JPH0434569B2 - - Google Patents
Info
- Publication number
- JPH0434569B2 JPH0434569B2 JP62036714A JP3671487A JPH0434569B2 JP H0434569 B2 JPH0434569 B2 JP H0434569B2 JP 62036714 A JP62036714 A JP 62036714A JP 3671487 A JP3671487 A JP 3671487A JP H0434569 B2 JPH0434569 B2 JP H0434569B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- carbon fiber
- manufactured
- prepreg
- cyanate ester
- 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.)
- Expired - Lifetime
Links
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 45
- 239000004917 carbon fiber Substances 0.000 claims description 45
- 229920005989 resin Polymers 0.000 claims description 45
- 239000011347 resin Substances 0.000 claims description 45
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 28
- 239000004643 cyanate ester Substances 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 17
- 239000003822 epoxy resin Substances 0.000 claims description 16
- 229920000647 polyepoxide Polymers 0.000 claims description 16
- 125000000524 functional group Chemical group 0.000 claims description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 10
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000835 fiber Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 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 10
- 238000000034 method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- -1 ammonium ions Chemical class 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 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
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001913 cyanates Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- IYWFQYVEPIHCPU-UHFFFAOYSA-N (2-propylphenyl) cyanate Chemical compound C(CC)C1=C(C=CC=C1)OC#N IYWFQYVEPIHCPU-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 102100034111 Activin receptor type-1 Human genes 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-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
- 102100040287 GTP cyclohydrolase 1 feedback regulatory protein Human genes 0.000 description 1
- 101710185324 GTP cyclohydrolase 1 feedback regulatory protein Proteins 0.000 description 1
- 101000799140 Homo sapiens Activin receptor type-1 Proteins 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 101100490437 Mus musculus Acvrl1 gene Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KPSLOKZNJBTGRP-UHFFFAOYSA-N [2-(2-cyanatophenoxy)phenyl] cyanate Chemical compound N#COC1=CC=CC=C1OC1=CC=CC=C1OC#N KPSLOKZNJBTGRP-UHFFFAOYSA-N 0.000 description 1
- LYADEUYNRWEPJU-UHFFFAOYSA-N [2-(2-cyanatophenyl)sulfonylphenyl] cyanate Chemical compound O(C#N)C1=C(C=CC=C1)S(=O)(=O)C1=C(C=CC=C1)OC#N LYADEUYNRWEPJU-UHFFFAOYSA-N 0.000 description 1
- NTQOTSRMQVHZDE-UHFFFAOYSA-N [2-[(2-cyanatophenyl)methyl]phenyl] cyanate Chemical compound N#COC1=CC=CC=C1CC1=CC=CC=C1OC#N NTQOTSRMQVHZDE-UHFFFAOYSA-N 0.000 description 1
- RBDWCSWYBOZGGD-UHFFFAOYSA-N [C].C(C=C)#N Chemical compound [C].C(C=C)#N RBDWCSWYBOZGGD-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
［産業上の利用分野］
本発明は新規な耐熱性、耐水性および衝撃特性
に優れた複合材料用プリプレグに関する。
［従来の技術］
従来、炭素繊維複合材料は、炭素繊維の高い比
強度、比剛性を利用して航空機材料として使用さ
れている。マトリツクス樹脂としては、フエノー
ル樹脂やエポキシ樹脂が主として使われているが
航空機の高速化および一次構造材（主翼、胴体な
ど）への適用に伴ない、これらの材料では耐熱
性、耐水性および高温吸水時の衝撃性に問題があ
つた。上記特性を改良するものとして、シアン酸
エステル系樹脂が検討されている。すなわち、耐
熱性および耐水性に優れたシアン酸エステル樹脂
をマトリツクス樹脂としたもので、さらにこの衝
撃性を向上させるべくポリスルホン樹脂を添加し
た系も見られる（特開昭57−165451号公報、特開
昭60−250026号公報）。しかし、複合材料物性と
しては十分満足なものではない。
複合材料として優れた物性を発現させるために
は、マトリツクス樹脂と炭素繊維との界面の接着
が重要であり、各樹脂毎に適した処理をすること
が必要となつてきた。
［発明が解決しようとする問題点］
本発明者らは、耐熱性、耐水性および衝撃性の
優れた複合材料プリプレグについて鋭意検討した
結果、次の発明に到達した。
すなわち、本発明の目的は、炭素繊維表面にシ
アン酸エステル系樹脂に適した処理を施すことに
より、耐熱性、耐水性さらに高温、吸水時の衝撃
特性の優れた複合材料用プリプレグを提供するこ
とにある。
［問題点を解決するための手段］
本発明は上記目的を達成するために次の構成を
有する。すなわち、
Ｘ線光電子分光法によつて求められる炭素繊維
表面の窒素含有官能基量（N1S／C1S）が0.06〜
0.25の範囲であり、ストランド強度が485Kgｆ／
mm2以上、ストランド伸度が1.6％以上の炭素繊維
とシアン酸エステル系樹脂からなることを特徴と
する複合材料用プリプレグである。
すなわち、エポキシ樹脂の場合、炭素繊維表面
の酸素含有官能基に対して、窒素含有官能基は、
ほぼ同等の効果であるが、シアン酸エステル系樹
脂に対しては、窒素含有官能基が非常に有効であ
ることを見い出し本発明に達した。
本発明において、Ｘ線光電子分光法によつて求
められる表面窒素原子／表面酸素原子（N1S／
C1S）は表面処理してなる炭素繊維表面の窒素含
有官能基（アミド基、アミノ基など）量を示す好
適な指標で、N1S／C1Sの値が大きいほど窒素含有
官能基量が多く、炭素繊維と樹脂との化学的接着
が強くなる。
このN1S／C1Sは0.06〜0.25、好ましくは0.08〜
0.20の範囲に保つべきであり、0.06未満の場合は
炭素繊維とシアン酸エステル系樹脂との接着が弱
く、複合材料を引張り破壊した際に炭素繊維が母
材樹脂から抜出す、所謂、“すぬけ”が生じ、炭
素繊維と樹脂の接着界面の破壊に吸収されるエネ
ルギーが小さいため、複合材料の引張強度が低下
する。一方、N1S／C1Sが0.25を越えると炭素繊維
と樹脂との接着が強くなり過ぎて、炭素繊維と樹
脂とが一体となつて破壊し、炭素繊維と樹脂の接
着界面の破壊に殆どエネルギーを吸収されなくな
るため、複合材料の引張強度が低下する。
本発明における炭素繊維は、炭素繊維を陽極と
してアンモニウムイオンを含有する電解質溶液中
で電解処理することによつて得られる。
この場合の電解質には、水溶液とした際、アン
モニウムイオンを含有する電解質であることが必
須であり、例えば、アンモニア、炭酸アンモニウ
ム、硫安、硝安の如きアンモニウム塩などが挙げ
られるが、特に効果が大きい上からアンモニウム
水が好ましい。
次に、本発明における酸素含有官能基量
（O1S／C1S）、および窒素含有官能基量（N1S／
C1S）の測定法について述べる。
上記特性はＸ線光電子分光法（国際電気社製モ
デルES−200）により、次の手順に従つて求め
た。
先ず、溶媒でサイジング剤などを除去した炭素
繊維（束）をカツトして銅製の試料支持台上に拡
げて並べた後、Ｘ線源としてALK1，２を用い、
試料チヤンバー中を１×10-8Torrに保つ。
測定時の帯電に伴なうピークの補正としてC1S
の主ピークの運動エネルギー値（K.E.）を
1202eVに合せる。
C1Sピーク面積をK.E.として1191〜1205eVの範
囲で直線のベースラインを引くことにより求め
る。
O1Sピーク面積をK.E.として947〜959eVの範囲
で直線のベースラインを引くことにより求める。
N1Sピーク面積をK.E.として1078〜1091eVの範
囲で直線のベースラインを引くことにより求め
る。
本発明において、酸素含有官能基量（O1S／C1S
とは、上記O1Sピーク面積とC1Sピーク面積との比
として定義され、同様に窒素含有官能基量
（N1S／C1S）とは、上記N1Sピーク面積とC1Sピー
ク面積との比として定義されたものである。
電解処理における該電解質以外の処理条件につ
いては、定電圧装置を用い炭素繊維を処理する電
気量を調整してＸ線光電子分光法によつて求めら
れるN1S／O1Sが0.06〜0.25の範囲に入るようにす
るものである。電気量の調整は、糸条の速度をｖ
［ｍ／min］、目付をｘ［ｇ／ｍ］、電解槽に付与す
る電気量をＡ［アンペア］とすれば、60A／（ｖ，
ｘ）［クーロン／ｇ］で表わされ、例えば、アン
モニア水溶液を電解質として用いた場合には、
N1S／O1Sを容易に0.06〜0.25の範囲としうる観点
から、１〜100［クーロン／ｇ］さらには３〜35
［クーロン／ｇ］程度するのが好ましい。
ここで、電解質水溶液の濃度は実用的な電導度
を得るのに必要な濃度以上とし、電解質水溶液の
温度は通常は常温とするが、電解質水溶液の沸点
以下の温度に加熱して処理効果を高めることも可
能であり、好ましい。
また、炭素繊維への通電方法としては炭素繊維
を陽極ローラに接する方法、電解液を通じて陽極
板から炭素繊維に通電する方法などが挙げられ、
通電された炭素繊維は電解質水溶液中において電
解反応の陽極として働く。電解質水溶液中の電極
板としては白金板などが好ましく用いられる。
本発明の出発原料炭素繊維としては、公知の技
術で作られた炭素繊維（黒鉛繊維を含む）が用い
られる。例えば、ピツチ系炭素繊維、レーヨン系
炭素繊維、アクリロニトリル系炭素繊維などが挙
げられるが、特に好ましくはアンリロニトリル系
炭素繊維である。
さらに、航空機の二次構造材のみならず、一次
構造材として使用するためには、炭素繊維のスト
ランド物性として、ストランド強度が485Kgｆ／
mm2以上、ストランド伸度が1.6％以上とするもの
であり、ストランド強度が540Kgｆ／mm2以上、ス
トランド伸度が1.8％以上が好ましい。
本発明に用いるシアン酸エステル系樹脂とは、
ａ 多官能性シアン酸エステルあるいは／および
該シアン酸エステルプレポリマー
ｂ 多官能性マレイミドと前記ａとを混合もしく
は予備反応させて得た樹脂組成物である。
ここで多官能性シアン酸エステルとは、二個以
上のシアン酸エステル基を有する化合物であり、
好適なシアン酸エステル類は下記一般式(1)で表さ
れる化合物である。
Ｒ（Ｏ−Ｃ≡Ｎ）n (1)
（式中、ｍは２以上６以下の整数であり、Ｒは
芳香族性の有機基、上記シアン酸エステル基は該
有機基Ｒの芳香環に結合しているもの）
具体的には、ジシアナートベンゼン、トリシア
ナートベンゼン、ジシアナートナフタレン、トリ
シアナートナフタレン、ジシアナートビフエニ
ル、ビス（シアナートフエニル）メタン、ビス
（シアナートフエニル）プロパン、ビス（シアナ
ートフエニル）エーテル、ビス（シアナートフエ
ニル）スルホン、およびノボラツクとハロゲン化
シアンとの反応により得られるシアン酸エステル
などが挙げられる。またこれら多官能性シアン酸
エステルをルイス酸、炭酸ナトリウムあるいは塩
化リチウムなどの塩類等の触媒の存在化に重合さ
せて得られるプレポリマーとしても用いる事がで
きる。
本発明の多官能性マレイミドとは下記一般式(2)
で表される化合物である。
（式中、R′は２個以上６個以下の芳香族性あ
るいは脂肪族性の有機基、X1，X2は水素、ハロ
ゲン、またはアルキル基、ｎは２以上６以下の整
数である。）
上式で表されるマレイミド類は無水マレイン酸
類とアミノ基を２〜６個有するポリアミン類と反
応させてマレアミド酸を調整し、次いで脱水反応
により得られる。用いるポリアミンは耐熱性の点
で芳香族ポリアミンが好ましいが、樹脂に可撓性
や柔軟性を付与したい場合には脂肪族アミンを用
いても良い。好適なアミン類としては、フエニレ
ンジアミン、キシリジアミン、シクロヘキサンジ
アミン、ジアミノジフエニル、ジアミノジフエニ
ルメタン、ジアミノジフエニルエーテル、ジアミ
ノジフエニルスルホン等が挙げられる。またマレ
イミドとこれらのアミンとの縮合反応物も使用さ
れる。
シアン酸エステル系樹脂に対して窒素含有官能
基がなぜ有効なのか明らかではないが、
−Ｏ−Ｃ≡ＮとNHまたは−NH2との反応が
関与していると考えられる。
本発明に用い得るエポキシ樹脂とは何の制限も
なくたいていのものが使用可能である。特に例示
するならば、エピコート828、エピコート1001（油
化シエルエポキシ社製）、DER−331（ダウ・ケミ
カル日本社製）のごとき液状あるいは固形のビス
フエノールＡ型エポキシ樹脂、ELM434，
ELM120（住友化学社製）、YH−434（東都化成社
製）、MY−720（チバ・ガイギー社製）のごとき
グリシジルアミン型エポキシ樹脂、エピクロン
830（大日本インキ化学工業社製）のごときビスフ
エノールＦ型エポキシ樹脂、エピコート152、エ
ピコート154（油化シエルエポキシ社製）のごとき
フエノールノボラツク型エポキシ樹脂、エピクロ
ン152（大日本インキ化学工業社製）のごときブロ
ム化ビスフエノールＡ型エポキシ樹脂、ESCN−
220（住友化学社製）のごときクレゾールノボラツ
ク型エポキシ樹脂、その他ビスフエノールＳ型エ
ポキシ樹脂、脂環式エポキシ樹脂などが挙げられ
る。
これらのポリエポキシ化合物は単独でもあるい
は数種類の混合物で使用しても一向に差し支えな
い。ただし熱可塑性樹脂を添加すると樹脂粘度が
上昇するため添加量が多くなる場合は低粘度で液
状のエピコート828（油化シエルエポキシ社製）の
ようなビスフエノールＡ型エポキシ樹脂、エピク
ロン830（大日本インキ化学工業社製）のようなビ
スフエノールＦ型エポキシ樹脂が好適である。
本発明に用い得るポリスルホン樹脂とは下記一
般式(3)で表される化合物である。
（Ar−SO2）p (3)
式中、Arは
[Industrial Application Field] The present invention relates to a novel prepreg for composite materials that has excellent heat resistance, water resistance, and impact properties. [Prior Art] Conventionally, carbon fiber composite materials have been used as aircraft materials by utilizing the high specific strength and specific stiffness of carbon fibers. Phenol resins and epoxy resins are mainly used as matrix resins, but as aircraft speeds increase and they are applied to primary structural materials (main wings, fuselage, etc.), these materials have improved heat resistance, water resistance, and high-temperature water absorption. There was a problem with the impact of time. Cyanate ester resins are being studied as a means of improving the above characteristics. In other words, the matrix resin is cyanate ester resin with excellent heat resistance and water resistance, and there are also systems in which polysulfone resin is added to further improve the impact resistance (Japanese Patent Application Laid-Open No. 165451/1983, Publication number 60-250026). However, the physical properties of the composite material are not fully satisfactory. In order to exhibit excellent physical properties as a composite material, adhesion at the interface between the matrix resin and the carbon fibers is important, and it has become necessary to perform appropriate treatments for each resin. [Problems to be Solved by the Invention] The inventors of the present invention have conducted intensive studies on composite material prepregs having excellent heat resistance, water resistance, and impact resistance, and as a result, have arrived at the following invention. That is, an object of the present invention is to provide a prepreg for composite materials that has excellent heat resistance, water resistance, and impact properties at high temperatures and water absorption by subjecting the carbon fiber surface to a treatment suitable for cyanate ester resin. It is in. [Means for Solving the Problems] The present invention has the following configuration to achieve the above object. That is, the amount of nitrogen-containing functional groups (N 1S /C 1S ) on the carbon fiber surface determined by X-ray photoelectron spectroscopy is 0.06 to
The range is 0.25, and the strand strength is 485Kgf/
A prepreg for composite materials characterized by being made of carbon fiber with a diameter of mm 2 or more and a strand elongation of 1.6% or more and a cyanate ester resin. In other words, in the case of epoxy resin, nitrogen-containing functional groups are
Although the effect is almost the same, the present invention was achieved by discovering that a nitrogen-containing functional group is very effective for cyanate ester resins. In the present invention, surface nitrogen atoms/surface oxygen atoms (N 1S /
C 1S ) is a suitable index that indicates the amount of nitrogen-containing functional groups (amide groups, amino groups, etc.) on the surface of the surface-treated carbon fiber, and the larger the value of N 1S /C 1S , the greater the amount of nitrogen-containing functional groups. , the chemical adhesion between carbon fiber and resin becomes stronger. This N 1S /C 1S is 0.06 to 0.25, preferably 0.08 to
If it is less than 0.06, the adhesion between the carbon fiber and the cyanate ester resin is weak, and when the composite material is tensile and fractured, the carbon fiber is pulled out from the base resin. The tensile strength of the composite material decreases because the amount of energy absorbed by the fracture of the adhesive interface between the carbon fiber and the resin is small. On the other hand, when N 1S /C 1S exceeds 0.25, the adhesion between carbon fiber and resin becomes too strong, and the carbon fiber and resin break together, and it takes almost no energy to break the adhesive interface between carbon fiber and resin. is no longer absorbed, and the tensile strength of the composite material decreases. The carbon fiber in the present invention is obtained by electrolytically treating the carbon fiber in an electrolyte solution containing ammonium ions using the carbon fiber as an anode. The electrolyte in this case must be an electrolyte that contains ammonium ions when made into an aqueous solution; examples include ammonium salts such as ammonia, ammonium carbonate, ammonium sulfate, and ammonium nitrate, which are particularly effective. From above, ammonium water is preferred. Next, the amount of oxygen-containing functional groups (O 1S /C 1S ) and the amount of nitrogen-containing functional groups (N 1S /
The measurement method for C 1S ) is described below. The above characteristics were determined by X-ray photoelectron spectroscopy (model ES-200, manufactured by Kokusai Denki Co., Ltd.) according to the following procedure. First, carbon fibers (bundles) from which the sizing agent was removed using a solvent were cut and spread out on a copper sample support stand, and then ALK1 and ALK2 were used as X-ray sources.
Maintain the inside of the sample chamber at 1×10 -8 Torr. C 1S as a correction for the peak due to charging during measurement
The kinetic energy value (KE) of the main peak of
Adjust to 1202eV. It is determined by drawing a straight baseline in the range of 1191 to 1205 eV with the C 1S peak area as KE. It is determined by drawing a straight baseline in the range of 947 to 959 eV with the O 1S peak area as KE. It is determined by drawing a straight baseline in the range of 1078 to 1091 eV with the N 1S peak area as KE. In the present invention, the amount of oxygen-containing functional groups (O 1S /C 1S
is defined as the ratio between the above O 1S peak area and C 1S peak area, and similarly, the amount of nitrogen-containing functional groups (N 1S /C 1S ) is defined as the ratio between the above N 1S peak area and C 1S peak area. It is defined as . Regarding the treatment conditions other than the electrolyte in the electrolytic treatment, the amount of electricity used to treat the carbon fibers was adjusted using a constant voltage device so that N 1S /O 1S determined by X-ray photoelectron spectroscopy was in the range of 0.06 to 0.25. It allows you to enter. To adjust the amount of electricity, adjust the speed of the yarn by v
[m/min], the basis weight is x [g/m], and the amount of electricity applied to the electrolytic cell is A [ampere], then 60A/(v,
x) Expressed in [coulombs/g], for example, when an ammonia aqueous solution is used as the electrolyte,
From the viewpoint that N 1S /O 1S can be easily set in the range of 0.06 to 0.25, 1 to 100 [coulombs/g] and further 3 to 35
It is preferable that the amount is about [coulombs/g]. Here, the concentration of the electrolyte aqueous solution is higher than the concentration necessary to obtain practical conductivity, and the temperature of the electrolyte aqueous solution is usually room temperature, but it is heated to a temperature below the boiling point of the electrolyte aqueous solution to enhance the treatment effect. It is also possible and preferred. In addition, methods for applying electricity to carbon fibers include a method in which the carbon fibers are brought into contact with an anode roller, a method in which electricity is applied to the carbon fibers from an anode plate through an electrolytic solution, etc.
The energized carbon fiber acts as an anode for an electrolytic reaction in an electrolyte aqueous solution. A platinum plate or the like is preferably used as the electrode plate in the electrolyte aqueous solution. As the starting material carbon fiber of the present invention, carbon fiber (including graphite fiber) made by a known technique is used. Examples include pitch carbon fibers, rayon carbon fibers, acrylonitrile carbon fibers, and anrylonitrile carbon fibers are particularly preferred. Furthermore, in order to be used not only as a secondary structural material for aircraft but also as a primary structural material, the strand strength of carbon fiber must be 485 Kgf/
mm 2 or more and strand elongation of 1.6% or more, preferably strand strength of 540 Kgf/mm 2 or more and strand elongation of 1.8% or more. The cyanate ester resin used in the present invention is a resin composition obtained by mixing or preliminarily reacting a polyfunctional cyanate ester or/and the cyanate ester prepolymer b polyfunctional maleimide with the above a. be. Here, the polyfunctional cyanate ester is a compound having two or more cyanate ester groups,
Suitable cyanate esters are compounds represented by the following general formula (1). R(O-C≡N) n (1) (wherein, m is an integer of 2 or more and 6 or less, R is an aromatic organic group, and the cyanate ester group is attached to the aromatic ring of the organic group R. Specifically, dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, tricyanatonaphthalene, dicyanatobiphenyl, bis(cyanatophenyl)methane, bis(cyanatophenyl) ) propane, bis(cyanatophenyl) ether, bis(cyanatophenyl) sulfone, and cyanate ester obtained by reaction of novolac with cyanogen halide. It can also be used as a prepolymer obtained by polymerizing these polyfunctional cyanate esters in the presence of a catalyst such as a Lewis acid, a salt such as sodium carbonate, or lithium chloride. The polyfunctional maleimide of the present invention is represented by the following general formula (2):
This is a compound represented by (In the formula, R' is an aromatic or aliphatic organic group of 2 to 6, X 1 and X 2 are hydrogen, halogen, or an alkyl group, and n is an integer of 2 to 6. ) The maleimide represented by the above formula can be obtained by reacting maleic anhydride with a polyamine having 2 to 6 amino groups to prepare maleamic acid, and then performing a dehydration reaction. The polyamine to be used is preferably an aromatic polyamine from the viewpoint of heat resistance, but an aliphatic amine may be used if flexibility and softness are desired to be imparted to the resin. Suitable amines include phenylene diamine, xylydiamine, cyclohexane diamine, diaminodiphenyl, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone, and the like. Also used are condensation products of maleimide and these amines. It is not clear why the nitrogen-containing functional group is effective for cyanate ester resins, but it is thought that the reaction between -O-C≡N and NH or -NH2 is involved. Most epoxy resins can be used in the present invention without any limitations. Particular examples include liquid or solid bisphenol A type epoxy resins such as Epicote 828, Epicote 1001 (manufactured by Yuka Ciel Epoxy Co., Ltd.), DER-331 (manufactured by Dow Chemical Japan Co., Ltd.), ELM434,
Glycidylamine type epoxy resins such as ELM120 (manufactured by Sumitomo Chemical), YH-434 (manufactured by Toto Kasei), MY-720 (manufactured by Ciba Geigy), Epiclon
Bisphenol F type epoxy resins such as 830 (manufactured by Dainippon Ink & Chemicals Co., Ltd.), phenol novolak type epoxy resins such as Epicote 152 and Epicote 154 (manufactured by Yuka Shell Epoxy Co., Ltd.), Epiclon 152 (manufactured by Dainippon Ink & Chemicals Co., Ltd.) Brominated bisphenol type A epoxy resin such as ESCN-
Examples include cresol novolac type epoxy resins such as 220 (manufactured by Sumitomo Chemical Co., Ltd.), other bisphenol S type epoxy resins, and alicyclic epoxy resins. These polyepoxy compounds may be used alone or in a mixture of several types without any problem. However, adding a thermoplastic resin increases the resin viscosity, so if the amount added is large, use a low viscosity, liquid bisphenol A epoxy resin such as Epicoat 828 (manufactured by Yuka Ciel Epoxy Co., Ltd.) or Epiclon 830 (Dainippon Co., Ltd.). Bisphenol F type epoxy resins such as those manufactured by Ink Kagaku Kogyo Co., Ltd.) are suitable. The polysulfone resin that can be used in the present invention is a compound represented by the following general formula (3). (Ar−SO2) p (3) where Ar is
【式】【formula】
【式】【formula】
ｐは20〜150、好ましくは40〜130であり、末端
基は塩素または水酸基である。）
多官能性シアン酸エステルと多官能性マレイミ
ドの混合比は使用する化合物の種類によつても異
なるが、大体10：０から４：６の範囲が好まし
い。
また、上記シアン酸エステル系樹脂とエポキシ
樹脂との混合比は、９：１から２：８の範囲が好
ましい。また、ポリスルホン樹脂は、樹脂の衝撃
性を向上し、一方、プリプレグのタツク・ドレー
プ性を損なわないようにする観点から、マトリツ
クス樹脂の40重量％以下、さらには８〜25重量％
混合するのが好ましい。
［効果］
以上の如く本発明は、シアン酸エステル系樹脂
と表面窒素含有官能基量を特定化した炭素繊維と
からなるプリプレグを提供することにより、耐熱
性、耐水性、高温、吸水時の衝撃特性に優れた複
合材料を得られるものである。
［実施例］
以下、実施例により本発明をさらに具体的に説
明する。
なお、本例中、ストランド物性、およびコンポ
ジツト物性は次の方法に従つて測定した。
＜ストランド物性＞
JIS−760の樹脂含浸ストランド試験方法に準
じ、樹脂処方としては“BAKELITE”
ERL4221／３フツ化ホウ素モノエチルアミン／
アセトン＝100／３／４（重量部）をよく混合して
用いる。
＜コンポジツト物性＞
（コンポジツト試験片の作製）
先ず円周約2.7mの鋼製ドラムに炭素繊維と組
合せる樹脂をシリコン塗布ペーパー上にコーテイ
ングした樹脂フイルムを巻き、次に該樹脂フイル
ム上にクリールから引き出した炭素繊維をトラバ
ースを介して巻き取り、配列して、さらにその繊
維の上から前記樹脂フイルムを再度かぶせて後、
加圧ロールで回転加圧して樹脂を繊維内に含浸せ
しめ、幅300mm、長さ2.7mの一方向プリプレグを
作製する。
このとき、繊維間への樹脂含浸を良くするため
にドラムは50〜60℃に加熱し、またプリプレグの
繊維目付はドラムの回転数とトラバースの送り速
度を調整することによつて、繊維目付200ｇ／m2、
樹脂量約35重量％のプリプレグを作製した。
このように作製したプリプレグを裁断、積層
し、オートクレイブを用いて180℃、７Kg／cm2下
で２時間加熱硬化して、引張強度測定用として肉
厚約１mm、またはILSS測定用として肉厚約２mm
の硬化板を作製した。
なお、上記方法は所謂樹脂フイルムを用いたド
ラム・ワインド法であるが、フエノール樹脂の場
合には下記のような溶液含浸法を用いた。
樹脂溶液を満たした樹脂槽で繊維に樹脂を含浸
せしめ、その繊維をドラム上のシリコンペーパー
に配列巻き取り後、溶媒を風乾、さらに乾燥せし
め、一方向にプリプレグを得る。
このプリプレグを積層後、約７Kg／cm2の圧力
下、180℃、２時間プレス成型して一方向硬化板
とした。
（引張強度および層間剪断強度（ILSS）の測
定）
上記硬化板は引張強度用として幅12.7mm、長さ
230mmの試験片とし、該試験片の両端に厚さ約1.2
mm、長さ50mmのGFRP製のタブを接着し（必要に
応じて試験片中央には弾性率および破壊歪を測定
するための歪ゲージを貼り付け）、島津製オート
グラフを用いて負荷速度１mm／minで測定した。
またILSS用試験片は幅12.7mm、長さ28mmとし、
測定は通常の３点曲げ試験治具を用いて支持スパ
ンを試験片肉厚の４倍に設定し、負荷速度2.5
mm／minで測定した。
（実施例１〜３、比較例１，２）
アクリロニトリル（AN）99.5モル％とイタコ
ン酸0.5モル％からなる固有粘度［η］が1.80の
共重合体にアンモニアを吹込み、共重合体のカル
ボキシル基末端水素をアンモニウム基で置換して
変性ポリマを作製し、この変性ポリマの濃度が20
重量％のジメチルスルホキシド（DMSO）溶液
を作製した。この溶液を温度60℃に調整し、温度
60℃、濃度50％のDMSO水溶液に吐出した。
凝固糸条を水洗、熱水中で４倍に延伸した後、
シリコーン系油剤処理を行なつた。
この糸条を130〜160℃に加熱されたローラ表面
に接触させて乾燥緻密化後、4.0Kg／cm2の加圧ス
チーム中で３倍に延伸して単糸繊度1.0d、トータ
ルデニール6000dの繊維束を得た。
上記アクリル系繊維束を230〜260℃の空気中
で、延伸率1.00で加熱して耐炎化度が水分率で
4.2％の耐炎化繊維に転換した。次いで、最高温
度が1500℃の窒素雰囲気中で300〜700℃の温度域
における昇温速度を約400℃／分、1000〜1200℃
の温度域における昇温速度を約400℃／分の条件
下で炭素化して原料炭素繊維を得た。
上記原料炭素繊維を通常の電解処理装置によ
り、３モル％のアンモニア水溶液を電解液とし
て、炭素繊維１ｇ当りの電気量（クーロン量）を
かえて、第１表に示す表面窒素量の電解表面処理
糸を得た。
これら電解表面処理糸のストランド強度はそれ
ぞれ510Kg ｆ／mm2（実施例１）、490Kg ｆ／mm2
（実施例２）、485Kg ｆ／mm2（実施例３）、450Kg
ｆ／mm2（比較例１）、435Kg ｆ／mm2（比較例
２）、ストランド伸度はそれぞれ2.0％（実施例
１）、1.9％（実施例２）、1.9％（実施例３）、1.7
％（比較例１）、1.7％（比較例２）であつた。
マトリツクス樹脂として、２，２−ビス（４−
シアナートフエニル）プロパンの予備反応物であ
るBT2160RX（三菱瓦斯化学社製）60部、ビスフ
エノールＦ型エポキシ樹脂エピクロン830（大日本
化学工業社製）40部、末端水酸基を有するポリエ
ーテルスルホン樹脂VICTREX100P（I.C.I社製）
25部からなる樹脂を用い、上記炭酸繊維と組合せ
たコンポジツト試験片を作製し、引張強度（炭素
繊維の体積含有率60％に換算した数値で示した）
と層間剪断強度（ILSS）を評価し、結果を第１
表に示した。 p is 20 to 150, preferably 40 to 130, and the terminal group is chlorine or hydroxyl. ) The mixing ratio of polyfunctional cyanate ester and polyfunctional maleimide varies depending on the type of compound used, but is preferably in the range of about 10:0 to 4:6. Further, the mixing ratio of the cyanate ester resin and the epoxy resin is preferably in the range of 9:1 to 2:8. In addition, from the viewpoint of improving the impact resistance of the resin while not impairing the tack and drape properties of the prepreg, polysulfone resin should be used in an amount of 40% by weight or less, and more preferably 8 to 25% by weight of the matrix resin.
Preferably, they are mixed. [Effects] As described above, the present invention provides a prepreg made of a cyanate ester resin and a carbon fiber with a specified amount of surface nitrogen-containing functional groups, thereby providing heat resistance, water resistance, high temperature, and impact resistance upon water absorption. A composite material with excellent properties can be obtained. [Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples. In this example, the strand physical properties and composite physical properties were measured according to the following methods. <Strand physical properties> According to JIS-760 resin-impregnated strand test method, the resin formulation is “BAKELITE”
ERL4221/Boron trifluoride monoethylamine/
Acetone = 100/3/4 (parts by weight) is thoroughly mixed and used. <Composite physical properties> (Preparation of composite test piece) First, a resin film coated with a resin to be combined with carbon fibers on silicone coated paper was wrapped around a steel drum with a circumference of approximately 2.7 m, and then a creel was applied onto the resin film. After winding and arranging the drawn carbon fibers through a traverse, and again covering the fibers with the resin film,
Rotate and press with a pressure roll to impregnate the resin into the fibers to create a unidirectional prepreg with a width of 300 mm and a length of 2.7 m. At this time, the drum was heated to 50 to 60°C to improve resin impregnation between the fibers, and the fiber weight of the prepreg was adjusted to 200 g by adjusting the drum rotation speed and traverse feed speed. / m2 ,
A prepreg with a resin content of approximately 35% by weight was produced. The prepared prepregs were cut and laminated, and heated and cured in an autoclave at 180℃ and 7 kg/ cm2 for 2 hours to obtain a wall thickness of approximately 1 mm for tensile strength measurement or a wall thickness for ILSS measurement. Approximately 2mm
A hardened plate was prepared. Note that the above method is a so-called drum winding method using a resin film, but in the case of a phenol resin, a solution impregnation method as described below was used. The fibers are impregnated with resin in a resin tank filled with a resin solution, the fibers are arranged and wound around silicone paper on a drum, the solvent is air-dried, and the fibers are further dried to obtain a unidirectional prepreg. After laminating this prepreg, it was press-molded at 180° C. for 2 hours under a pressure of about 7 kg/cm 2 to obtain a unidirectionally cured plate. (Measurement of tensile strength and interlaminar shear strength (ILSS)) The above cured plate has a width of 12.7 mm and a length for tensile strength.
A 230 mm test piece, with a thickness of approximately 1.2 mm on both ends of the test piece.
A GFRP tab with a length of 50 mm and a length of 50 mm was glued (if necessary, a strain gauge was attached to the center of the specimen to measure the elastic modulus and fracture strain), and a load rate of 1 mm was applied using a Shimadzu Autograph. /min. In addition, the test piece for ILSS was 12.7 mm wide and 28 mm long.
The measurement was carried out using a normal three-point bending test jig, with the support span set to four times the thickness of the specimen, and a loading rate of 2.5.
Measured in mm/min. (Examples 1 to 3, Comparative Examples 1 and 2) Ammonia was blown into a copolymer of 99.5 mol% acrylonitrile (AN) and 0.5 mol% itaconic acid and had an intrinsic viscosity [η] of 1.80. A modified polymer is prepared by substituting the terminal hydrogen with an ammonium group, and the concentration of this modified polymer is 20%.
A wt% dimethyl sulfoxide (DMSO) solution was prepared. Adjust the temperature of this solution to 60℃, and
It was discharged into a 50% DMSO aqueous solution at 60°C. After washing the coagulated yarn with water and stretching it 4 times in hot water,
A silicone oil treatment was performed. After drying and densifying this yarn by contacting it with the surface of a roller heated to 130-160℃, it was drawn three times in a pressurized steam of 4.0Kg/ cm2 to obtain a single yarn fineness of 1.0d and a total denier of 6000d. A fiber bundle was obtained. The above acrylic fiber bundle was heated in air at 230 to 260°C with a stretching ratio of 1.00, and the degree of flame resistance was determined by the moisture content.
Converted to 4.2% flame resistant fiber. Next, in a nitrogen atmosphere with a maximum temperature of 1500°C, the temperature increase rate in the temperature range of 300 to 700°C was approximately 400°C/min, and 1000 to 1200°C.
Raw material carbon fibers were obtained by carbonization at a heating rate of about 400°C/min in the temperature range of . The above raw material carbon fibers were subjected to electrolytic surface treatment using a normal electrolytic treatment apparatus using a 3 mol % ammonia aqueous solution as an electrolyte, changing the amount of electricity (coulomb amount) per 1 g of carbon fiber, and giving the amount of surface nitrogen shown in Table 1. Got the thread. The strand strengths of these electrolytically surface-treated yarns are 510Kg f/mm 2 (Example 1) and 490Kg f/mm 2 , respectively.
(Example 2), 485Kg f/mm 2 (Example 3), 450Kg
f/mm 2 (Comparative Example 1), 435Kg f/mm 2 (Comparative Example 2), strand elongation is 2.0% (Example 1), 1.9% (Example 2), 1.9% (Example 3), respectively. 1.7
% (Comparative Example 1) and 1.7% (Comparative Example 2). As a matrix resin, 2,2-bis(4-
60 parts of BT2160RX (manufactured by Mitsubishi Gas Chemical Co., Ltd.) which is a preliminary reaction product of (cyanatophenyl) propane, 40 parts of bisphenol F type epoxy resin Epicron 830 (manufactured by Dainippon Chemical Industry Co., Ltd.), polyether sulfone resin having a terminal hydroxyl group VICTREX100P (manufactured by ICI)
Using a resin consisting of 25 parts, a composite test piece was prepared in combination with the above carbonated fiber, and the tensile strength (expressed as a value converted to a volume content of 60% of carbon fiber) was prepared.
and interlaminar shear strength (ILSS), and the results are
Shown in the table.
【表】
物性が得られた。
（実施例 ４）
実施例２で用いたプリプレグを疑似等方的に48
枚積層し、オートクレーブ中で、６Kg ｆ／cm2の
圧力下で180℃２時間成形し積層板を得た。この
試験片に、1000lb.inch／inchの衝撃を加えた後、
高さ25cm、幅125mmに切断し、飽和吸水量の70％
に達するまで吸水させた後、121℃の恒温槽中で
圧縮試験を行なつた。衝撃後圧縮強度は21Kg
ｆ／mm2と高いものであつた。
（比較例 ３）
実施例１と同様に焼成して得た炭素繊維を硫酸
水溶液中で電解処理して、N1S／C1S＝0.03、
O1S／C1S＝0.18の炭素繊維を得た。電解処理糸の
ストランド強度は500Kg ｆ／mm2、ストランド伸
度は1.9％であつた。
この炭素繊維を用い実施例４と同様に121℃に
おける衝撃後の圧縮強度を測定したところ18Kg
ｆ／mm2であり、実施例４と比べ低いものであつ
た。
（比較例 ４，５）
ELM434（住友化学社製）60部、ELM120（住友
化学社製）20部、エピコート152（油化シエルエポ
キシ社製）20部、４，4′−ジアミノジフエニルメ
タン（住友化学社製）48部、末端水酸基を有する
ポリエーテルスルホン樹脂VICTREX100p（I.C.I.
社製）16部からなるエポキシ樹脂組成物と比較例
３で用いた炭素繊維（O1S／C1S＝0.18）からなる
プリプレグを用い、実施例４と同様に吸水サンプ
ルの121℃における衝撃後の圧縮強度は、18Kg
ｆ／mm2であり、実施例２で使用した炭素繊維
（N1S／C1S＝0.10）からなるプリプレグの場合も
18Kg ｆ／mm2で炭素繊維の差はなかつた。[Table] Physical properties were obtained.
(Example 4) The prepreg used in Example 2 was prepared in a quasi-isotropic manner.
The sheets were laminated and molded in an autoclave at 180° C. for 2 hours under a pressure of 6 kg f/cm 2 to obtain a laminate. After applying an impact of 1000lb.inch/inch to this test piece,
Cut to 25cm high and 125mm wide, 70% of saturated water absorption.
After absorbing water until reaching the temperature, a compression test was conducted in a constant temperature bath at 121°C. Compressive strength after impact is 21Kg
It had a high f/ mm2 . (Comparative Example 3) Carbon fibers obtained by firing in the same manner as in Example 1 were electrolytically treated in a sulfuric acid aqueous solution, and N 1S /C 1S = 0.03,
Carbon fibers with O 1S /C 1S =0.18 were obtained. The electrolytically treated yarn had a strand strength of 500 kg f/mm 2 and a strand elongation of 1.9%. Using this carbon fiber, the compressive strength after impact at 121°C was measured in the same manner as in Example 4, and it was found to be 18 kg.
f/mm 2 , which was lower than that of Example 4. (Comparative Examples 4 and 5) 60 parts of ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), 20 parts of ELM120 (manufactured by Sumitomo Chemical Co., Ltd.), 20 parts of Epicote 152 (manufactured by Yuka Ciel Epoxy Co., Ltd.), 4,4'-diaminodiphenylmethane ( 48 parts (manufactured by Sumitomo Chemical Co., Ltd.), polyether sulfone resin VICTREX100p (ICI
Using a prepreg made of an epoxy resin composition consisting of 16 parts (manufactured by Co., Ltd.) and the carbon fiber (O 1S /C 1S = 0.18) used in Comparative Example 3, the water-absorbed sample after impact at 121°C was measured in the same manner as in Example 4. Compressive strength is 18Kg
f/mm 2 , and also in the case of the prepreg made of carbon fiber (N 1S /C 1S = 0.10) used in Example 2.
There was no difference in carbon fiber at 18Kg f/ mm2 .
Claims (1)
維表面の窒素含有官能基量（N1S／C1S）が0.06〜
0.25の範囲であり、ストランド強度が485Kgｆ／
mm2以上、ストランド伸度が1.6％以上の炭素繊維
とシアン酸エステル系樹脂からなることを特徴と
する複合材料用プリプレグ。 ２ エポキシ樹脂および／またはポリスルホン樹
脂を含有することを特徴とする特許請求の範囲第
１項記載の複合材料用プリプレグ。[Claims] 1. The amount of nitrogen-containing functional groups (N 1S /C 1S ) on the carbon fiber surface determined by X-ray photoelectron spectroscopy is 0.06 to
The range is 0.25, and the strand strength is 485Kgf/
A prepreg for composite materials characterized by being made of carbon fiber with a diameter of mm 2 or more and a strand elongation of 1.6% or more and a cyanate ester resin. 2. The prepreg for composite material according to claim 1, which contains an epoxy resin and/or a polysulfone resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3671487A JPS63205328A (en) | 1987-02-19 | 1987-02-19 | Prepreg for composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3671487A JPS63205328A (en) | 1987-02-19 | 1987-02-19 | Prepreg for composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63205328A JPS63205328A (en) | 1988-08-24 |
| JPH0434569B2 true JPH0434569B2 (en) | 1992-06-08 |
Family
ID=12477424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3671487A Granted JPS63205328A (en) | 1987-02-19 | 1987-02-19 | Prepreg for composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63205328A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100465445B1 (en) * | 2001-07-31 | 2005-01-13 | 삼성전자주식회사 | Photo-induced Alignment Material for Liquid Crystal Alignment Film |
| CN108582910A (en) * | 2018-07-11 | 2018-09-28 | 精功（绍兴）复合材料有限公司 | Carbon fiber high-temperature prepreg and laminated board thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6015439A (en) * | 1983-07-07 | 1985-01-26 | Toho Rayon Co Ltd | Prepreg for impact-resistant composite material |
| JPS60250026A (en) * | 1984-05-28 | 1985-12-10 | Mitsubishi Rayon Co Ltd | Epoxy resin composition |
-
1987
- 1987-02-19 JP JP3671487A patent/JPS63205328A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6015439A (en) * | 1983-07-07 | 1985-01-26 | Toho Rayon Co Ltd | Prepreg for impact-resistant composite material |
| JPS60250026A (en) * | 1984-05-28 | 1985-12-10 | Mitsubishi Rayon Co Ltd | Epoxy resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63205328A (en) | 1988-08-24 |
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