JP5924848B1 - Aqueous liquid of sizing agent for reinforced fiber, reinforced fiber and fiber reinforced composite material - Google Patents
Aqueous liquid of sizing agent for reinforced fiber, reinforced fiber and fiber reinforced composite material Download PDFInfo
- Publication number
- JP5924848B1 JP5924848B1 JP2015192923A JP2015192923A JP5924848B1 JP 5924848 B1 JP5924848 B1 JP 5924848B1 JP 2015192923 A JP2015192923 A JP 2015192923A JP 2015192923 A JP2015192923 A JP 2015192923A JP 5924848 B1 JP5924848 B1 JP 5924848B1
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- mass
- sizing agent
- aqueous liquid
- modified polyolefin
- 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.)
- Active
Links
- 238000004513 sizing Methods 0.000 title claims abstract description 67
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 65
- 239000007788 liquid Substances 0.000 title claims abstract description 60
- 239000000835 fiber Substances 0.000 title claims description 32
- 239000003733 fiber-reinforced composite Substances 0.000 title claims description 9
- 239000000463 material Substances 0.000 title claims description 9
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 97
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 62
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 28
- 239000011159 matrix material Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001139 pH measurement Methods 0.000 claims abstract description 7
- -1 ethylene, propylene Chemical group 0.000 claims description 25
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 21
- 239000004917 carbon fiber Substances 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 229920000098 polyolefin Polymers 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- 229930182556 Polyacetal Natural products 0.000 claims description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 2
- 229920001230 polyarylate Polymers 0.000 claims description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 2
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 229920001470 polyketone Polymers 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims 1
- 238000005728 strengthening Methods 0.000 claims 1
- 239000004711 α-olefin Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 38
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 18
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- 239000004743 Polypropylene Substances 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 229920001155 polypropylene Polymers 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- OWWIWYDDISJUMY-UHFFFAOYSA-N 2,3-dimethylbut-1-ene Chemical compound CC(C)C(C)=C OWWIWYDDISJUMY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Abstract
【課題】強化繊維用サイジング剤の水性液それ自体の安定性、強化繊維用サイジング剤を付着した強化繊維へのマトリックス樹脂の濡れ性及び強化繊維用サイジング剤を付着した強化繊維のマトリックス樹脂中での開繊性のいずれにも優れ、結果として強化繊維用サイジング剤を付着した強化繊維とマトリックス樹脂との接着性に優れた強化繊維用サイジング剤の水性液、かかる水性液中の強化繊維用サイジング剤を付着した強化繊維及びかかる強化繊維を含む強化繊維複合材料を提供する。【解決手段】特定の変性ポリオレフィン樹脂と水とを含有して成る強化繊維用サイジング剤の水性液であって、該変性ポリオレフィン樹脂の重量平均分子量と酸価が質量平均分子量／酸価＝３０００〜２００００の範囲にあり、特定のｐＨ測定方法で求められるｐＨが７．０以上であることを特徴とする強化繊維用サイジング剤の水性液を用いた。【選択図】なしThe stability of an aqueous liquid of a reinforcing fiber sizing agent itself, the wettability of a matrix resin to a reinforcing fiber having a reinforcing fiber sizing agent attached thereto, and the reinforcing fiber matrix resin having a reinforcing fiber sizing agent attached thereto. An aqueous liquid of a sizing agent for reinforcing fibers excellent in adhesion between the reinforcing fiber to which the sizing agent for reinforcing fibers is adhered and the matrix resin is excellent, and as a result, sizing for reinforcing fibers in the aqueous liquid A reinforcing fiber having an agent attached thereto and a reinforcing fiber composite material including the reinforcing fiber are provided. A sizing agent for reinforcing fibers comprising a specific modified polyolefin resin and water, wherein the weight average molecular weight and acid value of the modified polyolefin resin are mass average molecular weight / acid value = 3000. An aqueous liquid of a sizing agent for reinforcing fibers, which is in the range of 20000 and has a pH required by a specific pH measurement method of 7.0 or more, was used. [Selection figure] None
Description
本発明は、強化繊維用サイジング剤の水性液、かかる水性液中の強化繊維用サイジング剤を付着した強化繊維及びかかる強化繊維を含む繊維強化複合材料に関する。 The present invention relates to an aqueous liquid of a sizing agent for reinforcing fibers, a reinforcing fiber to which a sizing agent for reinforcing fiber in such an aqueous liquid is attached, and a fiber-reinforced composite material including the reinforcing fiber.
従来、強化繊維用サイジング剤として、エチレン−プロピレン共重合体等を主鎖とし、無水マレイン酸及び(メタ)クリル酸エステルでグラフト変性したもの（例えば、特許文献１参照）、変性ポリプロピレン樹脂とアミン化合物との中和物（例えば、特許文献２参照）等が、水性液の形態で使用されている。しかし、これら従来の強化繊維用サイジング剤の水性液には、強化繊維用サイジング剤の水性液それ自体の安定性、強化繊維用サイジング剤を付着した強化繊維へのマトリックス樹脂の濡れ性及び強化繊維用サイジング剤を付着した強化繊維のマトリックス樹脂中での開繊性がいずれも不良であり、結果として強化繊維用サイジング剤を付着した強化繊維とマトリックス樹脂との接着性も不良という問題がある。 Conventionally, as a sizing agent for reinforcing fibers, an ethylene-propylene copolymer or the like as a main chain and graft-modified with maleic anhydride and (meth) acrylic acid ester (for example, see Patent Document 1), modified polypropylene resin and amine A neutralized product with a compound (see, for example, Patent Document 2) is used in the form of an aqueous liquid. However, the aqueous liquids of these conventional reinforcing fiber sizing agents include the stability of the aqueous fiber of the reinforcing fiber sizing agent itself, the wettability of the matrix resin to the reinforcing fibers with the reinforcing fiber sizing agent attached thereto, and the reinforcing fibers. There is a problem that the fiber opening property of the reinforcing fiber to which the reinforcing sizing agent is adhered is poor in the matrix resin, and as a result, the adhesion between the reinforcing fiber to which the reinforcing fiber sizing agent is adhered and the matrix resin is also poor.
本発明が解決しようとする課題は、強化繊維用サイジング剤の水性液それ自体の安定性、強化繊維用サイジング剤を付着した強化繊維へのマトリックス樹脂の濡れ性及び強化繊維用サイジング剤を付着した強化繊維のマトリックス樹脂中での開繊性のいずれにも優れ、結果として強化繊維用サイジング剤を付着した強化繊維とマトリックス樹脂との接着性に優れた強化繊維用サイジング剤の水性液、かかる水性液中の強化繊維用サイジング剤を付着した強化繊維及びかかる強化繊維を含む強化繊維複合材料を提供する処にある。 The problems to be solved by the present invention are the stability of the aqueous liquid of the reinforcing fiber sizing agent itself, the wettability of the matrix resin to the reinforcing fiber to which the reinforcing fiber sizing agent is attached, and the sizing agent for the reinforcing fiber attached. An aqueous liquid of a sizing agent for reinforcing fibers, which is excellent in both the fiber-opening properties of the reinforcing fibers in the matrix resin, and as a result, has excellent adhesion between the reinforcing fibers to which the sizing agent for reinforcing fibers is adhered and the matrix resin, such aqueous The object of the present invention is to provide a reinforcing fiber to which a sizing agent for reinforcing fiber in liquid is attached, and a reinforcing fiber composite material including such a reinforcing fiber.
本発明者らは、前記の課題を解決するべく研究した結果、特定の変性ポリオレフィン樹脂を含有し、ｐＨが７．０以上である強化繊維用サイジング剤の水性液が正しく好適であることを見出した。 As a result of researches to solve the above-mentioned problems, the present inventors have found that an aqueous liquid of a sizing agent for reinforcing fibers containing a specific modified polyolefin resin and having a pH of 7.0 or more is suitable. It was.
すなわち本発明は、下記の変性ポリオレフィン樹脂と水とを含有して成る強化繊維用サイジング剤の水性液であって、該変性ポリオレフィン樹脂の重量平均分子量と酸価が質量平均分子量／酸価＝３０００〜２００００の範囲にあり、下記のｐＨ測定方法で求められるｐＨが７．０以上であることを特徴とする強化繊維用サイジング剤の水性液に係る。また本発明は、かかる強化繊維用サイジング剤の水性液中の変性ポリオレフィンが付着している強化繊維及びかかる強化繊維とポリオレフィン系マトリックス樹脂とを含む繊維強化複合材料に係る。 That is, the present invention is an aqueous liquid of a sizing agent for reinforcing fibers comprising the following modified polyolefin resin and water, wherein the weight average molecular weight and acid value of the modified polyolefin resin are mass average molecular weight / acid value = 3000. It is in the range of ˜20,000, and relates to an aqueous liquid of a sizing agent for reinforcing fibers, characterized in that the pH required by the following pH measurement method is 7.0 or more. The present invention also relates to a reinforcing fiber to which a modified polyolefin in an aqueous liquid of the reinforcing fiber sizing agent is attached, and a fiber-reinforced composite material including the reinforcing fiber and a polyolefin-based matrix resin.
変性ポリオレフィン樹脂：分子中にオレフィンから形成されている構成単位を９０〜９９．９質量％及び不飽和カルボン酸から形成されている構成単位を０．１〜１０質量％（合計１００質量％）の割合で有し、質量平均分子量が５００００〜２０００００であり、且つ融点が７０℃〜１４０℃であるもの。 Modified polyolefin resin: 90 to 99.9% by mass of structural units formed from olefin in the molecule and 0.1 to 10% by mass (total 100% by mass) of structural units formed from unsaturated carboxylic acid What has a ratio, a mass average molecular weight is 50000-200000, and melting | fusing point is 70 to 140 degreeC.
ｐＨ測定方法：強化繊維用サイジング剤の水性液を固形分濃度が１質量％となるように調製した試料のｐＨを溶液温度２５℃でガラス電極（ＪＩＳ Ｚ ８８０２に準ずる）を用いて測定した値 pH measurement method: a value obtained by measuring the pH of a sample prepared from an aqueous liquid of a sizing agent for reinforcing fibers so that the solid content concentration is 1% by mass using a glass electrode (according to JIS Z 8802) at a solution temperature of 25 ° C.
先ず、本発明に係る強化繊維用サイジング剤の水性液（以下、本発明の水性液という）について説明する。本発明の水性液は、前記の変性ポリオレフィン樹脂と水とを含有して成る強化繊維用サイジング剤の水性液であって、該変性ポリオレフィン樹脂の質量平均分子量と酸価が質量平均分子量／酸価＝３０００〜２００００の範囲にあり、また前記のｐＨ測定方法で求められるｐＨが７．０以上であるものである。 First, the aqueous liquid of the sizing agent for reinforcing fibers according to the present invention (hereinafter referred to as the aqueous liquid of the present invention) will be described. The aqueous liquid of the present invention is an aqueous liquid of a sizing agent for reinforcing fibers comprising the modified polyolefin resin and water, and the mass average molecular weight and acid value of the modified polyolefin resin are the mass average molecular weight / acid value. The pH is in the range of 3000 to 20000, and the pH required by the pH measurement method is 7.0 or more.
変性ポリオレフィン樹脂は、分子中にオレフィンから形成されている構成単位を９０〜９９．９質量％及び不飽和カルボン酸から形成されている構成単位を０．１〜１０質量％（合計１００質量％）の割合で有し、質量平均分子量が５００００〜２０００００であり、且つ融点が７０℃〜１４０℃であるものである。変性ポリオレフィン樹脂の分子量が５００００未満の場合は強化繊維とマトリックス樹脂との接着性が不足し、また強化繊維ストランドの集束性が劣り、逆に変性ポリオレフィン樹脂の分子量が２０００００を超える場合はサイジング剤の水性液それ自体の安定性が悪くなる。また変性ポリオレフィン樹脂の融点が７０℃未満の場合はサイジング剤それ自体の耐熱性が劣り、逆に変性ポリオレフィン樹脂の融点が１４０℃を超える場合はマトリックス樹脂中における強化繊維の開繊性が悪くなる。本発明において、変性ポリオレフィン樹脂の質量平均分子量は、ＧＰＣ法で測定されるポリスチレン換算の値である。 The modified polyolefin resin has 90 to 99.9% by mass of structural units formed from olefins in the molecule and 0.1 to 10% by mass (100% by mass in total) of structural units formed from unsaturated carboxylic acids. The mass average molecular weight is 50,000 to 200,000, and the melting point is 70 ° C to 140 ° C. When the molecular weight of the modified polyolefin resin is less than 50000, the adhesion between the reinforcing fiber and the matrix resin is insufficient, and the binding property of the reinforcing fiber strand is poor. Conversely, when the molecular weight of the modified polyolefin resin exceeds 200,000, the sizing agent The stability of the aqueous liquid itself deteriorates. Further, when the melting point of the modified polyolefin resin is less than 70 ° C., the heat resistance of the sizing agent itself is inferior, and conversely, when the melting point of the modified polyolefin resin exceeds 140 ° C., the fiber opening of the reinforcing fiber in the matrix resin is deteriorated. . In the present invention, the mass average molecular weight of the modified polyolefin resin is a value in terms of polystyrene measured by the GPC method.
変性ポリオレフィン樹脂の構成単位を形成することとなるオレフィンとしては、エチレン、プロピレン、１−ブテン、ブタジエン、１−ペンテン、３−メチル−１−ブテン、４−メチル−１−ペンテン、１−ヘキセン、２−ヘキセン、２，３−ジメチルブテン、ジシクロペンタジエン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン等が挙げられるが、なかでもエチレン、プロピレン及び炭素数４〜１２のα−オレフィンから選ばれる少なくとも一つが好ましい。 Examples of the olefin that will form the structural unit of the modified polyolefin resin include ethylene, propylene, 1-butene, butadiene, 1-pentene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 2,3-dimethylbutene, dicyclopentadiene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and the like, among which ethylene, propylene, and α-carbon having 4 to 12 carbon atoms are included. At least one selected from olefins is preferred.
変性ポリオレフィン樹脂の構成単位を形成することとなる不飽和カルボン酸としては、マレイン酸、無水マレイン酸、フマル酸、無水マレイン酸、イタコン酸、無水イタコン酸、アクリル酸、メタクリル酸等の、カルボキシル基及び必要に応じてヒドロキシル基やアミノ基やエポキシ基等の官能基が導入された重合性二重結合を有する化合物等が挙げられるが、なかでもマレイン酸、無水マレイン酸、フマル酸、無水マレイン酸、イタコン酸、無水イタコン酸等の不飽和ジカルボン酸が好ましい。 The unsaturated carboxylic acid that will form the structural unit of the modified polyolefin resin includes maleic acid, maleic anhydride, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, acrylic acid, methacrylic acid, and the like. And compounds having a polymerizable double bond into which a functional group such as a hydroxyl group, amino group, or epoxy group is introduced, if necessary, maleic acid, maleic anhydride, fumaric acid, maleic anhydride, among others. Unsaturated dicarboxylic acids such as itaconic acid and itaconic anhydride are preferred.
本発明の処理剤に供する変性ポリオレフィン樹脂は、前述のように、分子中にオレフィンから形成されている構成単位を９０〜９９．９質量％及び不飽和カルボン酸から形成されている構成単位を０．１〜１０質量％（合計１００質量％）の割合で有するものであるが、なかでもオレフィンから形成されている構成単位を９６〜９９．５質量％及び不飽和カルボン酸から形成されている構成単位を０．５〜４質量％（合計１００質量％）の割合で有するものが好ましい。分子中に不飽和カルボン酸から形成されている構成単位が０．１質量％未満の場合はサイジング剤の水性液それ自体の安定性が悪くなり、逆に１０質量％を超える場合は強化繊維とマトリックス樹脂との接着性が悪くなる。 As described above, the modified polyolefin resin used in the treatment agent of the present invention contains 90 to 99.9% by mass of structural units formed of olefins in the molecule and 0 of structural units formed of unsaturated carboxylic acids. 0.1 to 10% by mass (total 100% by mass), among which 96 to 99.5% by mass of structural units formed from olefins and unsaturated carboxylic acids What has a unit in the ratio of 0.5-4 mass% (total 100 mass%) is preferable. When the structural unit formed from unsaturated carboxylic acid in the molecule is less than 0.1% by mass, the stability of the aqueous liquid of the sizing agent itself deteriorates. Adhesiveness with the matrix resin is deteriorated.
変性ポリオレフィン樹脂の質量平均分子量と酸価は、質量平均分子量／酸価＝３０００〜２００００の範囲であるが、質量平均分子量／酸価＝１００００〜２００００の範囲が好ましい。ポリオレフィン樹脂の質量平均分子量／酸価＝３０００未満の場合は強化繊維とマトリックス樹脂との接着性が悪くなり、逆に２００００を超える場合はサイジング剤の水性液それ自体の安定性が悪くなる。本発明において、変性ポリオレフィン樹脂の酸価はＪＩＳ Ｋ ００７０に準じて測定される値である。 The mass average molecular weight and the acid value of the modified polyolefin resin are in the range of mass average molecular weight / acid value = 3000 to 20000, but are preferably in the range of mass average molecular weight / acid value = 10000 to 20000. When the mass average molecular weight / acid value of the polyolefin resin is less than 3000, the adhesion between the reinforcing fiber and the matrix resin is deteriorated, and when it exceeds 20000, the stability of the aqueous liquid of the sizing agent itself is deteriorated. In the present invention, the acid value of the modified polyolefin resin is a value measured according to JIS K 0070.
本発明の水性液のｐＨは、前述したように７．０以上である。水性液のｐＨが７．０未満である場合は水性液それ自体の安定性が悪くなる。水性液のｐＨの調整は、変性ポリオレフィン樹脂の水性液にアルカリ成分を加えることで行うが、水酸化カリウム、水酸化ナトリウム、モルホリン、アンモニア、メチルアミン、エチルアミン、ジメチルアミン、トリエチルアミン、エタノールアミン、ジメチルエタノールアミン等を用いてｐＨを７．０以上にすることが好ましい。 The pH of the aqueous liquid of the present invention is 7.0 or higher as described above. When the pH of the aqueous liquid is less than 7.0, the stability of the aqueous liquid itself deteriorates. The pH of the aqueous liquid is adjusted by adding an alkaline component to the aqueous liquid of the modified polyolefin resin, but potassium hydroxide, sodium hydroxide, morpholine, ammonia, methylamine, ethylamine, dimethylamine, triethylamine, ethanolamine, dimethyl It is preferable to adjust the pH to 7.0 or higher using ethanolamine or the like.
本発明において、固形分はサイジング剤の水性液から水を除いた成分のことであり、固形分濃度はサイジング剤の水性液に含まれる水以外の成分の割合である。かかる固形分濃度は、熱風乾燥器を用いて、試料を１０５℃で２時間乾燥し、乾燥前後の試料の質量より、（乾燥後の試料の質量（ｇ）／乾燥前の試料の質量（ｇ））×１００で算出できる。 In the present invention, the solid content is a component obtained by removing water from the aqueous liquid of the sizing agent, and the solid content concentration is a ratio of components other than water contained in the aqueous liquid of the sizing agent. The solid content concentration was determined by drying the sample at 105 ° C. for 2 hours using a hot air dryer, and calculating (mass of the sample after drying (g) / mass of the sample before drying (g )) X100.
本発明の水性液における変性ポリオレフィン樹脂と水との含有割合は特に制限されないが、変性ポリオレフィン樹脂を０質量％超５０質量％以下及び水を５０質量％以上１００質量％未満（合計１００質量％）の割合で含有して成ることが好ましい。 The content ratio of the modified polyolefin resin and water in the aqueous liquid of the present invention is not particularly limited, but the modified polyolefin resin is more than 0% by mass and less than 50% by mass and the water is 50% by mass to less than 100% by mass (total 100% by mass). It is preferable to contain in the ratio.
本発明の水性液は、公知の方法で調製できる。例えば、酸変性ポリオレフィンを、エーテル系溶剤、アルコール系溶剤、芳香族系溶剤及び水に加熱溶解させ、アルカリを添加し、冷却した後に、エーテル系溶剤、アルコール系溶剤及び芳香族系溶剤を減圧除去することにより得られる。使用する水は、水中に微量に存在するカルシウム、マグネシウム等の硬度成分や鉄等の重金属を除去した水が好ましく、イオン交換水又は蒸留水を用いることができる。 The aqueous liquid of the present invention can be prepared by a known method. For example, heat-dissolve acid-modified polyolefin in ether solvent, alcohol solvent, aromatic solvent and water, add alkali and cool, then remove ether solvent, alcohol solvent and aromatic solvent under reduced pressure Can be obtained. The water used is preferably water from which hardness components such as calcium and magnesium and heavy metals such as iron are removed, and ion-exchanged water or distilled water can be used.
次に本発明に係る強化繊維（以下、本発明の強化繊維という）について説明する。本発明の強化繊維は、本発明の水性液中の変性ポリオレフィン樹脂が付着している強化繊維である。強化繊維としては、その種類に特に制限はないが、炭素繊維、ガラス繊維、アラミド繊維、バサルト繊維、ポリエチレン繊維、ポリエチレンテレフタレート繊維、ポリブチレンテレフタレート繊維、ポリエチレンナフタレート繊維、ポリアリレート繊維、ポリアセタール繊維、ＰＢＯ繊維、ポリフェニレンサルフィド繊維及びポリケトン繊維から選ばれる少なくとも一つが好ましい。 Next, the reinforcing fiber according to the present invention (hereinafter referred to as the reinforcing fiber of the present invention) will be described. The reinforcing fiber of the present invention is a reinforcing fiber to which the modified polyolefin resin in the aqueous liquid of the present invention is attached. As the reinforcing fiber, the type is not particularly limited, but carbon fiber, glass fiber, aramid fiber, basalt fiber, polyethylene fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polyethylene naphthalate fiber, polyarylate fiber, polyacetal fiber, At least one selected from PBO fiber, polyphenylene sulfide fiber and polyketone fiber is preferable.
強化繊維に本発明の水性液中の変性ポリオレフィン樹脂を付着させる際には、本発明の水性液中に強化繊維を浸漬する方法、本発明の水性液をスプレーする方法、本発明の水性液中にオイリオングローラーの一部を浸し、回転させて、オイリングローラー表面に本発明の水性液が常に存在する状態にした状態で、かかるオイリングローラー表面に強化繊維を接触走行させる方法等が挙げられる。 When attaching the modified polyolefin resin in the aqueous liquid of the present invention to the reinforcing fibers, a method of immersing the reinforcing fibers in the aqueous liquid of the present invention, a method of spraying the aqueous liquid of the present invention, and an aqueous liquid of the present invention. And a method in which a reinforcing fiber is brought into contact with the surface of the oiling roller in a state where the aqueous liquid of the present invention is always present on the surface of the oiling roller.
本発明の水性液が塗布された強化繊維を、接触型や非接触型のヒーターで処理することにより、水分を除去し、本発明の水性液中の変性ポリオレフィン樹脂を強化繊維に付着させることが望ましい。 By treating the reinforcing fiber coated with the aqueous liquid of the present invention with a contact or non-contact type heater, moisture can be removed and the modified polyolefin resin in the aqueous liquid of the present invention can be adhered to the reinforcing fiber. desirable.
最後に本発明に係る繊維強化複合材料（以下、本発明の繊維強化複合材料という）について説明する。本発明の強化繊維複合材料は、ポリオレフィン系マトリックス樹脂と本発明の強化繊維とを含むものであり、この強化繊維には本発明の水性液中の変性ポリオレフィン樹脂が付着している。 Finally, the fiber-reinforced composite material according to the present invention (hereinafter referred to as the fiber-reinforced composite material of the present invention) will be described. The reinforcing fiber composite material of the present invention includes a polyolefin-based matrix resin and the reinforcing fiber of the present invention, and the modified polyolefin resin in the aqueous liquid of the present invention adheres to the reinforcing fiber.
本発明の繊維強化複合材料に供するポリオレフィン系マトリックス樹脂としては、その種類に特に制限はなく、ポリエチレン、ポリプロピレン、プロピレン−エチレン共重合体、プロピレン−ブテン共重合体、プロピレン−エチレン−ブテン共重合体等が挙げられる。これらのポリオレフィン系マトリックス樹脂は、本発明の強化繊維との接着性をさらに向上させる等の目的で、その一部または全部が変性したものであっても差し支えない。 The polyolefin-based matrix resin used for the fiber-reinforced composite material of the present invention is not particularly limited in type, and polyethylene, polypropylene, propylene-ethylene copolymer, propylene-butene copolymer, propylene-ethylene-butene copolymer. Etc. These polyolefin matrix resins may be partially or wholly modified for the purpose of further improving the adhesiveness with the reinforcing fiber of the present invention.
本発明の繊維強化複合材料の製造方法としては、特に制限はなく、チョップドファイバーや長繊維ペレット等を用いたコンパウンド射出成型、ＵＤシートや織物シート等を用いたプレス成型、その他にフィラメントワインディング成型等の公知の方法を採用できる。本発明の繊維強化複合材料中における本発明の強化繊維の含有量についても特に制限はなく、強化繊維の種類、形態、熱可塑性マトリックス樹脂の種類等により適宜選択することができる。 The method for producing the fiber-reinforced composite material of the present invention is not particularly limited, and is a compound injection molding using chopped fibers or long fiber pellets, a press molding using a UD sheet or a woven sheet, and a filament winding molding or the like. These known methods can be employed. There is no restriction | limiting in particular also about content of the reinforced fiber of this invention in the fiber reinforced composite material of this invention, According to the kind of reinforcement fiber, a form, the kind of thermoplastic matrix resin, etc., it can select suitably.
以上説明した本発明によると、強化繊維用サイジング剤の水性液それ自体の安定性、強化繊維用サイジング剤を付着した強化繊維へのマトリックス樹脂の濡れ性及び強化繊維用サイジング剤を付着した強化繊維のマトリックス樹脂中での開繊性のいずれにも優れ、結果として強化繊維用サイジング剤を付着した強化繊維とマトリックス樹脂との接着性に優れた強化繊維用サイジング剤の水性液、かかる水性液中の強化繊維用サイジング剤を付着した強化繊維及びかかる強化繊維を含む強化繊維複合材料を提供することができるという効果がある。 According to the present invention described above, the stability of the aqueous liquid of the reinforcing fiber sizing agent itself, the wettability of the matrix resin to the reinforcing fiber to which the reinforcing fiber sizing agent is attached, and the reinforcing fiber to which the sizing agent for reinforcing fiber is attached. An aqueous liquid of a sizing agent for reinforcing fibers excellent in adhesiveness between the reinforcing fiber to which the sizing agent for reinforcing fibers is adhered and the matrix resin is excellent in both of the opening properties in the matrix resin, and in such an aqueous liquid. There is an effect that it is possible to provide a reinforcing fiber to which the sizing agent for reinforcing fiber is attached and a reinforcing fiber composite material including the reinforcing fiber.
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明がこれらの実施例に限定されるというものではない。尚、以下の実施例及び比較例において、部は質量部を、また％は質量％を意味する。 Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.
試験区分１ （変性ポリオレフィン樹脂の調製）
・変性ポリオレフィン樹脂（ＤＯ−１）の調製
ポリプロピレン樹脂をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を加えてポリプロピレンに無水マレイン酸をグラフト共重合させて、分子中にプロピレンから形成された構成単位を９９．２質量％及び無水マレイン酸から形成された構成単位を０．８質量％（合計１００質量％）の割合で有する質量平均分子量９００００、酸価４．６ＫＯＨｍｇ／ｇ、融点１３５℃の変性ポリオレフィン樹脂（ＤＯ−１）を得た。
Test category 1 (Preparation of modified polyolefin resin)
-Preparation of modified polyolefin resin (DO-1) Polypropylene resin is heated and dissolved with stirring in an autoclave, maleic anhydride is added, and maleic anhydride is graft-copolymerized onto polypropylene to form propylene in the molecule. A mass average molecular weight of 90000 having a unit of 99.2% by mass and a unit formed from maleic anhydride in a proportion of 0.8% by mass (total of 100% by mass), an acid value of 4.6 KOHmg / g, and a melting point of 135 ° C. A modified polyolefin resin (DO-1) was obtained.
・変性ポリオレフィン樹脂（ＤＯ−２）の調製
プロピレン−エチレン共重合体（プロピレンから形成された構成単位９０モル％、エチレンから形成された構成単位１０モル％）をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を加えてプロピレン−エチレン共重合体に無水マレイン酸をグラフト共重合させて、分子中にプロピレンから形成された構成単位を９２．３質量％、エチレンから形成された構成単位を６．８質量％及び無水マレイン酸から形成された構成単位を０．９質量％（合成１００質量％）の割合で有する質量平均分子量８００００、酸価５．１ＫＯＨｍｇ／ｇ、融点１３０℃の変性ポリオレフィン樹脂（ＤＯ−２）を得た。
-Preparation of modified polyolefin resin (DO-2) Propylene-ethylene copolymer (90 mol% of structural units formed from propylene, 10 mol% of structural units formed from ethylene) was heated and dissolved while stirring in an autoclave, Maleic anhydride is added and maleic anhydride is graft-copolymerized to the propylene-ethylene copolymer to give 92.3% by mass of the structural unit formed from propylene in the molecule and 6. A modified polyolefin resin having a weight average molecular weight of 80000, an acid value of 5.1 KOHmg / g, and a melting point of 130 ° C. having a structural unit formed from 8% by mass and maleic anhydride in a proportion of 0.9% by mass (100% by mass of synthesis) DO-2) was obtained.
・変性ポリオレフィン樹脂（ＤＯ−３）の調製
プロピレン−１−ブテン共重合体（プロピレンから形成された構成単位７６モル％、１−ブテンから形成された構成単位２４モル％）をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を加えてプロピレン−１−ブテン共重合体に無水マレイン酸をグラフト共重合させて、分子中にプロピレンから形成された構成単位を６９．７質量％、１−ブテンから形成された構成単位を２９．３質量％及び無水マレイン酸から形成された構成単位を１．０質量％（合計１００質量％）の割合で有する質量平均分子量８００００、酸価５．７ＫＯＨｍｇ／ｇ、融点８０℃の変性ポリオレフィン樹脂（ＤＯ−３）を得た。
-Preparation of modified polyolefin resin (DO-3) While stirring propylene-1-butene copolymer (76 mol% of structural units formed from propylene, 24 mol% of structural units formed from 1-butene) in an autoclave It is dissolved by heating, maleic anhydride is added, and maleic anhydride is graft copolymerized with the propylene-1-butene copolymer, so that the structural unit formed from propylene in the molecule is 69.7% by mass from 1-butene. A mass average molecular weight of 80000 having a structural unit formed from 29.3% by mass and a structural unit formed from maleic anhydride in a proportion of 1.0% by mass (total of 100% by mass), acid value of 5.7 KOH mg / g, A modified polyolefin resin (DO-3) having a melting point of 80 ° C. was obtained.
・変性ポリオレフィン樹脂（ＤＯ−４）の調製
ポリプロピレン樹脂をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を加えてポリプロピレンに無水マレイン酸をグラフト共重合させて、分子中にプロピレンから形成された構成単位を９８．８質量％及び無水マレイン酸から形成された構成単位を１．２質量％（合計１００質量％）の割合で有する質量平均分子量７５０００、酸価６．９ＫＯＨｍｇ／ｇ、融点１２０℃の変性ポリオレフィン樹脂（ＤＯ−４）を得た。
-Preparation of modified polyolefin resin (DO-4) Polypropylene resin is heated and dissolved with stirring in an autoclave, maleic anhydride is added, and maleic anhydride is graft-copolymerized onto polypropylene to form propylene in the molecule. A mass average molecular weight of 75,000 having a unit of 98.8% by mass and a unit formed from maleic anhydride in a proportion of 1.2% by mass (total of 100% by mass), an acid value of 6.9 KOHmg / g, and a melting point of 120 ° C. A modified polyolefin resin (DO-4) was obtained.
・変性ポリオレフィン樹脂（ＤＯ−５）の調製
プロピレン−１−ブテン−エチレン共重合体（プロピレンから形成された構成単位８５モル％、１−ブテンから形成された構成単位１０モル％、エチレンから形成された構成単位５モル％）をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を加えてプロピレン−１−ブテン−エチレン共重合体に無水マレイン酸をグラフト共重合させて、分子中にプロピレンから形成された構成単位を８０．９質量％、１−ブテンから形成された構成単位を１２．７質量％、エチレンから形成された構成単位を３．２質量％及び無水マレイン酸から形成された構成単位を３．２質量％（合計１００質量％）の割合で有する質量平均分子量７００００、酸価１８．３ＫＯＨｍｇ／ｇ、融点１３０℃の変性ポリオレフィン樹脂（ＤＯ−５）を得た。
-Preparation of modified polyolefin resin (DO-5) Propylene-1-butene-ethylene copolymer (85 mol% of structural units formed from propylene, 10 mol% of structural units formed from 1-butene, formed from ethylene 5 mol%) was heated and dissolved with stirring in an autoclave, maleic anhydride was added, and the propylene-1-butene-ethylene copolymer was graft copolymerized with maleic anhydride to form propylene in the molecule. 80.9% by mass of the structural unit formed, 12.7% by mass of the structural unit formed from 1-butene, 3.2% by mass of the structural unit formed from ethylene, and the structural unit formed from maleic anhydride Having a mass average molecular weight of 70,000, an acid value of 18.3 KOHmg / g, and a melting point of 130 ° C. A modified polyolefin resin (DO-5) was obtained.
・変性ポリオレフィン樹脂（ＤＯ−６）の調製
プロピレン−１−ブテン共重合体（プロピレンから形成された構成単位８０モル％、１−ブテンから形成された構成単位２０モル％）をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を加えてプロピレン−１−ブテン共重合体に無水マレイン酸をグラフト共重合させて、分子中にプロピレンから形成された構成単位を７３．１質量％、１−ブテンから形成された構成単位を２４．４質量％及び無水マレイン酸から形成された構成単位を２．５質量％（合成１００質量％）の割合で有する質量平均分子量６００００、酸価１４．３ＫＯＨｍｇ／ｇ、融点９５℃の変性ポリオレフィン樹脂（ＤＯ−６）を得た。
-Preparation of modified polyolefin resin (DO-6) While stirring propylene-1-butene copolymer (80 mol% of structural units formed from propylene, 20 mol% of structural units formed from 1-butene) in an autoclave It is dissolved by heating, maleic anhydride is added, and maleic anhydride is graft copolymerized with the propylene-1-butene copolymer, so that the structural unit formed from propylene in the molecule is 73.1% by mass from 1-butene. A mass average molecular weight of 60000 having a structural unit formed from 24.4% by mass and a structural unit formed from maleic anhydride in a proportion of 2.5% by mass (synthesis 100% by mass), acid value of 14.3 KOH mg / g, A modified polyolefin resin (DO-6) having a melting point of 95 ° C. was obtained.
・変性ポリオレフィン樹脂（ＤＯ−７）の調製
プロピレン−１−ブテン共重合体（プロピレンから形成された構成単位７６モル％、１−ブテンから形成された構成単位２４モル％）をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を加えてプロピレン−１−ブテン共重合体に無水マレイン酸をグラフト共重合させて、分子中にプロピレンから形成された構成単位を６８．６量％、１−ブテンから形成された構成単位を２８．９質量％及び無水マレイン酸から形成された構成単位を２．５質量％（合計１００質量％）の割合で有する質量平均分子量７００００、酸価１４．３ＫＯＨｍｇ／ｇ、融点７０℃の変性ポリオレフィン樹脂（ＤＯ−７）を得た。
-Preparation of modified polyolefin resin (DO-7) While stirring propylene-1-butene copolymer (76 mol% of structural units formed from propylene, 24 mol% of structural units formed from 1-butene) in an autoclave It is dissolved by heating, maleic anhydride is added, and maleic anhydride is graft copolymerized with the propylene-1-butene copolymer, so that 68.6% by weight of the structural unit formed from propylene in the molecule is obtained from 1-butene. A weight average molecular weight of 70,000 having an amount of 28.9% by mass of the formed unit and 2.5% by mass (100% by mass in total) of units formed from maleic anhydride, an acid value of 14.3 KOHmg / g, A modified polyolefin resin (DO-7) having a melting point of 70 ° C. was obtained.
・変性ポリオレフィン樹脂（ＲＤＯ−１）の調製
プロピレン−１−ブテン共重合体（プロピレンから形成された構成単位９０モル％、１−ブテンから形成された構成単位１０モル％）をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を加えてプロピレン−１−ブテン共重合体に無水マレイン酸をグラフト共重合させて、分子中にプロピレンから形成された構成単位を７９．５量％、１−ブテンから形成された構成単位を１１．８質量％及び無水マレイン酸から形成された構成単位を８．７質量％（合計１００質量％）の割合で有する質量平均分子量５５０００、酸価５０ＫＯＨｍｇ／ｇ、融点９０℃の変性ポリオレフィン樹脂（ＲＤＯ−１）を得た。
-Preparation of modified polyolefin resin (RDO-1) Propylene-1-butene copolymer (90 mol% of structural units formed from propylene, 10 mol% of structural units formed from 1-butene) with stirring in an autoclave It is dissolved by heating, maleic anhydride is added, and maleic anhydride is graft copolymerized with the propylene-1-butene copolymer, so that the structural unit formed from propylene in the molecule is 79.5% by weight from 1-butene. Mass average molecular weight 55000 having a constitutional unit formed of 11.8% by mass and a constitutional unit formed from maleic anhydride at a ratio of 8.7% by mass (total of 100% by mass), acid value 50 KOH mg / g, melting point 90 A modified polyolefin resin (RDO-1) at 0 ° C. was obtained.
・変性ポリオレフィン樹脂（ＲＤＯ−２）の調製
ポリプロピレン樹脂をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を加えてポリプロピレンに無水マレイン酸をグラフト共重合させて、分子中にプロピレンから形成された構成単位を６５．０質量％及び無水マレイン酸から形成された構成単位を３５．０質量％（合計１００質量％）の割合で有する質量平均分子量５５０００、酸価２００ＫＯＨｍｇ／ｇ、融点１５５℃の変性ポリオレフィン樹脂（ＲＤＯ−２）を得た。
-Preparation of modified polyolefin resin (RDO-2) Polypropylene resin was heated and dissolved with stirring in an autoclave, maleic anhydride was added, and graft copolymerization of maleic anhydride with polypropylene was carried out, and the structure formed from propylene in the molecule A modified polyolefin having a mass average molecular weight of 55000, an acid value of 200 KOHmg / g, and a melting point of 155 ° C., having a unit of 65.0% by mass and a unit of 35.0% by mass (total 100% by mass) formed from maleic anhydride Resin (RDO-2) was obtained.
・変性ポリオレフィン樹脂（ＲＤＯ−３）の調製
プロピレン−エチレン共重合体（プロピレンから形成された構成単位を８０モル％、エチレンから形成された構成単位を２０モル％）をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を加えてプロピレン−エチレン共重合体に無水マレイン酸をグラフト共重合させて、分子中にプロピレンから形成された構成単位を７８．３質量％、エチレンから形成された構成単位を１３．０質量％及び無水マレイン酸から形成された構成単位を８．７質量％（合計１００質量％）の割合で有する質量平均分子量１００００、酸価５０ＫＯＨｍｇ／ｇ、融点６０℃の変性ポリオレフィン樹脂（ＲＤＯ−３）を得た。
Preparation of modified polyolefin resin (RDO-3) Propylene-ethylene copolymer (80 mol% of structural units formed from propylene and 20 mol% of structural units formed from ethylene) is heated and dissolved while stirring in an autoclave. Then, maleic anhydride is added and maleic anhydride is graft-copolymerized to the propylene-ethylene copolymer to obtain 78.3% by mass of a structural unit formed from propylene in the molecule and a structural unit formed from ethylene. A modified polyolefin resin having a weight average molecular weight of 10,000, an acid value of 50 KOH mg / g, and a melting point of 60 ° C. having a constitutional unit formed from 13.0 mass% and maleic anhydride in a proportion of 8.7 mass% (total of 100 mass%) RDO-3) was obtained.
・変性ポリオレフィン樹脂（ＲＤＯ−４）の調製
ポリプロピレン樹脂をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を加えてポリプロピレンに無水マレイン酸をグラフト共重合させて、分子中にプロピレンから形成された構成単位を９９．７質量％及び無水マレイン酸から形成された構成単位を０．３質量％（合計１００質量％）の割合で有する質量平均分子量１４００００、酸価１．７ＫＯＨｍｇ／ｇ、融点１６０℃の変性ポリオレフィン樹脂（ＲＤＯ−４）を得た。
-Preparation of modified polyolefin resin (RDO-4) A structure in which polypropylene resin is heated and dissolved while stirring in an autoclave, maleic anhydride is added, and maleic anhydride is graft-copolymerized onto polypropylene to form propylene in the molecule. A mass average molecular weight of 140000 having a unit of 99.7% by mass and a unit formed from maleic anhydride in a proportion of 0.3% by mass (total of 100% by mass), an acid value of 1.7 KOHmg / g, and a melting point of 160 ° C. A modified polyolefin resin (RDO-4) was obtained.
以上で調製した変性ポリオレフィン樹脂（ＤＯ−１）〜（ＤＯ−７）、（ＲＤＯ−１）〜（ＲＤＯ−４）及びポリプロピレン樹脂（ＲＤＯ−５）について、それらの構成単位の種類と割合、質量平均分子量、酸価、質量平均分子量／酸価を表１にまとめて示した。 About the modified polyolefin resins (DO-1) to (DO-7), (RDO-1) to (RDO-4) and the polypropylene resin (RDO-5) prepared above, the types and proportions of their structural units, and the mass The average molecular weight, acid value, and mass average molecular weight / acid value are summarized in Table 1.
試験区分２ （強化繊維用サイジング剤の水性液の調製）
・実施例１
イオン交換水１５０ｇ、変性ポリオレフィン樹脂（ＤＯ−１）６０ｇ、テトラヒドロフラン７０ｇ、イソプロピルアルコール５ｇ及びトルエン５ｇを撹拌機付きフラスコに入れ、７０℃に昇温した後、同温度で２時間、加熱溶解した。次に、ジメチルエタノールアミン１．３ｇを加え、２時間かけて徐々に４０℃まで冷却した後、９１ＫＰａの減圧度で有機溶剤を留去し、変性ポリオレフィン樹脂の水分散体を得た。更に、水を加えて濃度調節を行い、変性ポリオレフィン樹脂の濃度が３０％の強化繊維用サイジング剤の水性液（実施例１）を得た。
Test Category 2 (Preparation of aqueous solution of sizing agent for reinforcing fibers)
Example 1
150 g of ion-exchanged water, 60 g of modified polyolefin resin (DO-1), 70 g of tetrahydrofuran, 5 g of isopropyl alcohol and 5 g of toluene were placed in a flask equipped with a stirrer, heated to 70 ° C., and heated and dissolved at the same temperature for 2 hours. Next, after adding 1.3 g of dimethylethanolamine and gradually cooling to 40 ° C. over 2 hours, the organic solvent was distilled off at a reduced pressure of 91 KPa to obtain an aqueous dispersion of a modified polyolefin resin. Further, the concentration was adjusted by adding water to obtain an aqueous liquid (Example 1) of a sizing agent for reinforcing fibers having a modified polyolefin resin concentration of 30%.
・実施例２〜７及び比較例１〜６の調製
実施例１と同様の方法で、強化繊維用サイジング剤の水性液（実施例２〜７）及び（比較例１〜６）を調製した。これらの内容を表２にまとめて示した。
-Preparation of Examples 2-7 and Comparative Examples 1-6 In the same manner as in Example 1, aqueous liquids of sizing agents for reinforcing fibers (Examples 2-7) and (Comparative Examples 1-6) were prepared. These contents are summarized in Table 2.
試験区分３（炭素繊維のサイジング及び評価）
・ｐＨの測定
試験区分２で調製した強化繊維用サイジング剤の水性液（実施例１〜７）及び（比較例１〜６）について、固形分濃度が１質量％となるように調製した試料を、溶液温度２５℃でガラス電極（ＪＩＳ Ｚ ８８０２に準ずる）を用いて測定した。結果を表２にまとめて示した。
Test category 3 (carbon fiber sizing and evaluation)
-Measurement of pH About the aqueous liquids (Examples 1 to 7) and (Comparative Examples 1 to 6) of the reinforcing fiber sizing agent prepared in Test Category 2, samples prepared so that the solid content concentration was 1% by mass. The measurement was performed using a glass electrode (according to JIS Z 8802) at a solution temperature of 25 ° C. The results are summarized in Table 2.
・安定性の評価
試験区分２で調製した強化繊維用サイジング剤の水性液（実施例１〜７）及び（比較例１〜６）を２５℃で１週間静置した後、その外観を肉眼で観察し、以下の基準で評価した。結果を表２にまとめて示した。
○：分離や沈殿は見られず、良好な安定性を保っていた。
×：沈殿や分離が生じた。
-Evaluation of stability After leaving the aqueous liquids (Examples 1 to 7) and (Comparative Examples 1 to 6) of the reinforcing fiber sizing agent prepared in Test Category 2 at 25 ° C for 1 week, the appearance was visually observed. Observed and evaluated according to the following criteria. The results are summarized in Table 2.
○: No separation or precipitation was observed, and good stability was maintained.
X: Precipitation and separation occurred.
・炭素繊維のサイジング
試験区分２で調製した強化繊維用サイジング剤の水性液（実施例１〜７）及び（比較例１〜６）を固形分濃度が２％となるようにそれぞれ水希釈し、処理浴に入れた。ポリアクリロニトリル系繊維から得た未サイジングの炭素繊維（引張強度３５００ＭＰａ、引張弾性率２．３×１０５ＭＰａ、１２０００フィラメント）を連続的に上記処理浴に浸漬し、各サイジング剤の希釈液が炭素繊維に対して５０質量％付着するようにローラーの絞り条件を調節して、該炭素繊維にサイジング剤の希釈液を付着させた。引き続き連続的に１２０℃のオーブンに５分間通して乾燥を実施し、各サイジング剤が固形分で１質量％付着した炭素繊維を得た。かくしてサイジング処理した炭素繊維について、接着性、濡れ性及び開繊性の評価を行なった。
Carbon fiber sizing The aqueous liquids (Examples 1 to 7) and (Comparative Examples 1 to 6) of the reinforcing fiber sizing agent prepared in Test Category 2 were each diluted with water so that the solid content concentration was 2%. Placed in treatment bath. Non-sized carbon fiber (tensile strength 3500 MPa, tensile elastic modulus 2.3 × 10 5 MPa, 12000 filament) obtained from polyacrylonitrile fiber is continuously immersed in the treatment bath, and a dilute solution of each sizing agent is carbon. The roller squeezing conditions were adjusted so that 50% by mass adhered to the fiber, and a diluted solution of the sizing agent was adhered to the carbon fiber. Subsequently, drying was carried out by continuously passing through an oven at 120 ° C. for 5 minutes to obtain a carbon fiber to which 1% by mass of each sizing agent adhered in solid content. The carbon fiber thus sized was evaluated for adhesion, wettability, and spreadability.
・接着性の評価
前記の試料から１本の炭素繊維を取り出し、緊張した状態でその両端をホルダーに接着剤で固定した。ポリプロピレン樹脂（プライムポリマー製、Ｊ３０００ＧＰ）を直径が９０〜１１０μｍの樹脂滴状粒となるように炭素繊維に付着させ、試験片とした。この試料片を２枚のブレードではさみ、この状態で２枚のブレードを０．０５ｍｍ／分の速度で繊維軸方向に移動させた時、これらのブレードによって樹脂滴状粒が炭素繊維から剥離する際に生じる最大応力Ｆをロードセルにて計測した。計測した値を用いて、下記の数１により界面せん断強度τを算出した。同様の操作を２０回行い、得られた界面せん断強度の平均値を以下の基準により評価した。結果を表２にまとめて示した。
◎：界面せん断強度が１８ＭＰａ以上
○：界面せん断強度が１４ＭＰａ〜１８ＭＰａ
×：界面せん断強度が１４ＭＰａ以下
-Evaluation of adhesiveness One carbon fiber was taken out from the sample, and both ends thereof were fixed to the holder with an adhesive in a tense state. A polypropylene resin (manufactured by Prime Polymer, J3000GP) was attached to the carbon fiber so as to form resin droplets having a diameter of 90 to 110 μm to obtain a test piece. When the sample piece is sandwiched between two blades and the two blades are moved in the fiber axis direction at a speed of 0.05 mm / min in this state, the resin droplets are separated from the carbon fibers by these blades. The maximum stress F generated during the measurement was measured with a load cell. Using the measured value, the interfacial shear strength τ was calculated by the following formula 1. The same operation was performed 20 times, and the average value of the obtained interface shear strength was evaluated according to the following criteria. The results are summarized in Table 2.
◎: Interfacial shear strength is 18 MPa or more ○: Interfacial shear strength is 14 MPa to 18 MPa
X: Interfacial shear strength is 14 MPa or less
数１において、
Ｆ：炭素繊維から樹脂滴状粒が剥離する際に生じる最大応力（ｋｇｆ）
Ｄ：１本の炭素繊維の直径（ｍｍ）
Ｌ：樹脂滴状粒の繊維軸方向の直径（ｍｍ）
In Equation 1,
F: Maximum stress (kgf) generated when resin droplets peel from carbon fiber
D: Diameter of one carbon fiber (mm)
L: Diameter of resin droplets in the fiber axis direction (mm)
・濡れ性の評価
前記の接着性評価における試験片の２０個について、各樹脂滴状粒の炭素繊維フィラメントに対する接触角を測定し、その平均値を求めた。サイジング剤未処理炭素繊維について、同様にして求めた接触角の平均値と比較を行い、以下の基準で評価した。結果を表２にまとめて示した。
○：サイジング剤未処理炭素繊維の接触角に比較して１度以上接触角が小さい。
×：サイジング剤未処理炭素繊維の接触角とほぼ同等（接触角の差が±１度未満）
-Evaluation of wettability The contact angle with respect to the carbon fiber filament of each resin droplet was measured about 20 test pieces in the above-mentioned adhesion evaluation, and the average value was calculated. The sizing agent-untreated carbon fiber was compared with the average value of contact angles obtained in the same manner, and evaluated according to the following criteria. The results are summarized in Table 2.
○: The contact angle is smaller by 1 degree or more than the contact angle of the untreated sizing agent carbon fiber.
X: Almost equivalent to the contact angle of untreated sizing agent carbon fiber (difference in contact angle is less than ± 1 degree)
・開繊性の評価
合計５本の直径１ｃｍのクロムメッキ梨地ピンを、左右に３ｃｍ間隔、上下に５ｃｍ間隔で、交互に上下にずらして配置し、前記のサイジング剤が塗布された試料をこれらのクロムメッキ梨地ピンに接触させながら全体として波状に糸速１ｍ／分で通過させて、通過前の炭素繊維束の幅Ｗ１と通過後の炭素繊維束の幅Ｗ２を測定し、下記の数２により変動幅を求め、以下の基準で評価した。結果を表２にまとめて示した。
・ Evaluation of spreadability A total of five 1 cm diameter chrome-plated satin pins are alternately shifted up and down at intervals of 3 cm on the left and right and 5 cm on the top and bottom, and the samples to which the above sizing agent is applied While passing through the chrome-plated satin pin of the wire, it was passed as a whole at a yarn speed of 1 m / min, and the width W1 of the carbon fiber bundle before passing and the width W2 of the carbon fiber bundle after passing were measured. The fluctuation range was calculated by the following criteria and evaluated according to the following criteria. The results are summarized in Table 2.
数２において、
Ｗ１：合計５本のクロムメッキ梨地ピンを通過する前の炭素繊維束の幅（ｍｍ）
Ｗ２：合計５本のクロムメッキ梨地ピンを通過した後の炭素繊維束の幅（ｍｍ）
In Equation 2,
W1: Width of the carbon fiber bundle (mm) before passing through a total of 5 chrome-plated satin pins
W2: Width of the carbon fiber bundle after passing through a total of five chrome-plated satin pins (mm)
○：変動幅が３ｍｍ以上
×：変動幅が３ｍｍ未満
○: Fluctuation width is 3 mm or more ×: Fluctuation width is less than 3 mm
表２において、
＊１：安定性が悪いため、測定しなかった
In Table 2,
* 1: Not measured due to poor stability
Claims (9)
変性ポリオレフィン樹脂：分子中にオレフィンから形成されている構成単位を９０〜９９．９質量％及び不飽和カルボン酸から形成されている構成単位を０．１〜１０質量％（合計１００質量％）の割合で有し、質量平均分子量が５００００〜２０００００であり、且つ融点が７０〜１４０℃であるもの。
ｐＨ測定方法：強化繊維用サイジング剤の水性液を固形分濃度が１質量％となるように調製した試料のｐＨを溶液温度２５℃でガラス電極（ＪＩＳ Ｚ ８８０２に準ずる）を用いて測定した値 An aqueous liquid of a sizing agent for reinforcing fibers comprising the following modified polyolefin resin and water, wherein the weight average molecular weight and acid value of the modified polyolefin resin are in the range of mass average molecular weight / acid value = 3000 to 20000. An aqueous liquid of a sizing agent for reinforcing fibers, characterized in that the pH required by the following pH measurement method is 7.0 or more.
Modified polyolefin resin: 90 to 99.9% by mass of structural units formed from olefin in the molecule and 0.1 to 10% by mass (total 100% by mass) of structural units formed from unsaturated carboxylic acid It has a ratio, a mass average molecular weight of 50,000 to 200,000, and a melting point of 70 to 140 ° C.
pH measurement method: a value obtained by measuring the pH of a sample prepared from an aqueous liquid of a sizing agent for reinforcing fibers so that the solid content concentration is 1% by mass using a glass electrode (according to JIS Z 8802) at a solution temperature of 25 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015192923A JP5924848B1 (en) | 2015-09-30 | 2015-09-30 | Aqueous liquid of sizing agent for reinforced fiber, reinforced fiber and fiber reinforced composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015192923A JP5924848B1 (en) | 2015-09-30 | 2015-09-30 | Aqueous liquid of sizing agent for reinforced fiber, reinforced fiber and fiber reinforced composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP5924848B1 true JP5924848B1 (en) | 2016-05-25 |
| JP2017066547A JP2017066547A (en) | 2017-04-06 |
Family
ID=56069520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015192923A Active JP5924848B1 (en) | 2015-09-30 | 2015-09-30 | Aqueous liquid of sizing agent for reinforced fiber, reinforced fiber and fiber reinforced composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5924848B1 (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08133794A (en) * | 1994-11-11 | 1996-05-28 | Asahi Fiber Glass Co Ltd | Glass fiber for direct injection molding and glass fiber reinforced thermoplastic resin composition |
| JP2004263359A (en) * | 2003-01-07 | 2004-09-24 | Mitsubishi Rayon Co Ltd | Carbon fiber bundle, chopped carbon fiber bundle, method for producing the same, carbon fiber-reinforced thermoplastic resin composition and molded product of the same |
| WO2005012604A2 (en) * | 2003-07-31 | 2005-02-10 | Mitsubishi Rayon Co., Ltd. | Carbon fiber bundle, process for producing the same, and thermoplastic resin composition and molded article thereof |
| JP2008514797A (en) * | 2004-09-29 | 2008-05-08 | イーストマン ケミカル カンパニー | Functionalized polyolefins and functionalized polyolefin emulsions containing alicyclic carboxylic acids |
| JP2011099186A (en) * | 2009-11-09 | 2011-05-19 | Dic Corp | Glass fiber sizing agent, method for producing glass fiber sizing agent, and glass fiber |
| JP2013032600A (en) * | 2011-08-01 | 2013-02-14 | Dic Corp | Sizing agent for carbon fiber, carbon fiber, and molded material |
| WO2014038574A1 (en) * | 2012-09-06 | 2014-03-13 | 三菱レイヨン株式会社 | Carbon fiber bundle for resin reinforcement purposes and method for producing same, and carbon-fiber-reinforced thermoplastic resin composition and molded product thereof |
| WO2015133569A1 (en) * | 2014-03-05 | 2015-09-11 | 三菱レイヨン株式会社 | Carbon fiber bundle for resin reinforcement and method for manufacturing carbon fiber bundle for resin reinforcement, carbon fiber-reinforced thermoplastic resin composition, and molded body |
-
2015
- 2015-09-30 JP JP2015192923A patent/JP5924848B1/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08133794A (en) * | 1994-11-11 | 1996-05-28 | Asahi Fiber Glass Co Ltd | Glass fiber for direct injection molding and glass fiber reinforced thermoplastic resin composition |
| JP2004263359A (en) * | 2003-01-07 | 2004-09-24 | Mitsubishi Rayon Co Ltd | Carbon fiber bundle, chopped carbon fiber bundle, method for producing the same, carbon fiber-reinforced thermoplastic resin composition and molded product of the same |
| WO2005012604A2 (en) * | 2003-07-31 | 2005-02-10 | Mitsubishi Rayon Co., Ltd. | Carbon fiber bundle, process for producing the same, and thermoplastic resin composition and molded article thereof |
| JP2008514797A (en) * | 2004-09-29 | 2008-05-08 | イーストマン ケミカル カンパニー | Functionalized polyolefins and functionalized polyolefin emulsions containing alicyclic carboxylic acids |
| JP2011099186A (en) * | 2009-11-09 | 2011-05-19 | Dic Corp | Glass fiber sizing agent, method for producing glass fiber sizing agent, and glass fiber |
| JP2013032600A (en) * | 2011-08-01 | 2013-02-14 | Dic Corp | Sizing agent for carbon fiber, carbon fiber, and molded material |
| WO2014038574A1 (en) * | 2012-09-06 | 2014-03-13 | 三菱レイヨン株式会社 | Carbon fiber bundle for resin reinforcement purposes and method for producing same, and carbon-fiber-reinforced thermoplastic resin composition and molded product thereof |
| WO2015133569A1 (en) * | 2014-03-05 | 2015-09-11 | 三菱レイヨン株式会社 | Carbon fiber bundle for resin reinforcement and method for manufacturing carbon fiber bundle for resin reinforcement, carbon fiber-reinforced thermoplastic resin composition, and molded body |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2017066547A (en) | 2017-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5650117B2 (en) | Carbon fiber reinforced resin composition | |
| JP5984875B2 (en) | Carbon fiber bundle and manufacturing method thereof | |
| KR101669377B1 (en) | Carbon fiber bundle for resin reinforcement purposes and method for producing same, and carbon-fiber-reinforced thermoplastic resin composition and molded product thereof | |
| KR101837219B1 (en) | Carbon fiber bundle, method for producing same, and molded article produced from same | |
| JP5430583B2 (en) | Water dispersion for fiber treatment | |
| CN111094407A (en) | Fiber-reinforced thermoplastic resin molded article | |
| JP6881936B2 (en) | Tape winding molding method, fiber reinforced resin composition for tape winding molding | |
| JP2012007280A (en) | Carbon fiber bundle and method for producing the same, and molded article from the same | |
| JP5924848B1 (en) | Aqueous liquid of sizing agent for reinforced fiber, reinforced fiber and fiber reinforced composite material | |
| JP2016160535A (en) | Polyparaphenylene terephthalamide fiber composite and manufacturing method therefor | |
| JP7021857B2 (en) | Injection molded product and its manufacturing method | |
| JP2012219425A (en) | Sizing agent for carbon fiber, carbon fiber bundle and method for producing carbon fiber bundle | |
| JP2023529886A (en) | Molding compositions based on polyamide, carbon fibers and hollow glass beads and their use | |
| JP6795369B2 (en) | Tape winding molding method, fiber reinforced resin composition for tape winding molding | |
| JP2019202435A (en) | Tape winding pipe provided with resin molded article, automobile component, construction material, and manufacturing method of tape winding pipe provided with resin molded article | |
| JP6921584B2 (en) | Reinforcing fiber bundles, molding materials and moldings | |
| JP2023003281A (en) | graft copolymer | |
| JPH07286050A (en) | Long-fiber glass-reinforced polyolefin resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20160224 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160418 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160418 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5924848 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |