JP6837354B2 - Manufacturing method of allyl group-containing resin, resin varnish and laminated board - Google Patents
Manufacturing method of allyl group-containing resin, resin varnish and laminated board Download PDFInfo
- Publication number
- JP6837354B2 JP6837354B2 JP2017040557A JP2017040557A JP6837354B2 JP 6837354 B2 JP6837354 B2 JP 6837354B2 JP 2017040557 A JP2017040557 A JP 2017040557A JP 2017040557 A JP2017040557 A JP 2017040557A JP 6837354 B2 JP6837354 B2 JP 6837354B2
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- JP
- Japan
- Prior art keywords
- structural unit
- resin
- allyl group
- group
- containing resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005989 resin Polymers 0.000 title claims description 322
- 239000011347 resin Substances 0.000 title claims description 322
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 title claims description 215
- 239000002966 varnish Substances 0.000 title claims description 88
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- -1 maleimide compound Chemical class 0.000 claims description 82
- 239000000463 material Substances 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 35
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000001624 naphthyl group Chemical group 0.000 claims description 10
- 239000000047 product Substances 0.000 description 69
- 238000006243 chemical reaction Methods 0.000 description 68
- 125000003172 aldehyde group Chemical group 0.000 description 49
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 39
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 28
- 239000000178 monomer Substances 0.000 description 27
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 26
- 239000003431 cross linking reagent Substances 0.000 description 25
- 239000011521 glass Substances 0.000 description 24
- 239000007787 solid Substances 0.000 description 23
- 239000003795 chemical substances by application Substances 0.000 description 20
- 239000002585 base Substances 0.000 description 19
- 239000007809 chemical reaction catalyst Substances 0.000 description 18
- 230000009477 glass transition Effects 0.000 description 18
- 239000004305 biphenyl Substances 0.000 description 17
- 235000010290 biphenyl Nutrition 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 16
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 15
- 239000004744 fabric Substances 0.000 description 15
- 238000005227 gel permeation chromatography Methods 0.000 description 15
- 238000005979 thermal decomposition reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 14
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 238000006266 etherification reaction Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000470 constituent Substances 0.000 description 10
- 239000000155 melt Substances 0.000 description 10
- SMQUZDBALVYZAC-UHFFFAOYSA-N ortho-hydroxybenzaldehyde Natural products OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000001299 aldehydes Chemical class 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 229920003192 poly(bis maleimide) Polymers 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 8
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 8
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 8
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 238000004925 denaturation Methods 0.000 description 7
- 230000036425 denaturation Effects 0.000 description 7
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000020169 heat generation Effects 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- 239000002798 polar solvent Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 230000008707 rearrangement Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 5
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 5
- 239000011151 fibre-reinforced plastic Substances 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 239000002648 laminated material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 238000006462 rearrangement reaction Methods 0.000 description 5
- 125000006839 xylylene group Chemical group 0.000 description 5
- NTCCNERMXRIPTR-UHFFFAOYSA-N 2-hydroxy-1-naphthaldehyde Chemical compound C1=CC=CC2=C(C=O)C(O)=CC=C21 NTCCNERMXRIPTR-UHFFFAOYSA-N 0.000 description 4
- 0 CCC(*N)*(*)OCC=C Chemical compound CCC(*N)*(*)OCC=C 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 125000004849 alkoxymethyl group Chemical group 0.000 description 4
- IYJMFNNRVITCDG-UHFFFAOYSA-N biphenylene;phenol Chemical group OC1=CC=CC=C1.C1=CC=C2C3=CC=CC=C3C2=C1 IYJMFNNRVITCDG-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 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 2
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- QDFXRVAOBHEBGJ-UHFFFAOYSA-N 3-(cyclononen-1-yl)-4,5,6,7,8,9-hexahydro-1h-diazonine Chemical compound C1CCCCCCC=C1C1=NNCCCCCC1 QDFXRVAOBHEBGJ-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
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-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
- 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-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
- 230000009471 action Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000005336 allyloxy group Chemical group 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
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 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 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
- 239000003086 colorant Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012772 electrical insulation material Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-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
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- NWZKSTUZKJCCMK-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)acetonitrile Chemical compound CC1=NC=CN1CC#N NWZKSTUZKJCCMK-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-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
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-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
- SIQHSJOKAUDDLN-UHFFFAOYSA-N 2-methyl-1-propylimidazole Chemical compound CCCN1C=CN=C1C SIQHSJOKAUDDLN-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-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
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- SZUPZARBRLCVCB-UHFFFAOYSA-N 3-(2-undecylimidazol-1-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC=CN1CCC#N SZUPZARBRLCVCB-UHFFFAOYSA-N 0.000 description 1
- VXPSQDAMFATNNG-UHFFFAOYSA-N 3-[2-(2,5-dioxopyrrol-3-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C(=CC=CC=2)C=2C(NC(=O)C=2)=O)=C1 VXPSQDAMFATNNG-UHFFFAOYSA-N 0.000 description 1
- MOSSLXZUUKTULI-UHFFFAOYSA-N 3-[3-(2,5-dioxopyrrol-3-yl)-4-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC=C(C=2C(NC(=O)C=2)=O)C=C1C1=CC(=O)NC1=O MOSSLXZUUKTULI-UHFFFAOYSA-N 0.000 description 1
- QCMKXHXKNIOBBC-UHFFFAOYSA-N 3-fluoroprop-1-ene Chemical compound FCC=C QCMKXHXKNIOBBC-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-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
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 238000005821 Claisen rearrangement reaction Methods 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- HFEHLDPGIKPNKL-UHFFFAOYSA-N allyl iodide Chemical compound ICC=C HFEHLDPGIKPNKL-UHFFFAOYSA-N 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
- 150000001555 benzenes Chemical group 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 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
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- BNHFWQQYLUPDOG-UHFFFAOYSA-N lithium;1,2,2,3-tetramethylpiperidine Chemical compound [Li].CC1CCCN(C)C1(C)C BNHFWQQYLUPDOG-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- NAKOELLGRBLZOF-UHFFFAOYSA-N phenoxybenzene;pyrrole-2,5-dione Chemical compound O=C1NC(=O)C=C1.O=C1NC(=O)C=C1.C=1C=CC=CC=1OC1=CC=CC=C1 NAKOELLGRBLZOF-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 230000004580 weight loss Effects 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
Description
本発明は、アリル基含有樹脂、樹脂ワニスおよび積層板の製造方法に関する。 The present invention relates to a method for producing an allyl group-containing resin, a resin varnish, and a laminated board.
従来、電子製品に用いられる部材、例えば絶縁性の積層板やその片面又は両面に銅箔が積層した積層板（銅張積層板）に、エポキシ樹脂が用いられている。積層板は、例えばエポキシ樹脂、硬化剤等が溶剤に溶解した樹脂ワニスをガラスクロス等の繊維質基材に含浸させ、乾燥してプリプレグとし、これを単独で又は複数枚を重ねて熱プレスすることで製造される。エポキシ樹脂の硬化剤としては、フェノールとホルムアルデヒドを用いたフェノールノボラック樹脂が広く使用されている。樹脂ワニスの溶剤としては一般に、メチルエチルケトン等の極性溶剤が用いられている。 Conventionally, an epoxy resin has been used for a member used in an electronic product, for example, an insulating laminated board or a laminated board (copper-clad laminated board) in which copper foil is laminated on one side or both sides thereof. The laminated board is made by impregnating a fibrous base material such as glass cloth with a resin varnish in which an epoxy resin, a curing agent or the like is dissolved in a solvent, drying the prepreg, and heat-pressing the prepreg alone or in combination of two or more. Manufactured by As a curing agent for the epoxy resin, a phenol novolac resin using phenol and formaldehyde is widely used. As the solvent for the resin varnish, a polar solvent such as methyl ethyl ketone is generally used.
近年、電子製品の高性能化が図られる中、積層板を構成する樹脂にさらなる高ガラス転移温度、低誘電率、低誘電正接が求められている。
エポキシ樹脂をフェノールノボラック樹脂で硬化させた硬化物の電気特性（低誘電率、低誘電正接）は、汎用の電子製品に要求されるレベルを満たすことはできても、高性能電子製品（スマートフォン、タブレット等）に要求されるレベルを満たすことは困難である。また、この硬化物は、近年開発が進んでいるパワーデバイスに用いるにはガラス転移温度が低く、熱膨張率も高い。
In recent years, as the performance of electronic products has been improved, the resin constituting the laminated board is required to have a higher glass transition temperature, a lower dielectric constant, and a lower dielectric loss tangent.
Although the electrical characteristics (low dielectric constant, low dielectric loss tangent) of the cured product obtained by curing the epoxy resin with phenol novolac resin can meet the levels required for general-purpose electronic products, high-performance electronic products (smartphones, smartphones, etc.) It is difficult to meet the level required for tablets, etc.). In addition, this cured product has a low glass transition temperature and a high coefficient of thermal expansion for use in power devices that have been developed in recent years.
非特許文献１には、ビスマレイミド化合物をアリルノボラック型フェノール樹脂で硬化させた多価フェノール硬化ビスマレイミド樹脂が、高ガラス転移温度、高熱分解温度、低熱膨張率を示すことが報告されている。 Non-Patent Document 1 reports that a polyhydric phenol-cured bismaleimide resin obtained by curing a bismaleimide compound with an allyl novolac type phenol resin exhibits a high glass transition temperature, a high thermal decomposition temperature, and a low thermal expansion rate.
しかし、前記多価フェノール硬化ビスマレイミド樹脂は、誘電率、誘電正接が高い。また、マレイミド硬化由来の硬さから、銅箔、繊維質基材等との密着性が悪い問題がある。 However, the polyvalent phenol-cured bismaleimide resin has a high dielectric constant and dielectric loss tangent. Further, due to the hardness derived from the curing of maleimide, there is a problem that the adhesion to the copper foil, the fibrous base material and the like is poor.
本発明は、上記事情に鑑みてなされたものであって、マレイミド化合物と組み合わせたときに、低誘電率、低誘電正接、高密着性の硬化物が得られるアリル基含有樹脂、前記アリル基含有樹脂を用いた樹脂ワニスおよび積層板の製造方法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 is an allyl group-containing resin containing an allyl group, which can obtain a cured product having a low dielectric constant, a low dielectric loss tangent, and a high adhesion when combined with a maleimide compound. It is an object of the present invention to provide a method for producing a resin varnish and a laminated board using a resin.
本発明は、以下の態様を有する。
〔１〕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）および下記式（４）で表される構成単位（４）のうちの少なくとも前記構成単位（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５０〜１００モル％であるアリル基含有樹脂。
The present invention has the following aspects.
[1] 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 configuration represented by the following formula (3). It has at least the structural unit (4) of the unit (3) 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 same as that of the structural unit (1), the structural unit (2), the structural unit (3), and the structural unit (4). Allyl group-containing resin in an amount of 50 to 100 mol% based on the 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 independently represent 0 or 1, respectively, and − * and − ** indicates a bonder, respectively. -* Is bonded to another structural unit, and-(R) p -**-** is bonded to another structural unit or hydrogen atom when p is 0, and when p is 1. Is bound to another building block, and-(R) q -**-** is bound to another building block or hydrogen atom when q is 0, and other when q is 1. Combine into building blocks. ]
〔２〕下記式（１）で表される構成単位（１）、下記式（２）で表される構成単位（２）および下記式（２Ａ）で表される構成単位（２Ａ）のうちの少なくとも１種と、下記式（３）で表される構成単位（３）、下記式（４）で表される構成単位（４）および下記式（４Ａ）で表される構成単位（４Ａ）のうちの少なくとも前記構成単位（４Ａ）と、を有し、
前記構成単位（２）と前記構成単位（２Ａ）と前記構成単位（４）と前記構成単位（４Ａ）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（２Ａ）と前記構成単位（３）と前記構成単位（４）と前記構成単位（４Ａ）との合計に対して５０〜１００モル％であるアリル基含有樹脂。
[2] Of the structural unit (1) represented by the following formula (1), the structural unit (2) represented by the following formula (2), and the structural unit (2A) represented by the following formula (2A). Of at least one type, a structural unit (3) represented by the following formula (3), a structural unit (4) represented by the following formula (4), and a structural unit (4A) represented by the following formula (4A). It has at least the above-mentioned structural unit (4A).
The total content of the structural unit (2), the structural unit (2A), the structural unit (4), and the structural unit (4A) is the total content of the structural unit (1), the structural unit (2), and the structural unit (2). An allyl group-containing resin that is 50 to 100 mol% with respect to the total of the structural unit (2A), the structural unit (3), the structural unit (4), and the structural unit (4A).
［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 independently represent 0 or 1, respectively, and − * and − ** indicates a bonder, respectively. -* Is bonded to another structural unit, and-(R) p -**-** is bonded to another structural unit or hydrogen atom when p is 0, and when p is 1. Is bound to another building block, and-(R) q -**-** is bound to another building block or hydrogen atom when q is 0, and other when q is 1. Combine into building blocks. ]
〔３〕前記構成単位（２Ａ）と前記構成単位（４Ａ）との合計の含有量が、前記構成単位（２）と前記構成単位（２Ａ）と前記構成単位（４）と前記構成単位（４Ａ）との合計に対して８０〜１００モル％である〔２〕に記載のアリル基含有樹脂。
〔４〕マレイミド基を２以上有するマレイミド化合物と、前記〔１〕〜〔３〕のいずれかに記載のアリル基含有樹脂と、溶剤とを含む樹脂ワニス。
〔５〕前記マレイミド化合物のマレイミド基と前記アリル基含有樹脂のアリル基とのモル比（マレイミド基／アリル基）が、０．５〜１．５である、〔４〕に記載の樹脂ワニス。
〔６〕前記〔４〕または〔５〕に記載の樹脂ワニスを繊維質基材に含浸させ、前記樹脂ワニスが含浸した繊維質基材を加熱加圧し、硬化させて積層板を得る、積層板の製造方法。
[3] The total content of the structural unit (2A) and the structural unit (4A) is the structural unit (2), the structural unit (2A), the structural unit (4), and the structural unit (4A). ), The allyl group-containing resin according to [2], which is 80 to 100 mol%.
[4] A resin varnish containing a maleimide compound having two or more maleimide groups, the allyl group-containing resin according to any one of the above [1] to [3], and a solvent.
[5] The resin varnish according to [4], wherein the molar ratio (maleimide group / allyl group) of the maleimide group of the maleimide compound to the allyl group of the allyl group-containing resin is 0.5 to 1.5.
[6] A laminated board obtained by impregnating a fibrous base material with the resin varnish according to the above [4] or [5], heating and pressurizing the fibrous base material impregnated with the resin varnish, and curing the laminated board. Manufacturing method.
本発明によれば、マレイミド化合物と組み合わせたときに、低誘電率、低誘電正接、高密着性の硬化物が得られるアリル基含有樹脂、前記アリル基含有樹脂を用いた樹脂ワニスおよび積層板の製造方法を提供できる。 According to the present invention, an allyl group-containing resin that can obtain a cured product having a low dielectric constant, a low dielectric loss tangent, and a high adhesion when combined with a maleimide compound, a resin varnish using the allyl group-containing resin, and a laminated board. A manufacturing method can be provided.
≪第一の態様のアリル基含有樹脂≫
本発明の第一の態様のアリル基含有樹脂（以下、「アリル基含有樹脂（ｉ）」ともいう。）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）および下記式（４）で表される構成単位（４）のうちの少なくとも前記構成単位（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 of the first aspect >>
The allyl group-containing resin of the first aspect of the present invention (hereinafter, also referred to as “allyl group-containing resin (i)”) is a structural unit (1) represented by the following formula (1) and the following formula (2). One or both of the structural units (2) represented by, and at least one of the structural units (3) represented by the following formula (3) and the structural unit (4) represented by the following formula (4). It has the structural unit (4). “Constituent unit” indicates a unit constituting the polymer.
アリル基含有樹脂（ｉ）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（ｉ）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 (i) is derived from the structural units (1) to (4) and contains a plurality of Ars. In the allyl group-containing resin (i), a plurality of Ars are bonded to each other via one R and are not directly bonded to each other.
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 of the structural unit (3) or (4) is the bond extending from R of the structural unit (1) or (2), and another structural unit (3) in which at least one of p and q is 1. Alternatively, it bonds to a bond extending from R in (4) or a hydrogen atom.
A 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 a 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 (R) p -** where p is 0 and (R) q -** where q is 0. Is one of. 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（ｉ）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（ｉ）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。
アリル基含有樹脂（ｉ）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。アリル基含有樹脂（ｉ）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 a benzene ring is preferable.
R may be a group represented by the formula (r1) or a group represented by the formula (r2).
In the above 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 (i) is produced by the production method (I) described later, it is represented by the formula (r1). The 4-position and 4'-position are preferable from the viewpoint that the reactivity of the cross-linking agent (B) corresponding to the group to be formed with the monomer (A) is good.
In the above formula (r2), the bonding positions of the two methylene groups on the benzene ring are not particularly limited, but when the allyl group-containing resin (i) is produced by the production method (I) described later, it is represented by the formula (r1). The para position is preferable from the viewpoint that the reactivity of the cross-linking agent (B) corresponding to the group to be formed with the monomer (A) is good.
The plurality of Ars contained in the allyl group-containing resin (i) may be the same or different. When the allyl group-containing resin (i) contains a plurality of Rs, the plurality of Rs 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 a structural unit represented by the following formulas (1-1), (1-2) or (1-3). Among these, the structural unit represented by the 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（ｉ）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（ｉ）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 positions of the -R- * and aldehyde groups in the benzene ring of the structural unit represented by the formula (1-1) are not particularly limited.
The bonding positions of the -R- * and aldehyde groups in the naphthalene ring of the structural unit represented by the formula (1-2) or (1-3) are not particularly limited. For example, in the formula (1-2), when the position where the hydroxy group is bonded is set to the 1-position, -R- * or the aldehyde group may be bonded at any of the 2 to 8 positions. In the formula (1-3), when the position where the hydroxy group is bonded is set to the 2-position, -R- * or the aldehyde group may be bonded at any of the 1st, 3rd to 8th positions.
The structural unit (1) is preferably a structural unit represented by the formula (1-1) in which the bonding position of the aldehyde group is the ortho position with respect to the hydroxy group. With such a structural unit, when the allyl group-containing resin (i) is produced by the production method (I) described later, a cross-linking agent for the monomer (A) corresponding to the structural unit represented by the formula (1-1). It has good reactivity with (B), and the monomer (A) can be easily recovered and recycled.
The structural unit (1) contained in the allyl group-containing resin (i) 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）におけるヒドロキシ基（−ＯＨ）が−Ｏ−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）におけるヒドロキシ基（−ＯＨ）が−Ｏ−ＣＨ２−ＣＨ＝ＣＨ２に変換された構造の構成単位が好ましい。アルデヒド基の好ましい結合位置は前記と同様である。
アリル基含有樹脂（ｉ）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 hydroxy group (-OH) in the above formulas (1-1), (1-2) or (1-3) is converted to -O-CH 2 -CH = CH 2. The structural unit of the structure is mentioned. Among these, a structural unit having a structure in which the hydroxy group (-OH) in the formula (1-1) is converted to -O-CH 2 -CH = CH 2 is preferable. The preferred bonding position of the aldehyde group is the same as described above.
The structural unit (2) contained in the allyl group-containing resin (i) 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 a structural unit represented by the following formula (3-1), (3-2) or (3-3). Among these, the structural unit represented by the 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（ｉ）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（ｉ）に含まれる構成単位（３）は１種でも２種以上でもよい。
The bonding positions of − *, − (R) p − **, − (R) q − **, and the aldehyde group in the benzene ring of the structural unit represented by the formula (3-1) are not particularly limited.
The bond positions of-*,-(R) p -**,-(R) q -**, and aldehyde groups in the naphthalene ring of the structural unit represented by the formula (3-2) or (3-3) are There is no particular limitation. For example, in the formula (3-2), when the position where the hydroxy group is bonded is set to the 1-position, -R- * or the aldehyde group may be bonded at any of the 2 to 8 positions. In the formula (3-3), when the position where the hydroxy group is bonded is set to the 2-position, -R- * or the aldehyde group may be bonded at any of the 1st, 3rd to 8th positions.
As the structural unit (3), a structural unit represented by the formula (3-1) in which the bond position of the aldehyde group is ortho-position with respect to the hydroxy group is preferable. With such a structural unit, when the allyl group-containing resin (i) is produced by the production method (I) described later, a cross-linking agent for the monomer (A) corresponding to the structural unit represented by the formula (3-1). It has good reactivity with (B), and the monomer (A) can be easily recovered and recycled.
The structural unit (3) contained in the allyl group-containing resin (i) 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）におけるヒドロキシ基（−ＯＨ）が−Ｏ−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）におけるヒドロキシ基（−ＯＨ）が−Ｏ−ＣＨ２−ＣＨ＝ＣＨ２に変換された構造の構成単位が好ましい。アルデヒド基の好ましい結合位置は前記と同様である。
アリル基含有樹脂（ｉ）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 hydroxy group (-OH) in the above formulas (3-1), (3-2) or (3-3) is converted to -O-CH 2 -CH = CH 2. The structural unit of the structure is mentioned. Among these, a structural unit having a structure in which the hydroxy group (-OH) in the formula (3-1) is converted to -O-CH 2 -CH = CH 2 is preferable. The preferred bonding position of the aldehyde group is the same as described above.
The structural unit (4) contained in the allyl group-containing resin (i) may be one type or two or more types.
アリル基含有樹脂（ｉ）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 (i) has a configuration other than the structural unit (1), the structural unit (2), the structural unit (3), and the structural unit (4), if necessary, as long as the effects of the present invention are not impaired. It may have additional units.
アリル基含有樹脂（ｉ）において、構成単位（２）と構成単位（４）との合計の含有量は、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（１００モル％）に対して５０〜１００モル％であり、７０〜１００モル％が好ましく、８０〜１００モル％が特に好ましい。この割合は、アリル基含有樹脂（ｉ）中のＡｒの総モル数（１００モル％）に対するアリル基のモル数の割合（モル％）に等しい。この割合が５０モル％以上であれば、アリル基含有樹脂（ｉ）をマレイミド硬化剤として用いた時に、硬化速度が良好である。また、得られる硬化物が、高ガラス転移温度、高熱分解温度、低誘電率、低誘電正接、高密着性を示す。 In the allyl group-containing resin (i), 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). ), It is 50 to 100 mol%, preferably 70 to 100 mol%, and particularly preferably 80 to 100 mol% with respect to the total (100 mol%). This ratio is equal to the ratio of the number of moles of allyl group (mol%) to the total number of moles of Ar (100 mol%) in the allyl group-containing resin (i). When this ratio is 50 mol% or more, the curing rate is good when the allyl group-containing resin (i) is used as the maleimide curing agent. Further, the obtained cured product exhibits a high glass transition temperature, a high thermal decomposition temperature, a low dielectric constant, a low dielectric loss tangent, and a high adhesion.
アリル基含有樹脂（ｉ）において、アリル基含有樹脂（ｉ）を構成する重合体１分子あたりの構成単位（１）と構成単位（２）と構成単位（３）と構成単位（４）との合計数は、２〜６２が好ましい。この合計数が上記上限値以下であれば、アリル基含有樹脂（ｉ）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（ｉ）を容易に極性溶剤に溶解して樹脂ワニスとすることができる。 In the allyl group-containing resin (i), 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 (i). The total number is preferably 2 to 62. When the total number is equal to or less than the above upper limit, the mass average molecular weight (Mw) of the allyl group-containing resin (i) becomes low, so that the allyl group-containing resin (i) is easily dissolved in the polar solvent and the resin varnish is used. Can be.
アリル基含有樹脂（ｉ）の質量平均分子量（Ｍｗ）は、３００〜８０００が好ましく、２０００〜５０００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（ｉ）の溶液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（ｉ）の結晶性を抑えることができ、溶剤に溶解する際の溶解性が優れる。
アリル基含有樹脂（ｉ）の分散度（Ｍｗ／数平均分子量（Ｍｎ））は、１．２０〜５．００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。
The mass average molecular weight (Mw) of the allyl group-containing resin (i) is preferably 300 to 8000, more preferably 2000 to 5000. When Mw is not more than the above upper limit value, the solution viscosity of the allyl group-containing resin (i) becomes sufficiently low. When Mw is at least the above lower limit value, the crystallinity of the allyl group-containing resin (i) can be suppressed, and the solubility when dissolved in a solvent is excellent.
The dispersity (Mw / number average molecular weight (Mn)) of the allyl group-containing resin (i) is preferably 1.20 to 5.00.
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（ｉ）の製造方法＞
アリル基含有樹脂（ｉ）の製造方法としては、例えば、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ヒドロキシ基に対して５０モル％以上のハロゲン化アリルとを反応させてアリル基含有樹脂（ｉ）を得る工程と、
を有するアリル基含有樹脂の製造方法。
<Manufacturing method of allyl group-containing resin (i)>
Examples of the method for producing the allyl group-containing resin (i) include the following production method (I).
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 compound represented by the following formula (b2). A step of reacting with at least one cross-linking 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).
A step of reacting the aldehyde group-containing resin with 50 mol% or more of allyl halide with the hydroxy group of the aldehyde group-containing resin to obtain an allyl group-containing resin (i).
A method for producing an allyl group-containing resin having.
（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, and metahydroxybenzaldehyde.
Examples of the monohydroxynaphthaldehyde include 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 6-hydroxy-2-naphthaldehyde and the like.
Any one of these may be used alone, or two or more thereof may be used in combination.
As the monomer (A), orthohydroxybenzaldehyde is preferable because it has good reactivity with the cross-linking agent (B) and the monomer remaining in the reaction can be easily recovered and recycled.
（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 of X include a chlorine atom and a bromine atom.
Examples of the compound represented by the formula (b1) include 4,4'-bis (alkoxymethyl) biphenyl, 2,2'-bis (alkoxymethyl) biphenyl, and 2,4'-bis (alkoxymethyl) biphenyl, 4 , 4'-bis (methyl halide) biphenyl, 2,2'-bis (methyl halide) biphenyl, 2,4'-bis (methyl halide) biphenyl, etc. (However, the number of carbon atoms in the alkoxy group is 1 to 4 Is mentioned.).
Examples of the compound represented by the formula (b2) include paraxylylene glycol dialkyl ether, metaxylylene glycol dialkyl ether, 1,4-bis (methyl halide) benzene and the like (however, the number of carbon atoms of the alkyl group is 1 to 1). 4).
These may be used alone or in combination of two or more.
Among the above, the cross-linking agent (B) is relatively inexpensive and has good reactivity with the monomer (A), so that it is 4,4'-bis (alkoxymethyl) biphenyl, 4,4'. -Bis (methyl halide) biphenyl, paraxylylene glycol dialkyl ether, 1,4-bis (methyl halogenated) 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 between monomer (A) and 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 an aldehyde having 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 between the monomer (A) and the cross-linking agent (B), the molar ratio of the cross-linking agent (B) to the monomer (A) (cross-linking agent (B) / monomer (A)) was 0.01 to 0.99. It is preferably 0.05 to 0.60, and more preferably 0.05 to 0.60. If the ratio of the cross-linking agent (B) to the monomer (A) is too low, the yield may decrease. If the ratio of the cross-linking agent (B) to the monomer (A) is too high, the reaction between the monomer (A) and the cross-linking agent (B) takes a long time, and the productivity may decrease.
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 cross-linking agent (B) may be carried out 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 cross-linking agent (B) is improved. In particular, when X contained in the cross-linking agent (B) is an alkoxy group, it is preferably carried out in the presence of an acidic catalyst.
When the X contained in the cross-linking agent (B) 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 the heat of the reaction to become HX. Since this HX functions as an acidic catalyst, the reaction rate becomes sufficiently high 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 acidic catalyst is not particularly limited as long as the reaction proceeds, and examples thereof include inorganic acids, organic acids, and alkaline metal compounds. 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. The acidic catalyst may be used alone or in combination of two or more.
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。 The amount of the acidic catalyst used is preferably 0.01 to 10% by mass, more preferably 0.10 to 1.00% by mass, based on the monomer (A). If the amount of the acidic catalyst used is too small, the effect of improving the reaction rate may be insufficient, and 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。
The reaction temperature of the monomer (A) and the cross-linking agent (B) is preferably 10 to 250 ° C, more preferably 60 to 200 ° C. If the reaction temperature is too low, the reaction will not proceed, and 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, alkali may be added to the resulting reaction product to neutralize the acidic catalyst.
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、構成単位（１）と構成単位（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ハロゲン化アリルと反応させる工程）に供される。
The reaction product obtained by the reaction of the monomer (A) and the cross-linking agent (B) contains an aldehyde group-containing resin having a structural unit (1) and a structural unit (3).
This reaction product is left as it is, or if necessary, it is subjected to treatments such as removal of unreacted raw materials by distillation, concentration, purification (washing, column chromatography, etc.), and the next step (aldehyde group-containing resin). And react with allyl halide).
（ハロゲン化アリル）
ハロゲン化アリルとしては、例えば塩化アリル、臭化アリル、フッ化アリル、ヨウ化アリル等が挙げられる。コストの点から、塩化アリルが好ましい。
(Allyl halide)
Examples of the allyl halide include allyl chloride, allyl bromide, allyl fluoride, allyl iodide and the like. Allyl chloride is preferable from the viewpoint of cost.
（アルデヒド基含有樹脂とハロゲン化アリルとの反応）
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、ハロゲン化アリルとを反応させると、アルデヒド基含有樹脂のヒドロキシ基（構成単位（１）、（３）のヒドロキシ基）が−Ｏ−ＣＨ２−ＣＨ＝ＣＨ２に変換される。構成単位（１）のヒドロキシ基が−Ｏ−ＣＨ２−ＣＨ＝ＣＨ２に変換されると構成単位（２）が生成し、構成単位（３）のヒドロキシ基が−Ｏ−ＣＨ２−ＣＨ＝ＣＨ２に変換されると構成単位（４）が生成する。
(Reaction between aldehyde group-containing resin and allyl halide)
When the aldehyde group-containing resin produced by the reaction of the monomer (A) and the cross-linking agent (B) is reacted with allyl halide, the hydroxy groups of the aldehyde group-containing resin (hydroxyls of the constituent units (1) and (3)) Group) is converted to -O-CH 2 -CH = CH 2. When the hydroxy group of the structural unit (1) is converted to -O-CH 2 -CH = CH 2 , the structural unit (2) is generated, and the hydroxy group of the structural unit (3) is -O-CH 2 -CH =. When converted to CH 2 , the structural unit (4) is generated.
上記反応において、アルデヒド基含有樹脂のヒドロキシ基（１００モル％）に対して５０モル％以上のハロゲン化アリルを反応させることで、アリル基含有樹脂（ｉ）が生成する。アルデヒド基含有樹脂と反応させるハロゲン化アリルの量は、アルデヒド基含有樹脂のヒドロキシ基に対して７０モル％以上が好ましく、８０モル％以上が特に好ましい。
アルデヒド基含有樹脂と反応させるハロゲン化アリルの量は、アルデヒド基含有樹脂のヒドロキシ基に対して過剰（１００モル％超）であってもよく、該量の上限は特に限定されないが、コスト、生産性の点では、２００モル％以下が好ましく、１２０モル％以下が特に好ましい。
したがって、アルデヒド基含有樹脂とハロゲン化アリルとの反応において、アルデヒド基含有樹脂のヒドロキシ基に対するハロゲン化アリルのモル比（ハロゲン化アリル／ヒドロキシ基）は、０．５以上であり、０．５〜２．０が好ましく、０．５〜１．２がより好ましく、０．７〜１．２がさらに好ましく、０．８〜１．２が特に好ましい。
In the above reaction, the allyl group-containing resin (i) is produced by reacting 50 mol% or more of allyl halide with the hydroxy group (100 mol%) of the aldehyde group-containing resin. The amount of allyl halide to be reacted with the aldehyde group-containing resin is preferably 70 mol% or more, particularly preferably 80 mol% or more, based on the hydroxy group of the aldehyde group-containing resin.
The amount of the allyl halide to be reacted with the aldehyde group-containing resin may be excessive (more than 100 mol%) with respect to the hydroxy group of the aldehyde group-containing resin, and the upper limit of the amount is not particularly limited, but the cost and production. In terms of properties, 200 mol% or less is preferable, and 120 mol% or less is particularly preferable.
Therefore, in the reaction between the aldehyde group-containing resin and the allyl halide, the molar ratio of the allyl halide to the hydroxy group (allyl halide / hydroxy group) of the aldehyde group-containing resin is 0.5 or more, and is 0.5 to 0.5. 2.0 is preferable, 0.5 to 1.2 is more preferable, 0.7 to 1.2 is further preferable, and 0.8 to 1.2 is particularly preferable.
アルデヒド基含有樹脂とハロゲン化アリルとの反応は通常、触媒の存在下で行われる。
触媒としては、例えば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属類、ジアザビシクロノネン、ジアザビシクロウンデセン、トリエチルアミン等のアミン類、ナトリウムｔｅｒｔ−ブトキシド、カリウムｔｅｒｔ−ブトキシド、リチウムジイソプロピルアミド、ケイ素−塩基性アミン、リチウムテトラメチルピペリジン等が挙げられる。これらの中でも、比較的安価であり、副反応が起こりにくい点で、アルカリ金属類、ジアザビシクロノネン、ジアザビシクロウンデセンが好ましい。触媒は１種単独で用いても２種以上を併用してもよい。
触媒の使用量は、ハロゲン化アリルの使用モル量に対して０．８〜１．０倍モルが好ましい。触媒の使用量が少なすぎると、反応速度が遅く、使用量が多すぎると、余剰のアルカリを除去しなくてはならなくなり、生産性が低下する。
The reaction between the aldehyde group-containing resin and allyl halide is usually carried out in the presence of a catalyst.
Examples of the catalyst include alkali metals such as sodium hydroxide and potassium hydroxide, amines such as diazabicyclononen, diazabicycloundecene and triethylamine, sodium tert-butoxide, potassium tert-butoxide and lithium diisopropylamide. Examples thereof include silicon-basic amine and lithium tetramethylpiperidin. Among these, alkali metals, diazabicyclononene, and diazabicycloundecene are preferable because they are relatively inexpensive and side reactions are unlikely to occur. The catalyst may be used alone or in combination of two or more.
The amount of the catalyst used is preferably 0.8 to 1.0 times the molar amount of allyl halide used. If the amount of the catalyst used is too small, the reaction rate will be slow, and if the amount used is too large, excess alkali must be removed, resulting in a decrease in productivity.
アルデヒド基含有樹脂とハロゲン化アリルとの反応温度は、アルデヒド基含有樹脂のヒドロキシ基とハロゲン化アリルとが反応する温度であれば特に限定されず、例えば１０〜１５０℃であってよく、３０〜１３０℃であってよい。 The reaction temperature of the aldehyde group-containing resin and allyl halide is not particularly limited as long as it is the temperature at which the hydroxy group of the aldehyde group-containing resin reacts with allyl halide, and may be, for example, 10 to 150 ° C., 30 to 150 ° C. It may be 130 ° C.
アルデヒド基含有樹脂とハロゲン化アリルとの反応により得られた反応生成物は、アリル基含有樹脂（ｉ）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。
The reaction product obtained by the reaction of the aldehyde group-containing resin with allyl halide contains the allyl group-containing resin (i).
After the reaction, if necessary, the reaction product may be subjected to treatments such as removal of unreacted raw materials by distillation and the like, concentration and purification (washing, column chromatography, etc.).
＜作用効果＞
アリル基含有樹脂（ｉ）は、アリル基を有するため、マレイミド化合物を硬化させるための硬化剤（マレイミド硬化剤）として用いることができる。マレイミド化合物の硬化は、加熱により行うことができる。
また、アリル基含有樹脂（ｉ）を用いてマレイミド化合物を硬化させた硬化物は、マレイミド化合物を用いているために、高ガラス転移温度、高熱分解温度、低熱線膨張率を示す。また、アリル基含有樹脂（ｉ）を用いているために、マレイミド化合物をアリルフェノール樹脂で硬化させた硬化物に比べて、低誘電率、低誘電正接であり、また、他部材（例えば銅張積層板に用いられる銅箔や、ガラスクロス等の繊維質基材等）との密着性に優れる。
<Effect>
Since the allyl group-containing resin (i) has an allyl group, it can be used as a curing agent (maleimide curing agent) for curing the maleimide compound. Curing of the maleimide compound can be performed by heating.
Further, the cured product obtained by curing the maleimide compound using the allyl group-containing resin (i) exhibits a high glass transition temperature, a high thermal decomposition temperature, and a low heat ray expansion rate because the maleimide compound is used. Further, since the allyl group-containing resin (i) is used, the maleimide compound has a lower dielectric constant and a lower dielectric loss tangent as compared with a cured product obtained by curing with an allyl phenol resin, and other members (for example, copper-clad). Excellent adhesion to copper foil used for laminated boards, fibrous base materials such as glass cloth, etc.).
アリル基含有樹脂（ｉ）は、アリル基とアルデヒド基とを有し、場合によってはヒドロキシ基も有する。
そのため、アリル基含有樹脂（ｉ）を用いてマレイミド化合物を硬化させる際には、以下の（１）〜（４）の反応が生じて硬化していると考えられる。
（１）マレイミド基とアリル基との反応。
（２）マレイミド基同士の反応。
（３）アリル基同士の反応。
（４）マレイミド基とヒドロキシ基との反応。
樹脂中にアルデヒド基を含有していることが、密着性の向上に寄与していると考えられる。
The allyl group-containing resin (i) has an allyl group and an aldehyde group, and in some cases also has a hydroxy group.
Therefore, when the maleimide compound is cured using the allyl group-containing resin (i), it is considered that the following reactions (1) to (4) occur and the maleimide compound is cured.
(1) Reaction of maleimide group and allyl group.
(2) Reaction between maleimide groups.
(3) Reaction between allyl groups.
(4) Reaction of maleimide group and hydroxy group.
It is considered that the inclusion of aldehyde groups in the resin contributes to the improvement of adhesion.
さらに、アリル基含有樹脂（ｉ）は、一般的にマレイミド化合物を溶解させるために用いられているような溶剤に対する溶解性に優れる。したがって、アリル基含有樹脂（ｉ）およびマレイミド化合物が共に溶剤に溶解した樹脂ワニスを得ることができる。
前記の溶剤としては、メチルエチルケトンのような極性のあるものが一般的である。
Further, the allyl group-containing resin (i) has excellent solubility in a solvent generally used for dissolving a maleimide compound. Therefore, a resin varnish in which the allyl group-containing resin (i) and the maleimide compound are both dissolved in a solvent can be obtained.
As the solvent, a polar solvent such as methyl ethyl ketone is generally used.
なお、アリル基含有樹脂（ｉ）は、マレイミド化合物と組み合わせなくても、上記（３）、（４）の反応により、単独で硬化させることができる。しかし、マレイミド化合物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、ガラス転移温度を高めることができる。そのため、マレイミド化合物と組み合わせて硬化反応に供することが好適である。 The allyl group-containing resin (i) can be cured alone by the reactions (3) and (4) above without being combined with the maleimide compound. However, by combining with a maleimide compound, the curing temperature can be lowered and the glass transition temperature can be increased as compared with the case of curing alone. Therefore, it is preferable to combine it with a maleimide compound and subject it to a curing reaction.
アリル基含有樹脂（ｉ）の用途としては、特に制限はない。例えば公知の熱硬化性成形材料の用途と同様であってよく、例えば封止材料、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。 The use of the allyl group-containing resin (i) is not particularly limited. For example, it may be similar to the use of a known thermosetting molding material, and examples thereof include a sealing material, a film material, and a laminated material. More specific examples of applications include semiconductor encapsulation materials, resin materials for encapsulating electronic components, electrical insulation 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, fiber reinforced plastic (FRP) materials, and the like.
≪第二の態様のアリル基含有樹脂≫
本発明の第二の態様のアリル基含有樹脂（以下、「アリル基含有樹脂（ｉｉ）」ともいう。）は、下記式（１）で表される構成単位（１）、下記式（２）で表される構成単位（２）および下記式（２Ａ）で表される構成単位（２Ａ）のうちの少なくとも１種と、下記式（３）で表される構成単位（３）、下記式（４）で表される構成単位（４）および下記式（４Ａ）で表される構成単位（４Ａ）のうちの少なくとも前記構成単位（４Ａ）と、を有する。
<< Allyl group-containing resin of the second aspect >>
The allyl group-containing resin of the second aspect of the present invention (hereinafter, also referred to as “allyl group-containing resin (ii)”) is a structural unit (1) represented by the following formula (1) and the following formula (2). At least one of the structural unit (2) represented by the following formula (2) and the structural unit (2A) represented by the following formula (2A), the structural unit (3) represented by the following formula (3), and the following formula ( It has at least the structural unit (4A) of the structural unit (4) represented by 4) and the structural unit (4A) represented by the following formula (4A).
各式中、Ａｒ、Ｒ、ｐ、ｑ、−＊および−＊＊はそれぞれ前記と同義であり、好ましい態様も同様である。
構成単位（１）、（２）、（３）、（４）はそれぞれ前記と同様であり、好ましい態様も同様である。
In each formula, Ar, R, p, q, − * and − ** have the same meanings as described above, and the preferred embodiments are also the same.
The structural units (1), (2), (3), and (4) are the same as described above, and the preferred embodiments are also the same.
構成単位（２Ａ）は、典型的には、構成単位（２）におけるアリル基が転位し、Ａｒに結合して形成された構成単位である。
構成単位（２Ａ）として具体的には、前記式（１−１）におけるベンゼン環に−ＣＨ２−ＣＨ＝ＣＨ２が結合した構造の構成単位、前記式（１−２）または（１−３）におけるナフタレン環に−ＣＨ２−ＣＨ＝ＣＨ２が結合した構造の構成単位等が挙げられる。各構成単位において、アルデヒド基の好ましい結合位置は前記と同様である。−ＣＨ２−ＣＨ＝ＣＨ２の結合位置は、典型的には、ヒドロキシ基に対してオルソまたはパラ位である。
構成単位（２Ａ）としては、上記の中でも、式（１−１）におけるベンゼン環に−ＣＨ２−ＣＨ＝ＣＨ２が結合した構造の構成単位が好ましい。
アリル基含有樹脂（ｉｉ）に含まれる構成単位（２Ａ）は１種でも２種以上でもよい。
The structural unit (2A) is typically a structural unit formed by rearranging the allyl group in the structural unit (2) and bonding to Ar.
Specifically, the structural unit (2A) is a structural unit having a structure in which −CH 2 −CH = CH 2 is bonded to the benzene ring in the above formula (1-1), or the above formula (1-2) or (1-3). ), The structural unit of the structure in which −CH 2 −CH = CH 2 is bonded to the naphthalene ring and the like can be mentioned. In each structural unit, the preferred bonding position of the aldehyde group is the same as described above. −CH 2 −CH = CH 2 bond position is typically in the ortho or para position with respect to the hydroxy group.
Among the above, the structural unit (2A) is preferably a structural unit having a structure in which −CH 2 −CH = CH 2 is bonded to the benzene ring in the formula (1-1).
The structural unit (2A) contained in the allyl group-containing resin (ii) may be one type or two or more types.
構成単位（４Ａ）は、典型的には、構成単位（４）におけるアリル基が転位し、Ａｒに結合して形成された構成単位である。
構成単位（４Ａ）として具体的には、前記式（３−１）におけるベンゼン環に−ＣＨ２−ＣＨ＝ＣＨ２が結合した構造の構成単位、前記式（３−２）または（３−３）におけるナフタレン環に−ＣＨ２−ＣＨ＝ＣＨ２が結合した構造の構成単位等が挙げられる。各構成単位において、アルデヒド基の好ましい結合位置は前記と同様である。−ＣＨ２−ＣＨ＝ＣＨ２の結合位置は、典型的には、ヒドロキシ基に対してオルソまたはパラ位である。
構成単位（４Ａ）としては、上記の中でも、式（３−１）におけるベンゼン環に−ＣＨ２−ＣＨ＝ＣＨ２が結合した構造の構成単位が好ましい。
アリル基含有樹脂（ｉｉ）に含まれる構成単位（４Ａ）は１種でも２種以上でもよい。
The structural unit (4A) is typically a structural unit formed by rearranging the allyl group in the structural unit (4) and binding it to Ar.
Specifically, the structural unit (4A) is a structural unit having a structure in which −CH 2 −CH = CH 2 is bonded to the benzene ring in the above formula (3-1), or the above formula (3-2) or (3-3). ), The structural unit of the structure in which −CH 2 −CH = CH 2 is bonded to the naphthalene ring and the like can be mentioned. In each structural unit, the preferred bonding position of the aldehyde group is the same as described above. −CH 2 −CH = CH 2 bond position is typically in the ortho or para position with respect to the hydroxy group.
Among the above, the structural unit (4A) is preferably a structural unit having a structure in which −CH 2 −CH = CH 2 is bonded to the benzene ring in the formula (3-1).
The structural unit (4A) contained in the allyl group-containing resin (ii) may be one type or two or more types.
アリル基含有樹脂（ｉｉ）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（２Ａ）、構成単位（３）、構成単位（４）および構成単位（４Ａ）以外の構成単位をさらに有していてもよい。 The allyl group-containing resin (ii) is, if necessary, a structural unit (1), a structural unit (2), a structural unit (2A), a structural unit (3), and a structural unit, as long as the effects of the present invention are not impaired. It may further have a structural unit other than (4) and the structural unit (4A).
アリル基含有樹脂（ｉｉ）において、構成単位（２）と構成単位（２Ａ）と構成単位（４）と構成単位（４Ａ）との合計の含有量は、構成単位（１）と構成単位（２）と構成単位（２Ａ）と構成単位（３）と構成単位（４）と構成単位（４Ａ）との合計（１００モル％）に対して５０〜１００モル％であり、７０〜１００モル％が好ましく、８０〜１００モル％が特に好ましい。この割合は、アリル基含有樹脂（ｉｉ）中のＡｒの総モル数（１００モル％）に対するアリル基のモル数の割合（モル％）に等しい。この割合が５０モル％以上であれば、アリル基含有樹脂（ｉｉ）をマレイミド硬化剤として用いた時に、硬化速度が良好である。また、得られる硬化物が、高ガラス転移温度、高熱分解温度、低誘電率、低誘電正接、高密着性を示す。 In the allyl group-containing resin (ii), the total content of the structural unit (2), the structural unit (2A), the structural unit (4), and the structural unit (4A) is the structural unit (1) and the structural unit (2). ), The constituent unit (2A), the constituent unit (3), the constituent unit (4), and the constituent unit (4A), which is 50 to 100 mol%, and 70 to 100 mol%. It is preferable, and 80 to 100 mol% is particularly preferable. This ratio is equal to the ratio of the number of moles of allyl group (mol%) to the total number of moles of Ar (100 mol%) in the allyl group-containing resin (ii). When this ratio is 50 mol% or more, the curing rate is good when the allyl group-containing resin (ii) is used as the maleimide curing agent. Further, the obtained cured product exhibits a high glass transition temperature, a high thermal decomposition temperature, a low dielectric constant, a low dielectric loss tangent, and a high adhesion.
アリル基含有樹脂（ｉｉ）中、構成単位（２Ａ）と構成単位（４Ａ）との合計の含有量は、構成単位（２）と構成単位（２Ａ）と構成単位（４）と構成単位（４Ａ）との合計に対して８０〜１００モル％が好ましく、９０〜１００モル％が特に好ましい。
なお、アリル基含有樹脂（ｉｉ）は、典型的には、後述する製造方法（ＩＩ）により製造される。つまりアリル基含有樹脂（ｉ）の構成単位（２）、（４）のアリル基の一部または全部を転位させ、構成単位（２Ａ）、構成単位（４Ａ）に変換することにより製造される。この場合、上記の構成単位（２Ａ）と構成単位（４Ａ）との合計の含有量は、アリル基の転位率に等しい。
The total content of the structural unit (2A) and the structural unit (4A) in the allyl group-containing resin (ii) is the structural unit (2), the structural unit (2A), the structural unit (4), and the structural unit (4A). ) Is preferably 80 to 100 mol%, and 90 to 100 mol% is particularly preferable.
The allyl group-containing resin (ii) is typically produced by the production method (II) described later. That is, it is produced by rearranging a part or all of the allyl groups of the constituent units (2) and (4) of the allyl group-containing resin (i) and converting them into the constituent units (2A) and the constituent units (4A). In this case, the total content of the structural unit (2A) and the structural unit (4A) is equal to the dislocation rate of the allyl group.
アリル基含有樹脂（ｉｉ）において、アリル基含有樹脂（ｉｉ）を構成する重合体１分子あたりの構成単位（１）と構成単位（２）と構成単位（２Ａ）と構成単位（３）と構成単位（４）と構成単位（４Ａ）との合計数は、２〜６２が好ましい。この合計数が上記上限値以下であれば、アリル基含有樹脂（ｉｉ）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（ｉｉ）を容易に極性溶剤に溶解して樹脂ワニスとすることができる。 The allyl group-containing resin (ii) is composed of a structural unit (1), a structural unit (2), a structural unit (2A), and a structural unit (3) per molecule of the polymer constituting the allyl group-containing resin (ii). The total number of the unit (4) and the constituent unit (4A) is preferably 2 to 62. When the total number is equal to or less than the above upper limit value, the mass average molecular weight (Mw) of the allyl group-containing resin (ii) is lowered, so that the allyl group-containing resin (ii) is easily dissolved in the polar solvent and the resin varnish is used. Can be.
アリル基含有樹脂（ｉｉ）の質量平均分子量（Ｍｗ）、分散度（Ｍｗ／Ｍｎ）それぞれの好ましい範囲は、アリル基含有樹脂（ｉ）と同様である。 The preferred ranges of the mass average molecular weight (Mw) and the dispersity (Mw / Mn) of the allyl group-containing resin (ii) are the same as those of the allyl group-containing resin (i).
＜アリル基含有樹脂（ｉｉ）の製造方法＞
アリル基含有樹脂（ｉｉ）の製造方法としては、例えば、以下の製造方法（ＩＩ）が挙げられる。
製造方法（ＩＩ）：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ヒドロキシ基に対して５０モル％以上のハロゲン化アリルとを反応させてアリル基含有樹脂（ｉ）を得る工程と、
前記アリル基含有樹脂（ｉ）のアリル基を転位反応させてアリル基含有樹脂（ｉｉ）を得る工程と、
を有するアリル基含有樹脂の製造方法。
<Manufacturing method of allyl group-containing resin (ii)>
Examples of the method for producing the allyl group-containing resin (ii) include the following production method (II).
Production method (II): 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). A step of reacting with at least one cross-linking 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).
A step of reacting the aldehyde group-containing resin with 50 mol% or more of allyl halide with the hydroxy group of the aldehyde group-containing resin to obtain an allyl group-containing resin (i).
A step of rearranging the allyl group of the allyl group-containing resin (i) to obtain an allyl group-containing resin (ii).
A method for producing an allyl group-containing resin having.
アルデヒド基含有樹脂を得る工程、アリル基含有樹脂（ｉ）を得る工程はそれぞれ、前記の製造方法（Ｉ）と同様にして行うことができる。 The step of obtaining the aldehyde group-containing resin and the step of obtaining the allyl group-containing resin (i) can be carried out in the same manner as in the above-mentioned production method (I), respectively.
（アリル基含有樹脂（ｉ）のアリル基の転位反応）
アリル基含有樹脂（ｉ）のアリル基は、構成単位（２）、（４）におけるアリル基である。構成単位（２）のアリル基が転位すると構成単位（２Ａ）が生成し、構成単位（４）のアリル基が転位すると構成単位（４Ａ）が生成する。
アリル基含有樹脂（ｉ）のアリル基の転位反応は、例えば、アリル基含有樹脂（ｉ）を加熱することにより実施できる。アリル基含有樹脂（ｉ）を加熱すると、Ａｒに結合した−Ｏ−ＣＨ２−ＣＨ＝ＣＨ２のアリル基がＡｒのオルソまたはパラ位に転位する、いわゆるクライゼン転位反応が生じる。加熱条件は、例えば１２０〜２００℃で１〜２０時間とすることができる。このときの加熱条件によって、アリル基の転位率を調整できる。加熱は、Ｎ２等の不活性雰囲気下で行うことが好ましい。
(Rearrangement reaction of allyl group of allyl group-containing resin (i))
The allyl group of the allyl group-containing resin (i) is the allyl group in the structural units (2) and (4). When the allyl group of the structural unit (2) is rearranged, the structural unit (2A) is generated, and when the allyl group of the structural unit (4) is rearranged, the structural unit (4A) is generated.
The rearrangement reaction of the allyl group of the allyl group-containing resin (i) can be carried out, for example, by heating the allyl group-containing resin (i). When the allyl group-containing resin (i) is heated, a so-called Claisen rearrangement reaction occurs in which the allyl group of -O-CH 2 -CH = CH 2 bonded to Ar is rearranged to the ortho or para position of Ar. The heating conditions can be, for example, 120 to 200 ° C. for 1 to 20 hours. The dislocation rate of the allyl group can be adjusted by the heating conditions at this time. The heating is preferably performed in an inert atmosphere such as N 2.
アリル基の転位反応により得られた反応生成物は、アリル基含有樹脂（ｉｉ）を含む。
反応後、必要に応じて、反応生成物に対し、水洗等の処理を行ってもよい。
The reaction product obtained by the rearrangement reaction of the allyl group contains an allyl group-containing resin (ii).
After the reaction, if necessary, the reaction product may be treated with water or the like.
＜作用効果＞
アリル基含有樹脂（ｉｉ）は、アリル基含有樹脂（ｉ）と同様に、アリル基を有するため、マレイミド硬化剤として用いることができる。
また、アリル基含有樹脂（ｉｉ）を用いてマレイミド化合物を硬化させた硬化物は、マレイミド化合物を用いているために、高ガラス転移温度、高熱分解温度、低熱線膨張率を示す。また、アリル基含有樹脂（ｉｉ）を用いているために、アリル基含有樹脂（ｉ）を用いている場合と同様に、マレイミド化合物をアリルフェノール樹脂で硬化させた硬化物に比べて、低誘電率、低誘電正接であり、また、他部材（例えば銅張積層板に用いられる銅箔や、ガラスクロス等の繊維質基材等）との密着性に優れる。
アリル基含有樹脂（ｉｉ）を用いてマレイミド化合物を硬化させる際には、アリル基含有樹脂（ｉ）の場合と同様に、前記（１）〜（４）の反応が生じて硬化していると考えられる。また、アリル基含有樹脂（ｉ）の場合と同様に、樹脂中にアルデヒド基を含有していることが、密着性の向上、溶剤への溶解性の向上に寄与していると考えられる。
アリル基含有樹脂（ｉｉ）は、アリル基含有樹脂（ｉ）と同様に、マレイミド化合物と組み合わせなくても単独で硬化させることができるが、マレイミド化合物と組み合わせて硬化反応に供することが好適である。
アリル基含有樹脂（ｉｉ）の用途としては、特に制限はなく、アリル基含有樹脂（ｉ）と同様の用途に使用できる。
<Effect>
Since the allyl group-containing resin (ii) has an allyl group like the allyl group-containing resin (i), it can be used as a maleimide curing agent.
Further, the cured product obtained by curing the maleimide compound using the allyl group-containing resin (ii) exhibits a high glass transition temperature, a high thermal decomposition temperature, and a low heat ray expansion rate because the maleimide compound is used. Further, since the allyl group-containing resin (ii) is used, the dielectric is lower than that of the cured product obtained by curing the maleimide compound with the allyl phenol resin, as in the case where the allyl group-containing resin (i) is used. It has a low dielectric loss tangent, and has excellent adhesion to other members (for example, copper foil used for copper-clad laminates, fibrous base materials such as glass cloth, etc.).
When the maleimide compound is cured using the allyl group-containing resin (ii), it is said that the reactions (1) to (4) described above occur and the maleimide compound is cured as in the case of the allyl group-containing resin (i). Conceivable. Further, as in the case of the allyl group-containing resin (i), it is considered that the inclusion of the aldehyde group in the resin contributes to the improvement of the adhesion and the solubility in the solvent.
Like the allyl group-containing resin (i), the allyl group-containing resin (ii) can be cured independently without being combined with the maleimide compound, but it is preferable that the allyl group-containing resin (ii) is subjected to a curing reaction in combination with the maleimide compound. ..
The use of the allyl group-containing resin (ii) is not particularly limited, and can be used in the same manner as the allyl group-containing resin (i).
≪樹脂ワニス≫
本発明の樹脂ワニス（以下、「本樹脂ワニス」ともいう。）は、マレイミド基を２以上有するマレイミド化合物と、本発明のアリル基含有樹脂と、溶剤とを含む。
ここで、本発明のアリル基含有樹脂とは、アリル基含有樹脂（ｉ）およびアリル基含有樹脂（ｉｉ）のいずれか一方または両方を示す。
アリル基含有樹脂は、マレイミド硬化剤として機能する。「マレイミド硬化剤」とは、前記マレイミド化合物を硬化させるための硬化剤を意味する。
本樹脂ワニスにおいては、マレイミド化合物のマレイミド基の一部と、アリル基含有樹脂のアリル基またはヒドロキシ基の一部とが反応した状態になっていてもよい。
本樹脂ワニスは、硬化反応触媒をさらに含むことができる。
本樹脂ワニスは、前記マレイミド化合物、前記アリル基含有樹脂、溶剤および硬化反応触媒以外の他の成分をさらに含むことができる。
≪Resin varnish≫
The resin varnish of the present invention (hereinafter, also referred to as “the present resin varnish”) contains a maleimide compound having two or more maleimide groups, an allyl group-containing resin of the present invention, and a solvent.
Here, the allyl group-containing resin of the present invention refers to either or both of the allyl group-containing resin (i) and the allyl group-containing resin (ii).
The allyl group-containing resin functions as a maleimide curing agent. The "maleimide curing agent" means a curing agent for curing the maleimide compound.
In this resin varnish, a part of the maleimide group of the maleimide compound may be in a state of reacting with a part of the allyl group or the hydroxy group of the allyl group-containing resin.
The resin varnish may further contain a curing reaction catalyst.
The resin varnish may further contain components other than the maleimide compound, the allyl group-containing resin, the solvent and the curing reaction catalyst.
＜マレイミド化合物＞
マレイミド化合物としては、マレイミド基を２以上有する化合物であれば特に限定されず、例えばビスマレイミド化合物、ポリフェニルメタンマレイミド等が挙げられる。
ビスマレイミド化合物としては、例えば４，４’−ジフェニルメタンビスマレイミド（例えば大和化成工業株式会社品のＢＭＩ−１１００）、アルキルビスマレイミド、ジフェニルメタンビスマレイミド、フェニレンビスマレイミド、ビスフェノールＡ ジフェニルエーテルビスマレイミド、３，３’−ジメチル−５，５’−ジエチル−４，４’−ジフェニルメタンビスマレイミド、４−メチル−１，３−フェニレンビスマレイミド、１，６’−ビスマレイミド−（２，２，４−トリメチル）ヘキサン、４，４’−ジフェニルエーテルビスマレイミド、４，４’−ジフェニルスルフォンビスマレイミド、１，３−ビス（３−マレイミドフェノキシ）ベンゼン、１，３−ビス（４−マレイミドフェノキシ）ベンゼン等が挙げられる。
ポリフェニルメタンマレイミドは、マレイミド基が置換した３以上のベンゼン環がメチレン基を介して結合した重合体であり、例えば大和化成工業株式会社品のＢＭＩ−２３００が挙げられる。
マレイミド化合物としては、本発明のアリル基含有樹脂との相溶性が良い点、硬化物の耐熱性、密着性がより優れる点、比較的安価である点から、４，４’−ジフェニルメタンビスマレイミド、ポリフェニルメタンマレイミドが好ましい。
これらのマレイミド化合物は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。
<Maleimide compound>
The maleimide compound is not particularly limited as long as it is a compound having two or more maleimide groups, and examples thereof include a bismaleimide compound and polyphenylmethane maleimide.
Examples of the bismaleimide compound include 4,4'-diphenylmethane bismaleimide (for example, BMI-1100 manufactured by Daiwa Kasei Kogyo Co., Ltd.), alkyl bismaleimide, diphenylmethane bismaleimide, phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3. '-Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane , 4,4'-Diphenyl ether bismaleimide, 4,4'-diphenylsulphon bismaleimide, 1,3-bis (3-maleimide phenoxy) benzene, 1,3-bis (4-maleimide phenoxy) benzene and the like.
Polyphenylmethane maleimide is a polymer in which three or more benzene rings substituted with maleimide groups are bonded via a methylene group, and examples thereof include BMI-2300 manufactured by Daiwa Kasei Kogyo Co., Ltd.
As the maleimide compound, 4,4'-diphenylmethanebismaleimide, which has good compatibility with the allyl group-containing resin of the present invention, has better heat resistance and adhesion of the cured product, and is relatively inexpensive. Polyphenylmethane maleimide is preferred.
These maleimide compounds may be used alone or in combination of two or more.
本樹脂ワニス中のマレイミド化合物の含有量は、マレイミド化合物のマレイミド基と本発明のアリル基含有樹脂のアリル基とのモル比（マレイミド基／アリル基）が、０．２〜１．４となる量が好ましい。マレイミド基／アリル基は、０．３〜１．２がより好ましく、０．４〜１．１がさらに好ましい。マレイミド基／アリル基が前記範囲の下限値以上であれば、本樹脂ワニスの硬化温度を低く、例えば２００℃以下にすることができる。マレイミド基／アリル基が前記範囲の下限値以上であれば、本樹脂ワニスの硬化物が、より高ガラス転移温度、高熱分解温度、低線膨張係数、低誘電率、低誘電正接を示すものとなる。 The content of the maleimide compound in the resin varnish is such that the molar ratio (maleimide group / allyl group) of the maleimide group of the maleimide compound to the allyl group of the allyl group-containing resin of the present invention is 0.2 to 1.4. The amount is preferred. The maleimide group / allyl group is more preferably 0.3 to 1.2, and even more preferably 0.4 to 1.1. When the maleimide group / allyl group is at least the lower limit of the above range, the curing temperature of the resin varnish can be lowered, for example, 200 ° C. or less. When the maleimide group / allyl group is equal to or higher than the lower limit of the above range, the cured product of this resin varnish exhibits a higher glass transition temperature, a higher thermal decomposition temperature, a low coefficient of linear expansion, a low dielectric constant, and a low dielectric loss tangent. Become.
＜溶剤＞
溶剤としては、本樹脂ワニスに含まれる成分（マレイミド化合物、本発明のアリル基含有樹脂、必要に応じて硬化反応触媒等）を溶解するものであれば特に制限はない。
溶剤として典型的には、極性溶剤が用いられる。極性溶剤としては、例えばアセトン、メチルエチルケトン、メチルイソブチルケトン、ジエチルケトン、メチルプロピルケトン、メチルアミルケトン、イソホロン、ジイソブチルケトン、ジアセトンアルコール、シクロヘキサノン等のケトン系溶剤、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチル−２−ピロリドン、メタノール、エタノール、ブタノール、酢酸エチル、酢酸ブチル、メチルセロソルブ、エチルジグリコールアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、テトラヒドロフラン等が挙げられる。これらの溶剤はいずれか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。上記の中でも、ケトン系溶剤が好ましく、メチルエチルケトンが特に好ましい。
<Solvent>
The solvent is not particularly limited as long as it dissolves the components contained in the resin varnish (maleimide compound, allyl group-containing resin of the present invention, curing reaction catalyst, etc., if necessary).
A polar solvent is typically used as the solvent. Examples of the polar solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl propyl ketone, methyl amyl ketone, isophorone, diisobutyl ketone, diacetone alcohol, and cyclohexanone, N, N-dimethylformamide, and N-. Examples thereof include methyl-2-pyrrolidone, methanol, ethanol, butanol, ethyl acetate, butyl acetate, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran and the like. Any one of these solvents may be used alone, or two or more of these solvents may be used in combination. Among the above, a ketone solvent is preferable, and methyl ethyl ketone is particularly preferable.
本樹脂ワニス中の溶剤の含有量は本樹脂ワニスの固形分濃度に応じて適宜設定される。
本樹脂ワニスの固形分濃度は、用途によっても異なるが、３０〜８０質量％が好ましく、５０〜７０質量％がより好ましい。
本樹脂ワニスの固形分濃度は、本樹脂ワニスの全質量に対する、本樹脂ワニスから溶剤を除いた質量の割合である。
The content of the solvent in the resin varnish is appropriately set according to the solid content concentration of the resin varnish.
The solid content concentration of the present resin varnish varies depending on the application, but is preferably 30 to 80% by mass, more preferably 50 to 70% by mass.
The solid content concentration of the resin varnish is the ratio of the mass of the resin varnish excluding the solvent to the total mass of the resin varnish.
＜硬化反応触媒＞
硬化反応触媒（硬化促進剤）としては、例えば、アリル基とマレイミド基との反応を促進する作用を有するものを用いることができる。このような作用を有する硬化反応触媒としては、例えば、イミダゾール化合物、有機過酸化物等が挙げられる。イミダゾール化合物としては、例えば２−エチル−４−メチルイミダゾール、２−メチルイミダゾール、２−エチルイミダゾール、２，４−ジメチルイミダゾール、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−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、１−ベンジル−２−メチルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾール、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、１−ビニル−２−メチルイミダゾール、１−プロピル−２−メチルイミダゾール、２−イソプロピルイミダゾール、１−シアノメチル−２−メチル−イミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾール、１−シアノエチル−２−ウンデシルイミダゾール、１−シアノエチル−２−フェニルイミダゾール等のイミダゾール類が挙げられる。有機過酸化物としては、例えばケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、パーオキシジカーボネート、パーオキシエステル等が挙げられる。ジアルキルパーオキサイドにおいて、アルキル基は、フェニル基等で置換されていてもよい。
上記のうち、イミダゾール類では、２−エチル−４−メチルイミダゾールが好ましく、有機過酸化物類では、ジアルキルパーオキサイドのジクミルパーオキサイドがより好ましい。これらは高温で比較的安定であり、溶剤溶解性もよく、取り扱いも容易である。
<Curing reaction catalyst>
As the curing reaction catalyst (curing accelerator), for example, one having an action of accelerating the reaction between the allyl group and the maleimide group can be used. Examples of the curing reaction catalyst having such an action include imidazole compounds and organic peroxides. Examples of the imidazole compound include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2 -Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2-methyl Imidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1 Examples thereof include imidazoles such as −cyanoethyl-2-phenylimidazole. Examples of the organic peroxide include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters and the like. In the dialkyl peroxide, the alkyl group may be substituted with a phenyl group or the like.
Of the above, 2-ethyl-4-methylimidazole is preferable for imidazoles, and dialkyl peroxide, which is a dialkyl peroxide, is more preferable for organic peroxides. They are relatively stable at high temperatures, have good solvent solubility and are easy to handle.
これらの硬化反応触媒はいずれか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。
本樹脂ワニス中の硬化反応触媒の含有量は、マレイミド化合物に対し、０．１〜５．０質量％が好ましい。
Any one of these curing reaction catalysts may be used alone, or two or more of them may be used in combination.
The content of the curing reaction catalyst in the resin varnish is preferably 0.1 to 5.0% by mass with respect to the maleimide compound.
＜他の成分＞
他の成分としては、例えば、無機フィラー（例えばカーボンブラック、ガラスクロス、シリカ等）、ワックス、難燃剤、カップリング剤等、本発明のアリル基含有樹脂以外のマレイミド硬化剤（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、マレイミド硬化剤として従来公知のものを用いることができ、例えばアリルノボラック型フェノール樹脂等のノボラック型樹脂等が挙げられる。
本樹脂ワニス中の他の硬化剤の含有量は、本発明の効果の点では、本樹脂ワニスの固形分（１００質量％）に対し、１０質量％以下が好ましく、０質量％が特に好ましい。
本樹脂ワニスの固形分は、本樹脂ワニスから溶剤を除いた部分である。
<Other ingredients>
Examples of other components include inorganic fillers (for example, carbon black, glass cloth, silica, etc.), waxes, flame retardants, coupling agents, and other maleimide curing agents other than the allyl group-containing resin of the present invention (hereinafter, other curing agents). (Also referred to as an agent), a filler, a mold release agent, a surface treatment agent, a colorant, a flexibility-imparting agent, and the like.
As the other curing agent, conventionally known ones can be used as the maleimide curing agent, and examples thereof include novolac type resins such as allyl novolac type phenol resins.
The content of the other curing agent in the resin varnish is preferably 10% by mass or less, particularly preferably 0% by mass, based on the solid content (100% by mass) of the present resin varnish in terms of the effect of the present invention.
The solid content of the resin varnish is the portion of the resin varnish from which the solvent has been removed.
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、例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 include carbon black, crystalline silica powder, molten silica powder, quartz glass powder, talc, calcium silicate powder, zirconium silicate powder, alumina powder, calcium carbonate powder and the like, and are crystalline. Silica powder and meltable silica powder are preferable.
Examples of the release agent include various waxes such as carnauba wax.
Examples of the surface treatment agent include known silane coupling agents and the like.
Examples of the colorant include carbon black and the like.
Examples of the flexibility-imparting agent include silicone resin, butadiene-acrylonitrile rubber, and the like.
＜樹脂ワニスの製造方法＞
本樹脂ワニスは、例えば、マレイミド化合物と本発明のアリル基含有樹脂と溶剤とを混合することにより製造できる。各成分の混合は、常法により行うことができる。
マレイミド化合物は、市販品を用いることができる。
本発明のアリル基含有樹脂は、前記の製造方法（Ｉ）又は（ＩＩ）により製造できる。
マレイミド化合物と本発明のアリル基含有樹脂と溶剤とを混合する際に、または混合した後、必要に応じて、硬化反応触媒や他の成分をさらに混合してもよい。
マレイミド化合物と本発明のアリル基含有樹脂と溶剤との混合の後、マレイミド化合物とアリル基含有樹脂を前反応させてもよい。上記の混合によって得られたワニス状態の混合物について前反応を行うことで、結晶性が高いマレイミド化合物が樹脂ワニスから析出するのを抑制することができる。
前反応を行う際の反応温度は５０〜１５０℃が好ましく、７０〜１３０℃がより好ましく、８０〜１２０℃がさらに好ましい。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、目的の本樹脂ワニスを安定的に得ることが難しくなる。
<Manufacturing method of resin varnish>
The present resin varnish can be produced, for example, by mixing a maleimide compound, the allyl group-containing resin of the present invention, and a solvent. Mixing of each component can be carried out by a conventional method.
As the maleimide compound, a commercially available product can be used.
The allyl group-containing resin of the present invention can be produced by the above-mentioned production method (I) or (II).
When or after mixing the maleimide compound, the allyl group-containing resin of the present invention, and the solvent, a curing reaction catalyst and other components may be further mixed, if necessary.
After mixing the maleimide compound, the allyl group-containing resin of the present invention, and the solvent, the maleimide compound and the allyl group-containing resin may be pre-reacted. By performing a prereaction on the varnished mixture obtained by the above mixing, it is possible to suppress the precipitation of highly crystalline maleimide compounds from the resin varnish.
The reaction temperature at the time of carrying out the pre-reaction is preferably 50 to 150 ° C, more preferably 70 to 130 ° C, still more preferably 80 to 120 ° C. If the reaction temperature is too low, the reaction will not proceed, and if it is too high, it will be difficult to control the reaction, and it will be difficult to stably obtain the desired resin varnish.
本樹脂ワニスは、マレイミド化合物と本発明のアリル基含有樹脂とを含むため、加熱することによって硬化させ、硬化物とすることができる。
本樹脂ワニスを硬化させる際の加熱温度（硬化温度）は６０〜２５０℃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時間以下の前硬化を行い、溶剤を除去し、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。
Since the present resin varnish contains a maleimide compound and the allyl group-containing resin of the present invention, it can be cured by heating to obtain a cured product.
The heating temperature (curing temperature) when curing the resin varnish is preferably 60 to 250 ° C.
As an example of the curing operation, a method of pre-curing at the above-mentioned suitable temperature for 30 seconds or more and 1 hour or less, removing the solvent, and then further performing post-curing at the above-mentioned suitable temperature for 1 to 20 hours is performed. Can be mentioned.
＜作用効果＞
本樹脂ワニスにあっては、マレイミド化合物を用いているために、本樹脂ワニスの硬化物が高ガラス転移温度、高熱分解温度、低熱線膨張率を示す。また、本樹脂ワニスの硬化物は、硬化剤として本発明のアリル基含有樹脂を用いているため、マレイミド化合物をアリルフェノール樹脂で硬化させた硬化物に比べて、他部材（例えば銅張積層板に用いられる銅箔や、ガラスクロス等の繊維質基材等）との密着性に優れ、低誘電率、低誘電正接である。
<Effect>
Since the resin varnish uses a maleimide compound, the cured product of the resin varnish exhibits a high glass transition temperature, a high thermal decomposition temperature, and a low heat ray expansion rate. Further, since the cured product of the present resin varnish uses the allyl group-containing resin of the present invention as the curing agent, other members (for example, copper-clad laminate) are compared with the cured product obtained by curing the maleimide compound with the allyl phenol resin. It has excellent adhesion to copper foil used in the above, fibrous base materials such as glass cloth, etc.), and has a low dielectric constant and low dielectric positive contact.
本樹脂ワニスの用途としては、特に制限はない。例えば公知の熱硬化性成形材料の用途と同様であってよく、例えば封止材料、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。
本樹脂ワニスから得られる硬化物は、高ガラス転移温度、高熱分解温度、低熱膨張率、低誘電率、低誘電正接であり、耐熱性、絶縁性に優れる。また、他部材（例えば銅張積層板に用いられる銅箔や、ガラスクロス等の繊維質基材等）との密着性に優れる。そのため、本樹脂ワニスは、電子部品に用いられる積層板の製造用の材料として有用である。
The use of this resin varnish is not particularly limited. For example, it may be similar to the use of a known thermosetting molding material, and examples thereof include a sealing material, a film material, and a laminated material. More specific examples of applications include semiconductor encapsulation materials, resin materials for encapsulating electronic components, electrical insulation 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, fiber reinforced plastic (FRP) materials, and the like.
The cured product obtained from this resin varnish has a high glass transition temperature, a high thermal decomposition temperature, a low thermal expansion rate, a low dielectric constant, and a low dielectric loss tangent, and is excellent in heat resistance and insulating properties. In addition, it has excellent adhesion to other members (for example, copper foil used for copper-clad laminates, fibrous base materials such as glass cloth, etc.). Therefore, this resin varnish is useful as a material for manufacturing laminated boards used for electronic parts.
≪積層板の製造方法≫
本発明の積層板の製造方法では、本樹脂ワニスを繊維質基材に含浸させ、本樹脂ワニスが含浸した繊維質基材を加熱加圧し、硬化させて積層板を得る。
≪Manufacturing method of laminated board≫
In the method for producing a laminated board of the present invention, the fibrous base material is impregnated with the resin varnish, and the fibrous base material impregnated with the resin varnish is heated and pressed to be cured to obtain a laminated board.
本発明の積層板の製造方法により製造される積層板は、繊維質基材と本樹脂ワニスの硬化物とを含む繊維強化樹脂層を備える。前記積層板が備える繊維強化樹脂層の数は１層でもよく２層以上でもよい。
前記積層板は、前記繊維強化樹脂層以外の他の層をさらに備えてもよい。他の層としては、例えば銅箔等の金属箔層が挙げられる。
The laminated board manufactured by the method for manufacturing a laminated board of the present invention includes a fiber-reinforced resin layer containing a fibrous base material and a cured product of the present resin varnish. The number of fiber-reinforced resin layers included in the laminated board may be one layer or two or more layers.
The laminated board may further include a layer other than the fiber reinforced resin layer. Examples of the other layer include a metal foil layer such as copper foil.
繊維質基材としては、例えばガラス繊維、炭素繊維、セラミック繊維、ステンレス繊維等の無機繊維；綿、麻、紙等の天然繊維；ポリエステル樹脂、ポリアミド樹脂等の合成有機繊維；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種以上を組合わせて用いてもよい。
繊維質基材の形状は特に限定されず、例えば短繊維、ヤーン、マット、シート等が挙げられる。
Examples of the fibrous base material include inorganic fibers such as glass fiber, carbon fiber, ceramic fiber and stainless fiber; natural fiber such as cotton, linen and paper; synthetic organic fiber such as polyester resin and polyamide resin; and the like. Any one of these may be used alone, or two or more thereof may be used in combination.
The shape of the fibrous base material is not particularly limited, and examples thereof include short fibers, yarns, mats, and sheets.
本発明の積層板の製造方法の一実施形態として、本樹脂ワニスを繊維質基材に含浸させ、乾燥（溶剤を除去）してプリプレグを得て、必要に応じて前記プリプレグを複数枚積層し、必要に応じて前記プリプレグまたはその積層物の片面又は両面にさらに金属箔を積層し、加熱加圧して硬化させる方法が挙げられる。 As one embodiment of the method for producing a laminated board of the present invention, the fibrous base material is impregnated with the resin varnish and dried (solvent is removed) to obtain a prepreg, and a plurality of the prepregs are laminated as needed. If necessary, a method of further laminating a metal foil on one side or both sides of the prepreg or a laminate thereof and heating and pressurizing the prepreg or a laminate thereof to cure the prepreg.
繊維質基材に含浸させる本樹脂ワニスの量としては、特に限定されない。例えば、本樹脂ワニスの固形分量が、繊維質基材（１００質量％）に対して３０〜５０質量％程度とされる。
本樹脂ワニスが含浸した繊維質基材を加熱加圧する際の加熱温度は、前述の硬化温度が好ましい。加圧条件としては、２〜２０ｋＮ／ｍ２が好ましい。
The amount of the resin varnish impregnated in the fibrous base material is not particularly limited. For example, the solid content of the present resin varnish is about 30 to 50% by mass with respect to the fibrous base material (100% by mass).
The above-mentioned curing temperature is preferable as the heating temperature when the fibrous base material impregnated with the resin varnish is heated and pressurized. The pressurizing condition is preferably 2 to 20 kN / m 2.
＜作用効果＞
本発明の積層板の製造方法により得られる積層板は、繊維質基材と本樹脂ワニスの硬化物とを含む繊維強化樹脂層を備えており、かかる繊維強化樹脂層は、前記硬化物が高ガラス転移温度、高熱分解温度、低熱膨張率、低誘電率、低誘電正接であることから、耐熱性、絶縁性に優れる。また、金属箔層を備える場合の金属箔層と繊維強化樹脂層との間の密着性や、繊維強化樹脂層内での繊維質基材と本樹脂ワニスの硬化物との間の密着性に優れる。
<Effect>
The laminated board obtained by the method for producing a laminated board of the present invention includes a fiber-reinforced resin layer containing a fibrous base material and a cured product of the present resin varnish, and the cured product is high in the fiber-reinforced resin layer. Since it has a glass transition temperature, a high thermal decomposition temperature, a low thermal expansion rate, a low dielectric constant, and a low dielectric tangent, it is excellent in heat resistance and insulation. Further, in the case where the metal foil layer is provided, the adhesion between the metal foil layer and the fiber reinforced resin layer and the adhesion between the fibrous base material and the cured product of the present resin varnish in the fiber reinforced resin layer are improved. Excellent.
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。
Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples.
In each of the following examples, "%" indicates "mass%" unless otherwise specified.
The measurement methods used in each of 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 Ｇ３０００Ｈ＋Ｇ２０００Ｈ＋Ｇ２０００Ｈ。
[Mass average molecular weight (Mw), dispersity (Mw / Mn) of resin]
The standard material was measured as polystyrene using the following GPC apparatus and column.
GPC device: HLC8120 GPC manufactured by Tosoh Corporation.
Column: TSKgel G3000H + G2000H + G2000H.
［樹脂の軟化点］
ＪＩＳ Ｋ ６９１０：１９９９に従って軟化点（℃）を測定した。
[Resin softening point]
The softening point (° C.) 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（Ｐ）を測定した。
[Melted viscosity of resin]
The melt viscosity (P) 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］
得られた成形物（硬化物）を幅１０．０ｍｍ×長さ５．５ｍｍ×厚さ１．５ｍｍの大きさに加工し、測定試料とした。この測定試料について、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℃〜４００℃の範囲でｔａｎδを測定し、ガラス転移温度（℃）を求めた。硬化物のガラス転移温度は、３００℃以上が好ましい。
[Glass transition temperature of cured product]
The obtained molded product (cured product) was processed into a size of 10.0 mm in width × 5.5 mm in length × 1.5 mm in thickness to prepare a measurement sample. For this measurement sample, tan δ was measured in the range of 30 ° C. to 400 ° C. at a heating rate of 2 ° C./min using a viscoelasticity measuring device (DMA7100 manufactured by Hitachi High-Tech Science Co., Ltd.) to determine the glass transition temperature (° C.). It was. The glass transition temperature of the cured product is preferably 300 ° C. or higher.
［硬化物の５％熱分解温度］
得られた成形物を微粉砕し、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。硬化物の５％熱分解温度は、３６５℃以上が好ましい。
[5% thermal decomposition temperature of cured product]
The obtained molded product was finely pulverized and used as a measurement sample. For this measurement sample, the thermogravimetric weight loss was measured in the range of 30 to 800 ° C. at a heating rate of 10 ° C./min in an air atmosphere using a differential thermogravimetric simultaneous measuring device (TG / DTA6300 manufactured by Seiko Instruments). The 5% thermal decomposition temperature (° C.) was determined. The 5% thermal decomposition temperature of the cured product is preferably 365 ° C. or higher.
［硬化物の比誘電率、誘電正接］
得られた成形物を幅５０．０ｍｍ×長さ５０．０ｍｍ×厚さ１．５ｍｍの大きさに加工し、測定試料とした。この測定試料について、空洞共振摂動法により周波数１ＧＨｚにおける比誘電率（εr）および誘電正接（ｔａｎδ）を求めた。硬化物の比誘電率は、４．００以下が好ましい。硬化物の誘電正接は、０．０１以下が好ましい。
[Relative permittivity of cured product, dielectric loss tangent]
The obtained molded product was processed into a size of 50.0 mm in width × 50.0 mm in length × 1.5 mm in thickness to prepare a measurement sample. For this measurement sample, the relative permittivity (ε r ) and the dielectric loss tangent (tan δ) at a frequency of 1 GHz were determined by the cavity resonance perturbation method. The relative permittivity of the cured product is preferably 4.00 or less. The dielectric loss tangent of the cured product is preferably 0.01 or less.
［硬化物の線膨張係数］
得られた成形物を幅５．０ｍｍ×長さ５．０ｍｍ×厚さ１．５ｍｍの大きさに加工し、測定試料とした。この測定試料について、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℃〜４００℃の範囲で測定し、常温線膨張係数（ｐｐｍ）を求めた。常温線膨張係数は、３０℃での線膨張係数を示す。硬化物の常温線膨張係数は、５０ｐｐｍ以下が好ましい。
[Coefficient of linear expansion of cured product]
The obtained molded product was processed into a size of width 5.0 mm × length 5.0 mm × thickness 1.5 mm to prepare a measurement sample. This measurement sample was measured in the range of 30 ° C. to 400 ° C. at a heating rate of 2 ° C./min using a thermomechanical analyzer (TMA7100 manufactured by Hitachi High-Tech Science Co., Ltd.), and the coefficient of linear expansion (ppm) was determined. .. The coefficient of linear expansion at room temperature indicates the coefficient of linear expansion at 30 ° C. The coefficient of linear expansion of the cured product at room temperature is preferably 50 ppm or less.
［引張り接着強さ］
ＪＩＳ Ｋ ６８４９：１９９４に準拠した方法にて、接着剤として熱硬化性成形材料を用い、被着材として幅１０．０ｍｍ×長さ５０．０ｍｍ×厚さ１．０ｍｍの銅板を用いて、２２０℃で２時間の条件で硬化させたものについて、引張り接着強さ（Ｎ／ｍｍ２）を測定した。
[Tension adhesive strength]
220 using a thermosetting molding material as an adhesive and a copper plate with a width of 10.0 mm, a length of 50.0 mm, and a thickness of 1.0 mm as an adherend in a method according to JIS K 6849: 1994. The tensile adhesive strength (N / mm 2 ) of the product cured at ° C. for 2 hours was measured.
＜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。
<Manufacturing of aldehyde group-containing resin>
[Synthesis Example 1]
(Reaction of orthohydroxybenzaldehyde with 4,4'-bis (methoxymethyl) biphenyl; molar ratio = 0.40)
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 carried out for 4 hours. Methanol produced as a by-product in the reaction was removed from the system. After completion of the reaction, the reaction was neutralized and washed with water to remove unreacted orthohydroxybenzaldehyde to obtain an aldehyde-containing biphenyl resin. The softening point of the obtained resin was 81 ° C., and the melt viscosity at 150 ° C. was 1.2P. The mass average molecular weight (Mw) was 815 and the dispersity (Mw / Mn) was 1.48 by gel permeation chromatography analysis (hereinafter, sometimes abbreviated as GPC).
〔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 with para-xylene glycol dimethyl ether; molar ratio = 0.40)
850 g (6.967 mol) of orthohydroxybenzaldehyde, 462.6 g (2.787 mol) of para-xylene glycol dimethyl ether, 8.5 g of paratoluenesulfonic acid in a reaction vessel with a content of 1 L equipped with a thermometer, a stirrer, and a cooling tube. 1%) was charged with respect to orthohydroxybenzaldehyde, 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 from the system. After completion of the reaction, the reaction was neutralized and washed with water to remove unreacted orthohydroxybenzaldehyde to obtain an aldehyde-containing xylylene resin. The softening point of the obtained resin was 1.8 ° C., and the melt viscosity at 150 ° C. was 1.7P. The mass average molecular weight (Mw) by GPC was 756, and the dispersity (Mw / Mn) was 1.44.
〔実施例１〕
（アルデヒド基含有ビフェニル樹脂のアリルエーテル化；変性率約５０モル％）
温度計、攪拌機、冷却管を備えた反応容器に、合成例１で得たアルデヒド含有ビフェニル樹脂１００．０ｇ、ノルマルブタノール５０．０ｇ、ジアザビシクロウンデセン３３．８ｇを仕込み５０℃まで昇温して溶解した。次に、４０℃まで温度を下げ、塩化アリル２０．４ｇを発熱に注意しながら２時間かけて添加した。その後、１時間エージングし、１１０℃まで昇温した後、２時間エージングを行った。次に、メチルイソブチルケトン（ＭＩＢＫ）を１００ｇ添加し、反応で発生した塩を水洗で除去した。水洗後、使用したノルマルブタノール、ＭＩＢＫを１３０℃で除去し、アリル基含有樹脂Ａ（アリルエーテル化フェノールビフェニレン樹脂）を得た。
アリル基含有樹脂Ａの軟化点は６５．２℃、１５０℃における溶融粘度は１．８Ｐ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１６７８、分散度（Ｍｗ／Ｍｎ）は１．８１であった。核磁気共鳴分析（ＮＭＲ）によるアリルエーテル化率は５１％であった。
アリルエーテル化率は、樹脂中のフェノール性水酸基とアリルオキシ基との合計に対するアリルオキシ基の割合（モル％）を示す。アリルエーテル化率を変性率ともいう。
[Example 1]
(Aldehyde group-containing biphenyl resin allyl etherified; denaturation rate of about 50 mol%)
In a reaction vessel equipped with a thermometer, a stirrer, and a cooling tube, 100.0 g of the aldehyde-containing biphenyl resin obtained in Synthesis Example 1, 50.0 g of normal butanol, and 33.8 g of diazabicycloundecene were charged and heated to 50 ° C. Dissolved. Next, the temperature was lowered to 40 ° C., and 20.4 g of allyl chloride was added over 2 hours while paying attention to heat generation. Then, it was aged for 1 hour, heated to 110 ° C., and then aged for 2 hours. Next, 100 g of methyl isobutyl ketone (MIBK) was added, and the salt generated in the reaction was removed by washing with water. After washing with water, the used normal butanol and MIBK were removed at 130 ° C. to obtain an allyl group-containing resin A (allyl etherified phenol biphenylene resin).
The softening point of the allyl group-containing resin A was 65.2 ° C., and the melt viscosity at 150 ° C. was 1.8P. The mass average molecular weight (Mw) was 1678 and the dispersity (Mw / Mn) was 1.81 by gel permeation chromatography analysis (hereinafter, sometimes abbreviated as GPC). The allyl etherification rate by nuclear magnetic resonance spectroscopy (NMR) was 51%.
The allyl etherification rate indicates the ratio (mol%) of the allyloxy group to the total of the phenolic hydroxyl group and the allyloxy group in the resin. The allyl etherification rate is also called the denaturation rate.
（樹脂ワニスおよび成形物（硬化物）の製造）
上記アリル基含有樹脂Ａの１００ｇ（固形分）、大和化成工業株式会社製のＢＭＩ−１１００（４，４’−ジフェニルメタンビスマレイミド、マレイミド当量１７９ｇ／ｅｑ）の３４．４ｇ、硬化反応触媒としてジクミルパーオキサイドの１．３ｇをメチルエチルケトンに固形分６０％になるように溶解し、樹脂ワニスＡを得た。マレイミド化合物のマレイミド基とアリル基含有樹脂のアリル基とのモル比（マレイミド基／アリル基）は１であった。
上記樹脂ワニスＡをガラスクロス（Ｅガラス）に、樹脂分４０％になるように含浸し、１００℃で１０分間乾燥させ、溶剤を除去してプリプレグを得た。このプリプレグを６枚重ねて２００℃でプレス成形し、その後、２２０℃で２時間アフターベークを行い、厚さ１．５ｍｍの成形物Ａを得た。樹脂分とは、成形物の総質量に対する樹脂の割合を示す。
(Manufacturing of resin varnish and molded product (cured product))
100 g (solid content) of the allyl group-containing resin A, 34.4 g of BMI-1100 (4,5'-diphenylmethanebismaleimide, maleimide equivalent 179 g / eq) manufactured by Daiwa Kasei Kogyo Co., Ltd., and dicumyl as a curing reaction catalyst. 1.3 g of peroxide was dissolved in methyl ethyl ketone so as to have a solid content of 60% to obtain a resin varnish A. The molar ratio (maleimide group / allyl group) of the maleimide group of the maleimide compound to the allyl group of the allyl group-containing resin was 1.
The resin varnish A was impregnated into a glass cloth (E glass) so as to have a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six of these prepregs were stacked and press-molded at 200 ° C., and then after-baked at 220 ° C. for 2 hours to obtain a molded product A having a thickness of 1.5 mm. The resin content indicates the ratio of the resin to the total mass of the molded product.
〔実施例２〕
（アルデヒド基含有ビフェニル樹脂のアリルエーテル化；変性率約７０モル％）
温度計、攪拌機、冷却管を備えた反応容器に、合成例１で得たアルデヒド含有ビフェニル樹脂１００．０ｇ、ノルマルブタノール５０．０ｇ、ジアザビシクロウンデセン４７．３ｇを仕込み５０℃まで昇温して溶解した。次に、４０℃まで温度を下げ、塩化アリル２８．６ｇを発熱に注意しながら２時間かけて添加した。その後、１時間エージングし、１１０℃まで昇温した後、２時間エージングを行った。次に、ＭＩＢＫを１００ｇ添加し、反応で発生した塩を水洗で除去した。水洗後、使用したノルマルブタノール、ＭＩＢＫを１３０℃で除去し、アリル基含有樹脂Ｂ（アリルエーテル化フェノールビフェニレン樹脂）を得た。
アリル基含有樹脂Ｂの軟化点は６１．５℃、１５０℃における溶融粘度は１．２Ｐであった。ＧＰＣによる質量平均分子量（Ｍｗ）は１５６９、分散度（Ｍｗ／Ｍｎ）は１．７６であった。ＮＭＲによるアリルエーテル化率は７０％であった。
[Example 2]
(Aldehyde group-containing biphenyl resin allyl etherified; denaturation rate of about 70 mol%)
In a reaction vessel equipped with a thermometer, a stirrer, and a cooling tube, 100.0 g of the aldehyde-containing biphenyl resin obtained in Synthesis Example 1, 50.0 g of normal butanol, and 47.3 g of diazabicycloundecene were charged and heated to 50 ° C. Dissolved. Next, the temperature was lowered to 40 ° C., and 28.6 g of allyl chloride was added over 2 hours, paying attention to heat generation. Then, it was aged for 1 hour, heated to 110 ° C., and then aged for 2 hours. Next, 100 g of MIBK was added, and the salt generated in the reaction was removed by washing with water. After washing with water, the used normal butanol and MIBK were removed at 130 ° C. to obtain an allyl group-containing resin B (allyl etherified phenol biphenylene resin).
The softening point of the allyl group-containing resin B was 61.5 ° C., and the melt viscosity at 150 ° C. was 1.2P. The mass average molecular weight (Mw) by GPC was 1569, and the dispersity (Mw / Mn) was 1.76. The allyl etherification rate by NMR was 70%.
（樹脂ワニスおよび成形物（硬化物）の製造）
上記アリル基含有樹脂Ｂの１００ｇ（固形分）、大和化成工業株式会社製のＢＭＩ−１１００の４８．２ｇ、硬化反応触媒としてジクミルパーオキサイドの１．５ｇをメチルエチルケトンに固形分６０％になるように溶解し、樹脂ワニスＢを得た。マレイミド基／アリル基のモル比は１であった。
上記樹脂ワニスＢをガラスクロス（Ｅガラス）に、樹脂分４０％になるように含浸し、１００℃で１０分間乾燥させ、溶剤を除去してプリプレグを得た。このプリプレグを６枚重ねて２００℃でプレス成形し、その後、２２０℃で２時間アフターベークを行い、厚さ１．５ｍｍの成形物Ｂを得た。
(Manufacturing of resin varnish and molded product (cured product))
100 g (solid content) of the allyl group-containing resin B, 48.2 g of BMI-1100 manufactured by Daiwa Kasei Kogyo Co., Ltd., and 1.5 g of dicumyl peroxide as a curing reaction catalyst are added to methyl ethyl ketone so that the solid content is 60%. To obtain a resin varnish B. The molar ratio of maleimide group / allyl group was 1.
The resin varnish B was impregnated into a glass cloth (E glass) so as to have a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six of these prepregs were stacked and press-molded at 200 ° C., and then after-baked at 220 ° C. for 2 hours to obtain a molded product B having a thickness of 1.5 mm.
〔実施例３〕
（アルデヒド基含有ビフェニル樹脂のアリルエーテル化；変性率約１００モル％）
温度計、攪拌機、冷却管を備えた反応容器に、合成例１で得たアルデヒド含有ビフェニル樹脂１００．０ｇ、ノルマルブタノール５０．０ｇ、ジアザビシクロウンデセン６０．８ｇを仕込み５０℃まで昇温して溶解した。次に、４０℃まで温度を下げ、塩化アリル３６．７ｇを発熱に注意しながら２時間かけて添加した。その後、１時間エージングし１１０℃まで昇温した後、２時間エージングを行った。次に、ＭＩＢＫを１００ｇ添加し、反応で発生した塩を水洗で除去した。水洗後、使用したノルマルブタノール、ＭＩＢＫを１３０℃で除去し、アリル基含有樹脂Ｃ（アリルエーテル化フェノールビフェニレン樹脂）を得た。
アリル基含有樹脂Ｃの軟化点は５８．９℃、１５０℃における溶融粘度は０．８Ｐであった。ＧＰＣによる質量平均分子量（Ｍｗ）は１４８０、分散度（Ｍｗ／Ｍｎ）は１．６２であった。ＮＭＲによるアリルエーテル化率は９８％であった。
[Example 3]
(Aldehyde group-containing biphenyl resin allyl etherified; denaturation rate of about 100 mol%)
In a reaction vessel equipped with a thermometer, a stirrer, and a cooling tube, 100.0 g of the aldehyde-containing biphenyl resin obtained in Synthesis Example 1, 50.0 g of normal butanol, and 60.8 g of diazabicycloundecene were charged and heated to 50 ° C. Dissolved. Next, the temperature was lowered to 40 ° C., and 36.7 g of allyl chloride was added over 2 hours, paying attention to heat generation. Then, after aging for 1 hour and raising the temperature to 110 ° C., aging was performed for 2 hours. Next, 100 g of MIBK was added, and the salt generated in the reaction was removed by washing with water. After washing with water, the used normal butanol and MIBK were removed at 130 ° C. to obtain an allyl group-containing resin C (allyl etherified phenol biphenylene resin).
The softening point of the allyl group-containing resin C was 58.9 ° C., and the melt viscosity at 150 ° C. was 0.8P. The mass average molecular weight (Mw) by GPC was 1480, and the dispersity (Mw / Mn) was 1.62. The allyl etherification rate by NMR was 98%.
（樹脂ワニスおよび成形物（硬化物）の製造）
上記アリル基含有樹脂Ｃの１００ｇ（固形分）、大和化成工業株式会社製のＢＭＩ−１１００の６８．８ｇ、硬化反応触媒としてジクミルパーオキサイドの１．７ｇをメチルエチルケトンに固形分６０％になるように溶解し、樹脂ワニスＣを得た。マレイミド基／アリル基のモル比は１であった。
上記樹脂ワニスＣをガラスクロス（Ｅガラス）に、樹脂分４０％になるように含浸し、１００℃で１０分間乾燥させ、溶剤を除去してプリプレグを得た。このプリプレグを６枚重ねて２００℃でプレス成形し、その後、２２０℃で２時間アフターベークを行い、厚さ１．５ｍｍの成形物Ｃを得た。
(Manufacturing of resin varnish and molded product (cured product))
100 g (solid content) of the allyl group-containing resin C, 68.8 g of BMI-1100 manufactured by Daiwa Kasei Kogyo Co., Ltd., and 1.7 g of dicumyl peroxide as a curing reaction catalyst are added to methyl ethyl ketone so that the solid content is 60%. To obtain a resin varnish C. The molar ratio of maleimide group / allyl group was 1.
The resin varnish C was impregnated into a glass cloth (E glass) so as to have a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six of these prepregs were stacked and press-molded at 200 ° C., and then after-baked at 220 ° C. for 2 hours to obtain a molded product C having a thickness of 1.5 mm.
別途、上記アリル基含有樹脂Ｃの１００ｇ（固形分）、大和化成工業株式会社製のＢＭＩ−２３００（ポリフェニルメタンマレイミド、マレイミド当量１８６ｇ／ｅｑ）の７１．５ｇ、硬化反応触媒としてジクミルパーオキサイドの１．７ｇをメチルエチルケトンに固形分６０％になるように溶解し、樹脂ワニスＤを得た。マレイミド基／アリル基のモル比は１であった。
上記樹脂ワニスＤをガラスクロス（Ｅガラス）に、樹脂分４０％になるように含浸し、１００℃で１０分間乾燥させ、溶剤を除去してプリプレグを得た。このプリプレグを６枚重ねて２００℃でプレス成形し、その後、２２０℃で２時間アフターベークを行い、厚さ１．５ｍｍの成形物Ｄを得た。
Separately, 100 g (solid content) of the allyl group-containing resin C, 71.5 g of BMI-2300 (polyphenylmethane maleimide, maleimide equivalent 186 g / eq) manufactured by Daiwa Kasei Kogyo Co., Ltd., and dicumyl peroxide as a curing reaction catalyst. 1.7 g of the above was dissolved in methyl ethyl ketone so as to have a solid content of 60% to obtain a resin varnish D. The molar ratio of maleimide group / allyl group was 1.
The resin varnish D was impregnated into a glass cloth (E glass) so as to have a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six of these prepregs were stacked and press-molded at 200 ° C., and then after-baked at 220 ° C. for 2 hours to obtain a molded product D having a thickness of 1.5 mm.
〔実施例４〕
（アルデヒド基含有キシリレン樹脂のアリルエーテル化；変性率約７０モル％）
温度計、攪拌機、冷却管を備えた反応容器に、合成例２で得たアルデヒド含有キシリレン樹脂１００．０ｇ、ノルマルブタノール５０．０ｇ、ジアザビシクロウンデセン７３．４ｇを仕込み５０℃まで昇温して溶解した。次に、４０℃まで温度を下げ、塩化アリル４４．３ｇを発熱に注意しながら２時間かけて添加した。その後、１時間エージングし１１０℃まで昇温後、２時間エージングを行った。次に、ＭＩＢＫを１００ｇ添加し、反応で発生した塩を水洗で除去した。水洗後、使用したノルマルブタノール、ＭＩＢＫを１３０℃で除去し、アリル基含有樹脂Ｄ（アリルエーテル化フェノールキシリレン樹脂）を得た。
アリル基含有樹脂Ｄの軟化点は軟化点６０．５℃、１５０℃における溶融粘度は１．１Ｐであった。ＧＰＣによる質量平均分子量（Ｍｗ）は１４２６、分散度（Ｍｗ／Ｍｎ）は１．７３であった。ＮＭＲによるアリルエーテル化率は７２％であった。
[Example 4]
(Aldehyde group-containing xylylene resin allyl etherification; denaturation rate of about 70 mol%)
In a reaction vessel equipped with a thermometer, a stirrer, and a cooling tube, 100.0 g of the aldehyde-containing xylylene resin obtained in Synthesis Example 2, 50.0 g of normal butanol, and 73.4 g of diazabicycloundecene were charged and heated to 50 ° C. Dissolved. Next, the temperature was lowered to 40 ° C., and 44.3 g of allyl chloride was added over 2 hours, paying attention to heat generation. Then, it was aged for 1 hour, heated to 110 ° C., and then aged for 2 hours. Next, 100 g of MIBK was added, and the salt generated in the reaction was removed by washing with water. After washing with water, the used normal butanol and MIBK were removed at 130 ° C. to obtain an allyl group-containing resin D (allyl etherified phenol xylylene resin).
The softening point of the allyl group-containing resin D was a softening point of 60.5 ° C., and the melt viscosity at 150 ° C. was 1.1P. The mass average molecular weight (Mw) by GPC was 1426, and the dispersity (Mw / Mn) was 1.73. The allyl etherification rate by NMR was 72%.
（樹脂ワニスおよび成形物（硬化物）の製造）
上記アリル基含有樹脂Ｄの１００ｇ（固形分）、大和化成工業株式会社製のＢＭＩ−１１００の６６．１ｇ、硬化反応触媒としてジクミルパーオキサイドの１．７ｇをメチルエチルケトンに固形分６０％になるように溶解し、樹脂ワニスＥを得た。マレイミド基／アリル基のモル比は１であった。
上記樹脂ワニスＥをガラスクロス（Ｅガラス）に、樹脂分４０％になるように含浸し、１００℃で１０分間乾燥させ、溶剤を除去してプリプレグを得た。このプリプレグを６枚重ねて２００℃でプレス成形し、その後、２２０℃で２時間アフターベークを行い、厚さ１．５ｍｍの成形物Ｅを得た。
(Manufacturing of resin varnish and molded product (cured product))
100 g (solid content) of the allyl group-containing resin D, 66.1 g of BMI-1100 manufactured by Daiwa Kasei Kogyo Co., Ltd., and 1.7 g of dicumyl peroxide as a curing reaction catalyst are added to methyl ethyl ketone so that the solid content is 60%. To obtain a resin varnish E. The molar ratio of maleimide group / allyl group was 1.
The resin varnish E was impregnated into a glass cloth (E glass) so as to have a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six of these prepregs were stacked and press-molded at 200 ° C., and then after-baked at 220 ° C. for 2 hours to obtain a molded product E having a thickness of 1.5 mm.
〔実施例５〕
（アルデヒド基含有ビフェニル樹脂のアリルエーテル化およびアリル基転位；変性率約１００モル％）
温度計、攪拌機、冷却管を備えた反応容器に、合成例１で得たアルデヒド含有ビフェニル樹脂１００．０ｇ、ノルマルブタノール５０．０ｇ、ジアザビシクロウンデセン６０．８ｇを仕込み５０℃まで昇温して溶解した。次に、４０℃まで温度を下げ、塩化アリル３６．７ｇを発熱に注意しながら２時間かけて添加した。その後、１時間エージングし１１０℃まで昇温後、２時間エージングを行った。次に、ＭＩＢＫを１００ｇ添加し、反応で発生した塩を水洗で除去した。水洗後、使用したノルマルブタノール、ＭＩＢＫを１３０℃で除去しながら１８０℃まで昇温した。次に、Ｎ２雰囲気下、１８０℃で５時間反応（転位反応）を行い、アリル基含有樹脂Ｅ（アリルエーテル化後、アリル基を転位させたフェノールビフェニレン樹脂）を得た。
アリル基含有樹脂Ｅの軟化点は６７．８℃、１５０℃における溶融粘度は２．１Ｐであった。ＧＰＣによる質量平均分子量（Ｍｗ）は１９２１、分散度（Ｍｗ／Ｍｎ）は１．９１であった。ＮＭＲによるアリルエーテル化率（アリル基転位前）は９８％、アリル基転位率は９９％であった。
[Example 5]
(Allyl etherification and allyl group rearrangement of aldehyde group-containing biphenyl resin; denaturation rate of about 100 mol%)
In a reaction vessel equipped with a thermometer, a stirrer, and a cooling tube, 100.0 g of the aldehyde-containing biphenyl resin obtained in Synthesis Example 1, 50.0 g of normal butanol, and 60.8 g of diazabicycloundecene were charged and heated to 50 ° C. Dissolved. Next, the temperature was lowered to 40 ° C., and 36.7 g of allyl chloride was added over 2 hours, paying attention to heat generation. Then, it was aged for 1 hour, heated to 110 ° C., and then aged for 2 hours. Next, 100 g of MIBK was added, and the salt generated in the reaction was removed by washing with water. After washing with water, the temperature was raised to 180 ° C. while removing the used normal butanol and MIBK at 130 ° C. Then, N 2 atmosphere, for 5 hours (rearrangement reaction) at 180 ° C., an allyl group-containing resin E (after allyl etherification, allyl group was dislocations phenol biphenylene resin) was obtained.
The softening point of the allyl group-containing resin E was 67.8 ° C., and the melt viscosity at 150 ° C. was 2.1P. The mass average molecular weight (Mw) by GPC was 1921, and the dispersity (Mw / Mn) was 1.91. The allyl etherification rate (before allyl group rearrangement) by NMR was 98%, and the allyl group rearrangement rate was 99%.
（樹脂ワニスおよび成形物（硬化物）の製造）
上記アリル基含有樹脂Ｅの１００ｇ（固形分）、大和化成工業株式会社製のＢＭＩ−１１００の４８．２ｇ、硬化反応触媒としてジクミルパーオキサイドの１．５ｇをメチルエチルケトンに固形分６０％になるように溶解し、樹脂ワニスＦを得た。マレイミド基／アリル基のモル比は１であった。
上記樹脂ワニスＦをガラスクロス（Ｅガラス）に、樹脂分４０％になるように含浸し、１００℃で１０分間乾燥させ、溶剤を除去してプリプレグを得た。このプリプレグを６枚重ねて２００℃でプレス成形し、その後、２２０℃で２時間アフターベークを行い、厚さ１．５ｍｍの成形物Ｆを得た。
(Manufacturing of resin varnish and molded product (cured product))
100 g (solid content) of the allyl group-containing resin E, 48.2 g of BMI-1100 manufactured by Daiwa Kasei Kogyo Co., Ltd., and 1.5 g of dicumyl peroxide as a curing reaction catalyst are added to methyl ethyl ketone so that the solid content is 60%. To obtain a resin varnish F. The molar ratio of maleimide group / allyl group was 1.
The resin varnish F was impregnated into a glass cloth (E glass) so as to have a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six of these prepregs were stacked and press-molded at 200 ° C., and then after-baked at 220 ° C. for 2 hours to obtain a molded product F having a thickness of 1.5 mm.
別途、上記アリル基含有樹脂Ｅの１００ｇ（固形分）、大和化成工業株式会社製のＢＭＩ−２３００の５０．１ｇ、硬化反応触媒としてジクミルパーオキサイドの１．５ｇをメチルエチルケトンに固形分６０％になるように溶解し、樹脂ワニスＧを得た。マレイミド基／アリル基のモル比は１であった。
上記樹脂ワニスＧをガラスクロス（Ｅガラス）に、樹脂分４０％になるように含浸し、１００℃で１０分間乾燥させ、溶剤を除去してプリプレグを得た。このプリプレグを６枚重ねて２００℃でプレス成形し、その後、２２０℃で２時間アフターベークを行い、厚さ１．５ｍｍの成形物Ｇを得た。
Separately, 100 g (solid content) of the above allyl group-containing resin E, 50.1 g of BMI-2300 manufactured by Daiwa Kasei Kogyo Co., Ltd., and 1.5 g of dicumyl peroxide as a curing reaction catalyst are added to methyl ethyl ketone to 60% solid content. The resin varnish G was obtained. The molar ratio of maleimide group / allyl group was 1.
The resin varnish G was impregnated into a glass cloth (E glass) so as to have a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six of these prepregs were stacked and press-molded at 200 ° C., and then after-baked at 220 ° C. for 2 hours to obtain a molded product G having a thickness of 1.5 mm.
〔実施例６〕
（アルデヒド基含有キシリレン樹脂のアリルエーテル化およびアリル基転位；変性率約７０モル％）
温度計、攪拌機、冷却管を備えた反応容器に、合成例２で得たアルデヒド含有キシリレン樹脂１００．０ｇ、ノルマルブタノール５０．０ｇ、ジアザビシクロウンデセン７３．４ｇを仕込み５０℃まで昇温して溶解した。次に、４０℃まで温度を下げ、塩化アリル４４．３ｇを発熱に注意しながら２時間かけて添加した。その後、１時間エージングし１１０℃まで昇温後、２時間エージングを行った。次に、ＭＩＢＫを１００ｇ添加し、反応で発生した塩を水洗で除去した。水洗後、使用したノルマルブタノール、ＭＩＢＫを１３０℃で除去しながら１８０℃まで昇温した。次に、Ｎ２雰囲気下、１８０℃で５時間反応（転位反応）を行い、アリル基含有樹脂Ｆ（アリルエーテル化後、アリル基を転位させたフェノールキシリレン樹脂）を得た。
アリル基含有樹脂Ｆの軟化点は６５．５℃、１５０℃における溶融粘度は１．８Ｐであった。ＧＰＣによる質量平均分子量（Ｍｗ）は１６８９、分散度（Ｍｗ／Ｍｎ）は１．８８であった。ＮＭＲによるアリルエーテル化率（アリル基転位前）は７１％、アリル基転位率は９９％であった。
[Example 6]
(Aldehyde group-containing xylylene resin allyl etherification and allyl group rearrangement; denaturation rate of about 70 mol%)
In a reaction vessel equipped with a thermometer, a stirrer, and a cooling tube, 100.0 g of the aldehyde-containing xylylene resin obtained in Synthesis Example 2, 50.0 g of normal butanol, and 73.4 g of diazabicycloundecene were charged and heated to 50 ° C. Dissolved. Next, the temperature was lowered to 40 ° C., and 44.3 g of allyl chloride was added over 2 hours, paying attention to heat generation. Then, it was aged for 1 hour, heated to 110 ° C., and then aged for 2 hours. Next, 100 g of MIBK was added, and the salt generated in the reaction was removed by washing with water. After washing with water, the temperature was raised to 180 ° C. while removing the used normal butanol and MIBK at 130 ° C. Then, N 2 atmosphere, for 5 hours (rearrangement reaction) at 180 ° C., (after allyl etherification, allyl group was dislocations phenol xylylene resin) allyl group-containing resin F was obtained.
The softening point of the allyl group-containing resin F was 65.5 ° C., and the melt viscosity at 150 ° C. was 1.8P. The mass average molecular weight (Mw) by GPC was 1689, and the dispersity (Mw / Mn) was 1.88. The allyl etherification rate (before allyl group rearrangement) by NMR was 71%, and the allyl group rearrangement rate was 99%.
（樹脂ワニスおよび成形物（硬化物）の製造）
上記アリル基含有樹脂Ｆの１００ｇ（固形分）、大和化成工業株式会社製のＢＭＩ−１１００の６６．１ｇ、硬化反応触媒としてジクミルパーオキサイドの１．７ｇをメチルエチルケトンに固形分６０％になるように溶解し、樹脂ワニスＨを得た。マレイミド基／アリル基のモル比は１であった。
上記樹脂ワニスＨをガラスクロス（Ｅガラス）に、樹脂分４０％になるように含浸し、１００℃で１０分間乾燥させ、溶剤を除去してプリプレグを得た。このプリプレグを６枚重ねて２００℃でプレス成形し、その後、２２０℃で２時間アフターベークを行い、厚さ１．５ｍｍの成形物Ｈを得た。
(Manufacturing of resin varnish and molded product (cured product))
100 g (solid content) of the allyl group-containing resin F, 66.1 g of BMI-1100 manufactured by Daiwa Kasei Kogyo Co., Ltd., and 1.7 g of dicumyl peroxide as a curing reaction catalyst are added to methyl ethyl ketone so that the solid content is 60%. To obtain a resin varnish H. The molar ratio of maleimide group / allyl group was 1.
The resin varnish H was impregnated into a glass cloth (E glass) so as to have a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six of these prepregs were stacked and press-molded at 200 ° C., and then after-baked at 220 ° C. for 2 hours to obtain a molded product H having a thickness of 1.5 mm.
〔比較例１〕
アリルフェノール樹脂として、群栄化学工業株式会社製の製品名：ＸＰＬ−４４３７Ｅ（アリルフェノールホルムアルデヒド樹脂）を用いた。この樹脂は常温で液状であり、２５℃での粘度はＥ型粘度計で３１Ｐａ・ｓであった。
上記アリルフェノール樹脂の１００ｇ、大和化成工業株式会社製のＢＭＩ１１００の１２０．９ｇ、硬化促進剤としてジクミルパーオキサイドの２．２ｇをメチルエチルケトンに固形分６０％になるように溶解し、樹脂ワニスＩを得た。
上記樹脂ワニスＩをガラスクロス（Ｅガラス）に、樹脂分４０％になるように含浸し、１００℃１０分乾燥させ、溶剤を除去してプリプレグを得た。このプリプレグを６枚重ねて２００℃でプレス成形し、その後、２２０℃で２時間アフターベークを行い、厚さ１．５ｍｍの成形物Ｉを得た。
[Comparative Example 1]
As the allylphenol resin, a product name: XPL-4437E (allylphenol formaldehyde resin) manufactured by Gun Ei Chemical Industry Co., Ltd. was used. This resin was liquid at room temperature, and the viscosity at 25 ° C. was 31 Pa · s on an E-type viscometer.
100 g of the above allyl phenol resin, 120.9 g of BMI1100 manufactured by Daiwa Kasei Kogyo Co., Ltd., and 2.2 g of dicumyl peroxide as a curing accelerator were dissolved in methyl ethyl ketone so as to have a solid content of 60%, and resin varnish I was added. Obtained.
The resin varnish I was impregnated into a glass cloth (E glass) so as to have a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six of these prepregs were stacked and press-molded at 200 ° C., and then after-baked at 220 ° C. for 2 hours to obtain a molded product I having a thickness of 1.5 mm.
上記成形物Ａ〜Ｉについて、ガラス転移温度、５％熱分解温度、常温線膨張係数、比誘電率、誘電正接を測定した。また、各成形物に用いた樹脂ワニスを用いて、引張り接着強さを測定した。結果を表１〜２に示した。
樹脂成形物Ａ〜Ｉに用いたアリル基含有樹脂、マレイミド化合物、硬化反応触媒それぞれの種類、アリル基含有樹脂に用いたアルデヒド基含有樹脂、アリル基の形態、変性率を表１〜２に併記した。
The glass transition temperature, 5% thermal decomposition temperature, room temperature linear expansion coefficient, relative permittivity, and dielectric loss tangent were measured for the above-mentioned molded products A to I. In addition, the tensile adhesive strength was measured using the resin varnish used for each molded product. The results are shown in Tables 1 and 2.
Tables 1 and 2 show the types of the allyl group-containing resin, the maleimide compound, and the curing reaction catalyst used in the resin moldings A to I, the aldehyde group-containing resin used in the allyl group-containing resin, the form of the allyl group, and the modification rate. did.
樹脂ワニスＡ〜Ｈから得た成形物Ａ〜Ｈは、樹脂ワニスＩから得た成形物Ｉに比べて、引張り接着強さが強く、密着性に優れていた。また、比誘電率、誘電正接が低かった。さらに、ガラス転移温度、５％熱分解温度、常温線膨張係数も充分に優れていた。 The molded products A to H obtained from the resin varnishes A to H had stronger tensile adhesive strength and excellent adhesion than the molded products I obtained from the resin varnish I. In addition, the relative permittivity and dielectric loss tangent were low. Further, the glass transition temperature, the 5% thermal decomposition temperature, and the coefficient of linear expansion at room temperature were also sufficiently excellent.
本樹脂ワニスによれば、高ガラス転移温度、高熱分解温度、低誘電率、低誘電正接、高密着性の硬化物が得られる。そのため本樹脂ワニスは、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、電気絶縁材料、銅張り積層板用樹脂材料、レジスト材料、電子部品の封止用樹脂材料、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、ビルドアップ積層板材料、ＦＲＰ等の幅広い用途に使用することができる。 According to this resin varnish, a cured product having a high glass transition temperature, a high thermal decomposition temperature, a low dielectric constant, a low dielectric loss tangent, and a high adhesion can be obtained. Therefore, this resin varnish is extremely useful as a highly functional polymer material, and as a thermally and electrically excellent material, a semiconductor encapsulation material, an electrically insulating material, a resin material for a copper-clad laminate, a resist material, and an electronic component. It can be used in a wide range of applications such as sealing resin materials, resin materials for liquid crystal color filters, paints, various coating agents, adhesives, build-up laminate materials, and FRP.
Claims (6)
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５０〜１００モル％であるアリル基含有樹脂。
The total content of the structural unit (2) and the structural unit (4) is the same as that of the structural unit (1), the structural unit (2), the structural unit (3), and the structural unit (4). Allyl group-containing resin in an amount of 50 to 100 mol% based on the total.
前記構成単位（２）と前記構成単位（２Ａ）と前記構成単位（４）と前記構成単位（４Ａ）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（２Ａ）と前記構成単位（３）と前記構成単位（４）と前記構成単位（４Ａ）との合計に対して５０〜１００モル％であるアリル基含有樹脂。
The total content of the structural unit (2), the structural unit (2A), the structural unit (4), and the structural unit (4A) is the total content of the structural unit (1), the structural unit (2), and the structural unit (2). An allyl group-containing resin that is 50 to 100 mol% with respect to the total of the structural unit (2A), the structural unit (3), the structural unit (4), and the structural unit (4A).
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