JPH02259166A - Sizing agent for reinforcing fiber - Google Patents
Sizing agent for reinforcing fiberInfo
- Publication number
- JPH02259166A JPH02259166A JP30757889A JP30757889A JPH02259166A JP H02259166 A JPH02259166 A JP H02259166A JP 30757889 A JP30757889 A JP 30757889A JP 30757889 A JP30757889 A JP 30757889A JP H02259166 A JPH02259166 A JP H02259166A
- Authority
- JP
- Japan
- Prior art keywords
- sizing agent
- fibers
- formula
- fiber
- reinforcing fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 52
- 238000004513 sizing Methods 0.000 title claims abstract description 52
- 239000012783 reinforcing fiber Substances 0.000 title claims abstract description 29
- 150000008107 benzenesulfonic acids Chemical class 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 239000004917 carbon fiber Substances 0.000 abstract description 28
- 239000004734 Polyphenylene sulfide Substances 0.000 abstract description 17
- 229920000069 polyphenylene sulfide Polymers 0.000 abstract description 17
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 229920006015 heat resistant resin Polymers 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 6
- 239000003365 glass fiber Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 abstract description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 abstract 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 27
- 239000000835 fiber Substances 0.000 description 25
- 239000002131 composite material Substances 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- -1 polyphenylene Polymers 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 230000000704 physical effect Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 9
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000011295 pitch Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000805 composite resin Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004695 Polyether sulfone Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- WRUAHXANJKHFIL-UHFFFAOYSA-N benzene-1,3-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(S(O)(=O)=O)=C1 WRUAHXANJKHFIL-UHFFFAOYSA-N 0.000 description 2
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- LFVLUOAHQIVABZ-UHFFFAOYSA-N Iodofenphos Chemical compound COP(=S)(OC)OC1=CC(Cl)=C(I)C=C1Cl LFVLUOAHQIVABZ-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は補強繊維で強化された熱可塑性樹脂複合材料、
特にポリフェニレンサルファイ１〜等の硫黄含有耐熱性
樹脂複合材料を製造するのに好適な補強繊維を与えるた
めのサイジング剤に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a thermoplastic resin composite material reinforced with reinforcing fibers,
In particular, the present invention relates to a sizing agent for providing reinforcing fibers suitable for producing sulfur-containing heat-resistant resin composite materials such as polyphenylene sulfide 1 and the like.
補強繊維と各種合成樹脂、金属あるいはセラミックス等
のマトリックスとの複合材料は、比強度、比弾性率など
の機械的性質に優れているため、航空機部品、宇宙機器
、精密機械、テニスラケッ１〜やゴルフシャツ１−など
のスポーツ用品等の広い分野において利用されている。Composite materials of reinforcing fibers and matrices such as various synthetic resins, metals, or ceramics have excellent mechanical properties such as specific strength and specific modulus, so they are used in aircraft parts, space equipment, precision machinery, tennis rackets, and golf balls. It is used in a wide range of fields such as sports goods such as shirts.
ところで、この補強繊維強化複合材料をより高強度、高
弾性のものに改善する方法については従来より種々の研
究がなされているが、一般に補強繊維の優れた特性を充
分に発揮させるためには補強繊維と７１〜リツクスとの
親和性、接着性を高めることが重要とされ、かかる観点
から補強繊維の表面を活性化させるための各種サイジン
グ剤が数多く提案されている。By the way, various studies have been conducted on methods to improve this reinforced fiber-reinforced composite material to have higher strength and higher elasticity, but in general, in order to fully utilize the excellent properties of reinforcing fibers, reinforcement It is considered important to increase the affinity and adhesion between fibers and 71~Rix, and from this point of view, a number of various sizing agents have been proposed for activating the surface of reinforcing fibers.
このようなサイジンク剤としては、従来がらエポキシ樹
脂系のものが多く用いられているが、該サイジング剤は
熱硬化性樹脂系の７１〜リツクス樹脂に対しては親和性
や含浸性に優れ、非常に良好な効果を奏するものの、７
トリツクス樹脂として熱可塑性樹脂であるポリアミド、
ポリカーボネー１−、ポリフェニレンオキサイＩく、ポ
リフェニレンサルファイ１く、ポリエーテルスルホン、
ポリスルホン、ポリエーテルエーテルケトン、ポリエー
テルイミド等を用いた場合トこは、濡わ性や含浸性が劣
り、複合材料中の補強繊維とマトリックス樹脂との接着
性が悪く、充分な物性発現性が得られないという難点が
ある。As such sizing agents, epoxy resin-based sizing agents have traditionally been used, but these sizing agents have excellent affinity and impregnating properties with thermosetting resins such as 71~Rix resins, and are very effective. Although it has a good effect on
Polyamide, which is a thermoplastic resin, is used as Trix resin.
Polycarbonate 1-, polyphenylene oxy-1, polyphenylene sulfite 1, polyether sulfone,
When using polysulfone, polyetheretherketone, polyetherimide, etc., the wettability and impregnation properties are poor, the adhesion between the reinforcing fibers in the composite material and the matrix resin is poor, and sufficient physical properties cannot be expressed. The problem is that you can't get it.
特にポリフェニレンサルファイドで代表される硫黄含有
耐熱性樹脂は、耐熱性、耐炎性、耐薬品性に優れている
上に、ポリイミド樹脂等と比べて安価であり且つ成形性
も良いので、補強繊維強化複合材料用のマトリックス樹
脂として近年注目されでいる。しかし、エポキシ樹脂系
サイジンク剤はポリフェニレンサルファイドに対する濡
れ性、含浸性が劣る上に、ポリフェニレンサルファイド
の成形温度が３００℃以」二という高温であるため、成
形時にサイジンク剤が熱分解してボイド発生の原因にな
り、充分なコンポジノ１〜物性が得られない。In particular, sulfur-containing heat-resistant resins, such as polyphenylene sulfide, have excellent heat resistance, flame resistance, and chemical resistance, and are cheaper than polyimide resins and have good moldability. It has recently attracted attention as a matrix resin for materials. However, epoxy resin-based sizing agents have poor wettability and impregnating properties with polyphenylene sulfide, and the molding temperature of polyphenylene sulfide is as high as 300°C or higher, so the sizing agent may thermally decompose during molding and cause voids. As a result, sufficient composite properties cannot be obtained.
このような問題を解決するために、ポリフェニレンサル
ファイドをマトリックスとする炭素繊維強化複合材料用
の炭素繊維のサイジンク剤として、ポリスルフォン、ポ
リフェニレンサルファイド等を用いることが提案されて
いる（例えば特開昭５６１２０７３０号、特開昭５６−
９０８３７号公報等）。これらのサイジング剤は、エポ
キシ樹脂系サイジング剤と比べると、耐熱性やポリフェ
ニレンサルファイドに対する含浸性等が優れている。In order to solve these problems, it has been proposed to use polysulfone, polyphenylene sulfide, etc. as a sizing agent for carbon fibers for carbon fiber reinforced composite materials having polyphenylene sulfide as a matrix (for example, Japanese Patent Laid-Open No. 56120730). No., JP-A-56-
90837, etc.). These sizing agents are superior in heat resistance and impregnating properties for polyphenylene sulfide, etc., as compared to epoxy resin-based sizing agents.
ところがこのようなサイジング剤も、以下に述べるよう
な問題点を有している。即ち、ポリスルフォン、ポリフ
ェニレンサルファイド等の重合体をサイジング剤として
用いた場合、該重合体白身の弾性率が大きいため、炭素
繊維束のしなやかさが失われ、該繊維束が硬くなるので
、サイジング剤の付着量を増加することができないとい
う欠点がある。更に、サイジング剤を炭素繊維束に均一
に塗布する場合、またサイジング剤付着量をコントロー
ルする場合、適当な溶媒にサイジング剤を溶解すること
が必要となるが、ポリフェニレンサルファイドを常温で
容易に溶解する溶媒がないため、特殊なコーティング方
法を採用しなければならないという難点がある。However, such sizing agents also have the following problems. That is, when a polymer such as polysulfone or polyphenylene sulfide is used as a sizing agent, since the elastic modulus of the polymer white is high, the flexibility of the carbon fiber bundle is lost and the fiber bundle becomes hard. The disadvantage is that it is not possible to increase the amount of adhesion. Furthermore, when uniformly applying a sizing agent to carbon fiber bundles or controlling the amount of sizing agent attached, it is necessary to dissolve the sizing agent in an appropriate solvent, but polyphenylene sulfide is easily dissolved at room temperature. The disadvantage is that a special coating method must be used since there is no solvent.
従って本発明の目的は、補強繊維及び硫黄含有耐熱性樹
脂に対するなじみが良く、補強繊維と硫黄含有耐熱性樹
脂との濡れ性、含浸性の改善効果が大きいと共に、補強
繊維束に塗布後も該繊維束の可撓性を損なわず、しかも
溶媒溶解性の良好な補強繊維用サイジング剤を提供する
ことにある。Therefore, the object of the present invention is to have good compatibility with the reinforcing fibers and the sulfur-containing heat-resistant resin, to have a large effect of improving the wettability and impregnability of the reinforcing fibers and the sulfur-containing heat-resistant resin, and to have a good compatibility even after being applied to the reinforcing fiber bundle. It is an object of the present invention to provide a sizing agent for reinforcing fibers that does not impair the flexibility of fiber bundles and has good solvent solubility.
本発明によれば、下記一般式（Ｉ）又は（ＩＩＩ）で示
されるベンゼンスルホン酸誘導体を主成分とすることを
特徴とする補強繊維用サイジング剤が提供される。According to the present invention, there is provided a sizing agent for reinforcing fibers, which is characterized by containing a benzenesulfonic acid derivative represented by the following general formula (I) or (III) as a main component.
（式中、Ｒは水素原子又は低級アルキル基を夫々示す。(In the formula, R represents a hydrogen atom or a lower alkyl group, respectively.
ハロゲン原子を、及びｎは１以」−の整数を、夫々示す
。）
なお、上記一般式（１）及び（ＩＩ）において、Ｒの低
級アルキル基としては０１〜Ｃ３のアルキル基が、Ｘの
ハロゲン原子としては塩素原子、臭素原子等が、またｎ
としては１〜１０の整数が、夫々好ましい。represents a halogen atom, and n represents an integer of 1 or less. ) In the above general formulas (1) and (II), the lower alkyl group of R is an alkyl group of 01 to C3, the halogen atom of X is a chlorine atom, a bromine atom, etc.
An integer of 1 to 10 is preferable.
本発明者らは、硫黄含有耐熱性樹脂、特にポリフェニレ
ンサルファイドに対して濡れ性、含浸性に優れ、しかも
塗布後も炭素繊維の可撓性を損なわす且つ溶媒溶解性に
も優れ、複合判料とした場合に優れたコンポジット物性
を示す補強繊維用のサイジング剤について鋭意検討した
結果、上記特定のサイジング剤かこれらの要求を満足す
ることを見出し、本発明を完成するに至った。The present inventors have developed a composite resin that has excellent wettability and impregnability with sulfur-containing heat-resistant resins, particularly polyphenylene sulfide, and also impairs the flexibility of carbon fibers even after application, and has excellent solvent solubility. As a result of intensive studies on sizing agents for reinforcing fibers that exhibit excellent composite physical properties when the above-described specific sizing agents are used, it was discovered that the above-mentioned specific sizing agent satisfies these requirements, leading to the completion of the present invention.
本発明において、サイジング剤として用いられる前記一
般式（１）で示されるベンゼンスルホン酸誘導体、即ち
ジベンゼンスルホン酸ジフェニルスルホンは、例えば松
のような反応式に従って容易に合成することができる。In the present invention, the benzenesulfonic acid derivative represented by the general formula (1), ie, diphenylsulfone dibenzenesulfonate, used as a sizing agent can be easily synthesized according to a reaction formula such as, for example, Pine.
（式中、ＸはＣＱ、Ｂｒなどのハロゲン原子を示し、ま
たＲは前記と同一。）
即ち、ビスフェノールＳとベンゼンスルホニルハライド
とを、有機溶媒中で反応させ、得られた生成物を有機溶
媒で抽出することによって、容易に得られる。この場合
、反応用有機溶媒としては、Ｎ−メチルピロリＩ−ン、
α−ピロリドン等が、また抽出用溶媒としては、トルエ
ン、キシレン等が好んで用いられる。また、ビスフェノ
ールＳとベンゼンスルホニルハライドとのモル比は１：
２〜１：５が好ましい。(In the formula, X represents a halogen atom such as CQ or Br, and R is the same as above.) That is, bisphenol S and benzenesulfonyl halide are reacted in an organic solvent, and the resulting product is mixed in an organic solvent. It can be easily obtained by extraction with In this case, the organic solvent for the reaction is N-methylpyrrolione,
α-pyrrolidone and the like are preferably used, and toluene, xylene and the like are preferably used as extraction solvents. Moreover, the molar ratio of bisphenol S and benzenesulfonyl halide is 1:
2 to 1:5 is preferred.
ビスフェノールＳとベンゼンスルホニルハライ１くを前
記有機溶媒に溶解し、系を５０〜２００°Ｃに加熱する
ことにより、反応が進行する。反応時間は０．５〜１０
時間、好適には１〜５時間である。反応系を一］二記時
間維持することにより、反応は終了する。The reaction proceeds by dissolving bisphenol S and benzenesulfonyl halide in the organic solvent and heating the system to 50 to 200°C. Reaction time is 0.5-10
time, preferably 1 to 5 hours. The reaction is completed by maintaining the reaction system for one to two hours.
得られた反応物を冷却して析出させた後、該析出物を前
記有機溶媒で抽出することにより、ジベンゼンスルホン
酸ジンエニルスルホンを主成分とする反応物が得られる
。After the obtained reaction product is cooled and precipitated, the precipitate is extracted with the organic solvent to obtain a reaction product containing dibenzenesulfonate dienyl sulfone as a main component.
また、前記一般式（ＩＴ）
＝７
（式中、Ａ、Ｂ及びｎは前記と同一、）で示されるベン
ゼンスルホン酸誘導体は、例えばビスフェノールＳとベ
ンゼンジスルホニルハライドとを反応させることによっ
て容易に得られる。Furthermore, the benzenesulfonic acid derivative represented by the general formula (IT) =7 (wherein A, B and n are the same as above) can be easily obtained by, for example, reacting bisphenol S and benzenedisulfonyl halide. can get.
この場合も、前記ビスフェノールＳとベンゼンスルホニ
ルハライドの反応のときと同様に、反応は有機溶媒中で
加熱下に行なわれ、得られた生成物を有機溶媒で抽出す
ることによって、目的とするベンゼンスルホン酸誘導体
を主成分とする反応物を得ることができる。ただ、ビス
フェノールＳとベンゼンスルホニルハライド
１〜１：５の範囲で、生成物の種類により適宜選択され
る。In this case, as in the case of the reaction between bisphenol S and benzenesulfonyl halide, the reaction is carried out in an organic solvent under heating, and the resulting product is extracted with an organic solvent to produce the desired benzenesulfonyl halide. A reactant containing an acid derivative as a main component can be obtained. However, the ratio of bisphenol S to benzenesulfonyl halide is 1 to 1:5, and is appropriately selected depending on the type of product.
以上のような方法で得られた前記ベンゼンスルホン酸誘
導体は、アセ１〜ン、メチルエチルケ１ヘン、ハロゲン
化炭化水素等の有機溶媒に溶解して溶液とするか、又は
界面活性剤を用いて水性エマルジョンの形態で、補強繊
維用サイジング剤として使用される。勿論このサイジン
グ剤に通常添加される助剤等を添加することは、何ら差
支えない。The benzenesulfonic acid derivative obtained by the above method can be dissolved in an organic solvent such as acetin, methyl ethyl alcohol, or a halogenated hydrocarbon to form a solution, or can be made into an aqueous solution using a surfactant. In the form of an emulsion, it is used as a sizing agent for reinforcing fibers. Of course, there is no problem in adding auxiliary agents and the like that are normally added to this sizing agent.
かかるサイジング剤はデイツプ法、スプレー法あるいは
ローラー法等の通常の方法により補強繊維に付着される
。Such a sizing agent is applied to the reinforcing fibers by a conventional method such as a dip method, a spray method, or a roller method.
本発明において用いられる補強繊維としては、炭素繊維
、ガラス繊維、ボロン繊維、セラミック繊維及び金属繊
維等がある。Examples of reinforcing fibers used in the present invention include carbon fibers, glass fibers, boron fibers, ceramic fibers, and metal fibers.
炭素繊維としては、ピッチ系、アクリル系、セルロース
系等の各種繊維を前原体として、公知の方法を用いて不
融化又は耐炎化処理を行ない、次いで不活性ガス雰囲気
中で８００〜３０００°Ｃで焼成した所謂炭化系、黒鉛
化系の何れのものも含まれるが、特に表面を酸化処理し
たものを用いることが望ましい。なお、セラミック繊維
としては、炭化珪素繊維、窒化珪素繊維、窒化硼素繊維
、アルミナ繊維等が挙げられる。The carbon fibers are prepared by using various types of fibers such as pitch, acrylic, and cellulose fibers as precursors, making them infusible or flameproofing using known methods, and then heating them at 800 to 3000°C in an inert gas atmosphere. This includes both so-called carbonized and graphitized materials that have been fired, but it is particularly desirable to use materials whose surfaces have been oxidized. Note that examples of the ceramic fiber include silicon carbide fiber, silicon nitride fiber, boron nitride fiber, and alumina fiber.
該サイジング剤の補強繊維に対する付着量は固形分で０
．１〜１０重量２、好ましくは０．５〜５重量％である
。この付着量が少なすぎると充分な濡れ性、含浸性が得
られなくなり、多すぎると繊維束が固くなり、糸扱い性
が困難どなったり、複合材の物性が低下したりするので
好ましくない。The amount of the sizing agent attached to the reinforcing fibers is 0 in terms of solid content.
．． 1 to 10% by weight2, preferably 0.5 to 5% by weight. If the amount attached is too small, sufficient wettability and impregnating properties cannot be obtained, and if it is too large, the fiber bundle becomes stiff, making it difficult to handle the yarn, and the physical properties of the composite material deteriorate, which is not preferable.
上記のようにサイジング剤が付与された補強繊維は一旦
ボビンに巻き上げられるか、あるいはそのまま連続的に
、コンポジット成形工程へ送られる。The reinforcing fibers to which the sizing agent has been applied as described above are once wound up onto a bobbin, or are continuously sent as they are to a composite forming process.
本発明のサイジング剤は補強繊維表面との濡れ性、含浸
性に優れ、その上各種マＩ〜リックス樹脂との濡れ性、
含浸性に優れ、特にポリフェニレンサルファイド、ポリ
エーテルスルホン、ポリスルホン等の硫黄含有耐熱性樹
脂に対して著しい含浸性改善効果を示す。The sizing agent of the present invention has excellent wettability and impregnability with the reinforcing fiber surface, and also has excellent wettability with various matrix resins.
It has excellent impregnating properties, and exhibits a remarkable impregnating property improvement effect particularly for sulfur-containing heat-resistant resins such as polyphenylene sulfide, polyether sulfone, and polysulfone.
本発明のサイジング剤は連続繊維及び短繊維（チョツプ
ドファイバー）の両者に適用することができる。従って
、前記７１〜リツクス樹脂と補強繊維とから複合材料を
形成する方法としてはフィラメンｌ〜ワインディング法
、プリプレグ法、シー１〜・モールディング法並びに射
出成形法等の通常採用される方法が挙げられる。例えば
射出成形法は、本発明のサイジング剤が付与された補強
繊維束をカッターで１〜２０ｍｍの長さに切り、ポリフ
ェニレンサルファイドとブレンダーで混合した後、押出
し機でペレット化し、ペレットを射出成形機にて成形し
、目的とする成形品を得るものである。The sizing agent of the present invention can be applied to both continuous fibers and short fibers (chopped fibers). Therefore, as a method for forming a composite material from the above-mentioned No. 71 Rix resin and reinforcing fibers, commonly used methods such as the filament winding method, the prepreg method, the Sea molding method, and the injection molding method can be mentioned. For example, in the injection molding method, reinforcing fiber bundles to which the sizing agent of the present invention has been applied are cut into lengths of 1 to 20 mm with a cutter, mixed with polyphenylene sulfide in a blender, and then pelletized with an extruder. to obtain the desired molded product.
本発明の補強繊維用サイジング剤は、補強繊維及び７ト
リツクス樹脂、特にポリフェニレンサルファイド等の硫
黄含有耐熱性７トリツクス樹脂に対する濡れ性、含浸性
に優れ、しかも補強繊維の可撓性を損なわず且つ溶媒溶
解性も良好であり、従って本発明のサイジンク剤で処理
された補強繊維を配合した耐熱性樹脂複合材料はボイド
発生が殆どなく、機械的物性が著しく改善されたものと
なる。The sizing agent for reinforcing fibers of the present invention has excellent wettability and impregnating properties for reinforcing fibers and 7-trix resins, particularly sulfur-containing heat-resistant 7-trix resins such as polyphenylene sulfide, and does not impair the flexibility of reinforcing fibers and is solvent-resistant. It also has good solubility, and therefore, a heat-resistant resin composite material containing reinforcing fibers treated with the sizing agent of the present invention has almost no void generation and has significantly improved mechanical properties.
以下、実施例により本発明を更に詳細に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
Ｎ−メチルピロリドン２００ｇにビスフェノール３５０
ｇを溶解させ、１−リエチルアミン４０ｇを加える。Example 1 350 g of bisphenol in 200 g of N-methylpyrrolidone
g and add 40 g of 1-ethylamine.
次いで、ベンゼンスルホニルクロライド７０ｇを加え、
温度を１３０℃に昇温し、２時間反応させる。この反応
物をＩＩｌの蒸留水に注ぎ、沈殿させ固形物を得る。Next, add 70g of benzenesulfonyl chloride,
The temperature is raised to 130°C and the reaction is allowed to proceed for 2 hours. The reaction mixture is poured into IIl of distilled water to precipitate and obtain a solid.
この固形物を風乾後１−ルエン５００鴫で抽出し、抽出
液ヲロータリーエバポレーターで１ヘルエンを留去し、
固形物を得る。該固形物をＧＰＣ１丁Ｒ，ＮＭＲにより
同定したところ、ジベンゼンスルホン酸ジフェニルスル
ホン（分子量５３１）
が主成分であった。又、ＤＳＣを用いて融点を測定した
ところ１１２℃であった。After air-drying this solid, it was extracted with 500 g of 1-luene, and the extract was distilled off using a rotary evaporator to remove 1-luene.
Obtain solids. When the solid substance was identified by GPC1-R and NMR, it was found that the main component was diphenylsulfone dibenzenesulfonate (molecular weight 531). Further, the melting point was measured using DSC and was found to be 112°C.
炭素繊維としてトレカＴ−３００６Ｋ（東し社製）を、
窒素雰囲気中にて８００°Ｃで５時間焼成後、連続的に
電解酸化処理した後、前記化合物の１重量２アセトン溶
液による浸漬処理を行ない、］ ＯＯ’Ｃの乾燥炉を通
し、表面処理炭素繊維を得た。該繊維をメチルエチルケ
トン（ＭＥＫ）によりツクスレー抽出を行ない、サイズ
剤付着量を測定したところ、１．５％であった。該表面
処理炭素繊維は可撓性に優れ、糸扱い性は良好であった
。Trading card T-3006K (manufactured by Toshisha Co., Ltd.) was used as carbon fiber.
After firing at 800°C for 5 hours in a nitrogen atmosphere, the carbon was subjected to continuous electrolytic oxidation treatment, and then immersed in a 1 weight 2 acetone solution of the above compound. Obtained fiber. The fibers were subjected to Tuxhlet extraction using methyl ethyl ketone (MEK), and the amount of sizing agent deposited was measured to be 1.5%. The surface-treated carbon fiber had excellent flexibility and good yarn handling properties.
糸扱い性の評価として繊維−繊維間及び繊維−金属間の
擦過試験を行なった９その結果を表−１に示す。なお、
繊維−繊維間の擦過試験は、東洋精機社製のラビングテ
スターを用い、荷重］、ＯＯｇ／３００フィラメント、
内角４５°、１回撚り、擦過長２０ｍｍ、２００回／分
の速さで５００回往復運動させた。また、繊維−金属間
の擦過試験は、大栄化学精機社のＴＭ式式台合力テスタ
ー用い、荷重２００ｇ／３０００フィラメント、０ ＝
１５０°、擦過長３０ｍｍ、クロムメツキ金属櫛を］５
０回／分の速さで３００回往復運動させた。何れも次の
基準で５点法により評価した。To evaluate yarn handling properties, fiber-to-fiber and fiber-to-metal abrasion tests were conducted.9 The results are shown in Table 1. In addition,
The rubbing test between fibers was carried out using a rubbing tester manufactured by Toyo Seiki Co., Ltd.
The inner angle was 45°, the material was twisted once, the rubbing length was 20 mm, and the material was reciprocated 500 times at a speed of 200 times/min. In addition, the abrasion test between fiber and metal was performed using a TM type stand resultant force tester manufactured by Daiei Kagaku Seiki Co., Ltd., load 200 g/3000 filament, 0 =
150°, rubbing length 30mm, chrome-plated metal comb]5
It was reciprocated 300 times at a speed of 0 times/min. All were evaluated using a 5-point method using the following criteria.
５・・毛羽なし、糸切れなし
４・毛羽ややあり
３・毛羽あり
２・毛羽多く、糸切れあり
１ 切断
次に該表面処理炭素繊維を一方向に並列に並ベボリフェ
ニレンサルファイＦ（ＰＰＳ）として１〜−ブレンのＴ
−１のシー１−をサンドイッチ状に重ね合せ、ホットプ
レスにて、３００°Ｃで５分間予備加熱、５分間加圧を
行ない、厚み約１ｍ、炭素繊維含量５０容積％の複合材
料を得た。得られた複合材料について、ボイド率測定及
びＡＳＴＭＤ６３８に準拠した引張り試験を行なった。5. No fluff, no yarn breakage 4. Some fluff, 3. Fuzz 2. A lot of fluff, yarn breakage 1. Next, the surface-treated carbon fibers were lined in parallel in one direction and were ) as 1~-T of Bren
-1 sheets 1- were stacked together in a sandwich shape, preheated at 300°C for 5 minutes, and pressurized for 5 minutes using a hot press to obtain a composite material with a thickness of about 1 m and a carbon fiber content of 50% by volume. . The obtained composite material was subjected to void ratio measurement and a tensile test in accordance with ASTM D638.
それらの結果を表−１に示す。The results are shown in Table-1.
実施例２
ベンゼンスルホニルクロライドの代りに、メタベンゼン
ジスルホニルクロライ１（を４Ｂｇ用いて、実施例１と
同様な条件でサイズ剤を合成した。得られたサイズ剤は
ｍ−ベンゼンジスルホン酸型ビスフェノールＳポリマー
（分子量９２３）を主成分とするものであった。Example 2 A sizing agent was synthesized under the same conditions as in Example 1 using 4Bg of metabenzenedisulfonyl chloride 1 instead of benzenesulfonyl chloride.The obtained sizing agent was m-benzenedisulfonic acid type bisphenol. The main component was S polymer (molecular weight 923).
該サイズ剤を用いて、０．５重量Ｉアセトン溶液による
炭素繊維の浸漬処理を、実施例１と同様にして行なった
。また、複合材料作製、物性評価についても実施例１と
同様な方法で行なった。それらの結果を表−１に示す。Using the sizing agent, carbon fibers were immersed in a 0.5 weight I acetone solution in the same manner as in Example 1. In addition, composite material preparation and physical property evaluation were performed in the same manner as in Example 1. The results are shown in Table-1.
実施例３
メタベンゼンジスルホニルクロライドの使用量を９６ｇ
とした以外は、実施例２と同様にしてサイズ剤を合成し
た。得られたサイズ剤はジ−ｍ−ベンゼンジスルホン酸
ジフェニルスルホン（分子量６９１）を主成分とするも
のであった。Example 3 The amount of metabenzenedisulfonyl chloride used was 96g.
A sizing agent was synthesized in the same manner as in Example 2 except for the following. The obtained sizing agent contained di-m-benzenedisulfonic acid diphenylsulfone (molecular weight 691) as a main component.
該サイズ剤を用いて、実施例２と同様にして、炭素繊維
の浸漬処理、複合材料作製、物性評価を行なった。それ
らの結果を表−１に示す。Using the sizing agent, in the same manner as in Example 2, carbon fiber was soaked, composite material was prepared, and physical properties were evaluated. The results are shown in Table-1.
実施例４
メタベンゼンジスルホニルクロライドの使用量を２４ｇ
とした以外は、実施例２と同様にしてサイズ剤を合成し
た。得られたサイズ剤はｍ−ベンゼンジスルホン酸型ビ
スフェノールＳポリマー（分子量１１を主成分とするも
のであった。Example 4 The amount of metabenzenedisulfonyl chloride used was 24g.
A sizing agent was synthesized in the same manner as in Example 2 except for the following. The obtained sizing agent was a m-benzenedisulfonic acid type bisphenol S polymer (mainly having a molecular weight of 11).
該サイズ剤を用いて、実施例２と同様にして、炭素繊維
の浸漬処理、複合材料作製、物性評価を行なった。それ
らの結果を表−１に示す。Using the sizing agent, in the same manner as in Example 2, carbon fiber was soaked, composite material was prepared, and physical properties were evaluated. The results are shown in Table-1.
実施例５
メタベンゼンジスルホニルクロライドの代りにオルソベ
ンゼンジスルホニルクロライドを用いた以外は、実施例
２と同様の方法でサイズ剤を合成した。得られたサイズ
剤は０−ベンゼンジスルホン酸型ビスフェノールＳポリ
マー（分子量９２３）を主成分とするものであった。Example 5 A sizing agent was synthesized in the same manner as in Example 2, except that orthobenzenedisulfonyl chloride was used instead of metabenzenedisulfonyl chloride. The obtained sizing agent was mainly composed of 0-benzenedisulfonic acid type bisphenol S polymer (molecular weight 923).
該サイズ剤を用いて、実施例２と同様にして、炭素繊維
の浸漬処理、複合材料作製、物性評価を行なった。それ
らの結果を表−１に示す。Using the sizing agent, in the same manner as in Example 2, carbon fiber was soaked, composite material was prepared, and physical properties were evaluated. The results are shown in Table-1.
実施例６
浸漬処理を３重量％アセトン溶液で行なった以外は、実
施例１と同様の方法で表面処理炭素繊維の作製、複合材
料作製、物性評価を行なった。それらの結果を表〜１に
示す。Example 6 Surface-treated carbon fibers were prepared, composite materials were prepared, and physical properties were evaluated in the same manner as in Example 1, except that the dipping treatment was performed with a 3% by weight acetone solution. The results are shown in Table 1.
実施例７
石油ピッチを熱重縮合反応させ、約５錦の光学的異方性
を有する軟化魚釣２３５℃の炭素質ピッチを得た。この
ピッチを３７０℃で円筒型遠心分離装置で分離して、９
８％の光学的異方性を有する軟化点２６５℃のピッチを
分離した。Example 7 Petroleum pitch was subjected to a thermal polycondensation reaction to obtain a softened carbonaceous pitch of 235°C having an optical anisotropy of about 5 brocades. This pitch was separated in a cylindrical centrifugal separator at 370°C and
A pitch with a softening point of 265° C. and an optical anisotropy of 8% was isolated.
このようにして得られたピッチを紡糸し、次いで不融化
及び焼成を行ない、炭素繊維を得た。該炭素繊維のモノ
フィラメント強度、弾性率を測定した結果、それぞれ３
５３ｋｇ／ｍｍ２．５０，４００ｋｇ／ｍｍ２であった
。次に該炭素繊維の３０００フィラメント束を電解酸化
を行ない、実施例１と同様の方法で表面処理炭素繊維の
作製、複合材料作製、物性評価を行なった。それらの結
果を表−１に示す。The pitch thus obtained was spun, then infusible and fired to obtain carbon fibers. As a result of measuring the monofilament strength and elastic modulus of the carbon fiber, each was 3.
It was 53kg/mm2.50,400kg/mm2. Next, 3,000 filament bundles of the carbon fibers were subjected to electrolytic oxidation, and in the same manner as in Example 1, surface-treated carbon fibers were prepared, composite materials were prepared, and physical properties were evaluated. The results are shown in Table-1.
比較例１
サイズ剤による浸漬処理を行なわなかった以外は、実施
例１と同様の方法で複合材料作製、物性評価を行なった
。それらの結果を表−１に示す。Comparative Example 1 A composite material was prepared and its physical properties were evaluated in the same manner as in Example 1, except that the dipping treatment with the sizing agent was not performed. The results are shown in Table-1.
比較例２
サイズ剤としてＩＣＩ社製Ｖｊｃｔｒｅｘ ＰＥＳ ２
００Ｐの７重量２塩化メチレン溶液にて浸漬処理を行な
った以外は、実施例１と同様の方法で表面処理炭素繊維
の作製、複合材料作製、物性評価を行なった。それらの
結果を表−１に示す。Comparative Example 2 Vjctrex PES 2 manufactured by ICI as a sizing agent
Surface-treated carbon fibers were prepared, composite materials were prepared, and physical properties were evaluated in the same manner as in Example 1, except that the immersion treatment was performed in a 00P 7 weight methylene dichloride solution. The results are shown in Table-1.
比較例３
サイズ剤として油化シェル社製エピコーｈ８２８の２重
量２アセ１−ン溶液にて浸漬処理を行なった以外は、実
施例１と同様の方法で表面処理炭素繊維の作製、複合材
料作製、物性評価を行なった。それらの結果を表−１に
示す。Comparative Example 3 Surface-treated carbon fibers were prepared and composite materials were prepared in the same manner as in Example 1, except that the sizing agent was immersed in a 2 weight 2 acetone solution of Epicor H828 manufactured by Yuka Shell Co., Ltd. , physical properties were evaluated. The results are shown in Table-1.
実施例８〜１０
実施例６で得られた表面処理炭素繊維を山水技研工業社
製ロービングカッターにて３ｍｍ長の短繊維に切断し、
チョツプドファイバーを得た。次に日本製鋼所社製ＴＥ
ＸＺ軸押出機（４５ｍｍφＤ）を用い、１〜−プレン社
製ポリフェニレンサルファイドＴ−４を１段フィーダー
から及び上記チョツプドファイバーを２段フィーダーか
ら投入し、炭素繊維／ＰＰＳコンパウンドペレットを得
た。該コンパウンド製造時、チョツプドファイバーのフ
ィーダーからの食い込みは良好であり、得られたペレッ
トも気泡等の発泡現象も見られず、良好なコンバラン１
くが得られた。コンパウンドの炭素繊維含量は２０重量
２．３０重量２．４０重量２の３種類を作製した。Examples 8 to 10 The surface-treated carbon fiber obtained in Example 6 was cut into short fibers with a length of 3 mm using a roving cutter manufactured by Sansui Giken Kogyo Co., Ltd.
Got chopped fiber. Next, TE made by Japan Steel Works, Ltd.
Using an XZ-axis extruder (45 mmφD), polyphenylene sulfide T-4 manufactured by 1-Prene Co., Ltd. was introduced from a first-stage feeder and the above-mentioned chopped fiber was introduced from a second-stage feeder to obtain carbon fiber/PPS compound pellets. During the production of the compound, the chopped fibers penetrated well from the feeder, and no foaming phenomena such as air bubbles were observed in the pellets obtained, indicating that the compound was a good combination.
was obtained. Three types of compounds were prepared, each having a carbon fiber content of 20% by weight, 2.30% by weight, and 2.40% by weight.
得られたコンパウンドを日本製鋼社製射出成形機Ｊ７５
３Ａにて射出成形し、物性試験用のデスｌ−ピースを作
製した。得られたテストピースについて、ＡＳＴＭ Ｄ
−７９０に増始して曲げ試験を行なった。その結果を表
−２に示す。The obtained compound was processed using an injection molding machine J75 manufactured by Nippon Steel Corporation.
3A injection molding to produce a dess L-piece for physical property testing. For the obtained test piece, ASTM D
The bending test was conducted starting at −790°C. The results are shown in Table-2.
実施例１ｊ
実施例７で得られた表面処理炭素繊維について、実施例
９と同様の方法でコンパラン１くの作製、テストピース
の作製、曲げ試験を行なった。その結果を表−２に示す
。Example 1j Regarding the surface-treated carbon fiber obtained in Example 7, a comparator was prepared, a test piece was prepared, and a bending test was performed in the same manner as in Example 9. The results are shown in Table-2.
実施例１２〜］−４
ガラス繊維として加ファイバーグラス社製ＥＲ２３１０
を用いた以外は、実施例８〜１０と同様にしてガラス繊
維／ＰＰＳコンパランｌくの作製、テストピースの作製
、曲げ試験を行なった。Example 12~]-4 ER2310 manufactured by Kafiber Glass Co., Ltd. as glass fiber
A glass fiber/PPS comparator was prepared, a test piece was prepared, and a bending test was carried out in the same manner as in Examples 8 to 10, except that a test piece was used.
比較例４
比較例３で得られた表面処理炭素繊維について、実施例
９と同様の方法でコンパウンドの作製、テストピースの
作製、曲げ試験を行なった。その結果を表−２に示す。Comparative Example 4 Regarding the surface-treated carbon fiber obtained in Comparative Example 3, a compound was prepared, a test piece was prepared, and a bending test was performed in the same manner as in Example 9. The results are shown in Table-2.
比較例５
サイズ剤による浸漬処理を行なわなかった以外は、実施
例１３と同様にしてコンパウンドの作製、テストピース
の作製、曲げ試験を行なった。その結果を表−２に示す
。Comparative Example 5 A compound was prepared, a test piece was prepared, and a bending test was conducted in the same manner as in Example 13, except that the dipping treatment with the sizing agent was not performed. The results are shown in Table-2.
Claims (1)
ンスルホン酸誘導体を主成分とすることを特徴とする補
強繊維用サイジング剤。 ▲数式、化学式、表等があります▼（ I ） （式中、Ｒは水素原子又は低級アルキル基を夫々示す。 ▲数式、化学式、表等があります▼（II） （式中、Ａは水素原子又は▲数式、化学式、表等があり
ます▼を、ＢはＸ又は▲数式、化学式、表等があります
▼を、Ｘはヒドロキシル基又はハロゲン原子を、及びｎ
は１以上の整数を、夫々示す。）(1) A sizing agent for reinforcing fibers characterized by containing a benzenesulfonic acid derivative represented by the following general formula (I) or (II) as a main component. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents a hydrogen atom or a lower alkyl group, respectively.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, A is a hydrogen atom Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, B is X or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, X is a hydroxyl group or a halogen atom, and n
represents an integer greater than or equal to 1. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30757889A JPH02259166A (en) | 1988-11-29 | 1989-11-29 | Sizing agent for reinforcing fiber |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-299606 | 1988-11-29 | ||
| JP29960688 | 1988-11-29 | ||
| JP30757889A JPH02259166A (en) | 1988-11-29 | 1989-11-29 | Sizing agent for reinforcing fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02259166A true JPH02259166A (en) | 1990-10-19 |
Family
ID=26561996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30757889A Pending JPH02259166A (en) | 1988-11-29 | 1989-11-29 | Sizing agent for reinforcing fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02259166A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006501320A (en) * | 2002-07-31 | 2006-01-12 | ブルーワー サイエンス アイ エヌ シー． | Photosensitive bottom antireflection film <Background of the invention> |
-
1989
- 1989-11-29 JP JP30757889A patent/JPH02259166A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006501320A (en) * | 2002-07-31 | 2006-01-12 | ブルーワー サイエンス アイ エヌ シー． | Photosensitive bottom antireflection film <Background of the invention> |
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