JP2021169552A - 繊維強化複合材料用エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料 - Google Patents
繊維強化複合材料用エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料 Download PDFInfo
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- JP2021169552A JP2021169552A JP2020072680A JP2020072680A JP2021169552A JP 2021169552 A JP2021169552 A JP 2021169552A JP 2020072680 A JP2020072680 A JP 2020072680A JP 2020072680 A JP2020072680 A JP 2020072680A JP 2021169552 A JP2021169552 A JP 2021169552A
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- epoxy resin
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 72
- -1 prepreg Substances 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- 239000004202 carbamide Substances 0.000 claims abstract description 19
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- 238000000113 differential scanning calorimetry Methods 0.000 claims description 7
- 230000001588 bifunctional effect Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 claims description 4
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- 238000010438 heat treatment Methods 0.000 claims description 4
- JJVKJJNCIILLRP-UHFFFAOYSA-N 2-ethyl-6-methylaniline Chemical compound CCC1=CC=CC(C)=C1N JJVKJJNCIILLRP-UHFFFAOYSA-N 0.000 claims description 3
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 3
- NWIVYGKSHSJHEF-UHFFFAOYSA-N 4-[(4-amino-3,5-diethylphenyl)methyl]-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=C(CC)C=2)=C1 NWIVYGKSHSJHEF-UHFFFAOYSA-N 0.000 claims description 3
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 3
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- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 2
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 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 abstract description 9
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
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- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
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- 230000000930 thermomechanical effect Effects 0.000 description 2
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- VXGWAWGQKJMAMN-UHFFFAOYSA-N (carbamoylamino) acetate Chemical compound CC(=O)ONC(N)=O VXGWAWGQKJMAMN-UHFFFAOYSA-N 0.000 description 1
- COSWCAGTKRUTQV-UHFFFAOYSA-N 1,1,3-trimethylurea Chemical compound CNC(=O)N(C)C COSWCAGTKRUTQV-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
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- QCQBUZVEQZFGQV-UHFFFAOYSA-N 2-octadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCCC1=NC=CN1 QCQBUZVEQZFGQV-UHFFFAOYSA-N 0.000 description 1
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- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 1
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- 229940018563 3-aminophenol Drugs 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
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- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- DZHMRSPXDUUJER-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;dihydrogen phosphate Chemical compound NC(N)=O.OP(O)(O)=O DZHMRSPXDUUJER-UHFFFAOYSA-N 0.000 description 1
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- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
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- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
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- 238000009787 hand lay-up Methods 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- UJQLDFMZDSDZEY-UHFFFAOYSA-N n-(acetylcarbamoyl)acetamide Chemical compound CC(=O)NC(=O)NC(C)=O UJQLDFMZDSDZEY-UHFFFAOYSA-N 0.000 description 1
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- 239000004745 nonwoven fabric Substances 0.000 description 1
- YBSLUBPQYDULIZ-UHFFFAOYSA-N oxalic acid;urea Chemical compound NC(N)=O.OC(=O)C(O)=O YBSLUBPQYDULIZ-UHFFFAOYSA-N 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 238000009864 tensile test Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
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- KCNSDMPZCKLTQP-UHFFFAOYSA-N tetraphenylen-1-ol Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=CC=CC=C2C2=C1C=CC=C2O KCNSDMPZCKLTQP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
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Abstract
Description
すなわち本発明は以下の通りである。
(b)芳香族ジアミン化合物、
(c)ジシアンジアミド、
(d)ウレア化合物、および
(e)アミンアダクト化合物
を、下記配合割合で配合してなることを特徴とする繊維強化複合材料用エポキシ樹脂組成物。
前記(b)芳香族ジアミン化合物の配合割合は、前記(a)エポキシ樹脂に対して0.2〜0.6当量;
前記(c)ジシアンジアミドの配合割合は、前記(a)〜(e)成分の全体に対し、0.5〜4.0質量%;
前記(d)ウレア化合物の配合割合は、前記(a)〜(e)成分の全体に対し、0.5〜2.0質量%;および
前記(e)アミンアダクト化合物の配合割合は、前記(a)〜(e)成分の全体に対し、0〜3.0質量%。
2.120℃、1.5時間の硬化条件でモールドから脱型可能な状態まで硬化し、得られた硬化物のガラス転移温度が110℃以上である、前記1に記載の繊維強化複合材料用エポキシ樹脂組成物。
3.前記硬化物は、180℃、2時間の後硬化によってガラス転移温度が180℃以上となる、前記2に記載の繊維強化複合材料用エポキシ樹脂組成物。
4.前記(a)エポキシ樹脂が、2官能のエポキシ樹脂0〜80質量%および3官能以上のエポキシ樹脂20〜100質量%からなる、前記1〜3のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
5.昇温速度10℃/分の示差走査型熱量分析(DSC分析)による反応開始温度(発熱ピーク開始温度)が、90℃以上120℃以下である、前記1〜4のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
6.前記(b)芳香族ジアミン化合物が、3,3’−ジアミノジフェニルサルフォン、4,4’−ジアミノジフェニルサルフォン、4,4’−メチレンビス(2,6−ジエチルアニリン)および4,4’−メチレンビス(2−エチル−6−メチル)ベンゼンアミンからなる群から選択される1種以上である、前記1〜5のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
7.前記(d)ウレア化合物が、3−(3,4’−ジクロロフェニル)−1,1−ジメチルウレア、2,4−トルエンビスジメチルウレアおよび4,4’−メチレンビス(フェニルジメチルウレア)からなる群から選択される1種以上である、前記1〜6のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
8.前記1〜7のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物を、ガラス繊維、クオーツ繊維、アラミド繊維またはカーボン繊維の何れかに含浸させた、プリプレグ。
9.前記8に記載のプリプレグの硬化物である、繊維強化複合材料。
とくに、本発明の樹脂組成物は、現在120℃硬化、180℃硬化に分かれたプロセスを低温側の120℃硬化に統一することができる。例えば、本発明におけるプリプレグをオートクレーブにより低温低圧条件(例えば120℃、90分、0.31MPa)で硬化させた場合、従来技術の120℃硬化物と同等の耐熱性および機械的特性を有するFRPを得ることができる。またこの硬化物を後硬化(例えば180℃、2時間、大気圧)することにより、従来技術の180℃硬化物と同等の耐熱性および機械的特性を有するFRPを得ることができる。前記後硬化は、オートクレーブを用いて加圧する必要がなく、例えば空気順環式オーブン等を用いて熱のみを加えればよい。したがって、180℃硬化物を製造する場合、オートクレーブにより180℃硬化する際に必要とされる副資材も不要となり、オートクレーブを用いた場合の製造コストを低減できる。また後硬化の際には、製品を積層治具から脱型しフリースタンディング状態で加熱することが可能であることから、モールド占有時間短縮による生産性向上を図ることができる。なお、本発明におけるプリプレグは、オートクレーブを用いて180℃硬化物を製造することもでき、この場合も、従来技術の180℃硬化物と同等な成形品質、耐熱性、機械的特性を有する硬化物を得ることができる。
さらに上述のように、本発明によれば120℃硬化物を製造する場合も、180℃硬化物を製造する場合も、まず120℃硬化物を製造すればよいことから、従来技術のようにそれぞれの硬化物に応じた材料を準備する必要がなく、またそれぞれの硬化物を保管管理する必要もなく、製造コストを低減することができる。
以上から、本発明によれば、低温低圧で成形可能であり、実用上十分な耐熱性および機械的特性を有し、かつ製造コストを大幅に低減可能な繊維強化複合材料用エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料を提供することができる。
本発明の樹脂組成物は、(a)1種類または2種類以上のエポキシ樹脂、(b)芳香族ジアミン化合物、(c)ジシアンジアミド、(d)ウレア化合物、および(e)アミンアダクト化合物を、下記配合割合で配合してなることを特徴とする。
前記(b)芳香族ジアミン化合物の配合割合は、前記(a)エポキシ樹脂に対して0.2〜0.6当量;
前記(c)ジシアンジアミドの配合割合は、前記(a)〜(e)成分の全体に対し、0.5〜4.0質量%;
前記(d)ウレア化合物の配合割合は、前記(a)〜(e)成分の全体に対し、0.5〜2.0質量%;および
前記(e)アミンアダクト化合物の配合割合は、前記(a)〜(e)成分の全体に対し、0〜3.0質量%。
(a)エポキシ樹脂としては、好適な形態において、そのすべてが3官能以上のエポキシ樹脂からなることができる。これとは別に、(a)エポキシ樹脂は、2官能のエポキシ樹脂を併用することもでき、この場合、(a)エポキシ樹脂は、2官能のエポキシ樹脂0〜80質量%および3官能以上のエポキシ樹脂20〜100質量%からなることが好ましい。
3官能以上のエポキシ樹脂は、それぞれ単独でまたは2種以上を組み合わせて使用することができる。
2官能のエポキシ樹脂は、それぞれ単独でまたは2種以上を組み合わせて使用することができる。
(b)芳香族ジアミン化合物は、(a)エポキシ樹脂を硬化させる作用を有する。本発明で使用される(b)芳香族ジアミン化合物は、上記作用を有するものであればとくに制限されないが、本発明の効果向上の観点から、3,3’−ジアミノジフェニルサルフォン、4,4’−ジアミノジフェニルサルフォン、4,4’−メチレンビス(2,6−ジエチルアニリン)および4,4’−メチレンビス(2−エチル−6−メチル)ベンゼンアミンからなる群から選択される1種以上が好ましい。
(c)ジシアンジアミドは、(a)エポキシ樹脂を硬化させる作用を有し、下記構造を有する。
(d)ウレア化合物は、(a)エポキシ樹脂の硬化反応を促進させる作用を有する。本発明で使用される(d)ウレア化合物は、上記作用を有するものであればとくに制限されないが、本発明の効果向上の観点から、3−(3,4’−ジクロロフェニル)−1,1−ジメチルウレア、2,4−トルエンビスジメチルウレアおよび4,4’−メチレンビス(フェニルジメチルウレア)からなる群から選択される1種以上が好ましい。
(e)アミンアダクト化合物は、(a)エポキシ樹脂の硬化反応を促進させる作用を有する。(e)アミンアダクト化合物はアミンのアダクト体であり、例えば、アミンと、エポキシ樹脂、イソシアネート化合物および尿素化合物からなる群から選ばれる少なくとも1つの化合物とのアダクト体が挙げられる。
本発明の樹脂組成物には、本発明の目的を逸脱することのない範囲内で用途に応じた添加剤を追加することが出来る。例えば難燃剤類や、硬化樹脂の靭性を向上させるための熱可塑樹脂類やゴム類、硬化の際の樹脂流動性制御や樹脂剛性向上のための無機粒子類等を添加可能な成分として挙げることが出来る。
なお本発明で言うガラス転移温度は、熱機械分析(TMA)により測定され、具体的な条件は以下の通りである。
使用機器:ブルカー・エイエックスエス社製TMA4000S型熱機械分析装置
昇温速度:10℃/分
測定モード:膨張モード
印加荷重:2g
測定雰囲気:空気
また前記DSC分析の具体的な条件は以下の通りである。
使用機器:TAインスツルメント社製DSC2500型示差走査型熱量分析装置
昇温速度:10℃/分
測定雰囲気:窒素ガス
この後硬化後の硬化物は、ガラス転移温度が180℃以上となり、高い耐熱性を有する。
具体的には、本発明のプリプレグは本発明の樹脂組成物を繊維基材に含浸させることにより得られる。
本発明のプリプレグに使用される繊維基材は、とくに制限されないが、例えば、ガラス繊維、クオーツ繊維、アラミド繊維またはカーボン繊維の何れかが好ましい。繊維基材の形態は、例えば、織物、ロービング、不織布、編物、チュールなどが挙げられる。
本発明におけるプリプレグの製造方法について特に制限されない。例えば、溶剤を使用するディッピング法、無溶剤法であるホットメルト法が挙げられる。
実施例および比較例では、以下の材料を使用した。
(a)エポキシ樹脂
・3官能以上のエポキシ樹脂(日鉄ケミカル&マテリアル(株)製YH−404、エポキシ当量=115)
・3官能以上のエポキシ樹脂(Huntsman Advanced Material社製MY−0510、エポキシ当量=101)
・3官能以上のエポキシ樹脂((株)プリンテック製VG3101L、エポキシ当量=210)
・2官能のエポキシ樹脂(日鉄ケミカル&マテリアル(株)製YD−128、エポキシ当量=191)
・2官能のエポキシ樹脂(DIC(株)製HP−4032SS、エポキシ当量=143)
・2官能のエポキシ樹脂((株)プリンテック製Epox MKSR35K、エポキシ当量=962)
・4,4’−ジアミノジフェニルサルフォン(和歌山精化工業(株)製)
・ジシアンジアミド(三菱ケミカル(株)製Dicy15)
・4,4’−メチレンビス(フェニルジメチルウレア)(CVC Thermoset Specialities社製Omicure U−24M)
・アミン−エポキシアダクト化合物(味の素ファインテクノ(株)製PN−40J)
続いて、前記120℃硬化物に対し、180℃、3時間の後硬化を行い、180℃硬化物を製造した。なおこの後硬化は、樹脂硬化物を金型を使用しないフリースタンディング状態で空気順環式オーブンを用いて大気圧下の加熱により行ったものである。得られた硬化物の外観、ガラス転移温度を調べた。
それぞれ結果を表1に示す。
・引張弾性率(ASTM D638に準拠して測定)
・引張伸度(ASTM D638に準拠して測定)
・曲げ強さ(ASTM D790に準拠して測定)
・曲げ弾性率(ASTM D790に準拠して測定)
・曲げ伸度(ASTM D790に準拠して測定)
・引張靱性(引張試験における荷重−歪曲線より算出)
・曲げ靱性(曲げ試験における荷重−歪曲線より算出)
これに対し、比較例1、2は、本発明における(c)ジシアンジアミドおよび(d)ウレア化合物を配合していないので、180℃での硬化は確認できたものの、120℃では硬化できなかった。
比較例3は、(c)成分の配合割合が本発明で規定する上限を超えているので、180℃硬化物の耐熱性が悪化した。
なお、比較例4〜8は、硬化度の確認のみを行い、その結果を表1に示した。
Claims (9)
- (a)1種類または2種類以上のエポキシ樹脂、
(b)芳香族ジアミン化合物、
(c)ジシアンジアミド、
(d)ウレア化合物、および
(e)アミンアダクト化合物
を、下記配合割合で配合してなることを特徴とする繊維強化複合材料用エポキシ樹脂組成物。
前記(b)芳香族ジアミン化合物の配合割合は、前記(a)エポキシ樹脂に対して0.2〜0.6当量;
前記(c)ジシアンジアミドの配合割合は、前記(a)〜(e)成分の全体に対し、0.5〜4.0質量%;
前記(d)ウレア化合物の配合割合は、前記(a)〜(e)成分の全体に対し、0.5〜2.0質量%;および
前記(e)アミンアダクト化合物の配合割合は、前記(a)〜(e)成分の全体に対し、0〜3.0質量%。 - 120℃、1.5時間の硬化条件でモールドから脱型可能な状態まで硬化し、得られた硬化物のガラス転移温度が110℃以上である、請求項1に記載の繊維強化複合材料用エポキシ樹脂組成物。
- 前記硬化物は、180℃、2時間の後硬化によってガラス転移温度が180℃以上となる、請求項2に記載の繊維強化複合材料用エポキシ樹脂組成物。
- 前記(a)エポキシ樹脂が、2官能のエポキシ樹脂0〜80質量%および3官能以上のエポキシ樹脂20〜100質量%からなる、請求項1〜3のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
- 昇温速度10℃/分の示差走査型熱量分析(DSC分析)による反応開始温度(発熱ピーク開始温度)が、90℃以上120℃以下である、請求項1〜4のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
- 前記(b)芳香族ジアミン化合物が、3,3’−ジアミノジフェニルサルフォン、4,4’−ジアミノジフェニルサルフォン、4,4’−メチレンビス(2,6−ジエチルアニリン)および4,4’−メチレンビス(2−エチル−6−メチル)ベンゼンアミンからなる群から選択される1種以上である、請求項1〜5のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
- 前記(d)ウレア化合物が、3−(3,4’−ジクロロフェニル)−1,1−ジメチルウレア、2,4−トルエンビスジメチルウレアおよび4,4’−メチレンビス(フェニルジメチルウレア)からなる群から選択される1種以上である、請求項1〜6のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
- 請求項1〜7のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物を、ガラス繊維、クオーツ繊維、アラミド繊維またはカーボン繊維の何れかに含浸させた、プリプレグ。
- 請求項8に記載のプリプレグの硬化物である、繊維強化複合材料。
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