JPH01162876A - Sizing of carbon fiber strand - Google Patents
Sizing of carbon fiber strandInfo
- Publication number
- JPH01162876A JPH01162876A JP62322476A JP32247687A JPH01162876A JP H01162876 A JPH01162876 A JP H01162876A JP 62322476 A JP62322476 A JP 62322476A JP 32247687 A JP32247687 A JP 32247687A JP H01162876 A JPH01162876 A JP H01162876A
- Authority
- JP
- Japan
- Prior art keywords
- strand
- carbon fiber
- epoxy resin
- resin
- roller
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 36
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000004513 sizing Methods 0.000 title claims abstract description 22
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 15
- 239000000839 emulsion Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 15
- 238000005299 abrasion Methods 0.000 abstract description 13
- 239000000835 fiber Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 238000003825 pressing Methods 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- -1 J-6 Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 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 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 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 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- LNRVTEQEGXVMEF-UHFFFAOYSA-N 2-hydroxy-2-methylpropanedioic acid Chemical compound OC(=O)C(O)(C)C(O)=O LNRVTEQEGXVMEF-UHFFFAOYSA-N 0.000 description 1
- QAOBWZAHOFFKKR-UHFFFAOYSA-N 2-hydroxy-2-propylpropanedioic acid Chemical compound CCCC(O)(C(O)=O)C(O)=O QAOBWZAHOFFKKR-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000004804 winding Methods 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、開繊性及び耐擦過性に優れた炭素繊維ストラ
ンドを得るための量サイジング方法に関するものである
。さらに詳しくは、プリプレグ製造工程でのガイド等で
の擦過における毛羽の発生がなく、取扱性がよく、しか
も、樹脂含浸の際における開繊性に優れた炭素繊維スト
ランドを得るためのサイジング方法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a sizing method for obtaining carbon fiber strands with excellent opening properties and abrasion resistance. More specifically, it relates to a sizing method for obtaining carbon fiber strands that do not generate fluff when rubbed by guides, etc. in the prepreg manufacturing process, are easy to handle, and have excellent opening properties during resin impregnation. It is.
炭素繊維ストランドは、その優れた特性、特に高比強度
、高比弾性の特性を生かし、各種の樹脂組成物をマトリ
ックスとした複合材料として、航空機、スポーツ用品等
の産業分野において広く利用されている。Carbon fiber strands are widely used in industrial fields such as aircraft and sporting goods as composite materials with various resin compositions as a matrix, taking advantage of their excellent properties, especially high specific strength and high specific elasticity. .
この炭素繊維ストランドは、ストランドのまま一方向に
引揃えられた状態で、或は織物状態で樹脂組成物を含浸
し、成形して複合材料とされる。This carbon fiber strand is impregnated with a resin composition in a unidirectionally aligned state as a strand or in a woven state, and then molded into a composite material.
このような加工工程において炭素ｍ組ストランドの取扱
性の安定化をはかり、また、＄１織等の高次加工におい
て炭素繊維ストランドの耐擦過性や、取扱性の向上をは
かるための各種のサイジング処理方法が提案されている
（例えば特公昭６０−４７９５３号公報、特開昭６２−
１１０９８４号公報）前掲特開昭６２−１１０９８４号
公報では、エポキシ樹脂に対するポリウレタン樹脂の配
合比が両樹脂の化学構造、エポキシ当量、カルボキシル
基当団により異り一概に決められないとし、約２〜３０
倍量のポリウレタン樹脂の過剰が使用されている。しか
しながら、この方法においてもストランドの耐擦過性及
び開繊性を同時に満足する炭素ｔＩ維ストランドは得ら
れていない。Various sizing methods are used to stabilize the handleability of carbon m-set strands in such processing steps, and to improve the abrasion resistance and handleability of carbon fiber strands in higher-order processing such as $1 weaving. Treatment methods have been proposed (for example, Japanese Patent Publication No. 47953/1983, Japanese Patent Application Laid-Open No. 62/1989).
110984)) In the above-mentioned Japanese Patent Application Laid-Open No. 110984/1984, it is stated that the blending ratio of polyurethane resin to epoxy resin cannot be determined unconditionally as it varies depending on the chemical structure, epoxy equivalent, and carboxyl group of both resins, and that it is about 2 to 2. 30
A double excess of polyurethane resin is used. However, even with this method, it has not been possible to obtain a carbon tI fiber strand that satisfies the abrasion resistance and opening properties of the strand at the same time.
炭素繊維ストランドを一方向に配列しこれに樹脂組成物
を含浸させた、所謂一方向プリプレグの製造においては
、炭素繊維ストランドの開繊性が重要な要求性能である
と同時に、炭素繊維ストランドの糸ガイド等との耐擦過
性も重要な要求特性であるが、この両者を同時に満足す
ることは、従来技術では困難であった。In the production of so-called unidirectional prepreg, in which carbon fiber strands are arranged in one direction and impregnated with a resin composition, the spreadability of the carbon fiber strands is an important performance requirement. Scratch resistance with guides and the like is also an important required property, but it has been difficult with conventional techniques to satisfy both of these requirements at the same time.
すなわち、一般に開繊性を高めると耐擦過性が低下し、
耐擦過性を高めると開繊性が低下する傾向があり、この
ため両者を同時に満足することは困Ｎ視されていた。In other words, in general, increasing the opening property reduces the abrasion resistance,
If the abrasion resistance is increased, the spreadability tends to be lowered, and therefore it has been considered difficult to satisfy both requirements at the same time.
本発明は、このような炭素繊維ストランドのサイズ剤付
与におけるプリプレグ製造時の開繊性と耐擦過性という
両立困難な特性を同時に満足し、かつ、炭素繊維複合材
料の本来的に具有すべき複合材料特性をも満足するとこ
ろの炭素繊維ストランドのサイジング方法を提供しよう
とするものである。The present invention simultaneously satisfies the properties that are difficult to achieve at the same time, such as opening properties and abrasion resistance during prepreg production when imparting a sizing agent to carbon fiber strands, and also achieves the characteristics that carbon fiber composite materials should inherently have. The present invention aims to provide a method for sizing carbon fiber strands that also satisfies material properties.
〔発明の構成及び作用） 本発明は下記の構成からなる。[Structure and operation of the invention] The present invention consists of the following configuration.
炭素繊維ストランドを、有効成分としてエポキシ樹脂（
Ａ）とフィルム流動開始温度９０〜１６０℃の水溶性ポ
リウレタン樹脂（Ｂ）とを重１１比＝Ｂ／Ａ ０．４〜
１．５の範囲で含む水エマルジョン液中に通した後、９
０〜１６０℃のローラーに押圧接触させつつ乾燥熱処理
することを特徴とする炭素繊維ストランドのサイジング
方法。Carbon fiber strands are used as an active ingredient in epoxy resin (
A) and a water-soluble polyurethane resin (B) having a film flow start temperature of 90 to 160°C at a weight ratio of 11 = B/A 0.4 to
After passing it through a water emulsion containing in the range of 1.5, 9
A method for sizing carbon fiber strands, which comprises subjecting carbon fiber strands to dry heat treatment while being pressed into contact with a roller at 0 to 160°C.
本発明によると、プリプレグ製造時の開繊性に優れるた
め樹脂組成物の含浸性及び拡幅性がよく、しかも、耐擦
過性に優れるため加工整経時にローラーやガイド等との
接触による毛羽の発生や糸切がなく、取扱性のよいサイ
ジング処理された炭素繊維ストランドを得ることができ
る。According to the present invention, since it has excellent fiber opening properties during prepreg production, it has good impregnating properties and widening properties of the resin composition, and also has excellent abrasion resistance, which causes fuzzing due to contact with rollers, guides, etc. during processing and warping. It is possible to obtain sized carbon fiber strands that are easy to handle and have no thread cutting.
本発明において炭素繊維ストランドとは、アクリロニト
リル系、レーヨン系、ピッチ系等の既知の炭素繊維の１
００〜１００ 、０００フイラメントが集束されたＩＩ
雑束であり、炭素繊維には黒鉛繊維を含む。In the present invention, the carbon fiber strand refers to one of known carbon fibers such as acrylonitrile-based, rayon-based, pitch-based, etc.
00~100,000 filaments focused II
It is a miscellaneous bundle, and the carbon fibers include graphite fibers.
本発明においてエポキシ樹脂とは、通常知られているエ
ポキシ樹脂、好ましくはビスフェノール△系エポキシ樹
脂、フェノールノボラック系エポキシ樹脂、ビニルエス
テル系エポキシ樹脂等のエポキシ樹脂である。In the present invention, the epoxy resin is a commonly known epoxy resin, preferably an epoxy resin such as a bisphenol Δ epoxy resin, a phenol novolac epoxy resin, or a vinyl ester epoxy resin.
また、ウレタン変成エポキシ樹脂等を主成分とするもの
も好ましい。Also preferred are those whose main component is a urethane-modified epoxy resin.
これらエポキシ樹脂の具体例は下記のとおりである。Specific examples of these epoxy resins are as follows.
■ビスフェノールＡ系エポキシ樹脂：（例えば、ビスフ
ェノールＡとエピクロルヒドリンとの反応によって１ｑ
られるエポキシ樹脂）シェル化学社製のエピコート８２
８、エピコート１００１、■フェノールノボラック系エ
ポキシ樹脂：（例えば、ノボラックタイプのフェノール
樹脂とエピクロルヒドリンとの反応によって得られるエ
ポキシ樹脂）シェル化学社製のエピコート １５２、エ
ビコト−１５４、■ビニルエステル系エポキシ樹脂：（
例えば、ビニルアセテート、ビニルクロライド、スチレ
ン、アクリロニトリル等のビニル化合物とグリシジルメ
タクリレートとの反応によって１ｑられるエポキシ樹脂
）、■エーテル系エポキシ樹脂：ボリオール、ポリエー
テルポリオール、多価フェノールのモノ、ジ又はトリグ
リシジルエーテル等、■エポキシ化ブタジェン系エポキ
シ樹脂：アデカアーガス社ＭＢＦ−１０００又はグツド
リッチ社製ハイカーとエポキシ化合物との反応によって
１９られるエポキシ樹脂等、■エポキシ化ソルビトール
系の非グリシジルタイプのエポキシ樹脂、■上記エポキ
シ樹脂を変成したちの：旭電化社製アデカレジンＥＰＩ
Ｊ−６、アデカレジンＥＰ○−４等のウレタン変成エポ
キシ樹脂等、■フェノキシ樹脂と称されている高分子量
のエポキシ樹脂ニジエル化学社製のエピコートＯＬ −
５３−８−４０、エピコート０Ｌ−５５−８−４０、ダ
ウケミカル社製のＤＥＲ６８４、ＥＫ４０、東部化学社
製のフエル−トＹＰ５０ＥＫ４０．大日本インキ社製の
エビクロンｌ−１−１５７、）（−３５３、Ｈ−３６０
等 。■Bisphenol A-based epoxy resin: (For example, 1q
Epikote 82 manufactured by Shell Chemical Co., Ltd.
8. Epicoat 1001, ■ Phenol novolac epoxy resin: (for example, an epoxy resin obtained by the reaction of a novolak type phenol resin and epichlorohydrin) Epikote 152, manufactured by Shell Chemical Co., Ltd., Ebikoto-154, ■ Vinyl ester epoxy resin: (
For example, epoxy resins produced by the reaction of vinyl compounds such as vinyl acetate, vinyl chloride, styrene, and acrylonitrile with glycidyl methacrylate), ■ Ether-based epoxy resins: mono-, di-, or triglycidyl of polyols, polyether polyols, and polyhydric phenols. Ether, etc., ■Epoxidized butadiene-based epoxy resin: 19 Epoxy resin produced by reaction of Adeka Argus MBF-1000 or Gutdrich Hiker with an epoxy compound, ■Epoxidized sorbitol-based non-glycidyl type epoxy resin, ■The above Modified epoxy resin: Adeka Resin EPI manufactured by Asahi Denka Co., Ltd.
Urethane-modified epoxy resins such as J-6, Adekal Resin EP○-4, etc.; ■ High molecular weight epoxy resin called phenoxy resin Epicoat OL manufactured by Nigel Chemical Co., Ltd.
53-8-40, Epicoat 0L-55-8-40, DER684, EK40 manufactured by Dow Chemical Company, Felt YP50EK40 manufactured by Tobu Chemical Company. Ebikuron l-1-157, ) (-353, H-360 manufactured by Dainippon Ink Co., Ltd.)
etc .
本発明において水溶性ポリウレタン樹脂とは、次に例示
するとおりである。In the present invention, the water-soluble polyurethane resin is as exemplified below.
ポリエーテル系のポリウレタン樹脂では、バーマリンＵ
Ａ−６０、ＵＡ−８０（三洋化成社製）、アイゼラック
スＳ−１０２０、Ｓ−１０４０ＳＳ −１０６０〈保土
谷化学社製）が挙げられる。ポリエステル系のポリウレ
タン樹脂では、アイゼラツクス４０４０−ｎ （保土谷
化学社製）、レザミンＷ −５０２０（大口糖化社製）
、インプラニールＤＬＮ、ＤＬＳ、（バイエル社製）、
ハイトランＡＰ−１０〜４０、△ＰＸ１０３、ＡＰＸ
１０１ＨＸＨＷ−３５０（大日本インキ化学ネ１製）
が挙げられる。Vermarine U is a polyether-based polyurethane resin.
Examples include A-60, UA-80 (manufactured by Sanyo Chemical Co., Ltd.), Izerax S-1020, and S-1040SS-1060 (manufactured by Hodogaya Chemical Co., Ltd.). Polyester-based polyurethane resins include Igelax 4040-n (manufactured by Hodogaya Chemical Co., Ltd.) and Rezamin W-5020 (manufactured by Oguchi Toka Co., Ltd.).
, Inplanil DLN, DLS, (manufactured by Bayer),
Hytran AP-10~40, △PX103, APX
101HXHW-350 (manufactured by Dainippon Ink Kagaku Net 1)
can be mentioned.
水溶性ポリウレタン樹脂は、通常法のようにして得られ
る。The water-soluble polyurethane resin can be obtained in a conventional manner.
（イ）末端に水酸基を含有するポリエーテル、ポリエス
テル、ポリアセクール、ポリブタジェンポリオール、ポ
リアクリルポリオール等と（ロ）有機ポリイソシアネー
ト〈ジフェニルメタンジイソシアネート、ジシクロヘキ
シルメタンジイソシアネート、トリレンジイソシアネー
ト、イソホロンジイソシアネート、キシリレンジイソシ
アネート、ヘキサメチレンジイソシアネート等）と（ハ
）少くとも１個以上のイソシアネート基と水酸基を有し
、少くとも１個以上のカルボキシル基を有してもよい化
合物Ｃタルトロン酸（オキシマロンＲ）、イソプロピル
タルトロン酸、ｎ−プロピルタルトロン酸、α −オキ
シコハク酸、α−オキシアジピン酸、メチルタルトロン
酸等 のヒドロキシカルボン酸）とを重付加反応させる
。上記化合物中に含まれるカルボキシル基は、アンモニ
ウム塩としておくことが複合材料とした場合の物性面か
ら好ましい。(a) Polyethers, polyesters, polyacecools, polybutadiene polyols, polyacrylic polyols, etc. containing terminal hydroxyl groups, and (b) organic polyisocyanates (diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate) , hexamethylene diisocyanate, etc.) and (c) a compound having at least one isocyanate group and a hydroxyl group, and may have at least one carboxyl group C. Tartronic acid (Oxymalone R), isopropyl tart hydroxycarboxylic acids such as rononic acid, n-propyltartronic acid, α-oxysuccinic acid, α-oxyadipic acid, and methyltartronic acid). The carboxyl group contained in the above compound is preferably in the form of an ammonium salt from the viewpoint of physical properties when used as a composite material.
フィルム流動開始温度は、島津製作所社製ｒ高化式フロ
ーテスター」を用い、フィルム厚さ １００μｍにて測
定した値で示す。The film flow start temperature is shown as a value measured at a film thickness of 100 μm using a Shimadzu Corporation RKoka Type Flow Tester.
本発明におけるエポキシ樹脂（Ａ）と水溶性ポリウレタ
ン樹脂（Ｂ）の重用比＝Ｂ／Ａは０．４〜１．５の範囲
である。In the present invention, the weight ratio of epoxy resin (A) to water-soluble polyurethane resin (B) = B/A is in the range of 0.4 to 1.5.
０．４未満では、耐擦過性が低く、毛羽の発生、糸切れ
が多くなり、加えてストランドの形態保持性も低下し、
プリプレグ製造時の単繊維の平行性が悪くなり、開繊性
、樹脂含浸性が低下する。一方１．５超では、ストラン
ドの開繊性が低下し、耐擦過性も低く毛羽の発生、糸切
れが多くなる。If it is less than 0.4, the abrasion resistance will be low, the occurrence of fuzz and yarn breakage will increase, and in addition, the shape retention of the strand will also decrease.
The parallelism of single fibers during prepreg production deteriorates, resulting in poor opening properties and resin impregnation properties. On the other hand, if it exceeds 1.5, the spreadability of the strand is reduced, the abrasion resistance is also low, and fluffing and thread breakage occur frequently.
これらの（Ａ＞及び（Ｂ＞成分を含む水ナイジング剤は
、下記の方法によって得られる。A water nizing agent containing these components (A> and (B>) can be obtained by the following method.
まず、エポキシ樹脂に通常５〜１０重量％の界面活性剤
を加え機械的に転相乳化する既知の方法によって、水分
散性エポキシ樹脂のエマルジョンを得る。この場合、界
面活性剤としては芳香族ノニオン系のものが好ましい。First, an emulsion of a water-dispersible epoxy resin is obtained by a known method of adding 5 to 10% by weight of a surfactant to an epoxy resin and mechanically emulsifying it by phase inversion. In this case, the surfactant is preferably an aromatic nonionic surfactant.
次いで、このエポキシ樹脂エマルジョンと水溶性ポリウ
レタン樹脂とを通常の機械的混合方法によって混合する
。Next, this epoxy resin emulsion and water-soluble polyurethane resin are mixed by a conventional mechanical mixing method.
本発明で使用するサイジング剤には、必要に応じ滑剤〈
例えば、オレイン酸アミド、ステアリン酸アミド等の高
級脂肪族アミドやオレイン酸エステル、ステアリン酸エ
ステル等の高級脂肪族エステルやオレイルアルコール、
ステアリルアルコール、セチルアルコール等の高級脂肪
族アルコール等）を添加してもよく、特に滑剤の添加は
、本発明の目的に沿って有効であって、１種又は２種以
上の滑剤を１０重量％以下使用するのが好ましい。The sizing agent used in the present invention may include a lubricant if necessary.
For example, higher aliphatic amides such as oleic acid amide and stearic acid amide, higher aliphatic esters such as oleic acid ester and stearic acid ester, oleyl alcohol,
Higher aliphatic alcohols such as stearyl alcohol and cetyl alcohol) may be added. In particular, the addition of a lubricant is effective in accordance with the purpose of the present invention, and one or more lubricants may be added in an amount of 10% by weight. It is preferable to use the following.
サイジング剤の炭素ｍ維への付＠量は、通常、炭素繊維
に対し０．３〜５重間％好ましくは０．１〜２重量％の
範囲である。The amount of the sizing agent applied to the carbon fibers is usually in the range of 0.3 to 5% by weight, preferably 0.1 to 2% by weight, based on the carbon fibers.
炭素繊維ストランドへのサイジング剤の含浸は、浸漬法
、ローラー転写接触法、スプレー法などの既知の方法に
よって行われる。Impregnation of the sizing agent into the carbon fiber strands is carried out by known methods such as a dipping method, a roller transfer contact method, and a spray method.
サイジング剤を付与された炭素ｌＩ雑ストランドは、次
いで９０〜１６０℃の熱ローラー上で押圧乾燦然処理す
る。この湯度範囲をはずれると、下記のとおり、本発明
の目的が達成されない。この抑圧乾燥熱処理温度とサイ
ジング剤の特性との組合せ関係は重要であって、この関
係を示すと下記のとおりである。The carbon lI miscellaneous strands to which the sizing agent has been applied are then pressed and dried on a heated roller at 90 to 160°C. If the hot water temperature is outside this range, the purpose of the present invention will not be achieved as described below. The combinational relationship between the suppressed drying heat treatment temperature and the properties of the sizing agent is important, and this relationship is shown below.
乾燥熱処理は熱ローラーでの押圧下にて行われるが、熱
ローラーは複数のものを直列的に配置して用いることも
できる。この際の熱ローラー温度は段階的に温度を変え
ることもできる。The dry heat treatment is performed under pressure with a hot roller, but a plurality of hot rollers can also be used by arranging them in series. The temperature of the heat roller at this time can also be changed stepwise.
例えば、第１０−ラー温度は９０〜１１５℃とするのが
好ましく、第２０−ラー以降のローラー温度を一層高め
ることもできるが、１６０℃を超えてはならない。温度
が過度に高くなると、ストランドが軟化し、ローラーへ
の巻付が多くなる傾向にある。For example, the temperature of the 10th roller is preferably 90 to 115°C, and the temperature of the rollers after the 20th roller can be further increased, but must not exceed 160°C. If the temperature gets too high, the strands tend to soften and become more wrapped around the rollers.
炭素繊維ストランドに対する（Ａ）、（Ｂ）両成分の付
着量は、０．３〜５重量％が適当である。０．３ｆｆ！
量％未満であると、耐擦過性に欠け、逆に５重量％を超
えると、剛直化による毛羽の発生や開繊性の低下の傾向
が強くなる。特に好ましくは０．７〜２重開％である。The amount of both components (A) and (B) attached to the carbon fiber strand is suitably 0.3 to 5% by weight. 0.3ff!
If it is less than 5% by weight, the abrasion resistance will be lacking, and if it exceeds 5% by weight, there will be a strong tendency for fluff to occur due to stiffness and a decrease in spreadability. Particularly preferred is 0.7 to 2%.
付着量調整はサイジング剤液のｍ度調整、サイジング剤
液付与量の調整等によって行われる。The amount of adhesion is adjusted by adjusting the degree of sizing agent, adjusting the amount of sizing agent applied, etc.
本発明によって１４られたサイジング処理炭素繊維スト
ランドは、偏平であって、開繊性がよい。このため、プ
リプレグ製造時樹脂の含浸性及びストランドの拡幅性が
浸れている。The sized carbon fiber strands according to the present invention are flat and have good opening properties. For this reason, the impregnating properties of the resin and the widening properties of the strands are affected during prepreg production.
さらに、耐擦過性に優れるため、ストランドガイドによ
る擦過時の単繊維切断による毛羽の発生、ストランド切
れの発生を減少させることができる。Furthermore, since it has excellent abrasion resistance, it is possible to reduce the occurrence of fuzz and strand breakage due to single fiber breakage during abrasion by the strand guide.
実茄例１
構成本数１２０００フイラメントのサイズなしのアクリ
ル系炭素繊維ストランド（単繊維引張り強さ４２０ｋｇ
ｆ／ ｍｎ＋’ 、引張り弾性率２１４００ｋｇ ｆ
／ ｍｍ７）を下表に示し−た成分のサイジング剤を有
効固形分濃度２６Ｑ／Ｊ２になるように水で希釈したサ
イジング浴に浸漬し、炭素繊維ストランドにサイジング
剤を含浸させた。Fruit example 1 Acrylic carbon fiber strand of no size with 12,000 filaments (single fiber tensile strength 420 kg)
f/mn+', tensile modulus 21400kg f
The carbon fiber strands were impregnated with the sizing agent by dipping the carbon fiber strands into a sizing bath in which a sizing agent having the components shown in the table below was diluted with water to an effective solids concentration of 26Q/J2.
第 １ 表
（注１） （Ｂ）成分：大日本インキ社製、フィルム
流動開始温度１０５〜１１０℃の水溶性ポリウレタン樹
脂。Table 1 (Note 1) Component (B): Water-soluble polyurethane resin manufactured by Dainippon Ink Co., Ltd. and having a film flow initiation temperature of 105 to 110°C.
この炭素！ｌ維ストランドを、第１０−ラー温度１１０
℃、第２０−ラー温度１２０℃、第３０−ラー温度１０
０℃、第４０−ラー温度９０℃の各ローラーにて押圧乾
燥熱処理した。This carbon! 1 fiber strand, 10th - 110
℃, 20th-Ra temperature 120℃, 30th-Ra temperature 10
Pressure drying heat treatment was carried out using rollers at 0°C and 40th roller temperature at 90°C.
得られた炭素繊維ストランドは、水分率が０．０１重量
％、サイジング剤の付着量が１．１重量％、炭素ｔａ８
ｇストランド幅が５．３ｍｍであって、仮撚なしにボビ
ンに巻取可能であった。The obtained carbon fiber strand had a moisture content of 0.01% by weight, a sizing agent adhesion amount of 1.1% by weight, and carbon ta8.
The g-strand width was 5.3 mm and could be wound onto a bobbin without false twisting.
また、この炭素繊維ストランドは、毛羽発生量が１０μ
９、擦過毛羽発生量が１５μっであり、取扱性及び耐擦
過性がいずれも良好であった。In addition, this carbon fiber strand has a fluff generation of 10 μm.
9. The amount of fuzz generated by rubbing was 15μ, and both the handleability and scratch resistance were good.
このサイズ処理したストランドを、エポキシ樹脂Ｎ、Ｎ
、Ｎ−，Ｎ−−テトラグリシジルジアミノジフェニルメ
タン（チバカイギー社製、ＭＹ−７２０）と硬化剤ジア
ミノジフェニルスルフォン（配合比４０Ｐ ＨＲ）から
なるエポキシ樹脂組成物のフィルム上に連続的に供給し
て平行に引揃え、ローラー間に通して加圧加熱し繊維間
に樹脂組成物を含浸させ、所謂ホットメルト法にてプリ
プレグを作成した。This size-treated strand is coated with epoxy resin N, N
, N-,N--tetraglycidyldiaminodiphenylmethane (manufactured by Ciba Kyigi, MY-720) and a curing agent diaminodiphenylsulfone (blending ratio 40P HR) were continuously fed onto a film of an epoxy resin composition in parallel. The fibers were aligned, passed between rollers and heated under pressure to impregnate the resin composition between the fibers, thereby producing a prepreg using the so-called hot melt method.
ス１−ランド１０にｇ当りゼロであり、また張力３００
ｑ／１２００フイラメントにおけるローラー上での炭素
繊維ストランド幅は７．１ｍｍであった。Zero per g for land 1-land 10, and tension 300
The carbon fiber strand width on the roller in the q/1200 filament was 7.1 mm.
以上のようにして得たプリプレグを用い、厚さ３ｍｍの
一方向成形板を成形し、ＡＳＴＭ−Ｄ〜２３４４に準じ
ＩＬＳＳ（層間せん断強度）を測定した結果は、下記の
とおりであった。Using the prepreg obtained as described above, a unidirectionally formed plate with a thickness of 3 mm was formed, and the ILSS (interlaminar shear strength) was measured according to ASTM-D~2344.The results were as follows.
室温： １３．２ｋｇ／ｍｍ’
１８０℃： ７，４ｋｑ／ｍｍ’
実施例２〜４及び比較例１〜４
実施例１における（Ａ）成分と（Ｂ）成分の配合比を下
記第２表のように変えたサイジング剤を使用した他は、
実流例１と同様にしてリイジング処理を行った。Room temperature: 13.2 kg/mm' 180°C: 7.4 kq/mm' Examples 2 to 4 and Comparative Examples 1 to 4 The blending ratio of component (A) and component (B) in Example 1 was as shown in Table 2 below. In addition to using a sizing agent changed from
Rising treatment was performed in the same manner as Actual Flow Example 1.
実施例と比較例の結果を第２表に示す。Table 2 shows the results of Examples and Comparative Examples.
実施例５及び６、並びに比較例５及び６第１表の成分の
うち（Ｂ）成分の水溶性ポリウレタンＢＪ ＦＩＢの種
類及び流＃ｌ開始１度を変えた他は、実施例１と同様に
して操作を行い、ヒートローラーへの巻付状況を調べた
ところ、第３表に示す結果を１ａた。Examples 5 and 6 and Comparative Examples 5 and 6 Among the components in Table 1, water-soluble polyurethane (B) component (B) was prepared in the same manner as in Example 1, except that the type of FIB and the flow #l start time were changed. When the winding condition around the heat roller was examined, the results shown in Table 3 were obtained.
第 ３ 表
（注）水溶性ポリウレタン樹脂はすべてポリエステル系
ポリウレタン樹脂（大日本インヤ社製）である。Table 3 (Note) All water-soluble polyurethane resins are polyester polyurethane resins (manufactured by Dainippon Inya Co., Ltd.).
特許出願人 東邦レーヨン林式会社 代理人弁理士 土 居 三 部Patent applicant: Toho Rayon Hayashiki Company Representative Patent Attorney, Third Department
Claims (1)
Ａ）とフィルム流動開始温度９０〜１６０℃の水溶性ポ
リウレタン樹脂（Ｂ）とを重量比Ｂ／Ａ＝０．４〜１．
５の範囲で含む水エマルジョン液中に通した後、９０〜
１６０℃のローラーに押圧接触させつつ乾燥熱処理する
ことを特徴とする炭素繊維ストランドのサイジング方法
。Carbon fiber strands are used as an active ingredient in epoxy resin (
A) and a water-soluble polyurethane resin (B) having a film flow initiation temperature of 90 to 160°C at a weight ratio of B/A = 0.4 to 1.
After passing it through a water emulsion containing in the range of 90 to 5
A method for sizing carbon fiber strands, characterized by subjecting them to dry heat treatment while being brought into pressure contact with a roller at 160°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62322476A JPH0665787B2 (en) | 1987-12-19 | 1987-12-19 | Carbon fiber strand sizing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62322476A JPH0665787B2 (en) | 1987-12-19 | 1987-12-19 | Carbon fiber strand sizing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01162876A true JPH01162876A (en) | 1989-06-27 |
| JPH0665787B2 JPH0665787B2 (en) | 1994-08-24 |
Family
ID=18144062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62322476A Expired - Fee Related JPH0665787B2 (en) | 1987-12-19 | 1987-12-19 | Carbon fiber strand sizing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0665787B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01292038A (en) * | 1988-05-19 | 1989-11-24 | Toray Ind Inc | Non-twisted carbon fiber bundle having excellent openability, production of said bundle and apparatus therefor |
| JPH11293562A (en) * | 1998-04-08 | 1999-10-26 | Ichinomiya Orimono:Kk | Carbon fiber yarn |
| JP2005320641A (en) * | 2004-05-06 | 2005-11-17 | Toray Ind Inc | Sizing agent, carbon fiber and carbon fiber-reinforced composite material |
| CN104389177A (en) * | 2014-11-06 | 2015-03-04 | 江苏航科复合材料科技有限公司 | Carbon fiber sizing agent and sizing method thereof |
| JP2017014628A (en) * | 2015-06-26 | 2017-01-19 | Dic株式会社 | Carbon fiber sizing agent and carbon fiber |
| JP2021519870A (en) * | 2018-03-28 | 2021-08-12 | ゾルテック コーポレイション | Conductive sizing for carbon fiber |
| WO2022052284A1 (en) * | 2020-09-11 | 2022-03-17 | 江苏恒神股份有限公司 | Carbon fiber bundle for filament winding, preparation method therefor and use thereof |
-
1987
- 1987-12-19 JP JP62322476A patent/JPH0665787B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01292038A (en) * | 1988-05-19 | 1989-11-24 | Toray Ind Inc | Non-twisted carbon fiber bundle having excellent openability, production of said bundle and apparatus therefor |
| JPH0529688B2 (en) * | 1988-05-19 | 1993-05-06 | Toray Industries | |
| JPH11293562A (en) * | 1998-04-08 | 1999-10-26 | Ichinomiya Orimono:Kk | Carbon fiber yarn |
| JP2005320641A (en) * | 2004-05-06 | 2005-11-17 | Toray Ind Inc | Sizing agent, carbon fiber and carbon fiber-reinforced composite material |
| CN104389177A (en) * | 2014-11-06 | 2015-03-04 | 江苏航科复合材料科技有限公司 | Carbon fiber sizing agent and sizing method thereof |
| JP2017014628A (en) * | 2015-06-26 | 2017-01-19 | Dic株式会社 | Carbon fiber sizing agent and carbon fiber |
| JP2021519870A (en) * | 2018-03-28 | 2021-08-12 | ゾルテック コーポレイション | Conductive sizing for carbon fiber |
| WO2022052284A1 (en) * | 2020-09-11 | 2022-03-17 | 江苏恒神股份有限公司 | Carbon fiber bundle for filament winding, preparation method therefor and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0665787B2 (en) | 1994-08-24 |
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