JPH02307979A - Sizing agent for carbon fiber - Google Patents
Sizing agent for carbon fiberInfo
- Publication number
- JPH02307979A JPH02307979A JP1129383A JP12938389A JPH02307979A JP H02307979 A JPH02307979 A JP H02307979A JP 1129383 A JP1129383 A JP 1129383A JP 12938389 A JP12938389 A JP 12938389A JP H02307979 A JPH02307979 A JP H02307979A
- Authority
- JP
- Japan
- Prior art keywords
- sizing agent
- poise
- viscosity
- epoxy resin
- bisphenol
- 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.)
- Pending
Links
- 238000004513 sizing Methods 0.000 title claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 42
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 27
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004844 aliphatic epoxy resin Substances 0.000 claims abstract description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims abstract description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims abstract description 3
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 claims abstract 2
- 125000002947 alkylene group Chemical group 0.000 claims abstract 2
- 239000000839 emulsion Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- -1 styryl phenyl ether Chemical compound 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 23
- 239000011347 resin Substances 0.000 abstract description 23
- 239000011159 matrix material Substances 0.000 abstract description 13
- 239000003822 epoxy resin Substances 0.000 abstract description 10
- 229920000647 polyepoxide Polymers 0.000 abstract description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- PBEHQFUSQJKBAS-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;phenol Chemical compound OC1=CC=CC=C1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 PBEHQFUSQJKBAS-UHFFFAOYSA-N 0.000 abstract 1
- 229930185605 Bisphenol Natural products 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 description 9
- 239000000835 fiber Substances 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 150000000376 2-oxazolines Chemical class 0.000 description 3
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- ZDNUPMSZKVCETJ-UHFFFAOYSA-N 2-[4-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=C(C=2OCCN=2)C=C1 ZDNUPMSZKVCETJ-UHFFFAOYSA-N 0.000 description 1
- ZXTHWIZHGLNEPG-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC=C1 ZXTHWIZHGLNEPG-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229960001019 oxacillin Drugs 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は新規な炭素繊維用サイジング剤に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a novel sizing agent for carbon fibers.
複合材料の強化材として用いられる炭素繊維は伸度が小
さく脆い繊維であるため、機械的損傷を受けやすく、摩
擦等によって毛羽を発生しやすい。そこで炭素繊維の取
扱い性を良くするために炭素ＩｆＲ，ａはサイジング剤
で処理されることが多い。Carbon fibers used as reinforcing materials in composite materials are brittle fibers with low elongation, so they are susceptible to mechanical damage and easily generate fuzz due to friction and the like. Therefore, in order to improve the handling properties of carbon fibers, carbon IfR,a is often treated with a sizing agent.
炭素繊維用のサイジング剤としては、従来多くのサイジ
ング剤が提案されている（特公昭５７−１５２２９号、
同５７−４９６７５号、特開昭６０−２４６８７２号、
同６ Ｓ −１０５１７８号、同６４−４５８７０号公
報等）。Many sizing agents have been proposed as sizing agents for carbon fibers (Japanese Patent Publication No. 57-15229,
No. 57-49675, JP-A No. 60-246872,
6S-105178, 64-45870, etc.).
しかしサイジング剤には、炭素繊維の取扱す性をｉくす
ると同時にマ）ＩＪラックス脂の含浸性をよくすること
、複合材料の性能を損なわないこと等多くの機能が要求
されている。However, sizing agents are required to have many functions, such as improving the handling properties of carbon fibers, improving the impregnating properties of IJ lux fat, and not impairing the performance of composite materials.
特に織物の炭素繊維は、！ｌ１ｌｆｔｈ性の点から取扱
い性に優れ、摩擦係数の少ないこと及び収束性があり、
ロール等への巻付きの少ないことが要求される。Especially woven carbon fiber! It has excellent handling properties in terms of l1lfth properties, low friction coefficient, and convergence.
It is required that there is little winding around rolls, etc.
またマトリックス樹脂は、エポキシ樹脂、不飽和ポリエ
ステル樹脂等の多くの種類が用いられ、サイジング剤を
改良して、多くの種類のマトリックス樹脂に対して含浸
性を良くすることは困難であった。Furthermore, many types of matrix resins are used, such as epoxy resins and unsaturated polyester resins, and it has been difficult to improve the impregnating properties of many types of matrix resins by improving the sizing agent.
本発明は炭素繊維の収束性、耐摩耗性に優れ且つエポキ
シ樹脂、不飽和ポリエステル樹脂等の樹脂含浸性に優れ
た炭素繊維用のサイジング剤を提供することにある。The object of the present invention is to provide a sizing agent for carbon fibers that has excellent convergence and abrasion resistance of carbon fibers, and is excellent in impregnation with resins such as epoxy resins and unsaturated polyester resins.
特に織物用の炭素繊維用として製織工程通過性が良好で
、ハンドレイアップ等の樹脂含浸工程においても樹脂含
浸速度の速い性能を示すサイジング剤を提供することに
ある。It is an object of the present invention to provide a sizing agent particularly for use in carbon fibers for textiles that has good weaving process passability and exhibits high resin impregnation speed even in resin impregnation processes such as hand lay-up.
本発明の要旨は、下記の（１）及び（６）を必須成分と
して、（１）〜（６）から選ばれた少なくとも３種の化
合物からなる混合物であり、２５Ｃの粘度が３０ポイズ
以上且っ５ｏ℃の粘度が１０００ポイズ以下であること
を特徴とする炭素繊維用サイジング剤にある。The gist of the present invention is a mixture consisting of at least three kinds of compounds selected from (1) to (6), with the following (1) and (6) as essential components, and which has a 25C viscosity of 30 poise or more and A sizing agent for carbon fibers characterized by having a viscosity of 1000 poise or less at 5oC.
（１） ２５℃ノ粘度が３０ポイズ以上のビスフェノー
ルＡ型エポキシ樹脂またはビスフェノールＦ型エポキシ
樹脂
（２）２５℃の粘度が５０ポイズ以下の長鎖脂肪族エポ
キシ樹脂
（３）２５℃の粘度が５０ポイズ以下の環状脂肪族エポ
キシ樹脂
（４）２−オキサゾリン誘導体
（５） 下記式で示されるジメタアクリル酸又はアク
リル酸のフルキレンオキ号イド付加物（６）不飽和脂肪
酸グリセライドのエチレンオキサイド付加物またはポリ
エチレンオキサイドスチリルフェニルエーテルの乳化剤
成分（１）はエピコート８２８等の商品名で知られるビ
スフェノールＡ型エポキシ樹脂、二ピコ−）８０７等の
商品名で知られるビスフェノールＦ型エポキシ樹脂であ
り、成分（１）の使用量は水分を除いたサイジング剤全
体の４０〜８０ｗｔ４であることが好ましい。(1) Bisphenol A epoxy resin or bisphenol F epoxy resin with a viscosity of 30 poise or more at 25°C (2) Long chain aliphatic epoxy resin with a viscosity of 50 poise or less at 25°C (3) A viscosity of 50 poise or less at 25°C Cycloaliphatic epoxy resin (4) 2-oxazoline derivative (5) Fullylene oxide adduct of dimethacrylic acid or acrylic acid represented by the following formula (6) Ethylene oxide adduct of unsaturated fatty acid glyceride or polyethylene oxide styryl The emulsifier component (1) of phenyl ether is a bisphenol A epoxy resin known under trade names such as Epicote 828, and a bisphenol F epoxy resin known under trade names such as Nipico-807. The amount is preferably 40 to 80 wt4 of the entire sizing agent excluding water.
成分（２）はエピコート８７１等の商品名で知られる長
鎖脂肪族エポキシ樹脂、成分（３）は七ロキサイド２０
２）等の商品名で知られる環状脂肪族エポキシ樹脂であ
り、成分（２）あるいは（３）の使用量は水分を除いた
サイジング剤全体の０〜８０ａｔ憾好ましくは４０〜８
０ ｗｔ鴫である。Component (2) is a long-chain aliphatic epoxy resin known by trade names such as Epicote 871, and component (3) is heptaoxide 20.
It is a cycloaliphatic epoxy resin known under the trade name 2), and the amount of component (2) or (3) used is 0 to 80 at, preferably 40 to 8 at, of the entire sizing agent excluding water.
0 wt crow.
成分（４）の２−オキサゾリン誘導体は例えば２−フェ
ニル２−オキサゾリン、１．３−あるいは１．４−フェ
ニレンビス（２−オキサゾリン）等である。The 2-oxazoline derivative of component (4) is, for example, 2-phenyl-2-oxazoline, 1,3- or 1,4-phenylenebis(2-oxazoline), and the like.
成分（４）あるいは（５）の使用量は水分を除いたすイ
ジング剤全体の０〜２０ ｗｔ’ｌであることが好まし
い。The amount of component (4) or (5) used is preferably 0 to 20 wt'l of the entire ising agent excluding water.
成分（６）の使用量は水分を除いたサイジング剤全体の
０．１〜２０ ｗｔ４好ましくは０５〜１０ｗｔ４であ
る。The amount of component (6) used is 0.1 to 20 wt4, preferably 05 to 10 wt4, based on the entire sizing agent excluding water.
炭素＃雑用サイジング剤における夫々の成分は、マ）
ＩＪラックスの反応性、樹脂含浸性、炭素繊維トウの収
束性、耐摩耗性に重要な作用を及？’ｌ’すが、夫々の
成分が複合してこれらの特性を向上させている。従って
、成分一つ一つの作用を説明することは国難であるが、
本発明のサイジング剤成分の作用は次の様なものと推定
される。Carbon #Each component in the miscellaneous sizing agent is
Does it have an important effect on IJ Lux's reactivity, resin impregnation, carbon fiber tow convergence, and abrasion resistance? However, each component is combined to improve these properties. Therefore, it is a national challenge to explain the effects of each ingredient.
The action of the sizing agent component of the present invention is presumed to be as follows.
成分（１）は、マトリックス樹脂と反応してコンポジッ
トの特性を向上させたり、マトリックス樹脂の含浸性を
向上させたり、炭素線維トウに収束性を与えるのに必須
の成分である。Component (1) is an essential component for improving the properties of the composite by reacting with the matrix resin, improving the impregnating property of the matrix resin, and imparting convergence to the carbon fiber tow.
成分（２）あるいは（３）は、成分（１）と同様にマト
リックス樹脂と反応してコンポジットの特性を向上させ
たり、マトリックス樹脂の含浸性を向上させたりするの
に必須の成分であると同時に、炭素繊維トウに柔軟性を
与え、耐摩耗性を向上させる成分である。Component (2) or (3), like component (1), is an essential component that reacts with the matrix resin to improve the properties of the composite and improves the impregnability of the matrix resin. , is a component that gives flexibility to carbon fiber tow and improves wear resistance.
成分（４）は、マトリックス樹脂がビニルエステル、不
飽和エステルの場合Ｋ、マトリックス樹脂と反応してコ
ンポジット性能を向上させたり、マトリックス樹脂の含
浸性を向上させるのに重要な働きをする成分である。Component (4) is K when the matrix resin is a vinyl ester or unsaturated ester, and is a component that plays an important role in reacting with the matrix resin to improve composite performance and impregnating properties of the matrix resin. .
成分（５）は、成分（２）と同様に炭素繊維トウに柔軟
性を与え、炭素繊維トウの耐摩耗性を向上させると同時
に、成分（４）と同様くマトリックスがビニルエステル
、不飽和エステルの場合に、マトリックス樹脂の含浸性
を向上させる成分である。Component (5), like component (2), gives flexibility to the carbon fiber tow and improves the abrasion resistance of the carbon fiber tow, and at the same time, like component (4), the matrix is vinyl ester or unsaturated ester. In this case, it is a component that improves the impregnating properties of the matrix resin.
成分（６）は、前述の成分と混合されて水エマルジョン
を作るときの乳化剤として必須の成分である。Component (6) is an essential component as an emulsifier when mixed with the above-mentioned components to make a water emulsion.
さらに本発明者らは、炭素繊維トウの収束性はサイジン
グ剤成分の粘度が高いほど良くなり、耐摩耗性はサイジ
ング剤成分の粘度が低いほど良くなることを見出し、炭
素＃Ｍ）つの収束性と耐摩耗性を両立させるＫは、水分
を除いたサイジング剤成分の２５℃の粘度が３０ポイズ
以上、５０℃の粘度が１０００ポイズ以下であるものが
好ましいことを見出した。Furthermore, the present inventors found that the higher the viscosity of the sizing agent component, the better the convergence of carbon fiber tows, and the lower the viscosity of the sizing agent component, the better the wear resistance. It has been found that it is preferable for K to achieve both wear resistance and abrasion resistance to have a viscosity of the sizing agent component excluding moisture of 30 poise or more at 25°C and 1000 poise or less at 50°C.
またこれらサイジング剤は、メチルエチルケトン等の有
機溶剤に溶解して用いるより、水エマルジョンで用いる
方が炭素繊維製造工程から考えると使い易い。特にサイ
ジング剤は、・通常炭素繊維焼成１稈の後に、同じ建屋
の中で使用される場合が多く、炭素繊維焼成工程では、
１０００℃以上の高温の炉を使用するので、有機溶剤を
用いるのは非常に危険である。そこで通常サイジング剤
は、水エマルジョンで用いられるが、その時エマルジョ
ンの安定性が低いとサイジング剤をたえず取替えること
が必要である。そこで本発明者らは、エマルジョンの安
定性が、工フルジョン粒子の大きさに大きく影響される
ことを見出し、サイジング剤成分をエマルジョン溶液に
した時のエマルジョン粒子で、２μｍ以下のものが５０
係以上であるものが好ましいことを見出した。In addition, it is easier to use these sizing agents in a water emulsion than by dissolving them in an organic solvent such as methyl ethyl ketone, considering the carbon fiber manufacturing process. In particular, sizing agents are often used in the same building after one culm of carbon fiber firing, and in the carbon fiber firing process,
Since a high-temperature furnace of 1000° C. or higher is used, it is extremely dangerous to use organic solvents. Therefore, sizing agents are usually used in water emulsions, but if the stability of the emulsion is low, it is necessary to constantly replace the sizing agents. Therefore, the present inventors discovered that the stability of emulsions is greatly influenced by the size of the engineered fulsion particles.
We found that it is preferable that the
水エマルジョンでサイジング剤を付着した炭素繊維トウ
は、後のコンポジット性能を考よると、水分を出来るだ
け除去する必要がある。しかし乾燥温度を下げると乾燥
時間が長くなり不都合である。そこで乾燥は１５０℃以
上の湿度で行う方が効率的である。本発明者らは、その
時サイジング剤成分が変質しないように、水分を除いた
サイジング剤成分の１０℃／分の昇温速度での熱減量が
１５０℃で１幅以下、２００℃で５４以下であることが
好ましいことを見出した。Considering the performance of the composite afterward, it is necessary to remove as much water as possible from the carbon fiber tow to which the sizing agent has been attached using a water emulsion. However, lowering the drying temperature increases the drying time, which is disadvantageous. Therefore, it is more efficient to dry at a humidity of 150° C. or higher. In order to prevent the sizing agent component from deteriorating at that time, the present inventors have determined that the heat loss of the sizing agent component excluding water at a heating rate of 10°C/min is 1 width or less at 150°C and 54 or less at 200°C. I found that certain things are preferable.
以下実施例により本発明を具体的に説明する。 The present invention will be specifically explained below using Examples.
サイジング剤付着炭素繊維の評価は下記の様に行った。Evaluation of the sizing agent-adhered carbon fibers was performed as follows.
（１） 柔軟性
サイジング剤付着繊維をカンチレバ一方式でトウを測定
台の端から１６０ｍ押し出したときの垂れる長さを測定
した。(1) The length of the flexible sizing agent-adhered fibers was measured when the tow was pushed out 160 m from the end of the measuring table using a cantilever method.
（２）耐摩耗性
サイジング剤付着繊維同志を９０℃に擦り合わせ、切れ
るまでＫかかった回数で評価した。(2) Abrasion resistance The fibers to which the sizing agent was attached were rubbed together at 90° C., and evaluated by the number of times K was applied until the fibers broke.
（３） 樹脂含浸性
エポキシ樹脂＋５４０（三菱レイヨン製）ヲ離型紙にコ
ートシたホットメルトフィルムにサイジング剤付着繊維
を巻揃えて、樹脂の含浸してｂないａｎ（一方向）フィ
ルムを作成し、それを７０℃の雰囲気下、５分間Ｓｌ！
型紙を上向きにおいて樹脂を含浸させ、そのときに離型
紙と反対側まで樹脂が含浸しているかを評価した。(3) A hot melt film coated with resin-impregnated epoxy resin +540 (manufactured by Mitsubishi Rayon) on a release paper is wound with sizing agent-adhered fibers to create a resin-impregnated AN (unidirectional) film. SL it for 5 minutes in an atmosphere of 70℃!
The paper pattern was impregnated with resin while facing upward, and it was evaluated whether the resin impregnated to the side opposite to the release paper.
クロス炭素繊維の樹脂含浸性は、サイジング剤付着炭素
ｕ＆＋１）をクロスに織プ、上記と同様にエポキシ樹脂
との含浸性を評価すると同時に、ビニルエステル系の樹
脂の含浸ａＫついても評価した。The resin impregnation properties of the cloth carbon fibers were evaluated by weaving sizing agent-adhered carbon u&+1) into the cloth and evaluating the impregnation properties with epoxy resin in the same manner as above, and at the same time, the impregnation aK with vinyl ester resin was also evaluated.
（４） エマルジョン粒子 漏湯製作所製、０ＡＰＡ−５００で測定した。(4) Emulsion particles Measured with 0APA-500 manufactured by Yuyu Seisakusho.
（５）ＴＧＡ
カーノの熱天秤で、昇温速度１０℃／分で１５０℃、２
００℃における重量減少を測定した。(5) TGA: 150°C at a heating rate of 10°C/min on a Curno thermobalance, 2
Weight loss at 00°C was measured.
ＢＰ８２８ ：ビスフェノールＡ型エポキシ樹脂（油化
シェルエポキシ■製）
ｆｃＰ８７１ ：脂肪族エポキシ樹脂
（油化シェルエポキシ■製）
セロ孝サイド２０２） ： 環状脂肪族エポキシ樹脂
（ダイセル化学工業■製）
ＰＢＯ：１，３フ二二レンビス−２−オキサシリ ン
ＢＧＭム：ビスフェノールＡのエチレンオキサイド付加
物のジメタクリレート
Ｇｘｏ：不飽和脂肪酸グリセライドのエチレンオキサイ
ド付加物
実施例１
サイジング剤として、÷÷モ→→第１表に示す組成のも
のを水エマルジヨン溶液とし、１．５幅濃度に調製した
。水分を除すたサイジング剤成分の粘度は、２５℃で３
６０ポイズ・ ５０℃で３８ポイズであった。ＴＧＡの
１５０℃及び２００℃における重量減少は殆んど０であ
った。BP828: Bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy ■) fcP871: Aliphatic epoxy resin (manufactured by Yuka Shell Epoxy ■) Serokoside 202): Cycloaliphatic epoxy resin (manufactured by Daicel Chemical Industries ■) PBO: 1 , 3 phenylene bis-2-oxacillin BGM: Dimethacrylate of ethylene oxide adduct of bisphenol A Gxo: Ethylene oxide adduct of unsaturated fatty acid glyceride Example 1 As a sizing agent, A water emulsion solution having the composition shown below was prepared to a concentration of 1.5. The viscosity of the sizing agent component after removing water is 3 at 25°C.
It was 60 poise and 38 poise at 50°C. The weight loss of TGA at 150°C and 200°C was almost 0.
水エマルジョンにした時のエマルジョン粒子ハ、２μｍ
以下が９４憾であった。Emulsion particles when made into a water emulsion are 2μm
The following were 94 regrets.
炭素繊維（三菱レイヨン■製パイロフィルＴＲ４０）ｓ
ｏｏｏフィラメントのノンサイジング糸を上記サイジン
グ剤溶液に十分浸漬させた後、空気中１４０℃で５分間
乾燥させた。サイジング剤付着量はα６゛７憾であった
。柔軟性は１８５■であり、耐摩耗回数は１７５回であ
った。エポキシ樹脂の含浸性も良く、圧力を加えずに７
０℃５分間で、殆んどの樹脂が含浸した。Carbon fiber (Pyrofil TR40 manufactured by Mitsubishi Rayon)
After fully immersing the ooo filament non-sized yarn in the above sizing agent solution, it was dried in air at 140° C. for 5 minutes. The amount of sizing agent deposited was α6゛7. The flexibility was 185 ■, and the abrasion resistance was 175 times. The epoxy resin has good impregnating properties and can be used without applying pressure.
Most of the resin was impregnated in 5 minutes at 0°C.
実施例２
実施例１ど同様にして、サイジング剤の成分を変更して
実験したところ、第１表のような結果が得られた。Example 2 An experiment was conducted in the same manner as in Example 1 by changing the components of the sizing agent, and the results shown in Table 1 were obtained.
実施例３
実施例１と同様にして、サイジング剤の成分を変更して
実験したところ、ｇｉ表のような結果が得られた。Example 3 An experiment was conducted in the same manner as in Example 1 by changing the components of the sizing agent, and the results shown in the gi table were obtained.
尚、サイジング剤付着炭素横維をクロスに織り、エポキ
シ樹脂の樹脂含浸性を調べたところ７０℃５分で殆んど
含浸し、良好な樹脂含浸性を示した。またビニルニスゲ
ル系マトリックス樹脂の含浸性も良好であった。Incidentally, when the sizing agent-attached carbon transverse fibers were woven into a cloth and the resin impregnation property of the epoxy resin was examined, most of the fibers were impregnated with the epoxy resin after 5 minutes at 70°C, indicating good resin impregnation properties. In addition, the impregnating properties of the vinyl varnish gel matrix resin were also good.
Claims (1)
〜（６）から選ばれた少なくとも３種の化合物からなる
混合物であり、２５℃の粘度が３０ポイズ以上且つ５０
℃の粘度が１０００ポイズ以下であることを特徴とする
炭素繊維用サイジング剤 （１）２５℃の粘度が３０ポイズ以上のビスフェノール
Ａ型エポキシ樹脂またはビスフェノールＦ型エポキシ樹
脂 （２）２５℃の粘度が５０ポイズ以下の長鎖脂肪族エポ
キシ樹脂 （３）２５℃の粘度が５０ポイズ以下の環状脂肪族エポ
キシ樹脂 （４）２−オキサゾリン誘導体 （５）下記式で示されるジメタアクリル酸又はアクリル
酸のアルキレンオキサイド付加物 ▲数式、化学式、表等があります▼ （Ｒ＿１：Ｈ又はＣＨ＿３ Ｒ＿２：ＣＨ＿２−ＣＨ＿２又はＣＨ＿２−ＣＨ＿２−
ＣＨ＿２Ｒ＿３：Ｒ＿３又は▲数式、化学式、表等があ
ります▼） （６）不飽和脂肪酸グリセライドのエチレンオキサイド
付加物またはポリエチレンオキサイドスチリルフエニル
エーテルの乳化剤 ２、水分を除いたサイジング剤成分の１０℃／分の昇温
速度での熱減量が１５０℃で１％以下、２００℃で５％
以下であることを特徴とする請求項１記載のサイジング
剤 ３、水エマルジョン溶液にしたときのエマルジョン粒子
が２μｍ以下のものが５０％以上であることを特徴とす
る請求項１又は２記載のサイジング剤[Claims] 1. The following (1) and (6) are essential components, (1)
It is a mixture consisting of at least three kinds of compounds selected from ~(6), and the viscosity at 25°C is 30 poise or more and 50 poise or more.
Sizing agent for carbon fibers characterized by having a viscosity of 1000 poise or less at 25°C (1) Bisphenol A epoxy resin or bisphenol F epoxy resin having a viscosity of 30 poise or more at 25°C (2) A sizing agent for carbon fibers having a viscosity at 25°C of 30 poise or more (3) Long-chain aliphatic epoxy resin with a viscosity of 50 poise or less at 25°C (4) 2-oxazoline derivative (5) Dimethacrylic acid or alkylene oxide of acrylic acid represented by the following formula Additives ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R_1: H or CH_3 R_2: CH_2-CH_2 or CH_2-CH_2-
CH_2R_3: R_3 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼) (6) Emulsifier 2 of ethylene oxide adduct of unsaturated fatty acid glyceride or polyethylene oxide styryl phenyl ether, sizing agent components excluding water at 10°C/min Thermal loss at a temperature increase rate of 1% or less at 150℃ and 5% at 200℃
The sizing agent 3 according to claim 1, characterized in that: the sizing agent 3 according to claim 1 or 2, characterized in that when made into a water emulsion solution, 50% or more of the emulsion particles are 2 μm or less agent
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1129383A JPH02307979A (en) | 1989-05-23 | 1989-05-23 | Sizing agent for carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1129383A JPH02307979A (en) | 1989-05-23 | 1989-05-23 | Sizing agent for carbon fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02307979A true JPH02307979A (en) | 1990-12-21 |
Family
ID=15008223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1129383A Pending JPH02307979A (en) | 1989-05-23 | 1989-05-23 | Sizing agent for carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02307979A (en) |
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|---|---|---|---|---|
| JPH11315470A (en) * | 1998-01-08 | 1999-11-16 | Ten Cate Advanced Composites Bv | Production of carbon fiber fabric |
| JP2004263359A (en) * | 2003-01-07 | 2004-09-24 | Mitsubishi Rayon Co Ltd | Carbon fiber bundle, chopped carbon fiber bundle, method for producing the same, carbon fiber-reinforced thermoplastic resin composition and molded product of the same |
| JPWO2003010383A1 (en) * | 2001-07-24 | 2004-11-18 | 三菱レイヨン株式会社 | Sizing agent for carbon fiber, aqueous dispersion thereof, sizing-treated carbon fiber, sheet using the carbon fiber, and carbon fiber reinforced composite material |
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-
1989
- 1989-05-23 JP JP1129383A patent/JPH02307979A/en active Pending
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|---|---|---|---|---|
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| JPWO2003010383A1 (en) * | 2001-07-24 | 2004-11-18 | 三菱レイヨン株式会社 | Sizing agent for carbon fiber, aqueous dispersion thereof, sizing-treated carbon fiber, sheet using the carbon fiber, and carbon fiber reinforced composite material |
| JP2004263359A (en) * | 2003-01-07 | 2004-09-24 | Mitsubishi Rayon Co Ltd | Carbon fiber bundle, chopped carbon fiber bundle, method for producing the same, carbon fiber-reinforced thermoplastic resin composition and molded product of the same |
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| WO2013099707A1 (en) | 2011-12-27 | 2013-07-04 | 東レ株式会社 | Carbon fiber coated with sizing agent, process for producing carbon fiber coated with sizing agent, prepreg, and carbon fiber reinforced composite material |
| WO2014017339A1 (en) | 2012-07-25 | 2014-01-30 | 東レ株式会社 | Prepreg and carbon-fiber-reinforced composite material |
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