JP6620981B2 - Thermosetting molding material, method for producing the same, and semiconductor sealing material - Google Patents
Thermosetting molding material, method for producing the same, and semiconductor sealing material Download PDFInfo
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- JP6620981B2 JP6620981B2 JP2015252274A JP2015252274A JP6620981B2 JP 6620981 B2 JP6620981 B2 JP 6620981B2 JP 2015252274 A JP2015252274 A JP 2015252274A JP 2015252274 A JP2015252274 A JP 2015252274A JP 6620981 B2 JP6620981 B2 JP 6620981B2
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- 229920001187 thermosetting polymer Polymers 0.000 title claims description 57
- 239000012778 molding material Substances 0.000 title claims description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000004065 semiconductor Substances 0.000 title claims description 18
- 239000003566 sealing material Substances 0.000 title claims description 17
- 229920005989 resin Polymers 0.000 claims description 136
- 239000011347 resin Substances 0.000 claims description 136
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 79
- 239000003822 epoxy resin Substances 0.000 claims description 75
- 229920000647 polyepoxide Polymers 0.000 claims description 75
- 125000003172 aldehyde group Chemical group 0.000 claims description 56
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 38
- 239000000178 monomer Substances 0.000 claims description 30
- 239000003431 cross linking reagent Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- NTCCNERMXRIPTR-UHFFFAOYSA-N 2-hydroxy-1-naphthaldehyde Chemical compound C1=CC=CC2=C(C=O)C(O)=CC=C21 NTCCNERMXRIPTR-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 57
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 33
- 239000000047 product Substances 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 238000010521 absorption reaction Methods 0.000 description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000004305 biphenyl Substances 0.000 description 17
- 235000010290 biphenyl Nutrition 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 17
- 238000005979 thermal decomposition reaction Methods 0.000 description 17
- 230000009477 glass transition Effects 0.000 description 15
- 239000000155 melt Substances 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- -1 phenol compound Chemical class 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000005227 gel permeation chromatography Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000002378 acidificating effect Effects 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- SMQUZDBALVYZAC-UHFFFAOYSA-N ortho-hydroxybenzaldehyde Natural products OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 125000004849 alkoxymethyl group Chemical group 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000004203 carnauba wax Substances 0.000 description 4
- 235000013869 carnauba wax Nutrition 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 125000006839 xylylene group Chemical group 0.000 description 4
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000008393 encapsulating agent Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011151 fibre-reinforced plastic Substances 0.000 description 3
- 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 3
- 230000020169 heat generation Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000002648 laminated material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 3
- 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 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 0 **(C=Cc1ccc2)C=Cc1c2O Chemical compound **(C=Cc1ccc2)C=Cc1c2O 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- OITQDWKMIPXGFL-UHFFFAOYSA-N 1-hydroxy-2-naphthaldehyde Chemical compound C1=CC=C2C(O)=C(C=O)C=CC2=C1 OITQDWKMIPXGFL-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- PRYNJOJHKYNLIS-UHFFFAOYSA-N 6-hydroxynaphthalene-2-carbaldehyde Chemical compound C1=C(C=O)C=CC2=CC(O)=CC=C21 PRYNJOJHKYNLIS-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- IYJMFNNRVITCDG-UHFFFAOYSA-N biphenylene;phenol Chemical group OC1=CC=CC=C1.C1=CC=C2C3=CC=CC=C3C2=C1 IYJMFNNRVITCDG-UHFFFAOYSA-N 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- AXORVIZLPOGIRG-UHFFFAOYSA-N β-methylphenethylamine Chemical compound NCC(C)C1=CC=CC=C1 AXORVIZLPOGIRG-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、熱硬化性成形材料、その製造方法および半導体封止材に関する。 The present invention relates to a thermosetting molding material, a manufacturing method thereof, and a semiconductor sealing material.
熱硬化性成形材料は、その熱硬化性を利用して、種々の用途に使用されている。たとえば電子製品の分野においては、熱硬化性の封止材料を用いて、半導体素子を種々の外部環境（温度、湿度、応力など）から保護するパッケージを成形することが行われている。封止材料としては、エポキシ樹脂とその硬化剤を含む組成物が広く使用されている。エポキシ樹脂の硬化剤としては、フェノール系硬化剤が広く使用されている。
近年、電子製品の高性能化が図られる中、電子製品に用いられる樹脂材料の特性に一層の向上が求められている。例えば封止材料には、硬化物の低吸水性（低吸湿性）、耐熱性等のさらなる向上が求められている。
Thermosetting molding materials are used for various applications by utilizing their thermosetting properties. For example, in the field of electronic products, a package for protecting a semiconductor element from various external environments (temperature, humidity, stress, etc.) is formed using a thermosetting sealing material. As the sealing material, a composition containing an epoxy resin and its curing agent is widely used. A phenolic curing agent is widely used as a curing agent for the epoxy resin.
In recent years, as the performance of electronic products has been improved, further improvements are required in the characteristics of resin materials used in electronic products. For example, the sealing material is required to further improve the low water absorption (low hygroscopicity) and heat resistance of the cured product.
特許文献１には、ビス（メトキシメチル）ビフェニルとフェノール化合物とを反応させて得られるフェノールノボラック縮合体と、エポキシ樹脂とを含むエポキシ樹脂組成物が提案されている。かかるエポキシ樹脂組成物の硬化物は、エポキシ樹脂用硬化剤として一般的なフェノールノボラック樹脂を用いる場合に比べて、吸水性、耐熱性、機械特性、接着特性等が優れるとされている。しかし、上記硬化物のガラス転移温度の高さ、線膨張係数の低さは充分ではない。 Patent Document 1 proposes an epoxy resin composition containing a phenol novolac condensate obtained by reacting bis (methoxymethyl) biphenyl with a phenol compound, and an epoxy resin. The cured product of such an epoxy resin composition is said to be superior in water absorption, heat resistance, mechanical properties, adhesive properties and the like as compared with the case where a general phenol novolac resin is used as a curing agent for epoxy resins. However, the cured product has a high glass transition temperature and a low coefficient of linear expansion.
特許文献２には、ビス（メトキシメチル）ビフェニル等のビフェニル化合物と、２価フェノール類および１価フェノール類とを反応させて得られるフェノールノボラック樹脂をエポキシ化したエポキシ樹脂と、硬化剤とを含むエポキシ樹脂組成物が提案されている。かかるエポキシ樹脂組成物の硬化物は、高いガラス転移温度と高い難燃性とを兼ね備えているとされている。しかし、上記硬化物の吸水性（吸湿性）の低さ、熱分解温度の高さは充分ではない。 Patent Document 2 includes an epoxy resin obtained by epoxidizing a phenol novolac resin obtained by reacting a biphenyl compound such as bis (methoxymethyl) biphenyl, a dihydric phenol and a monohydric phenol, and a curing agent. Epoxy resin compositions have been proposed. A cured product of such an epoxy resin composition is said to have both a high glass transition temperature and high flame retardancy. However, the cured product has low water absorption (hygroscopicity) and high thermal decomposition temperature.
本発明は、上記事情に鑑みてなされたものであって、高ガラス転移温度、高熱分解温度、低線膨張係数、低吸水性の硬化物が得られる熱硬化性成形材料およびその製造方法、ならびに前熱硬化性成形材料を用いた半導体封止材を提供することを目的とする。 The present invention has been made in view of the above circumstances, and has a high glass transition temperature, a high thermal decomposition temperature, a low linear expansion coefficient, a thermosetting molding material from which a cured product having a low water absorption can be obtained, and a method for producing the same, and It aims at providing the semiconductor sealing material using the pre-thermosetting molding material.
本発明は、以下の態様を有する。
＜１＞アリル基含有樹脂と、エポキシ樹脂とを含み、
前記アリル基含有樹脂が、下記式（１）で表される構成単位（１）および下記式（２）で表される構成単位（２）のいずれか一方または両方と、下記式（３）で表される構成単位（３）と、下記式（４）で表される構成単位（４）と、を有し、
前記構成単位（２）と前記構成単位（４）との合計の含有量が、前記構成単位（１）と前記構成単位（２）と前記構成単位（３）と前記構成単位（４）との合計に対して１０〜８０モル％である熱硬化性成形材料。
The present invention has the following aspects.
<1> including an allyl group-containing resin and an epoxy resin,
The allyl group-containing resin is either one or both of the structural unit (1) represented by the following formula (1) and the structural unit (2) represented by the following formula (2), and the following formula (3): The structural unit (3) represented, and the structural unit (4) represented by the following formula (4),
The total content of the structural unit (2) and the structural unit (4) is the structural unit (1), the structural unit (2), the structural unit (3), and the structural unit (4). The thermosetting molding material which is 10-80 mol% with respect to the sum total.
［式中、Ａｒはベンゼン環またはナフタレン環を示し、Ｒは下記式（ｒ１）または（ｒ２）で表される基を示し、ｐおよびｑはそれぞれ独立に０または１を示し、−＊および−＊＊はそれぞれ結合手を示す。−＊は、他の構成単位に結合し、−（Ｒ）ｐ−＊＊の−＊＊は、ｐが０である場合は他の構成単位または水素原子に結合し、ｐが１である場合は他の構成単位に結合し、−（Ｒ）ｑ−＊＊の−＊＊は、ｑが０である場合は他の構成単位または水素原子に結合し、ｑが１である場合は他の構成単位に結合する。］ [In the formula, Ar represents a benzene ring or a naphthalene ring, R represents a group represented by the following formula (r1) or (r2), p and q each independently represent 0 or 1, and — * and — Each ** represents a bond. -* Is bonded to another structural unit,-** of-(R) p -** is bonded to another structural unit or a hydrogen atom when p is 0, and p is 1 Is bonded to another structural unit, and-** of-(R) q -** is bonded to another structural unit or a hydrogen atom when q is 0, and is bonded to another structural unit when q is 1. Join the building unit. ]
＜２＞前記エポキシ樹脂の含有量が、前記アリル基含有樹脂に対して５〜５０質量％である、＜１＞の熱硬化性成形材料。
＜３＞前記＜１＞の熱硬化性成形材料の製造方法であって、
モノヒドロキシベンズアルデヒドおよびモノヒドロキシナフトアルデヒドからなる群から選ばれる少なくとも１種のモノマー（Ａ）と、下記式（ｂ１）で表される化合物および下記式（ｂ２）で表される化合物からなる群から選ばれる少なくとも１種の架橋剤（Ｂ）とを反応させて、前記構成単位（１）と前記構成単位（３）とを有するアルデヒド基含有樹脂を得る工程と、
前記アルデヒド基含有樹脂と、前記アルデヒド基含有樹脂のアルデヒド基に対して１０〜８０モル％のアリルアミンとを反応させて前記アリル基含有樹脂を得る工程と、
前記アリル基含有樹脂とエポキシ樹脂とを混合する工程と、
を有する熱硬化性成形材料の製造方法。
<2> The thermosetting molding material according to <1>, wherein the content of the epoxy resin is 5 to 50% by mass with respect to the allyl group-containing resin.
<3> A method for producing the thermosetting molding material according to <1>,
Selected from the group consisting of at least one monomer (A) selected from the group consisting of monohydroxybenzaldehyde and monohydroxynaphthaldehyde, a compound represented by the following formula (b1) and a compound represented by the following formula (b2) Reacting with at least one crosslinking agent (B) to obtain an aldehyde group-containing resin having the structural unit (1) and the structural unit (3);
Reacting the aldehyde group-containing resin with 10 to 80 mol% of allylamine with respect to the aldehyde group of the aldehyde group-containing resin to obtain the allyl group-containing resin;
Mixing the allyl group-containing resin and the epoxy resin;
A method for producing a thermosetting molding material.
［式中、Ｘは炭素数１〜４のアルコキシ基またはハロゲン原子である。］ [Wherein, X represents an alkoxy group having 1 to 4 carbon atoms or a halogen atom. ]
＜４＞前記＜１＞または＜２＞の熱硬化性成形材料の硬化物からなる半導体封止材。 <4> A semiconductor encapsulant comprising a cured product of the thermosetting molding material according to <1> or <2>.
本発明によれば、高ガラス転移温度、高熱分解温度、低線膨張係数、低吸水性の硬化物が得られる熱硬化性成形材料およびその製造方法、ならびに前熱硬化性成形材料を用いた半導体封止材を提供できる。 According to the present invention, a thermosetting molding material capable of obtaining a cured product having a high glass transition temperature, a high thermal decomposition temperature, a low linear expansion coefficient, and a low water absorption, a method for producing the same, and a semiconductor using the pre-thermosetting molding material A sealing material can be provided.
＜熱硬化性成形材料＞
本発明の熱硬化性成形材料は、アリル基含有樹脂と、エポキシ樹脂とを含む。
本発明の熱硬化性成形材料においては、アリル基含有樹脂のヒドロキシ基の一部とエポキシ樹脂のエポキシ基の一部とが反応した状態になっていてもよい。
本発明の熱硬化性成形材料は、硬化促進剤をさらに含むことができる。
本発明の熱硬化性成形材料は、前記アリル基含有樹脂、エポキシ樹脂および硬化促進剤以外の他の成分をさらに含むことができる。
<Thermosetting molding material>
The thermosetting molding material of the present invention contains an allyl group-containing resin and an epoxy resin.
In the thermosetting molding material of the present invention, a part of the hydroxy group of the allyl group-containing resin and a part of the epoxy group of the epoxy resin may be in a reacted state.
The thermosetting molding material of the present invention can further contain a curing accelerator.
The thermosetting molding material of this invention can further contain other components other than the said allyl group containing resin, an epoxy resin, and a hardening accelerator.
（アリル基含有樹脂）
本発明におけるアリル基含有樹脂は、下記式（１）で表される構成単位（１）および下記式（２）で表される構成単位（２）のいずれか一方または両方と、下記式（３）で表される構成単位（３）と、下記式（４）で表される構成単位（４）と、を有する。
「構成単位」は、重合体を構成する単位を示す。
(Allyl group-containing resin)
The allyl group-containing resin in the present invention includes one or both of the structural unit (1) represented by the following formula (1) and the structural unit (2) represented by the following formula (2), and the following formula (3). ) And a structural unit (4) represented by the following formula (4).
“Structural unit” indicates a unit constituting the polymer.
アリル基含有樹脂は、構成単位（１）〜（４）に由来して、複数のＡｒを含む。アリル基含有樹脂において複数のＡｒは、１つのＲを介して互いに結合しており、直接結合しない。 The allyl group-containing resin is derived from the structural units (1) to (4) and includes a plurality of Ar. In the allyl group-containing resin, a plurality of Ar are bonded to each other through one R, and are not directly bonded.
したがって、構成単位（１）または（２）のＲから伸びる結合手（−＊）は、構成単位（３）または（４）のＡｒから伸びる結合手に結合する。
構成単位（３）または（４）のＡｒから伸びる結合手は、構成単位（１）もしくは（２）のＲから伸びる結合手、ｐおよびｑの少なくとも一方が１である別の構成単位（３）もしくは（４）のＲから伸びる結合手、または水素原子に結合する。
ｐおよびｑの少なくとも一方が１である構成単位（３）または（４）のＲから伸びる結合手は、別の構成単位（３）もしくは（４）のＡｒから伸びる結合手に結合する。
ここで、構成単位（３）または（４）において、Ａｒから伸びる結合手とは、−＊、ｐが０である（Ｒ）ｐ−＊＊およびｑが０である（Ｒ）ｑ−＊＊のいずれかである。Ｒから伸びる結合手とは、ｐが１である（Ｒ）ｐ−＊＊およびｑが１である（Ｒ）ｑ−＊＊のいずれかである。
Therefore, the bond (-*) extending from R of the structural unit (1) or (2) is bonded to the bond extending from Ar of the structural unit (3) or (4).
The bond extending from Ar in the structural unit (3) or (4) is a bond extending from R in the structural unit (1) or (2), and another structural unit (3) in which at least one of p and q is 1. Alternatively, it is bonded to a bond extending from R in (4) or a hydrogen atom.
The bond extending from R of the structural unit (3) or (4) in which at least one of p and q is 1 is bonded to the bond extending from Ar of another structural unit (3) or (4).
Here, in the structural unit (3) or (4), the bond extending from Ar is-*, p is 0 (R) p -** and q is 0 (R) q -** One of them. The bond extending from R is either (R) p -** where p is 1 and (R) q -** where q is 1.
前記式（１）〜（４）中、Ａｒは、ベンゼン環でもよくナフタレン環でもよく、ベンゼン環が好ましい。
Ｒは、前記式（ｒ１）で表される基でもよく、前記式（ｒ２）で表される基でもよい。
前記式（ｒ１）中、ビフェニレン環における２つのメチレン基の結合位置はそれぞれ特に限定されないが、アリル基含有樹脂を後述する製造方法（Ｉ）により製造する場合、式（ｒ１）で表される基に対応する架橋剤（Ｂ）のモノマー（Ａ）との反応性が良好である点から、４位および４’位であることが好ましい。
前記式（ｒ２）中、ベンゼン環における２つのメチレン基の結合位置はそれぞれ特に限定されないが、アリル基含有樹脂を後述する製造方法（Ｉ）により製造する場合、式（ｒ１）で表される基に対応する架橋剤（Ｂ）のモノマー（Ａ）との反応性が良好である点から、パラ位であることが好ましい。
本発明のアリル基含有樹脂に含まれる複数のＡｒはそれぞれ同じでもよく異なってもよい。本発明のアリル基含有樹脂がＲを複数含む場合、この複数のＲはそれぞれ同じでもよく異なってもよい。
In the formulas (1) to (4), Ar may be a benzene ring or a naphthalene ring, and is preferably a benzene ring.
R may be a group represented by the formula (r1) or a group represented by the formula (r2).
In the formula (r1), the bonding positions of the two methylene groups in the biphenylene ring are not particularly limited, but when the allyl group-containing resin is produced by the production method (I) described later, the group represented by the formula (r1) From the viewpoint of good reactivity with the monomer (A) of the crosslinking agent (B) corresponding to, it is preferable that they are at the 4th and 4 'positions.
In the formula (r2), the bonding positions of the two methylene groups in the benzene ring are not particularly limited, but when the allyl group-containing resin is produced by the production method (I) described later, the group represented by the formula (r1) From the viewpoint of good reactivity of the crosslinking agent (B) with the monomer (A) corresponding to the above, the para position is preferred.
A plurality of Ar contained in the allyl group-containing resin of the present invention may be the same or different. When the allyl group-containing resin of the present invention contains a plurality of R, the plurality of R may be the same or different.
構成単位（１）として具体的には、下記式（１−１）、（１−２）または（１−３）で表される構成単位が挙げられる。これらの中でも式（１−１）で表される構成単位が好ましい。 Specific examples of the structural unit (1) include structural units represented by the following formula (1-1), (1-2), or (1-3). Among these, the structural unit represented by Formula (1-1) is preferable.
式（１−１）で表される構成単位のベンゼン環における−Ｒ−＊、アルデヒド基それぞれの結合位置は特に限定されない。
式（１−２）または（１−３）で表される構成単位のナフタレン環における−Ｒ−＊、アルデヒド基それぞれの結合位置は特に限定されない。例えば式（１−２）中、ヒドロキシ基が結合した位置を１位とした場合、−Ｒ−＊やアルデヒド基が結合するのは２〜８位のいずれでもよい。式（１−３）中、ヒドロキシ基が結合した位置を２位とした場合、−Ｒ−＊やアルデヒド基が結合するのは１、３〜８位のいずれでもよい。
構成単位（１）としては、式（１−１）で表され、アルデヒド基の結合位置が、ヒドロキシ基に対してオルソ位である構成単位が好ましい。かかる構成単位であれば、アリル基含有樹脂を後述する製造方法（Ｉ）により製造する場合に、式（１−１）で表される構成単位に対応するモノマー（Ａ）の架橋剤（Ｂ）との反応性が良く、また、モノマー（Ａ）を容易に回収リサイクルできる。
アリル基含有樹脂に含まれる構成単位（１）は１種でも２種以上でもよい。
The bonding position of each of —R— * and the aldehyde group in the benzene ring of the structural unit represented by the formula (1-1) is not particularly limited.
The bonding position of each of —R— * and the aldehyde group in the naphthalene ring of the structural unit represented by the formula (1-2) or (1-3) is not particularly limited. For example, in the formula (1-2), when the position where the hydroxy group is bonded is defined as the 1st position, -R- * or the aldehyde group may be bonded at any of the 2nd to 8th positions. In the formula (1-3), when the position to which the hydroxy group is bonded is the 2nd position, the --R- * or aldehyde group may be bonded to the 1st or 3rd to 8th positions.
As the structural unit (1), a structural unit represented by the formula (1-1), in which the binding position of the aldehyde group is ortho to the hydroxy group is preferable. If it is this structural unit, when manufacturing an allyl group containing resin by the manufacturing method (I) mentioned later, the crosslinking agent (B) of the monomer (A) corresponding to the structural unit represented by Formula (1-1). The monomer (A) can be easily recovered and recycled.
The structural unit (1) contained in the allyl group-containing resin may be one type or two or more types.
構成単位（２）として具体的には、前記式（１−１）、（１−２）または（１−３）におけるアルデヒド基（−ＣＨＯ）が−ＣＨ＝Ｎ−ＣＨ２−ＣＨ＝ＣＨ２に変換された構造の構成単位が挙げられる。これらの中でも式（１−１）におけるアルデヒド基（−ＣＨＯ）が−ＣＨ＝Ｎ−ＣＨ２−ＣＨ＝ＣＨ２に変換された構造の構成単位が好ましく、−ＣＨ＝Ｎ−ＣＨ２−ＣＨ＝ＣＨ２の結合位置が、ヒドロキシ基に対してオルソ位であるものが特に好ましい。
アリル基含有樹脂に含まれる構成単位（２）は１種でも２種以上でもよい。
Specifically, as the structural unit (2), the aldehyde group (—CHO) in the formula (1-1), (1-2), or (1-3) is —CH═N—CH 2 —CH═CH 2. The structural unit of the structure converted into is mentioned. Among these, a structural unit having a structure in which the aldehyde group (—CHO) in the formula (1-1) is converted to —CH═N—CH 2 —CH═CH 2 is preferable, and —CH═N—CH 2 —CH═ It is particularly preferable that the bonding position of CH 2 is ortho to the hydroxy group.
The structural unit (2) contained in the allyl group-containing resin may be one type or two or more types.
構成単位（３）として具体的には、下記式（３−１）、（３−２）または（３−３）で表される構成単位が挙げられる。これらの中でも式（３−１）で表される構成単位が好ましい。 Specific examples of the structural unit (3) include structural units represented by the following formula (3-1), (3-2), or (3-3). Among these, the structural unit represented by Formula (3-1) is preferable.
式（３−１）で表される構成単位のベンゼン環における−＊、−（Ｒ）ｐ−＊＊、−（Ｒ）ｑ−＊＊、アルデヒド基それぞれの結合位置は特に限定されない。
式（３−２）または（３−３）で表される構成単位のナフタレン環における−＊、−（Ｒ）ｐ−＊＊、−（Ｒ）ｑ−＊＊、アルデヒド基それぞれの結合位置は特に限定されない。例えば式（３−２）中、ヒドロキシ基が結合した位置を１位とした場合、−Ｒ−＊やアルデヒド基が結合するのは２〜８位のいずれでもよい。式（３−３）中、ヒドロキシ基が結合した位置を２位とした場合、−Ｒ−＊やアルデヒド基が結合するのは１、３〜８位のいずれでもよい。
構成単位（３）としては、式（３−１）で表され、アルデヒド基の結合位置が、ヒドロキシ基に対してオルソ位である構成単位が好ましい。かかる構成単位であれば、アリル基含有樹脂を後述する製造方法（Ｉ）により製造する場合に、式（３−１）で表される構成単位に対応するモノマー（Ａ）の架橋剤（Ｂ）との反応性が良く、また、モノマー（Ａ）を容易に回収リサイクルできる。
アリル基含有樹脂に含まれる構成単位（３）は１種でも２種以上でもよい。
There are no particular limitations on the bonding positions of-*,-(R) p -**,-(R) q -**, and the aldehyde group in the benzene ring of the structural unit represented by formula (3-1).
The bonding positions of-*,-(R) p -**,-(R) q -**, and the aldehyde group in the naphthalene ring of the structural unit represented by formula (3-2) or (3-3) are as follows. There is no particular limitation. For example, in the formula (3-2), when the position to which the hydroxy group is bonded is defined as the 1st position, -R- * or the aldehyde group may be bonded to any of the 2nd to 8th positions. In the formula (3-3), when the position to which the hydroxy group is bonded is the 2nd position, the --R- * or aldehyde group may be bonded to the 1st or 3rd to 8th positions.
As the structural unit (3), a structural unit represented by the formula (3-1), in which the binding position of the aldehyde group is ortho to the hydroxy group is preferable. If it is this structural unit, when manufacturing an allyl group containing resin by the manufacturing method (I) mentioned later, the crosslinking agent (B) of the monomer (A) corresponding to the structural unit represented by Formula (3-1). The monomer (A) can be easily recovered and recycled.
The structural unit (3) contained in the allyl group-containing resin may be one type or two or more types.
構成単位（４）として具体的には、前記式（３−１）、（３−２）または（３−３）におけるアルデヒド基（−ＣＨＯ）が−ＣＨ＝Ｎ−ＣＨ２−ＣＨ＝ＣＨ２に変換された構造の構成単位が挙げられる。これらの中でも式（３−１）におけるアルデヒド基（−ＣＨＯ）が−ＣＨ＝Ｎ−ＣＨ２−ＣＨ＝ＣＨ２に変換された構造の構成単位が好ましく、−ＣＨ＝Ｎ−ＣＨ２−ＣＨ＝ＣＨ２の結合位置が、ヒドロキシ基に対してオルソ位であるものが特に好ましい。
アリル基含有樹脂に含まれる構成単位（４）は１種でも２種以上でもよい。
Specifically, as the structural unit (4), the aldehyde group (—CHO) in the formula (3-1), (3-2), or (3-3) is —CH═N—CH 2 —CH═CH 2. The structural unit of the structure converted into is mentioned. Among these, a structural unit having a structure in which the aldehyde group (—CHO) in the formula (3-1) is converted to —CH═N—CH 2 —CH═CH 2 is preferable, —CH═N—CH 2 —CH═ It is particularly preferable that the bonding position of CH 2 is ortho to the hydroxy group.
The structural unit (4) contained in the allyl group-containing resin may be one type or two or more types.
アリル基含有樹脂は、必要に応じて、本発明の効果を損なわない範囲で、構成単位（１）、構成単位（２）、構成単位（３）および構成単位（４）以外の構成単位をさらに有していてもよい。 The allyl group-containing resin further includes structural units other than the structural unit (1), the structural unit (2), the structural unit (3), and the structural unit (4) as long as the effects of the present invention are not impaired. You may have.
アリル基含有樹脂において、前記構成単位（２）と前記構成単位（４）との合計の含有量は、前記構成単位（１）と前記構成単位（２）と前記構成単位（３）と前記構成単位（４）との合計（１００モル％）に対して１０〜８０モル％であり、２５〜７０モル％が好ましく、２５〜５０モル％が特に好ましい。
この割合は、アリル基含有樹脂中のアルデヒド基とアリル基との合計に対するアリル基の割合（モル％）に等しい。
この割合が上記範囲の下限値以上であれば、本発明の熱硬化性成形材料を硬化させたときに、高ガラス転移温度、高熱分解温度、低線膨張係数、低吸水性の硬化物が得られる。この割合が上記範囲の上限値以下であれば、本発明のアリル基含有樹脂の、結晶性を抑制しハンドリング性が向上する。また、コストも抑制できる。
In the allyl group-containing resin, the total content of the structural unit (2) and the structural unit (4) is the structural unit (1), the structural unit (2), the structural unit (3), and the structural unit. It is 10-80 mol% with respect to the sum (100 mol%) with a unit (4), 25-70 mol% is preferable and 25-50 mol% is especially preferable.
This ratio is equal to the ratio (mol%) of allyl groups to the total of aldehyde groups and allyl groups in the allyl group-containing resin.
If this ratio is at least the lower limit of the above range, a cured product having a high glass transition temperature, a high thermal decomposition temperature, a low linear expansion coefficient, and a low water absorption is obtained when the thermosetting molding material of the present invention is cured. It is done. If this ratio is below the upper limit of the said range, crystallinity of the allyl group containing resin of this invention will be suppressed and handling property will improve. Moreover, cost can be suppressed.
アリル基含有樹脂を構成する全構成単位の合計（１００モル％）に対する、前記構成単位（１）と前記構成単位（２）と前記構成単位（３）と前記構成単位（４）との合計の割合は、１０モル％以上が好ましく、５０モル％以上がより好ましく、９０モル％以上がさらに好ましく、１００モル％であってもよい。 The total of the structural unit (1), the structural unit (2), the structural unit (3), and the structural unit (4) with respect to the total (100 mol%) of all the structural units constituting the allyl group-containing resin. The ratio is preferably 10 mol% or more, more preferably 50 mol% or more, further preferably 90 mol% or more, and may be 100 mol%.
アリル基含有樹脂において、アリル基含有樹脂を構成する重合体１分子あたりの前記構成単位（１）と前記構成単位（２）と前記構成単位（３）と前記構成単位（４）との合計数は、２〜３１が好ましい。
上記の合計数が上記上限値以下であれば、アリル基含有樹脂の質量平均分子量（Ｍｗ）が低くなることで、アリル基含有樹脂の軟化点や溶融粘度が低くなる傾向がある。
In the allyl group-containing resin, the total number of the structural unit (1), the structural unit (2), the structural unit (3), and the structural unit (4) per molecule of the polymer constituting the allyl group-containing resin. Is preferably 2 to 31.
If said total number is below the said upper limit, there exists a tendency for the softening point and melt viscosity of allyl group containing resin to become low because the mass mean molecular weight (Mw) of allyl group containing resin becomes low.
アリル基含有樹脂の質量平均分子量（Ｍｗ）は、３００〜４０００が好ましく、４００〜２０００がより好ましい。Ｍｗが上記上限値以下であると、アリル基含有樹脂の溶融粘度が充分に低くなる。Ｍｗが上記下限値以上であると、アリル基含有樹脂の結晶性を抑えることができ、アリル基含有樹脂とエポキシ樹脂とを溶融混合する際の相溶性が優れる。
アリル基含有樹脂の分散度（Ｍｗ／数平均分子量（Ｍｎ））は、１．２０〜２．００が好ましい。
本発明において、ＭｗおよびＭｎは、標準物質をポリスチレンとしたゲル浸透クロマトグラフィー（ＧＰＣ）により測定される値である。
300-4000 are preferable and, as for the mass mean molecular weight (Mw) of allyl group containing resin, 400-2000 are more preferable. When the Mw is not more than the above upper limit, the melt viscosity of the allyl group-containing resin is sufficiently low. When the Mw is not less than the above lower limit, the crystallinity of the allyl group-containing resin can be suppressed, and the compatibility when the allyl group-containing resin and the epoxy resin are melt-mixed is excellent.
The dispersity (Mw / number average molecular weight (Mn)) of the allyl group-containing resin is preferably 1.20 to 2.00.
In the present invention, Mw and Mn are values measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
アリル基含有樹脂の軟化点は、５０〜９５℃であることが好ましく、６５〜８０℃であることがより好ましい。軟化点が上記下限値以上であれば、ブロッキング性が良好である。軟化点が上記上限値以下であれば、アリル基含有樹脂の溶融粘度が充分に低く、これを含む熱硬化性成形材料の流動性が高く成形しやすい。
アリル基含有樹脂の軟化点は、ＪＩＳ Ｋ ６９１０：１９９９に従って測定される。
The softening point of the allyl group-containing resin is preferably 50 to 95 ° C, and more preferably 65 to 80 ° C. If the softening point is not less than the above lower limit, the blocking property is good. If the softening point is less than or equal to the above upper limit, the melt viscosity of the allyl group-containing resin is sufficiently low, and the fluidity of the thermosetting molding material containing the resin is high and easy to mold.
The softening point of the allyl group-containing resin is measured according to JIS K 6910: 1999.
アリル基含有樹脂の１５０℃における溶融粘度は、１０Ｐ以下が好ましく、８Ｐ以下がより好ましく、３Ｐ以下が特に好ましい。溶融粘度が上記上限値以下であれば、アリル基含有樹脂を含む熱硬化性成形材料の流動性が高く成形しやすい。
アリル基含有樹脂の溶融粘度は、溶融粘度計（たとえばブルックフィールド社製のＣＡＰ２０００ ＶＩＳＣＯＭＥＴＥＲ）により測定される。
アリル基含有樹脂の軟化点や溶融粘度は、質量平均分子量（Ｍｗ）、アリル基の含有量等により調整できる。
The melt viscosity at 150 ° C. of the allyl group-containing resin is preferably 10 P or less, more preferably 8 P or less, and particularly preferably 3 P or less. When the melt viscosity is not more than the above upper limit value, the thermosetting molding material containing the allyl group-containing resin has high fluidity and is easy to mold.
The melt viscosity of the allyl group-containing resin is measured by a melt viscometer (for example, CAP2000 VISCOMETER manufactured by Brookfield).
The softening point and melt viscosity of the allyl group-containing resin can be adjusted by the mass average molecular weight (Mw), the allyl group content, and the like.
（エポキシ樹脂）
エポキシ樹脂としては、特に限定されず、公知のエポキシ樹脂であってよく、例えばフェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビフェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、アントラセン型エポキシ樹脂、ナフトール型エポキシ樹脂、キシリレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、スチルベン型エポキシ樹脂、硫黄原子含有エポキシ樹脂、リン原子含有エポキシ樹脂等が挙げられる。これらのエポキシ樹脂はいずれか１種を単独で用いてもよく２種以上を組合わせて用いてもよい。
(Epoxy resin)
The epoxy resin is not particularly limited and may be a known epoxy resin, such as a phenol novolac type epoxy resin, an orthocresol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a biphenol type epoxy resin, Naphthalene type epoxy resin, anthracene type epoxy resin, naphthol type epoxy resin, xylylene type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, A phosphorus atom containing epoxy resin etc. are mentioned. Any one of these epoxy resins may be used alone, or two or more thereof may be used in combination.
エポキシ樹脂としては、特に制限はないが、ビフェニル型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビフェノール型エポキシ樹脂、トリフェニル型エポキシ樹脂、オルソクレゾール型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂等が挙げられる。
上記の中でも、耐熱性、低吸水性の点で、ビフェニル型エポキシ樹脂が好ましい。
There are no particular restrictions on the epoxy resin, but biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenol type epoxy resin, triphenyl type epoxy resin, orthocresol type epoxy resin, dicyclopentadiene type epoxy Examples thereof include resins.
Among these, a biphenyl type epoxy resin is preferable in terms of heat resistance and low water absorption.
熱硬化性成形材料中のエポキシ樹脂の含有量は、前記アリル基含有樹脂に対して５〜５０質量％であることが好ましく、１０〜３０質量％がより好ましく、１０〜２０質量％が特に好ましい。エポキシ樹脂の含有量が上記上限値以下であれば、熱硬化性成形材料の硬化物が、より高ガラス転移温度、高熱分解温度、低線膨張係数、低吸水性となる。エポキシ樹脂の含有量が上記下限値以上であれば、熱硬化性成形材料の硬化温度を低く、例えば２００℃以下にすることができる。 The content of the epoxy resin in the thermosetting molding material is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, and particularly preferably 10 to 20% by mass with respect to the allyl group-containing resin. . If content of an epoxy resin is below the said upper limit, the hardened | cured material of a thermosetting molding material will become a higher glass transition temperature, a high thermal decomposition temperature, a low linear expansion coefficient, and a low water absorption. If content of an epoxy resin is more than the said lower limit, the curing temperature of a thermosetting molding material can be made low, for example, can be 200 degrees C or less.
（硬化促進剤）
硬化促進剤としては、特に限定されず、エポキシ基とヒドロキシ基との反応を促進するものとして公知の硬化促進剤であってよい。例えばリン系化合物、第３級アミン、イミダゾール化合物、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。リン系化合物としては、トリフェニルホスフィン、トリス−２，６−ジメトキシフェニルホスフィン、トリ−ｐ−トリルホスフィン、亜リン酸トリフェニル等が挙げられる。第３級アミンとしては、２−ジメチルアミノメチルフェノール、ベンジルジメチルアミン、α−メチルベンジルメチルアミン、１，８−ジアザビシクロ［５．４．０］ウンデセン−７、１，８−ジアザビシクロ［５．４．０］ウンデセン−７等が挙げられる。イミダゾール化合物としては、２−メチルイミダゾール、２−フェニルイミダゾール、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、２−エチル−４−メチルイミダゾール等が挙げられる。これらの硬化促進剤はいずれか１種を単独で用いてもよく２種以上を組合わせて用いてもよい。
硬化促進剤の含有量は、エポキシ樹脂に対し、０．５〜５．０質量％が好ましい。
(Curing accelerator)
It does not specifically limit as a hardening accelerator, You may be a hardening accelerator well-known as what accelerates | stimulates reaction with an epoxy group and a hydroxyl group. Examples thereof include phosphorus compounds, tertiary amines, imidazole compounds, organic acid metal salts, Lewis acids, amine complex salts, and the like. Examples of the phosphorus compound include triphenylphosphine, tris-2,6-dimethoxyphenylphosphine, tri-p-tolylphosphine, and triphenyl phosphite. As the tertiary amine, 2-dimethylaminomethylphenol, benzyldimethylamine, α-methylbenzylmethylamine, 1,8-diazabicyclo [5.4.0] undecene-7, 1,8-diazabicyclo [5.4]. 0.0] undecene-7 and the like. Examples of the imidazole compound include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, and the like. Any one of these curing accelerators may be used alone, or two or more thereof may be used in combination.
As for content of a hardening accelerator, 0.5-5.0 mass% is preferable with respect to an epoxy resin.
（他の成分）
前記他の成分としては、例えば、前記アリル基含有樹脂以外の硬化剤（以下、他の硬化剤ともいう。）、充填材（フィラー）、離型剤、表面処理剤、着色剤、可撓性付与剤等が挙げられる。
他の硬化剤としては、エポキシ樹脂に用いられる硬化剤として従来公知のものを用いることができ、例えばフェノールノボラック樹脂、トリフェニルメタン型フェノール樹脂等のフェノール樹脂、酸無水物、アミン樹脂等が挙げられる。
熱硬化性成形材料中の他の硬化剤の含有量は、本発明の効果の点では、熱硬化性成型材料に対し、１０質量％以下が好ましく、０質量％が特に好ましい。
(Other ingredients)
Examples of the other components include a curing agent other than the allyl group-containing resin (hereinafter also referred to as other curing agent), a filler (filler), a release agent, a surface treatment agent, a colorant, and flexibility. Examples include an imparting agent.
As other curing agents, those conventionally known as curing agents used for epoxy resins can be used, and examples thereof include phenol resins such as phenol novolac resins and triphenylmethane type phenol resins, acid anhydrides, amine resins and the like. It is done.
The content of the other curing agent in the thermosetting molding material is preferably 10% by mass or less and particularly preferably 0% by mass with respect to the thermosetting molding material in terms of the effects of the present invention.
充填材（フィラー）としては、カーボンブラック、結晶性シリカ粉、溶融性シリカ粉、石英ガラス粉、タルク、ケイ酸カルシウム粉、ケイ酸ジルコニウム粉、アルミナ粉、炭酸カルシウム粉等が挙げられ、結晶性シリカ粉、溶融性シリカ粉が好ましい。
離型剤としては、たとえばカルナバワックス等の各種ワックス類等が挙げられる。
表面処理剤としては、公知のシランカップリング剤等が挙げられる。
着色剤としては、カーボンブラック等が挙げられる。
可撓性付与剤としては、シリコーン樹脂、ブタジエン−アクリロニトリルゴム等が挙げられる。
Examples of the filler (filler) include carbon black, crystalline silica powder, fusible silica powder, quartz glass powder, talc, calcium silicate powder, zirconium silicate powder, alumina powder, and calcium carbonate powder. Silica powder and fusible silica powder are preferred.
Examples of the release agent include various waxes such as carnauba wax.
Examples of the surface treatment agent include known silane coupling agents.
Examples of the colorant include carbon black.
Examples of the flexibility imparting agent include silicone resin and butadiene-acrylonitrile rubber.
（熱硬化性成形材料の製造方法）
本発明の熱硬化性成形材料の製造方法としては、たとえば、以下の製造方法（Ｉ）が挙げられる。
製造方法（Ｉ）：モノヒドロキシベンズアルデヒドおよびモノヒドロキシナフトアルデヒドからなる群から選ばれる少なくとも１種のモノマー（Ａ）と、下記式（ｂ１）で表される化合物および下記式（ｂ２）で表される化合物からなる群から選ばれる少なくとも１種の架橋剤（Ｂ）とを反応させて、前記構成単位（１）と前記構成単位（３）とを含むアルデヒド基含有樹脂を得る工程と、
前記アルデヒド基含有樹脂と、前記アルデヒド基含有樹脂のアルデヒド基に対して１０〜８０モル％のアリルアミンとを反応させて前記アリル基含有樹脂を得る工程と、
前記アリル基含有樹脂とエポキシ樹脂とを混合する工程と、
を有する熱硬化性成形材料の製造方法。
アリル基含有樹脂とエポキシ樹脂とを混合する際に、またはアリル基含有樹脂とエポキシ樹脂とを混合した後、必要に応じて、硬化促進剤や他の成分をさらに混合してもよい。
(Method for producing thermosetting molding material)
As a manufacturing method of the thermosetting molding material of this invention, the following manufacturing methods (I) are mentioned, for example.
Production method (I): At least one monomer (A) selected from the group consisting of monohydroxybenzaldehyde and monohydroxynaphthaldehyde, a compound represented by the following formula (b1), and a formula (b2) Reacting at least one crosslinking agent (B) selected from the group consisting of compounds to obtain an aldehyde group-containing resin containing the structural unit (1) and the structural unit (3);
Reacting the aldehyde group-containing resin with 10 to 80 mol% of allylamine with respect to the aldehyde group of the aldehyde group-containing resin to obtain the allyl group-containing resin;
Mixing the allyl group-containing resin and the epoxy resin;
A method for producing a thermosetting molding material.
When the allyl group-containing resin and the epoxy resin are mixed, or after the allyl group-containing resin and the epoxy resin are mixed, a curing accelerator and other components may be further mixed as necessary.
「モノマー（Ａ）」
モノヒドロキシベンズアルデヒドとしては、オルソヒドロキシベンズアルデヒド、パラヒドロキシベンズアルデヒド、メタヒドロキシベンズアルデヒド等が挙げられる。
モノヒドロキシナフトアルデヒドとしては、１−ヒドロキシ−２−ナフトアルデヒド、２−ヒドロキシ−１−ナフトアルデヒド、６−ヒドロキシ−２−ナフトアルデヒド等が挙げられる。
これらはいずれか１種を単独で用いてもよく２種以上を併用してもよい。
モノマー（Ａ）としては、架橋剤（Ｂ）との反応性が良い点、反応で残留したモノマーを容易に回収リサイクル可能である点から、オルソヒドロキシベンズアルデヒドが好ましい。
"Monomer (A)"
Examples of monohydroxybenzaldehyde include orthohydroxybenzaldehyde, parahydroxybenzaldehyde, metahydroxybenzaldehyde and the like.
Examples of monohydroxynaphthaldehyde include 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 6-hydroxy-2-naphthaldehyde and the like.
Any of these may be used alone or in combination of two or more.
As the monomer (A), orthohydroxybenzaldehyde is preferable from the viewpoint of good reactivity with the crosslinking agent (B) and the ability to easily recover and recycle the monomer remaining in the reaction.
「架橋剤（Ｂ）」
前記式（ｂ１）または（ｂ２）中、Ｘのハロゲン原子としては、塩素原子、臭素原子等が挙げられる。
前記式（ｂ１）で表される化合物（以下、「化合物（ｂ１）」ともいう。）としては、４，４’−ビス（アルコキシメチル）ビフェニル、２，２’−ビス（アルコキシメチル）ビフェニル、２，４’−ビス（アルコキシメチル）ビフェニル、４，４’−ビス（ハロゲン化メチル）ビフェニル、２，２’−ビス（ハロゲン化メチル）ビフェニル、２，４’−ビス（ハロゲン化メチル）ビフェニル等（ただし、アルコキシ基の炭素数は１〜４である。）が挙げられる。
前記式（ｂ２）で表される化合物（以下、「化合物（ｓ２）」ともいう。）としては、パラキシリレングリコールジアルキルエーテル、メタキシリレングリコールジアルキルエーテル、１，４−ビス（ハロゲン化メチル）ベンゼン等（ただし、アルキル基の炭素数は１〜４である。）が挙げられる。
これらは１種単独で用いても２種以上を組合わせて用いてもよい。
架橋剤（Ｂ）としては、上記のなかでも、比較的安価であり、モノマー（Ａ）との反応性が良好である点から、４，４’−ビス（アルコキシメチル）ビフェニル、４，４’−ビス（ハロゲン化メチル）ビフェニル、パラキシリレングリコールジアルキルエーテル、１，４−ビス（ハロゲン化メチル）ベンゼンが好ましい。
"Crosslinking agent (B)"
In the formula (b1) or (b2), examples of the halogen atom for X include a chlorine atom and a bromine atom.
Examples of the compound represented by the formula (b1) (hereinafter, also referred to as “compound (b1)”) include 4,4′-bis (alkoxymethyl) biphenyl, 2,2′-bis (alkoxymethyl) biphenyl, 2,4'-bis (alkoxymethyl) biphenyl, 4,4'-bis (halogenated methyl) biphenyl, 2,2'-bis (halogenated methyl) biphenyl, 2,4'-bis (halogenated methyl) biphenyl Etc. (however, the carbon number of the alkoxy group is 1 to 4).
Examples of the compound represented by the formula (b2) (hereinafter, also referred to as “compound (s2)”) include paraxylylene glycol dialkyl ether, metaxylylene glycol dialkyl ether, and 1,4-bis (methyl halide). Benzene and the like (however, the alkyl group has 1 to 4 carbon atoms).
These may be used alone or in combination of two or more.
Among the above, as the crosslinking agent (B), 4,4′-bis (alkoxymethyl) biphenyl, 4,4 ′ is relatively inexpensive and has good reactivity with the monomer (A). -Bis (halogenated methyl) biphenyl, paraxylylene glycol dialkyl ether, and 1,4-bis (halogenated methyl) benzene are preferred.
「モノマー（Ａ）と架橋剤（Ｂ）との反応」
モノマー（Ａ）と架橋剤（Ｂ）との反応では、複数のモノマー（Ａ）のＡｒが架橋剤（Ｂ）によって架橋され、前記構成単位（１）と前記構成単位（３）とを有するアルデヒド基含有樹脂が生成する。
"Reaction of monomer (A) with cross-linking agent (B)"
In the reaction between the monomer (A) and the cross-linking agent (B), Ar of a plurality of monomers (A) is cross-linked by the cross-linking agent (B), and the aldehyde has the structural unit (1) and the structural unit (3). A group-containing resin is produced.
モノマー（Ａ）と架橋剤（Ｂ）との反応において、モノマー（Ａ）に対する架橋剤（Ｂ）のモル比（架橋剤（Ｂ）／モノマー（Ａ））は、０．０１〜０．９９であることが好ましく、０．０５〜０．６０であることがより好ましい。
モノマー（Ａ）に対する架橋剤（Ｂ）の比率が低すぎると、歩留まりが低下するおそれがある。モノマー（Ａ）に対する架橋剤（Ｂ）の比率が高すぎると、モノマー（Ａ）と架橋剤（Ｂ）との反応に時間がかかり、生産性が低下するおそれがある。
In the reaction of the monomer (A) and the crosslinking agent (B), the molar ratio of the crosslinking agent (B) to the monomer (A) (crosslinking agent (B) / monomer (A)) is 0.01 to 0.99. It is preferable that it is 0.05 to 0.60.
If the ratio of the crosslinking agent (B) to the monomer (A) is too low, the yield may be reduced. If the ratio of the crosslinking agent (B) to the monomer (A) is too high, the reaction between the monomer (A) and the crosslinking agent (B) takes time, and the productivity may be reduced.
モノマー（Ａ）と架橋剤（Ｂ）との反応は、酸性触媒の存在下で行ってもよい。前記反応を酸性触媒下で行うと、モノマー（Ａ）と架橋剤（Ｂ）との反応速度が向上する。特に架橋剤（Ｂ）が有するＸがアルコキシ基の場合は、酸性触媒の存在下で行うことが好ましい。
架橋剤（Ｂ）が有するＸがハロゲン原子の場合は、酸性触媒を別途加えなくてもよい。Ｘがハロゲン原子の場合、反応させる際の熱によりハロゲン原子が脱離しＨＸとなる。このＨＸが酸性触媒として機能するため、酸性触媒を別途加えなくても反応速度が充分に速くなる。
The reaction between the monomer (A) and the crosslinking agent (B) may be performed in the presence of an acidic catalyst. When the reaction is carried out under an acidic catalyst, the reaction rate between the monomer (A) and the crosslinking agent (B) is improved. When X which a crosslinking agent (B) has especially is an alkoxy group, it is preferable to carry out in presence of an acidic catalyst.
When X which a crosslinking agent (B) has is a halogen atom, it is not necessary to add an acidic catalyst separately. When X is a halogen atom, the halogen atom is desorbed by heat at the time of reaction to become HX. Since this HX functions as an acidic catalyst, the reaction rate can be sufficiently increased without adding an acidic catalyst separately.
酸性触媒としては、反応が進行すれば特に制限はなく、例えば無機酸、有機酸、アルカリ性金属化合物等が挙げられる。具体例としては、塩酸、硫酸、リン酸、シュウ酸、トリフルオロ酢酸、ｐ−トルエンスルホン酸、メタンスルホン酸、３フッ化ホウ素、塩化アルミニウム、塩化鉄、塩化亜鉛等が挙げられる。酸性触媒は１種単独で用いても２種以上を併用してもよい。 The acid catalyst is not particularly limited as long as the reaction proceeds, and examples thereof include inorganic acids, organic acids, alkaline metal compounds and the like. Specific examples include hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, boron trifluoride, aluminum chloride, iron chloride, zinc chloride and the like. An acidic catalyst may be used individually by 1 type, or may use 2 or more types together.
酸性触媒の使用量は、モノマー（Ａ）に対して０．０１〜１０質量％が好ましく、０．１０〜１．００質量％がより好ましい。
酸性触媒媒の使用量が少なすぎると、反応速度の向上効果が不充分になるおそれがあり、使用量が多すぎると、反応が急激に進み反応をコントロールすることが難しくなる。
0.01-10 mass% is preferable with respect to a monomer (A), and, as for the usage-amount of an acidic catalyst, 0.10-1.00 mass% is more preferable.
If the amount of the acidic catalyst medium used is too small, the effect of improving the reaction rate may be insufficient. If the amount used is too large, the reaction proceeds rapidly and it becomes difficult to control the reaction.
モノマー（Ａ）と架橋剤（Ｂ）との反応温度は、１０〜２５０℃が好ましく、６０〜２００℃がより好ましい。反応温度があまりに低いと反応は進まず、あまりに高すぎると反応をコントロールすることが難しくなり、目的のアルデヒド基含有樹脂を安定的に得ることが難しくなる。
反応の終了時、得られた反応生成物にアルカリを添加して酸性触媒を中和してもよい。
10-250 degreeC is preferable and, as for the reaction temperature of a monomer (A) and a crosslinking agent (B), 60-200 degreeC is more preferable. If the reaction temperature is too low, the reaction will not proceed. If it is too high, it will be difficult to control the reaction, and it will be difficult to stably obtain the desired aldehyde group-containing resin.
At the end of the reaction, the acidic catalyst may be neutralized by adding alkali to the obtained reaction product.
モノマー（Ａ）と架橋剤（Ｂ）との反応により得られた反応生成物は、前記構成単位（１）と前記構成単位（３）とを有するアルデヒド基含有樹脂を含む。
この反応生成物はそのまま、または必要に応じて、蒸留等による未反応の原料の除去、濃縮、精製（洗浄、カラムクロマトグラフィー、等）等の処理を行って、次の工程（アルデヒド基含有樹脂とアリルアミンと反応させる工程）に供される。
The reaction product obtained by the reaction of the monomer (A) and the crosslinking agent (B) contains an aldehyde group-containing resin having the structural unit (1) and the structural unit (3).
This reaction product is processed as it is, or if necessary, by removing unreacted raw materials by distillation, concentration, purification (washing, column chromatography, etc.), etc. And the step of reacting with allylamine.
「アルデヒド基含有樹脂とアリルアミンとの反応」
モノマー（Ａ）と架橋剤（Ｂ）との反応により生成したアルデヒド基含有樹脂と、アリルアミンとを反応させると、アルデヒド基含有樹脂のアルデヒド基（構成単位（１）、（３）のアルデヒド基）が−ＣＨ＝Ｎ−ＣＨ２−ＣＨ＝ＣＨ２に変換される。
このとき、アルデヒド基含有樹脂のアルデヒド基（１００モル％）に対して１０〜８０モル％のアリルアミンを反応させることで、本発明のアリル基含有樹脂が生成する。
アルデヒド基含有樹脂と反応させるアリルアミンの量は、アルデヒド基含有樹脂のアルデヒド基に対して２５〜７０モル％が好ましく、２５〜５０モル％が特に好ましい。
したがって、アルデヒド基含有樹脂とアリルアミンとの反応において、アルデヒド基含有樹脂のアルデヒド基に対するアリルアミンのアミノ基のモル比（アミノ基／アルデヒド基）は、０．１０〜０．８０が好ましく、０．２５〜０．７０がより好ましく、０．２５〜０．５０が特に好ましい。
"Reaction of aldehyde group-containing resin with allylamine"
When the aldehyde group-containing resin produced by the reaction between the monomer (A) and the crosslinking agent (B) is reacted with allylamine, the aldehyde group of the aldehyde group-containing resin (the aldehyde groups of the structural units (1) and (3)) Is converted to —CH═N—CH 2 —CH═CH 2 .
At this time, the allyl group-containing resin of the present invention is produced by reacting 10 to 80 mol% of allylamine with the aldehyde group (100 mol%) of the aldehyde group-containing resin.
The amount of allylamine to be reacted with the aldehyde group-containing resin is preferably 25 to 70 mol%, particularly preferably 25 to 50 mol%, relative to the aldehyde group of the aldehyde group-containing resin.
Therefore, in the reaction between the aldehyde group-containing resin and allylamine, the molar ratio of the amino group of allylamine to the aldehyde group of the aldehyde group-containing resin (amino group / aldehyde group) is preferably 0.10 to 0.80, 0.25 -0.70 is more preferable, and 0.25-0.50 is particularly preferable.
アルデヒド基含有樹脂とアリルアミンとの反応温度は、１０〜１５０℃が好ましく、３０〜９０℃がより好ましい。反応温度があまりに低いと反応が進みにくい。反応温度がアリルアミンの沸点（９７℃）以下であれば、製造安定性に優れる。 10-150 degreeC is preferable and, as for the reaction temperature of aldehyde group containing resin and allylamine, 30-90 degreeC is more preferable. If the reaction temperature is too low, the reaction is difficult to proceed. If reaction temperature is below the boiling point (97 degreeC) of allylamine, it is excellent in manufacturing stability.
アルデヒド基含有樹脂とアリルアミンとの反応により得られた反応生成物は、前記アリル基含有樹脂を含む。
反応後、必要に応じて、反応生成物に対し、蒸留等による未反応の原料の除去、濃縮、精製（洗浄、カラムクロマトグラフィー、等）等の処理を行ってもよい。
この反応生成物はそのまま、または必要に応じて、蒸留等による未反応の原料の除去、濃縮、精製（洗浄、カラムクロマトグラフィー、等）等の処理を行って、次の工程（アリル基含有樹脂とエポキシ樹脂とを混合する工程）に供される。
The reaction product obtained by the reaction of the aldehyde group-containing resin and allylamine contains the allyl group-containing resin.
After the reaction, if necessary, the reaction product may be subjected to treatment such as removal of unreacted raw materials by distillation or the like, concentration, purification (washing, column chromatography, etc.) and the like.
This reaction product is processed as it is or if necessary, by removing unreacted raw materials by distillation, concentration, purification (washing, column chromatography, etc.), etc. And a step of mixing the epoxy resin with the epoxy resin.
「アリル基含有樹脂とエポキシ樹脂との混合」
上記のようにして得られたアリル基含有樹脂と、エポキシ樹脂と、必要に応じて硬化促進剤、他の成分等を混合することにより熱硬化性成形材料が得られる。
エポキシ樹脂、硬化促進剤、他の成分はそれぞれ、前記と同様のものが挙げられ、好ましい態様も同様である。
各成分の混合は、常法により行うことができる。例えば各成分を、アリル基含有樹脂およびエポキシ樹脂が溶融し、熱硬化性成形材料が完全には硬化しない温度（例えば６０〜１３０℃）にて熱溶融混合することにより熱硬化性成形材料が得られる。
"Mixing of allyl group-containing resin and epoxy resin"
A thermosetting molding material can be obtained by mixing the allyl group-containing resin obtained as described above, an epoxy resin, and a curing accelerator and other components as required.
Examples of the epoxy resin, curing accelerator, and other components are the same as those described above, and preferred embodiments are also the same.
Mixing of each component can be performed by a conventional method. For example, a thermosetting molding material is obtained by heat-mixing each component at a temperature (for example, 60 to 130 ° C.) at which the allyl group-containing resin and the epoxy resin are melted and the thermosetting molding material is not completely cured. It is done.
（作用効果）
本発明の熱硬化性成形材料にあっては、構成単位（１）および構成単位（２）のいずれか一方または両方と、構成単位（３）と、構成単位（４）とを有し、構成単位（２）と構成単位（４）との合計の含有量が、構成単位（１）と構成単位（２）と構成単位（３）と構成単位（４）との合計に対して１０〜８０モル％であるアリル基含有樹脂と、エポキシ樹脂とを含むため、加熱することによって硬化させ、高ガラス転移温度、高熱分解温度、低線膨張係数、低吸水性（低吸湿性）の硬化物を得ることができる。これは以下の理由によると考えられる。
(Function and effect)
The thermosetting molding material of the present invention has one or both of the structural unit (1) and the structural unit (2), the structural unit (3), and the structural unit (4). The total content of the unit (2) and the structural unit (4) is 10 to 80 with respect to the total of the structural unit (1), the structural unit (2), the structural unit (3), and the structural unit (4). Because it contains an allyl group-containing resin and an epoxy resin, the cured product has a high glass transition temperature, a high thermal decomposition temperature, a low linear expansion coefficient, and a low water absorption (low hygroscopicity). Obtainable. This is considered to be due to the following reason.
従来のフェノール系硬化剤（フェノールノボラック樹脂等）を用いてエポキシ樹脂を硬化させる場合、ヒドロキシ基とエポキシ基との反応（エポキシ硬化系）により必ずヒドロキシ基が発生する。このヒドロキシ基が吸水率を増加させていた。
本発明の熱硬化性成形材料にあっては、アリル基含有樹脂がヒドロキシ基のほかアルデヒド基および−ＣＨ＝Ｎ−ＣＨ２−ＣＨ＝ＣＨ２を有するため、アリル基含有樹脂とエポキシ樹脂とを反応させたときに、（１）ヒドロキシ基とエポキシ基との反応、（２）−ＣＨ＝Ｎ−ＣＨ２−ＣＨ＝ＣＨ２のイミン部分とアルデヒド基との反応、（３）−ＣＨ＝Ｎ−ＣＨ２−ＣＨ＝ＣＨ２のアリル基同士の反応、の３種の反応が生じて硬化する。
硬化系全体における（１）の反応（エポキシ硬化系）の割合が低くなり、また、上記（２）、（３）の反応ではヒドロキシ基は発生しないため、得られる硬化物中のヒドロキシ基の含有量が少なくなって吸水性が低くなる。
また、エポキシ硬化系の割合が低くなっても、他の硬化系（（２）、（３）の反応）を併用しているため、硬化が充分に進み、高ガラス転移温度、高熱分解温度、低線膨張係数を達成できる。
また、前記アリル基含有樹脂にあっては、複数のＡｒを結合する基Ｒが前記式（ｒ１）または（ｒ２）で表される基であるため、複数のＡｒを結合する基がメチレン基である場合（架橋剤としてホルムアルデヒドを用いたフェノールノボラック樹脂等）に比べて、硬化物の耐熱性が高くなる。
なお、前記アリル基含有樹脂は、エポキシ樹脂と組み合わせなくても、上記（２）、（３）の反応により、単独で硬化させることができる。しかし、エポキシ樹脂と組み合わせることで、単独で硬化させる場合に比べて、硬化温度を低くすることができる。そのため、エポキシ樹脂と組み合わせて硬化反応に供することが好適である。
When an epoxy resin is cured using a conventional phenolic curing agent (such as a phenol novolac resin), a hydroxy group is always generated by a reaction between the hydroxy group and the epoxy group (epoxy curing system). This hydroxy group increased the water absorption rate.
In the heat-curable molding material of the present invention, since the allyl group-containing resin has other aldehyde group and -CH = N-CH 2 -CH = CH 2 hydroxy groups, an allyl group-containing resin and an epoxy resin When reacted, (1) reaction between hydroxy group and epoxy group, (2) reaction between imine moiety of —CH═N—CH 2 —CH═CH 2 and aldehyde group, (3) —CH═N Three types of reaction of reaction between allyl groups of —CH 2 —CH═CH 2 occur and cure.
The proportion of the reaction (1) (epoxy curing system) in the entire curing system is low, and no hydroxy group is generated in the reactions (2) and (3). The amount decreases and the water absorption decreases.
In addition, even if the proportion of the epoxy curing system is low, other curing systems (reactions (2) and (3)) are used in combination, so that curing proceeds sufficiently and a high glass transition temperature, a high thermal decomposition temperature, Low linear expansion coefficient can be achieved.
In the allyl group-containing resin, the group R that binds a plurality of Ars is a group represented by the formula (r1) or (r2), and therefore the group that binds a plurality of Ars is a methylene group. The heat resistance of the cured product is higher than in some cases (such as a phenol novolac resin using formaldehyde as a crosslinking agent).
The allyl group-containing resin can be cured alone by the reactions (2) and (3) without being combined with an epoxy resin. However, by combining with an epoxy resin, the curing temperature can be lowered as compared with the case of curing alone. Therefore, it is suitable to use for a curing reaction in combination with an epoxy resin.
本発明の熱硬化性成形材料を硬化させる際の加熱温度（硬化温度）は、１５０〜２５０℃が好ましい。
硬化操作の一例としては、前記の好適な温度で３０秒間以上１時間以下の硬化を行い、その後さらに、前記の好適な温度で１〜２０時間の後硬化を行う方法が挙げられる。
The heating temperature (curing temperature) for curing the thermosetting molding material of the present invention is preferably 150 to 250 ° C.
As an example of the curing operation, there may be mentioned a method in which curing is carried out at the preferred temperature for 30 seconds to 1 hour, and then post-curing is carried out at the preferred temperature for 1 to 20 hours.
本発明の熱硬化性成形材料の用途としては、特に制限はなく、公知の熱硬化性成形材料の用途と同様であってよい。たとえば封止材料、フィルム材料、積層材料等が挙げられる。より具体的な用途の例としては、半導体封止材料、電子部品の封止用樹脂材料、電気絶縁材料、銅張り積層板用樹脂材料、ビルドアップ積層板材料、レジスト材料、液晶のカラーフィルター用樹脂材料、塗料、各種コーティング剤、接着剤、繊維強化プラスチック（ＦＲＰ）材料等が挙げられる。半導体封止材料として用いる場合、本発明の熱硬化性成形材料は溶剤を含まないことが好ましい。
本発明の熱硬化性成形材料の硬化物は、高ガラス転移温度、高熱分解温度、低線膨張係数、低吸水性である。そのため、本発明の熱硬化性成形材料は、半導体封止材料として有用である。
There is no restriction | limiting in particular as a use of the thermosetting molding material of this invention, You may be the same as the use of a well-known thermosetting molding material. For example, a sealing material, a film material, a laminated material, etc. are mentioned. Examples of more specific applications include semiconductor sealing materials, resin materials for sealing electronic components, electrical insulating materials, resin materials for copper-clad laminates, build-up laminate materials, resist materials, and liquid crystal color filters Examples thereof include resin materials, paints, various coating agents, adhesives, and fiber reinforced plastic (FRP) materials. When used as a semiconductor sealing material, the thermosetting molding material of the present invention preferably contains no solvent.
The cured product of the thermosetting molding material of the present invention has a high glass transition temperature, a high thermal decomposition temperature, a low linear expansion coefficient, and a low water absorption. Therefore, the thermosetting molding material of the present invention is useful as a semiconductor sealing material.
＜半導体封止材＞
本発明の半導体封止材は、前述の本発明の熱硬化性成形材料の硬化物からなる。
半導体封止材の形状は、特に限定されず、公知の半導体封止材と同様であってよい。
本発明の熱硬化性成形材料を用いて半導体封止材を形成（半導体を封止）する方法としては、公知の方法、例えばトランスファー成形法、圧縮成形法等を用いることができる。
<Semiconductor encapsulant>
The semiconductor sealing material of the present invention comprises a cured product of the above-described thermosetting molding material of the present invention.
The shape of the semiconductor sealing material is not particularly limited, and may be the same as a known semiconductor sealing material.
As a method for forming a semiconductor encapsulant (sealing a semiconductor) using the thermosetting molding material of the present invention, a known method such as a transfer molding method or a compression molding method can be used.
（作用効果）
本発明の半導体封止材は、高ガラス転移温度、高熱分解温度、低線膨張係数、低吸水性である。そのため、耐熱性および温度変化に対する寸法安定性が高く、はんだリフロ時等に吸湿水分の急激な気化によるクラックが発生しにくく、電子製品の信頼性の向上に寄与する。
(Function and effect)
The semiconductor sealing material of the present invention has a high glass transition temperature, a high thermal decomposition temperature, a low linear expansion coefficient, and a low water absorption. Therefore, heat resistance and dimensional stability against temperature change are high, cracks due to rapid vaporization of moisture absorption during solder reflow and the like are less likely to occur, and contributes to the improvement of the reliability of electronic products.
以下に、本発明を実施例によってさらに詳しく説明するが、本発明は実施例に限定されるものではない。
以下の各例において「％」は、特に限定のない場合は「質量％」を示す。
以下の各例で用いた測定方法を以下に示す。
EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the examples.
In the following examples, “%” indicates “% by mass” unless otherwise specified.
The measurement methods used in the following examples are shown below.
［樹脂の質量平均分子量（Ｍｗ）、分散度（Ｍｗ／Ｍｎ）］
下記のＧＰＣ装置及びカラムを使用し、標準物質をポリスチレンとして測定した。
ＧＰＣ装置：東ソー社製のＨＬＣ８１２０ＧＰＣ。
カラム：ＴＳＫｇｅｌ Ｇ３０００ＨＸＬ＋Ｇ２０００Ｈ＋Ｇ２０００Ｈ。
[Mass average molecular weight (Mw) of resin, dispersity (Mw / Mn)]
Using the following GPC apparatus and column, the standard substance was measured as polystyrene.
GPC apparatus: HLC8120GPC manufactured by Tosoh Corporation.
Column: TSKgel G3000HXL + G2000H + G2000H.
［樹脂の軟化点］
ＪＩＳ Ｋ ６９１０：１９９９に従って軟化点を測定した。
[Softening point of resin]
The softening point was measured according to JIS K 6910: 1999.
［樹脂の溶融粘度］
１５０℃に設定した溶融粘度計（ブルックフィールド社製ＣＡＰ２０００ ＶＩＳＣＯＭＥＴＥＲ）により、１５０℃における溶融粘度を測定した。
[Melt viscosity of resin]
The melt viscosity at 150 ° C. was measured with a melt viscometer (CAP2000 VISCOMETER manufactured by Brookfield) set at 150 ° C.
［硬化物のガラス転移温度（Ｔｇ）］
熱硬化性成形材料を１７５℃、１２０秒の条件でトランスファー成形して樹脂成形物（幅２ｍｍ×長さ３０ｍｍ×厚さ１ｍｍ）を作製し、２００℃、５時間の条件で後硬化させた。後硬化させた樹脂成形物について、粘弾性測定装置（日立ハイテクサイエンス社製 ＤＭＡ７１００）を用いて２℃／分の昇温速度で３０℃〜３００℃の範囲でｔａｎδを測定し、Ｔｇ（℃）を求めた。
[Glass transition temperature (Tg) of cured product]
The thermosetting molding material was transfer molded at 175 ° C. for 120 seconds to produce a resin molded product (width 2 mm × length 30 mm × thickness 1 mm) and post-cured at 200 ° C. for 5 hours. For the post-cured resin molded product, tan δ was measured in the range of 30 ° C. to 300 ° C. at a temperature increase rate of 2 ° C./min using a viscoelasticity measuring device (DMA7100 manufactured by Hitachi High-Tech Science Co.), and Tg (° C.). Asked.
［硬化物の５％熱分解温度］
熱硬化性成形材料を１７５℃、１２０秒の条件でトランスファー成形して樹脂成形物（幅２ｍｍ×長さ３０ｍｍ×厚さ１ｍｍ）を作製し、２００℃、５時間の条件で後硬化させた。後硬化させた樹脂成形物を微粉砕し、測定試料とした。この測定試料について、示差熱熱重量同時測定装置（セイコーインスツルメンツ社製 ＴＧ／ＤＴＡ６３００）により、エアー雰囲気下で１０℃／分の昇温速度で３０℃〜８００℃の範囲で熱重量減量を測定し、５％熱分解温度（℃）を求めた。
[5% thermal decomposition temperature of cured product]
The thermosetting molding material was transfer molded at 175 ° C. for 120 seconds to produce a resin molded product (width 2 mm × length 30 mm × thickness 1 mm) and post-cured at 200 ° C. for 5 hours. The post-cured resin molded product was pulverized to obtain a measurement sample. With respect to this measurement sample, the thermogravimetric weight loss was measured in the range of 30 ° C. to 800 ° C. at a temperature increase rate of 10 ° C./min under an air atmosphere by using a differential thermothermal gravimetric simultaneous measurement device (TG / DTA 6300 manufactured by Seiko Instruments Inc.). A 5% thermal decomposition temperature (° C.) was determined.
［硬化物の線膨張係数］
熱硬化性成型材料を１７５℃、１２０秒の条件でトランスファー成形して樹脂成形物（幅５ｍｍ×長さ５ｍｍ×厚さ５ｍｍ）を作製し、２００℃、５時間の条件で後硬化させた。後硬化させた樹脂成形物について、熱機械分析装置（日立ハイテクサイエンス社製 ＴＭＡ７１００）を用いて２℃／分の昇温速度で３０℃〜３００℃の範囲で測定し、Ｔｇ前線膨張係数（ｐｐｍ）およびＴｇ後線膨張係数（ｐｐｍ）を求めた。Ｔｇ前線膨張係数は、３０℃での線膨張係数を示し、Ｔｇ後線膨張係数は、Ｔｇ＋１０℃〜Ｔｇ＋３０℃の範囲内の任意の温度での線膨張係数を示す。Ｔｇは、前述の測定方法により測定される値である。
[Linear expansion coefficient of cured product]
The thermosetting molding material was transfer molded at 175 ° C. for 120 seconds to produce a resin molded product (width 5 mm × length 5 mm × thickness 5 mm) and post-cured at 200 ° C. for 5 hours. The post-cured resin molded product was measured in the range of 30 ° C. to 300 ° C. at a rate of temperature increase of 2 ° C./min using a thermomechanical analyzer (TMA7100 manufactured by Hitachi High-Tech Science Co., Ltd.). ) And Tg post linear expansion coefficient (ppm). The Tg pre-linear expansion coefficient indicates a linear expansion coefficient at 30 ° C., and the post-Tg linear expansion coefficient indicates a linear expansion coefficient at an arbitrary temperature within the range of Tg + 10 ° C. to Tg + 30 ° C. Tg is a value measured by the measurement method described above.
［硬化物の吸水率］
熱硬化性成型材料を１７５℃、１２０秒の条件でトランスファー成形して円盤状の試験片（直径５０ｍｍ×厚さ５ｍｍ）を作製した。作製した試験片と純水（２０ｍＬ）をプレッシャークッカーに入れ、１２１℃のオーブンに２０時間入れた。その後、試験片の質量を測定し、以下の式により吸水率を算出した。
吸水率＝（オーブンに入れて２０時間後の試験片の質量−オーブンに入れる前の試験片の質量）／オーブンに入れる前の試験片の質量×１００
[Water absorption of cured product]
The thermosetting molding material was transfer molded at 175 ° C. for 120 seconds to prepare a disk-shaped test piece (diameter 50 mm × thickness 5 mm). The prepared test piece and pure water (20 mL) were placed in a pressure cooker and placed in an oven at 121 ° C. for 20 hours. Thereafter, the mass of the test piece was measured, and the water absorption was calculated according to the following formula.
Water absorption rate = (mass of test piece after 20 hours in the oven−mass of test piece before entering the oven) / mass of test piece before entering the oven × 100
＜アルデヒド基含有樹脂の製造＞
〔合成例１〕
（オルソヒドロキシベンズアルデヒドと４，４’−ビス（メトキシメチル）ビフェニルの反応：モル比＝０．４０）
温度計、攪拌機、冷却管を備えた内容量１Ｌの反応容器にオルソヒドロキシベンズアルデヒド８５０ｇ（６．９６７モル）、４，４’−ビス（メトキシメチル）ビフェニル６７４．５ｇ（２．７８７モル）、パラトルエンスルホン酸８．５ｇ（オルソヒドロキシベンズアルデヒドに対して１％）を仕込み、１６０℃まで昇温し、４時間反応を行った。反応で副生するメタノールは、系外へ除去した。反応終了後、中和、水洗を行い、未反応オルソヒドロキシベンズアルデヒドを除去し、アルデヒド含有ビフェニル樹脂を得た。得られた樹脂の軟化点は８１℃、１５０℃における溶融粘度は１．２Ｐであった。ゲル浸透クロマトグラフ分析（以下、ＧＰＣと略記することもある。）による質量平均分子量（Ｍｗ）は８１５、分散度（Ｍｗ／Ｍｎ）は１．４８であった。
<Manufacture of aldehyde group-containing resin>
[Synthesis Example 1]
(Reaction of orthohydroxybenzaldehyde and 4,4′-bis (methoxymethyl) biphenyl: molar ratio = 0.40)
Into a 1 L reaction vessel equipped with a thermometer, a stirrer, and a condenser, orthohydroxybenzaldehyde 850 g (6.967 mol), 4,4′-bis (methoxymethyl) biphenyl 674.5 g (2.787 mol), para 8.5 g of toluenesulfonic acid (1% with respect to orthohydroxybenzaldehyde) was charged, the temperature was raised to 160 ° C., and the reaction was performed for 4 hours. Methanol produced as a by-product in the reaction was removed out of the system. After completion of the reaction, neutralization and washing with water were performed to remove unreacted orthohydroxybenzaldehyde to obtain an aldehyde-containing biphenyl resin. The resulting resin had a softening point of 81 ° C. and a melt viscosity at 150 ° C. of 1.2 P. The mass average molecular weight (Mw) by gel permeation chromatographic analysis (hereinafter sometimes abbreviated as GPC) was 815, and the dispersity (Mw / Mn) was 1.48.
〔合成例２〕
（オルソヒドロキシベンズアルデヒドとパラキシレングリコールジメチルエーテルの反応：モル比＝０．４０）
温度計、攪拌機、冷却管を備えた内容量１Ｌの反応容器にオルソヒドロキシベンズアルデヒド８５０ｇ（６．９６７モル）、パラキシレングリコールジメチルエーテル４６２．６ｇ（２．７８７モル）、パラトルエンスルホン酸８．５ｇ（オルソヒドロキシベンズアルデヒドに対して１％）を仕込み、１６０℃まで昇温し、４時間反応を行った。反応で副生するメタノールは、系外へ除去した。反応終了後、中和、水洗を行い、未反応オルソヒドロキシベンズアルデヒドを除去し、アルデヒド含有キシリレン樹脂を得た。得られた樹脂の軟化点は８０℃、１５０℃における溶融粘度は１．７Ｐであった。ＧＰＣによる質量平均分子量（Ｍｗ）は７５６、分散度（Ｍｗ／Ｍｎ）は１．４４であった。
[Synthesis Example 2]
(Reaction of orthohydroxybenzaldehyde and para-xylene glycol dimethyl ether: molar ratio = 0.40)
850 g (6.967 mol) of orthohydroxybenzaldehyde, 462.6 g (2.787 mol) of paraxylene glycol dimethyl ether, and 8.5 g of paratoluenesulfonic acid (into a 1 L reaction vessel equipped with a thermometer, a stirrer, and a cooling tube ( 1%) with respect to orthohydroxybenzaldehyde was added, the temperature was raised to 160 ° C., and the reaction was carried out for 4 hours. Methanol produced as a by-product in the reaction was removed out of the system. After completion of the reaction, neutralization and water washing were performed to remove unreacted orthohydroxybenzaldehyde to obtain an aldehyde-containing xylylene resin. The resulting resin had a softening point of 80 ° C. and a melt viscosity at 150 ° C. of 1.7 P. The mass average molecular weight (Mw) by GPC was 756, and the dispersity (Mw / Mn) was 1.44.
＜アリル基含有樹脂の製造＞
〔合成例３〕
（アルデヒド基含有ビフェニル樹脂とアリルアミンの反応：変性率約３０モル％）
合成例１で得たアルデヒド含有ビフェニル樹脂１００．０ｇを、トルエン１００．０ｇに溶解し、８０℃まで昇温した。そこにアリルアミン７．６ｇを、発熱に注意しながら２時間かけて添加した。その後、使用したトルエンを１６０℃で除去し、アリル基含有樹脂Ａを得た。アリル基含有樹脂Ａの軟化点は８２．３℃、１５０℃における溶融粘度は３．６Ｐであった。ＧＰＣによる質量平均分子量（Ｍｗ）は９１３、分散度（Ｍｗ／Ｍｎ）は１．６５であった。１３Ｃ−核磁気共鳴分析（以下、ＮＭＲと略記することもある。）によるアルデヒド基変性率は３１モル％であった。
アルデヒド基変性率は、樹脂中のアルデヒド基とアリル基との合計に対するアリル基の割合を示す。
<Manufacture of allyl group-containing resin>
[Synthesis Example 3]
(Reaction of aldehyde group-containing biphenyl resin and allylamine: modification rate of about 30 mol%)
100.0 g of the aldehyde-containing biphenyl resin obtained in Synthesis Example 1 was dissolved in 100.0 g of toluene, and the temperature was raised to 80 ° C. Thereto was added 7.6 g of allylamine over 2 hours while paying attention to heat generation. Thereafter, the toluene used was removed at 160 ° C. to obtain an allyl group-containing resin A. The softening point of the allyl group-containing resin A was 82.3 ° C., and the melt viscosity at 150 ° C. was 3.6P. The mass average molecular weight (Mw) by GPC was 913, and the dispersity (Mw / Mn) was 1.65. The aldehyde group modification rate by 13 C-nuclear magnetic resonance analysis (hereinafter sometimes abbreviated as NMR) was 31 mol%.
The aldehyde group modification rate indicates the ratio of allyl groups to the total of aldehyde groups and allyl groups in the resin.
〔合成例４〕
（アルデヒド基含有ビフェニル樹脂とアリルアミンの反応：変性率約５０モル％）
合成例１で得たアルデヒド含有ビフェニル樹脂１００．０ｇを、トルエン１００．０ｇに溶解し、８０℃まで昇温した。そこにアリルアミン１２．７ｇを、発熱に注意しながら２時間かけて添加した。その後、使用したトルエンを１６０℃で除去し、アリル基含有樹脂Ｂを得た。アリル基含有樹脂Ｂの軟化点は７８．９℃、１５０℃における溶融粘度は２．５Ｐであった。ＧＰＣによる質量平均分子量（Ｍｗ）は９３５、分散度（Ｍｗ／Ｍｎ）は１．７０であった。ＮＭＲによるアルデヒド基変性率は５０モル％であった。
[Synthesis Example 4]
(Reaction of aldehyde group-containing biphenyl resin and allylamine: modification rate of about 50 mol%)
100.0 g of the aldehyde-containing biphenyl resin obtained in Synthesis Example 1 was dissolved in 100.0 g of toluene, and the temperature was raised to 80 ° C. Thereto, 12.7 g of allylamine was added over 2 hours while paying attention to heat generation. Thereafter, the used toluene was removed at 160 ° C. to obtain an allyl group-containing resin B. The allyl group-containing resin B had a softening point of 78.9 ° C and a melt viscosity at 150 ° C of 2.5P. The mass average molecular weight (Mw) by GPC was 935, and the dispersity (Mw / Mn) was 1.70. The aldehyde group modification rate by NMR was 50 mol%.
〔合成例５〕
（アルデヒド基含有キシリレン樹脂とアリルアミンの反応：変性率約３０モル％）
合成例２で得たアルデヒド含有キシリレン樹脂１００．０ｇを、トルエン１００．０ｇに溶解し、８０℃まで昇温した。そこにアリルアミン９．９ｇを、発熱に注意しながら２時間かけて添加した。その後、使用したトルエンを１６０℃で除去し、アリル基含有樹脂Ｃを得た。アリル基含有樹脂Ｃの軟化点は８０．６℃、１５０℃における溶融粘度は２．９Ｐであった。ＧＰＣによる質量平均分子量（Ｍｗ）は８８１、分散度（Ｍｗ／Ｍｎ）は１．５９であった。ＮＭＲによるアルデヒド基変性率は３２モル％であった。
[Synthesis Example 5]
(Reaction of aldehyde group-containing xylylene resin and allylamine: modification rate of about 30 mol%)
100.0 g of the aldehyde-containing xylylene resin obtained in Synthesis Example 2 was dissolved in 100.0 g of toluene, and the temperature was raised to 80 ° C. Thereto, 9.9 g of allylamine was added over 2 hours while paying attention to heat generation. Thereafter, the used toluene was removed at 160 ° C. to obtain an allyl group-containing resin C. The softening point of the allyl group-containing resin C was 80.6 ° C., and the melt viscosity at 150 ° C. was 2.9 P. The mass average molecular weight (Mw) by GPC was 881, and the dispersity (Mw / Mn) was 1.59. The aldehyde group modification rate by NMR was 32 mol%.
＜比較用のフェノールアラルキル樹脂の合成＞
〔合成例６〕
（フェノールとパラキシレングリコールジメチルエーテルとの反応：一般的な封止用途のフェノールキシレンアラルキル樹脂）
温度計、攪拌機、冷却管を備えた内容量１Ｌのガラス製フラスコにフェノール２３５ｇ（２．５モル）、パラキシレングリコールジメチルエーテル１６６ｇ（１．０モル）を入れ、この溶液にパラトルエンスルホン酸０．４ｇを添加し、１５０℃にて３時間反応させた。このとき発生するメタノールは系外へ除去した。反応終了後、９５℃まで冷却し、４８％ＫＯＨ水溶液で中和した。未反応モノマーを除去した後、水洗し、多価ヒドロキシ樹脂Ｄを得た。多価ヒドロキシ樹脂Ｄの軟化点は６９℃、１５０℃における溶融粘度は０．２Ｐであった。ＧＰＣによる質量平均分子量（Ｍｗ）は８０１、分散度（Ｍｗ／Ｍｎ）は１．５３であった。
<Synthesis of phenol aralkyl resin for comparison>
[Synthesis Example 6]
(Reaction of phenol with para-xylene glycol dimethyl ether: phenol-xylene aralkyl resin for general sealing applications)
235 g (2.5 mol) of phenol and 166 g (1.0 mol) of paraxylene glycol dimethyl ether were placed in a 1 L glass flask equipped with a thermometer, a stirrer, and a cooling tube. 4 g was added and reacted at 150 ° C. for 3 hours. Methanol generated at this time was removed out of the system. After completion of the reaction, the reaction mixture was cooled to 95 ° C. and neutralized with a 48% KOH aqueous solution. After removing the unreacted monomer, it was washed with water to obtain a polyvalent hydroxy resin D. The softening point of the polyvalent hydroxy resin D was 69 ° C., and the melt viscosity at 150 ° C. was 0.2P. The mass average molecular weight (Mw) by GPC was 801, and the degree of dispersion (Mw / Mn) was 1.53.
〔合成例７〕
（フェノールと４，４’−ビス（メトキシメチル）ビフェニルとの反応：一般的な封止用途のフェノールビフェニルアラルキル樹脂）
温度計、攪拌機、冷却管を備えた内容量１Ｌのガラス製フラスコにフェノール３７６ｇ（４．０モル）、４，４’−ビス（メトキシメチル）ビフェニル２４２ｇ（１．０モル）を入れ、この溶液にパラトルエンスルホン酸０．６ｇを添加し、１５０℃にて３時間反応させた。このとき発生するメタノールは系外へ除去した。反応終了後、９５℃まで冷却し、４８％ＫＯＨ水溶液で中和した。未反応モノマーを除去した後、水洗し、多価ヒドロキシ樹脂Ｅを得た。多価ヒドロキシ樹脂Ｅの軟化点は６９℃、１５０℃における溶融粘度は０．９Ｐであった。ＧＰＣによる質量平均分子量（Ｍｗ）は６１６、分散度（Ｍｗ／Ｍｎ）は１．２３であった。
[Synthesis Example 7]
(Reaction of phenol with 4,4'-bis (methoxymethyl) biphenyl: phenol biphenyl aralkyl resin for general sealing applications)
376 g (4.0 mol) of phenol and 242 g (1.0 mol) of 4,4′-bis (methoxymethyl) biphenyl were placed in a 1 L glass flask equipped with a thermometer, stirrer and condenser, and this solution Was added with 0.6 g of paratoluenesulfonic acid and reacted at 150 ° C. for 3 hours. Methanol generated at this time was removed out of the system. After completion of the reaction, the reaction mixture was cooled to 95 ° C. and neutralized with a 48% KOH aqueous solution. After removing the unreacted monomer, it was washed with water to obtain a polyvalent hydroxy resin E. The softening point of the polyvalent hydroxy resin E was 69 ° C., and the melt viscosity at 150 ° C. was 0.9P. The mass average molecular weight (Mw) by GPC was 616, and the dispersity (Mw / Mn) was 1.23.
＜熱硬化性成形材料の調製および評価＞
〔実施例１〜１２、比較例１〜４〕
表１〜２に示す調合で各材料を、２軸ミキシングロール（ダイシン機械社製）を用いて、１００℃で熱溶融混合し、冷却して固形の熱硬化性成形材料を得た。
表１〜２中、硬化剤Ａ〜Ｅはそれぞれ、上記アリル基含有樹脂Ａ〜Ｃ、多価ヒドロキシ樹脂Ｄ、Ｅである。エポキシ樹脂１は、フェノールビフェニレン型エポキシ樹脂（日本化薬製、製品名：ＮＣ３０００Ｈ）である。エポキシ樹脂２は、トリフェニルメタン型エポキシ樹脂（日本化薬製、製品名：ＥＰＰＮ−５０２Ｈ）である。
球状シリカの配合量は、カルナバワックスを除く仕込量全量に対する球状シリカの割合が８３％になる量とした。２−メチルイミダゾールの配合量は、実施例１〜１２では全樹脂量（エポキシ樹脂、硬化剤）に対して１％になる量とし、比較例１〜４ではエポキシ樹脂に対して２％になる量とした。カルナバワックスの配合量は、カルナバワックスを除く仕込量全量に対して１％になる量とした。
得られた熱硬化性成形材料について、前記の手順で、硬化物のガラス転移温度、５％熱分解温度、線膨張係数（Ｔｇ前、Ｔｇ後）、吸水率を測定した。結果を表１〜２に示す。
<Preparation and evaluation of thermosetting molding material>
[Examples 1 to 12, Comparative Examples 1 to 4]
The materials shown in Tables 1 and 2 were melted and mixed at 100 ° C. using a biaxial mixing roll (manufactured by Daishin Machinery Co., Ltd.) and cooled to obtain a solid thermosetting molding material.
In Tables 1 and 2, curing agents A to E are the allyl group-containing resins A to C and the polyvalent hydroxy resins D and E, respectively. The epoxy resin 1 is a phenol biphenylene type epoxy resin (manufactured by Nippon Kayaku, product name: NC3000H). The epoxy resin 2 is a triphenylmethane type epoxy resin (manufactured by Nippon Kayaku, product name: EPPN-502H).
The blending amount of the spherical silica was such that the ratio of the spherical silica to the total charged amount excluding carnauba wax was 83%. The blending amount of 2-methylimidazole is 1% with respect to the total resin amount (epoxy resin, curing agent) in Examples 1 to 12, and 2% with respect to the epoxy resin in Comparative Examples 1 to 4. The amount. The blending amount of carnauba wax was 1% with respect to the total charged amount excluding carnauba wax.
With respect to the obtained thermosetting molding material, the glass transition temperature, 5% thermal decomposition temperature, linear expansion coefficient (before Tg, after Tg), and water absorption rate of the cured product were measured by the above procedure. The results are shown in Tables 1-2.
表１に示すとおり、実施例１〜６の熱硬化性成形材料の硬化物は、ガラス転移温度および５％熱分解温度が高く、線膨張係数および吸水率が低かった。一方、比較例１〜２の熱硬化性成形材料の硬化物は、実施例１〜６に比べて、ガラス転移温度が低く、線膨張係数が高かった。特に比較例１では、５％熱分解温度が低く、吸水率が高かった。
表２に示すとおり、エポキシ樹脂の種類を変更した実施例７〜１２、比較例３〜４の評価結果においても、実施例１〜６、比較例１〜２の評価結果と同様の傾向が見られた。
また、表１〜２の結果から、アリル基含有樹脂に対するエポキシ樹脂の配合量が少ない方が、５％熱分解温度が高く、吸水率が低い傾向にあること、３官能以上の多官能のエポキシ樹脂よりも２官能のエポキシ樹脂を用いた方が、５％熱分解温度が高く、吸水率が低い傾向にあること、が確認できた。
As shown in Table 1, the cured products of the thermosetting molding materials of Examples 1 to 6 had high glass transition temperature and 5% thermal decomposition temperature, and low linear expansion coefficient and water absorption. On the other hand, the hardened | cured material of the thermosetting molding material of Comparative Examples 1-2 was low in glass transition temperature, and its linear expansion coefficient was high compared with Examples 1-6. Particularly in Comparative Example 1, the 5% thermal decomposition temperature was low and the water absorption was high.
As shown in Table 2, also in the evaluation results of Examples 7 to 12 and Comparative Examples 3 to 4 in which the type of epoxy resin was changed, the same tendency as the evaluation results of Examples 1 to 6 and Comparative Examples 1 to 2 was observed. It was.
In addition, from the results of Tables 1 and 2, the smaller the amount of the epoxy resin relative to the allyl group-containing resin, the higher the 5% thermal decomposition temperature and the lower the water absorption rate, the trifunctional or higher polyfunctional epoxy. It was confirmed that the bifunctional epoxy resin was higher than the resin and the 5% thermal decomposition temperature was higher and the water absorption rate tended to be lower.
本発明の熱硬化性成形材料によれば、高ガラス転移温度、高熱分解温度、低線膨張係数、低吸水性の硬化物が得られる。そのため、本発明の熱硬化性成形材料は、高機能性高分子材料として極めて有用であり、熱的、電気的に優れた材料として、半導体封止材料、電子部品の封止用樹脂材料、電気絶縁材料、銅張り積層板用樹脂材料、ビルドアップ積層板材料、レジスト材料、液晶のカラーフィルター用樹脂材料、塗料、各種コーティング剤、接着剤、ＦＲＰ材料等の幅広い用途に使用することができる。 According to the thermosetting molding material of the present invention, a cured product having a high glass transition temperature, a high thermal decomposition temperature, a low linear expansion coefficient, and a low water absorption is obtained. Therefore, the thermosetting molding material of the present invention is extremely useful as a highly functional polymer material, and as a thermally and electrically excellent material, a semiconductor sealing material, a resin material for sealing electronic parts, It can be used for a wide range of applications such as insulating materials, copper-clad laminate resin materials, build-up laminate materials, resist materials, liquid crystal color filter resin materials, paints, various coating agents, adhesives, and FRP materials.
Claims (3)
前記アリル基含有樹脂が、下記式（１）で表される構成単位（１）および下記式（２）で表される構成単位（２）のいずれか一方または両方と、下記式（３）で表される構成単位（３）と、下記式（４）で表される構成単位（４）と、を有し、
前記構成単位（２）と前記構成単位（４）との合計の含有量が、前記構成単位（１）と前記構成単位（２）と前記構成単位（３）と前記構成単位（４）との合計に対して１０〜８０モル％であり、
前記エポキシ樹脂の含有量が、前記アリル基含有樹脂に対して５〜３０質量％である熱硬化性成形材料。
The allyl group-containing resin is either one or both of the structural unit (1) represented by the following formula (1) and the structural unit (2) represented by the following formula (2), and the following formula (3): The structural unit (3) represented, and the structural unit (4) represented by the following formula (4),
The total content of the structural unit (2) and the structural unit (4) is the structural unit (1), the structural unit (2), the structural unit (3), and the structural unit (4). Ri 10 to 80 mol% der with respect to the total,
The content of the epoxy resin, the allyl group-containing 5 to 30% by mass Ru thermosetting molding material to the resin.
モノヒドロキシベンズアルデヒドおよびモノヒドロキシナフトアルデヒドからなる群から選ばれる少なくとも１種のモノマー（Ａ）と、下記式（ｂ１）で表される化合物および下記式（ｂ２）で表される化合物からなる群から選ばれる少なくとも１種の架橋剤（Ｂ）とを反応させて、前記構成単位（１）と前記構成単位（３）とを有するアルデヒド基含有樹脂を得る工程と、
前記アルデヒド基含有樹脂と、前記アルデヒド基含有樹脂のアルデヒド基に対して１０〜８０モル％のアリルアミンとを反応させて前記アリル基含有樹脂を得る工程と、
前記アリル基含有樹脂と前記エポキシ樹脂とを混合する工程と、
を有する熱硬化性成形材料の製造方法。
Selected from the group consisting of at least one monomer (A) selected from the group consisting of monohydroxybenzaldehyde and monohydroxynaphthaldehyde, a compound represented by the following formula (b1) and a compound represented by the following formula (b2) Reacting with at least one crosslinking agent (B) to obtain an aldehyde group-containing resin having the structural unit (1) and the structural unit (3);
Reacting the aldehyde group-containing resin with 10 to 80 mol% of allylamine with respect to the aldehyde group of the aldehyde group-containing resin to obtain the allyl group-containing resin;
A step of mixing the epoxy resin and the allyl group-containing resin,
A method for producing a thermosetting molding material.
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