KR20220106227A - Maleimide resin mold, method for manufacturing maleimide resin mold, maleimide resin composition, and cured product thereof - Google Patents
Maleimide resin mold, method for manufacturing maleimide resin mold, maleimide resin composition, and cured product thereof Download PDFInfo
- Publication number
- KR20220106227A KR20220106227A KR1020227024381A KR20227024381A KR20220106227A KR 20220106227 A KR20220106227 A KR 20220106227A KR 1020227024381 A KR1020227024381 A KR 1020227024381A KR 20227024381 A KR20227024381 A KR 20227024381A KR 20220106227 A KR20220106227 A KR 20220106227A
- Authority
- KR
- South Korea
- Prior art keywords
- maleimide resin
- resin molded
- maleimide
- molded body
- film
- Prior art date
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- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 229920005989 resin Polymers 0.000 title claims abstract description 187
- 239000011347 resin Substances 0.000 title claims abstract description 187
- 239000011342 resin composition Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 150000002170 ethers Chemical class 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 7
- 239000004917 carbon fiber Substances 0.000 abstract description 7
- 239000003566 sealing material Substances 0.000 abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 5
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- 239000002131 composite material Substances 0.000 abstract description 4
- 239000003365 glass fiber Substances 0.000 abstract description 4
- 239000011208 reinforced composite material Substances 0.000 abstract description 4
- 239000003973 paint Substances 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000012774 insulation material Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 78
- 239000000243 solution Substances 0.000 description 43
- 239000002904 solvent Substances 0.000 description 33
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000009826 distribution Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 239000013557 residual solvent Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 238000005227 gel permeation chromatography Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 150000003949 imides Chemical class 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- -1 maleimide compound Chemical class 0.000 description 10
- 238000010298 pulverizing process Methods 0.000 description 10
- 238000000465 moulding Methods 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 235000011054 acetic acid Nutrition 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000004982 aromatic amines Chemical class 0.000 description 6
- 238000010533 azeotropic distillation Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
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- 235000019645 odor Nutrition 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
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- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
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- 239000004952 Polyamide Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 238000001879 gelation Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QMTFKWDCWOTPGJ-KVVVOXFISA-N (z)-octadec-9-enoic acid;tin Chemical compound [Sn].CCCCCCCC\C=C/CCCCCCCC(O)=O QMTFKWDCWOTPGJ-KVVVOXFISA-N 0.000 description 1
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-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
- 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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
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- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
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- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
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- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
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- 230000001771 impaired effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 125000005641 methacryl group Chemical group 0.000 description 1
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- 235000010755 mineral Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/36—Amides or imides
- C08F22/40—Imides, e.g. cyclic imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/04—Homopolymers or copolymers of nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
고신뢰성 반도체 밀봉재 용도, 전기·전자부품 절연재료 용도, 및 적층판(프린트 배선 유리섬유 강화 복합재료)이나 CFRP(탄소섬유 강화 복합재료)를 비롯한 각종 복합재료 용도, 각종 접착제 용도, 각종 도료 용도, 구조용 부재 등에 유용한 작업성, 생산성이 뛰어나고, 환경폭로가 적은 말레이미드 수지 성형체, 말레이미드 수지 조성물 및 그 경화물에 제공한다. 말레이미드 수지 성형체는 말레이미드 수지와 유기용제를 함유하고, 필름상 또는 플레이크상이다.High-reliability semiconductor sealing material use, electrical/electronic component insulation material use, and various composite materials including laminates (printed wiring glass fiber reinforced composite material) and CFRP (carbon fiber reinforced composite material), various adhesive applications, various paint applications, structural use It is provided for a maleimide resin molded article, a maleimide resin composition, and a cured product thereof, which is useful for a member and the like, has excellent workability and productivity, and is less exposed to the environment. The maleimide resin molded body contains a maleimide resin and an organic solvent, and is in the form of a film or flakes.
Description
본 발명은 말레이미드 수지 성형체, 말레이미드 수지 성형체의 제조 방법, 말레이미드 수지 조성물 및 그 경화물에 관한 것이다. 상세하게는, 고신뢰성 반도체 밀봉재 용도, 전기·전자부품 절연재료 용도, 및 적층판(프린트 배선 유리섬유 강화 복합재료)이나 CFRP(탄소섬유 강화 복합재료)를 비롯한 각종 복합재료 용도, 각종 접착제 용도, 각종 도료 용도, 구조용 부재 등에 유용한 작업성, 생산성이 뛰어나고, 환경폭로가 적은 말레이미드 수지 성형체, 말레이미드 수지 성형체의 제조 방법, 말레이미드 수지 조성물 및 그 경화물에 관한 것이다.The present invention relates to a maleimide resin molded article, a method for producing a maleimide resin molded article, a maleimide resin composition, and a cured product thereof. Specifically, high-reliability semiconductor sealing material use, electrical/electronic component insulation material use, and various composite materials including laminates (printed wiring glass fiber reinforced composite material) and CFRP (carbon fiber reinforced composite material), various adhesive applications, various The present invention relates to a maleimide resin molded article useful for use in paints, structural members, etc., excellent in workability and productivity, and little exposure to the environment, a method for producing a maleimide resin molded article, a maleimide resin composition, and a cured product thereof.
말레이미드 수지는 에폭시 수지를 넘는 내열성을 가짐과 아울러 에폭시 수지와 동등한 성형성을 갖고, 또한 저선팽창계수, 고Tg라고 하는 성질도 갖는 화합물이다. 폴리말레이미드 화합물은 단독으로 가교시키거나, 또는 각종의 말레이미드 화합물 또는 가교제와 반응시킴으로써, 내열성, 난연성이 우수한 재료를 부여할 수 있어 밀봉재료, 기반재료, 절연재료 등의 각종 용도로 사용되고 왔다. 특히 매우 높은 내열성 및 성형성을 양립하는 것이 필요한 고내열 기반재료, 플렉시블 기판재료, 고내열 저유전재료, 고내열 CFRP용 재료(탄소섬유 복합재료), 차량탑재용 SiC 파워 디바이스용 고내열 밀봉재료 용도에 사용된다.Maleimide resin is a compound which has heat resistance exceeding an epoxy resin, has moldability equivalent to an epoxy resin, and also has the property of a low coefficient of linear expansion and high Tg. The polymaleimide compound can be crosslinked alone or reacted with various maleimide compounds or crosslinking agents to provide a material excellent in heat resistance and flame retardancy, and has been used in various applications such as sealing materials, base materials, and insulating materials. In particular, high heat resistance base materials, flexible substrate materials, high heat resistance low dielectric materials, high heat resistance CFRP materials (carbon fiber composite materials) that require both very high heat resistance and moldability, and high heat resistance sealing materials for SiC power devices for vehicle mounting used for the purpose
종래, 말레이미드 수지는 자기반응성을 갖기 때문에 그 인출에 있어서는 재결정 등 결정 분체에서의 인출이나, 또는 재침전에 의한 수지 분말상으로서 시판되고 있는 것이 대부분이고(특허문헌 1을 참조), 사용시에는 분말이 날리거나 하는 것에 의해 작업성·생산성 뿐만 아니라, 환경에의 오염(오염, 및 인체에의 흡입) 등의 문제가 있었다. 또한 결정화, 침전의 때에 용제 등의 혼입이 있어 전부 제거할 수 없다고 하는 과제가 있고, 제조시에 사용하는 아세트산류가 혼입되고, 만들어진 제품에 아세트산의 악취가 남아 작업자의 안전성에 관계되는 과제가 된다. 이러한 배경으로부터, 작업성, 생산성, 환경 안전성이 우수한 말레이미드 성형체가 요망되고 있다. 예를 들면, 특허문헌 2는 이배퍼레이터를 사용한 말레이미드 수지 용액의 용융 인출 방법을 개시하고 있다.Conventionally, since maleimide resins have self-reactivity, most of them are commercially available as resin powders by extraction from crystalline powder such as recrystallization, or by re-precipitation (see Patent Document 1). In addition to workability and productivity, there were problems such as pollution to the environment (contamination and inhalation to the human body). In addition, there is a problem that solvents are mixed during crystallization and precipitation and cannot be completely removed, and acetic acids used during production are mixed, and the odor of acetic acid remains in the manufactured product, which is a problem related to the safety of workers. . From such a background, the maleimide molded body excellent in workability|operativity, productivity, and environmental safety is desired. For example, patent document 2 is disclosing the melt-drawing method of the maleimide resin solution using the evaporator.
그러나, 특허문헌 2에서는 소량 스케일에서는 큰 변화는 없었지만, 합성량을 많게 했을 경우 용매 증류제거에 장시간을 요하기 때문에, 그 동안에 자기중합이 진행될 우려가 있다. 따라서, 실생산에서의 제조에 있어서는 중합이나 겔화의 리스크가 매우 크고, 분자량 증가에 의한 점도의 상승 및 생산할 때마다 특성이 다른 등의, 성형성·안정 생산성의 관점에서 과제가 있다. 또한, 이 중합을 억제하기 위해서 용제 회수 온도를 낮추면, 특히 50℃ 이상의 연화점을 갖는 말레이미드 수지의 경우 용제의 제거가 곤란하게 되어 용제의 잔류가 많아지기(특히 30000ppm을 초과하는 용제의 잔류) 때문에, 성형시의 보이드나 크랙의 생성의 우려, 및 작업자에의 폭로 등 안전성에도 문제가 있다. 또한, 이들 말레이미드 수지의 합성에 있어서는 아세트산이나 톨루엔, 크실렌과 같은 인체에의 영향이 있는 물질을 사용할 경우가 있기 때문에 용제의 잔류는 특히 문제가 된다.However, in Patent Document 2, although there is no significant change on a small scale, when the synthesis amount is increased, since a long time is required for solvent distillation, there is a possibility that self-polymerization proceeds during that time. Therefore, in production in actual production, the risk of polymerization or gelation is very large, and there is a problem in terms of moldability and stable productivity, such as an increase in viscosity due to an increase in molecular weight and different characteristics at each production. In addition, if the solvent recovery temperature is lowered to suppress this polymerization, especially in the case of a maleimide resin having a softening point of 50° C. or higher, it becomes difficult to remove the solvent, and the residual solvent increases (particularly, the residual solvent exceeding 30000 ppm). , there is also a problem in safety such as fear of generation of voids or cracks during molding, and exposure to workers. In addition, in the synthesis of these maleimide resins, since substances having an effect on the human body such as acetic acid, toluene, and xylene may be used, the residual solvent is particularly problematic.
그래서, 본 발명은 작업성·생산성이 뛰어나고, 환경폭로가 적은 말레이미드 수지 성형체를 제공하는 것을 목적으로 한다.Then, this invention is excellent in workability|operativity and productivity, and an object of this invention is to provide the maleimide resin molded object with little environmental exposure.
본 발명자들은 상기 과제를 해결하기 위해서 예의 검토한 결과, 종래의 결정 상이나 분말상이 아니라, 필름상 또는 플레이크상의 성형체로서 인출함으로써 작업성, 생산성 등이 뛰어나고, 환경폭로가 적어지는 것을 찾아내고, 본 발명을 완성하기에 이르렀다.As a result of intensive studies to solve the above problems, the present inventors have found that workability, productivity, etc. are excellent, and environmental exposure is reduced by withdrawing as a molded body in the form of a film or flake rather than in a conventional crystal or powder form, and the present invention came to complete.
즉, 본 발명은,That is, the present invention is
[1] 말레이미드 수지와 유기용제를 함유하고, 필름상 또는 플레이크상인 말레이미드 수지 성형체,[1] A maleimide resin molded article containing a maleimide resin and an organic solvent and in the form of a film or flakes;
[2] 상기 유기용제의 함유량이 30000ppm 이하인 전항 [1]에 기재의 말레이미드 수지 성형체,[2] The maleimide resin molded article according to the above [1], wherein the content of the organic solvent is 30000 ppm or less;
[3] 상기 유기용제가 탄소수 3∼10의 방향족 탄화수소, 케톤류, 에스테르류 및 에테르류에서 선택되는 적어도 1종인 전항 [1] 또는 [2]에 기재의 말레이미드 수지 성형체,[3] The maleimide resin molded article according to the preceding [1] or [2], wherein the organic solvent is at least one selected from aromatic hydrocarbons having 3 to 10 carbon atoms, ketones, esters and ethers;
[4] 두께가 10㎛∼3㎜인 전항 [1]∼[3] 중 어느 한 항에 기재의 말레이미드 수지 성형체,[4] The maleimide resin molded product according to any one of [1] to [3], wherein the thickness is 10 µm to 3 mm;
[5] 상기 말레이미드 수지가 평균 관능기수가 2∼20인 반복단위를 갖는 노볼락형 말레이미드 수지인 전항 [1]∼[4] 중 어느 한 항에 기재의 말레이미드 수지 성형체,[5] The maleimide resin molded product according to any one of [1] to [4], wherein the maleimide resin is a novolac-type maleimide resin having a repeating unit having an average number of functional groups of 2 to 20;
[6] 상기 말레이미드 수지의 연화점이 50∼150℃인 전항 [1]∼[5] 중 어느 한 항에 기재의 말레이미드 수지 성형체,[6] The maleimide resin molded article according to any one of [1] to [5] above, wherein the softening point of the maleimide resin is 50 to 150°C;
[7] 말레이미드 수지를 유기용제에 용해한 용액을, 지지체의 표면 상에 도포하고, 건조하는 말레이미드 화합물 성형체의 제조 방법,[7] A method for producing a maleimide compound molded article in which a solution of a maleimide resin dissolved in an organic solvent is applied on the surface of a support and dried;
[8] 상기 유기용제가 탄소수 3∼10의 방향족 탄화수소, 케톤류, 에스테르류, 에테르류에서 선택되는 적어도 1종인 전항 [7]에 기재의 말레이미드 화합물 성형체의 제조 방법,[8] The method for producing a maleimide compound molded article according to the preceding [7], wherein the organic solvent is at least one selected from aromatic hydrocarbons having 3 to 10 carbon atoms, ketones, esters, and ethers;
[9] 건조온도가 80∼200℃인 전항 [7] 또는 [8]에 기재의 말레이미드 화합물 성형체의 제조 방법,[9] The method for producing a maleimide compound molded article according to the above [7] or [8], wherein the drying temperature is 80 to 200 °C;
[10] 전항 [7]∼[9] 중 어느 한 항에 기재된 제조 방법에 의해 얻어진 말레이미드 수지 성형체,[10] A maleimide resin molded article obtained by the production method according to any one of [7] to [9] above;
[11] 전항 [1]∼[6] 및 전항 [10] 중 어느 한 항에 기재된 말레이미드 수지 성형체를 포함하는 말레이미드 수지 조성물,[11] A maleimide resin composition comprising the maleimide resin molded article according to any one of [1] to [6] and [10],
[12] 말레이미드 수지와 가교반응 가능한 화합물 및 경화촉진제에서 선택되는 적어도 어느 하나를 더 포함하는 전항 [11]에 기재의 말레이미드 수지 조성물,[12] The maleimide resin composition according to the preceding [11], further comprising at least one selected from a compound capable of crosslinking with the maleimide resin and a curing accelerator;
[13] 전항 [11] 또는 [12]에 기재된 말레이미드 수지 조성물의 경화물,[13] A cured product of the maleimide resin composition according to the preceding [11] or [12];
에 관한 것이다.is about
본 발명의 말레이미드 수지 성형체는 필름상 또는 플레이크상으로 성형되어 있기 때문에 유기용제 함유량을 억제할 수 있고, 작업성·생산성이 뛰어나고, 환경폭로가 적은 말레이미드 수지 성형체를 제공할 수 있다. 또한, 유기용제의 양을 억제할 수 있기 때문에 성형시의 보이드나 크랙의 생성을 막을 수 있다.Since the maleimide resin molded body of the present invention is molded into a film or flake shape, the content of the organic solvent can be suppressed, and it is possible to provide a maleimide resin molded body having excellent workability and productivity and little exposure to the environment. In addition, since the amount of the organic solvent can be suppressed, the formation of voids and cracks during molding can be prevented.
도 1은 합성예 2로부터 얻어진 중합반응 종료시의 말레이미드 수지 용액(V1)의 분자량 분포를 나타내는 도면이다.
도 2는 실시예 1로부터 얻어진 말레이미드 수지 성형체(M1)의 분자량 분포를 나타내는 도면이다.
도 3은 비교예 1로부터 얻어진 대량 합성시 용매 증류제거 후의 말레이미드 수지(B1)의 분자량 분포를 나타내는 도면이다.
도 4는 비교예 4의 말레이미드 수지(C1)의 아세트산의 정량을 나타내는 도면이다.1 is a view showing the molecular weight distribution of a maleimide resin solution (V1) at the end of a polymerization reaction obtained in Synthesis Example 2. FIG.
It is a figure which shows the molecular weight distribution of the maleimide resin molded object (M1) obtained in Example 1. FIG.
3 is a view showing the molecular weight distribution of maleimide resin (B1) after solvent distillation during mass synthesis obtained in Comparative Example 1. FIG.
Fig. 4 is a diagram showing the amount of acetic acid in the maleimide resin (C1) of Comparative Example 4;
이하, 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 말레이미드 수지 성형체는 말레이미드 수지와 유기용제를 함유하고, 필름상 또는 플레이크상으로 성형되어 있는 것을 특징으로 한다.The maleimide resin molded article of the present invention is characterized in that it contains a maleimide resin and an organic solvent, and is molded into a film or flake shape.
종래 일반적으로 결정상 또는 분말상으로 공급되고 있던 말레이미드 수지와 비교하여, 필름상 또는 플레이크상의 성형체로 공급하는 것이 가능하기 때문에, 작업성의 면에 있어서 분진 등의 문제가 일어나지 않아 매우 취급이 용이하다. 즉 본 발명의 말레이미드 수지 성형체는 용이하게 말레이미드 수지 조성물을 조제할 수 있다.Compared with maleimide resins that have been conventionally supplied in a crystalline or powder form, since it is possible to supply them in a film or flake molded body, problems such as dust do not occur in terms of workability, and handling is very easy. That is, the maleimide resin molded object of this invention can prepare a maleimide resin composition easily.
수지 성형체란 수지 용액을 지지체의 표면 상에 도포한 후, 과열 건조조건 하에서 용제를 제거하고, 지지체로부터 형상을 유지한 채 박리한 것을 말하고, 예를 들면 필름상, 시트상, 섬유상, 판상, 봉상 등을 들 수 있다. The resin molded body refers to a product that is peeled off while maintaining its shape from the support by applying a resin solution on the surface of the support, removing the solvent under overheating drying conditions, for example, in the form of a film, sheet, fiber, plate, rod and the like.
여기에서, 필름상이란 평균 두께가 10㎛∼3㎜ 두께의 시트의 형태를 말한다. 플레이크상이란 필름상의 성형체를 파쇄한 상태를 말한다. 또한, 플레이크상이란 취급 작업시에 분말상과 같이 비산하지 않는 정도의 크기이면 특별하게 한정되지 않지만, 구체적으로는 장경 부분의 평균이 0.1㎝∼5㎝인 것이 바람직하고, 보다 바람직하게는 0.1∼3㎝이다.Here, the film form refers to the form of a sheet having an average thickness of 10 µm to 3 mm. A flake shape means the state which crushed the film-form molded object. In addition, the flake form is not particularly limited as long as it is a size that does not scatter like a powder during handling operation. is cm.
또한, 평균 두께는 시트 또는 필름을 복수매 겹쳐서 임의의 10점을 노기스로 측정하고, 얻어진 두께를 겹친 매수로 나눔으로써 구할 수 있다.In addition, an average thickness can be calculated|required by overlapping several sheets or a film, measuring arbitrary 10 points|pieces with a nogise, and dividing the obtained thickness by the number of overlapping sheets.
이어서, 설명의 편의상 본 발명의 말레이미드 수지 성형체의 제조 방법에 대하여 설명한다.Next, for convenience of description, the manufacturing method of the maleimide resin molded object of this invention is demonstrated.
본 발명의 말레이미드 수지 성형체는 말레이미드 수지를 유기용제에 용해한 용액(이하, 「말레이미드 수지 용액」 또는 「수지 용액」이라고도 칭한다)을 지지체의 표면 상에 도포하여 필름상 또는 시트상으로 성형한 후, 가열조건 하, (필요에 따라서 감압조건 하)용제를 제거하고, 지지체로부터 필름을 박리함으로써 얻을 수 있다. 즉, 본 발명의 말레이미드 수지 성형체의 제조 방법은 수지 용액을 지지체의 표면 상에 도포하는 공정과, 가열 건조하는 공정과, 지지체로부터 박리하는 공정에 의해 행하여진다.The maleimide resin molded article of the present invention is formed by applying a solution (hereinafter also referred to as “maleimide resin solution” or “resin solution”) in which a maleimide resin is dissolved in an organic solvent on the surface of a support to form a film or sheet. Thereafter, under heating conditions, the solvent is removed (under reduced pressure if necessary), and the film is peeled off the support. That is, the manufacturing method of the maleimide resin molded object of this invention is performed by the process of apply|coating a resin solution on the surface of a support body, the process of heat-drying, and the process of peeling from a support body.
(말레이미드 수지)(Maleimide resin)
본 발명에 있어서 사용할 수 있는 말레이미드 수지로서는 공지의 것을 사용할 수 있지만, 점도, 연화점의 관점으로부터 평균 관능기수가 2∼20인 반복단위를 갖는 노볼락형의 말레이미드 수지가 바람직하다.As the maleimide resin usable in the present invention, a known maleimide resin can be used, but from the viewpoint of viscosity and softening point, a novolak-type maleimide resin having a repeating unit having an average number of functional groups of 2 to 20 is preferable.
본 발명에 있어서 사용할 수 있는 말레이미드 수지로서는, 예를 들면 하기 식 (1)로 나타내어지는 구조를 갖는다.As maleimide resin which can be used in this invention, it has a structure represented by following formula (1), for example.
(식 중, 복수 존재하는 R은 각각 독립하여 존재하고, 수소원자, 탄소수 1∼10의 알킬기 또는 페닐기를 나타낸다. X는 하기 구조식 (a)∼(e)로 나타내어진다. n은 평균값이며 1<n≤5를 나타낸다.)(Wherein, a plurality of R's exist independently of each other and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. X is represented by the following structural formulas (a) to (e). n is an average value and 1< represents n≤5.)
또는, 말레이미드 수지의 혼합물도 들 수 있지만, 본 발명은 이것들에 한정되는 것은 아니다.Alternatively, a mixture of maleimide resins may also be mentioned, but the present invention is not limited thereto.
상기 식 (1)로 나타내어지는 말레이미드 수지의 제법은 특별하게 한정되지 않고, 말레이미드 수지의 합성법으로서 공지의 어떠한 방법으로 제조해도 좋다. 구체적인 제조 방법으로서는 예를 들면, 일본국 특허공개 2009-001783호 공보와 같은 방법을 사용하는 것이 바람직하다.The manufacturing method of the maleimide resin represented by said Formula (1) is not specifically limited, You may manufacture by any well-known method as a synthesis method of a maleimide resin. As a specific manufacturing method, it is preferable to use the method similar to Unexamined-Japanese-Patent No. 2009-001783, for example.
(말레이미드 수지 용액)(Maleimide resin solution)
본 발명에 있어서의 말레이미드 수지 용액이란 상기 말레이미드 수지를 유기용매에 용해한 것을 의미한다. The maleimide resin solution in this invention means what melt|dissolved the said maleimide resin in the organic solvent.
말레이미드 수지 용액은 말레이미드 수지를 유기용매에 용해한 것이면 특별하게 한정되지 않고, 공지의 용액 중합법이나 여러가지 제어 중합법에 의해 합성된 중합체 용액 외에, 중합 중에 고체상 중합체가 일부 석출된 것이여도 좋고, 중합이 종료된 용액에 침전제를 첨가해서 중합체를 침전시킨 것이라도 좋다.The maleimide resin solution is not particularly limited as long as the maleimide resin is dissolved in an organic solvent, and in addition to a polymer solution synthesized by a known solution polymerization method or various controlled polymerization methods, a solid polymer may be partially precipitated during polymerization, A polymer may be precipitated by adding a precipitating agent to the solution after polymerization has been completed.
사용할 수 있는 유기용매로서는 특별하게 한정되지 않고, 예를 들면 탄소수 3∼10의 방향족 탄화수소, 케톤류, 에스테르류, 에테르류에서 선택되는 적어도 1종의 유기용제가 바람직하다. 또한, 중합 후의 반응액에 수세 등의 처리를 하는 것이 바람직하다.The organic solvent that can be used is not particularly limited, and for example, at least one organic solvent selected from aromatic hydrocarbons having 3 to 10 carbon atoms, ketones, esters, and ethers is preferable. Moreover, it is preferable to perform a process, such as washing with water, to the reaction liquid after superposition|polymerization.
유기용제의 사용량은 말레이미드 수지와 상기 용제의 혼합물 중에서 통상 10∼70중량%이며, 바람직하게는 15∼70중량%이다.The amount of the organic solvent to be used is usually 10 to 70% by weight, preferably 15 to 70% by weight, in the mixture of the maleimide resin and the solvent.
말레이미드 수지는 융점, 연화점을 갖는 것을 사용할 수 있다. 특히 융점을 갖는 경우에는 200℃ 이하가 바람직하고, 또한 연화점을 갖는 경우에는 50∼150℃인 것이 바람직하다.As the maleimide resin, one having a melting point and a softening point can be used. In particular, when it has a melting point, it is preferably 200°C or less, and when it has a softening point, it is preferably 50 to 150°C.
말레이미드 수지 용액의 점도(콘플레이트법, 150℃ 용융점도)는 5.0mPa·s∼10000Pa·s가 바람직하고, 10mPa·s∼100Pa·s가 보다 바람직하고, 10mPa·s∼10Pa·s가 특히 바람직하다. 콘플레이트법에서의 150℃ 용융점도가 10000Pa·s 이하이면 도포 작업성이 저하할 일이 없어 바람직하다.The viscosity (corn plate method, melt viscosity at 150°C) of the maleimide resin solution is preferably 5.0 mPa·s to 10000 Pa·s, more preferably 10 mPa·s to 100 Pa·s, and particularly preferably 10 mPa·s to 10 Pa·s. desirable. If the melt viscosity at 150°C in the corn plate method is 10000 Pa·s or less, the coating workability is not deteriorated, which is preferable.
(지지체 표면 상에 도포하는 공정)(Step of applying on the surface of the support)
다음에 얻어진 말레이미드 수지 용액을 지지체의 표면에 도포하고, 필름상 또는 시트상으로 성형한다.Next, the obtained maleimide resin solution is apply|coated to the surface of a support body, and it shape|molds into a film form or a sheet form.
말레이미드 수지 용액을 도포하는 지지체로서는 표면이 평활하면 특별하게 한정되지 않지만, 바람직하게는 금속, 이형처리를 실시하고 있지 않은 PET 필름, 이미드 필름 등을 들 수 있다.Although it will not specifically limit as a support body to which the maleimide resin solution is apply|coated as long as the surface is smooth, Preferably, a metal, PET film which is not given a mold release treatment, an imide film, etc. are mentioned.
지지체의 표면에 도포할 때의 막두께 및 면적이 지지체의 표면 100㎠당 각각, 건조 막두께 10㎛∼3㎜, 면적 100㎠ 이하로 되도록 행하는 것이 바람직하다.It is preferable to carry out so that the film thickness and area at the time of apply|coating to the surface of a support body may become 10 micrometers - 3 mm of dry film thickness, respectively, and 100 cm<2> or less in area per 100 cm<2> of surface of a support body.
도포시의 필름의 WET 막두께는 10㎛∼5㎜가 바람직하고, 10㎛∼4.5㎜가 보다 바람직하고, 200㎛∼4.3㎜가 특히 바람직하다. 상기 범위를 초과하면 잔용제 저감 효과가 충분하게 얻어지지 않을 경우가 있고, 밑돌면 말레이미드 수지 성형체의 생산성이 낮아질 경우가 있다.10 micrometers - 5 mm are preferable, as for the WET film thickness of the film at the time of application|coating, 10 micrometers - 4.5 mm are more preferable, 200 micrometers - 4.3 mm are especially preferable. When it exceeds the said range, the residual solvent reducing effect may not fully be acquired, and when it is less than the said range, productivity of a maleimide resin molded object may become low.
(가열 건조하는 공정과 지지체의 표면으로부터 박리하는 공정)(The process of heating and drying, and the process of peeling from the surface of a support body)
이어서, 지지체의 표면에 말레이미드 수지 용액을 도포한 후, 가열 건조조건 하, (필요에 따라서 감압조건 하)용제를 제거하고, 지지체의 표면으로부터 필름상 또는 시트상으로 성형한 건조도막을 박리하여 인출한다.Then, after applying the maleimide resin solution to the surface of the support, the solvent is removed under heat-drying conditions (under reduced pressure if necessary), and the dried coating film formed into a film or sheet is peeled off from the surface of the support. withdraw
건조온도는 80∼250℃가 바람직하고, 바람직하게는 80℃∼200℃, 특히 100℃∼200℃가 바람직하다. 건조온도는 250℃ 초과하면 수지의 열화가 진행하기 쉽기 때문에, 필요로 하는 가공 특성에 따라 설정된다. 또한 80℃ 미만에서는 용제의 제거가 곤란해서 용제의 잔량이 많아지기 때문에, 성형시의 보이드나 크랙의 생성, 끈적거림이 있고, 필름의 형상을 유지할 수 없어 박리 분쇄할 수 없는 경우가 있다.The drying temperature is preferably 80 to 250°C, preferably 80°C to 200°C, particularly preferably 100°C to 200°C. If the drying temperature exceeds 250° C., deterioration of the resin tends to proceed, so it is set according to the required processing characteristics. Also, if the temperature is less than 80°C, the solvent is difficult to remove and the residual amount of the solvent is large. Therefore, there are voids, cracks, and stickiness during molding, and the shape of the film cannot be maintained and peeling and pulverization may not be possible.
지지체의 표면으로부터 박리하고, 인출한 필름상의 말레이미드 수지 성형체의 막두께는 특별하게 한정되지 않지만, 바람직하게는 10㎛∼3㎜, 보다 바람직하게는 30㎛∼1㎜이다. 막두께가 3㎜를 초과하면 잔용제량의 저감효과가 충분하게 얻어지지 않는다.Although the film thickness of the film-form maleimide resin molded object peeled from the surface of a support body and taken out is although it does not specifically limit, Preferably it is 10 micrometers - 3 mm, More preferably, they are 30 micrometers - 1 mm. When the film thickness exceeds 3 mm, the effect of reducing the amount of residual solvent cannot be sufficiently obtained.
또한 얻어진 필름상의 말레이미드 수지 성형체는 분쇄함으로써 플레이크상 형상의 말레이미드 수지 성형체로서 사용할 수도 있다.Moreover, the obtained film-form maleimide resin molded object can also be used as a flake-shaped maleimide resin molded object by grind|pulverizing.
상기 공정에 의해 얻어진 말레이미드 수지 성형체는 잔용제가 30000ppm 이하이다. 바람직하게는 5000ppm 이하이며, 보다 바람직하게는 3000ppm 이하이며, 특히 바람직하게는 1000ppm 이하이며, 특히 600ppm 이하가 바람직하다. 또한 측정 검출한계로서 하한값은 5ppm이다.The maleimide resin molded body obtained by the said process has a residual solvent of 30000 ppm or less. Preferably it is 5000 ppm or less, More preferably, it is 3000 ppm or less, Especially preferably, it is 1000 ppm or less, Especially 600 ppm or less is preferable. In addition, as a measurement detection limit, the lower limit is 5 ppm.
또한, 얻어진 말레이미드 수지 성형체는 용제에 가용인 것이 바람직하다. 완전 용해된다고 하는 것은 말레이미드 수지가 고분자량화 반응이 진행하고 있지 않은 것을 의미한다.Moreover, it is preferable that the obtained maleimide resin molded object is soluble in a solvent. To be completely dissolved means that the high molecular weight reaction of the maleimide resin is not progressing.
이와 같이 하여 얻어지는 말레이미드 수지 성형체는, 종래의 결정상 또는 분말상으로 공급되고 있는 말레이미드 수지와 비교하여 작업성·생산성이 뛰어나기 때문에, 용이하게 말레이미드 수지 조성물을 조제할 수 있다.Since the maleimide resin molded object obtained in this way is excellent in workability|operativity and productivity compared with the maleimide resin supplied in the conventional crystalline or powder form, a maleimide resin composition can be prepared easily.
이어서, 본 발명의 말레이미드 수지 조성물에 대하여 설명한다.Next, the maleimide resin composition of this invention is demonstrated.
본 발명의 말레이미드 수지 조성물은 말레이미드 수지 성형체와 가교반응 가능한 화합물을 포함할 수 있다. 가교 가능한 화합물은 말레이미드 수지 성형체와 가교반응을 일으키고, 말레이미드 수지의 경화제로서 작용한다. 가교 가능한 화합물로서는 아미노기, 시아네이트기, 페놀성 수산기, 알콜성 수산기, 알릴기, 메탈릴기, 아크릴기, 메타크릴기, 비닐기, 공역 디엔기를 갖는 화합물 등을 들 수 있다. 예를 들면, 내열성이 필요할 때는 아민 화합물, 유전 특성이 필요할 때는 시아네이트에스테르 화합물을 배합하는 것이 바람직하다. 말레이미드 수지는 자기중합도 가능하므로 단독 사용도 가능하다.The maleimide resin composition of the present invention may include a compound capable of cross-linking the maleimide resin molded body. The crosslinkable compound causes a crosslinking reaction with the maleimide resin molded article, and acts as a curing agent for the maleimide resin. Examples of the crosslinkable compound include compounds having an amino group, a cyanate group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an allyl group, a methallyl group, an acryl group, a methacryl group, a vinyl group, and a conjugated diene group. For example, it is preferable to mix|blend an amine compound when heat resistance is needed, and a cyanate ester compound when dielectric property is needed. Maleimide resin can also be self-polymerized, so it can be used alone.
본 발명의 말레이미드 수지 조성물에는, 필요에 따라서 경화용의 촉매(경화촉진제)를 배합할 수 있다. 예를 들면 2-메틸이미다졸, 2-에틸이미다졸, 2-페닐이미다졸, 2-에틸-4-메틸이미다졸, 2-운데실이미다졸, 1-시아노에틸-2-에틸-4-메틸이미다졸 등의 이미다졸류, 트리에틸아민, 트리에틸렌디아민, 2-(디메틸아미노메틸)페놀, 1,8-디아자-비시클로(5,4,0)-7-운데센, 트리스(디메틸아미노메틸)페놀, 벤질 디메틸아민 등의 아민류, 트리페닐포스핀, 트리부틸포스핀, 트리옥틸포스핀 등의 포스핀류, 옥틸산 주석, 옥틸산 아연, 디부틸주석디말레에이트, 나프텐산 아연, 나프텐산 코발트, 올레산 주석 등의 유기금속염, 염화아연, 염화알루미늄, 염화주석 등의 금속 염화물, 디-tert-부틸퍼옥사이드, 디쿠밀퍼옥사이드 등의 유기과산화물, 아조비스이소부틸로니트릴, 아조비스디메틸발레로니트릴 등의 아조 화합물, 염산, 황산, 인산 등의 광산, 3불화붕소 등의 루이스산, 탄산 나트륨이나 염화리튬 등의 염류 등을 들 수 있다. 경화용의 촉매의 배합량은 본 발명의 말레이미드 수지 성형체 100중량부에 대하여 바람직하게는 10중량부 이하, 보다 바람직하게는 5중량부 이하의 범위이다.A catalyst for hardening (curing accelerator) can be mix|blended with the maleimide resin composition of this invention as needed. For example, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2 -Imidazoles such as ethyl-4-methylimidazole, triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo(5,4,0)-7 -amines such as undecene, tris(dimethylaminomethyl)phenol, and benzyl dimethylamine; phosphines such as triphenylphosphine, tributylphosphine and trioctylphosphine; tin octylate; zinc octylate; Organometallic salts such as maleate, zinc naphthenate, cobalt naphthenate, and tin oleate, metal chlorides such as zinc chloride, aluminum chloride, and tin chloride, organic peroxides such as di-tert-butyl peroxide and dicumyl peroxide, azobisiso and azo compounds such as butyronitrile and azobisdimethylvaleronitrile, mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, Lewis acids such as boron trifluoride, and salts such as sodium carbonate and lithium chloride. Preferably the compounding quantity of the catalyst for hardening is 10 weight part or less with respect to 100 weight part of maleimide resin molded objects of this invention, More preferably, it is the range of 5 weight part or less.
본 발명의 말레이미드 수지 조성물에 유기용제를 첨가해서 바니시상의 조성물(이하, 단지 바니시라고 한다)로 할 수 있다. 본 발명의 말레이미드 수지 조성물을 필요에 따라서 톨루엔, 크실렌, 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 디메틸포름아미드, 디메틸아세트아미드, N-메틸피롤리돈 등의 용제에 용해시켜 말레이미드 수지 조성물 바니시로 하고, 탄소섬유, 유리섬유, 폴리에스테르섬유, 폴리아미드섬유, 알루미나섬유, 종이 등의 기재에 함침시켜서 가열 건조해서 얻은 프리프레그를 열프레스 성형함으로써, 본 발명의 말레이미드 수지 조성물의 경화물로 할 수 있다. An organic solvent can be added to the maleimide resin composition of the present invention to obtain a varnish-like composition (hereinafter simply referred to as varnish). If necessary, the maleimide resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl formamide, dimethyl acetamide, N-methylpyrrolidone, and the like to form a maleimide resin composition. A cured product of the maleimide resin composition of the present invention by hot-press molding a prepreg obtained by making a varnish, impregnating a substrate such as carbon fiber, glass fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and drying it by heating. can be done with
이 때의 용제는 본 발명의 말레이미드 수지 조성물과 상기 용제의 혼합물 중에서 통상 10∼70중량%, 바람직하게는 15∼70중량%를 차지한다. 또한 액상 조성물이면, 그대로 예를 들면 RTM 방식으로 카본섬유를 함유하는 말레이미드 수지 조성물의 경화물을 얻을 수도 있다.At this time, the solvent is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the maleimide resin composition of the present invention and the solvent. Moreover, if it is a liquid composition, the hardened|cured material of the maleimide resin composition containing carbon fiber can also be obtained as it is, for example by RTM method.
또한, 본 발명의 말레이미드 수지 조성물을 필름형 조성물의 개질제로서도 사용할 수 있다. 구체적으로는 B-스테이지에 있어서의 가요성 등을 향상시킬 경우에 사용할 수 있다. 이러한 필름형의 수지 조성물은, 본 발명의 말레이미드 수지 조성물을 상기 말레이미드 수지 조성물 바니시로서 박리 필름 상에 도포하고, 가열 하에서 용제를 제거한 후, B스테이지화를 행함으로써 시트상의 접착제로서 얻어진다. 이 시트상 접착제는 다층기판 등에 있어서의 층간 절연층으로서 사용할 수 있다.Moreover, the maleimide resin composition of this invention can be used also as a modifier of a film-form composition. Specifically, it can be used to improve the flexibility and the like in the B-stage. Such a film-type resin composition is obtained as a sheet-like adhesive by applying the maleimide resin composition of the present invention as the maleimide resin composition varnish on a release film, removing the solvent under heating, and then performing B-staging. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.
본 발명의 말레이미드 수지 조성물을 가열 용융하고, 저점도화해서 유리섬유, 카본섬유, 폴리에스테르섬유, 폴리아미드섬유, 알루미나섬유 등의 강화섬유에 함침시킴으로써 프리프레그를 얻을 수 있다.A prepreg can be obtained by heating and melting the maleimide resin composition of the present invention, lowering the viscosity, and impregnating the reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers.
또한, 상기 바니시를 강화섬유에 함침시켜서 가열 건조시킴으로써 프리프레그를 얻을 수도 있다.In addition, a prepreg may be obtained by impregnating the varnish into the reinforcing fiber and drying it by heating.
이들 강화섬유에 본 발명의 말레이미드 수지 조성물을 함침시키는 방법에도 특별히 제한은 없지만, 용제를 사용하지 않는 방법이 바람직하기 때문에, 본 발명의 말레이미드 수지 조성물을 60∼110℃로 가온하여 유동성이 있는 상태에서 함침시키는 핫멜트법이 바람직하다.The method for impregnating the reinforcing fibers with the maleimide resin composition of the present invention is not particularly limited, but since a method without using a solvent is preferred, the maleimide resin composition of the present invention is heated to 60 to 110 ° C. The hot-melt method of impregnating in a state is preferable.
얻어지는 프리프레그(강화섬유에 말레이미드 수지 조성물을 함침시킨 것)에 차지하는 말레이미드 수지 조성물의 비율은, 강화섬유의 형태에도 의하지만 통상 20중량% 이상 80중량% 이하, 바람직하게는 25중량% 이상 65중량% 이하, 보다 바람직하게는 30중량% 이상 50%이하이다. 이 범위보다 말레이미드 수지 조성물의 비율이 많으면 상대적으로 강화섬유의 비율이 줄어듦으로써 충분한 보강 효과가 얻어지지 않고, 반대로 말레이미드 수지 조성물이 적으면 성형성이 손상될 경우가 있다.The proportion of the maleimide resin composition to the obtained prepreg (reinforcing fibers impregnated with the maleimide resin composition) is usually 20% by weight or more and 80% by weight or less, preferably 25% by weight or more, although depending on the shape of the reinforcing fibers. 65% by weight or less, more preferably 30% by weight or more and 50% or less. When the proportion of the maleimide resin composition is greater than this range, a sufficient reinforcing effect cannot be obtained due to a relatively reduced proportion of the reinforcing fibers. Conversely, when the proportion of the maleimide resin composition is small, the moldability may be impaired.
이 프리프레그는 공지의 방법에 의해 경화시켜서 최종 성형품으로 할 수 있다. 예를 들면, 프리프레그를 적층하여 오토클레이브 중에서 2 내지 10kgf/㎠로 가압하고, 150℃∼200℃에서 30분 내지 3시간 가열 경화시켜서 성형체로 할 수 있지만, 내열성을 더욱 향상시키기 위해서 포스트큐어로서 180℃ 내지 280℃의 온도범위에서 온도를 단계적으로 가온하면서 1시간 내지 12시간 처리함으로써 섬유강화 복합재 성형품으로 할 수 있다. This prepreg can be cured by a known method to obtain a final molded article. For example, a prepreg can be laminated and pressed at 2 to 10 kgf/cm 2 in an autoclave and heat-cured at 150° C. to 200° C. for 30 minutes to 3 hours to obtain a molded product. It can be made into a fiber-reinforced composite molded article by processing for 1 hour to 12 hours while heating the temperature stepwise in a temperature range of 180 ° C. to 280 ° C.
상기 프리프레그를 소망의 형태로 재단, 필요에 따라 동박 등과 적층 후, 적층물에 프레스 성형법이나 오토클레이브 성형법, 시트 와인딩 성형법 등으로 압력을 가하면서 적층판용 말레이미드 수지 조성물을 가열 경화시킴으로써 적층판을 얻을 수 있다.After the prepreg is cut into a desired shape and, if necessary, laminated with copper foil, etc., a laminate is obtained by heating and curing the maleimide resin composition for a laminate while applying pressure to the laminate by a press molding method, an autoclave molding method, a sheet winding molding method, etc. can
또한, 표면에 동박을 겹쳐서 만든 적층판에 회로를 형성하고, 그 위에 프리프레그나 동박 등을 겹쳐서 상기 조작을 반복하여 다층의 회로기판을 얻을 수 있다.In addition, a circuit is formed on a laminated board made by stacking copper foil on the surface, and prepreg or copper foil is stacked thereon, and the above operation is repeated to obtain a multilayer circuit board.
본 발명의 프리프레그의 경화물은, 액정 유리기판 반송용 로봇핸드 용도, 규소 웨이퍼 반송용 디스크 용도, 항공우주용 부재 용도, 자동차의 엔진부재 용도 등, 경량이고 고강도이며 또한 고내열성이 요구되는 부재에 널리 적용할 수 있다.The cured product of the prepreg of the present invention is a member requiring light weight, high strength, and high heat resistance, such as a robot hand for liquid crystal glass substrate transport, a disk for silicon wafer transport, aerospace member use, and automobile engine member use. can be widely applied to
본 발명의 말레이미드 수지 조성물의 구체적인 용도로서는, 접착제, 도료, 코팅제, 성형재료(시트, 필름, FRP 등을 포함한다), 전자재료용 절연재료(프린트 기판, 전선피복 등을 포함하는 밀봉재 외에, 밀봉재, 기판용의 시아네이트 수지 조물)나, 레지스트용 경화제로서 아크릴산 에스테르계 수지 등, 타수지 등으로의 첨가제 등을 들 수 있다. 특히 FRP 용도에 있어서는 환경에의 배려, 및 보이드에 의한 결함 배제의 문제로부터 최근 무용제화가 크게 진행되고 있다. 또한 성형시의 보이드나 성형불량, 내전압성 저하 등의 문제로부터, 반도체 밀봉의 용도에 있어서도 용제가 공정 중에 들어갈 수 없는 환경이 있다.Specific uses of the maleimide resin composition of the present invention include adhesives, paints, coatings, molding materials (including sheets, films, FRP, etc.), insulating materials for electronic materials (in addition to sealing materials including printed circuit boards and wire coverings, etc.); As a sealing material, cyanate resin composition for board|substrates), and a hardening|curing agent for resists, additives to other resins, such as an acrylic acid ester type resin, etc. are mentioned. In particular, in FRP applications, solvent-free development is progressing significantly in recent years from the problem of environmental consideration and defect exclusion due to voids. In addition, from problems such as voids during molding, poor molding, and lowering of withstand voltage, there is an environment in which solvents cannot enter during the process even in semiconductor encapsulation applications.
(실시예)(Example)
이하에 실시예에 의거하여 본 발명의 내용을 구체적으로 설명하지만, 본 발명은 이것에 의해 한정되는 것은 아니다. 또한, 본문 중 「부」 및 「%」는 특별히 언급이 없는 한, 각각 「중량부」 및 「중량%」를 나타낸다. 실시예 중, 연화점 및 용융점도는 하기의 방법으로 측정했다.The content of the present invention will be specifically described below based on Examples, but the present invention is not limited thereto. In addition, "part" and "%" in the text represent "part by weight" and "% by weight", respectively, unless otherwise specified. In the Examples, the softening point and the melt viscosity were measured by the following method.
·연화점: JISK-7234에 준한 방법으로 측정・Softening point: Measured by the method according to JISK-7234
·용융점도: 콘플레이트법에 의한 150℃에 있어서의 점도·Melt viscosity: Viscosity at 150°C by corn plate method
·잔용제량의 정량은 시마즈 세이사쿠쇼사 제품 가스 크로마토그래피 GC-2010을 사용해서 행하고, 컬럼으로서는 DB-WAX(Agilene Technologies사 제품) 길이 30m, 내경 0. 25㎜를 사용했다.- Quantification of residual solvent amount was performed using Shimadzu Corporation's gas chromatography GC-2010, and DB-WAX (made by Agilene Technologies) length 30m, and inner diameter 0.25mm were used as a column.
승온 프로그램으로서는 70℃에서 5분 유지하고, 10℃/min의 승온속도로 140℃까지 승온한 후, 20℃/min의 승온속도로 220℃까지 승온하고, 220℃에서 5분 유지하는 프로그램을 사용했다.As a temperature increase program, the program is maintained at 70°C for 5 minutes, raises the temperature to 140°C at a heating rate of 10°C/min, then increases the temperature to 220°C at a heating rate of 20°C/min, and maintains the temperature at 220°C for 5 minutes. did.
·분자량의 데이터 취득에는 겔 투과 크로마토그래피(GPC 시마즈 세이사쿠쇼사 제품 LC-20AD)를 사용했다. 컬럼에는 KF-603, KF-602.5, KF-602, KF-601을 사용하고, 컬럼 온도 40℃, 이동상을 THF로 하고, 유속 0.5ml/min의 조건에서 RI 검출기에 의해 측정을 행하였다.- Gel permeation chromatography (LC-20AD by GPC Shimadzu Corporation) was used for data acquisition of molecular weight. KF-603, KF-602.5, KF-602, and KF-601 were used for the column, the column temperature was 40°C, the mobile phase was THF, and the measurement was performed with an RI detector under the conditions of a flow rate of 0.5 ml/min.
(합성예 1)(Synthesis Example 1)
온도계, 냉각관, 딘스타크 공비증류 트랩, 교반기를 부착한 플라스크에 아닐린 559부와 톨루엔 500부를 투입하고, 실온에서 35% 염산 167부를 1시간으로 적하했다. 적하 종료 후 가열해서 공비해 오는 물과 톨루엔을 냉각·분액한 후, 유기층인 톨루엔만을 계내로 되돌려서 탈수를 행하였다. 이어서 4,4'-비스(클로로메틸)비페닐 251부를 60∼70℃로 유지하면서 1시간 걸쳐서 첨가하고, 동 온도에서 2시간 더 반응을 행하였다. 반응 종료 후, 승온을 하면서 톨루엔을 증류제거해서 계내를 190∼200℃로 하고, 이 온도에서 15시간 반응을 했다. 그 후 냉각하면서 30% 수산화나트륨 수용액 500부를 계내가 격렬하게 환류하지 않도록 천천히 적하하고, 80℃ 이하에서 증류제거한 톨루엔을 계내로 되돌리고, 70℃∼80℃에서 정치했다. 분리한 하층의 수층을 제거하고, 반응액의 수세를 세정액이 중성으로 될 때까지 반복했다. 이어서 유층으로부터 가열 감압 하에 있어서 과잉의 아닐린과 톨루엔을 증류제거함으로써 방향족 아민 수지 335부(A1)를 얻었다. 방향족 아민 수지(A1)의 연화점은 59℃, 용융점도는 0.05Pa·s이었다.Into a flask equipped with a thermometer, a cooling tube, a Dean-Stark azeotropic distillation trap, and a stirrer, 559 parts of aniline and 500 parts of toluene were charged, and 167 parts of 35% hydrochloric acid were added dropwise at room temperature in 1 hour. After completion of the dropwise addition, heating and azeotropic water and toluene were cooled and liquid-separated, and only toluene, which was an organic layer, was returned to the system to perform dehydration. Subsequently, 251 parts of 4,4'-bis(chloromethyl)biphenyl were added over 1 hour while maintaining the temperature at 60 to 70°C, and the reaction was further carried out at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while raising the temperature, the system inside was set to 190 to 200°C, and the reaction was performed at this temperature for 15 hours. Then, while cooling, 500 parts of 30% sodium hydroxide aqueous solution was dripped slowly so that the inside of the system might not be refluxed violently, and toluene distilled off at 80 degrees C or less was returned to the system inside, and it left still at 70 degreeC - 80 degreeC. The separated lower aqueous layer was removed, and washing of the reaction solution with water was repeated until the washing solution became neutral. Next, 335 parts of aromatic amine resins (A1) were obtained by distilling off excess aniline and toluene from the oil layer under heating and reduced pressure. The softening point of the aromatic amine resin (A1) was 59°C, and the melt viscosity was 0.05 Pa·s.
(합성예 2)(Synthesis Example 2)
온도계, 냉각관, 딘스타크 공비증류 트랩, 교반기를 부착한 플라스크에 무수 말레산 88부와 톨루엔 300부를 투입하고, 가열해서 공비해 오는 물과 톨루엔을 냉각·분액한 후, 유기층인 톨루엔만을 계내로 되돌려서 탈수를 행하였다. 다음에 방향족 아민 수지(A1) 116부를 N-메틸-2-피롤리돈 116부에 용해한 수지 용액을, 계내를 80∼85℃로 유지하면서 1시간 걸쳐서 적하했다. 적하 종료 후, 동 온도에서 2시간 반응을 행하고, p-톨루엔술폰산 2부를 첨가하여 환류 조건에서 공비해 오는 축합수와 톨루엔을 냉각·분액한 후, 유기층인 톨루엔만을 계내로 되돌려서 탈수를 행하면서 10시간 반응을 행하였다. 반응 종료 후, 톨루엔을 120부 추가하고, 수세를 반복해서 p-톨루엔술폰산 및 과잉의 무수 말레산을 제거하고, 가열해서 공비에 의해 물을 계내로부터 제거했다. 이어서 반응용액을 농축하여 말레이미드 수지를 70% 함유하는 말레이미드 수지 용액(V1)을 얻었다. 얻어진 말레이미드 수지 용액(V1)의 분자량 분포를 GPC에 의해 측정한 결과, 도 1에 나타내는 결과가 얻어졌다.88 parts of maleic anhydride and 300 parts of toluene were put into a flask equipped with a thermometer, a cooling tube, a Dean-Stark azeotropic distillation trap, and a stirrer, and after heating and cooling and separating the azeotropic water and toluene, only toluene, which is an organic layer, was introduced into the system. It returned and dehydrated. Next, the resin solution which melt|dissolved 116 parts of aromatic amine resin (A1) in 116 parts of N-methyl- 2-pyrrolidone was dripped over 1 hour, maintaining the system inside at 80-85 degreeC. After completion of the dropwise addition, the reaction is carried out at the same temperature for 2 hours, 2 parts of p-toluenesulfonic acid is added to cool and liquid-separate the condensed water and toluene azeotroped under reflux conditions, and only toluene, which is an organic layer, is returned into the system to dehydrate while performing dehydration. The reaction was performed for 10 hours. After completion of the reaction, 120 parts of toluene was added, and water washing was repeated to remove p-toluenesulfonic acid and excess maleic anhydride, followed by heating and azeotropic removal of water from the system. Then, the reaction solution was concentrated to obtain a maleimide resin solution (V1) containing 70% maleimide resin. As a result of measuring the molecular weight distribution of the obtained maleimide resin solution (V1) by GPC, the result shown in FIG. 1 was obtained.
(합성예 3)(Synthesis Example 3)
온도계, 냉각관, 딘스타크 공비증류 트랩, 교반기를 부착한 플라스크에 아닐린 559부와 톨루엔 500부를 투입하고, 실온에서 35% 염산 167부를 1시간으로 적하했다. 적하 종료 후 가열해서 공비해 오는 물과 톨루엔을 냉각·분액한 후, 유기층인 톨루엔만을 계내로 되돌려서 탈수를 행하였다. 이어서 4,4'-비스(클로로메틸)벤젠 175부를 60∼70℃로 유지하면서 1시간 걸쳐서 첨가하고, 동 온도에서 2시간 더 반응을 행하였다. 반응 종료 후, 승온을 하면서 톨루엔을 증류제거해서 계내를 190∼200℃로 하고, 이 온도에서 15시간 반응을 했다. 그 후 냉각하면서 30% 수산화 나트륨 수용액 500부를 계내가 격렬하게 환류하지 않도록 천천히 적하하고, 80℃ 이하에서 증류제거한 톨루엔을 계내로 되돌려 70℃∼80℃에서 정치했다. 분리한 하층의 수층을 제거하고, 반응액의 수세를 세정액이 중성으로 될 때까지 반복했다. 이어서 유층으로부터 가열 감압 하에 있어서 과잉의 아닐린과 톨루엔을 증류제거함으로써 방향족 아민 수지 280부(A2)를 얻었다. 방향족 아민 수지(A2)는 반고형의 수지상이었다.Into a flask equipped with a thermometer, a cooling tube, a Dean-Stark azeotropic distillation trap, and a stirrer, 559 parts of aniline and 500 parts of toluene were charged, and 167 parts of 35% hydrochloric acid were added dropwise at room temperature in 1 hour. After completion of the dropwise addition, heating and azeotropic water and toluene were cooled and liquid-separated, and only toluene, which was an organic layer, was returned to the system to perform dehydration. Subsequently, 175 parts of 4,4'-bis(chloromethyl)benzene was added over 1 hour while maintaining the temperature at 60 to 70°C, and the reaction was further carried out at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while raising the temperature, the system inside was set to 190 to 200°C, and the reaction was performed at this temperature for 15 hours. Thereafter, while cooling, 500 parts of a 30% aqueous sodium hydroxide solution was slowly added dropwise so as not to reflux violently in the system, and toluene distilled off at 80°C or lower was returned to the system and left still at 70°C to 80°C. The separated lower aqueous layer was removed, and washing of the reaction solution with water was repeated until the washing solution became neutral. Subsequently, 280 parts of aromatic amine resins (A2) were obtained by distilling off excess aniline and toluene from the oil layer under heating and reduced pressure. The aromatic amine resin (A2) was in the form of a semi-solid resin.
(합성예 4)(Synthesis Example 4)
온도계, 냉각관, 딘스타크 공비증류 트랩, 교반기를 부착한 플라스크에 무수 말레산 88부와 톨루엔 300부를 투입하고, 가열해서 공비해 오는 물과 톨루엔을 냉각·분액한 후, 유기층인 톨루엔만을 계내로 되돌려서 탈수를 행하였다. 다음에 방향족 아민 수지(A2) 91.7부를 N-메틸-2-피롤리돈 91.7부에 용해한 수지 용액을, 계내를 80∼85℃로 유지하면서 1시간 걸쳐서 적하했다. 적하 종료 후, 동 온도에서 2시간 반응을 행하고, p-톨루엔술폰산 2부를 첨가하여 환류 조건에서 공비해 오는 축합수와 톨루엔을 냉각·분액한 후, 유기층인 톨루엔만을 계내로 되돌려서 탈수를 행하면서 10시간 반응을 행하였다. 반응 종료 후, 톨루엔을 120부 추가하고, 수세를 반복해서 p-톨루엔술폰산 및 과잉의 무수 말레산을 제거하고, 가열해서 공비에 의해 물을 계내로부터 제거했다. 이어서 반응 용액을 농축하여 말레이미드 수지를 70% 함유하는 말레이미드 수지 용액(V2)을 얻었다.88 parts of maleic anhydride and 300 parts of toluene were put into a flask equipped with a thermometer, a cooling tube, a Dean-Stark azeotropic distillation trap, and a stirrer, and after heating and cooling and separating the azeotropic water and toluene, only toluene, which is an organic layer, was introduced into the system. It returned and dehydrated. Next, the resin solution which melt|dissolved 91.7 parts of aromatic amine resin (A2) in 91.7 parts of N-methyl- 2-pyrrolidone was dripped over 1 hour, maintaining the system inside at 80-85 degreeC. After completion of the dropwise addition, the reaction is carried out at the same temperature for 2 hours, 2 parts of p-toluenesulfonic acid is added to cool and liquid-separate the condensed water and toluene azeotroped under reflux conditions, and only toluene, which is an organic layer, is returned into the system to dehydrate while performing dehydration. The reaction was performed for 10 hours. After completion of the reaction, 120 parts of toluene was added, and water washing was repeated to remove p-toluenesulfonic acid and excess maleic anhydride, followed by heating and azeotropic removal of water from the system. Subsequently, the reaction solution was concentrated to obtain a maleimide resin solution (V2) containing 70% maleimide resin.
(실시예 1)(지지체: 이미드 필름)(Example 1) (Support: imide film)
합성예 2에 의해 얻어진 말레이미드 수지 용액(V1)을, 어플리케이터를 이용하여 시판의 이미드 필름(도레이 듀퐁 제품 「캡톤(등록상표) 100H」)에 유연도포(WET 막두께 200㎛)하고, 도포된 수지막을 180℃에서 15분 건조시킴으로써 용매를 제거했다. The maleimide resin solution (V1) obtained in Synthesis Example 2 was flexible coated (WET film thickness 200 μm) on a commercially available imide film (“Kapton (registered trademark) 100H” manufactured by DuPont Toray) using an applicator, and applied The solvent was removed by drying the obtained resin film at 180 degreeC for 15 minutes.
얻어진 말레이미드 수지 성형체는 두께 125㎛의 필름상이며, 박리, 분쇄함으로써 플레이크상 형상의 본 발명의 말레이미드 수지 성형체(M1)로 했다. The obtained maleimide resin molded body was in the form of a film with a thickness of 125 micrometers, and it was set as the maleimide resin molded body (M1) of this invention of flake shape by peeling and grinding|pulverizing.
얻어진 말레이미드 수지 성형체(M1)의 잔용제는 0.236%(2360ppm)이었다. 얻어진 말레이미드 수지 성형체(M1)의 분자량 분포를 GPC에 의해 측정한 결과, 도 2에 나타내는 결과가 얻어졌다. 합성예 2에 의해 얻어진 말레이미드 수지 용액(V1)의 GPC에 의해 측정된 분자량 분포(도 1)와 비교한 결과, 본 공정에 의한 분자량 분포의 변화는 보여지지 않았다(GPC에 의한 측정).The residual solvent of the obtained maleimide resin molded body (M1) was 0.236 % (2360 ppm). As a result of measuring the molecular weight distribution of the obtained maleimide resin molded object (M1) by GPC, the result shown in FIG. 2 was obtained. As a result of comparison with the molecular weight distribution (FIG. 1) measured by GPC of the maleimide resin solution (V1) obtained in Synthesis Example 2, there was no change in the molecular weight distribution by this step (measured by GPC).
(실시예 2)(지지체: 이미드 필름)(Example 2) (Support: imide film)
합성예 2에 의해 얻어진 말레이미드 수지 용액(V1)을, 어플리케이터를 이용하여 시판의 이미드 필름(도레이 듀퐁 제품 「캡톤(등록상표) 100H」)에 유연도포(WET 막두께 200㎛)하고, 도포된 수지막을 200℃에서 15분 건조시킴으로써 용매를 제거했다. The maleimide resin solution (V1) obtained in Synthesis Example 2 was flexible coated (WET film thickness 200 μm) on a commercially available imide film (“Kapton (registered trademark) 100H” manufactured by DuPont Toray) using an applicator, and applied The solvent was removed by drying the obtained resin film at 200 degreeC for 15 minutes.
얻어진 말레이미드 수지 성형체는 두께 125㎛의 필름상이며, 박리, 분쇄함으로써 플레이크상 형상의 본 발명의 말레이미드 수지 성형체(M2)로 했다.The obtained maleimide resin molded body was in the form of a film with a thickness of 125 micrometers, and it was set as the maleimide resin molded body (M2) of this invention of flake shape by peeling and grinding|pulverizing.
얻어진 말레이미드 수지 성형체(M2)의 잔용제는 0.293%(2930ppm)이었다. 또한, 본 공정에 의한 분자량 분포의 변화는 보여지지 않았다(GPC에 의한 측정).The residual solvent of the obtained maleimide resin molded body (M2) was 0.293% (2930 ppm). In addition, no change in molecular weight distribution was observed by this process (measured by GPC).
(실시예 3)(지지체: 이미드 필름)(Example 3) (Support: imide film)
합성예 2에 의해 얻어진 말레이미드 수지 용액(V1)을, 어플리케이터를 이용하여 시판의 이미드 필름(도레이 듀퐁 제품 「캡톤(등록상표) 100H」)에 유연도포(WET 막두께 200㎛)하고, 도포된 수지막을 200℃에서 10분 건조시킴으로써 용매를 제거했다.The maleimide resin solution (V1) obtained in Synthesis Example 2 was flexible coated (WET film thickness 200 μm) on a commercially available imide film (“Kapton (registered trademark) 100H” manufactured by DuPont Toray) using an applicator, and applied The solvent was removed by drying the obtained resin film at 200 degreeC for 10 minutes.
얻어진 말레이미드 수지 성형체는 두께 125㎛의 필름상이며, 박리, 분쇄함으로써 플레이크상 형상의 본 발명의 말레이미드 수지 성형체(M3)로 했다.The obtained maleimide resin molded body was in the form of a 125-micrometer-thick film, and it was set as the maleimide resin molded body (M3) of this invention of flake shape by peeling and grinding|pulverizing.
얻어진 말레이미드 수지 성형체(M3)의 잔용제는 0.398%(3980ppm)이었다. 또한, 본 공정에 의한 분자량 분포의 변화는 보여지지 않았다(GPC에 의한 측정).The residual solvent of the obtained maleimide resin molded body (M3) was 0.398% (3980 ppm). In addition, no change in molecular weight distribution was observed by this process (measured by GPC).
(실시예 4)(지지체: 이미드 필름)(Example 4) (Support: imide film)
합성예 2에 의해 얻어진 말레이미드 수지 용액(V1)을, 어플리케이터를 이용하여 시판의 이미드 필름(도레이 듀퐁 제품 「캡톤(등록상표) 100H」)에 유연도포(WET 막두께 200㎛)하고, 도포된 수지막을 200℃에서 5분 건조시킴으로써 용매를 제거했다. The maleimide resin solution (V1) obtained in Synthesis Example 2 was flexible coated (WET film thickness 200 μm) on a commercially available imide film (“Kapton (registered trademark) 100H” manufactured by DuPont Toray) using an applicator, and applied The solvent was removed by drying the obtained resin film at 200 degreeC for 5 minutes.
얻어진 말레이미드 수지 성형체는 두께 125㎛의 필름상이며, 박리, 분쇄함으로써 플레이크상 형상의 본 발명의 말레이미드 수지 성형체(M4)로 했다.The obtained maleimide resin molded object was 125-micrometer-thick film form, and it was made into flake-shaped maleimide resin molded object (M4) of this invention by peeling and grinding|pulverizing.
얻어진 말레이미드 수지 성형체(M4)의 잔용제는 0.0901%(901ppm)이었다. The residual solvent of the obtained maleimide resin molded body (M4) was 0.0901 % (901 ppm).
또한, 본 공정에 의한 분자량 분포의 변화는 보여지지 않았다(GPC에 의한 측정).In addition, no change in molecular weight distribution was observed by this process (measured by GPC).
(실시예 5)(지지체: SUS판)(Example 5) (Support: SUS plate)
합성예 2에 의해 얻어진 말레이미드 수지 용액(V1)을, 어플리케이터를 이용하여 SUS판에 유연도포(WET 막두께 200㎛)하고, 도포된 수지막을 180℃에서 15분 건조시킴으로써 용매를 제거했다.The maleimide resin solution (V1) obtained in Synthesis Example 2 was flexible coated on a SUS plate (WET film thickness of 200 µm) using an applicator, and the applied resin film was dried at 180° C. for 15 minutes to remove the solvent.
얻어진 말레이미드 수지 성형체는 두께 113㎛의 필름상이며, 박리, 분쇄함으로써 플레이크상 형상의 본 발명의 말레이미드 수지 성형체(M5)로 했다.The obtained maleimide resin molded body was in the form of a film with a thickness of 113 micrometers, and it was set as the maleimide resin molded body (M5) of this invention of flake shape by peeling and grinding|pulverizing.
얻어진 말레이미드 수지 성형체(M5)의 잔용제는 0.163%(1638ppm)이었다. The residual solvent of the obtained maleimide resin molded body (M5) was 0.163 % (1638 ppm).
또한, 본 공정에 의한 분자량 분포의 변화는 보여지지 않았다(GPC에 의한 측정).In addition, no change in molecular weight distribution was observed by this process (measured by GPC).
(실시예 6)(지지체: SUS판)(Example 6) (Support: SUS plate)
합성예 4에 의해 얻어진 말레이미드 수지 용액(V2)을, 어플리케이터를 이용하여 SUS판에 유연도포(WET 막두께 200㎛)하고, 도포된 수지막을 180℃에서 15분 건조시킴으로써 용매를 제거했다.The maleimide resin solution (V2) obtained in Synthesis Example 4 was flexible coated (WET film thickness 200 µm) on a SUS plate using an applicator, and the applied resin film was dried at 180°C for 15 minutes to remove the solvent.
얻어진 말레이미드 수지 성형체는 두께 113㎛의 필름상이며, 박리, 분쇄함으로써 플레이크상 형상의 본 발명의 말레이미드 수지 성형체(M6)로 했다.The obtained maleimide resin molded body was in the form of a film with a thickness of 113 micrometers, and it was set as the maleimide resin molded body (M6) of this invention of flake shape by peeling and grinding|pulverizing.
얻어진 말레이미드 수지 성형체(M6)의 잔용제는 0.3%≤(3000ppm≤)이었다. 또한, 본 공정에 의한 분자량 분포의 변화는 보여지지 않았다(GPC에 의한 측정).The residual solvent of the obtained maleimide resin molded body (M6) was 0.3%<=(3000 ppm<=). In addition, no change in molecular weight distribution was observed by this process (measured by GPC).
(실시예 7)(지지체: 경면 동박)(Example 7) (Support: mirror copper foil)
합성예 2에 의해 얻어진 말레이미드 수지 용액(V1)을, 어플리케이터를 이용하여 전해동박(후쿠다 킨조쿠 하쿠분 고교 가부시키가이샤 제품 18μ 전해동박 CF-T9FZ-HTE)의 경면에 유연도포(WET 막두께 200㎛)하고, 도포된 수지막을 180℃에서 15분 건조시킴으로써 용매를 제거했다.Using an applicator, the maleimide resin solution (V1) obtained in Synthesis Example 2 was applied to the mirror surface of an electrodeposited copper foil (Fukuda Kinzoku Hakubun Kogyo Co., Ltd. 18 μm Electrolytic Copper Foil CF-T9FZ-HTE) by flexible coating (WET film thickness 200 μm). ), and the applied resin film was dried at 180°C for 15 minutes to remove the solvent.
얻어진 말레이미드 수지 성형체는 두께 152㎛의 필름상이며, 박리, 분쇄함으로써 플레이크상 형상의 본 발명의 말레이미드 수지 성형체(M7)로 했다.The obtained maleimide resin molded body was in the form of a 152-micrometer-thick film, and it was set as the maleimide resin molded body (M7) of this invention of flake shape by peeling and grinding|pulverizing.
얻어진 말레이미드 수지 성형체(M7)의 잔용제는 0.0728%(728ppm)이었다. The residual solvent of the obtained maleimide resin molded body (M7) was 0.0728 % (728 ppm).
또한, 본 공정에 의한 분자량 분포의 변화는 보여지지 않았다(GPC에 의한 측정).In addition, no change in molecular weight distribution was observed by this process (measured by GPC).
(실시예 8)(지지체: PET 필름)(Example 8) (Support: PET film)
합성예 2에 의해 얻어진 말레이미드 수지 용액(V1)을, 어플리케이터를 이용하여 이형처리하고 있지 않은 PET 필름(파낙 가부시키가이샤 제품 루미러 38-S10)에 유연도포(WET 막두께 200㎛)하고, 도포된 수지막을 160℃에서 1시간분 건조시킴으로써 용매를 제거했다.The maleimide resin solution (V1) obtained in Synthesis Example 2 was flexible coated (WET film thickness 200 μm) on a PET film (Lumirer 38-S10 manufactured by Panak Co., Ltd.) that had not been subjected to release treatment using an applicator, The solvent was removed by drying the apply|coated resin film at 160 degreeC for 1 hour.
얻어진 말레이미드 수지 성형체는 두께 146㎛의 필름상이며, 박리, 분쇄함으로써 플레이크상 형상의 본 발명의 말레이미드 수지 성형체(M8)로 했다.The obtained maleimide resin molded body was in the form of a 146-micrometer-thick film, and it was set as the maleimide resin molded body (M8) of this invention of flake shape by peeling and grinding|pulverizing.
얻어진 말레이미드 수지 성형체(M8)의 잔용제는 0.0571%(571ppm)이었다. 또한, 본 공정에 의한 분자량 분포의 변화는 보여지지 않았다(GPC에 의한 측정).The residual solvent of the obtained maleimide resin molded body (M8) was 0.0571 % (571 ppm). In addition, no change in molecular weight distribution was observed by this process (measured by GPC).
(비교예 1)(Comparative Example 1)
합성예 2에 의해 얻어진 말레이미드 수지 용액(V1) 300mL를, 로터리 이배퍼레이터를 사용하여 가열 감압 하 160℃에서 용제를 증류제거하여 말레이미드 수지(B1)를 수지 블록상으로 얻었다. 얻어진 말레이미드 수지(B1)의 분자량 분포를 GPC에 의해 측정한 결과, 도 3에 나타내는 결과가 얻어졌다. 합성예 2에 의해 얻어진 말레이미드 수지 용액(V1)의 GPC에 의해 측정된 분자량 분포(도 1)와 비교한 결과, 대량 합성시 용매 증류제거 후의 말레이미드 수지(B1)가 고분자량화 되어 있는 것을 확인했다. 얻어진 말레이미드 수지(B1)의 잔용제는 0.1%(1000ppm) 이하이었다.The solvent was distilled off from 300 mL of the maleimide resin solution (V1) obtained in Synthesis Example 2 at 160°C under heating and reduced pressure using a rotary evaporator to obtain a maleimide resin (B1) in the form of a resin block. As a result of measuring the molecular weight distribution of the obtained maleimide resin (B1) by GPC, the result shown in FIG. 3 was obtained. As a result of comparison with the molecular weight distribution (FIG. 1) measured by GPC of the maleimide resin solution (V1) obtained in Synthesis Example 2, it was found that the maleimide resin (B1) after solvent distillation during mass synthesis had a high molecular weight. Confirmed. The residual solvent of the obtained maleimide resin (B1) was 0.1 % (1000 ppm) or less.
(비교예 2)(Comparative Example 2)
합성예 2에 의해 얻어진 말레이미드 수지 용액(V1) 1.0L를, 로터리 이배퍼레이터를 사용하여 가열 감압 하 180℃에서 용제를 증류제거한 결과 겔화되어 있는 것을 확인할 수 있었다. 얻어진 말레이미드 수지(B2)는 유동성이 없어졌다.Gelation was confirmed as a result of distilling 1.0 L of the maleimide resin solution (V1) obtained by Synthesis Example 2 at 180° C. under heating and reduced pressure using a rotary evaporator. The obtained maleimide resin (B2) lost fluidity|liquidity.
<말레이미드 수지 성형체의 제조 방법에 있어서의 건조온도의 비교><Comparison of drying temperature in the manufacturing method of a maleimide resin molded article>
(비교예 3)(Comparative Example 3)
실시예 1과 마찬가지로, 합성예 2에 의해 얻어진 말레이미드 수지 용액(V1)을, 어플리케이터를 이용하여 시판의 이미드 필름(도레이 듀퐁 제품 「캡톤(등록상표) 100H」)에 유연도포(WET 막두께 200㎛)하고, 도포된 수지막을 50℃의 열풍으로 1시간, 가열·건조시킴으로써 용매를 제거했다.In the same manner as in Example 1, the maleimide resin solution (V1) obtained in Synthesis Example 2 was flexible coated (WET film thickness) on a commercially available imide film (“Kapton (registered trademark) 100H” manufactured by DuPont Toray) using an applicator. 200 µm), and the solvent was removed by heating and drying the applied resin film with hot air at 50°C for 1 hour.
얻어진 말레이미드 수지 성형체는 끈적거림이 있고, 필름의 형상을 유지할 수 없어 박리하여 분쇄할 수 없었다.The obtained maleimide resin molded body was sticky, and the shape of the film could not be maintained, so it could not peel and grind|pulverize.
(비교예 4)(Comparative Example 4)
실시예 1과 마찬가지로, 합성예 2에 의해 얻어진 말레이미드 수지 용액(V1)을, 어플리케이터를 이용하여 시판의 이미드 필름(도레이 듀퐁 제품 「캡톤(등록상표) 100H」)에 유연도포(WET 막두께 200㎛)하고, 도포된 수지막을 250℃의 열풍으로 1시간, 가열·건조시킴으로써 용매를 제거했다.In the same manner as in Example 1, the maleimide resin solution (V1) obtained in Synthesis Example 2 was flexible coated (WET film thickness) on a commercially available imide film (“Kapton (registered trademark) 100H” manufactured by DuPont Toray) using an applicator. 200 micrometers), and the solvent was removed by heating and drying the apply|coated resin film with hot air at 250 degreeC for 1 hour.
얻어진 말레이미드 수지 성형체는 필름상이며 또한, 박리하여 플레이크화할 수 있었지만, 고분자량화가 진행되어 아세톤 등의 각종 용제에 불용으로 되었다.The obtained maleimide resin molded body was in the form of a film, and was peeled and flaked, but high molecular weight progressed and became insoluble in various solvents, such as acetone.
<악취의 비교><Comparison of odors>
(실시예 9, 비교예 5)(Example 9, Comparative Example 5)
실시예 1에서 얻어진 말레이미드 수지 성형체(M1) 및 비교용으로 4,4'-비스말레이미드디페닐메탄(TCI사 제품 이하 C1이라고 한다)을 준비하고, 악취의 비교를 행하였다.The maleimide resin molded body (M1) obtained in Example 1 and 4,4'-bismaleimide diphenylmethane (hereinafter referred to as C1 manufactured by TCI) were prepared for comparison, and the odor was compared.
또한, 아세트산의 정량은 시마즈 세이사쿠쇼사 제품 가스 크로마토그래피 GC-2010Plus를 이용하여 행하고, 컬럼으로서는 DB-WAX(Agilene Technologies사 제품) 길이 30m, 내경 0. 25㎜를 사용했다. 승온 프로그램으로서는 60℃에서 7분 유지하고, 20℃/min의 승온속도로 220℃까지 승온하고, 220℃에서 5분 유지하는 프로그램을 사용했다.In addition, acetic acid was quantified using Shimadzu Corporation's gas chromatography GC-2010Plus, and DB-WAX (manufactured by Agilene Technologies) had a length of 30 m and an inner diameter of 0.25 mm as a column. As a temperature increase program, the program which hold|maintained at 60 degreeC for 7 minutes, heated up to 220 degreeC at the heating rate of 20 degreeC/min, and hold|maintained at 220 degreeC for 5 minutes was used.
그 결과, 비교예 5에서는 아세트산의 악취가 나는 것을 확인하고, 실시예 9에서는 악취는 느껴지지 않았다.As a result, in Comparative Example 5, it was confirmed that an odor of acetic acid was produced, and in Example 9, an odor was not felt.
또한, 가스 크로마토그래피로 측정한 결과, 비교예 5에서는 아세트산이 검출되었다(도 4를 참조. 유지시간 11.298분). 또한, 산가를 측정한 결과, 산가 10mgKOH/g으로 되고, 아세트산 1% 상당에 해당하는 것을 확인했다.In addition, as a result of measurement by gas chromatography, acetic acid was detected in Comparative Example 5 (see Fig. 4, holding time 11.298 minutes). Moreover, as a result of measuring an acid value, it became an acid value of 10 mgKOH/g, and it confirmed that it corresponded to 1% of acetic acid.
<형상 및 용제 용해성의 비교><Comparison of shape and solvent solubility>
(실시예 10∼14, 비교예 6, 7)(Examples 10 to 14, Comparative Examples 6 and 7)
실시예 1, 5, 6, 7, 8에서 얻어진 말레이미드 수지 성형체(M1, M5∼M8) 및 비교용으로 말레이미드 수지 C1, 비교예 2에 기재된 말레이미드 수지(B2)를 사용해서 아세톤으로의 용해 시험을 행하였다.Using the maleimide resin molded bodies (M1, M5 to M8) obtained in Examples 1, 5, 6, 7, and 8, and maleimide resin C1 for comparison, and the maleimide resin (B2) described in Comparative Example 2 for comparison with acetone A dissolution test was performed.
수지 농도 50%로 맞추어 검토를 한 결과, 말레이미드 수지 성형체 M1, M5∼M8은 완전 용해되었지만, 말레이미드 수지(C1)와 말레이미드 수지(B2)는 완전 용해되지 않았다.As a result of examination in accordance with the resin concentration of 50%, the maleimide resin molded bodies M1 and M5 to M8 were completely dissolved, but the maleimide resin (C1) and the maleimide resin (B2) were not completely dissolved.
이상으로부터, 실시예 10∼14에서는 완전 용해되었기 때문에 말레이미드 수지 성형체(M1, M5∼M8)는 고분자량화 반응이 진행되어 있지 않은 것을 알 수 있다. 한편, 비교예 6과 7에서는 완전 용해할 수 없었기 때문에 말레이미드 수지(C1, B2)는 고분자량화 반응이 진행되어 있는 것을 알 수 있다.From the above, since it melt|dissolved completely in Examples 10-14, it turns out that high molecular weight reaction did not advance in the maleimide resin molded objects (M1, M5-M8). On the other hand, in Comparative Examples 6 and 7, since it was not completely dissolved, it turns out that the high molecular weight reaction is progressing in the maleimide resins (C1, B2).
<말레이미드 수지 조성물의 조제, 경화물 특성의 비교><Preparation of maleimide resin composition, comparison of properties of cured product>
(실시예 15)(Example 15)
실시예 1에 의해 얻어진 말레이미드 수지 성형체(M1)를 10부, 경화촉진제로서 2-에틸-4-메틸이미다졸(2E4MZ 시코쿠 카세이 가부시키가이샤 제품)을 0.21부 배합해 교반에 의해 균일하게 혼합·혼련하고, 본 발명의 말레이미드 수지 조성물을 얻었다. 이 말레이미드 수지 조성물을, 어플리케이터를 이용하여 시판의 이미드 필름(도레이 듀퐁 제품 「캡톤(등록상표) 100H」)에 유연도포(WET 막두께 200㎛)하고, 도포된 수지막을 경화 조건 160℃×2h+180℃×6h에서 용매를 제거하면서 경화시킴으로써 경화물을 얻었다. 얻어진 경화물의 물성을 평가한 결과를 표 1에 나타낸다.10 parts of the maleimide resin molded body (M1) obtained in Example 1 and 0.21 parts of 2-ethyl-4-methylimidazole (2E4MZ Shikoku Kasei Co., Ltd.) as a curing accelerator were blended and uniformly mixed by stirring. - It kneaded and obtained the maleimide resin composition of this invention. This maleimide resin composition was flexible coated (WET film thickness 200 µm) on a commercially available imide film (“Kapton (registered trademark) 100H” manufactured by DuPont Toray) using an applicator, and the applied resin film was cured under a curing condition of 160°C × Hardened|cured material was obtained by hardening, removing a solvent at 2h+180 degreeC x 6h. Table 1 shows the results of evaluating the physical properties of the obtained cured product.
(비교예 8)(Comparative Example 8)
EPPN-502H(니폰 카야쿠 제품 에폭시당량 169g/e.q. 연화점 67.5℃ EP1)를 61부, 페놀노볼락(메이와 카세이 제품 H-1, 수산기당량 106g/e.q.) 38중량부, 트리페닐포스핀(TPP 쥰세이 카가쿠 시약) 1중량부를 배합하고, 믹싱 롤을 이용하여 균일하게 혼합·혼련하여 에폭시 수지 조성물을 얻었다. 이 에폭시 수지 조성물을 태블릿화 후, 트랜스퍼 성형으로 수지 조성물 성형체를 조제하고, 경화 조건 160℃×2h+180℃×6h에서 경화물을 얻었다. 얻어진 경화물의 하기의 물성을 평가했다. 결과를 표 1에 나타낸다.61 parts of EPPN-502H (Nippon Kayaku Epoxy equivalent 169 g/e.q. softening point 67.5° C. EP1), 38 parts by weight of phenol novolac (H-1 manufactured by Meiwa Kasei, hydroxyl equivalent 106 g/e.q.), triphenylphosphine (TPP) 1 part by weight of Junsei Chemicals reagent) was blended and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition. After tabletting this epoxy resin composition, the resin composition molded object was prepared by transfer molding, and the hardened|cured material was obtained on hardening conditions 160 degreeC x 2h + 180 degreeC x 6h. The following physical properties of the obtained hardened|cured material were evaluated. A result is shown in Table 1.
(비교예 9)(Comparative Example 9)
EOCN-1020-55(니폰 카야쿠 제품 에폭시당량 194g/e.q. 연화점 54.8℃ EP2)를 65부, 페놀노볼락(메이와 카세이사 제품 H-1, 수산기당량 106g/e.q.) 34중량부, TPP(쥰세이 카가쿠 시약) 1중량부를 배합하고, 믹싱 롤을 이용하여 균일하게 혼합·혼련하여 에폭시 수지 조성물을 얻었다. 이 에폭시 수지 조성물을 태블릿화 후, 트랜스퍼 성형으로 수지 조성물 성형체를 조제하고, 경화 조건 160℃×2h+180℃×6h에서 경화물을 얻었다. 얻어진 경화물의 하기의 물성을 평가했다. 결과를 표 1에 나타낸다.65 parts of EOCN-1020-55 (Nippon Kayaku Epoxy equivalent 194 g/e.q. softening point 54.8° C. EP2), phenol novolac (H-1 manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent 106 g/e.q.) 34 parts by weight, TPP (Junsei) Kagaku reagent) 1 part by weight was blended, and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition. After tabletting this epoxy resin composition, the resin composition molded object was prepared by transfer molding, and the hardened|cured material was obtained on hardening conditions 160 degreeC x 2h + 180 degreeC x 6h. The following physical properties of the obtained hardened|cured material were evaluated. A result is shown in Table 1.
얻어진 경화물에 대해서 하기의 측정을 실시했다.The following measurement was performed about the obtained hardened|cured material.
·DMA・DMA
측정항목: 30℃, 200℃, 250℃의 저장탄성률,Measurement items: storage modulus of 30℃, 200℃, 250℃,
: 유리전이온도(tanδ 최대시의 온도) : Glass transition temperature (temperature at maximum tanδ)
측정 방법: 동적 점탄성 측정기 TA-instruments 제품, Q-800Measuring method: dynamic viscoelasticity measuring instrument TA-instruments product, Q-800
측정 온도범위: 30℃∼350℃Measurement temperature range: 30℃~350℃
승온속도: 2℃/minTemperature increase rate: 2℃/min
시험편 사이즈: 5㎜×50㎜로 잘라낸 것을 사용했다(두께는 약 800㎛).Test piece size: What was cut out to 5 mm x 50 mm was used (thickness is about 800 micrometers).
표 1로부터, 본 발명의 말레이미드 수지 조성물의 경화물은 에폭시 수지와 같은 경화 조건에서 성형 가능하고, 또한 얻어진 경화물은 고내열 에폭시 수지를 사용했을 경우와 비교하여 고온에서의 탄성률 변화가 적은 것을 알 수 있다.From Table 1, it can be seen that the cured product of the maleimide resin composition of the present invention can be molded under the same curing conditions as the epoxy resin, and the obtained cured product has little change in elastic modulus at high temperature compared to the case of using a high heat-resistant epoxy resin. Able to know.
본 발명을 특정의 형태를 참조해서 상세하게 설명했지만, 본 발명의 정신과 범위를 벗어나지 않고 다양한 변경 및 수정이 가능한 것은 당업자에게 있어서 명확하다.Although this invention was demonstrated in detail with reference to the specific form, it is clear for those skilled in the art that various changes and correction are possible without departing from the mind and range of this invention.
또한, 본 출원은, 2016년 8월 31일자로 출원된 일본국 특허출원(특원2016-169417)에 근거하고 있고, 그 전체가 인용에 의해 원용된다. 또한, 여기에 인용되는 모든 참조는 전체로서 받아들인다.In addition, this application is based on the Japan patent application (Japanese Patent Application No. 2016-169417) for which it applied on August 31, 2016, The whole is used by reference. Also, all references cited herein are incorporated in their entirety.
본 발명의 말레이미드 수지 성형체는 용이하게 말레이미드 수지 조성물을 조제할 수 있고, 고내열 기판재료, 플렉시블 기판재료, 고내열 저유전재료, 고내열 CFRP용 재료(탄소섬유 복합재료), 차량탑재용 SiC 파워 디바이스용 고내열 밀봉재료 용도 등의 광범위한 용도에 매우 유용하다.The maleimide resin molded article of the present invention can easily prepare a maleimide resin composition, and a high heat-resistant substrate material, a flexible substrate material, a high heat-resistant low-k material, a high-heat-resistant CFRP material (carbon fiber composite material), for vehicle mounting It is very useful for a wide range of applications such as high heat-resistant sealing materials for SiC power devices.
Claims (14)
상기 말레이미드 수지가 하기 식 (1)로 나타내어지는 구조를 갖는 말레이미드 수지 성형체.
(식 (1) 중, 복수 존재하는 R은 각각 독립하여 존재하고, 수소원자, 탄소수 1∼10의 알킬기 또는 페닐기를 나타낸다. X는 하기 구조식 (a)∼(e)에서 선택된다. n은 평균값이며 1<n≤5를 나타낸다.)
The maleimide resin molded body in which the said maleimide resin has a structure represented by following formula (1).
(In formula (1), a plurality of R's each independently exist and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. X is selected from the following structural formulas (a) to (e). n is an average value and 1<n≤5.)
상기 유기용제의 함유량이 5ppm 이상 30000ppm 이하인 말레이미드 수지 성형체.3. The method of claim 1 or 2,
The maleimide resin molded body whose content of the said organic solvent is 5 ppm or more and 30000 ppm or less.
상기 유기용제가 탄소수 3∼10의 방향족 탄화수소, 케톤류, 에스테르류 및 에테르류에서 선택되는 적어도 1종인 말레이미드 수지 성형체.3. The method of claim 1 or 2,
wherein the organic solvent is at least one selected from aromatic hydrocarbons having 3 to 10 carbon atoms, ketones, esters and ethers.
두께가 10㎛∼3㎜인 말레이미드 수지 성형체.3. The method of claim 1 or 2,
A maleimide resin molded article having a thickness of 10 µm to 3 mm.
상기 말레이미드 수지의 연화점이 50∼150℃인 말레이미드 수지 성형체.3. The method of claim 1 or 2,
A maleimide resin molded body having a softening point of 50 to 150° C. of the maleimide resin.
상기 말레이미드 수지가 하기 식 (1)로 나타내어지는 구조를 갖는, 말레이미드 수지 성형체의 제조 방법.
(식 (1) 중, 복수 존재하는 R은 각각 독립하여 존재하고, 수소원자, 탄소수 1∼10의 알킬기 또는 페닐기를 나타낸다. X는 하기 구조식 (a)∼(e)에서 선택된다. n은 평균값이며 1<n≤5를 나타낸다.)
The manufacturing method of the maleimide resin molded object in which the said maleimide resin has a structure represented by following formula (1).
(In formula (1), a plurality of R's each independently exist and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. X is selected from the following structural formulas (a) to (e). n is an average value and 1<n≤5.)
상기 유기용제가 탄소수 3∼10의 방향족 탄화수소, 케톤류, 에스테르류 및 에테르류에서 선택되는 적어도 1종인 말레이미드 수지 성형체의 제조 방법.9. The method according to claim 7 or 8,
The method for producing a maleimide resin molded body, wherein the organic solvent is at least one selected from aromatic hydrocarbons having 3 to 10 carbon atoms, ketones, esters and ethers.
건조온도가 80∼200℃인 말레이미드 수지 성형체의 제조 방법.9. The method according to claim 7 or 8,
A method for producing a maleimide resin molded body having a drying temperature of 80 to 200°C.
말레이미드 수지와 가교반응 가능한 화합물 및 경화촉진제에서 선택되는 적어도 어느 하나를 더 포함하는 말레이미드 수지 조성물.13. The method of claim 12,
A maleimide resin composition further comprising at least one selected from a compound capable of crosslinking with the maleimide resin and a curing accelerator.
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| JPJP-P-2016-169417 | 2016-08-31 | ||
| JP2016169417 | 2016-08-31 | ||
| KR1020197005653A KR20190046815A (en) | 2016-08-31 | 2017-08-28 | Maleimide resin molded article, method of producing maleimide resin molded article, maleimide resin composition and cured product thereof |
| PCT/JP2017/030694 WO2018043380A1 (en) | 2016-08-31 | 2017-08-28 | Maleimide resin mold, method for manufacturing maleimide resin mold, maleimide resin composition, and cured product thereof |
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| KR102601953B1 (en) | 2023-11-14 |
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