる繊維強化樹脂組成物であって、
成分（Ｄ）カーボンブラックの、９５０℃、７分間熱したときの揮発分が３質量％以下であることを特徴とする。
Hereinafter, the present invention will be described in detail.
The fiber reinforced resin composition (hereinafter referred to as the fiber reinforced resin composition of the present invention), which is the first aspect of the present invention, has the following components (A) polyolefin resin (B) acid-modified polyolefin resin (C) reinforced fiber ( D) including carbon black,
Component (A) + (B) :( C) = 10 to 95:90 to 5 (mass ratio), and
A fiber reinforced resin composition containing component (D) in a range of 0.05 to 10.0% by mass,
The component (D) carbon black has a volatile content of 3% by mass or less when heated at 950 ° C. for 7 minutes.
本発明の繊維強化樹脂組成物は、揮発分が３質量％以下、好ましくは１質量％以下、より好ましくは０．５質量％以下である上記成分（Ｄ）カーボンブラックを用いることに特徴がある。カーボンブラックの揮発分が３質量％を超えると、繊維強化樹脂組成物の補強効果が得られない。 The fiber reinforced resin composition of the present invention is characterized by using the above component (D) carbon black having a volatile content of 3% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less. . When the volatile content of carbon black exceeds 3% by mass, the reinforcing effect of the fiber reinforced resin composition cannot be obtained.
カーボンブラックの揮発分は、水分を除去したカーボンブラックをるつぼに入れ、９５０℃で７分間加熱したときの質量の減少量を測定し、加熱前の質量に基づいて算出する。 The volatile matter of the carbon black is calculated based on the mass before heating by measuring the amount of decrease in mass when the carbon black from which moisture has been removed is placed in a crucible and heated at 950 ° C. for 7 minutes.
上記揮発分３質量％以下のカーボンブラックを得る方法としては、例えば、カーボンブラックを不活性雰囲気下で２０００℃以上の温度で加熱する方法が挙げられるが、これに限定されるものではない。 Examples of a method for obtaining carbon black having a volatile content of 3% by mass or less include a method in which carbon black is heated at a temperature of 2000 ° C. or higher in an inert atmosphere, but is not limited thereto.
成分（Ｄ）カーボンブラックの官能基の表面密度指数は、０．０３以下が好ましく、０．０１５以下がより好ましく、０．０１以下が特に好ましい。ここで、官能基の表面密度指数は、次式によって求められる。
官能基の表面密度指数＝揮発分／窒素吸着比表面積
The surface density index of the functional group of component (D) carbon black is preferably 0.03 or less, more preferably 0.015 or less, and particularly preferably 0.01 or less. Here, the surface density index of the functional group is obtained by the following equation.
Surface density index of functional group = volatile matter / nitrogen adsorption specific surface area
窒素吸着比表面積は、カーボンブラックの細孔を含む全表面積を表し、ＪＩＳ Ｋ ６２１７−１９９７に準拠して求められる。 The nitrogen adsorption specific surface area represents the total surface area including pores of carbon black, and is determined according to JIS K 6217-1997.
官能基の表面密度指数は、カーボンブラックの表面に存在する官能基の量を示し、この量が多いと、カーボンブラックの表面の官能基の密度が高く、官能基が多く存在すると、酸変性ポリオレフィン樹脂と繊維表面との結合が阻害され好ましくないと思われる。なお、カーボンブラック表面に存在する官能基は、カルボキシル基、水酸基、カルボニル基などであり、１００〜１０００℃で揮発すると言われている。 The surface density index of the functional group indicates the amount of the functional group present on the surface of the carbon black. When this amount is large, the density of the functional group on the surface of the carbon black is high. The binding between the resin and the fiber surface is hindered, which seems undesirable. In addition, the functional group which exists in the carbon black surface is a carboxyl group, a hydroxyl group, a carbonyl group, etc., and it is said that it volatilizes at 100-1000 degreeC.
成分（Ｄ）カーボンブラックの配合量は、０．０５〜１０．０質量％、好ましくは０．１〜５．０質量％、より好ましくは０．６〜３．０質量％の範囲である。０．０５質量％未満では、繊維強化樹脂組成物の黒系着色が不十分となり、１０．０質量％を超えて添加してもそれ以上の効果は得られず、経済的でない。 The amount of component (D) carbon black is 0.05 to 10.0% by mass, preferably 0.1 to 5.0% by mass, more preferably 0.6 to 3.0% by mass. If it is less than 0.05% by mass, the black coloration of the fiber reinforced resin composition becomes insufficient, and even if it is added in excess of 10.0% by mass, no further effect is obtained, which is not economical.
本発明で用いるカーボンブラックは特に限定されないが、オイルファーネスブラックか黒鉛化カーボンが好ましく黒鉛化カーボンであることが特に好ましい。揮発分が３質量％以下のカーボンブラックとして、市販のものを用いることができる。好ましい市販品としては、例えば、トーカブラック＃３８５５、トーカブラック＃３８００、トーカブラック＃８３００（東海カーボン(株)製）、三菱カーボンブラック＃９００（三菱化学(株)製）などが挙げられる。 The carbon black used in the present invention is not particularly limited, but oil furnace black or graphitized carbon is preferable, and graphitized carbon is particularly preferable. A commercially available carbon black having a volatile content of 3% by mass or less can be used. Examples of preferable commercial products include Toka Black # 3855, Toka Black # 3800, Toka Black # 8300 (manufactured by Tokai Carbon Co., Ltd.), Mitsubishi Carbon Black # 900 (manufactured by Mitsubishi Chemical Corporation), and the like.
カーボンブラックは、一次粒子径が１０〜８０ｎｍのものが好ましく、１０〜３０ｎｍのものが特に好ましい。一次粒子径は、電子顕微鏡を用い、カーボンブラック凝集体を構成する球状成分２，０００〜５，０００個を測定して求める。
カーボンブラックのＤＢＰ吸着量は、２０〜１２０ｃｍ３／１００ｇのものが好ましく、４０〜７０ｃｍ３／１００ｇのものが特に好ましい。ＤＢＰ吸着量は、ＪＩＳ Ｋ ６２１７−１９９７に基づいて測定する。
カーボンブラックのｐＨは、５以上であることが好ましく、８以上であることが特に好ましい。ｐＨは、カーボンブラックと蒸留水の混合液をガラス電極メーターで測定する。
The carbon black preferably has a primary particle diameter of 10 to 80 nm, particularly preferably 10 to 30 nm. The primary particle size is determined by measuring 2,000 to 5,000 spherical components constituting the carbon black aggregate using an electron microscope.
DBP adsorption amount of carbon black is preferably one of 20~120cm 3 / 100g, particularly preferably from 40~70cm 3 / 100g. The DBP adsorption amount is measured based on JIS K 6217-1997.
The pH of carbon black is preferably 5 or more, and particularly preferably 8 or more. The pH is measured using a glass electrode meter with a mixture of carbon black and distilled water.
なお、カーボンブラックは、カーボンブラック単体で用いてもよいが、カーボンブラック樹脂組成物の形態で用いる方が好ましい。カーボンブラック樹脂組成物としては、例えば、カーボンブラックおよびその他の顔料、染料、添加剤を含むポリオレフィン樹脂組成物（例えば、カーボンブラック含量：１０〜５０質量％）などが挙げられる。カーボンブラックの分散性向上の為には、ポリオレフィン系ワックス、特にポリプロピレン系ワックスを含むものが好ましい。 Carbon black may be used alone, but is preferably used in the form of a carbon black resin composition. Examples of the carbon black resin composition include a polyolefin resin composition containing carbon black and other pigments, dyes, and additives (for example, carbon black content: 10 to 50% by mass). In order to improve the dispersibility of carbon black, those containing polyolefin wax, particularly polypropylene wax are preferred.
カーボンブラック樹脂組成物は、カーボンブラックと上記成分を、例えば、二軸押出機やバンバリーミキサーなどに入れて溶融混練し、ペレット状にして用いるのが好ましい。 The carbon black resin composition is preferably used by making carbon black and the above components melted and kneaded in a twin-screw extruder, a Banbury mixer or the like, and pelletized.
本発明の繊維強化樹脂組成物で用いられる成分（Ａ）ポリオレフィン樹脂としては、ポリプロピレン、低密度ポリエチレン、エチレン−α−オレフィン（例えば、１−ブテン、１−ヘキセン、１−オクテン、１−デセンなど）共重合体、高密度ポリエチレンなどが挙げられ、ポリプロピレンが好ましい。 Examples of the component (A) polyolefin resin used in the fiber reinforced resin composition of the present invention include polypropylene, low-density polyethylene, ethylene-α-olefin (for example, 1-butene, 1-hexene, 1-octene, 1-decene, etc. ) Copolymers, high density polyethylene and the like, and polypropylene is preferable.
ポリプロピレン種としては、プロピレン単独重合体、プロピレンランダム共重合体（例えば、プロピレン・エチレンランダム共重合体）、プロピレンブロック共重合体（例えば、プロピレン・エチレンブロック共重合体）などが挙げられ、適当な市販品を用いることもできる。好ましい市販品としては、例えば、Ｊ−３０００ＧＰ（ホモポリプロピレン；出光石油化学(株)製）、Ｊ−６０８３ＨＰ（プロピレンブロック共重合体；出光石油化学(株)製）などが挙げられる。 Examples of the polypropylene species include propylene homopolymer, propylene random copolymer (for example, propylene / ethylene random copolymer), propylene block copolymer (for example, propylene / ethylene block copolymer), and the like. Commercial products can also be used. Examples of preferable commercial products include J-3000GP (homopolypropylene; manufactured by Idemitsu Petrochemical Co., Ltd.), J-6083HP (propylene block copolymer; manufactured by Idemitsu Petrochemical Co., Ltd.), and the like.
成分（Ａ）ポリオレフィン樹脂として用いるポリプロピレンのメルトフローレート（ＭＦＲ）は、好ましくは１〜６００ｇ／１０分、より好ましくは６０〜３００ｇ／１０分、さらに好ましくは１００〜２００ｇ／１０分（ＪＩＳ Ｋ ７２１０−１９９９に準拠し、温度２３０℃、荷重２．１６ｋｇの条件で測定）である。ＭＦＲが１ｇ／１０分以下であると成形体中の強化繊維の分散性が低下し、成形体の外観不良が見られることがあり、ＭＦＲが６００ｇ/１０分より大きいと、衝撃強度が低下するため好ましくない。 The melt flow rate (MFR) of polypropylene used as the component (A) polyolefin resin is preferably 1 to 600 g / 10 minutes, more preferably 60 to 300 g / 10 minutes, still more preferably 100 to 200 g / 10 minutes (JIS K 7210). -Measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg in accordance with 1999. When the MFR is 1 g / 10 min or less, the dispersibility of the reinforcing fibers in the molded body is lowered, and the appearance of the molded body may be deteriorated. When the MFR is larger than 600 g / 10 min, the impact strength is lowered. Therefore, it is not preferable.
ポリプロピレンの立体規則性指標は、好ましくは８５％以上、より好ましくは９５％以上である。ここで、ポリプロピレンの立体規則性指標は、１３Ｃ−ＮＭＲ測定による。すなわち、ＮＭＲ試料管にポリプロピレン試料２２０ｍｇを採取し、これに１，２，４−トリクロロベンゼン／重ベンゼン混合溶媒（容量比９０／１０）３ｍＬを加えた後、キャップをして１３０℃で均一に溶解後、１３Ｃ−ＮＭＲの測定を次に示す測定条件で行う。 The stereoregularity index of polypropylene is preferably 85% or more, more preferably 95% or more. Here, the stereoregularity index of polypropylene is based on 13 C-NMR measurement. Specifically, 220 mg of a polypropylene sample was collected in an NMR sample tube, and 3 mL of 1,2,4-trichlorobenzene / heavy benzene mixed solvent (volume ratio 90/10) was added thereto, and then the cap was capped and uniformly applied at 130 ° C. After dissolution, 13 C-NMR measurement is performed under the following measurement conditions.
装置：ＪＮＭ−ＥＸ４００（日本電子(株)製）
パルス幅：９μｓ（４５°）
パルス繰り返し時間：４秒
スペクトル幅：２００００Ｈｚ
測定温度：１３０℃
積算回数：１０００〜１００００回
Device: JNM-EX400 (manufactured by JEOL Ltd.)
Pulse width: 9μs (45 °)
Pulse repetition time: 4 seconds Spectral width: 20000 Hz
Measurement temperature: 130 ° C
Integration count: 1000-10000 times
上記特性を有するポリプロピレンは、特開平１１−７１４３１号公報、特開２００２−２４９６２４号公報に記載の公知の重合方法を用いて製造することができる。プロピレン重合体は、重合用触媒を用いてプロピレンなどをスラリー重合、気相重合、或いは、液相塊状重合することにより製造されるものであり、前記プロピレン重合体を製造する重合方式としては、バッチ重合、連続重合のどちらの方式も採用することができる。 Polypropylene having the above characteristics can be produced using a known polymerization method described in JP-A Nos. 11-71431 and 2002-249624. The propylene polymer is produced by slurry polymerization, gas phase polymerization, or liquid phase bulk polymerization of propylene or the like using a polymerization catalyst. As a polymerization method for producing the propylene polymer, batches are used. Either polymerization or continuous polymerization can be employed.
成分（Ａ）ポリオレフィン樹脂として用いるポリプロピレンの分子量（Ｍｗ）は、通常１０，０００〜６００，０００、好ましくは５０，０００〜３００，０００であり、ポリプロピレンの分子量は、特開２００２−２２６５１０号公報に記載のように水素添加量などで調整することができる。 Component (A) The molecular weight (Mw) of polypropylene used as the polyolefin resin is usually 10,000 to 600,000, preferably 50,000 to 300,000. The molecular weight of polypropylene is described in JP-A No. 2002-226510. It can be adjusted by the amount of hydrogenation as described.
本発明の繊維強化樹脂組成物で用いられる成分（Ｂ）酸変性ポリオレフィン樹脂とは、分子中にカルボキシル基や無水カルボン酸基を有するポリオレフィン樹脂であり、ポリプロピレンを不飽和カルボン酸またはその誘導体で変性したものが好ましい。変性方法としては、グラフト変性や共重合化を用いることができる。 The component (B) acid-modified polyolefin resin used in the fiber-reinforced resin composition of the present invention is a polyolefin resin having a carboxyl group or a carboxylic anhydride group in the molecule, and the polypropylene is modified with an unsaturated carboxylic acid or a derivative thereof. Is preferred. As the modification method, graft modification or copolymerization can be used.
変性に用いる不飽和カルボン酸としては、例えば、アクリル酸、メタクリル酸、マレイン酸、ナジック酸、フマル酸、イタコン酸、クロトン酸、シトラコン酸、ソルビン酸、メサコン酸、アンゲリカ酸などが挙げられる。またその誘導体としては、酸無水物、エステル、アミド、イミド、金属塩などが挙げられ、具体的には、例えば、無水マレイン酸、無水イタコン酸、無水シトラコン酸、無水ナジック酸、アクリル酸メチル、メタクル酸メチル、アクリル酸エチル、アクリル酸ブチル、マレイン酸モノエチルエステル、アクリルアミド、マレイン酸モノアミド、マレイミド、Ｎ−ブチルマレイミド、アクリル酸ナトリウム、メタクリル酸ナトリウムなどが挙げられる。これらの中でも、不飽和ジカルボン酸、およびその誘導体が好ましく、特に無水マレイン酸または無水フタル酸が好適である。 Examples of the unsaturated carboxylic acid used for modification include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, and angelic acid. Examples of the derivative include acid anhydrides, esters, amides, imides, metal salts, and the like. Specifically, for example, maleic anhydride, itaconic anhydride, citraconic anhydride, nadic anhydride, methyl acrylate, Examples include methyl methacrylate, ethyl acrylate, butyl acrylate, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, maleimide, N-butylmaleimide, sodium acrylate, and sodium methacrylate. Among these, unsaturated dicarboxylic acids and derivatives thereof are preferable, and maleic anhydride or phthalic anhydride is particularly preferable.
カルボン酸付加量は、好ましくは０．１〜１４質量％、より好ましくは、０．６〜８質量％である。酸付加量は、以下の方法で測定する。
（ｉ）ドデシルコハク酸と濃度調整用のポリプロピレンパウダーＨ７００（商品名；出光石油化学(株)製）を用いて、ピーク面積とマレイン酸量との関係式を算出して検量線とする。
（ii）試料から、２３０℃の熱プレスにより、１０分加熱後、４分間加圧（５ＭＰａ）、冷却プレスにより３分間加圧（５ＭＰａ）を行い、厚みが０．１ｍｍ程度のフィルムを作成する。
（iii）このフィルムをメチルエチルケトン（ＭＥＫ）にて６５℃、３時間洗浄後、１１０℃、２時間真空乾燥する。
（iv）乾燥後２時間以内に、フィルムのＦＴ−ＩＲ透過スペクトルを測定し、ＦＴ−ＩＲスペクトルの１６７０〜１８１０ｃｍ−１のピーク面積を計算し、（ｉ）の検量線と比較してマレイン酸付加量を求める。
The carboxylic acid addition amount is preferably 0.1 to 14% by mass, and more preferably 0.6 to 8% by mass. The acid addition amount is measured by the following method.
(I) Using dodecyl succinic acid and polypropylene powder H700 for adjusting the concentration (trade name; manufactured by Idemitsu Petrochemical Co., Ltd.), a relational expression between the peak area and the amount of maleic acid is calculated and used as a calibration curve.
(Ii) From the sample, heat for 10 minutes at 230 ° C., then pressurize for 4 minutes (5 MPa), and pressurize for 3 minutes (5 MPa) with a cooling press to create a film with a thickness of about 0.1 mm. .
(Iii) This film is washed with methyl ethyl ketone (MEK) at 65 ° C. for 3 hours and then vacuum-dried at 110 ° C. for 2 hours.
(Iv) Within 2 hours after drying, the FT-IR transmission spectrum of the film was measured, the peak area of 1670-1810 cm −1 of the FT-IR spectrum was calculated, and maleic acid was compared with the calibration curve of (i) Find the additional amount.
変性化は、本発明の繊維強化樹脂組成物の製造に先立って予め行ってもよいし、繊維強化樹脂組成物製造の際の溶融混練過程において行ってもよい。繊維強化樹脂組成物の製造に先立って予め行った場合は、繊維強化樹脂ペレットを作製するときに、成分（Ａ）ポリオレフィン樹脂に、成分（Ｂ）酸変性ポリオレフィン樹脂を適量添加する。 The modification may be performed in advance prior to the production of the fiber reinforced resin composition of the present invention, or may be performed in the melt-kneading process during the production of the fiber reinforced resin composition. When it is performed in advance prior to the production of the fiber reinforced resin composition, an appropriate amount of the component (B) acid-modified polyolefin resin is added to the component (A) polyolefin resin when the fiber reinforced resin pellet is produced.
成分（Ｂ）酸変性ポリオレフィン樹脂は、成分（Ａ）ポリオレフィン樹脂に対し、好ましくは０．５〜５０質量％、より好ましくは１〜１０質量％添加する。 The component (B) acid-modified polyolefin resin is preferably added in an amount of 0.5 to 50 mass%, more preferably 1 to 10 mass%, relative to the component (A) polyolefin resin.
変性化を溶融混練過程で行う場合は、ポリオレフィン樹脂と不飽和カルボン酸を、有機過酸化物の存在下、押出機中で混練することにより、不飽和カルボン酸をグラフト共重合することによって酸変性を行う。上記有機過酸化物としては、例えば、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、アゾビスイソブチロニトリル、ジクミルパーオキサイド、ｔ−ブチルヒドロパーオキサイド、α，α’−ビス（ｔ−ブチルパーオキシジイソプロピル）ベンゼン、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３、ジ−ｔ−ブチルパーオキサイド、クメンヒドロパーオキサイド、ｔ−ブチルヒドロパーオキサイドなどを用いることができる。 When the modification is performed in the melt-kneading process, the polyolefin resin and the unsaturated carboxylic acid are kneaded in an extruder in the presence of an organic peroxide, and the acid modification is performed by graft copolymerization of the unsaturated carboxylic acid. I do. Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, dicumyl peroxide, t-butyl hydroperoxide, α, α′-bis (t-butylperoxydiisopropyl). ) Benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, di-t-butyl Peroxide, cumene hydroperoxide, t-butyl hydroperoxide and the like can be used.
成分（Ｂ）酸変性ポリオレフィン樹脂のＭＦＲ（前記の方法で測定）は、５〜８００ｇ／１０分であることが好ましい。酸変性ポリオレフィン樹脂のＭＦＲが５ｇ／１０分より低いと、成分（ｃ）強化繊維の分散不良を起こしやすく、８００ｇ／１０分より高いと、耐衝撃強度が低下する場合があり、好ましくない。 The MFR (measured by the above method) of the component (B) acid-modified polyolefin resin is preferably 5 to 800 g / 10 minutes. When the MFR of the acid-modified polyolefin resin is lower than 5 g / 10 minutes, the component (c) reinforcing fiber tends to be poorly dispersed. When the MFR is higher than 800 g / 10 minutes, the impact strength may be lowered, which is not preferable.
成分（Ｂ）酸変性ポリオレフィン樹脂の結晶化温度（Ｔｃ）は、好ましくは９０〜１２５℃であり、より好ましくは１１０〜１２０℃の範囲である。 The crystallization temperature (Tc) of the component (B) acid-modified polyolefin resin is preferably 90 to 125 ° C, more preferably 110 to 120 ° C.
成分（Ｂ）酸変性ポリオレフィン樹脂の極限粘度は、好ましくは０．４〜１．６ｄＬ／ｇ、より好ましくは０．５〜０．８ｄＬ／ｇの範囲である。 The intrinsic viscosity of the component (B) acid-modified polyolefin resin is preferably 0.4 to 1.6 dL / g, more preferably 0.5 to 0.8 dL / g.
本発明の繊維強化樹脂組成物で用いられる成分（Ｃ）強化繊維としては、ガラス繊維、炭素繊維などの無機繊維、シリコン繊維、シリコン・チタン・炭素繊維、ボロン繊維、鉄、チタンなどの金属繊維、アラミド繊維、ポリエステル繊維、ポリアミド繊維、ビニロンなどの有機合成繊維、絹、綿、麻などの天然繊維など、公知のものを幅広く用いることができる。これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。補強効果および、入手の容易性からガラス繊維、炭素繊維が好ましく、ガラス繊維が特に好ましい。 Component (C) reinforcing fibers used in the fiber reinforced resin composition of the present invention include inorganic fibers such as glass fibers and carbon fibers, metal fibers such as silicon fibers, silicon / titanium / carbon fibers, boron fibers, iron and titanium. A wide variety of known materials such as organic synthetic fibers such as aramid fiber, polyester fiber, polyamide fiber and vinylon, and natural fibers such as silk, cotton and hemp can be used. These may be used alone or in combination of two or more. Glass fiber and carbon fiber are preferable from the viewpoint of reinforcing effect and availability, and glass fiber is particularly preferable.
ガラス繊維としては、Ｅガラス（Electrical glass）、Ｃガラス（Chemical glass）、Ａガラス（Alkali glass）、Ｓガラス（High strength glass）および耐アルカリガラスなどのガラスを溶融紡糸してフィラメント状の繊維にしたものを挙げることができる。 Glass fibers such as E glass (Electrical glass), C glass (Chemical glass), A glass (Alkali glass), S glass (High strength glass), and alkali-resistant glass are melt-spun into filamentous fibers. Can be mentioned.
ガラス長繊維の原料としては、連続状ガラス繊維束が用いられ、これはガラスロービングとして市販されている。通常、その平均繊維径は４〜３０μｍ、フィラメント集束本数は４００〜１０，０００本、およびテックス番手は３００〜２０，０００ｇ／ｋｍであるが、平均繊維径９〜２３μｍ、集束本数２，０００〜８，０００本のものが好ましい。 A continuous glass fiber bundle is used as a raw material for the long glass fiber, which is commercially available as glass roving. Usually, the average fiber diameter is 4 to 30 μm, the filament focusing number is 400 to 10,000, and the tex count is 300 to 20,000 g / km, but the average fiber diameter is 9 to 23 μm and the focusing number is 2,000 to 2,000. 8,000 are preferred.
成分（Ｃ）強化繊維の繊維径は、好ましくは３〜３０μｍであり、更に好ましくは８〜２０μｍである。繊維径が過小であると、繊維が破損しやすいため、強化繊維束の生産性が低下することがあり、また繊維強化樹脂ペレットを連続製造するときに、繊維を多数本束ねなければならなくなり、繊維束をつなぐ手間が煩雑となったり生産性が低下するため好ましくない。また、好ましいペレット長が決まっていることから繊維径が過大であると、繊維のアスペクト比が低下することとなり、補強効果が充分発揮されなくなることがあることから好ましくない。 The fiber diameter of the component (C) reinforcing fiber is preferably 3 to 30 μm, and more preferably 8 to 20 μm. If the fiber diameter is too small, the fiber is likely to break, so the productivity of the reinforced fiber bundle may decrease, and when continuously producing fiber reinforced resin pellets, many fibers must be bundled, This is not preferable because the labor for connecting the fiber bundles becomes complicated and the productivity is lowered. Moreover, since the preferable pellet length is determined, if the fiber diameter is excessive, the aspect ratio of the fiber is lowered, and the reinforcing effect may not be sufficiently exhibited, which is not preferable.
成分（Ｃ）強化繊維は、その少なくとも一部が樹脂成分中で互いに略平行に並んでいる形態を有することが好ましい。このような形態のものは、一般にアスペクト比が高く、物性（曲げ強度、引張り強度）が高くなるため、本発明の効果が顕著に現れる。 The component (C) reinforcing fiber preferably has a form in which at least a part thereof is arranged substantially in parallel with each other in the resin component. Such a form generally has a high aspect ratio and high physical properties (bending strength and tensile strength), so that the effects of the present invention are remarkably exhibited.
本発明の繊維強化樹脂組成物中のガラス繊維の繊維長は、好ましくは０．１〜２００ｍｍ、好ましくは４〜１２ｎｍである。 The fiber length of the glass fiber in the fiber reinforced resin composition of this invention becomes like this. Preferably it is 0.1-200 mm, Preferably it is 4-12 nm.
その他、ガラス繊維として、ガラスチョップドストランドを用いることもできる。チョップドストランドとしては、長さが通常３〜５０ｍｍ、繊維径が３〜２５μｍ程度、好ましくは８〜１４μｍのものである。 In addition, a glass chopped strand can be used as the glass fiber. The chopped strand has a length of usually 3 to 50 mm and a fiber diameter of about 3 to 25 μm, preferably 8 to 14 μm.
成分（Ａ）ポリオレフィン樹脂および成分（Ｂ）酸変性ポリオレフィン樹脂との界面接着性付与または向上のため、成分（Ｃ）強化繊維は、表面処理（例えば、シランカップリング剤処理）が施されているものが好ましい。このような処理のされた強化繊維を用いると、強度と外観が良好な成形体を得ることができる。 In order to impart or improve the interfacial adhesion between the component (A) polyolefin resin and the component (B) acid-modified polyolefin resin, the component (C) reinforcing fiber is subjected to surface treatment (for example, silane coupling agent treatment). Those are preferred. By using such treated reinforcing fibers, it is possible to obtain a molded article having good strength and appearance.
成分（Ｃ）強化繊維の表面処理剤としては、いわゆるシラン系カップリング剤、チタン系カップリング剤として従来公知のものを用いることができる。シラン系化合物としては、例えば、γ−アミノプロピルトリエトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシランビニルトリエトキシシラン、ビニル−トリス（β−メトキシエトキシ）シラン、γ−メタクリロキシプロピルトリメトキシシラン、β−（２，４−エポキシシクロヘキシル）エトキシメトキシシラン、γ−（２−アミノエチル）アミノプロピルトリメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシランなどのアミノシランやエポキシシランを用いることができ、特に、アミノ系シラン化合物が好ましい。 As the surface treatment agent for the component (C) reinforcing fiber, a conventionally known one can be used as a so-called silane coupling agent or titanium coupling agent. Examples of the silane compound include γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (2,4-epoxycyclohexyl) ethoxymethoxysilane, γ- (2 -Aminoethyl) aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, and other aminosilanes and epoxysilanes can be used, and amino-based silane compounds are particularly preferable.
本発明の繊維強化樹脂組成物において、成分（Ａ）ポリオレフィン樹脂および成分（Ｂ）酸変性ポリオレフィン樹脂の合計量と、成分（Ｃ）強化繊維との質量比（成分（Ａ）＋（Ｂ）：成分（Ｃ））は、１０〜９５：９０〜５である。成分（Ｃ）強化繊維の配合量が少なすぎると、樹脂を強化する機能が十分でなく、剛性、強度の向上が不十分であり、多すぎると、強化繊維の樹脂成分への分散性が低下する。 In the fiber reinforced resin composition of the present invention, the mass ratio of the total amount of component (A) polyolefin resin and component (B) acid-modified polyolefin resin to component (C) reinforced fiber (component (A) + (B): Component (C)) is 10-95: 90-5. If the amount of the component (C) reinforcing fiber is too small, the function of reinforcing the resin is not sufficient, and the improvement of rigidity and strength is insufficient, and if too much, the dispersibility of the reinforcing fiber in the resin component is lowered. To do.
次に、本発明の繊維強化樹脂組成物の製造方法を説明する。
カーボンブラックまたはカーボンブラック樹脂組成物は、本発明の繊維強化樹脂組成物を製造する際に直接添加・混合してもよいし、成分（Ａ）〜（Ｃ）からなる繊維強化樹脂ペレットを予め製造しておき、これにカーボンブラックまたはカーボンブラック樹脂組成物を添加・混合してもよい。さらに、射出成形品を製造する際に、繊維強化樹脂ペレットとカーボンブラック樹脂組成物をブレンドして射出成形品を製造してもよい。
Next, the manufacturing method of the fiber reinforced resin composition of this invention is demonstrated.
Carbon black or carbon black resin composition may be added or mixed directly when producing the fiber reinforced resin composition of the present invention, or fiber reinforced resin pellets comprising components (A) to (C) are produced in advance. In addition, carbon black or a carbon black resin composition may be added to and mixed with this. Furthermore, when producing an injection molded product, the fiber reinforced resin pellet and the carbon black resin composition may be blended to produce an injection molded product.
上記成分（Ａ）〜（Ｃ）からなる繊維強化樹脂ペレットは、数千本からなる前記強化繊維のロービングを含浸ダイスに導き、フィラメント間に溶融した樹脂成分（成分（Ａ）および（Ｂ））を均一に含浸させた後、所望の長さ（２〜２００ｍｍ）に切断することにより製造できる。具体的には、例えば、押出機先端に設けられた含浸ダイス中に、押出機より溶融した樹脂成分を供給する一方、連続状ガラス繊維束を溶融樹脂中に通過させ、該ガラス繊維束に該溶融樹脂を含浸させたのちノズルを通して引抜き、２〜５０ｍｍの長さにペレタイズする。 The fiber reinforced resin pellets composed of the above components (A) to (C) are resin components (components (A) and (B)) melted between the filaments by guiding the roving of the above-mentioned thousands of reinforcing fibers to an impregnation die. Can be produced by uniformly impregnating and then cutting to a desired length (2 to 200 mm). Specifically, for example, a resin component melted from the extruder is supplied into an impregnation die provided at the tip of the extruder, while a continuous glass fiber bundle is passed through the molten resin, and the glass fiber bundle After impregnating the molten resin, the resin is drawn through a nozzle and pelletized to a length of 2 to 50 mm.
ポリオレフィン樹脂、不飽和カルボン酸もしくはその無水物、有機過酸化物をドライブレンドして押出機のホッパーに投入し、ポリオレフィン樹脂の酸変性も同時に行いながら、ガラス繊維束を供給する方法も取り得る。 A method of supplying a glass fiber bundle while dry-blending a polyolefin resin, an unsaturated carboxylic acid or an anhydride thereof, and an organic peroxide and putting it into a hopper of an extruder and simultaneously performing acid modification of the polyolefin resin can be taken.
強化繊維のロービングに樹脂成分を含浸させるための方法としては、特に制限はなく、ロービングを樹脂粉体流動床に通した後、樹脂の融点以上に加熱する方法（特公昭５２−３９８５号公報）、強化繊維のロービングをポリオレフィン樹脂粉体流動層中に通して、これにポリオレフィン樹脂粉体を付着させた後、ポリオレフィン樹脂の融点以上に加熱してポリオレフィン樹脂を含浸させる方法（特公昭５２−３９８５号公報）、クロスヘッドダイを用いて強化繊維のロービングに溶融したポリオレフィン樹脂を含浸させる方法（特開昭６２−６０６２５号公報、特開昭６３−１３２０３６号公報、特開昭６３−２６４３２６号公報、特開平１−２０８１１８号公報）、ポリオレフィン樹脂繊維と強化繊維のロービングとを混繊した後、樹脂の融点以上に加熱して樹脂を含浸させる方法（特開昭６１−１１８２３５号公報）、ダイ内部に複数のロッドを配置し、これにロービングをじぐざぐ状に巻き掛けて開繊させ、溶融樹脂を含浸させる方法（特開平１０−２６４１５２号公報）など、何れの方法も用いることができる。 The method for impregnating the reinforcing fiber roving with the resin component is not particularly limited, and is a method in which the roving is passed through the resin powder fluidized bed and heated to the melting point of the resin or higher (Japanese Patent Publication No. 52-3985). A method of passing a reinforcing fiber roving through a polyolefin resin powder fluidized bed, adhering the polyolefin resin powder to the fluidized bed, and then impregnating the polyolefin resin by heating above the melting point of the polyolefin resin (Japanese Patent Publication No. 52-3985). And a method of impregnating a molten polyolefin resin into a reinforcing fiber roving using a crosshead die (Japanese Patent Laid-Open Nos. 62-60625, 63-1332036, and 63-264326). JP-A-1-208118), polyolefin resin fibers and reinforcing fiber rovings are mixed, and then the resin A method of impregnating a resin by heating above the melting point (Japanese Patent Laid-Open No. Sho 61-118235), arranging a plurality of rods inside the die, winding them around in a roving manner, and opening the molten resin Any method such as a method of impregnation (JP-A-10-264152) can be used.
上記の他、樹脂を溶融する過程において、２以上のフィード部を持つ押出機を使用し、トップフィードから樹脂と樹脂の分解剤（ポリプロピレン系樹脂の場合有機過酸化物が好ましい）を、サイドフィードから別の樹脂を投入する製造方法も使用できる。また、樹脂を溶融する過程において、２台以上の押出機（押出し部）を使用し、そのうち１台以上の押出機には樹脂と樹脂の分解剤（ポリプロピレン系樹脂の場合有機過酸化物が好ましい）を投入する製造方法も使用できる。 In addition to the above, in the process of melting the resin, an extruder having two or more feed parts is used, and a resin and a resin decomposing agent (an organic peroxide is preferable in the case of polypropylene resin) from the top feed, side feed. A manufacturing method in which another resin is charged can also be used. In the process of melting the resin, two or more extruders (extruding sections) are used, and one or more of the extruders is preferably a resin and a resin decomposing agent (in the case of polypropylene resin, an organic peroxide is preferable). ) Can also be used.
上記各種の製造方法において、少なくとも１個所の押出機に樹脂（ポリプロピレン系樹脂など）、不飽和カルボン酸およびその誘導体、分解剤および／または架橋剤（ポリプロピレン系樹脂の場合有機過酸化物が好ましい）を投入する製造方法も使用できる。 In the above various production methods, at least one extruder is provided with resin (polypropylene resin, etc.), unsaturated carboxylic acid and derivatives thereof, decomposition agent and / or crosslinking agent (in the case of polypropylene resin, organic peroxide is preferred). The manufacturing method which throws in can also be used.
さらに、短繊維強化樹脂ペレットを製造するには、上記各成分を所定の割合にてロールミル、バンバリーミキサー、ニーダーなどでよく混練分散させ、一軸押出機、二軸押出機などで混練してペレット状とする。各成分は、タンブラー式ブレンダー、ヘンシェルミキサー、リボンミキサーなどを用いてドライブレンドしてもよい。 Furthermore, in order to produce short fiber reinforced resin pellets, the above components are well kneaded and dispersed at a predetermined ratio using a roll mill, a Banbury mixer, a kneader, etc., and then kneaded with a single screw extruder, twin screw extruder or the like to form a pellet. And Each component may be dry blended using a tumbler blender, a Henschel mixer, a ribbon mixer, or the like.
繊維強化樹脂ペレットの形状は、特に制限されないが、ペレット状が好ましい。繊維強化樹脂ペレットのペレット長は通常２〜２００ｍｍの範囲である。繊維長が短かすぎると、剛性、耐熱性および衝撃強度の改善効果が十分でなく、反り変形も大きくなる場合があり、また、ペレット長が長すぎると成形が困難となる場合がある。ペレット長は３〜１００ｍｍの範囲が好ましく、５〜１１ｍｍの範囲であるのがより好ましく、６〜１０ｍｍの範囲であるのがさらに好ましい。 The shape of the fiber reinforced resin pellet is not particularly limited, but a pellet shape is preferable. The pellet length of the fiber reinforced resin pellet is usually in the range of 2 to 200 mm. If the fiber length is too short, the effect of improving rigidity, heat resistance and impact strength may not be sufficient, warpage deformation may increase, and if the pellet length is too long, molding may be difficult. The pellet length is preferably in the range of 3 to 100 mm, more preferably in the range of 5 to 11 mm, and still more preferably in the range of 6 to 10 mm.
本発明の繊維強化樹脂組成物には、用途に応じて各種の添加剤、例えば、分散剤、滑剤、可塑剤、難燃剤、酸化防止剤（フェノール系酸化防止剤、リン酸化防止剤、イオウ系酸化防止剤）、帯電防止剤、光安定剤、紫外線吸収剤、結晶化促進剤（増核剤）、発泡剤、架橋剤、抗菌剤などの改質用添加剤、顔料、染料などの着色剤、酸化チタン、ベンガラ、アゾ顔料、アントラキノン顔料、フタロシアニン、タルク、炭酸カルシウム、マイカ、クレーなどの粒子状充填剤、ワラストナイトなどの短繊維状充填剤、チタン酸カリウムなどのウィスカーなどの公知の添加剤を添加することができる。 The fiber reinforced resin composition of the present invention has various additives depending on applications, such as dispersants, lubricants, plasticizers, flame retardants, antioxidants (phenolic antioxidants, phosphoric antioxidants, sulfur series). Antioxidants), antistatic agents, light stabilizers, UV absorbers, crystallization accelerators (nucleating agents), foaming agents, cross-linking agents, modifying additives such as antibacterial agents, colorants such as pigments and dyes , Titanium oxide, bengara, azo pigments, anthraquinone pigments, particulate fillers such as phthalocyanine, talc, calcium carbonate, mica, clay, short fiber fillers such as wollastonite, whiskers such as potassium titanate, etc. Additives can be added.
本発明の繊維強化樹脂組成物は、引張り強度が１４０ＭＰａ以上であり、かつ、成分（Ｄ）カーボンブラックを含まない、成分（Ａ）、（Ｂ）および（Ｃ）からなる繊維強化樹脂組成物と比較した引張り強度の保持率が９０％以上であり、また、曲げ強度が２２０ＭＰａ以上であり、かつ、成分（Ｄ）カーボンブラックを含まない、成分（Ａ）、（Ｂ）および（Ｃ）からなる繊維強化樹脂組成物と比較した曲げ強度の保持率が９０％以上である。本発明の繊維強化樹脂組成物は、従来問題とされていたカーボンブラックを添加することによる強度低下が非常に少なく、黒系着色が必要とされ、同時に強度を要求される用途に使用できる。 The fiber reinforced resin composition of the present invention has a tensile strength of 140 MPa or more and a fiber reinforced resin composition comprising components (A), (B), and (C) that does not contain component (D) carbon black. The tensile strength retention compared is 90% or higher, the bending strength is 220 MPa or higher, and the component (D) does not contain carbon black, and consists of components (A), (B), and (C). The retention rate of bending strength compared with the fiber reinforced resin composition is 90% or more. The fiber reinforced resin composition of the present invention can be used for applications where strength reduction due to the addition of carbon black, which has been regarded as a problem in the past, is very small, black coloration is required, and strength is required at the same time.
次に、本発明の第２の態様である、上記本発明の繊維強化樹脂組成物からなる成形品（以下、本発明の成形品という）について説明する。 Next, a molded product made of the fiber-reinforced resin composition of the present invention (hereinafter referred to as the molded product of the present invention), which is the second aspect of the present invention, will be described.
本発明の成形品の成形方法は、射出成形法、押出成形法、中空成形法、圧縮成形法、射出圧縮成形法，ガス注入射出成形、または発泡射出成形などの公知の成形法をなんら制限なく適用できる。特に射出成形法、圧縮成形法および射出圧縮成形法が好ましい。 The molding method of the molded product of the present invention is not limited to a known molding method such as an injection molding method, an extrusion molding method, a hollow molding method, a compression molding method, an injection compression molding method, a gas injection injection molding, or a foam injection molding. Applicable. In particular, an injection molding method, a compression molding method, and an injection compression molding method are preferable.
本発明の成形品の成形に際し、必要に応じて希釈材（ポリオレフィン樹脂など）を添加することができる。希釈材の配合比率については、繊維強化樹脂組成物（ペレット）中の強化繊維含有量と、最終成形品に求められる強化繊維含有量とによって決まってくるが、剛性、耐衝撃性、耐久性の改良効果の点から、２０〜８５質量％の範囲であることが好ましい。 When molding the molded article of the present invention, a diluent (polyolefin resin or the like) can be added as necessary. The blending ratio of the diluent is determined by the reinforcing fiber content in the fiber reinforced resin composition (pellet) and the reinforcing fiber content required for the final molded product, but it has rigidity, impact resistance, and durability. From the viewpoint of the improvement effect, it is preferably in the range of 20 to 85% by mass.
繊維強化樹脂組成物（ペレット）と希釈材との配合は、ドライブレンド方式が好ましい。繊維強化樹脂組成物中の繊維長を保持し、より高い剛性、耐衝撃性、耐久性の改良効果を得るためには、ドライブレンド後は押出機を通さず、直接射出成形機などの成形機に供することが好ましい。 The dry blend method is preferable for blending the fiber reinforced resin composition (pellet) and the diluent. In order to maintain the fiber length in the fiber reinforced resin composition and obtain higher rigidity, impact resistance, and durability improvement effects, the molding machine such as a direct injection molding machine is not used after dry blending. It is preferable to use for.
成形後に残存する強化繊維の質量平均繊維長は、１ｍｍ以上であることが好ましく、２ｍｍ以上であることがより好ましい。 The mass average fiber length of the reinforcing fibers remaining after the molding is preferably 1 mm or more, and more preferably 2 mm or more.
本発明の成形品は、高い強度が要求され、かつ黒系着色が必要とされるフロントエンドモジュール、クーリングモジュールなどの自動車部品として好適に使用できる。 The molded article of the present invention can be suitably used as an automotive part such as a front end module or a cooling module that requires high strength and requires black coloring.
次に、実施例および比較例を挙げて、本発明をより具体的に説明する。
（１）カーボンブラック樹脂組成物の製造
下記表１に記載の物性を有する下記カーボンブラックａ〜ｅを用い、これらとポリプロピレン（製品名：Ｊ−３０００ＧＰ；出光石油化学(株)製）、ポリプロピレンワックス（製品名：Ｃｅｒｉｄｕｓｔ６０７１；クラリアントジャパン社製）、酸化防止剤（製品名：イルガノックス１０１０；チバ・スペシャリティー・ケミカルズ社製）を、表１に記載の配合割合で、二軸押出機に入れ、カーボンブラック樹脂組成物Ａ〜Ｅをそれぞれ製造した。なお、用いた市販のカーボンブラックを、９５０℃で７分間加熱し、揮発分を測定した。
Next, the present invention will be described more specifically with reference to examples and comparative examples.
(1) Production of Carbon Black Resin Composition Using the following carbon blacks a to e having the physical properties shown in Table 1 below, these and polypropylene (product name: J-3000GP; manufactured by Idemitsu Petrochemical Co., Ltd.), polypropylene wax (Product name: Ceridust 6071; manufactured by Clariant Japan), an antioxidant (Product name: Irganox 1010; manufactured by Ciba Specialty Chemicals) in a twin-screw extruder at the blending ratio shown in Table 1, Carbon black resin compositions A to E were produced. The commercially available carbon black used was heated at 950 ° C. for 7 minutes, and the volatile content was measured.
＜カーボンブラック＞
ａ：トーカブラック＃３８５５、東海カーボン(株)製
ｂ：トーカブラック＃３８００、東海カーボン(株)製
ｃ：三菱カーボンブラック＃９００、三菱化学(株)製
ｄ：トーカブラック＃８３００、東海カーボン(株)製
ｅ：デグサカラー用チャンネルブラック Ｓｐｅｃｉａｌ Ｂｌａｃｋ ５、デグサジャパン(株)製
<Carbon black>
a: Talker Black # 3855, manufactured by Tokai Carbon Co., Ltd. b: Talker Black # 3800, manufactured by Tokai Carbon Co., Ltd. c: Mitsubishi Carbon Black # 900, manufactured by Mitsubishi Chemical Corporation d: Talker Black # 8300, manufactured by Tokai Carbon ( Co., Ltd. e: Channel black for Degussa Color Special Black 5, Degussa Japan Co., Ltd.
（２）長繊維ガラス繊維強化ポリプロピレンペレットの製造
プロピレン単独重合体（Ｊ−３０００ＧＰ；出光石油化学(株)製）に、過酸化物（パーカドックス−１４；化薬アクゾ（株）製）を加え、溶融混練氏、ＭＦＲ＝８０ｇ／１０分まで分解して得たものと、マレイン酸変性プロピレン重合体（Ｈ−１０００Ｐ；出光石油化学(株)製）とを、下記表２に示す割合で混合し、２８０℃で溶融して５０ｍφ押出機からダイ内の含浸槽へ供給した。次にアミノシランを含むカップリング剤で処理されたガラス繊維（ＥＲ２３１０Ｔ−４４１Ｎ、繊維径１７μｍ、収束本数約４０００本；日本電気硝子(株)製）を、２００℃で予熱して、２８０℃に加熱された上記の溶融された樹脂が供給されている含浸槽へ導いた。含浸槽中には、１０本のロッド（直径１０ｍｍ）を直線状に配置した。供給速度を２０ｍ／分に調整しつつ、上記ガラス繊維（ガラスロービング）を含浸槽内に送り込み、槽内のロッドにかけて溶融樹脂を含浸させ、含浸槽から引き出して冷却し、ペレタイザで切断してガラス繊維強化ポリプロピレンペレットを得た。ペレットの形状はやや楕円で、長径約２．２ｍｍ、短径約１．８ｍｍであった。
(2) Manufacture of long fiber glass fiber reinforced polypropylene pellets Proper homopolymer (J-3000GP; manufactured by Idemitsu Petrochemical Co., Ltd.) was added with peroxide (Perkadox-14; manufactured by Kayaku Akzo Co., Ltd.). , Melt kneaded, MFR = 80 g / 10 minutes decomposed and mixed with maleic acid-modified propylene polymer (H-1000P; manufactured by Idemitsu Petrochemical Co., Ltd.) in the proportions shown in Table 2 below And it melted at 280 degreeC and supplied to the impregnation tank in die | dye from a 50 mphi extruder. Next, glass fibers treated with a coupling agent containing aminosilane (ER2310T-441N, fiber diameter 17 μm, convergent number of about 4000; manufactured by Nippon Electric Glass Co., Ltd.) are preheated at 200 ° C. and heated to 280 ° C. The above molten resin was introduced into an impregnation tank to which the molten resin was supplied. Ten rods (diameter 10 mm) were arranged linearly in the impregnation tank. While adjusting the supply speed to 20 m / min, the glass fiber (glass roving) is fed into the impregnation tank, impregnated with the molten resin through the rod in the tank, cooled from the impregnation tank, cooled with a pelletizer, and cut into glass. Fiber reinforced polypropylene pellets were obtained. The shape of the pellet was slightly elliptical, with a major axis of about 2.2 mm and a minor axis of about 1.8 mm.
（３）繊維強化樹脂組成物からなる試験片の製造
上記（２）で製造した長繊維ガラス繊維強化ポリプロピレンペレットと上記（１）で製造したカーボンブラック樹脂組成物を、下記表２に記載の配合割合でドライブレンドし、ＪＩＳ Ｋ ７１５２−１９９９の多目的試験片を、ＪＩＳ Ｋ ６９２１−１９９７に従って成形し、試験片とした、これを下記試験で用いた。また、カーボンブラック樹脂組成物の代わりに希釈材としてポリプロピレン系樹脂（ホモポリプロピレンＪ−３０００ＧＰ、出光石油化学(株)製）を添加した繊維強化樹脂組成物からなる試験片（比較基準）も同様にして製造した。得られた試験片（成形品）の物性を下記表２に示す。
(3) Manufacture of a test piece comprising a fiber reinforced resin composition The long fiber glass fiber reinforced polypropylene pellets manufactured in the above (2) and the carbon black resin composition manufactured in the above (1) are blended as shown in Table 2 below. A multi-purpose test piece of JIS K 7152-1999 was molded according to JIS K 6921-1997 and used as a test piece in the following test. Similarly, a test piece (comparison standard) made of a fiber reinforced resin composition in which a polypropylene resin (Homopolypropylene J-3000GP, manufactured by Idemitsu Petrochemical Co., Ltd.) is added as a diluent instead of the carbon black resin composition. Manufactured. The physical properties of the obtained test piece (molded product) are shown in Table 2 below.
なお、下記表２中の物性値の測定方法、算出方法は、それぞれ次のとおりである。
(i)引張り強度（ＭＰａ）：
ＪＩＳ Ｋ ７１６２−１９９４に準拠して測定
(ii)引張り強度の保持率（％）：
実施例または比較例の引張り強度／比較基準の引張り強度×１００
In addition, the measurement method and calculation method of the physical property values in Table 2 below are as follows.
(i) Tensile strength (MPa):
Measured according to JIS K 7162-1994
(ii) Tensile strength retention rate (%):
Tensile strength of Examples or Comparative Examples / Tensile strength of comparative standards × 100
(iii)曲げ強度（ＭＰａ）：
ＪＩＳ Ｋ ７１７１−１９４１に準拠して測定
(iv)曲げ強度の保持率（％）：
実施例または比較例の曲げ強度／比較基準の曲げ強度×１００
(iii) Bending strength (MPa):
Measured according to JIS K 7171-1941
(iv) Bending strength retention rate (%):
Bending strength of example or comparative example / bending strength of comparative reference × 100
(v)曲げ弾性率（ＭＰａ）：
ＪＩＳ Ｋ ７１７１−１９４１に準拠して測定
(v) Flexural modulus (MPa):
Measured according to JIS K 7171-1941
(vi)２３℃シャルピー衝撃強度（ＫＪ／ｍ２）：
ＪＩＳ Ｋ ７７１１−１９９６に準拠し、２３℃で測定
(vi) 23 ° C. Charpy impact strength (KJ / m 2 ):
Measured at 23 ° C. according to JIS K 7711-1996
(vii)残存ガラス繊維長（ｍｍ）：
上記（vi）のサンプルを６００℃、２時間加熱灰化し、画像処理装置（ルーゼックス社製）で５００〜２０００本分の画像を取り込み、各繊維長を測定し、下記の式に基づき重量平均繊維長を計算した。
重量平均繊維長＝Σ（繊維長）２／Σ繊維長
(vii) Residual glass fiber length (mm):
The sample of (vi) is heated and incinerated at 600 ° C. for 2 hours, images of 500 to 2000 pieces are captured with an image processing apparatus (manufactured by Luzex), each fiber length is measured, and the weight average fiber is calculated based on the following formula: The length was calculated.
Weight average fiber length = Σ (fiber length) 2 / Σ fiber length
表１および２から、揮発分３質量％以下のカーボンブラックを用い、カーボンブラックの含有量が０．８質量％である実施例１〜４の繊維強化樹脂組成物からなる成形品は、カーボンブラックを含まない繊維強化樹脂組成物からなる成形品の引張り強度および曲げ強度の９０％以上を保持しており、カーボンブラックを添加することによって生じる強度低下が抑えられていることがわかる。 From Tables 1 and 2, a molded article made of the fiber reinforced resin composition of Examples 1 to 4 using carbon black having a volatile content of 3% by mass or less and having a carbon black content of 0.8% by mass is carbon black. It can be seen that 90% or more of the tensile strength and bending strength of a molded article made of a fiber reinforced resin composition containing no carbon is retained, and the strength reduction caused by the addition of carbon black is suppressed.
本発明の繊維強化樹脂組成物は黒系着色による強度低下が抑えられているため、強度が要求され、かつ黒系着色が必要なフロントエンドモジュール、クーリングモジュールなどの自動車部品などの製造材料として有用である。 The fiber reinforced resin composition of the present invention is useful as a manufacturing material for automobile parts such as front end modules and cooling modules that require strength and require black coloring because the strength reduction due to black coloring is suppressed. It is.
Claims (9)
（Ａ）ポリオレフィン樹脂
（Ｂ）酸変性ポリオレフィン樹脂
（Ｃ）強化繊維
（Ｄ）カーボンブラック
を含み、
成分（Ａ）＋（Ｂ）：（Ｃ）＝１０〜９５：９０〜５（質量比）の範囲であり、かつ、
成分（Ｄ）が０．０５〜１０．０質量％の範囲で含まれる繊維強化樹脂組成物であって、
成分（Ｄ）カーボンブラックの、９５０℃、７分間熱したときの揮発分が３質量％以下であることを特徴とする繊維強化樹脂組成物。 Including the following components (A) polyolefin resin (B) acid-modified polyolefin resin (C) reinforcing fiber (D) carbon black,
Component (A) + (B) :( C) = 10 to 95:90 to 5 (mass ratio), and
A fiber reinforced resin composition containing component (D) in a range of 0.05 to 10.0% by mass,
A fiber reinforced resin composition, wherein the component (D) carbon black has a volatile content of 3% by mass or less when heated at 950 ° C. for 7 minutes.
上記成分（Ｄ）を含まない、成分（Ａ）、（Ｂ）および（Ｃ）からなる繊維強化樹脂組成物と比較した引張り強度の保持率が９０％以上であることを特徴とする請求項１または２に記載の繊維強化樹脂組成物。 The tensile strength is 140 MPa or more, and
2. The tensile strength retention compared to a fiber reinforced resin composition comprising components (A), (B), and (C) that does not contain component (D) is 90% or more. Or the fiber reinforced resin composition of 2.
上記成分（Ｄ）を含まない、成分（Ａ）、（Ｂ）および（Ｃ）からなる繊維強化樹脂組成物と比較した曲げ強度の保持率が９０％以上であることを特徴とする請求項１〜３のいずれか１項に記載の繊維強化樹脂組成物。 The bending strength is 220 MPa or more, and
The retention of bending strength compared to a fiber reinforced resin composition comprising components (A), (B), and (C) that does not contain the component (D) is 90% or more. The fiber reinforced resin composition of any one of -3.
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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