JP5789093B2 - Sizing agent for carbon fiber, carbon fiber strand and fiber reinforced composite material - Google Patents
Sizing agent for carbon fiber, carbon fiber strand and fiber reinforced composite material Download PDFInfo
- Publication number
- JP5789093B2 JP5789093B2 JP2010247971A JP2010247971A JP5789093B2 JP 5789093 B2 JP5789093 B2 JP 5789093B2 JP 2010247971 A JP2010247971 A JP 2010247971A JP 2010247971 A JP2010247971 A JP 2010247971A JP 5789093 B2 JP5789093 B2 JP 5789093B2
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- Prior art keywords
- sizing agent
- carbon fiber
- weight
- general formula
- water
- Prior art date
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- 239000003795 chemical substances by application Substances 0.000 title claims description 94
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- 125000001931 aliphatic group Chemical group 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 16
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Landscapes
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、熱可塑性マトリックス樹脂を補強するために用いられる炭素繊維用サイジング剤、これを用いた炭素繊維ストランドおよび繊維強化複合材料に関する。さらに詳しくは、本発明は、熱可塑性マトリックス樹脂との優れた接着性を炭素繊維ストランドに付与することができる炭素繊維用サイジング剤、これを用いた炭素繊維ストランドおよび繊維強化複合材料に関する。 The present invention relates to a carbon fiber sizing agent used for reinforcing a thermoplastic matrix resin, a carbon fiber strand using the same, and a fiber reinforced composite material. More specifically, the present invention relates to a carbon fiber sizing agent that can impart excellent adhesion to a thermoplastic matrix resin to a carbon fiber strand, a carbon fiber strand using the carbon fiber strand, and a fiber reinforced composite material.
自動車用途、航空・宇宙用途、スポーツ・レジャー用途、一般産業用途等に、プラスチック材料（マトリックス樹脂と称される）を炭素繊維で補強した繊維強化複合材料が幅広く利用されつつある。これらの複合材料に使用される炭素繊維は、通常、フィラメント形状で製造され、その後ホットメルト法やドラムワインディング法等により一方向プリプレグと呼ばれるシート状の中間材料に加工されたり、フィラメントワインディング法による加工や、場合によっては織物またはチョップドファイバー形状に加工されたりする等、各種高次加工工程を経て、強化繊維として使用されている。 Fiber reinforced composite materials in which plastic materials (referred to as matrix resins) are reinforced with carbon fibers are being widely used for automobile applications, aerospace applications, sports / leisure applications, general industrial applications, and the like. Carbon fibers used in these composite materials are usually manufactured in a filament shape, and then processed into a sheet-like intermediate material called a unidirectional prepreg by the hot melt method or the drum winding method, or processed by the filament winding method. In some cases, it is used as a reinforcing fiber through various high-order processing steps such as processing into a woven fabric or chopped fiber shape.
上記のマトリックス樹脂のうち、成型が容易でリサイクル面でも有利な為注目されているポリオレフィン系樹脂、ナイロン樹脂、ポリカーボネート樹脂、ポリアセタール樹脂、ＡＢＳ樹脂、ポリフェニレンサルフィド樹脂、ポリエーテルイミド樹脂などのいわゆる熱可塑性樹脂を用いた繊維強化複合材料の場合、炭素繊維は一般的に１〜１５ｍｍ長に切断されたチョップドファイバー形状で使用されることが多い。このチョップドファイバーと熱可塑性樹脂とを混練したペレットを製造する際には、チョップドファイバーの集束性が重要で、これが不適切であると、チョップドファイバーの供給量の不安定化、ストランド切れなどが発生し、得られた複合材料の物性が低下することがある。これを防止するため、炭素繊維に適切な集束性を付与する目的で、各種熱可塑性樹脂を主剤とするサイジング剤を付与する技術が多数提案され（特許文献１〜４参照）、工業的に広く利用されている。 Among the above matrix resins, so-called heat such as polyolefin resin, nylon resin, polycarbonate resin, polyacetal resin, ABS resin, polyphenylene sulfide resin, polyetherimide resin, etc., which are attracting attention because they are easy to mold and advantageous in terms of recycling. In the case of a fiber-reinforced composite material using a plastic resin, carbon fibers are generally used in the form of chopped fibers cut to a length of 1 to 15 mm. When producing pellets in which this chopped fiber and thermoplastic resin are kneaded, it is important to focus the chopped fiber. If this is not appropriate, the supply amount of chopped fiber may become unstable or the strand may break. In addition, the physical properties of the obtained composite material may deteriorate. In order to prevent this, many techniques for applying a sizing agent mainly composed of various thermoplastic resins have been proposed for the purpose of imparting appropriate bundling properties to carbon fibers (see Patent Documents 1 to 4). It's being used.
一方、近年においては、補強剤として用いる炭素繊維の引張強度などの特性をより効果的に得るため、長繊維ペレットと呼ばれる形態や、熱硬化性樹脂をマトリックスとする複合材料の様に、炭素繊維を一方向シートやテープ状、織物の状態で熱可塑性樹脂を含浸させて成型するケースも増加している。このような場合には、コンポジット成型時に熱溶融した熱可塑性樹脂が速やかに炭素繊維ストランド内部、具体的に繊維−繊維間に含浸することが、成型工程時間の短縮化、得られた複合材料の物性向上の面で重要である。 On the other hand, in recent years, in order to more effectively obtain properties such as tensile strength of carbon fibers used as a reinforcing agent, carbon fibers such as a form called a long fiber pellet or a composite material using a thermosetting resin as a matrix are used. There are an increasing number of cases in which a unidirectional sheet, tape, or fabric is impregnated with a thermoplastic resin and molded. In such a case, it is possible to quickly impregnate the inside of the carbon fiber strand, specifically, between the fibers and fibers, with the thermoplastic resin melted at the time of molding the composite. This is important in terms of improving physical properties.
しかしこの様な、繊維強化複合材料の用途・用法の多様化、さらなる機械的強度向上が望まれる昨今において、従来技術に記載されたサイジング剤を適用しても、成型時のマトリックス樹脂と炭素繊維との濡れ性および接着性の悪さをさらに助長する結果となり、複合材料としての機械的特性をさらに低いものとする場合があった。 However, in recent years when diversification of applications and usages of fiber-reinforced composite materials and further improvement in mechanical strength are desired, even if the sizing agent described in the prior art is applied, matrix resin and carbon fiber at the time of molding are used. As a result, the wettability and the poor adhesiveness are further promoted, and the mechanical properties of the composite material may be further lowered.
よって、熱可塑性樹脂をマトリックス樹脂とする繊維強化複合材料の分野において、より炭素繊維とマトリックス樹脂との親和性を高め、強固に接着し得るサイジング剤の開発が望まれている。 Therefore, in the field of fiber reinforced composite materials using a thermoplastic resin as a matrix resin, it is desired to develop a sizing agent that can further enhance the affinity between the carbon fiber and the matrix resin and can be firmly bonded.
かかる従来の技術背景に鑑み、本発明の目的は、熱可塑性マトリックス樹脂を補強するために用いられる炭素繊維ストランドに対して、熱可塑性マトリックス樹脂との優れた接着性を付与することができる炭素繊維用サイジング剤と、それを用いた炭素繊維ストランド、繊維強化複合材料を提供することにある。 In view of such a conventional technical background, an object of the present invention is to provide carbon fibers capable of imparting excellent adhesiveness with a thermoplastic matrix resin to carbon fiber strands used for reinforcing the thermoplastic matrix resin. It is to provide a sizing agent for use, a carbon fiber strand using the sizing agent, and a fiber-reinforced composite material.
本発明者らは、上記課題を解決するために鋭意検討した結果、特定の成分を必須に含有する炭素繊維用サイジング剤であれば、上記課題を解決できることを見出し、本発明に到達した。
すなわち、本発明は、熱可塑性マトリックス樹脂を補強するために用いられる炭素繊維用サイジング剤であって、エポキシ化合物と水酸基含有アミン化合物との反応生成物を必須に含む、炭素繊維用サイジング剤である。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a sizing agent for carbon fiber that essentially contains a specific component, and have reached the present invention.
That is, the present invention is a carbon fiber sizing agent used to reinforce a thermoplastic matrix resin, and a carbon fiber sizing agent that essentially includes a reaction product of an epoxy compound and a hydroxyl group-containing amine compound. .
前記エポキシ化合物は、分子構造中に芳香環を有し、かつエポキシ基を２個以上有する芳香族エポキシ化合物であることが好ましい。 The epoxy compound is preferably an aromatic epoxy compound having an aromatic ring in the molecular structure and having two or more epoxy groups.
前記水酸基含有アミン化合物は、下記一般式（１）および／または下記一般式（２）で示される化合物であることが好ましい。 The hydroxyl group-containing amine compound is preferably a compound represented by the following general formula (1) and / or the following general formula (2).
サイジング剤の不揮発分に占める前記反応生成物の重量割合は、７０〜１００重量％であることが好ましい。 The weight ratio of the reaction product to the non-volatile content of the sizing agent is preferably 70 to 100% by weight.
本発明の炭素繊維用サイジング剤は、サイジング剤の不揮発分を示唆走査熱量計（ＤＳＣ）で測定したとき、融解吸熱量が３Ｊ／ｇ以上の吸熱ピークを有しないことが好ましい。 The sizing agent for carbon fiber of the present invention preferably has no endothermic peak with a melting endotherm of 3 J / g or more when the nonvolatile content of the sizing agent is measured by a suggestion scanning calorimeter (DSC).
前記熱可塑性マトリックス樹脂は、ポリアミド系樹脂であることが好ましい。 The thermoplastic matrix resin is preferably a polyamide resin.
本発明の炭素繊維用サイジング剤は、さらに水を含有し、前記反応生成物が水に分散した状態または水に溶解した状態であることが好ましい。 The carbon fiber sizing agent of the present invention preferably further contains water, and the reaction product is preferably dispersed in water or dissolved in water.
本発明の炭素繊維ストランドは、原料炭素繊維ストランドに対して、上記の炭素繊維用サイジング剤を付着させたものである。 The carbon fiber strand of the present invention is obtained by adhering the above-described carbon fiber sizing agent to a raw material carbon fiber strand.
本発明の繊維強化複合材料は、熱可塑性マトリックス樹脂と上記の炭素繊維ストランドとを含むものである。 The fiber reinforced composite material of the present invention includes a thermoplastic matrix resin and the above carbon fiber strand.
本発明の炭素繊維用サイジング剤は、熱可塑性マトリックス樹脂を補強するために用いられる炭素繊維ストランドに対して、熱可塑性マトリックス樹脂との優れた接着性を付与することができる。
本発明の強化繊維用サイジング剤で処理して得られる炭素繊維ストランドは、熱可塑性マトリックス樹脂に対して優れた接着性を有する。本発明の繊維強化複合材料は、熱可塑性マトリックス樹脂と本発明の炭素繊維ストランドとの接着性が優れる。
The carbon fiber sizing agent of the present invention can impart excellent adhesion to a thermoplastic matrix resin to carbon fiber strands used to reinforce the thermoplastic matrix resin.
The carbon fiber strand obtained by processing with the sizing agent for reinforcing fibers of the present invention has excellent adhesion to the thermoplastic matrix resin. The fiber-reinforced composite material of the present invention is excellent in adhesiveness between the thermoplastic matrix resin and the carbon fiber strand of the present invention.
本発明は、熱可塑性マトリックス樹脂を補強するために用いられる炭素繊維用のサイジング剤であり、エポキシ化合物と水酸基含有アミン化合物との反応生成物を必須に含む、炭素繊維用サイジング剤である。以下に詳細に説明する。 The present invention is a carbon fiber sizing agent used to reinforce a thermoplastic matrix resin, and a carbon fiber sizing agent that essentially contains a reaction product of an epoxy compound and a hydroxyl group-containing amine compound. This will be described in detail below.
［エポキシ化合物］
本発明のエポキシ化合物とは、分子構造末端に反応性のエポキシ基を少なくとも１つ有する化合物である。エポキシ化合物としては、エピクロルヒドリンと活性水素化合物から得られるグリシジルエーテル型が代表的であり、その他にグリシジルエステル型、グリシジルアミン型、脂環型等が挙げられる。エポキシ化合物は、１種でもよく、２種以上を併用してもよい。
[Epoxy compound]
The epoxy compound of the present invention is a compound having at least one reactive epoxy group at the end of the molecular structure. The epoxy compound is typically a glycidyl ether type obtained from epichlorohydrin and an active hydrogen compound, and other examples include glycidyl ester type, glycidyl amine type, and alicyclic type. One epoxy compound may be used, or two or more epoxy compounds may be used in combination.
グリシジルエーテル型のエポキシ化合物としては、例えば、アルコール類を原料として製造される下記一般式（３）で示される官能基を有するエポキシ化合物、フェノール類を原料として製造される下記一般式（４）で示される官能基を有するエポキシ化合物等が挙げられる。グリシジルエステル型のエポキシ化合物としては、例えば、フタル酸誘導体や合成樹脂脂肪酸などのカルボン酸を原料として製造される下記一般式（５）で示される官能基を有するエポキシ化合物等が挙げられる。グリシジルアミン型のエポキシ化合物としては、例えば、下記一般式（６）で示される官能基を有するエポキシ化合物や下記一般式（７）で示される官能基を有するエポキシ化合物等が挙げられる。脂環型のエポキシ化合物としては、例えば、下記一般式（８）で示される官能基を有するエポキシ化合物等が挙げられる。これらの中でも、繊維とマトリックス樹脂の接着性向上の理由から、一般式（４）で示される官能基を有するエポキシ化合物が好ましい。 Examples of the glycidyl ether type epoxy compound include an epoxy compound having a functional group represented by the following general formula (3) manufactured using alcohols as a raw material and a general formula (4) manufactured using phenols as a raw material. And epoxy compounds having the functional groups shown. Examples of the glycidyl ester type epoxy compound include an epoxy compound having a functional group represented by the following general formula (5), which is produced using a carboxylic acid such as a phthalic acid derivative or a synthetic resin fatty acid as a raw material. Examples of the glycidylamine type epoxy compound include an epoxy compound having a functional group represented by the following general formula (6) and an epoxy compound having a functional group represented by the following general formula (7). Examples of the alicyclic epoxy compound include an epoxy compound having a functional group represented by the following general formula (8). Among these, an epoxy compound having a functional group represented by the general formula (4) is preferable for the purpose of improving the adhesion between the fiber and the matrix resin.
エポキシ化合物の分子構造中に含まれるエポキシ基は、後述する水酸基含有アミン化合物との反応生成物の水溶化の点から、２個以上が好ましく、２〜１０個が好ましく、２〜６個がさらに好ましい。 The number of epoxy groups contained in the molecular structure of the epoxy compound is preferably 2 or more, preferably 2 to 10, more preferably 2 to 6 from the viewpoint of water-solubilization of the reaction product with the hydroxyl group-containing amine compound described later. preferable.
エポキシ化合物のエポキシ当量は、１００〜１５００ｇ／ｅｑが好ましく、１２０〜１０００ｇ／ｅｑがより好ましく、１５０〜８００ｇ／ｅｑがさらに好ましい。エポキシ当量が１００ｇ／ｅｑ未満の場合、後述する水酸基含有アミン化合物との反応生成物を製造することが困難となることがある。エポキシ当量が１５００ｇ／ｅｑ超の場合、後述する水酸基含有アミン化合物との反応生成物の水溶化が困難となることがある。なお、エポキシ当量とは、ＪＩＳ−Ｋ７２３６に準拠したものをいう。 The epoxy equivalent of the epoxy compound is preferably 100 to 1500 g / eq, more preferably 120 to 1000 g / eq, and further preferably 150 to 800 g / eq. When the epoxy equivalent is less than 100 g / eq, it may be difficult to produce a reaction product with a hydroxyl group-containing amine compound described later. When the epoxy equivalent is more than 1500 g / eq, it may be difficult to water-solubilize the reaction product with the hydroxyl group-containing amine compound described later. In addition, an epoxy equivalent means the thing based on JIS-K7236.
エポキシ化合物の重量平均分子量は、１００〜１００００が好ましく、１００〜８０００がより好ましく、１５０〜７０００がさらに好ましい。重量平均分子量が１００未満の場合、後述する水酸基含有アミン化合物との反応生成物の耐熱性に劣ることがある。重量平均分子量が１００００超の場合、後述する水酸基含有アミン化合物との反応生成物を製造することが困難となることがある。なお、重量平均分子量は、東ソー（株）製高速ゲルパーミエーションクロマトグラフィー装置ＨＬＣ−８２２０ＧＰＣを用い、試料濃度２ｍｇ／ｃｃで分離カラム（昭和電工（株）製Ｓｈｏｄｅｘ（登録商標）ＫＦ−Ｇ、ＫＦ−４０２ＨＱ、ＫＦ−４０３ＨＱ）に注入し、ＲＩ検出器で測定されたチャートより算出した値を用いた。 100-10000 are preferable, as for the weight average molecular weight of an epoxy compound, 100-8000 are more preferable, and 150-7000 are more preferable. When the weight average molecular weight is less than 100, the heat resistance of the reaction product with the hydroxyl group-containing amine compound described later may be inferior. When the weight average molecular weight exceeds 10,000, it may be difficult to produce a reaction product with a hydroxyl group-containing amine compound described later. The weight average molecular weight is a separation column (Shodex (registered trademark) KF-G, KF manufactured by Showa Denko KK) using a high-speed gel permeation chromatography apparatus HLC-8220GPC manufactured by Tosoh Corporation and a sample concentration of 2 mg / cc. -402HQ, KF-403HQ), and values calculated from the chart measured by the RI detector were used.
本発明のエポキシ化合物は、繊維とマトリックス樹脂の接着性向上の点から、分子構造中に芳香環を有し、かつ、エポキシ基を２個以上有する芳香族エポキシ化合物がさらに好ましい。
上記の芳香族エポキシ化合物としては、ハイドロキノン、レゾルシン、ピロカテコールなどの単核多価フェノール化合物のポリグリシジルエーテル化合物；ジヒドロキシナフタレン、ビフェノール、ビスフェノールＦ、ビスフェノールＡ、フェノールノボラック、オルソクレゾールノボラック、レゾルシンノボラック、ビスフェノールＦノボラック、ビスフェノールＡノボラック、ジシクロペンタジエン変性フェノール、トリフェニルメタン、テトラフェニルエタンなどの多核多価フェノール化合物のポリグリシジルエーテル化合物などが挙げられる。
The epoxy compound of the present invention is more preferably an aromatic epoxy compound having an aromatic ring in the molecular structure and two or more epoxy groups from the viewpoint of improving the adhesion between the fiber and the matrix resin.
Examples of the aromatic epoxy compound include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, and pyrocatechol; dihydroxynaphthalene, biphenol, bisphenol F, bisphenol A, phenol novolac, orthocresol novolak, resorcin novolak, Examples thereof include polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as bisphenol F novolak, bisphenol A novolak, dicyclopentadiene-modified phenol, triphenylmethane, and tetraphenylethane.
これら芳香族エポキシ化合物の中でも、下記一般式（９）で示される化合物、下記一般式（１０）で示される化合物、下記一般式（１１）で示される化合物、下記一般式（１２）で示される化合物が好ましく、下記一般式（９）で示される化合物がさらに好ましい。 Among these aromatic epoxy compounds, the compound represented by the following general formula (9), the compound represented by the following general formula (10), the compound represented by the following general formula (11), and the following general formula (12) A compound is preferable, and a compound represented by the following general formula (9) is more preferable.
一般式（９）において、Ｒ５、Ｒ６、Ｒ７及びＲ８は、それぞれ独立して、水素原子又はメチル基である。ｎは０〜３０の数であり、０〜２０が好ましく、０〜１０が更に好ましい。 In the general formula (9), R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom or a methyl group. n is a number from 0 to 30, preferably 0 to 20, and more preferably 0 to 10.
一般式（１２）において、ｍは０〜１０の数であり、０〜８が好ましく、０〜５が更に好ましい。 In General formula (12), m is a number of 0-10, 0-8 are preferable and 0-5 are still more preferable.
上述のエポキシ化合物の製造方法としては、特に限定はなく、公知の方法を採用できる。また、上述のエポキシ化合物は、一般に市販されているものであり、本発明の炭素繊維用サイジング剤では、それら市販のエポキシ化合物を使用することができる。 There is no limitation in particular as a manufacturing method of the above-mentioned epoxy compound, A well-known method is employable. Moreover, the above-mentioned epoxy compounds are generally commercially available, and these commercially available epoxy compounds can be used in the sizing agent for carbon fibers of the present invention.
［水酸基含有アミン化合物］
本発明の水酸基含有アミン化合物は、分子構造中に水酸基を有する一級アミン化合物又は二級アミン化合物であり、本発明のエポキシ化合物との反応生成物を得るために用いられる。水酸基含有アミン化合物は、１種でもよく、２種以上を併用してもよい。
[Hydroxyl-containing amine compound]
The hydroxyl group-containing amine compound of the present invention is a primary amine compound or a secondary amine compound having a hydroxyl group in the molecular structure, and is used for obtaining a reaction product with the epoxy compound of the present invention. The hydroxyl group-containing amine compound may be one kind or a combination of two or more kinds.
水酸基含有アミン化合物としては、モノアルカノールアミン、ジアルカノールアミン等が挙げられる。これらの中でも、反応生成物の水溶化の点から、水酸基含有アミン化合物は、上記一般式（１）および／または上記一般式（２）で示される化合物であることが好ましい。 Examples of the hydroxyl group-containing amine compound include monoalkanolamine and dialkanolamine. Among these, from the viewpoint of water-solubilization of the reaction product, the hydroxyl group-containing amine compound is preferably a compound represented by the above general formula (1) and / or the above general formula (2).
一般式（１）において、Ｒ１は、水素原子又は炭素数１〜１０の脂肪族炭化水素基である。これらの中でも、繊維とマトリックス樹脂との接着性が向上する点及び乳化安定性の点から、Ｒ１は、炭素数１〜８の脂肪族炭化水素基が好ましく、炭素数１〜５の脂肪族炭化水素基がさらに好ましい。脂肪族炭化水素基は、飽和であっても不飽和であってもよく、直鎖であっても分岐を有していてもよい。 In the general formula (1), R 1 is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Among these, R 1 is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and an aliphatic group having 1 to 5 carbon atoms from the viewpoint of improving the adhesion between the fiber and the matrix resin and the stability of the emulsion. More preferred are hydrocarbon groups. The aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or branched.
一般式（１）において、Ｒ２は、炭素数１〜１０の脂肪族炭化水素基である。これらの中でも、繊維とマトリックス樹脂との接着性が向上する点及び乳化安定性の点から、Ｒ２は、炭素数１〜８の脂肪族炭化水素基が好ましく、炭素数１〜５の脂肪族炭化水素基がさらに好ましい。脂肪族炭化水素基は、飽和であっても不飽和であってもよく、直鎖であっても分岐を有していてもよい。 In general formula (1), R 2 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Among these, R 2 is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and an aliphatic group having 1 to 5 carbon atoms from the viewpoint of improving the adhesion between the fiber and the matrix resin and the stability of the emulsion. More preferred are hydrocarbon groups. The aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or branched.
一般式（２）において、Ｒ３及びＲ４は、それぞれ独立して、炭素数１〜１０の脂肪族炭化水素基である。これらの中でも、繊維とマトリックス樹脂との接着性が向上する点及び乳化安定性の点から、Ｒ３及びＲ４は、炭素数１〜８の脂肪族炭化水素基が好ましく、炭素数１〜５の脂肪族炭化水素基がさらに好ましい。脂肪族炭化水素基は、飽和であっても不飽和であってもよく、直鎖であっても分岐を有していてもよい。 In General formula (2), R < 3 > and R < 4 > are respectively independently a C1-C10 aliphatic hydrocarbon group. Among these, R 3 and R 4 are preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms and 1 to 5 carbon atoms from the viewpoint of improving the adhesion between the fiber and the matrix resin and the emulsion stability. The aliphatic hydrocarbon group is more preferable. The aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or branched.
水酸基含有アミン化合物としては、例えば、モノエタノールアミン、モノプロパノールアミン、ジエタノールアミン、メチルエタノールアミン、エチルエタノールアミン、ブチルエタノールアミン、ジプロパノールアミン等が挙げられる。 Examples of the hydroxyl group-containing amine compound include monoethanolamine, monopropanolamine, diethanolamine, methylethanolamine, ethylethanolamine, butylethanolamine, dipropanolamine and the like.
［反応生成物］
本発明の反応生成物は、前述のエポキシ化合物と前述の水酸基含有アミン化合物との反応生成物であり、エポキシ化合物のエポキシ基をアミン化合物の活性水素が開環させることにより反応が起こるものが好ましい。
[Reaction product]
The reaction product of the present invention is a reaction product of the above-mentioned epoxy compound and the above-mentioned hydroxyl group-containing amine compound, and preferably has a reaction caused by ring opening of the active hydrogen of the amine compound on the epoxy group of the epoxy compound. .
反応生成物に対する水酸基含有アミン化合物の反応比率については、反応生成物のエポキシ基に対して、０．５〜２．５当量が好ましく、０．５〜２．０当量がより好ましく、１．０〜２．０当量がさらに好ましい。０．５当量を下回ると十分な水溶性が得られ難くなる場合があり、２．５当量を上回ると未反応の水酸基含有アミン化合物の割合が大きくなり、接着性が低くなる場合がある。 About the reaction ratio of the hydroxyl-containing amine compound with respect to a reaction product, 0.5-2.5 equivalent is preferable with respect to the epoxy group of a reaction product, 0.5-2.0 equivalent is more preferable, 1.0 -2.0 equivalents are more preferred. If the amount is less than 0.5 equivalent, sufficient water solubility may be difficult to obtain. If the amount exceeds 2.5 equivalent, the proportion of the unreacted hydroxyl-containing amine compound may increase and the adhesiveness may decrease.
本発明の反応生成物は、水溶性を向上させる点から、反応生成物を生成する際に、蟻酸、酢酸、プロピオン酸、乳酸などのカルボン酸を併用して、カルボン酸との塩を形成させてもよい。カルボン酸を使用する場合、水酸基含有アミン化合物のアミノ基に対して、０．５〜１．２当量が好ましく、０．６〜１．１当量がより好ましく、０．７〜１．０当量がさらに好ましい。０．５当量を下回ると十分な水溶性が得られ難くなる場合があり、１．２当量を上回ると水溶液が増粘し、取り扱いが困難になる場合がある。 Since the reaction product of the present invention improves water solubility, a carboxylic acid such as formic acid, acetic acid, propionic acid, or lactic acid is used in combination to form a salt with the carboxylic acid. May be. When using carboxylic acid, 0.5-1.2 equivalent is preferable with respect to the amino group of a hydroxyl-containing amine compound, 0.6-1.1 equivalent is more preferable, 0.7-1.0 equivalent is Further preferred. If it is less than 0.5 equivalent, sufficient water solubility may be difficult to obtain, and if it exceeds 1.2 equivalent, the aqueous solution may be thickened and handling may be difficult.
本発明の反応生成物を製造する方法としては、特に限定はなく、公知の方法を採用できる。例えば、エポキシ化合物を軟化点以上の温度まで加温して液状とし、攪拌下で水酸基含有アミン化合物を滴下して反応させることにより反応生成物を作成し、その後水を徐々に添加して水溶化物とする方法等である。反応生成物の水溶性が不足する場合は、反応生成物を作成後、カルボン酸を有する化合物を添加することにより水溶性の塩を作成し、その後水を徐々に添加して水溶化物とすることもできる。更に、反応生成物の水溶化の方法としては、ホモジナイザー、ホモミキサー、ボールミル等を用いて機械せん断力を加えつつ、水を徐々に添加して転相乳化する方法等も挙げられる。 There is no limitation in particular as a method of manufacturing the reaction product of this invention, A well-known method is employable. For example, the epoxy compound is heated to a temperature equal to or higher than the softening point to form a liquid, and a reaction product is prepared by dropping and reacting the hydroxyl group-containing amine compound with stirring. And the like. If the water solubility of the reaction product is insufficient, create a reaction product, then create a water-soluble salt by adding a compound having a carboxylic acid, and then gradually add water to make the water-soluble product. You can also. Further, examples of the water-solubilization method for the reaction product include a method in which water is gradually added and a phase inversion emulsification is performed while applying mechanical shearing force using a homogenizer, a homomixer, a ball mill or the like.
また、本発明の反応生成物は、示唆走査熱量計（ＤＳＣ）で測定したときに、結晶融解に基づく融解吸熱量が３Ｊ／ｇ以上の吸熱ピークを有しないことが好ましい。すなわち、本発明の反応生成物は、結晶融解に基づく吸熱ピークを有しないか、有する場合であっても該吸熱ピークに基づく融解吸熱量が３Ｊ／ｇ未満であることが好ましい。その理由は必ずしも明確ではないが以下の様に考えられる。 Moreover, it is preferable that the reaction product of the present invention does not have an endothermic peak having a melting endotherm based on crystal melting of 3 J / g or more as measured by a suggestion scanning calorimeter (DSC). That is, the reaction product of the present invention preferably has an endothermic peak based on crystal melting, or even if it has a melting endotherm based on the endothermic peak, it is preferably less than 3 J / g. The reason is not necessarily clear, but is considered as follows.
一般的な結晶性化合物は、温度の上昇と共に、分子鎖が規則正しく配列した結晶領域の分子間力が弱まり、その性状が固体状から液状へと急激に変化する。そしてその性状変化は、ＤＳＣ測定において、吸熱量が３Ｊ／ｇ以上の明確な吸熱ピークとなり確認される。しかし、この急激な性状変化は時として、コンポジット成型の際に、加温溶融されたマトリックス樹脂中にサイジング剤成分が溶出・拡散していく原因となり、サイジング剤が繊維とマトリックス樹脂との接着に全く寄与しなくなる場合がある。
それに対して、本発明の反応生成物は、上記の一般的な結晶性化合物に比較して、加温時の固体状から液状への性状変化が緩慢な為、コンポジット成型の際にも繊維表面上にサイジング剤成分が十分に残存している為、繊維とマトリックス樹脂との接着性を向上できると考えられる。
In general crystalline compounds, as the temperature rises, the intermolecular force of the crystalline region in which molecular chains are regularly arranged is weakened, and the properties rapidly change from solid to liquid. The property change is confirmed by a clear endothermic peak having an endotherm of 3 J / g or more in DSC measurement. However, this sudden property change sometimes causes the sizing agent components to elute and diffuse into the heated and melted matrix resin during composite molding, which causes the sizing agent to adhere to the fiber and matrix resin. There may be no contribution at all.
On the other hand, the reaction product of the present invention has a slow property change from solid to liquid during heating compared to the above general crystalline compound, so that the fiber surface can be used even during composite molding. It is considered that the adhesiveness between the fibers and the matrix resin can be improved because the sizing agent component remains sufficiently on the top.
本発明の反応生成物は、結晶融解に基づく融解吸熱量が２Ｊ／ｇ以上の吸熱ピークを有しないこと（結晶融解に基づく吸熱ピークを有しないか、有する場合であっても該吸熱ピークに基づく融解吸熱量が２Ｊ／ｇ未満）が好ましく、結晶融解に基づく融解吸熱量が１Ｊ／ｇ以上の吸熱ピークを有しないこと（結晶融解に基づく吸熱ピークを有しないか、有する場合であっても該吸熱ピークに基づく融解吸熱量が１Ｊ／ｇ未満）がより好ましく、吸熱ピークを有しないことがさらに好ましい。
結晶融解に基づく融解吸熱量が３Ｊ／ｇ以上の吸熱ピークを有しない温度範囲としては、ガラス転移終了時の温度から３００℃の範囲であればよい。
The reaction product of the present invention does not have an endothermic peak with a melting endotherm based on crystal melting of 2 J / g or more (even if it does not have an endothermic peak based on crystal melting or is based on the endothermic peak). The melting endotherm is preferably less than 2 J / g, and the melting endotherm based on crystal melting does not have an endothermic peak of 1 J / g or more (even if it does not have an endothermic peak based on crystal melting or not) More preferably, the melting endotherm based on the endothermic peak is less than 1 J / g), and it is even more preferable that there is no endothermic peak.
The temperature range in which the melting endotherm based on crystal melting does not have an endothermic peak of 3 J / g or more may be in the range of 300 ° C. from the temperature at the end of the glass transition.
さらに、本発明の反応生成物は、ＤＳＣ測定において、上述の様に結晶融解に基づく吸熱ピークを有さないことと同義的に、化合物の結晶化に基づく発熱ピークも有さない。 Furthermore, in the DSC measurement, the reaction product of the present invention does not have an exothermic peak due to crystallization of a compound, in the same meaning as having no endothermic peak due to crystal melting as described above.
なお、本発明でいう吸熱ピークの結晶融解に基づく融解吸熱量とは、ＪＩＳ−Ｋ７１２１、Ｋ７１２２に準拠し、後述するＤＳＣ測定により得られるＤＳＣ曲線上に発現する吸熱ピークにおいて、吸熱前後でベースラインから離れる点とベースラインに戻る点とを結んだ直線と、ピーク曲線により囲まれた面積の積分値により計算される値（単位：Ｊ／ｇ）として定義される。 The melting endotherm based on the crystal melting of the endothermic peak referred to in the present invention is based on JIS-K7121, K7122, and is the baseline before and after the endotherm in the endothermic peak expressed on the DSC curve obtained by DSC measurement described later. Defined as a value (unit: J / g) calculated by the integral value of the area surrounded by the straight line connecting the point away from the point and the point returning to the baseline and the peak curve.
［炭素繊維用サイジング剤］
本発明のサイジング剤は、熱可塑性マトリックス樹脂を補強するために用いられる炭素繊維用であり、前述のエポキシ化合物と前述の水酸基含有アミン化合物との反応生成物を必須に含有するものである。
サイジング剤の不揮発分に占める前記反応生成物の重量割合は、７０〜１００重量％が好ましく、９０〜９９．５重量％がより好ましく、９５〜９９重量％がさらに好ましい。７０重量％未満の場合、接着性が不十分となることがある。なお、本発明における不揮発分とは、サイジング剤を１０５℃で熱処理して溶媒等を除去し、恒量に達した時の絶乾成分をいう。
[Carbon fiber sizing agent]
The sizing agent of the present invention is for carbon fibers used to reinforce a thermoplastic matrix resin, and essentially contains a reaction product of the aforementioned epoxy compound and the aforementioned hydroxyl group-containing amine compound.
The weight ratio of the reaction product in the nonvolatile content of the sizing agent is preferably 70 to 100% by weight, more preferably 90 to 99.5% by weight, and still more preferably 95 to 99% by weight. If it is less than 70% by weight, the adhesion may be insufficient. The non-volatile content in the present invention refers to an absolutely dry component when the sizing agent is heat treated at 105 ° C. to remove the solvent and the like and reach a constant weight.
本発明のサイジング剤は、アセトン、メチルエチルケトン等の有機溶剤に分散させた状態や溶解させた状態のものも使用できるが、取扱い時の人体への安全性や、火災等の災害防止、自然環境の汚染防止等の観点から、さらに水を含有し、前記反応生成物が水に分散した状態（水分散体）または水に溶解した状態（水溶液）であることが好ましい。 The sizing agent of the present invention can be used in a state dispersed or dissolved in an organic solvent such as acetone or methyl ethyl ketone, but it is safe for the human body during handling, disaster prevention such as fire, natural environment From the standpoint of preventing contamination, it is preferable that water is further contained and the reaction product is dispersed in water (aqueous dispersion) or dissolved in water (aqueous solution).
なお、上記水分散体や水溶液には、製造時の操作性や水分散体の経日安定性を向上させる目的で、上記水分散体や水溶液の利点を損なわない範囲で有機溶剤等の水以外の溶媒を含有することができる。
有機溶剤としては、メチルアルコール、エチルアルコール、イソプロピルアルコール等のアルコール類；エチレングリコール、プロピレングリコール、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル等のグリコールまたはグリコールエーテル類；アセトン、メチルエチルケトン等のケトン類が例示できる。その含有量としては、溶媒の種類にもよるが、水分散体や水溶液の利点を損なわないために、サイジング剤の不揮発分に対して１００重量％以下が好ましく、５０重量％以下がさらに好ましい。
In addition, the water dispersion or the aqueous solution is not limited to water such as an organic solvent within the range that does not impair the advantages of the water dispersion and the aqueous solution for the purpose of improving the operability during production and the stability of the aqueous dispersion over time. The solvent can be contained.
Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; glycols or glycol ethers such as ethylene glycol, propylene glycol, ethylene glycol monoisopropyl ether, and ethylene glycol monobutyl ether; ketones such as acetone and methyl ethyl ketone. It can be illustrated. The content is preferably 100% by weight or less, more preferably 50% by weight or less, based on the nonvolatile content of the sizing agent, in order not to impair the advantages of the aqueous dispersion and aqueous solution, although it depends on the type of solvent.
本発明のサイジング剤が水分散体又は水溶液の場合、その不揮発分の濃度については、特に限定はなく、そのサイジング剤の不揮発分組成により、水分散体としての安定性や、製品として取り扱いやすい粘度等を考慮して適宜選択されるものである。製品の輸送コスト等を考慮すれば、１０重量％以上が好ましく、２０〜６０重量％がさらに好ましく、３０〜５０重量％が特に好ましい。
本発明のサイジング剤を構成する上記で説明した以外の成分としては、例えば、各種界面活性剤や、各種平滑剤、酸化防止剤、難燃剤、抗菌剤、結晶核剤、消泡剤等を挙げることができ、１種または２種以上を組み合わせて用いてもよい。
When the sizing agent of the present invention is an aqueous dispersion or an aqueous solution, the concentration of the non-volatile content is not particularly limited, and the stability of the aqueous dispersion and the viscosity easy to handle as a product are determined by the non-volatile composition of the sizing agent. These are selected as appropriate. Considering the transportation cost of the product, it is preferably 10% by weight or more, more preferably 20 to 60% by weight, and particularly preferably 30 to 50% by weight.
Examples of components other than those described above constituting the sizing agent of the present invention include various surfactants, various smoothing agents, antioxidants, flame retardants, antibacterial agents, crystal nucleating agents, antifoaming agents, and the like. One type or a combination of two or more types may be used.
特に、界面活性剤は、本発明のサイジング剤中に水不溶性または難溶性である樹脂成分を有する場合に、乳化剤として使用することによって、水系乳化を効率よく実施することができる。よって、サイジング剤を水分散体にすることができる。界面活性剤を使用するときの不揮発分全体に占める重量割合は、５〜４０重量％が好ましく、１０〜３０重量％がより好ましく、１５〜２５重量％がさらに好ましい。
界面活性剤としては、特に限定されず、非イオン系界面活性剤、アニオン系界面活性剤、カチオン系界面活性剤および両性界面活性剤から、公知のものを適宜選択して使用することができる。界面活性剤は、１種または２種以上を併用してもよい。
In particular, when the surfactant has a resin component that is water-insoluble or hardly soluble in the sizing agent of the present invention, aqueous surfactant emulsification can be efficiently carried out by using it as an emulsifier. Therefore, the sizing agent can be made into an aqueous dispersion. The weight ratio of the entire non-volatile content when using the surfactant is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, and still more preferably 15 to 25% by weight.
The surfactant is not particularly limited, and a known one can be appropriately selected from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. Surfactant may use together 1 type (s) or 2 or more types.
非イオン系界面活性剤としては、たとえば、アルキレンオキサイド付加非イオン系界面活性剤（高級アルコール、高級脂肪酸、アルキルフェノール、スチレン化フェノール、ベンジルフェノール、ソルビタン、ソルビタンエステル、ヒマシ油、硬化ヒマシ油等にエチレンオキサイド、プロピレンオキサイド等のアルキレンオキサイド（２種以上の併用可）を付加させたもの）、ポリアルキレングリコールに高級脂肪酸等を付加させたもの、エチレンオキサイド／プロピレンオキサイド共重合体等を挙げることができる。
アニオン系界面活性剤としては、たとえば、カルボン酸（塩）、高級アルコール・高級アルコールエーテルの硫酸エステル塩、スルホン酸塩、高級アルコール・高級アルコールエーテルの燐酸エステル塩等を挙げることができる。
Nonionic surfactants include, for example, alkylene oxide-added nonionic surfactants (higher alcohols, higher fatty acids, alkylphenols, styrenated phenols, benzylphenols, sorbitans, sorbitan esters, castor oil, hydrogenated castor oil, etc. And alkylene oxides such as oxides and propylene oxides (two or more types can be used together), polyalkylene glycols added with higher fatty acids, and ethylene oxide / propylene oxide copolymers. .
Examples of the anionic surfactant include carboxylic acid (salt), sulfate ester salt of higher alcohol / higher alcohol ether, sulfonate salt, phosphate ester salt of higher alcohol / higher alcohol ether, and the like.
カチオン系界面活性剤としては、たとえば、第４級アンモニウム塩型カチオン系界面活性剤（ラウリルトリメチルアンモニウムクロライド、オレイルメチルエチルアンモニウムエトサルフェート等）、アミン塩型カチオン系界面活性剤（ポリオキシエチレンラウリルアミン乳酸塩等）等を挙げることができる。 Examples of cationic surfactants include quaternary ammonium salt type cationic surfactants (such as lauryltrimethylammonium chloride and oleylmethylethylammonium etosulphate), amine salt type cationic surfactants (polyoxyethylene laurylamine), and the like. Lactate etc.).
両性界面活性剤としては、たとえば、アミノ酸型両性界面活性剤（ラウリルアミノプロピオン酸ナトリウム等）、ベタイン型両性界面活性剤（ステアリルジメチルベタイン、ラウリルジヒドロキシエチルベタイン等）等を挙げることができる。 Examples of amphoteric surfactants include amino acid type amphoteric surfactants (such as sodium laurylaminopropionate), betaine type amphoteric surfactants (such as stearyl dimethyl betaine, lauryl dihydroxyethyl betaine), and the like.
サイジング剤を製造する方法としては、特に限定はなく、公知の方法を採用できる。例えば、生成された前述の反応生成物を含有する水溶液そのものをサイジング剤として使用することもでき、反応生成物を含有する水溶液に、必要に応じて、水、有機溶媒、その他成分を加えて混合撹拌し、サイジング剤を調製することもできる。 There is no limitation in particular as a method of manufacturing a sizing agent, A well-known method is employable. For example, the generated aqueous solution containing the aforementioned reaction product itself can also be used as a sizing agent, and if necessary, water, an organic solvent, and other components are added to the aqueous solution containing the reaction product and mixed. The sizing agent can also be prepared by stirring.
また、本発明のサイジング剤は、サイジング剤の不揮発分を示唆走査熱量計（ＤＳＣ）で測定したときに、結晶融解に基づく融解吸熱量が３Ｊ／ｇ以上の吸熱ピークを有しないことが好ましい。すなわち、結晶融解に基づく吸熱ピークを有しないか、有する場合であっても該吸熱ピークに基づく融解吸熱量が３Ｊ／ｇ未満であることが好ましい。測定方法やその理由は、反応生成物のところで記載したものと同様である。 The sizing agent of the present invention preferably does not have an endothermic peak with a melting endotherm based on crystal melting of 3 J / g or more when the nonvolatile content of the sizing agent is measured by a suggestion scanning calorimeter (DSC). That is, it is preferable that the endothermic peak based on the endothermic peak is less than 3 J / g even if it has no endothermic peak based on crystal melting. The measuring method and the reason thereof are the same as those described in the reaction product.
本発明のサイジング剤の不揮発分は、結晶融解に基づく融解吸熱量が２Ｊ／ｇ以上の吸熱ピークを有しないこと（結晶融解に基づく吸熱ピークを有しないか、有する場合であっても該吸熱ピークに基づく融解吸熱量が２Ｊ／ｇ未満）が好ましく、結晶融解に基づく融解吸熱量が１Ｊ／ｇ以上の吸熱ピークを有しないこと（結晶融解に基づく吸熱ピークを有しないか、有する場合であっても該吸熱ピークに基づく融解吸熱量が１Ｊ／ｇ未満）がより好ましく、吸熱ピークを有しないことがさらに好ましい。
結晶融解に基づく融解吸熱量が３Ｊ／ｇ以上の吸熱ピークを有しない温度範囲としては、ガラス転移終了時の温度から３００℃の範囲であればよい。
The non-volatile content of the sizing agent of the present invention has no endothermic peak with a melting endotherm based on crystal melting of 2 J / g or more (even if it has no endothermic peak based on crystal melting, the endothermic peak The melting endotherm based on the crystal melting is preferably less than 2 J / g), and the melting endotherm based on the crystal melting does not have an endothermic peak of 1 J / g or more (the endothermic peak based on the crystal melting has or does not have). Is more preferably less than 1 J / g based on the endothermic peak, and more preferably no endothermic peak.
The temperature range in which the melting endotherm based on crystal melting does not have an endothermic peak of 3 J / g or more may be in the range of 300 ° C. from the temperature at the end of the glass transition.
さらに、本発明のサイジング剤の不揮発分は、ＤＳＣ測定において、上述の様に結晶融解に基づく吸熱ピークを有さないことと同義的に、化合物の結晶化に基づく発熱ピークも有さない。 Furthermore, the non-volatile content of the sizing agent of the present invention does not have an exothermic peak due to crystallization of a compound, as defined above in DSC measurement, which is synonymous with not having an endothermic peak due to crystal melting.
本発明の炭素繊維用サイジング剤は、接着阻害の点から、シランカップリング剤を実質的に含有しないほうが好ましい。具体的には、サイジング剤の不揮発分に占めるシランカップリング剤の重量割合は、１重量％以下が好ましく、０．５重量％以下がより好ましく、０．１重量％以下がさらに好ましく、０重量％が特に好ましい。シランカップリング剤としては、例えば、γ−アミノプロピルトリエトキシシラン、γ−（２−アミノエチル）アミノプロピルトリメトキシシラン、γ−グリシドオキシプロピルトリメトキシシラン、γ−メタアクロキシプロピルトリメトキシシラン、ビニルトリス−β−メトキシエトキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン塩酸塩、γ−クロロプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−アミノプロピルメチルジメトキシシラン、γ−（２−アミノエチル）アミノプロピルメチルジメトキシシラン等を挙げることができる。 The sizing agent for carbon fiber of the present invention preferably contains substantially no silane coupling agent from the viewpoint of adhesion inhibition. Specifically, the weight ratio of the silane coupling agent in the nonvolatile content of the sizing agent is preferably 1% by weight or less, more preferably 0.5% by weight or less, further preferably 0.1% by weight or less, and 0% by weight. % Is particularly preferred. Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Vinyltris-β-methoxyethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane Examples thereof include hydrochloride, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, and the like.
〔炭素繊維ストランド〕
本発明の炭素繊維ストランドは、原料炭素繊維ストランドに対して、上記の炭素繊維用サイジング剤を付着させたものであり、熱可塑性マトリックス樹脂を補強するための強化繊維である。
[Carbon fiber strand]
The carbon fiber strand of the present invention is a reinforcing fiber for reinforcing a thermoplastic matrix resin, which is obtained by adhering the sizing agent for carbon fiber to a raw carbon fiber strand.
原料炭素繊維ストランドへのサイジング剤の不揮発分の付着量は適宜選択でき、炭素繊維ストランドが所望の機能を有するための必要量とすればよいが、その付着量は原料炭素繊維ストランドに対して０．１〜２０重量％が好ましい。連続繊維の状態の炭素繊維ストランドにおいては、その付着量は原料炭素繊維ストランドに対して０．１〜１０重量％がより好ましく、０．５〜５重量％がさらに好ましい。また、所定の長さに切断された状態のストランドにおいては０．５〜２０重量％がより好ましく、１〜１０重量％がさらに好ましい。
サイジング剤の付着量が０．１重量％未満であると、樹脂含浸性、接着性に関する本発明の効果が得られにくく、また、炭素繊維ストランドの集束性が不足し、取扱い性が悪くなることがある。また、サイジング剤の付着量が２０重量％超であると、炭素繊維ストランドが剛直になり過ぎて、かえって取扱い性が悪くなったり、コンポジット成型の際に樹脂含浸性が悪くなったりすることがあり好ましくない。
The adhesion amount of the non-volatile component of the sizing agent to the raw carbon fiber strand can be selected as appropriate, and it may be a necessary amount for the carbon fiber strand to have a desired function, but the adhesion amount is 0 with respect to the raw carbon fiber strand. .1 to 20% by weight is preferable. In the carbon fiber strand in a continuous fiber state, the adhesion amount is more preferably 0.1 to 10% by weight, and further preferably 0.5 to 5% by weight with respect to the raw carbon fiber strand. Moreover, in the strand cut | disconnected by the predetermined length, 0.5 to 20 weight% is more preferable, and 1 to 10 weight% is further more preferable.
When the amount of sizing agent is less than 0.1% by weight, the effects of the present invention relating to resin impregnation and adhesion are difficult to obtain, and the carbon fiber strands are not sufficiently converged, resulting in poor handling. There is. In addition, if the amount of sizing agent is more than 20% by weight, the carbon fiber strands may become too rigid, resulting in poor handling properties or resin impregnation properties during composite molding. It is not preferable.
本発明の炭素繊維ストランドの製造方法は、前述のサイジング剤を含み、不揮発分の重量割合が０．５〜１０重量％であり、水と不揮発分の合計の重量割合が９０重量％以上である処理液を調製する調製工程と、原料炭素繊維ストランドに対して不揮発分の付着量が０．１〜２０重量％となるよう、原料炭素繊維ストランドに該処理液を付着させる付着工程とを含むものである。
調製工程において、処理液に占める不揮発分の重量割合は、１〜１０重量％がより好ましく、２〜５重量％がさらに好ましい。水と不揮発分の合計の重量割合は、９５重量％以上がより好ましく、９９重量％以上がさらに好ましく、１００重量％が特に好ましい。
付着工程において、好ましい不揮発分の付着量については、前段落の通りである。サイジング剤を原料炭素繊維ストランドに付着させる方法については、特に限定はないが、サイジング剤をキスローラー法、ローラー浸漬法、スプレー法その他公知の方法で、原料炭素繊維ストランドに付着させる方法であればよい。これらの方法のうちでも、ローラー浸漬法が、サイジング剤を原料炭素繊維ストランドに均一付着できるので好ましい。
得られた付着物の乾燥方法については、特に限定はなく、例えば、加熱ローラー、熱風、熱板等で加熱乾燥することができる。
The manufacturing method of the carbon fiber strand of the present invention includes the sizing agent described above, the weight ratio of the nonvolatile content is 0.5 to 10% by weight, and the total weight ratio of water and the nonvolatile content is 90% by weight or more. A preparation step for preparing the treatment liquid, and an attachment step for attaching the treatment liquid to the raw carbon fiber strand so that the amount of non-volatile matter attached to the raw carbon fiber strand is 0.1 to 20% by weight. .
In the preparation step, the weight ratio of the nonvolatile content in the treatment liquid is more preferably 1 to 10% by weight, and further preferably 2 to 5% by weight. The total weight ratio of water and nonvolatile components is more preferably 95% by weight or more, further preferably 99% by weight or more, and particularly preferably 100% by weight.
In the adhering step, the preferable adhering amount of the nonvolatile content is as described in the previous paragraph. The method for adhering the sizing agent to the raw carbon fiber strand is not particularly limited as long as it is a method for adhering the sizing agent to the raw carbon fiber strand by a kiss roller method, roller dipping method, spray method or other known methods. Good. Among these methods, the roller dipping method is preferable because the sizing agent can be uniformly attached to the raw carbon fiber strands.
There is no limitation in particular about the drying method of the obtained deposit, For example, it can heat-dry with a heating roller, a hot air, a hot plate, etc.
なお、本発明のサイジング剤の原料炭素繊維ストランドへの付着にあたっては、サイジング剤の構成成分全てを混合後に付着させてもよいし、構成成分を別々に二段階以上に分けて付着させてもよい。また、本発明の効果を阻害しない範囲で、エポキシ樹脂、ビニルエステル樹脂、フェノール樹脂などの熱硬化性樹脂および／または本発明のポリマー成分以外のウレタン樹脂、ポリエステル樹脂、ナイロン樹脂、アクリル系樹脂などの熱可塑性樹脂を原料炭素繊維ストランドに付着させてもよい。 In addition, in adhering the raw material carbon fiber strand of the sizing agent of the present invention, all the constituent components of the sizing agent may be attached after mixing, or the constituent components may be attached separately in two or more stages. . In addition, a thermosetting resin such as an epoxy resin, a vinyl ester resin, and a phenol resin and / or a urethane resin other than the polymer component of the present invention, a polyester resin, a nylon resin, an acrylic resin, etc. The thermoplastic resin may be attached to the raw carbon fiber strand.
本発明の炭素繊維ストランドは、各種熱可塑性樹脂をマトリックス樹脂とする複合材料の強化繊維として使用され、使用させる形態としては、連続繊維の状態でも、所定の長さに切断された状態でもよい。 The carbon fiber strand of the present invention is used as a reinforcing fiber of a composite material using various thermoplastic resins as a matrix resin, and the form to be used may be a continuous fiber state or a state cut to a predetermined length.
〔繊維強化複合材料〕
本発明の繊維強化複合材料は、熱可塑性マトリックス樹脂と前述の強化繊維としての炭素繊維ストランドを含むものである。炭素繊維ストランドは本発明のサイジング剤により処理されているので、炭素繊維ストランドおよび熱可塑性マトリックス樹脂との親和性が良好となり、接着性に優れた繊維強化複合材料となる。
ここで、本発明の熱可塑性マトリックス樹脂とは、熱可塑性樹脂からなるマトリックス樹脂をいい、１種または２種以上含んでいてもよい。熱可塑性マトリックス樹脂としては特に制限はなく、ポリオレフィン系樹脂、ポリアミド系樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリアセタール樹脂、ＡＢＳ樹脂、フェノキシ樹脂、ポリメチルメタクリレート樹脂、ポリフェニレンサルフィド樹脂、ポリエーテルイミド樹脂、ポリエーテルケトン樹脂等が挙げられる。これら熱可塑性マトリックス樹脂は、炭素繊維ストランドとの接着性をさらに向上させるなどの目的で、その一部または全部が変性したものであっても差し支えない。
[Fiber-reinforced composite materials]
The fiber-reinforced composite material of the present invention includes a thermoplastic matrix resin and carbon fiber strands as the aforementioned reinforcing fibers. Since the carbon fiber strand is treated with the sizing agent of the present invention, the affinity with the carbon fiber strand and the thermoplastic matrix resin is improved, and the fiber-reinforced composite material having excellent adhesiveness is obtained.
Here, the thermoplastic matrix resin of the present invention refers to a matrix resin made of a thermoplastic resin, and may include one or more kinds. There is no particular limitation on the thermoplastic matrix resin, and polyolefin resin, polyamide resin, polycarbonate resin, polyester resin, polyacetal resin, ABS resin, phenoxy resin, polymethyl methacrylate resin, polyphenylene sulfide resin, polyetherimide resin, poly Examples include ether ketone resins. These thermoplastic matrix resins may be partially or wholly modified for the purpose of further improving the adhesion to the carbon fiber strands.
これら熱可塑性マトリックス樹脂の中でも、本発明のサイジング剤による接着性向上効果がより高いポリアミド系樹脂が好ましい。ここで、ポリアミド系樹脂とは、二塩基性脂肪酸とジアミン、ω−アミノ酸、ラクタムあるいはこれらの誘導体から合成される、主鎖に複数のアミド基を有する高分子化合物であり、ホモポリマーやコポリマー（共重合体）なども含まれる。また、主鎖や末端に置換基を導入した変性体でもよい。 Among these thermoplastic matrix resins, a polyamide-based resin having a higher effect of improving the adhesion by the sizing agent of the present invention is preferable. Here, the polyamide-based resin is a polymer compound having a plurality of amide groups in the main chain, synthesized from dibasic fatty acid and diamine, ω-amino acid, lactam or derivatives thereof. Copolymer) and the like. Moreover, the modified body which introduce | transduced the substituent into the principal chain or the terminal may be sufficient.
繊維強化複合材料の製造方法としては、特に限定はなく、チョップドファイバー、長繊維ペレットなどによるコンパウンド射出成型、ＵＤシート、織物シートなどによるプレス成型、その他フィラメントワインディング成型など公知の方法を採用できる。
繊維強化複合材料中の炭素繊維ストランドの含有量についても特に限定はなく、繊維の種類、形態、熱可塑性マトリックス樹脂の種類などにより適宜選択すればよいが、得られる繊維強化複合材料に対して、５〜７０重量％が好ましく、２０〜６０重量％がより好ましい。
The method for producing the fiber reinforced composite material is not particularly limited, and known methods such as compound injection molding using chopped fibers and long fiber pellets, press molding using UD sheets and woven sheets, and other filament winding molding can be employed.
The content of the carbon fiber strand in the fiber reinforced composite material is not particularly limited, and may be appropriately selected depending on the type of fiber, the form, the type of thermoplastic matrix resin, etc. 5 to 70% by weight is preferable, and 20 to 60% by weight is more preferable.
以下、実施例により本発明を具体的に説明するが、ここに記載した実施例に限定されるものではない。なお、以下の実施例に示されるパーセント（％）は特に限定しない限り、「重量％」を示す。各特性値の測定は以下に示す方法に基づいて行った。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, it is not limited to the Example described here. The percent (%) shown in the following examples represents “% by weight” unless otherwise specified. Each characteristic value was measured based on the following method.
＜接着性＞
複合材料界面特性評価装置ＨＭ４１０（東栄産業株式会社製）を使用し、マイクロドロップレット法により接着性を評価した。
実施例および比較例で製造した炭素繊維ストランドより、炭素繊維フィラメントを取り出し、複合材料界面特性評価装置にセッティングする。装置上で溶融したポリアミド樹脂Ｔ−８６０（東洋紡社製）のドロップを炭素繊維フィラメント上に形成させ、室温で十分に冷却し、測定用の試料を得た。再度測定試料を装置にセッティングし、ドロップを装置ブレードで挟み、炭素繊維フィラメントを装置上で０．０６ｍｍ／分の速度で走行させ、炭素繊維フィラメントからドロップを引き抜く際の最大引き抜き荷重Ｆを測定した。
次式により界面剪断強度τを算出し、炭素繊維フィラメントとポリアミド樹脂との接着性を評価した。
界面剪断強度τ（単位：ＭＰａ）＝Ｆ／πｄｌ
（Ｆ：最大引き抜き荷重 ｄ：炭素繊維フィラメント直径 ｌ：ドロップの引き抜き方向の粒子径）
<Adhesiveness>
The composite material interface property evaluation apparatus HM410 (manufactured by Toei Sangyo Co., Ltd.) was used, and the adhesiveness was evaluated by the microdroplet method.
Carbon fiber filaments are taken out from the carbon fiber strands produced in the examples and comparative examples, and set in a composite material interface property evaluation apparatus. A drop of polyamide resin T-860 (manufactured by Toyobo Co., Ltd.) melted on the apparatus was formed on the carbon fiber filament and sufficiently cooled at room temperature to obtain a sample for measurement. The measurement sample was set in the apparatus again, the drop was sandwiched between the apparatus blades, the carbon fiber filament was run on the apparatus at a speed of 0.06 mm / min, and the maximum extraction load F when the drop was extracted from the carbon fiber filament was measured. .
The interfacial shear strength τ was calculated by the following formula, and the adhesion between the carbon fiber filament and the polyamide resin was evaluated.
Interfacial shear strength τ (unit: MPa) = F / πdl
(F: Maximum pulling load d: Carbon fiber filament diameter l: Particle diameter in the pulling direction of the drop)
＜マトリックス樹脂濡れ性＞
上述の接着性評価における測定用試料について、引き抜き方向のドロップ径が１００〜１２０μｍの範囲にあるドロップを２０個選定し、炭素繊維フィラメントに対する接触角を測定し、その平均値ａを得た。サイジング剤未処理炭素繊維ストランドより取り出した炭素繊維フィラメントを用いて同様にして得た接触角の平均値ｂと比較して、下記基準に従いマトリックス樹脂濡れ性を評価した。
◎： ａ−ｂ≦−１．５°
○：−１．５°＜ａ−ｂ≦−０．５°
△：−０．５°＜ａ−ｂ＜０．５°
×： ０．５°≦ａ−ｂ＜１．５°
××： １．５°≦ａ−ｂ
<Matrix resin wettability>
About the sample for a measurement in the above-mentioned adhesive evaluation, 20 drops with a drop diameter in the range of 100 to 120 μm were selected, the contact angle with respect to the carbon fiber filament was measured, and the average value a was obtained. The matrix resin wettability was evaluated according to the following criteria in comparison with the average value b of the contact angles obtained in the same manner using carbon fiber filaments taken out from the sizing agent-untreated carbon fiber strands.
A: ab ≦ −1.5 °
○: −1.5 ° <ab ≦ −0.5 °
Δ: −0.5 ° <ab−0.5 °
×: 0.5 ° ≦ ab−1.5 °
XX: 1.5 ° ≦ ab
＜融解吸熱量＞
ＪＩＳ−Ｋ７１２１、Ｋ７１２２に準拠し、示差走査熱量計（ＤＳＣ）（パーキンエルマー・インスツルメント社製ＪＡＤＥ ＤＳＣ ＬＡＢ ＳＹＳＴＥＭ）により、試料重量約１０ｍｇ、昇温速度１０℃／分の条件下で測定した。具体的には、１０±１ｍｇで精秤した試料を示差走査熱量計にセットし、予備測定にて確認した試料溶融温度Ｔｍ＋３０℃まで昇温する。次に、予備測定にて確認したガラス転移点Ｔｇ−５０℃まで降温した後、昇温速度１０℃／分で３００℃まで昇温する。得られたＤＳＣ曲線の上に発現する吸熱ピークにおいて、吸熱前後でベースラインから離れる点とベースラインに戻る点とを結んだ直線と、ピーク曲線により囲まれた面積の積分値により計算される値（単位：Ｊ／ｇ）を融解吸熱量とした。
<Melting endotherm>
Based on JIS-K7121, K7122, a differential scanning calorimeter (DSC) (JADE DSC LAB SYSTEM manufactured by PerkinElmer Instruments) was measured under the conditions of a sample weight of about 10 mg and a heating rate of 10 ° C./min. . Specifically, a sample precisely weighed at 10 ± 1 mg is set in a differential scanning calorimeter, and the temperature is raised to the sample melting temperature Tm + 30 ° C. confirmed by the preliminary measurement. Next, after the temperature is lowered to the glass transition point Tg-50 ° C. confirmed by the preliminary measurement, the temperature is raised to 300 ° C. at a temperature raising rate of 10 ° C./min. In the endothermic peak that appears on the obtained DSC curve, a value calculated by the integral value of the area surrounded by the straight line connecting the point away from the baseline and the point returning to the baseline before and after the endotherm, and the peak curve (Unit: J / g) was defined as the melting endotherm.
〔エポキシ化合物と水酸基含有アミン化合物との反応生成物の製造〕
〔製造例１〕
反応器中に、一般式（９）で示されるエポキシ化合物Ｅｑ−ａ（Ｒ５〜Ｒ８：ＣＨ３、ｎ：０、理論分子量：３４０）１６２部およびエチレングリコールモノイソプロピルエーテル３２部を仕込み、９０〜１１０℃で溶融、撹拌均一化した。次にジエタノールアミン９０部を撹拌下で添加し、９０〜１１０℃で２時間反応させ、アミン付加を行った(当量で１：１)。続いて酢酸４８部を徐々に添加し中和反応を行った後、７０〜８０℃に冷却して水６６８部を徐々に添加して水溶化し、不揮発分３０重量％の水エマルジョンである、アミン変性芳香族エポキシ化合物を含むサイジング剤Ｓ−１を得た。なお、理論分子量は、化学式に基づいて求めた式量である。
[Production of reaction product of epoxy compound and hydroxyl-containing amine compound]
[Production Example 1]
In a reactor, 162 parts of an epoxy compound Eq-a represented by the general formula (9) (R 5 to R 8 : CH 3 , n: 0, theoretical molecular weight: 340) and 32 parts of ethylene glycol monoisopropyl ether are charged. The mixture was melted at 90 to 110 ° C. and homogenized with stirring. Next, 90 parts of diethanolamine was added with stirring, and the mixture was reacted at 90 to 110 ° C. for 2 hours to carry out amine addition (equivalent 1: 1). Subsequently, 48 parts of acetic acid was gradually added to carry out a neutralization reaction, followed by cooling to 70 to 80 ° C. and gradually adding 668 parts of water to make it water-soluble, which was an aqueous emulsion having a nonvolatile content of 30% by weight. Sizing agent S-1 containing a modified aromatic epoxy compound was obtained. The theoretical molecular weight is a formula weight determined based on the chemical formula.
〔製造例２〕
反応器中に、一般式（９）で示されるエポキシ化合物Ｅｑ−ｂ（Ｒ５〜Ｒ８：ＣＨ３、ｎ：２、理論分子量：９０８）２２３部およびエチレングリコールモノイソプロピルエーテル３５部を仕込み、９０〜１１０℃で溶融、撹拌均一化した。次にジエタノールアミン５２部を撹拌下で添加し、９０〜１１０℃で２時間反応させ、アミン付加を行った(当量で１：１)。続いて酢酸２５部を徐々に添加し中和反応を行った後、７０〜８０℃に冷却して水６６５部を徐々に添加して水溶化し、不揮発分３０重量％の水エマルジョンである、アミン変性芳香族エポキシ化合物を含むサイジング剤Ｓ−２を得た。
[Production Example 2]
Into a reactor, 223 parts of an epoxy compound Eq-b (R 5 to R 8 : CH 3 , n: 2, theoretical molecular weight: 908) represented by the general formula (9) and 35 parts of ethylene glycol monoisopropyl ether were charged, The mixture was melted at 90 to 110 ° C. and homogenized with stirring. Next, 52 parts of diethanolamine was added with stirring, and the mixture was reacted at 90 to 110 ° C. for 2 hours to carry out amine addition (1: 1 by equivalent). Subsequently, 25 parts of acetic acid was gradually added to carry out a neutralization reaction, followed by cooling to 70 to 80 ° C. and gradually adding 665 parts of water to make it water-soluble, which was an aqueous emulsion having a nonvolatile content of 30% by weight. Sizing agent S-2 containing a modified aromatic epoxy compound was obtained.
〔製造例３〕
反応器中に、一般式（９）で示されるエポキシ化合物Ｅｑ−ｃ（Ｒ５〜Ｒ８：ＣＨ３、ｎ：３、理論分子量：１１９２）２３４部およびエチレングリコールモノイソプロピルエーテル６０部を仕込み、９０〜１１０℃で溶融、撹拌均一化した。次にジエタノールアミン４１部を撹拌下で添加し、９０〜１１０℃で２時間反応させ、アミン付加を行った(当量で１：１)。続いて酢酸２５部を徐々に添加し中和反応を行った後、７０〜８０℃に冷却して水６４０部を徐々に添加して水溶化し、不揮発分３０重量％の水エマルジョンである、アミン変性芳香族エポキシ化合物Ｓ−３を含むサイジング剤を得た。
[Production Example 3]
Into a reactor, 234 parts of an epoxy compound Eq-c represented by the general formula (9) (R 5 to R 8 : CH 3 , n: 3, theoretical molecular weight: 1192) and 60 parts of ethylene glycol monoisopropyl ether were charged, The mixture was melted at 90 to 110 ° C. and homogenized with stirring. Next, 41 parts of diethanolamine was added under stirring and reacted at 90 to 110 ° C. for 2 hours to carry out amine addition (1: 1 by equivalent). Subsequently, 25 parts of acetic acid was gradually added to carry out a neutralization reaction, followed by cooling to 70 to 80 ° C. and gradually adding 640 parts of water to make it water-soluble, which was an aqueous emulsion having a nonvolatile content of 30% by weight. A sizing agent containing a modified aromatic epoxy compound S-3 was obtained.
〔製造例４〕
反応器中に、一般式（１０）で示されるエポキシ化合物Ｅｑ−ｄ（理論分子量：２７２）１５２部およびエチレングリコールモノイソプロピルエーテル３５部を仕込み、９０〜１１０℃で溶融、撹拌均一化した。次にジエタノールアミン１０５部を撹拌下で添加し、９０〜１１０℃で２時間反応させ、アミン付加を行った(当量で１：１)。続いて酢酸４３部を徐々に添加し中和反応を行った後、７０〜８０℃に冷却して水６６５部を徐々に添加して水溶化し、不揮発分３０重量％の水エマルジョンである、アミン変性芳香族エポキシ化合物を含むサイジング剤Ｓ−４を得た。
[Production Example 4]
In a reactor, 152 parts of an epoxy compound Eq-d (theoretical molecular weight: 272) represented by the general formula (10) and 35 parts of ethylene glycol monoisopropyl ether were charged, melted at 90 to 110 ° C., and homogenized with stirring. Next, 105 parts of diethanolamine was added with stirring and reacted at 90 to 110 ° C. for 2 hours to carry out amine addition (1: 1 in equivalent). Subsequently, 43 parts of acetic acid was gradually added to carry out a neutralization reaction, followed by cooling to 70 to 80 ° C. and gradually adding 665 parts of water to make it water-soluble, which was an aqueous emulsion having a nonvolatile content of 30% by weight. A sizing agent S-4 containing a modified aromatic epoxy compound was obtained.
〔製造例５〕
反応器中に、一般式（１１）で示されるエポキシ化合物Ｅｑ−ｅ（理論分子量：５５６）１５２部およびエチレングリコールモノイソプロピルエーテル７０部を仕込み、９０〜１１０℃で溶融、撹拌均一化した。次にジエタノールアミン１００部を撹拌下で添加し、９０〜１１０℃で２時間反応させ、アミン付加を行った(当量で１：１)。続いて酢酸４８部を徐々に添加し中和反応を行った後、７０〜８０℃に冷却して水６３０部を徐々に添加して水溶化し、不揮発分３０重量％の水エマルジョンである、アミン変性芳香族エポキシ化合物を含むサイジング剤Ｓ−５を得た。
[Production Example 5]
In a reactor, 152 parts of an epoxy compound Eq-e (theoretical molecular weight: 556) represented by the general formula (11) and 70 parts of ethylene glycol monoisopropyl ether were charged, melted at 90 to 110 ° C., and homogenized with stirring. Next, 100 parts of diethanolamine was added with stirring, and the mixture was reacted at 90 to 110 ° C. for 2 hours to carry out amine addition (equivalent 1: 1). Subsequently, 48 parts of acetic acid was gradually added to carry out a neutralization reaction, followed by cooling to 70 to 80 ° C. and gradually adding 630 parts of water to make it water-soluble, which was an aqueous emulsion having a nonvolatile content of 30% by weight. Sizing agent S-5 containing a modified aromatic epoxy compound was obtained.
〔製造例６〕
反応器中に、一般式（１２）で示されるエポキシ化合物Ｅｑ−ｆ（ｍ：１、理論分子量：７２０）１８７部およびエチレングリコールモノイソプロピルエーテル３５部を仕込み、９０〜１１０℃で溶融、撹拌均一化した。次にジエタノールアミン７６部を撹拌下で添加し、９０〜１１０℃で２時間反応させ、アミン付加を行った(当量で１：１)。続いて酢酸３７部を徐々に添加し中和反応を行った後、７０〜８０℃に冷却して水６６５部を徐々に添加して水溶化し、不揮発分３０重量％の水エマルジョンである、アミン変性芳香族エポキシ化合物を含むサイジング剤Ｓ−６を得た。
[Production Example 6]
In a reactor, 187 parts of an epoxy compound Eq-f (m: 1, theoretical molecular weight: 720) represented by the general formula (12) and 35 parts of ethylene glycol monoisopropyl ether were charged, melted at 90 to 110 ° C., and stirred uniformly. Turned into. Next, 76 parts of diethanolamine was added with stirring, and the mixture was reacted at 90 to 110 ° C. for 2 hours to carry out amine addition (equivalent 1: 1). Subsequently, 37 parts of acetic acid was gradually added to carry out a neutralization reaction, followed by cooling to 70 to 80 ° C. and gradually adding 665 parts of water to make it water-soluble, which was an aqueous emulsion having a nonvolatile content of 30% by weight. Sizing agent S-6 containing a modified aromatic epoxy compound was obtained.
〔製造例７〕
反応器中に、製造例２と同じエポキシ化合物Ｅｑ−ｂ２３５部およびエチレングリコールモノイソプロピルエーテル３５部を仕込み、９０〜１１０℃で溶融、撹拌均一化した。次にメチルエタノールアミン３９部を撹拌下で添加し、９０〜１１０℃で２時間反応させ、アミン付加を行った(当量で１：１)。続いて酢酸２６部を徐々に添加し中和反応を行った後、７０〜８０℃に冷却して水６６５部を徐々に添加して水溶化し、不揮発分３０重量％の水エマルジョンである、アミン変性芳香族エポキシ化合物を含むサイジング剤Ｓ−７を得た。
[Production Example 7]
In the reactor, 235 parts of the same epoxy compound Eq-b as in Production Example 2 and 35 parts of ethylene glycol monoisopropyl ether were charged, melted at 90 to 110 ° C., and homogenized with stirring. Next, 39 parts of methylethanolamine was added with stirring, and the mixture was reacted at 90 to 110 ° C. for 2 hours to carry out amine addition (equivalent 1: 1). Subsequently, 26 parts of acetic acid was gradually added to carry out a neutralization reaction, followed by cooling to 70 to 80 ° C. and gradually adding 665 parts of water to make it water-soluble, which was a water emulsion having a nonvolatile content of 30% by weight. Sizing agent S-7 containing a modified aromatic epoxy compound was obtained.
〔製造例８〕
反応器中に、製造例２と同じエポキシ化合物Ｅｑ−ｂ２２７部およびエチレングリコールモノイソプロピルエーテル３５部を仕込み、９０〜１１０℃で溶融、撹拌均一化した。次にエチルエタノールアミン４４部を撹拌下で添加し、９０〜１１０℃で２時間反応させ、アミン付加を行った(当量で１：１)。続いて酢酸２９部を徐々に添加し中和反応を行った後、７０〜８０℃に冷却して水６６５部を徐々に添加して水溶化し、不揮発分３０重量％の水エマルジョンである、アミン変性芳香族エポキシ化合物を含むサイジング剤Ｓ−８を得た。
[Production Example 8]
The reactor was charged with 227 parts of the same epoxy compound Eq-b as in Production Example 2 and 35 parts of ethylene glycol monoisopropyl ether, and was melted at 90 to 110 ° C. and homogenized with stirring. Next, 44 parts of ethylethanolamine was added with stirring, and the mixture was reacted at 90 to 110 ° C. for 2 hours to carry out amine addition (1: 1 by equivalent). Subsequently, 29 parts of acetic acid was gradually added to carry out a neutralization reaction, and then cooled to 70 to 80 ° C., and 665 parts of water was gradually added to become water-soluble, which was an aqueous emulsion having a nonvolatile content of 30% by weight. Sizing agent S-8 containing a modified aromatic epoxy compound was obtained.
〔製造例９〕
反応器中に、製造例２と同じエポキシ化合物Ｅｑ−ｂ１５８部およびエチレングリコールモノイソプロピルエーテル３０部を仕込み、９０〜１１０℃で溶融、撹拌均一化した。次にジエタノールアミン９２部を撹拌下で添加し、９０〜１１０℃で２時間反応させ、アミン付加を行った(当量で１：２．５)。続いて酢酸５０部を徐々に添加し中和反応を行った後、７０〜８０℃に冷却して水６７０部を徐々に添加して水溶化し、不揮発分３０重量％の水エマルジョンである、アミン変性芳香族エポキシ化合物を含むサイジング剤Ｓ−９を得た。
[Production Example 9]
In the reactor, 158 parts of the same epoxy compound Eq-b as in Production Example 2 and 30 parts of ethylene glycol monoisopropyl ether were charged, melted at 90 to 110 ° C., and homogenized with stirring. Next, 92 parts of diethanolamine was added under stirring and reacted at 90 to 110 ° C. for 2 hours to carry out amine addition (equivalent 1: 2.5). Subsequently, 50 parts of acetic acid was gradually added to carry out a neutralization reaction, and then cooled to 70 to 80 ° C. and gradually added with 670 parts of water to be water-solubilized, which was an aqueous emulsion having a nonvolatile content of 30% by weight. Sizing agent S-9 containing a modified aromatic epoxy compound was obtained.
上記製造例１〜９のサイジング剤を製造する際に使用したエポキシ化合物のエポキシ基数、エポキシ当量、重量平均分子量を表１に示した。エポキシ基数は、エポキシ化合物に含まれるエポキシ基の数を示す。エポキシ当量は、前述したようにＪＩＳ−Ｋ７２３６に準拠して測定した値を示す。重量平均分子量は、前述したようにＧＰＣを用いて測定した値を示す。 Table 1 shows the number of epoxy groups, epoxy equivalent, and weight average molecular weight of the epoxy compounds used in producing the sizing agents of Production Examples 1 to 9. The number of epoxy groups indicates the number of epoxy groups contained in the epoxy compound. An epoxy equivalent shows the value measured based on JIS-K7236 as mentioned above. A weight average molecular weight shows the value measured using GPC as mentioned above.
上記製造例１〜９における水エマルジョンを１０５℃で熱処理、溶媒等を除去して得られた絶乾物について、ＤＳＣ測定により融解吸熱量を測定した。その結果を表２に示した。 With respect to the absolutely dried product obtained by heat-treating the water emulsion in Production Examples 1 to 9 at 105 ° C. and removing the solvent, the melting endotherm was measured by DSC measurement. The results are shown in Table 2.
〔実施例１〕
サイジング剤Ｓ−１を水で希釈して、不揮発分濃度１０重量％のサイジング剤エマルジョンを調製し、サイジング剤未処理炭素繊維ストランド（繊度８００ｔｅｘ、フィラメント数１２０００本）を浸漬・含浸させた後、１０５℃で１５分間熱風乾燥させて、理論付着量が５％であるサイジング剤処理炭素繊維ストランドを得た。本ストランドについて、前述の方法によりマトリックス樹脂接着性、濡れ性を評価した。その結果を表３に示した。
[Example 1]
After sizing agent S-1 was diluted with water to prepare a sizing agent emulsion having a non-volatile content of 10% by weight, sizing agent-untreated carbon fiber strands (fineness 800 tex, number of filaments 12,000) were immersed and impregnated. The sizing agent-treated carbon fiber strand having a theoretical adhesion amount of 5% was obtained by drying with hot air at 105 ° C. for 15 minutes. About this strand, the matrix resin adhesiveness and wettability were evaluated by the above-mentioned method. The results are shown in Table 3.
〔実施例２〜９〕
実施例１において、サイジング剤Ｓ−１を表３に示すサイジング剤Ｓ−２〜Ｓ−９に変更する以外は実施例１と同様にして、サイジング剤処理炭素繊維ストランドを得、各特性を評価した。その結果を表３に示した。
[Examples 2 to 9]
In Example 1, except for changing the sizing agent S-1 to the sizing agents S-2 to S-9 shown in Table 3, a sizing agent-treated carbon fiber strand was obtained in the same manner as in Example 1, and each characteristic was evaluated. did. The results are shown in Table 3.
〔比較例１〕
加圧反応器中に、アミノエチルピペラジンとアジピン酸からなる塩の５０％水溶液１６０ｇとビスアミノプロピルポリエチレングリコールとアジピン酸からなる塩の５０％水溶液４０ｇを仕込み、窒素置換後、２５０℃で１ＭＰａの加圧下で２時間重合した。その後系内を常圧まで放圧後、さらに２時間重合し、反応を終了した。その後撹拌下で冷却しつつ水を８８ｇ添加して３時間撹拌溶解し、不揮発分５０重量％の水エマルジョンである、親水性ポリアミド樹脂を含むサイジング剤ＰＡ−１を得た。得られたＰＡ−１を水で希釈して、不揮発分濃度１０重量％のサイジング剤エマルジョンＲ−１を調製した以外は、実施例１と同様にしてサイジング剤処理炭素繊維ストランドを得、各特性を評価した。その結果を表３に示した。
[Comparative Example 1]
A pressurized reactor was charged with 160 g of a 50% aqueous solution of a salt composed of aminoethylpiperazine and adipic acid and 40 g of a 50% aqueous solution of a salt composed of bisaminopropyl polyethylene glycol and adipic acid. After purging with nitrogen, 1 MPa at 250 ° C. Polymerization was performed under pressure for 2 hours. Thereafter, after the inside of the system was released to normal pressure, polymerization was further continued for 2 hours to complete the reaction. Then, 88 g of water was added while cooling with stirring, and the mixture was stirred and dissolved for 3 hours to obtain a sizing agent PA-1 containing a hydrophilic polyamide resin, which was a water emulsion having a nonvolatile content of 50% by weight. The sizing agent-treated carbon fiber strand was obtained in the same manner as in Example 1 except that the obtained PA-1 was diluted with water to prepare a sizing agent emulsion R-1 having a nonvolatile content concentration of 10% by weight. Evaluated. The results are shown in Table 3.
〔比較例２〕
乳化器中にＮ−メトキシメチル化ポリアミド（ＤＩＣ社製“ラッカマイド（登録商標）５００３”、Ｎ−メトキシメチル化率：３０％）１０５ｇ、ポリオキシエチレン３〜１０モル付加ラウリルジエタノールアミドエーテル４５ｇ、エチレングリコール１２０ｇを仕込み、９０〜１００℃で溶融、撹拌均一化した。その後７０〜８０℃まで冷却し、ホモミキサーによる撹拌下で、水７３０ｇを徐々に投入し、不揮発分１５重量％の水エマルジョンである、ポリアミド水分散体を含むサイジング剤ＰＡ−２を得た。得られたＰＡ−２を水で希釈して、不揮発分濃度１０重量％のサイジング剤エマルジョンＲ−２を調製した以外は、実施例１と同様にしてサイジング剤処理炭素繊維ストランドを得、各特性を評価した。その結果を表３に示した。
[Comparative Example 2]
In an emulsifier, 105 g of N-methoxymethylated polyamide (“Racamide (registered trademark) 5003” manufactured by DIC, N-methoxymethylation rate: 30%), 45 g of polyoxyethylene 3 to 10 mol added lauryl diethanolamide ether, ethylene 120 g of glycol was charged and melted at 90 to 100 ° C. and homogenized with stirring. Thereafter, the mixture was cooled to 70 to 80 ° C., and 730 g of water was gradually added under stirring by a homomixer to obtain a sizing agent PA-2 containing a water dispersion of polyamide, which was a water emulsion having a nonvolatile content of 15% by weight. The obtained PA-2 was diluted with water to obtain a sizing agent-treated carbon fiber strand in the same manner as in Example 1 except that a sizing agent emulsion R-2 having a nonvolatile concentration of 10% by weight was prepared. Evaluated. The results are shown in Table 3.
〔比較例３〕
撹拌装置を備えたオートクレーブ中に、無水マレイン酸変性ポリプロピレン樹脂（プロピレン／無水マレイン酸グラフト共重合比率（重量％）：９５／５、重量平均分子量：３００００）２２８ｇ、ポリオキシエチレン８モル付加オレイルエーテル５７ｇ、および水酸化ナトリウム１５ｇを仕込み、窒素ガス還流、撹拌下で１７０〜１８０℃まで昇温した。ついで撹拌下水７００ｇを徐々に投入、１７０〜１８０℃で２時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分３０重量％の水エマルジョンである、ポリプロピレン水分散体を含むサイジング剤ＰＰ−１を得た。得られたＰＰ−１を水で希釈して、不揮発分濃度１０重量％のサイジング剤エマルジョンＲ−３を調製した以外は、実施例１と同様にしてサイジング剤処理炭素繊維ストランドを得、各特性を評価した。その結果を表３に示した。
[Comparative Example 3]
In an autoclave equipped with a stirrer, maleic anhydride-modified polypropylene resin (propylene / maleic anhydride graft copolymerization ratio (% by weight): 95/5, weight average molecular weight: 30000) 228 g, polyoxyethylene 8 mol addition oleyl ether 57 g and 15 g of sodium hydroxide were charged, and the temperature was raised to 170 to 180 ° C. under nitrogen gas reflux and stirring. Next, 700 g of stirred water was gradually added and stirred at 170 to 180 ° C. for 2 hours to uniformly dissolve the contents. Thereafter, the mixture was cooled to room temperature, moisture was adjusted, and a sizing agent PP-1 containing a polypropylene aqueous dispersion, which was a water emulsion having a nonvolatile content of 30% by weight, was obtained. The sizing agent-treated carbon fiber strand was obtained in the same manner as in Example 1 except that the obtained PP-1 was diluted with water to prepare a sizing agent emulsion R-3 having a nonvolatile content concentration of 10% by weight. Evaluated. The results are shown in Table 3.
〔比較例４〕
不揮発分３０重量％のウレタン樹脂水エマルジョンであるＤＩＣ社製“ハイドラン（登録商標）ＨＷ−３１０”を水で希釈して、不揮発分濃度１０重量％のサイジング剤エマルジョンＲ−４を調製した以外は、実施例１と同様にしてサイジング剤処理炭素繊維ストランドを得、各特性を評価した。その結果を表３に示した。
[Comparative Example 4]
Except for diluting hydride (registered trademark) HW-310 made by DIC, which is a urethane resin water emulsion having a nonvolatile content of 30% by weight, with water to prepare a sizing agent emulsion R-4 having a nonvolatile content of 10% by weight. In the same manner as in Example 1, sizing agent-treated carbon fiber strands were obtained, and each characteristic was evaluated. The results are shown in Table 3.
表１〜３から明らかなように、比較例と比較して実施例では、いずれもマトリックス樹脂濡れ性及び接着性に関し良好な結果が得られた。 As is clear from Tables 1 to 3, in the Examples as compared with the Comparative Examples, good results were obtained with respect to the matrix resin wettability and the adhesiveness.
Claims (7)
下記一般式（９）で示される化合物、下記一般式（１０）で示される化合物、下記一般式（１１）で示される化合物及び下記一般式（１２）で示される化合物から選ばれる少なくとも１種の芳香族エポキシ化合物と水酸基含有アミン化合物との反応生成物を必須に含み、
サイジング剤の不揮発分に占める前記反応生成物の重量割合が９０〜１００重量％であり、
サイジング剤の不揮発分を示唆走査熱量計（ＤＳＣ）で測定したとき、融解吸熱量が３Ｊ／ｇ以上の吸熱ピークを有しない、
炭素繊維用サイジング剤。
At least one selected from the compound represented by the following general formula (9), the compound represented by the following general formula (10), the compound represented by the following general formula (11) and the compound represented by the following general formula (12) required to look contains a reaction product of an aromatic epoxy compound and a hydroxyl group-containing amine compound,
The weight ratio of the reaction product in the nonvolatile content of the sizing agent is 90 to 100% by weight,
When the non-volatile content of the sizing agent is measured with a suggestion scanning calorimeter (DSC), the melting endotherm has no endothermic peak of 3 J / g or more,
Carbon fiber sizing agent.
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