JP2018172809A - 強化繊維束、成型材料及び成形体 - Google Patents
強化繊維束、成型材料及び成形体 Download PDFInfo
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- JP2018172809A JP2018172809A JP2017070958A JP2017070958A JP2018172809A JP 2018172809 A JP2018172809 A JP 2018172809A JP 2017070958 A JP2017070958 A JP 2017070958A JP 2017070958 A JP2017070958 A JP 2017070958A JP 2018172809 A JP2018172809 A JP 2018172809A
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- JP
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- Prior art keywords
- resin
- butene
- fiber bundle
- olefin
- reinforcing fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 70
- 239000012778 molding material Substances 0.000 title description 7
- 229920005989 resin Polymers 0.000 claims abstract description 206
- 239000011347 resin Substances 0.000 claims abstract description 206
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 94
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 150000007942 carboxylates Chemical group 0.000 claims abstract description 15
- 239000000155 melt Substances 0.000 claims abstract description 7
- 239000012783 reinforcing fiber Substances 0.000 claims description 102
- 229920005672 polyolefin resin Polymers 0.000 claims description 62
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 38
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 32
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 6
- 229920006122 polyamide resin Polymers 0.000 claims description 5
- 229920001225 polyester resin Polymers 0.000 claims description 5
- 239000004645 polyester resin Substances 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 abstract description 29
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 28
- 239000000203 mixture Substances 0.000 abstract description 19
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 16
- 230000008021 deposition Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 66
- -1 polypropylene Polymers 0.000 description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 34
- 229920000049 Carbon (fiber) Polymers 0.000 description 26
- 239000004917 carbon fiber Substances 0.000 description 26
- 125000002843 carboxylic acid group Chemical group 0.000 description 23
- 239000011159 matrix material Substances 0.000 description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- 229920001155 polypropylene Polymers 0.000 description 19
- 239000002253 acid Substances 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 239000004743 Polypropylene Substances 0.000 description 14
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 14
- 239000000523 sample Substances 0.000 description 14
- 238000005259 measurement Methods 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 239000000839 emulsion Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- 239000011342 resin composition Substances 0.000 description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 238000000921 elemental analysis Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
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- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 6
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- 239000000126 substance Substances 0.000 description 6
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000009102 absorption Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000011088 calibration curve Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
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- 239000008188 pellet Substances 0.000 description 4
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- 238000004513 sizing Methods 0.000 description 4
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- 229920002554 vinyl polymer Polymers 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 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
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-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
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- SGVYKUFIHHTIFL-UHFFFAOYSA-N 2-methylnonane Chemical compound CCCCCCCC(C)C SGVYKUFIHHTIFL-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound 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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
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- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical group C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
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- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical group CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
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- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
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- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
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- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
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- 239000004342 Benzoyl peroxide Substances 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
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- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
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Landscapes
- Reinforced Plastic Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
重合体鎖に結合したカルボン酸塩を少なくとも含むオレフィン系樹脂(B)と、
強化繊維(C)と
を含み、以下の要件を満たす強化繊維束。
ブテン系樹脂(A)は、ブテン由来の構造単位が50モル%を超え、100モル%以下であり、ASTM1238規格に準じ、190℃、2.16kg荷重の条件で決定されるメルトフローレート(MFR)が0.01〜20g/10分の範囲にあり、
ブテン系樹脂(A)のMFRがオレフィン系樹脂(B)のMFRよりも小さく、
ブテン系樹脂(A)100質量部に対して、オレフィン系樹脂(B)は3〜50質量部であり、
ブテン系樹脂(A)とオレフィン系樹脂(B)の合計の含有率が0.3〜5質量%である。
プロピレン系樹脂、ブテン系樹脂、ポリアミド樹脂、ポリエステル樹脂およびポリエーテル樹脂からなる群より選ばれる樹脂(D)30〜99量部と
を含む(但し、前記強化繊維束と樹脂(D)との合計が100質量部である)ことを特徴とする成形材料。
酸価=(5.611×A×F)/B(mgKOH/g)
A:0.1規定水酸化カリウム−エタノール標準液使用量(ml)
F:0.1規定水酸化カリウム−エタノール標準液のファクター
B:試料採取量(g)。
中和されていないカルボン酸基のモル数=酸価×1000/56(モル/g)。
転化率%=(1−r)×100(%)
r:中和されていないカルボン酸基のモル数/カルボン酸基の総モル数。
ブテン系樹脂(A)>樹脂(D)>オレフィン系樹脂(B)
○:短繊維が裁断前とほぼ同じ状態を保っている。
×:短繊維が大きくばらけたり、割れが生じている。
樹脂の付着した強化繊維束を約5g取り、120℃で3時間乾燥し、その質量W1(g)を測定した。次いで強化繊維束を窒素雰囲気中で、450℃で15分間加熱後、室温まで冷却しその質量W2(g)を測定した。W1(g)およびW2(g)を用いて付着量は次式にて算出した。
付着量=[(W1−W2)/W2]×100(質量%)
(重合体の分子量)
ブテン系重合体を含むオレフィン系重合体の分子量の測定例としては、以下の条件でのGPC法で求める方法を挙げることが出来る。本願実施例ではこの方法を用いる。
液体クロマトグラフ:Polymer Laboratories社製 PL―GPC220型高温ゲル浸透クロマトグラフ(示差屈折率計装置内蔵)
カラム:東ソー株式会社製 TSKgel GMHHR−H(S)−HT×2本および同GMHHR−H(S)×1本を直列接続した。
移動相媒体:1,2,4-トリクロロベンゼン(安定剤0.025%含有)
流速:1.0ml/分
測定温度:150℃
検量線の作成方法:標準ポリスチレンサンプルを使用した。
サンプル濃度:0.15%(w/v)
サンプル溶液量:500μl
検量線作成用標準サンプル:東ソー社製単分散ポリスチレン
分子量較正方法:標準較正法(ポリスチレン換算)
オレフィン系樹脂について、有機化合物元素分析、誘導結合プラズマ(ICP)発光分析、IR(赤外吸収)スペクトル分析、1H−NMR測定および13C−NMR測定を実施し、プロピレン系樹脂の含有元素量、官能基構造の同定、各帰属プロトン、カーボンのピーク強度より単量体構造の含有割合について評価を実施した。
オレフィン系樹脂(B)(プロピレン系樹脂)に対して、以下の操作をおこなうことでカルボン酸塩含有量および中和されていないカルボン酸含有量を測定した。
酸価=(5.611×A×F)/B(mgKOH/g)
A:0.1規定水酸化カリウム−エタノール標準液使用量(ml)
F:0.1規定水酸化カリウム−エタノール標準液のファクター(1.02)
B:試料採取量(0.50g)
中和されていないカルボン酸基のモル数=酸価×1000/56(モル/g)
転化率%=(1−r)×100(%)
r:中和されていないカルボン酸基のモル数/カルボン酸基の総モル数。
特許5584977号の実施例に記載の方法と同様にして決定した。
擦過毛羽数が0〜10個/mを合格とし、それを超えると不合格とした。
本発明の強化繊維束とマトリックス樹脂との界面剪断せん断強度(フラグメンテーション法)の評価は以下の方法で測定した。マトリックス樹脂(D)からなる100μm厚の樹脂フィルム(20cm×20cm角)を2枚作製した。そして一方の樹脂フィルム上に、強化繊維束から取り出した20cm長の単繊維1本を直線状に配置し、他方の樹脂フィルムを単繊維を挟むように重ねて配置した。これを200℃で3分間、4MPaの圧力で加圧プレスし、単繊維が樹脂に埋め込まれたサンプルを作製した。このサンプルをさらに切出して、単繊維が中央に埋没した厚さ0.2mm、幅5mm、長さ30mmの試験片を得た。さらに同じ方法で合計5個の試験片を作製した。
τ=(σf・d)/2Lc、 Lc=(4/3)・L
後述する実施例に記載のローラー含浸法にて得られた炭素繊維束をSUS304の試験片上に置き、120℃で乾燥させた。乾燥後、180°ピール法により下記の基準で粘着性を評価した。
○:繊維束がSUS304から簡単に剥がれる。
×:繊維束がSUS304と接着しており、剥がれ難い。
後述する実施例に記載のローラー含侵法にて得られた炭素繊維束を100℃以上に加熱した金属棒上を滑らせ、開繊状態を下記基準にて開繊性を評価した。
○:均一に繊維が広がる。
×:集束した繊維部分が残る。
炭素繊維束(三菱レイヨン社製、製品名:パイロフィル(登録商標)TR50S12L、フィラメント数12000本、ストランド強度5000MPa、ストランド弾性率242GPa)をアセトン中に浸漬し、10分間超音波を作用させた後、炭素繊維束を引き上げさらに3回アセトンで洗浄し、室温で8時間乾燥することにより付着しているサイジング剤を除去して用いた。
ブテン系樹脂(A)として、公知のマグネシウム化合物担持型チタン触媒を用いてショアD硬度が65、ASTM1238規格に従い、190℃、2.16kg荷重の条件で測定したメルトフローレイト(MFR)が0.5g/10分であるブテン単独重合体を100質量部、プロピレン系樹脂(B1)の原料として、無水マレイン酸変性プロピレン系重合体(重量平均分子量Mw=20,000、酸価:45mg−KOH/g)10質量部、界面活性剤として、オレイン酸カリウム3質量部を混合した。この混合物を2軸スクリュー押出機(池貝鉄工株式会社製、PCM−30,L/D=40)のホッパーより3000g/時間の速度で供給し、同押出機のベント部に設けた供給口より、20%の水酸化カリウム水溶液を90g/時間の割合で連続的に供給し、加熱温度210℃で連続的に押出した。押出した樹脂混合物を、同押出機口に設置したジャケット付きスタティックミキサーで110℃まで冷却し、さらに80℃の温水中に投入してエマルションを得た。得られたエマルションは固形分濃度:45%であった。
製造例1で製造したエマルションを、ローラー含浸法を用いて、前記三菱レーヨン性強化繊維に付着させた。次いで、オンラインで130℃、2分乾燥して低沸点成分を除去し、本発明の強化繊維束を得た。エマルションの付着量は0.90%であった。
市販のエポキシ系化合物を含む強化炭素繊維束を用いた以外は実施例1と同様にして本発明の強化繊維束を得た。炭素繊維束は毛羽立ちがやや目立つ状態であった。IFSSは11MPaであった。粘着性は×(剥がれ難い)であった。開繊性は○(均一に繊維が広がる)であった。
Claims (4)
- ブテン系樹脂(A)と、
重合体鎖に結合したカルボン酸塩を少なくとも含むオレフィン系樹脂(B)と、
強化繊維(C)と
を含み、以下の要件を満たす強化繊維束。
ブテン系樹脂(A)は、ブテン由来の構造単位が50モル%を超え、100モル%以下であり、ASTM1238規格に準じ、190℃、2.16kg荷重の条件で決定されるメルトフローレート(MFR)が0.01〜20g/10分の範囲にあり、
ブテン系樹脂(A)のMFRがオレフィン系樹脂(B)のMFRよりも小さく、
ブテン系樹脂(A)100質量部に対して、オレフィン系樹脂(B)は3〜50質量部であり、
ブテン系樹脂(A)とオレフィン系樹脂(B)の合計の含有率が0.3〜5質量%である。 - 強化繊維(C)のフィラメント数が40,000本以上であることを特徴とする請求項1に記載の強化繊維束。
- ブテン系樹脂(A)のショアA硬度が50〜90であるかまたはショアD硬度が45〜65であることを特徴とする請求項1に記載の強化繊維束。
- 請求項1に記載の強化繊維束1〜70質量部と、
プロピレン系樹脂、ブテン系樹脂、ポリアミド樹脂、ポリエステル樹脂およびポリエーテル樹脂からなる群より選ばれる樹脂(D)30〜99質量部と
を含む(但し、前記強化繊維束と樹脂(D)との合計が100質量部である)ことを特徴とする成形材料。
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JP2016006245A (ja) * | 2014-05-22 | 2016-01-14 | ユニチカ株式会社 | 繊維収束剤、繊維状強化材および繊維強化樹脂組成物 |
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JPS60199978A (ja) * | 1984-03-21 | 1985-10-09 | 竹本油脂株式会社 | 合成繊維処理用油剤 |
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