CN103059309A - Resin composition and use thereof - Google Patents
Resin composition and use thereof Download PDFInfo
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- CN103059309A CN103059309A CN2011103709181A CN201110370918A CN103059309A CN 103059309 A CN103059309 A CN 103059309A CN 2011103709181 A CN2011103709181 A CN 2011103709181A CN 201110370918 A CN201110370918 A CN 201110370918A CN 103059309 A CN103059309 A CN 103059309A
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- 239000011342 resin composition Substances 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 16
- -1 nitrogen-oxygen heterocyclic compound Chemical class 0.000 claims abstract description 8
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract 10
- 229920005989 resin Polymers 0.000 claims description 80
- 239000011347 resin Substances 0.000 claims description 80
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims description 43
- 239000003351 stiffener Substances 0.000 claims description 33
- 239000004593 Epoxy Substances 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 17
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 13
- GTBXZWADMKOZQJ-UHFFFAOYSA-N 1-phenanthrol Chemical compound C1=CC2=CC=CC=C2C2=C1C(O)=CC=C2 GTBXZWADMKOZQJ-UHFFFAOYSA-N 0.000 claims description 12
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- 150000004780 naphthols Chemical class 0.000 claims description 12
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 12
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229920003987 resole Polymers 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 239000003063 flame retardant Substances 0.000 claims description 5
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 3
- 125000000101 thioether group Chemical group 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract description 5
- 239000003822 epoxy resin Substances 0.000 abstract description 4
- 229920000647 polyepoxide Polymers 0.000 abstract description 4
- 239000004848 polyfunctional curative Substances 0.000 abstract 4
- 238000002360 preparation method Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 239000002250 absorbent Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 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 6
- 230000000694 effects Effects 0.000 description 6
- 239000012779 reinforcing material Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 229940106691 bisphenol a Drugs 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 238000000710 polymer precipitation Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- JXZUHDMMANYKMX-UHFFFAOYSA-N 1-ethyl-4-methylimidazole Chemical compound CCN1C=NC(C)=C1 JXZUHDMMANYKMX-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-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
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- DAXPJQXRIHVGCK-UHFFFAOYSA-N CC(C(CC1)CCC1OC)(c1ccc(C)cc1)P(c1ccccc1)([IH]c1ccccc1)=C Chemical compound CC(C(CC1)CCC1OC)(c1ccc(C)cc1)P(c1ccccc1)([IH]c1ccccc1)=C DAXPJQXRIHVGCK-UHFFFAOYSA-N 0.000 description 1
- WAKYBUFFQWPDEX-UHFFFAOYSA-N CC(C1)C(CCCC2)C2C(O)=C1P(CC1C2CCCC1)(C1C2=CCC=C1)=O Chemical compound CC(C1)C(CCCC2)C2C(O)=C1P(CC1C2CCCC1)(C1C2=CCC=C1)=O WAKYBUFFQWPDEX-UHFFFAOYSA-N 0.000 description 1
- XSXSIQHTWYVTJC-UHFFFAOYSA-N CCCC1=C(C)C(C)=C(CCC)[ClH]P1(C1=CC(C)=CCC1C)=C Chemical compound CCCC1=C(C)C(C)=C(CCC)[ClH]P1(C1=CC(C)=CCC1C)=C XSXSIQHTWYVTJC-UHFFFAOYSA-N 0.000 description 1
- PPDHLBCKTMXEOU-UHFFFAOYSA-N CCCCC(C1C)C(C2CCCCC2)(c2ccc(C)cc2)P1(C1CCCCC1)=O Chemical compound CCCCC(C1C)C(C2CCCCC2)(c2ccc(C)cc2)P1(C1CCCCC1)=O PPDHLBCKTMXEOU-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 210000001072 colon Anatomy 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical class [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Epoxy Resins (AREA)
- Laminated Bodies (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
A resin composition comprising: an epoxy resin and a hardener, the hardener is a stable solution, and the hardener is prepared by the following steps: adding a nitrogen-oxygen heterocyclic compound with the following formula I or II and a DOPO series compound into an organic solvent to provide a reaction solution:[ formula I ]]
Description
Technical field
The present invention is about a kind of resin combination, especially about a kind of with a stable state solution as the resin combination of stiffening agent and use the prepreg (prepreg) and laminated plates (laminate) that said composition was consisted of.
Background technology
Printed circuit board (PCB) is the circuit substrate of electronic installation, and it carries other electronic components and with these member electrical communication, so that stable circuit working environment to be provided.Common printed circuit board base board is the laminated plates (copper clad laminate, CCL) of Copper Foil coating, and it mainly is comprised of resin, reinforcing material and Copper Foil.Common resin such as Resins, epoxy, resol, polyamine formaldehyde, silicone and Teflon etc.; Reinforcing material commonly used is then such as glasscloth, glass fibre mats, insulation paper, linen etc.
Generally speaking, printed circuit board (PCB) can followingly make.To be impregnated in just like the reinforcing material of glass fabric in the resin, and the glass fabric that will contain behind the resin pickup is cured to semi-harden state (being B-stage (B-stage)) to obtain a prepreg (prepreg).Subsequently, with the prepreg of certain number of plies stacked and in the stacked tinsel at least one outside of this stacked prepreg so that a sandwich to be provided, and this sandwich is carried out a hot press operation (being C-stage (C-stage)) and obtains a metal coating laminated plates.The tinsel on etching metal coating laminated plates surface is to form specific circuit pattern (circuit pattern).Then, dig out several holes in this metal coating laminated plates, and the plating electro-conductive material is finished the preparation of printed circuit board (PCB) to form through hole (via holes) in these holes.
Consider rear end electronics work program, printed circuit board (PCB) must reach to a certain degree at aspects such as thermotolerance, dimensional stability, chemical stability, workability, toughness and physical strengths.Generally speaking, use the printed circuit board (PCB) of Resins, epoxy preparation can have above-mentioned characteristic concurrently, so Resins, epoxy is the resin of normal use in the industry.Resins, epoxy is the organic high molecular compound that contains two or two above epoxide groups in molecule of general reference, is a kind of reactive monomeric.The molecule of high epoxide group number can obtain a highly cross-linked reticulated structure after polymerization, though this highly cross-linked reticulated structure has quite high hardness and glass transfer temperature and endurance, but usually there are easily the shortcomings such as crisp and shock-resistance is relatively poor, are unfavorable for rear end processing.
Based on the use shortcoming of above-mentioned Resins, epoxy, use comprises more at present
The nitrogen oxygen helerocyclics of structure comes the substituted epoxy resin, maybe this nitrogen oxygen helerocyclics is used as stiffening agent and Resins, epoxy mediation.This nitrogen oxygen helerocyclics structurally has a high proportion of phenyl ring and carbon-nitrogen bond knot, therefore has excellent thermal properties (such as thermotolerance, glass tansition temperature (Tg), flame retardant resistance etc.) and chemistry and mechanical properties.In addition, this nitrogenous oxygen helerocyclics is after carrying out ring-opening polymerization, the polymkeric substance that consists of structurally has great amount of hydroxy group (hydroxyl group), not only when independent use, can the self-crosslinking reaction make the phenolic aldehyde laminated plates, when with Resins, epoxy and time spent, also can promote thermal properties and the mechanical properties of the finished product, and can reduce the shrinkability of product, make more senior laminated plates.
Yet, add merely the laminated plates that the nitrogen oxygen helerocyclics consists of, it is not enough that its flame resistivity is still disliked; Therefore, usually can add phosphonium flame retardant (such as DOPO) to improve flame resistivity.For example, in TaiWan, China patent I285653 number, be directly the powder of nitrogen oxygen helerocyclics with the DOPO based compound to be mixed, and under High Temperature High Pressure, directly be solidified into substrate, strengthen the flame resistivity of substrate.Yet this method for making exists and is difficult to control reaction homogeneity and need expends mass energy so that the problem such as High Temperature High Pressure operating environment to be provided.In addition, the gained laminated plates still has the space of improvement on characteristic electron and dimensional stability.
Given this, the invention provides a kind of resin combination for the laminated plates preparation, it comprises a stable state solution, and this stable state solution contains the polymerisate of nitrogen oxygen helerocyclics and DOPO based compound, and the effect of stiffening agent can be provided.By the laminated plates that this resin combination makes, have excellent physico-chemical property (high Tg, good moisture resistance, excellent dimensions stability, good flame resistivity etc.) and electrical properties (low Df, Dk).
Summary of the invention
A purpose of the present invention is to provide a kind of resin combination, comprises:
One Resins, epoxy; And
One stiffening agent, it is a stable state solution, can be made by the program of following steps:
(a) nitrogen oxygen helerocyclics (N, O-heterocyclic compound) and the DOPO based compound (DOPO-based compound) of interpolation one tool following formula I or II in an organic solvent, so that a reaction soln to be provided:
[formula I]
[formula II]
Wherein,
R1 is selected from the group of following group: through or C1 to C10 alkyl, warp that is unsubstituted or C1 to the C10 cycloalkyl that is unsubstituted, and through or C6 to C20 aryl, the warp that is unsubstituted or C6 to the C20 aryloxy, the warp that are unsubstituted or C1 to the C15 unsaturated alkyl that is unsubstituted, naphthols base, phenanthrol base, reach dicyclopentadienyl;
R2 and R3 are separately independently for being selected from the group of following group: H, halogen, warp or C1 to the C10 alkyl, warp that are unsubstituted or C1 to the C10 cycloalkyl that is unsubstituted, and warp or C6 to C20 aryl, the warp that is unsubstituted or C6 to the C20 aryloxy, the warp that are unsubstituted or C1 to the C15 unsaturated alkyl that is unsubstituted, naphthols base, phenanthrol base, reach dicyclopentadienyl;
W1 is selected from the group of following group: H, halogen, ether, thioether group, alkylsulfonyl, sulfinyl, carbonyl, warp or C1 to C10 alkyl, the warp that is unsubstituted or C1 to the C10 cycloalkyl that is unsubstituted, and through or C6 to C20 aryl, warp that is unsubstituted or C6 to the C20 aryloxy, the warp that are unsubstituted or C1 to the C15 unsaturated alkyl that is unsubstituted, naphthols base, phenanthrol base, reach dicyclopentadienyl;
W2 is selected from the group of following group: through or C1 to C10 alkyl, warp that is unsubstituted or C1 to the C10 cycloalkyl that is unsubstituted, and through or C6 to C20 aryl, the warp that is unsubstituted or C6 to the C20 aryloxy, the warp that are unsubstituted or C1 to the C15 unsaturated alkyl that is unsubstituted, naphthols base, phenanthrol base, reach dicyclopentadienyl;
M and n independently are 1 to 3 integer separately; P is 1 to 3 integer; And q is 1 to 4 integer;
(b) heat this reaction soln, to carry out ring-opening polymerization, provide a polymers soln; And
(c) cool off this polymers soln obtaining this stable state solution,
Wherein, this organic solvent does not react with this nitrogen oxygen helerocyclics and this DOPO based compound; And in the gross weight of this nitrogen oxygen helerocyclics and this DOPO based compound, the content of this DOPO based compound is that about 0.01 % by weight is to about 50 % by weight; In solid substance, the content of this stiffening agent is that about 20 weight parts of per 100 weight part Resins, epoxy are to about 200 weight parts.
Another object of the present invention is to provide a kind of prepreg, it is by with base material impregnation resin combination described above and carry out drying and make.
A further object of the present invention is to provide a kind of laminated plates, comprises synthetic layer and a metal level, and this synthetic layer is made of above-mentioned prepreg.
For above-mentioned purpose of the present invention, technical characterictic and advantage can be become apparent, hereinafter be elaborated with the part specific embodiment.
Description of drawings
Figure 1 shows that the infrared spectrum analysis result as the stable state solution of the stiffening agent of resin combination of the present invention;
Fig. 2 a is depicted as the dsc analysis result as the stable state solution of the stiffening agent of resin combination of the present invention; And
Fig. 2 b is depicted as the dsc analysis result as another stable state solution of the stiffening agent of resin combination of the present invention.
Embodiment
Below will describe particularly according to part embodiment of the present invention; But, not deviating under the spirit of the present invention, the present invention still can put into practice by multiple multi-form embodiment, protection domain of the present invention should be interpreted as being limited to the content that specification sheets is stated.In addition, unless Wen Zhongyou illustrates in addition, (especially in the aftermentioned patent claim) employed " one ", " being somebody's turn to do " and similar term are interpreted as comprising odd number and plural form in this specification sheets, " being substituted " as used in this specification word is to replace hydrogen with substituting group, and this substituting group can be dehydrogenation any group or atom in addition.Unless and Wen Zhongyou illustrates in addition, when in this specification sheets, describing composition contained in solution, mixture or the composition, be to calculate with the contained solid substance of this composition, that is, do not include the weight of solvent in.
The characteristics of resin combination of the present invention are, as stiffening agent with a kind of stable state solution, this stable state solution comprise by nitrogen oxygen helerocyclics and DOPO based compound carry out ring-opening polymerization and polymkeric substance, the solvent compatibility of this polymkeric substance tool excellence and relative little molecular weight, the obvious polymer precipitation of nothing so can store for a long time.Resin combination of the present invention can be used to prepare laminated plates, can give physico-chemical property (high Tg, good moisture resistance, excellent dimensions stability, good flame resistivity etc.) and the electrical properties (low Df, Dk) of product excellence.
Particular words it, comprise a Resins, epoxy and the stable state solution as stiffening agent in the resin combination of the present invention, wherein, this stable state solution can make by the program that comprises following steps:
(a) in an organic solvent, add a nitrogen oxygen helerocyclics and a DOPO based compound, so that a reaction soln to be provided;
(b) heat this reaction soln, to carry out ring-opening polymerization, provide a polymers soln; And
(c) cool off this polymers soln to obtain this stable state solution.
In above-mentioned steps (a), employed nitrogen oxygen helerocyclics is the structure of tool following formula I or II:
[formula I]
[formula II]
Wherein,
R1 is selected from the group of following group: through or C1 to C10 alkyl, warp that is unsubstituted or C1 to the C10 cycloalkyl that is unsubstituted, and through or C6 to C20 aryl, the warp that is unsubstituted or C6 to the C20 aryloxy, the warp that are unsubstituted or C1 to the C15 unsaturated alkyl that is unsubstituted, naphthols base, phenanthrol base, reach dicyclopentadienyl;
R2 and R3 are separately independently for being selected from the group of following group: H, halogen (such as F, Cl, Br, I etc.), warp or C1 to C10 alkyl, the warp that is unsubstituted or C1 to the C10 cycloalkyl that is unsubstituted, reaching warp or C6 to C20 aryl, the warp that is unsubstituted or C6 to the C20 aryloxy, the warp that are unsubstituted or C1 to the C15 unsaturated alkyl that is unsubstituted, naphthols base, phenanthrol base, reaching dicyclopentadienyl;
W1 is selected from the group of following group: H, halogen, ether, thioether group, alkylsulfonyl, sulfinyl, carbonyl, warp or C1 to C10 alkyl, the warp that is unsubstituted or C1 to the C10 cycloalkyl that is unsubstituted, and through or C6 to C20 aryl, warp that is unsubstituted or C6 to the C20 aryloxy, the warp that are unsubstituted or C1 to the C15 unsaturated alkyl that is unsubstituted, naphthols base, phenanthrol base, reach dicyclopentadienyl;
W2 is selected from the group of following group: through or C1 to C10 alkyl, warp that is unsubstituted or C1 to the C10 cycloalkyl that is unsubstituted, and through or C6 to C20 aryl, the warp that is unsubstituted or C6 to the C20 aryloxy, the warp that are unsubstituted or C1 to the C15 unsaturated alkyl that is unsubstituted, naphthols base, phenanthrol base, reach dicyclopentadienyl;
M and n independently are 1 to 3 integer separately; P is 1 to 3 integer; And q is 1 to 4 integer.
In formula I and formula II, m and n correspond respectively to the bond number of W1 and W2.Take formula I as example, under the situation of bound by theory not, when m was 1, W1 was the group (such as H, halogen, methyl etc.) of the single bond of tool, and this moment, the nitrogen oxygen helerocyclics was the compound of the single nitrogen oxa-of tool ring structure; And when m was 2, W1 was the linking group of the two bonds of tool, and this moment, the nitrogen oxygen helerocyclics was the compound of tool dinitrogen oxa-ring structure, by that analogy.
In part embodiment of the present invention, in preparation during this stable state solution, provide desired nitrogen oxygen helerocyclics with the chemical synthesis of phenolic compound, aldehyde cpd and amine compound, know clearly as described in the rear attached embodiment.Preferably, W1 and W2 are separately independently for being selected from the group of following group:
[formula I ']
[formula II ']
Wherein, an object lesson that is applicable to prepare the nitrogen oxygen helerocyclics of described stable state solution is
In step (a), the DOPO based compound refer to 9,10-dihydro-9-oxy assorted-10-phosphorus phenanthrene-10-oxide compound (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, DOPO) and derivative thereof.In part embodiment of the present invention, when preparation stable state solution, use the DOPO based compound that is selected from following group:
But, though the DOPO based compound can improve the flame resistivity matter of products made thereby, can adversely increase the water-absorbent of product.Therefore, in stable state solution of the present invention, in the gross weight of nitrogen oxygen helerocyclics and DOPO based compound, the content of DOPO based compound is preferably about 0.01 % by weight to about 50 % by weight, is more preferred from about 10 % by weight to about 40 % by weight.Because the content of DOPO based compound is lower than 0.01 % by weight, then can't effectively improve the flame resistivity matter of products made thereby; And if the content of DOPO based compound is higher than 50 % by weight, may the water-absorbent of products made thereby will be increased significantly adversely.In part embodiment of the present invention, when preparation stable state solution, in the gross weight of nitrogen oxygen helerocyclics and DOPO based compound, about 20 % by weight of the consumption of DOPO based compound are to about 40 % by weight.
Employed organic solvent in (a) step, can be the used nitrogen oxygen helerocyclics of any solubilized and DOPO based compound and not with the solvent of these compounds reaction, be preferably the solvent that has simultaneously catalytic effect.In addition, based on operation ease, the organic solvent that is suitable in (a) step the related maximum operating temperature (being generally the temperature of ring-opening polymerization) of the preparation process that adopts boiling point to be higher than at least this stable state solution, change the concentration of reaction soln to avoid solvent in operating process, to volatilize, cause the difficulty that successive process carries out (feeding-up and can't stir such as solution), or affect the quality (uneven such as extent of polymerization) of obtained polymers soln.
In under the above-mentioned situation of selecting condition, can adopt the solvent that is selected from following group in (a) step: pimelinketone, acetone, butanone, methyl iso-butyl ketone (MIBK), N, dinethylformamide (N, N-dimethyl formamide, DMF), N,N-dimethylacetamide (N, N '-dimethyl acetamide, DMAc), N-Methyl pyrrolidone (N-methyl-pyrolidone, NMP) and aforesaid arbitrary combination.In part embodiment of the present invention, when preparation stable state solution, use DMF as organic solvent.
Organic solvent is in the consumption of (a) step, except the effect that must reach the used nitrogen oxygen helerocyclics of dissolving and DOPO based compound, need be enough to the ring-opening polymerization polymer that stabilizing dissolved/the dispersion ring-opening polymerization produces, so that the ring-opening polymerization polymer stabilizing dissolved/be scattered in the solvent and can not precipitate.Generally speaking, in the gross weight of nitrogen oxygen helerocyclics and the DOPO based compound of 100 weight parts, the usage quantity of this organic solvent is generally at least about 10 weight parts, for example, about 10 weight parts are preferably about 20 weight parts to about 120 weight parts to about 150 weight parts.Yet the affiliated field of the present invention has knows the knowledgeable usually after considering the disclosure of this specification sheets in light of actual conditions, can select to change according to actual demand the consumption of organic solvent, is not limited with aforementioned amount ranges.In part embodiment of the present invention, when preparation stable state solution, in the gross weight of nitrogen oxygen helerocyclics and the DOPO based compound of 100 weight parts, be the organic solvent of about 100 weight parts of use.
In nitrogen oxygen helerocyclics and DOPO based compound uniform dissolution form reaction soln in organic solvent after, at step (b) reacting by heating solution to carry out open loop addition/polyreaction.Heat the temperature that reaches, be higher than at least the softening temperature of nitrogen oxygen helerocyclics, so that in the situation of not using expensive and environmentally harmful catalyzer, carry out the open loop addition/polyreaction of nitrogen oxygen helerocyclics.In addition, this temperature should be lower than the boiling point of solvent, changes the concentration of reaction soln to avoid solvent to volatilize in operating process, causes the difficulty that successive process carries out or affects the quality of prepared polymers soln.
Can adopt any suitable means to provide energy to this reaction soln, carry out the heating of step (b).For example, can be by for example heat energy (such as water-bath, oil bath, electric heater, heat exchanger tube), radiating capacity (such as UV-irradiation, gammairradiation) or aforesaid arbitrary combination, this reaction soln energy is provided, to promote its temperature to desired temperature, to carry out open loop addition/polyreaction.Pass homogeneity and reaction homogeneity in order to improve heat, better in temperature-rise period stirring reaction solution simultaneously.
After step (b) is carried out ring-opening polymerization and is obtained a polymers soln, then in step (c), reduce the temperature of polymers soln, to stop in fact ring-opening polymerization, obtain the stable state solution as resin combination stiffening agent of the present invention.Indication " stops in fact " herein, refer between the nitrogen oxygen helerocyclics, between the polymkeric substance and the polyreaction between nitrogen oxygen helerocyclics and the polymkeric substance by considerably negative catalysis, so that the molecular weight of the polymkeric substance that forms can obviously not change between the specific shelf lives, avoid polymer precipitation.The temperature that stops open loop addition/polyreaction is decided according to nitrogen oxygen helerocyclics and the DOPO based compound kind of reacting, and is preferably room temperature, so not as limit.Skill personage in the field of the present invention can comply with the suitable temperature of its common knowledge-chosen to stop open loop addition/polyreaction after considering description of the present invention and rear attached embodiment in light of actual conditions.In addition, any suitable operation can be carried out, to reach the cooling purpose in step (c).For example, the polymers soln that step (b) can be consisted of places the atmosphere surrounding of a room temperature, maybe this polymers soln is placed a normal temperature water-bath, perhaps and with aforementioned the two, to reduce the temperature of this polymers soln.
After the cooling of step (c), can obtain the stable state solution as the stiffening agent of resin combination of the present invention, this stable state solution also can shorten the integrally curing time except the effect that stiffening agent can be provided.
In resin combination of the present invention, the Resins, epoxy that adopts is the resin that a part contains at least two cycloalkyl groups, such as novolac epoxy, brominated Resins, epoxy etc.In part embodiment of the present invention, use novolac epoxy.
In resin combination of the present invention, except using stable state solution as the stiffening agent, also can and with other existing stiffening agents.The kind of indication " existing stiffening agent " there is no particular restriction herein, for example can be and be selected from one of following group or many persons: Dyhard RU 100 (dicyandiamide, Dicy), 4,4 '-two amido sulfobenzides (4,4 '-diaminodiphenyl sulfone, DDS) or resol (Novolac) etc.Consumption as for stiffening agent then can optionally be adjusted by the user.Generally speaking, in solid substance, the content of stiffening agent is preferably about 20 weight parts of per 100 weight part Resins, epoxy to about 200 weight parts, is more preferred from about 70 weight parts of per 100 weight part Resins, epoxy to about 120 weight parts, but not as limit.
Further comprise among the embodiment of other existing stiffening agents at resin combination of the present invention, the blending ratio of stable state solution and other stiffening agents there is no particular restriction, can optionally be allocated by the user.In part embodiment of the present invention, the employed stiffening agent of per 100 weight part Resins, epoxy can be separately consisted of or is made of the mixture of the resol of about 60 weight part stable state solution and about 40 weight parts by about 80 weight parts to the stable state solution of about 120 weight parts.
Resin combination of the present invention can optionally further comprise other additives, and such as hardening accelerator, filler, dispersion agent (such as silane coupling agent), toughner, fire retardant etc., and these additives can be used alone or in combination.For example, can add be selected from following group hardening accelerator so that the hardening effect of improvement to be provided, but not as limit: imidazoles (imidazole), 1-Methylimidazole (1-methyl-imidazole, 1MI), glyoxal ethyline (2-methyl-imidazole, 2MI), 2-ethyl-4-methylimidazole (2-ethyl-4-methyl-imidazole, 2E4MI), 2-phenylimidazole (2-phenyl-imidazole, 2PI) and aforesaid arbitrary combination.If the use hardening accelerator, the visual user of its addition needs and selectes, and is generally about 0.01 weight part of per 100 weight part Resins, epoxy to about 1 weight part.Again for example, can add the filler that is selected from following group, with characteristics such as the workability of modified epoxy resin, flame retardant resistance, thermotolerance, wet fastnesss, but not as limit: silicon-dioxide, glass powder, talcum, kaolin, white mountain range soil, mica and aforesaid arbitrary combination; If the use filler, the visual user's of its addition needs are selected, are generally per 100 weight part Resins, epoxy, 0.01 weight part, 120 weight parts.In part embodiment of the present invention, use the additives such as silane coupling agent, 2E4MI and silica filler.
Resin combination of the present invention can be by with Resins, epoxy, evenly mix with agitator as the stable state solution of stiffening agent and the additive that optionally adds, and be dissolved or dispersed in and make the varnish shape in the solvent, for the following process utilization.
The present invention provides a kind of prepreg in addition, makes a base material (reinforcing material) surface adhere to aforesaid resin combination fully, and carries out drying and obtain.Reinforcing material commonly used comprises: glasscloth (glass fabric, glassine paper, glassmat etc.), kraft paper, short flannel cotton paper, natural fiber cloth, organic fibre cloth etc.In part embodiment of the present invention, be to use 7628 glasscloths as reinforcing material, adhere to after aforementioned stable state solution or the resin combination and in 2 to 5 minutes (the B-stage) of 175 ℃ of lower heat dryings, make whereby the prepreg of semi-harden state.
Above-mentioned prepreg can be used for making the lamination version.Therefore, the present invention provides a kind of laminated plates in addition, and it comprises synthetic layer and a metal level, and this synthetic layer is made of above-mentioned prepreg.Wherein, above-mentioned prepreg that can stacked plural layer, and the stacked tinsel of at least one outer surface (such as Copper Foil) of the synthetic layer that consists of in this stacked prepreg to be providing a sandwich, and this sandwich is carried out a hot press operation and obtains this laminated plates.In addition, can be via the tinsel of further this laminated plates of patterning, and make printed circuit board (PCB).
Further illustrate the present invention with following specific embodiment, wherein, the measuring instrument that adopts and method are as follows respectively:
[colloid chromatograph (gel permeation chromatography, GPC) analysis]
The colloid chromatograph of Waters company (model: waters 600).
[infrared spectrum analysis]
Fourier transform infrared spectrometer (the model: Spectrum100) of Perkin-Elmer company.
[means of differential scanning calorimetry (differential scanning calorimetry, DSC) analysis]
The differential scanning calorimeter of Perkin-Elmer company (model: DSC 7).
[glass transfer temperature test]
Utilize dynamic mechanical analysis instrument (dynamic mechanical analyzer, DMA) to measure glass tansition temperature (Tg).The test specification of glass tansition temperature is interconnected IPC-TM-650.2.4.25C and the 24C detection method with encapsulating association (The Institute for Interconnecting and Packaging Electronic Circuits, IPC) of electronic circuit.
[water-absorbent test]
Carry out pressure cooker cooking test (pressure cooker test, PCT) test, laminated plates is placed pressurized vessel, under 121 ℃, saturated humidity (100%R.H.) and 1.2 atmospheric environment 1 hour, the moisture-proof ability of testing printed circuit board.
[specific inductivity and the dissipation factor measure]
According to ASTM D150 standard, under operating frequency 1 GHz (GHz), calculate specific inductivity (dielectric constant, Dk) and the dissipation factor (dissipation factor, Df).
[thermal expansivity test]
Thermodilatometric analysis instrument (type TA 2940) with TA instrument company measures, the measurement condition is to heat up at 50 ℃ to 260 ℃ the temperature range temperature rise rate with 10 ℃ of per minutes, measures thermal linear expansion coefficient on the basal plane of sample (laminated plates of 3 mm square) and the coefficient of thermal expansion of thickness direction (Z-direction).
[heat decomposition temperature test]
Utilize thermogravimetric analyzer (thermogravimetric analyzer, TGA) to measure and compare with the initial stage quality, the temperature when quality reduces 5% is heat decomposition temperature.
[flame retardancy test]
Utilize UL94V: the vertical combustion testing method, printed circuit board (PCB) is fixed with the vertical position, with the Bunsen burner burning, relatively its spontaneous combustion is extinguished and combustion-supporting characteristic.
[toughness test]
Laminated plates is lain against on the tool of plane, vertical and the laminated plates Surface Contact with cross metal fixture, grant again vertical pressure, after remove this cross tool, observe cross shape vestige on the substrate, inspect this laminate surface, occur then to be judged to be good without white scrimp, show slightly lineae ablicantes for general, it is bad that crackle or fracture person occur.
Embodiment
[preparation of nitrogen oxygen helerocyclics]
With the dihydroxyphenyl propane (bisphenol A) of 784 grams, the aniline of 458 grams and the toluene of 600 grams, adding one is equiped with heating unit, thermometer, stirrer, cooling tube, splashes in 3 liters the detachable reaction flask of four-hole of device and reclaim under reduced pressure device, to form a resulting solution, be warming up to about 40 ℃ and stir.Lower in stirring, in 20 minutes, dropwise add the toluene solution of the 819 44 % by weight formaldehyde that restrain to this resulting solution, this moment, the temperature of this resulting solution rose to about 90 ℃, heated and kept this resulting solution in about 90 ℃ temperature and reacted 3 hours, and its reaction formula is as follows.
Subsequently stopped heating and stirring also left standstill about 20 minutes, after this resulting solution is divided into two layers, remove the water on upper strata and the emulsification of trace, soon reheat to about 90 ℃ and with the decompression (being lower than about 90 mmhg) mode reclaim solvent, when the temperature to about 130 ℃ and reclaim whole solvents after, namely obtain weight about 1380 the gram nitrogen oxygen helerocyclics 1.
[preparation of stable state solution]
With the ratio shown in the table 1, the nitrogen oxygen helerocyclics 1,9 that in 2 liters of reactors, adds, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (DOPO) and N, dinethylformamide (DMF), under stirring state, reactor is heated to about 100 to 110 ℃ temperature, and held temperature about 2 hours, subsequently stopped heating and with reactor cooling to room temperature, obtain stable state solution 1.Repeat the aforesaid operations step, the consumption that only changes nitrogen oxygen helerocyclics 1 and DOPO is respectively 300 grams and 200 grams, obtains stable state solution 2.
Measure weight and the number molecular-weight average of stable state solution 1 and 2, and with outcome record in table 1.
Table 1
| Composition | Unit | Stable state solution 1 | Stable state solution 2 | |
| Nitrogen oxygen helerocyclics 1 | Gram | 400 | 300 | |
| | Gram | 100 | 200 | |
| DMF | Gram | 500 | 500 | |
| Weight average molecular weight | Gram/mole | 2720 | 2953 | |
| The number molecular-weight average | Gram/mole | 1614 | 1785 |
Figure 1 shows that the infrared spectrum analysis result of stable state solution 1 and 2.As seen from the figure, it is in about 3150 to having of about 3350/ centimeters and about 2930/ centimeters hydroxyl that produces after the open loop of nitrogen oxygen helerocyclics and the characteristic peak of stretching methyl.And the intensity of about 1230/ centimeters reduce and the density loss of the strength increase representative-COC-of about 1383/ centimeters and-concentration of CNC-increases the result that this also reacts for the ring-opening polymerization work.In addition, the characteristic peak of PH bond is about 2430/ centimeters, yet, in Fig. 1, do not see this absorption peak, this represents DOPO and produces the bond reaction and the PH bond is disappeared with nitrogen oxygen helerocyclics 1.In addition, the absorption peak of 1200/ centimeters then is the characteristic peak of the P=O on the DOPO.As seen from the above description, the nitrogen oxygen helerocyclics 1 in the stable state solution 1 and 2 open loop and with the DOPO bond.
Fig. 2 a and 2b respectively are the dsc analysis result of stable state solution 1 and 2, and by the dsc analysis result as can be known, the maximum temperature of about 80 ℃ extremely about 90 ℃ of the fusing points of the polymkeric substance of the ring-opening reaction gained in the stable state solution 1 and ring-opening reaction is about 211 ℃; And the fusing point of the polymkeric substance of the ring-opening reaction gained in the stable state solution 2 to tie up to about 80 ℃ of maximum temperatures to about 90 ℃ and ring-opening reaction be about 205 ℃.
[preparation of resin combination]
＜embodiment 1 〉
With the ratio shown in the table 2, with bisphenol-A phenolic Resins, epoxy (Kolon company: Kolon
Stable state solution 1 and 2-ethyl-4-methylimidazole (aldrich company), silica filler (3M company), and silane coupling agent (Dow Corning company:
Under room temperature, use agitator to mix about 60 minutes, add again subsequently butanone (MEK).Above-mentioned mixture after 120 minutes, is made resin combination 1 in stir about under the room temperature.
＜embodiment 2 〉
Prepare resin combination 2 in the mode identical with embodiment 1, the consumption of just adjusting stable state solution 1 is about 100 weight parts, and is as shown in table 2.
＜embodiment 3 〉
Prepare resin combination 3 in the mode identical with embodiment 1, the consumption of just adjusting stable state solution 1 is about 120 weight parts, and is as shown in table 2.
＜embodiment 4 〉
Prepare resin combination 4 in the mode identical with embodiment 1, just use the stable state solution 2 of about 80 weight parts to replace stable state solution 1, as shown in table 2.
＜embodiment 5 〉
Prepare resin combination 5 in the mode identical with embodiment 4, the consumption of just adjusting stable state solution 1 is about 120 weight parts, and is as shown in table 2.
＜embodiment 6 〉
Prepare resin combination 6 in the mode identical with embodiment 1, just use the stable state solution 2 of about 60 weight parts and the resol stiffening agent of about 40 weight parts (Hexion company) to replace stable state solution 1 as stiffening agent, as shown in table 2.
＜comparing embodiment 1 〉
With the mode identical with embodiment 1 prepare control resin composition 1 ', just use the resol stiffening agent (Hexion company) of about 100 weight parts to replace stable state solution 1 as stiffening agent, as shown in table 2.
＜comparing embodiment 2 〉
With the mode identical with embodiment 1 prepare control resin composition 2 ', just use phosphorous epoxy resin (the DOPO-cresol-novolak Resins, epoxy (DOPO-cresol novolac epoxy, DOPO-CNE) of 100 weight parts; Colon company; About 20 % by weight of DOPO content) replace bisphenol-A phenolic Resins, epoxy, and use about 50 weight parts benzoxazine (Kun Meng, model: 610) replace stable state solution 1 as stiffening agent, as shown in table 1.
[preparation of laminated plates]
Respectively with resin combination 1 to 6 and control resin composition 1 ' and 2 ' prepare laminated plates.Utilize roll coater, respectively these resin combinations are coated on 7628 glasscloths, then, are placed in the drying machine, and 175 ℃ of lower heat dryings 2 to 5 minutes, made thereby went out the prepreg (the Resin adhesive content about 50% of prepreg) of semi-harden state.Then five prepregs are laminated, and at each Copper Foil of laminated one 1 ounce of outermost layer of its two side.Then it is carried out hot pressing, obtain whereby thickness and respectively be about 1 millimeter laminated plates 1 to 6 (corresponding resin combination 1 to 6) and contrast laminated plates 1 ' and 2 ' (corresponding contrast laminated plates 1 ' with 2 ').Wherein hot pressing condition is: be warming up to 200 ℃ with 2.0 ℃/minute heat-up rates, and under 200 ℃, with the pressure hot pressing of 15 kilograms/square centimeter of total heads (8 kilograms/square centimeter of first pressing) 90 minutes.
Measure laminated plates 1 to 6 and contrast laminated plates 1 ' and 2 ' glass tansition temperature (Tg), water-absorbent, specific inductivity (Dk), the dissipation factor (Df), thermal expansivity (α
1), Z axis rate of expansion, flame retardancy and toughness, and with outcome record in table 2.
Table 2
As shown in table 2, the prepared laminated plates of resin combination of the present invention (laminated plates 1 to 6) all can reach gratifying degree on all physico-chemical properties, and has excellent wet fastness (water-absorbent is low).In addition, particularly on dimensional stability (thermal expansivity and Z axis expand), the dimensional change of the prepared laminated plates of resin combination of the present invention is obviously less, under bound by theory not, be to provide preferably cross-linking effect because of the stable state solution through ring-opening polymerization, and then can obtain the comparatively complete laminated plates of structure.Review the contrast laminated plates 1 ', do not contain the DOPO based compound in its composition, so non-constant of flame resistivity, and contrast laminated plates 2 ' made by nitrogen oxygen helerocyclics and DOPO based compound without ring-opening polymerization, its many in nature (such as the glass tansition temperature, water-absorbent etc.) neither such as the made laminated plates of resin combination of the present invention, this can illustrate, the present invention uses the stable state solution contain through the DOPO of ring-opening polymerization based compound as stiffening agent, except desired flame resistivity matter can be provided, more can exempt the disadvantage (too high such as water-absorbent) due to the independent DOPO of the interpolation based compound in the prior art.
In addition, the ratio (embodiment 4 and 5) of the consumption (embodiment 1 to 3) that resin combination of the present invention can be by for example adjusting stable state solution or contained DOPO based compound or with other existing stiffening agents and with (embodiment 6), adjust the physico-chemical property of prepared laminated plates, range of application is very extensive.
Above-described embodiment only is illustrative principle of the present invention and effect thereof, and sets forth technical characterictic of the present invention, but not is used for limiting protection category of the present invention.Anyly be familiar with present technique person under know-why of the present invention and spirit, can unlabored change or arrangement, all belong to the scope that the present invention advocates.
Claims (13)
1. resin combination, its feature comprises:
One Resins, epoxy; And
One stiffening agent, it is a stable state solution, is made by following steps:
(a) nitrogen oxygen helerocyclics and the DOPO based compound of interpolation one tool following formula I or II in an organic solvent, so that a reaction soln to be provided:
[formula I]
[formula II]
Wherein,
Wherein, R1 is selected from the group of following group: through or C1 to C10 alkyl, warp that is unsubstituted or C1 to the C10 cycloalkyl that is unsubstituted, and through or C6 to C20 aryl, the warp that is unsubstituted or C6 to the C20 aryloxy, the warp that are unsubstituted or C1 to the C15 unsaturated alkyl that is unsubstituted, naphthols base, phenanthrol base, reach dicyclopentadienyl;
R2 and R3 are separately independently for being selected from the group of following group: H, halogen, warp or C1 to the C10 alkyl, warp that are unsubstituted or C1 to the C10 cycloalkyl that is unsubstituted, and warp or C6 to C20 aryl, the warp that is unsubstituted or C6 to the C20 aryloxy, the warp that are unsubstituted or C1 to the C15 unsaturated alkyl that is unsubstituted, naphthols base, phenanthrol base, reach dicyclopentadienyl;
W1 is selected from the group of following group: H, halogen, ether, thioether group, alkylsulfonyl, sulfinyl, carbonyl, warp or C1 to C10 alkyl, the warp that is unsubstituted or C1 to the C10 cycloalkyl that is unsubstituted, and through or C6 to C20 aryl, warp that is unsubstituted or C6 to the C20 aryloxy, the warp that are unsubstituted or C1 to the C15 unsaturated alkyl that is unsubstituted, naphthols base, phenanthrol base, reach dicyclopentadienyl;
W2 is selected from the group of following group: through or C1 to C10 alkyl, warp that is unsubstituted or C1 to the C10 cycloalkyl that is unsubstituted, and through or C6 to the C20 aryl, the warp that are unsubstituted or to be unsubstituted be C6 to C20 aryloxy, warp or C1 to the C15 unsaturated alkyl that is unsubstituted, naphthols base, phenanthrol base, reach dicyclopentadienyl;
M and n independently are 1 to 3 integer separately; P is 1 to 3 integer; And q is 1 to 4 integer;
(b) heat this reaction soln, to carry out ring-opening polymerization, provide a polymers soln; And
(c) cool off this polymers soln obtaining this stable state solution,
Wherein, this organic solvent does not react with this nitrogen oxygen helerocyclics and this DOPO based compound; And in the gross weight of this nitrogen oxygen helerocyclics and this DOPO based compound, the content of this DOPO based compound is 0.01 % by weight to 50 % by weight,
Wherein, in solid substance, the content of this stiffening agent is that about 20 weight parts of per 100 weight part Resins, epoxy are to about 200 weight parts in this resin combination.
2. resin combination as claimed in claim 1, it is characterized in that: in the gross weight of this nitrogen oxygen helerocyclics and this DOPO based compound, the content of this DOPO based compound is 10 % by weight to 40 % by weight.
3. resin combination as claimed in claim 1, it is characterized in that: m and n independently are 2 or 3 separately, and W1 and W2 are separately independently for being selected from the group of following group:
4. resin combination claimed in claim 1, it is characterized in that: this DOPO based compound is selected from following group:
5. such as each described resin combination in the claim 1 to 4, it is characterized in that: this nitrogen oxygen helerocyclics is
And this DOPO based compound is
6. such as described resin combination as described in each in the claim 1 to 4, it is characterized in that: this organic solvent is selected from following group: pimelinketone, acetone, butanone, methyl iso-butyl ketone (MIBK), N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone and aforesaid arbitrary combination.
7. such as described resin combination as described in each in the claim 1 to 4, it is characterized in that: the content of this stiffening agent is that about 70 weight parts of per 100 weight part Resins, epoxy are to about 120 weight parts.
8. such as described resin combination as described in each in the claim 1 to 4, it is characterized in that: this stiffening agent more comprises Dyhard RU 100,4,4 '-two amido sulfobenzide or resol.
9. such as described resin combination as described in each in the claim 1 to 4, it is characterized in that: more comprise a kind of additive that is selected from following group: hardening accelerator, filler, dispersion agent, toughner, fire retardant and aforesaid arbitrary combination.
10. such as 9 described resin combinations of claim, it is characterized in that: this hardening accelerator is selected from following group: imidazoles, 1-Methylimidazole, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole and aforesaid arbitrary combination, wherein the content of this hardening accelerator is that about 0.01 weight part of per 100 weight part Resins, epoxy is to about 1 weight part.
11. 9 described resin combinations such as claim, it is characterized in that: this filler is selected from following group: silicon-dioxide, glass powder, talcum, kaolin, white mountain range soil, mica and aforesaid arbitrary combination, wherein the content of this filler is that about 0.1 weight part of per 100 weight part Resins, epoxy is to about 120 weight parts.
12. a prepreg is characterized in that: this cured sheets is with each described resin combination in a base material impregnation such as the claim 1 to 11, and carries out drying and make.
13. a laminated plates is characterized in that: comprise synthetic layer and a metal level, this synthetic layer is made of the prepreg such as claim 12.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW100137867 | 2011-10-19 | ||
| TW100137867A TWI421274B (en) | 2011-10-19 | 2011-10-19 | Stable solution of the ring-opened polymer and the use thereof |
| TW100141572 | 2011-11-15 | ||
| TW100141572A TWI475040B (en) | 2011-11-15 | 2011-11-15 | Resin composition and uses of the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103059309A true CN103059309A (en) | 2013-04-24 |
| CN103059309B CN103059309B (en) | 2015-06-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110370918.1A Active CN103059309B (en) | 2011-10-19 | 2011-11-21 | Resin composition and use thereof |
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| CN (1) | CN103059309B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201121986A (en) * | 2009-12-31 | 2011-07-01 | Univ Nat Chunghsing | Phosphorus-containing benzoxazine-based bisphenols, derivatives thereof, and preparing method for the same |
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2011
- 2011-11-21 CN CN201110370918.1A patent/CN103059309B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201121986A (en) * | 2009-12-31 | 2011-07-01 | Univ Nat Chunghsing | Phosphorus-containing benzoxazine-based bisphenols, derivatives thereof, and preparing method for the same |
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| CN103059309B (en) | 2015-06-10 |
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