JP5577399B2 - 燐−変性フェノールノボラック樹脂、これを含む硬化剤及びエポキシ樹脂組成物 - Google Patents
燐−変性フェノールノボラック樹脂、これを含む硬化剤及びエポキシ樹脂組成物 Download PDFInfo
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- 229920003986 novolac Polymers 0.000 title claims description 70
- 239000003822 epoxy resin Substances 0.000 title claims description 57
- 229920000647 polyepoxide Polymers 0.000 title claims description 57
- 150000002989 phenols Chemical class 0.000 title claims description 56
- 239000003795 chemical substances by application Substances 0.000 title claims description 50
- 239000000203 mixture Substances 0.000 title claims description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 36
- 239000011574 phosphorus Substances 0.000 claims description 35
- 229910052698 phosphorus Inorganic materials 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- 239000004593 Epoxy Substances 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 15
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 description 35
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- 239000011889 copper foil Substances 0.000 description 16
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- 229940008406 diethyl sulfate Drugs 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000012039 electrophile Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012038 nucleophile Substances 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
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- 239000003643 water by type Substances 0.000 description 2
- -1 106 Substances 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
-
- 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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
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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
- C08G59/40—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
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- 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
- C08G59/68—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 catalysts used
- C08G59/688—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 catalysts used containing phosphorus
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
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- Phenolic Resins Or Amino Resins (AREA)
Description
(式中、nは1〜12の整数である。)
本発明の一具現例による燐-変性フェノールノボラック樹脂は、軟化点が50乃至200℃であることができる。
(式中、nは1〜12の整数である。)
本発明の一具現例によるエポキシ樹脂組成物において、燐-変性フェノールノボラック樹脂は、軟化点が50乃至200℃であることができる。
このような燐-変性フェノールノボラック樹脂(DOPO-PNと略称する)を製造する方法の一例は特に限定されるものではないが、4-ヒドロキシベンズアルデヒド(4-hydroxybenzaldehyde)とDOPOとの反応を通じて、DOPO-HBを生成して(反応式1)、これをアルデヒドと反応させて得られることができる(反応式2)。
[反応式2]
求核剤である-P(O)−H基とアルデヒドまたはケトン内の求電子剤であるC=O基との求核付加反応はよく知られた反応である。この反応を利用してDOPOと4-ヒドロキシベンズアルデヒドを反応させてOH基とリン成分を一緒に持ったDOPO-HBを合成する(反応式1参照)。
Oven-35℃ Isotherm
Carrier-THF
Injection-100μl、35℃
Detection-RI Detector
Flow-1ml/min
1HNMR、spectrumはTMSまたはDMSO-d6を内部標準物質としてVarian Germini300(300、75MHz)を利用して得た。DSC Thermogramは、TA Instruments DSC2910を利用して30〜300℃で1分当り20℃の過熱率で求め、Thermogravimetric分析は、TA TGA Q-500 Seriesを使用して1分当り10℃の過熱率で測定した。
(1)DOPO-HBの合成
求核剤である-P(O)−H基とアルデヒドまたはケトン内の求電子剤であるC=O基との求核付加反応はよく知られた反応である。この反応を利用してDOPOと4-ヒドロキシベンズアルデヒド(4-Hydroxybenzaldehyde)を反応させて、OH基とリン成分を共に持ったDOPO-HBを合成した(反応式1参照)。
Melting point:241℃
1H NMR(300MHz、DMSO−d6)δ5.01(1H、dd、J=5.7、6.0Hz)、5.18(1H、t、J=11.3Hz)、6.14-6.30(1H、m)、6.66-8.20(12H、m)、9.45(1H、d、J=14.5Hz)
(2)DOPO-PN合成
DOPO-HBとホルムアルデヒドを利用してDOPO-PNを合成した。
軟化点:81℃
重量平均分子量:923
1HNMR(300MHz、DMSO-d6)δ3.50(2H、dd、J=3.0、4.4Hz)、4.32(1H、t、J=40.9Hz)、6.56-8.28(10H、m)、9.79(1H、s)
前記実施例1と同一な方法で燐-変性フェノールノボラック樹脂(DOPO-PN)を製造するが、但し、(2)段階でDOPO-HBを101.56g、0.3molで使用し、ホルムアルデヒドを8.10g(0.24mol)で使用した。
前記実施例1と同一な方法で燐-変性フェノールノボラック樹脂(DOPO-PN)を製造するが、但し、DOPO-HBを101.56g、0.3molで使用し、ホルムアルデヒドを8.60g(0.255mol)で使用した。
前記実施例1から得られる燐-変性フェノールノボラック樹脂(DOPO-PN)に対して多様な溶剤に対する溶解性を評価して、その結果を次の表1に示した。
前記実施例1から得られた燐-変性フェノールノボラック樹脂(DOPO-PN)を硬化剤として使用してエポキシ樹脂組成物を合成した。
硬化物のガラス転移温度(Tg)を、DSC分析を通じて得、その結果は次の表3のようである。
同一な配合物に対してTGAを使用して熱分解温度を測定して、その結果を次の表4に示した。
硬化物の燐含量による難燃等級の傾向性を評価して、その結果を次の表5に示した。
前記実施例4と同一な方法でエポキシ樹脂組成物及び硬化物を製造するが、但し、実施例2で得られた燐-変性フェノールノボラック樹脂(DOPO-PN)を使用して、実施例4のF4のような形態で硬化物を製造した。
前記実施例4と同一な方法でエポキシ樹脂組成物及び硬化物を製造するが、但し、実施例3の燐-変性フェノールノボラック樹脂を使用して、実施例4のF4のような形態で硬化物を製造した。
前記実施例5と同一な組成でエポキシ硬化剤組成物を造成して同一な方法で硬化物を製造するが、但し、主剤としてフェノールノボラックエポキシ樹脂の代りに燐-変性エポキシ樹脂(燐含量2.9%、エポキシ当量290、((株)コーロン製品)を利用した。
Claims (15)
- 次の化学式1で表示される繰り返し単位からなり、重量平均分子量が400乃至4000であり、軟化点が50乃至200℃である燐−変性フェノールノボラック樹脂であって、
前記燐−変性フェノールノボラック樹脂は、9,10−ジヒドロ−9−オキサ−10−ホスファフェナトレン−10−オキシド(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)と4−ヒドロキシベンズアルデヒドとの反応で得られた化合物1当量に対して、アルデヒドを0.4〜0.95の当量比で反応させて得られることを特徴とする燐−変性フェノールノボラック樹脂。
・・・(化学式1)
(式中、2<n≦12、nは整数である。) - 燐含量が1重量%以上のものであることを特徴とする請求項1に記載の燐-変性フェノールノボラック樹脂。
- 2-メトキシエタノール、1-メトキシ-2-プロパノール及びジメチルホルムアミドに可溶であることを特徴とする請求項1に記載の燐-変性フェノールノボラック樹脂。
- 請求項1乃至3のうち何れか一つに記載の燐-変性フェノールノボラック樹脂を含むことを特徴とするエポキシ硬化剤。
- エポキシ樹脂と、
次の化学式1で表示される繰り返し単位からなり、重量平均分子量400乃至3,000であり、軟化点が50乃至200℃である燐-変性フェノールノボラック樹脂を含む硬化剤と、
を含んでなり、
前記燐−変性フェノールノボラック樹脂は、9,10−ジヒドロ−9−オキサ−10−ホスファフェナトレン−10−オキシド(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)と4−ヒドロキシベンズアルデヒド(4-hydroxybenzaldehyde)との反応で得られた化合物1当量に対して、アルデヒドを0.4〜0.95の当量比で反応させて得られることを特徴とするエポキシ樹脂組成物。
(式中、2<n≦12、nは整数である。) - 燐-変性フェノールノボラック樹脂は、燐含量が1重量%以上のものであることを特徴とする請求項5に記載のエポキシ樹脂組成物。
- 燐-変性フェノールノボラック樹脂は、2-メトキシエタノール、1-メトキシ-2-プロパノール及びジメチルホルムアミドに可溶であることを特徴とする請求項5に記載のエポキシ樹脂組成物。
- 硬化剤は、燐-変性フェノールノボラック樹脂と燐-変性されないフェノールノボラック樹脂の混合物であり、燐-変性フェノールノボラック樹脂を全体硬化剤のうちで20重量%以上含むものであることを特徴とする請求項5に記載のエポキシ樹脂組成物。
- エポキシ樹脂は、燐-変性エポキシ樹脂であることを特徴とする請求項5に記載のエポキシ樹脂組成物。
- 請求項5乃至8の何れか一つに記載のエポキシ樹脂組成物の硬化物。
- 請求項9に記載のエポキシ樹脂組成物の硬化物。
- 燐含量が1重量%以上であることを特徴とする請求項10に記載の硬化物。
- 燐含量が3重量%以上であることを特徴とする請求項11に記載の硬化物。
- ガラス転移温度が120℃以上であることを特徴とする請求項10に記載の硬化物。
- ガラス転移温度が120℃以上であることを特徴とする請求項11に記載の硬化物。
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