CN102585440A - High-CTI (comparative tracking index) halogen-free flame retardant resin composition for copper-clad laminate - Google Patents
High-CTI (comparative tracking index) halogen-free flame retardant resin composition for copper-clad laminate Download PDFInfo
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- CN102585440A CN102585440A CN2012100122847A CN201210012284A CN102585440A CN 102585440 A CN102585440 A CN 102585440A CN 2012100122847 A CN2012100122847 A CN 2012100122847A CN 201210012284 A CN201210012284 A CN 201210012284A CN 102585440 A CN102585440 A CN 102585440A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 34
- 230000000052 comparative effect Effects 0.000 title abstract description 8
- 239000011342 resin composition Substances 0.000 title abstract 5
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title abstract 2
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 60
- 239000003822 epoxy resin Substances 0.000 claims abstract description 58
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 36
- 150000002367 halogens Chemical class 0.000 claims abstract description 36
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000945 filler Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 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 claims description 30
- 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 claims description 29
- -1 phenol phenol aldehyde Chemical class 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 239000011888 foil Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910001593 boehmite Inorganic materials 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 11
- 229930185605 Bisphenol Natural products 0.000 claims description 10
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 claims description 9
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 9
- 229920003986 novolac Polymers 0.000 claims description 9
- 230000001588 bifunctional effect Effects 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 5
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 5
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-methyl phenol Natural products CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 5
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- 229940015043 glyoxal Drugs 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 17
- 229940106691 bisphenol a Drugs 0.000 description 10
- 125000003700 epoxy group Chemical group 0.000 description 9
- 239000003292 glue Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000011190 CEM-3 Substances 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000011580 syndromic disease Diseases 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- PSKIKYIARRTJSA-UHFFFAOYSA-N C(C)(=O)OCCCCC.COCC(C)O Chemical compound C(C)(=O)OCCCCC.COCC(C)O PSKIKYIARRTJSA-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000009840 oxygen flask method Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
The invention discloses a high-CTI (comparative tracking index) halogen-free flame retardant resin composition for a copper-clad laminate. The composition comprises the following components in parts by weight: 30-70 parts of polyepoxy resin, 1-5 part of curing agent, 0.01-1 parts of curing promoter, and 20-60 parts of filler. The resin composition disclosed by the invention remains high heat resistance while being endued with a high CTI value. The resin composition disclosed by the invention not only contains phosphorus epoxy resin, but also is added with some tough epoxy resins, so that the processing characteristics are greatly improved. The copper-clad laminate fabricated with the resin composition disclosed by the invention has the characteristics of high heat resistance, high CTI value, no halogen, good processing characteristics and the like.
Description
Technical field
The present invention relates to be used for the high CTI value halogen free flame-retardant type resin combination of copper clad foil substrate.
Background technology
Along with scientific and technical develop rapidly, the formation that large-scale industry is integrated causes the infringement that can't remedy to mankind itself's living environment, and is very urgent thereby environment protection becomes.In recent years, the electronic technology develop rapidly, electronic product is serious day by day to the influence that environment produces; Electronic waste product particularly, present most electronic products are halogen flame retardant, after the halogen burning; Not only the amount of being fuming is big, and the smell is awful, and can produce the very strong hydrogen halide of corrodibility.According to another bibliographical information; The time can produce Dioxins at halogen-containing fire retardant in Pintsch process and burning in recent years; Carcinogenic substances such as diphenylene-oxide; " about scrapping the electric/electronic device instruction " and " using the objectionable impurities instruction about restriction in electric/electronic device " have been put into effect in Europe; Electronic product must not contain lead (Lead), cadmium (Cadmium), mercury (Mercury), sexavalent chrome six kinds of materials such as (Hexavalent Chromium) after requiring on July in 2006 1, the relevant decree of the also corresponding proposition halogen-free flameproof of Japan, and special SONY proposes all to adopt the Halogen material; Therefore the baseplate material of developing halogen-free flame-retardant is imperative, has become the focus of industry.
On the other hand, human lives's security more and more extensively receives the concern of society.For improving the safe reliability of electronic product; Special in the insulating material that uses under the wet environment condition (like motor, electrical equipment etc.) safe reliability, exploitation high-insulativity product assurance electronic product safe reliability is exactly an important developing direction in recent years.The CTI value that the macromolecular material copper-clad plate is tested (Comparative Tracking Index); Refer to material surface to be able to take 50 electrolytic solution (0.1% aqueous ammonium chloride solution) and do not form the maximum voltage value of tracking; It weighs the insulation safety performance of this material to a certain extent; This value is high more, and (CTI>=600V is 0 grade to represent the insulativity of material good more;<600V is 1 grade to 400V≤CTI;<400V is 2 grades to 250V≤CTI;<250V is 3 grades to 175V≤CTI;<175V is 4 grades to 100V≤CTI; CTI 100V is 5 grades), therefore high CTI product (CTI is more than 600V) has become electron trade researchdevelopment trend.
In recent years the high CTI sheet material of some mainly is the CEM-3 material; But since electric relevant industries implementation is unleaded; The hot environment of product application requires also correspondingly improving constantly, and the thermotolerance of material is proposed new requirement, so the CEM-3 material reaches above requirement and just has some unable to do what one wishes; And also there is the bad problem of thermotolerance in the FR4 sheet material of more existing high CTI; This kind sheet material generally all is with ATH (white lake) CTI to be provided, but ATH adds and can produce stable on heating decline, and ATH adds less the fire-retardant requirement that do not reach again.
Summary of the invention
The object of the present invention is to provide the high CTI value halogen free flame-retardant type resin combination that is used for copper clad foil substrate.
The technical scheme that the present invention taked is:
Be used for the high CTI value halogen free flame-retardant type resin combination of copper clad foil substrate, contain following parts by weight of component: 30～70 parts of poly epoxy resins, 1～5 part in solidifying agent, 0.01～1 part of curing catalyst, 20～60 parts of fillers.
Preferably, said composition contains following parts by weight of component: 40～60 parts of poly epoxy resins, 1.5～3 parts in solidifying agent, 0.05～0.5 part of curing catalyst, 25～55 parts of fillers.
Preferably, poly epoxy resin is the bifunctional epoxy resin, novolac epoxy, at least a in the phosphorous epoxy resin.
Preferably, said bifunctional epoxy resin is at least a in bisphenol A type epoxy resin, the bisphenol f type epoxy resin;
Said novolac epoxy is at least a in phenol phenol aldehyde type epoxy resin, ortho-cresol phenolic aldehyde type epoxy resin, the bisphenol A-type novolac epoxy;
Said phosphorous epoxy resin is 9; The 10-dihydro-9-oxy is assorted-and the DOPO modified epoxy), 10-(2 10-phospho hetero phenanthrene-10-oxide modifying epoxy resin (is called for short:; The 5-dihydroxy phenyl)-9; The 10-dihydro-9-oxy is assorted-and the DOPO-HQ modified epoxy), 10-(2 10-phospho hetero phenanthrene-10-oxide modifying epoxy resin (is called for short:; 9-dihydroxyl naphthyl)-9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide modifying epoxy resin (is called for short: at least a the DOPO-NQ modified epoxy).
Preferably, said composition contains following parts by weight of component: 30～40 parts of phosphorous epoxy resins, 5～10 parts of bifunctional epoxy resins, 5～10 parts of novolac epoxys, 1.5～3 parts in solidifying agent, 0.05～0.5 part of curing catalyst, 25～55 parts of fillers.
Preferably, said composition contains following parts by weight of component: 30～39 parts of phosphorous epoxy resins, 10～21 parts of bifunctional epoxy resins, 1.5～3 parts in solidifying agent, 0.05～0.5 part of curing catalyst, 25～55 parts of fillers.
Preferably, said composition contains following parts by weight of component: 30～49 parts of phosphorous epoxy resins, 10～21 parts of novolac epoxys, 1.5～3 parts in solidifying agent, 0.05～0.5 part of curing catalyst, 25～55 parts of fillers.
Preferably, filler is made up of white lake, boehmite; Or filler is made up of silicon-dioxide, white lake, boehmite.
Preferably, the particle diameter of filler is 1～5 μ m.
Preferably, the weight proportion of white lake is 10～25 parts.
Preferably, the weight proportion of boehmite is 10～50 parts.
Preferably, solidifying agent is a Dyhard RU 100.
Preferably, curing catalyst is any in glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-ethyl imidazol(e), 2-phenylimidazole, undecyl imidazole, the benzyldimethylamine.
Boehmite of the present invention is also claimed the hydration Alpha-alumina.
The invention has the beneficial effects as follows:
Resin combination of the present invention has been endowed high CTI value when keeping high heat resistance; Resin combination of the present invention not only has phosphorous epoxy resin; Some tough epoxy resins have also been added; Improve processing characteristics greatly, adopt imidazoles simultaneously, the speed of response of the may command course of processing as curing catalyst.
The copper clad foil substrate that resin combination of the present invention is made has the thermotolerance height, CTI value height, halogen, and characteristic such as good processability.
The flame retardant effect of resin combination of the present invention is mainly provided by the phosphorus in the phosphorous epoxy resin, filler boehmite, white lake, makes system reach the requirement of Halogen.
The present invention just can reach taking into account of system thermotolerance and high CTI value through the ratio of adjustment system boehmite and white lake, and since its hardness, therefore to add this filler than little many of silicon-dioxide also less to the processing influence of subsequent substrate.
Embodiment
Embodiment below in conjunction with concrete is further described the present invention, but is not limited thereto.
Boehmite, particle diameter are 1～5 μ m, and model: 613L is available from prosperous source, Bangbu quartz material ltd;
White lake, particle diameter are 1～5 μ m, model: H-42M, the clear and production of Japan;
Silicon-dioxide, particle diameter are 1～5 μ m, model: DB1003, and the East China Sea silicon powder is produced;
Undecyl imidazole changes into available from Japanese four countries;
The DOPO modified epoxy, model: PE-315, the massfraction of phosphorus are 3.6%, available from Taiwan Jinyi Chemicals Co., Ltd.;
Bisphenol A type epoxy resin, model 901 is available from Hongchang Electronic Material Inustry Co., Ltd., Guangzhou;
The bisphenol A-type novolac epoxy, model: 3180, available from Korea S kolon company;
The DOPO-NQ modified epoxy, model: YEP-220 is available from wide mountain, Quzhou chemical industry ltd;
The DOPO-HQ modified epoxy, model: G261 is available from Yixing ancient cooking vessel wound company;
Bisphenol f type epoxy resin, model: 201, available from Hongchang Electronic Material Inustry Co., Ltd., Guangzhou.
Embodiment 1
A kind of high CTI value halogen free flame-retardant type resin combination contains following parts by weight of component: 39 parts of DOPO modified epoxies, 21 parts of bisphenol A type epoxy resins, 2 parts of Dyhard RU 100s, 0.3 part of undecyl imidazole, 10 parts in white lake, 28 parts of boehmites.
Embodiment 2
A kind of high CTI value halogen free flame-retardant type resin combination contains following parts by weight of component: 39 parts of DOPO modified epoxies, 21 parts of bisphenol-A phenolic type epoxy resin, 2 parts of Dyhard RU 100s, 0.2 part of undecyl imidazole, 19 parts in white lake, 19 parts of boehmites.
Embodiment 3
A kind of high CTI value halogen free flame-retardant type resin combination contains following parts by weight of component: 31.5 parts of DOPO modified epoxies, 17 parts of bisphenol-A phenolic type epoxy resin, 1.5 parts of Dyhard RU 100s, 0.5 part of undecyl imidazole, 20 parts in white lake, 30 parts of boehmites.
Embodiment 4
A kind of high CTI value halogen free flame-retardant type resin combination contains following parts by weight of component: 30 parts of DOPO-NQ modified epoxies, 5 parts of bisphenol f type epoxy resins; 5 parts of ortho-cresol phenolic aldehyde type epoxy resin, 3 parts of Dyhard RU 100s, 0.05 part of 2-ethyl imidazol(e); 25 parts in white lake, 30 parts of boehmites.
Embodiment 5
A kind of high CTI value halogen free flame-retardant type resin combination contains following parts by weight of component: 35 parts of DOPO-HQ modified epoxies, 8 parts of bisphenol f type epoxy resins; 8 parts of phenol phenol aldehyde type epoxy resins, 1.5 parts of Dyhard RU 100s, 0.3 part of 2-ethyl-4-methylimidazole; 20 parts in white lake, 10 parts of boehmites.
Embodiment 6
A kind of high CTI value halogen free flame-retardant type resin combination contains following parts by weight of component: 40 parts of DOPO-HQ modified epoxies, 10 parts of bisphenol A type epoxy resins; 10 parts of ortho-cresol phenolic aldehyde type epoxy resin, 2 parts of Dyhard RU 100s, 0.5 part of 2-phenylimidazole; 10 parts in white lake, 15 parts of boehmites.
Embodiment 7
A kind of high CTI value halogen free flame-retardant type resin combination contains following parts by weight of component: 30 parts of DOPO-NQ modified epoxies, 1 part of Dyhard RU 100,1 part of 2-ethyl-4-methylimidazole, 10 parts in white lake, 10 parts of boehmites.
Embodiment 8
A kind of high CTI value halogen free flame-retardant type resin combination contains following parts by weight of component: 35 parts of phenol phenol aldehyde type epoxy resins, 35 parts of bisphenol f type epoxy resins, 5 parts of Dyhard RU 100s, 0.01 part of benzyldimethylamine, 10 parts in white lake, 50 parts of boehmites.
Embodiment 9
A kind of high CTI value halogen free flame-retardant type resin combination contains following parts by weight of component: 30 parts of DOPO-NQ modified epoxies, 15 parts of bisphenol A type epoxy resins, 1.5 parts of Dyhard RU 100s, 0.05 part of 2-ethyl imidazol(e), 25 parts in white lake, 30 parts of boehmites.
Embodiment 10
A kind of high CTI value halogen free flame-retardant type resin combination contains following parts by weight of component: 35 parts of DOPO modified epoxies, 10 parts of bisphenol f type epoxy resins, 3 parts of Dyhard RU 100s, 0.5 part of 2-ethyl-4-methylimidazole, 15 parts in white lake, 10 parts of boehmites.
Embodiment 11
A kind of high CTI value halogen free flame-retardant type resin combination contains following parts by weight of component: 30 parts of DOPO-HQ modified epoxies, 18 parts of phenol phenol aldehyde type epoxy resins, 3 parts of Dyhard RU 100s, 0.5 part of 2-phenylimidazole, 15 parts in white lake, 10 parts of boehmites.
Embodiment 12
A kind of high CTI value halogen free flame-retardant type resin combination contains following parts by weight of component: 34 parts of DOPO-HQ modified epoxies, 10 parts of ortho-cresol phenolic aldehyde type epoxy resin, 1.5 parts of Dyhard RU 100s, 0.05 part of 2-phenylimidazole, 25 parts in white lake, 30 parts of boehmites.
Comparative Examples 1
A kind of resin combination contains following parts by weight of component: 39 parts of DOPO modified epoxies, 21 parts of bisphenol A type epoxy resins, 2 parts of Dyhard RU 100s, 0.3 part of undecyl imidazole, 38 parts in white lake.
Comparative Examples 2
A kind of resin combination contains following parts by weight of component: 39 parts of DOPO modified epoxies, 21 parts of bisphenol A type epoxy resins, 2 parts of Dyhard RU 100s, 0.3 part of undecyl imidazole, 38 parts of boehmites.
Comparative Examples 3
A kind of resin combination contains following parts by weight of component: 39 parts of DOPO modified epoxies, 21 parts of bisphenol A type epoxy resins, 2 parts of Dyhard RU 100s, 0.3 part of undecyl imidazole, 38 parts of silicon-dioxide.
The moulding process of copper clad foil substrate comprises the steps:
1. resin combination is prepared into the thermoset glue:
1) under the room temperature, in proportion container, adds resin combination (except the filler), solvent and thinner, stir, add filler, stirred 6 hours, get glue;
2) sampling, the test glue is controlled its gel time at the gel time of 170 ℃ of hot plates between 200～300 seconds through the addition of curing catalyst, gets the thermoset glue.
With N DMF, pimelinketone, butanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether amyl acetate etc. or its combination as solvent, with acetone, butanone or its combination as thinner.
2. impregnation:
The adhesive plaster that will soak above-mentioned thermoset glue through conditions such as control squeegee roller speed, linear speed, wind-warm syndrome and furnace temperature, makes prepreg through vertical or horizontal type impregnation machine;
With vertical impregnation machine is example:
The proportion of glue: 1.10～1.20;
Squeegee roller speed :-1.8～-2.5 ± 0.1 M/min;
Main line speed: 5～14 M/min;
Wind-warm syndrome: 130～160 ℃;
Furnace temperature: 140～180 ℃.
Make prepreg through above condition.
3. compacting:
After the prepreg that cuts and Copper Foil combined, put into the vacuum hotpressing machine, compacting obtaining copper clad foil substrate.
Temperature formula: 130 ℃/30min+160 ℃/30min+180 ℃/20min+210 ℃/180min
Pressure formula: 20Kgfcm-2/30min+50Kgfcm
-2/ 15min+95Kgfcm
-2/ 150min+20Kgfcm
-2/ 65min
Vacuum is set: 30mmHg/130min+760mmHg/130min
With the copper clad foil substrate of the resin combination preparation of embodiment 1～8 and Comparative Examples 1～3, The performance test results is seen table 1 and table 2.Can know that by table resin combination of the present invention can be prepared into resistance toheat and resistance to flame can be good, the copper clad foil substrate of CTI excellent performance, and the processing characteristics of this substrate is preferable, content of halogen and fire-retardant also all in standard range.Can know that with Comparative Examples 1～3 data comparison white lake in the component of the present invention and boehmite play an important role to the good performance of covering the Copper Foil base by embodiment 1.
The copper clad foil substrate of the resin combination preparation of embodiment 4～8, The performance test results is seen table 2.Can know by table, compare with the test result of embodiment 4～6, can know that the copper clad foil substrate CTI performance of resin combination preparation of embodiment 4～6 is more excellent by embodiment in the table 1 1～3,7～8.
The performance test methods of above each item index is following:
A. second-order transition temperature:, measure according to the DSC method of IPC-TM-650 2.4.25 defined according to differential scanning calorimetry;
B.CTI (relative discharge tracking index): the method according to GB/T 4207-84 defined is tested;
C. difficult to burn property: according to the test of UL94 method regulation;
D. anti-immersed solder property: whether the sample (base material of 10cm * 10cm) sample kept 2 hours in 121 ℃, the pressure cooking treatment unit of 105Kpa after is immersed in 30 seconds in the tin stove that is heated to 260 ℃, change with visual inspection;
E. processibility: sample (base material of 28cm * 28cm) is holed, and the abrasion situation of drill point is compared the processing characteristics of base material before and after the comparison boring;
F. content of halogen: measure according to JPCA-ES-01-2003 " without halide copper-clad plate TP ", adopt the content of halogen of oxygen flask combustion method and ion-chromatographic determination veneer sheet.
Claims (10)
1. be used for the high CTI value halogen free flame-retardant type resin combination of copper clad foil substrate, contain following parts by weight of component: 30～70 parts of poly epoxy resins, 1～5 part in solidifying agent, 0.01～1 part of curing catalyst, 20～60 parts of fillers.
2. high CTI value halogen free flame-retardant type resin combination according to claim 1, it is characterized in that: said composition contains following parts by weight of component: 40～60 parts of poly epoxy resins, 1.5～3 parts in solidifying agent, 0.05～0.5 part of curing catalyst, 25～55 parts of fillers.
3. high CTI value halogen free flame-retardant type resin combination according to claim 1 and 2 is characterized in that: poly epoxy resin is at least a in bifunctional epoxy resin, novolac epoxy, the phosphorous epoxy resin.
4. high CTI value halogen free flame-retardant type resin combination according to claim 3 is characterized in that:
Said bifunctional epoxy resin is at least a in bisphenol A type epoxy resin, the bisphenol f type epoxy resin;
Said novolac epoxy is at least a in phenol phenol aldehyde type epoxy resin, ortho-cresol phenolic aldehyde type epoxy resin, the bisphenol A-type novolac epoxy;
Said phosphorous epoxy resin is 9; The 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide modifying epoxy resin, 10-(2; The 5-dihydroxy phenyl)-9; The 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide modifying epoxy resin, 10-(2,9-dihydroxyl naphthyl)-9, and the 10-dihydro-9-oxy is assorted-at least a in 10-phospho hetero phenanthrene-10-oxide modifying epoxy resin.
5. high CTI value halogen free flame-retardant type resin combination according to claim 1 and 2, it is characterized in that: filler is made up of white lake, boehmite; Or filler is made up of white lake, boehmite, silicon-dioxide.
6. high CTI value halogen free flame-retardant type resin combination according to claim 1 and 2 is characterized in that: the particle diameter of filler is 1～5 μ m.
7. high CTI value halogen free flame-retardant type resin combination according to claim 5 is characterized in that: the weight proportion of white lake is 10～25 parts.
8. high CTI value halogen free flame-retardant type resin combination according to claim 5 is characterized in that: the weight proportion of boehmite is 10～50 parts.
9. high CTI value halogen free flame-retardant type resin combination according to claim 1 and 2 is characterized in that: solidifying agent is a Dyhard RU 100.
10. high CTI value halogen free flame-retardant type resin combination according to claim 1 and 2 is characterized in that: curing catalyst is any in glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-ethyl imidazol(e), 2-phenylimidazole, undecyl imidazole, the benzyldimethylamine.
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Effective date of registration: 20200430 Address after: 214028 No.26, Xiqin Road, Xinwu District, Wuxi City, Jiangsu Province Patentee after: WUXI GRACE ELECTRONIC MATERIAL TECHNOLOGY Co.,Ltd. Address before: 510530, No. 1, Po pan Road, Guangzhou, Guangdong, Luogang District Patentee before: GUANGZHOU GRACE ELECTRONIC INDUSTRY Co.,Ltd. |