CN1358780A - Brominated Epoxy Resins with High Glass Transition Temperature for Fiberglass Laminates - Google Patents
Brominated Epoxy Resins with High Glass Transition Temperature for Fiberglass Laminates Download PDFInfo
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- CN1358780A CN1358780A CN 01139771 CN01139771A CN1358780A CN 1358780 A CN1358780 A CN 1358780A CN 01139771 CN01139771 CN 01139771 CN 01139771 A CN01139771 A CN 01139771A CN 1358780 A CN1358780 A CN 1358780A
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- brominated
- resin
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- 230000009477 glass transition Effects 0.000 title claims abstract 9
- 239000011152 fibreglass Substances 0.000 title claims description 10
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 title abstract description 19
- 239000003822 epoxy resin Substances 0.000 claims abstract description 97
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 97
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003365 glass fiber Substances 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims description 75
- 239000011347 resin Substances 0.000 claims description 75
- 239000004593 Epoxy Substances 0.000 claims description 67
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 230000001588 bifunctional effect Effects 0.000 claims 2
- 238000002156 mixing Methods 0.000 abstract description 6
- 230000009257 reactivity Effects 0.000 abstract description 5
- 239000012776 electronic material Substances 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 abstract 1
- 239000005340 laminated glass Substances 0.000 abstract 1
- 238000010030 laminating Methods 0.000 abstract 1
- 239000004033 plastic Substances 0.000 description 25
- 229920003023 plastic Polymers 0.000 description 25
- 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 22
- 239000007788 liquid Substances 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 229940106691 bisphenol a Drugs 0.000 description 10
- 238000003825 pressing Methods 0.000 description 10
- 239000002966 varnish Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 9
- -1 phenyl aldehyde Chemical class 0.000 description 9
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000011120 plywood Substances 0.000 description 7
- 235000013824 polyphenols Nutrition 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003351 stiffener Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000002460 imidazoles Chemical class 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 229940015043 glyoxal Drugs 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000011112 process operation Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical group C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000009172 bursting Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- WLOHKZPZHBMVBK-UHFFFAOYSA-N 2-(chloromethyl)oxirane Chemical compound ClCC1CO1.ClCC1CO1 WLOHKZPZHBMVBK-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
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- FLBUMFXTSUZXHH-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1.C1=CNC(C=2C=CC=CC=2)=N1 FLBUMFXTSUZXHH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
A brominated epoxy resin with high glass transition temperature for glass fiber laminated plates is prepared from the following main components: the novel brominated epoxy resin is prepared by reacting (D) tetrabromobisphenol A with at least one of , (B) and (C) three epoxy resins, adding the rest of , (B) and (C) three epoxy resins, and uniformly mixing. The novel brominated epoxy resin can be applied to a glass fiber laminated plate, shows appropriate reactivity and a wide laminating processing interval, and the laminated glass fiber laminated plate has high glass transition temperature (Tg) and excellent heat resistance and is suitable for being used as a high-performance electronic material.
Description
Technical field
The present invention is relevant a kind of in fiberglass layer plywood processing procedure, have suitable reactivity, the novel brominated epoxy resin of broad pressing processing interval, its process operation is good, the substrate of gained pressing has high glass tansition temperature (Tg) and excellent heat resistance, is suitable for to make the high-performance electronic material.
Background technology
Along with printed circuit board (PCB) develop into gently, thin, small-sized and complicated, so also urgent further to the demand of high performance material.Usually material Tg value is a very useful pointer, the expression material bears dynamic stress as vibration, high temperature under a service temperature ... very bad etc. ability, if material temperature often causes the interlayer bond bad than the Tg height, and following the intensity damage with Copper Foil falls, cause the material deterioration, so desire to develop a big important topic and the trend that the material of high glass tansition temperature (Tg) and excellent heat resistance is the fiberglass layer plywood.
The FR-4 substrate that can buy in the market, be to use the difunctionality brominated epoxy resin to make, the Tg value is between 130～140 ℃, and a kind of method that improves Tg usually is blending polyfunctional epoxy resin such as ortho-cresol formaldehyde novolac type Resins, epoxy (o-cresol formaldehyde novolacepoxy), four functional group's Resins, epoxy (tetra functional epoxy), phenolic resin varnish type epoxy resin (phenol novolac epoxy) etc., though use above-mentioned polyfunctional epoxy resin can improve Tg and have excellent heat resistance, but when hardening with the two cyanogen ammoniums (dicyandiamide) of stiffening agent commonly used, but cause the fast and narrow partially problem of pressing processing interval (working window) of gel time (gel time), so that need give accurate control procedure for processing, avoid faulty materials to produce, often influence production good article rate and production capacity.
Summary of the invention
The purpose of this invention is to provide the brominated epoxy resin of a kind of fiberglass layer plywood with high glass tansition temperature, has suitable reactivity, broad pressing processing interval, process operation is good, and high Tg and excellent thermotolerance, electrical properties, flame resistivity matter, and low water absorbable, can solve above-mentioned use polyfunctional epoxy resin such as ortho-cresol cresol novolak epoxy, four functional group's Resins, epoxy, phenolic resin varnish type epoxy resin etc., the not good problem of fiberglass layer plywood process operation that causes.
For achieving the above object, brominated epoxy resin provided by the invention, be to (A) phenol-phenyl aldehyde polyfunctional epoxy resin (formula I) 10～70 weight %, (B) difunctionality basic ring epoxy resins 0～55 weight %, (C) brominated difunctionality basic ring epoxy resins 0～20 weight % and (D) tetrabromo third diphenol 15～40 weight %, earlier will (D) and (A), (B), (C) three's at least a (containing a kind of) Resins, epoxy reacts, and then adding (A), (B), (C) remaining part, mixing and getting weight average molecular weight (MW) is 1500～4000, the dispersed index of molecular weight distribution (ratio of Mw/Mn) is 1.5～4.0, epoxy equivalent (weight) (EEW) is 300～450g/eq, glass tansition temperature (Tg) is 150～190 ℃ of brominated epoxy resins, and structural formula is as follows.
Wherein the epoxy equivalent (weight) of (A) (EEW) is 210～260g/eq, and average sense radix is 2～6, and molecular-weight average (Mw) is phenol-phenyl aldehyde polyfunctional epoxy resin of 400～2500.
Wherein (B) comprises bisphenol A epoxide resin, bisphenol F epoxy resin for difunctionality basic ring epoxy resins, and epoxy equivalent (weight) (B) (EEW) scope is 170～500g/eq.
Wherein (C) is tetrabromo bisphenol-a epoxy resin for brominated difunctionality basic ring epoxy resins, and the epoxy equivalent (weight) (EEW) of this brominated difunctionality basic ring epoxy resins is 300～500g/eq, brominated amount=30～55%.
Wherein (D) is 544 tetrabromo-bisphenol for molecular weight (MW).
The outstanding feature of the present invention, be to propose phenol-phenyl aldehyde polyfunctional epoxy resin, the epoxy functionalized radix that has high-density benzene ring structure and suitable number on its chemical structure, therefore have excellent heat resistance and high Tg, the epoxy functionalized radix of this suitable number and benzene ring structure is three-dimensional restricted simultaneously, makes it have suitable reactivity, and higher resin melting viscosity, so broad pressing processing interval is arranged, the fiberglass layer plywood of high-performance so can be provided.
In substrate heat compacting journey, how controlling resin flows (resin flow) is extremely important in a proper range, bigger than normal because of resin flows, will cause defectives such as white edge, white angle .., otherwise if resin flows is less than normal, then easily have weavy grain to appear ... take place etc. problem.Barlett in 1978 and Bloechle two people propose the resin gummosis amount formula of resin in hot pressing rheological behaviour and are:
F(t)＝(C/12)×(P/A)∫dt/n(t)
Wherein C is a constant, P is a pressure, A is the base material area, ∫ dt/n (t) is the flow integration, from formula, can understand and work as pressure, the base material area is fixedly the time, resin flows and (1) resin viscosity and (2) preimpregnation (prepreg) gel time of weaving cotton cloth is relevant, be that resin flows is subjected to the weave cotton cloth influence of gel time of (1) resin viscosity and (2) preimpregnation, also be that the minimum melting viscosity of resin and the preimpregnation gel time of weaving cotton cloth needs suitable its scope of control, enable pressing and be easy to controlling performance, and the minimum melting viscosity of resin is maintained at the interior time of 4000～10000poise scope in the hot pressing rheological behaviour, is called the pressing processing interval, the base material of pressing processing interval broadness, the processing procedure that can be fit to different hot pressing temperature rise rates, the product suitability is wider, and the homogeneity of the substrate of pressing simultaneously is also preferable.
The novel brominated resins that phenol-the phenyl aldehyde polyfunctional epoxy resin is synthesized into thus, comprise (A) phenol-phenyl aldehyde polyfunctional epoxy resin, content is 10～70 weight %, (B) difunctionality basic ring epoxy resins, content is 0～55 weight %, (C) brominated difunctionality basic ring epoxy resins, and content is 0～20 weight %, (D) tetrabromo-bisphenol, content are 15～40 weight %.With (D) with (A), (B), (C) three's at least a (containing a kind of) Resins, epoxy is reacted into brominated epoxy resin (EP-0) earlier, and then adds (A), (B), (C) remaining part mixes and promptly gets brominated epoxy resin provided by the invention.And aforementioned brominated epoxy resin (EP-0), reactive mode is with reactants dissolved between 90～120 ℃, fully the dissolving back adds catalyst, it is 100～130 ℃ that catalyst adds temperature, the most suitable with 115～130 ℃, catalyst all can use with level Four microcosmic salt or imidazoles (imidazole) class, and can get preferable form and aspect with the level Four microcosmic salt, the catalyst addition is with respect to 0.06～0.1% of tetrabromo-bisphenol weight, temperature of reaction is 150～200 ℃, being fit to temperature of reaction is 160～180 ℃, and the reaction times is 60～180 minutes.
(A) phenol-phenyl aldehyde polyfunctional epoxy resin in the above-mentioned novel brominated epoxy resin be for phenol and phenyl aldehyde in the presence of acidic catalyst, phenol-phenyl aldehyde the resol that carries out condensation reaction and get, continuous again with 1-chloro-2,3-propylene oxide (epichlorohydrin) synthesizes phenol-phenyl aldehyde polyfunctional epoxy resin in the presence of sodium hydroxide (NaOH), synthetic reaction condition is as using 1-chloro-2, the epoxidised processing procedure of 3-propylene oxide, institute's synthetic phenol-its epoxy equivalent (weight) of phenyl aldehyde polyfunctional epoxy resin (EEW)=210～260g/eq, average sense radix=2～6, average molecular weight Mw=400～2500.(B) difunctionality basic ring epoxy resins comprises bisphenol A epoxide resin (digycidyl ether of 2,2-bis (4-hydroxyphenyl) propane), bisphenol F epoxy resin (diglycidyl ether of 2,2-bis (4-hydroxyphenyl) methane is bisphenol F epoxy), epoxy equivalent (weight) (B) (EEW) scope is 170～500g/eq.(C) brominated difunctionality basic ring epoxy resins is tetrabromo bisphenol-a epoxy resin (diglycidyl ether of 2,2-bis (3,5dibromo-4-hydroxyphenyl) propane), and epoxy equivalent (weight) (C) (EEW)=300～500g/eq, brominated amount=30～55%.(D) tetrabromo-bisphenol (tetrabromobisphenol A is called for short TBBA), molecular weight Mw=544.
Novel brominated epoxy resin composition of the present invention, its Mw=1500～4000, the dispersed index of molecular weight distribution (ratio of Mw/Mn)=1.5～4.0, EEW=300～500g/eq, can use stiffening agent such as Dyhard RU 100, dihydroxyphenyl propane, tetrabromo-bisphenol, multifunctional novolac resin (multifunctional novolac), prepared layer plywood varnish is formed, when using Dyhard RU 100 as stiffening agent, the Dyhard RU 100 usage quantity is 2～8phr, is preferably 2～4phr most, and when using polyphenol (polyhydricphenolic) as stiffening agent, the polyphenol consumption is phenol OH base and epoxide equivalent ratio=0.5～1.5, appropriate amount ratio=0.9～1.1.
Also need add promotor in the clear coat composition that is prepared from by novel brominated resins of the present invention, suitable promotor has imidazoles (imidazole) class and benzyl dimethyl amine (benzyldimethylamine).Be preferably most 2-phenylimidazole (2-phenyl imidazole) and glyoxal ethyline (2-methylimidazole), the promotor addition is 0.01～0.15phr.
Embodiment
Below with embodiment the present invention is elaborated, but do not limit category of the present invention, in the example, " umber " reaches " % " and respectively means " parts by weight " and reach " weight % ", novel brominated epoxy resin of the present invention can be made Copper Foil Resins, epoxy laminate patch by the known method of industry, said composition for example, make stiffening agent with Dyhard RU 100 (dicydiamide) commonly used, imidazoles (imidazole) or tertiary amine class are done promotor, and solvent (appropriate solvent has N, N ' dimethyl amide (DMF), acetone, butanone) adjust under the viscosity, impregnated glass fiber cloth passes through heating so that the impregnated fiberglass cloth drying becomes prepreg then, one or both sides at this prepreg are placed Copper Foil, and make one or more prepreg laminated, and depress this laminate patch of heating adding at last, and make copper clad laminate.
Embodiment 1:
With 9.5 parts of phenol-phenyl aldehyde type polyfunctional epoxy resin (EEW=240, South Asia plastics industry limited-liability company, name of an article NPPN-433), 53.7 a part epoxy equivalent (weight) is bisphenol A type epoxy resin (the South Asia plastics industry limited-liability company of 186g/eq, the name of an article: NPEL-128E), 27.2 part) tetrabromo-bisphenol (TBBA), 4.8 a part epoxy equivalent (weight) (EEW) is tetrabromo-bisphenol type Resins, epoxy (the South Asia plastics industry limited-liability company of 390g/eq, the name of an article: NPEB-400), 4.8 part four functional group's Resins, epoxy (EEW=220g/eq, (South Asia plastics industry limited-liability company, the name of an article: NPPN-431) these five kinds of chemical substances in 170 ℃ down reaction after 120 minutes and brominated epoxy resin " EP-1 ", and brominated epoxy resin " EP-1 " is dissolved in 20% acetone, be mixed with 80% solution, so the Resins, epoxy " EP-1 " of gained has epoxy equivalent (weight) (EEW)=390g/eq, weight average molecular weight=2300, brominated amount=18.2%.
The batching that the present invention is applied to copper clad laminate is with 100 parts of brominated epoxy resins " EP-1 ", and 2.5 parts of Dyhard RU 100s and 0.07 part of 2-phenylimidazole are dissolved in N, N ' dimethyl formamide, and to be adjusted into 65% resin liquid.
(label is a South Asia resin glass cloth with glasscloth, cloth kind 7628) the above-mentioned resin liquid of impregnation, then in 170 ℃ (impregnation machines), dry several minutes, the minimum melting viscosity that can adjust dry back prepreg by adjustment control time of drying is between 4000～10000poise, at last with 8 prepregs layer by layer mutually repeatedly between the thick Copper Foil of two 35um, at 25kg/cm
2Under the pressure, the control heating schedule:
85℃?→?85℃?→?185℃?→?185℃??→??130℃
20min 30min 120min slowly cool off and the thick copper clad laminate of 1.6mm.
Embodiment 2:
With 40 parts of epoxy equivalent (weight)s (EEW) is bisphenol A type epoxy resin (the South Asia plastics industry limited-liability company of 186g/eq, the name of an article: NPEL-128E) with 13 parts of phenol-phenyl aldehyde type polyfunctional epoxy resins, 28 parts of tetrabromo-bisphenols (TBBA), and 2 part of four functional group's Resins, epoxy (South Asia plastics industry limited-liability company, the name of an article: NPPN-431), 4 kinds of chemical substances are after reacting 120 minutes under 170 ℃, being cooled to 130 ℃ adds 12 parts of epoxy equivalent (weight)s (EEW) again and is the bisphenol A type epoxy resin of 186g/eq (South Asia plastics industry limited-liability company, the name of an article: NPEL-128E) and 5 parts of tetrabromo-bisphenol type Resins, epoxy (South Asia plastics industry limited-liability company that epoxy equivalent (weight) is 390g/eq, the name of an article: NPEB-400), make brominated epoxy resin " EP-2 " after mixing evenly, and brominated epoxy resin " EP-2 " is dissolved in 20% acetone, be mixed with 80% solution, so and Resins, epoxy " EP-2 " have epoxy equivalent (weight) EEW=394g/eq, weight average molecular weight=2138, bromine content=18.8%.
" EP-2 " makes resin liquid by Resins, epoxy, and make copper clad laminate by this resin liquid, more than used basic skills be same as embodiment 1, lacquer formulation is used 2.5 parts of Dyhard RU 100s and 0.07 part of 2-phenylimidazole, be dissolved in N, N ' dimethyl formamide is adjusted into 65% resin liquid, and being controlled in the impregnation machine inner drying time, the minimum melting viscosity of adjusting dry back prepreg is between 4000～10000poise.
Embodiment 3:
With 20.2 parts of epoxy equivalent (weight)s (EEW) is bisphenol A type epoxy resin (the South Asia plastics industry limited-liability company of 186g/eq, the name of an article: NPEL-128E) with 49.5 parts of phenol-phenyl aldehyde type polyfunctional epoxy resins, 21.2 part tetrabromo-bisphenol (TBBA), 3 kinds of chemical substances are after reacting 120 minutes under 170 ℃, being cooled to 130 ℃ adds 7 parts of epoxy equivalent (weight)s (EEW) again and is the tetrabromo-bisphenol type Resins, epoxy of 390g/eq (South Asia plastics industry limited-liability company, the name of an article: NPEB-400) and 2 part of four functional group's Resins, epoxy (South Asia plastics industry limited-liability company, the name of an article: NPPN-431), make brominated epoxy resin " EP-3 " after mixing evenly, and brominated epoxy resin " EP-3 " is dissolved in 20% acetone, be mixed with 80% solution, so and Resins, epoxy " EP-3 " have epoxy equivalent (weight) (EEW)=378, weight average molecular weight=3366, bromine content=15.8%." EP-3 " makes resin liquid by Resins, epoxy, and make copper clad laminate by this resin liquid, more than used basic skills be same as embodiment 1, do not exist together and be to use 2.5 parts of Dyhard RU 100s and 0.05 part of 2-phenylimidazole, be dissolved in N, N ' dimethyl amide is adjusted into 65% resin liquid, and is controlled in impregnation machine time of drying, and the minimum melting viscosity of adjusting dry back prepreg is between 4000～10000poise.
Comparative example 1:
With 9.5 parts of ortho-cresol type phenolic aldehyde polyfunctional epoxy resin (EEW=210g/eq, average sense radix=12～13, South Asia plastics industry limited-liability company, the name of an article: NPCN-704), 53.2 a part epoxy equivalent (weight) (EEW) is bisphenol A type epoxy resin (the South Asia plastics industry limited-liability company of 186g/eq, the name of an article: NPEL-128E), 27.2 part tetrabromo-bisphenol (TBBA), 4.8 a part epoxy equivalent (weight) is tetrabromo-bisphenol type Resins, epoxy (the South Asia plastics industry limited-liability company of 390g/eq, the name of an article: NPEB-400), 4.8 part four sense Resins, epoxy (EEW=220g/eq, South Asia plastics industry limited-liability company, the name of an article: NPPN-431) these five kinds of chemical substances in 170 ℃ down reaction after 120 minutes and brominated epoxy resin " EP-4 ", and brominated epoxy resin " EP-4 " is dissolved in 20%, be mixed with 80% solution, so and Resins, epoxy " EP-4 " have epoxy equivalent (weight)=372g/eq, weight average molecular weight=3500, bromine content=18.2%.
With 100 parts above-mentioned and brominated epoxy resin " EP-4 ", 2.5 part Dyhard RU 100 and 0.03 part of 2-phenylimidazole are dissolved in N, N ' dimethyl formamide, to be adjusted into 65% resin liquid and to be controlled in impregnation machine time of drying, the minimum melting viscosity of adjusting dry back prepreg is between 4000～10000poise.
Comparative example 2:
With 37 parts of epoxy equivalent (weight)s (EEW) is bisphenol A type epoxy resin (the South Asia plastics industry limited-liability company of 186g/eq, the name of an article: NPEL-128E) with 10 parts of o-Hydroxytoluene formaldehyde epoxy resin (EEW=210g/eq, South Asia plastics industry limited-liability company, name of an article NPCN-704), 26 parts of tetrabromo-bisphenols (TBBA), and 5 part of four functional group's Resins, epoxy (South Asia plastics industry limited-liability company, the name of an article: NPPN-431), 4 kinds of chemical substances are after reacting 120 minutes under 170 ℃, being cooled to 130 ℃ adds 15 parts of epoxy equivalent (weight)s (EEW) again and is the bisphenol A type epoxy resin of 186g/eq (South Asia plastics industry limited-liability company, the name of an article: NPEL-128E), 7 parts of epoxy equivalent (weight)s (EEW) are tetrabromo-bisphenol type Resins, epoxy (the South Asia plastics industry limited-liability company of 390g/eq, the name of an article: NPEB-400), mix even back and get brominated epoxy resin " EP-5 ", and brominated epoxy resin " EP-5 " is dissolved in 20% acetone, be mixed with 80% solution, so and Resins, epoxy " EP-5 " have epoxy equivalent (weight) (EEW)=354g/eq, weight average molecular weight=2800, bromine content=18.7%.
By above-mentioned and Resins, epoxy " EP-5 " make resin liquid, and make copper clad laminate by this resin liquid, more than used basic skills be same as embodiment 1, do not exist together and be to use 2.5 parts of Dyhard RU 100s and 0.02 part of 2-phenylimidazole to be dissolved in N, N ' dimethyl amide, be adjusted into 65% resin liquid, and be controlled in impregnation machine time of drying, the minimum melting viscosity of adjusting dry back prepreg is between 4000～10000poise.
Comparative example 3:
With 17 parts of epoxy equivalent (weight)s (EEW) is 186g/eq bisphenol A type epoxy resin (South Asia plastics industry limited-liability company, the name of an article: NPEL-128E) with 35 parts of phenol aldehyde type polyfunctional epoxy resin (EEW=178g/eq, South Asia plastics industry limited-liability company, name of an article NPPN-638), 19 parts of tetrabromo-bisphenols (TBBA), and 5 part of four functional group's Resins, epoxy (South Asia plastics industry limited-liability company, the name of an article: NPPN-431), 4 kinds of chemical substances are after reacting 120 minutes under 170 ℃, being cooled to 130 ℃ adds 9 parts of epoxy equivalent (weight)s (EEW) again and is the tetrabromo-bisphenol type Resins, epoxy of 390g/eq (South Asia plastics industry limited-liability company, the name of an article: NPEB-400), and 15 parts of ortho-cresol phenolic aldehyde polyfunctional epoxy resins (EEW=210g/eq), mix even back and get brominated epoxy resin " EP-6 ", and brominated epoxy resin " EP-6 " is dissolved in 25% acetone, be mixed with 75% solution, so and Resins, epoxy " EP-6 " have epoxy equivalent (weight) (EEW)=370, weight average molecular weight=4000, bromine content=15.6%.
By above-mentioned and Resins, epoxy " EP-6 " make resin liquid, and make copper clad laminate by this resin liquid, more than used basic skills be same as embodiment 1, do not exist together and be to use 2.5 parts of Dyhard RU 100s and 0.02 part of 2-phenylimidazole, be dissolved in N, N ' dimethyl amide is adjusted into 65% resin liquid and is controlled in impregnation machine time of drying, and the minimum melting viscosity of adjusting dry back prepreg is between 4000～10000poise.
Comparative example 4:
Select the standard type difunctionality brominated epoxy resin that to buy by market for use, EEW=420g/eq, bromine content=19.3%, weight average molecular weight=2600 (South Asia plastics industry limited-liability company, name of an article NPEB-450), to make brominated resins " EP-7 " after 95 parts of 5 part of four sense Resins, epoxy of adding of above-mentioned difunctionality basic ring epoxy resins (EEW=220g/eq) mixing, and brominated resins " EP-7 " is dissolved in 20% acetone, be mixed with 80% solution.
By above-mentioned and Resins, epoxy " EP-7 " make resin liquid, and make copper clad laminate by this resin liquid, more than used basic skills be same as embodiment 1, do not exist together and be to use 2.5 parts of Dyhard RU 100s and 0.05 part of glyoxal ethyline, be dissolved in N, N ' dimethyl amide is adjusted into 65% resin liquid and is controlled in impregnation machine time of drying, and the minimum melting viscosity of adjusting dry back prepreg is between 4000～10000poise.
Table 1, table 2 are the formula table of all embodiment and comparison and the rerum natura table of prepreg and copper clad laminate.
Table 1 embodiment and comparative example prescription
Unit: g
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| EP-1 (solid-state) | ??100 | ||||||
| EP-2 (solid-state) | ??100 | ||||||
| EP-3 (solid-state) | ??100 | ||||||
| EP-4 (solid-state) | ??100 | ||||||
| EP-5 (solid-state) | ??100 | ||||||
| EP-6 (solid-state) | ??100 | ||||||
| EP-7 (solid-state) | ????100 | ||||||
| Acetone | ??25 | ??25 | ??25 | ??25 | ??25 | ??33.3 | ????25 |
| Dyhard RU 100 | ??2.5 | ??2.5 | ??2.5 | ??2.5 | ??2.5 | ??2.5 | ????2.5 |
| Glyoxal ethyline | ???- | ??- | ???- | ???- | ???- | ???- | ????0.05 |
| The 2-phenylimidazole | ??0.07 | ??0.07 | ??0.05 | ??0.03 | ??0.02 | ??0.02 | ????- |
| N, N ' dimethyl amide | ??30 | ??30 | ??30 | ??30 | ??30 | ??30 | ????30 |
Table 2 embodiment and comparative example rerum natura comparison sheet
Annotate:
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Varnish gel time (170 ℃) | 292 seconds | 310 seconds | 315 seconds | 304 seconds | 285 seconds | 170 seconds | 286 seconds |
| Prepreg gel time (170 ℃) | 133 seconds | 130 seconds | 134 seconds | 100 seconds | 95 seconds | 80 seconds | 136 seconds |
| The minimum melting viscosity of prepreg (poise) *1 | ??4200 | ???6000 | ???5200 | ???5000 | ???5300 | ?5200 | ?4800 |
| The glass tansition temperature (℃, DSC) *2 | ??150 | ???150 | ???170 | ???151 | ???152 | ?174 | ?140 |
| Water-intake rate % (half an hour, pressure cooker was handled the back) *3 | ??0.2％ | ???0.2％ | ???0.18％ | ???0.2％ | ???0.2％ | ?0.18％ | ?0.23％ |
| 288 ℃ of anti-scolding tin thermotolerances (half an hour, pressure cooker was handled the back) *4 | 5 minutes | 5 minutes | 5 minutes | 5 minutes | 5 minutes | 5 minutes | 3 minutes 40 seconds |
| The stripping strength of Copper Foil (lb/in) | ??11.5 | ???11.5 | ???9 | ???11 | ???11 | ?8 | ?12 |
| Flame resistivity (UL-94) | ??V0 | ???V0 | ???V0 | ???V0 | ???V0 | ?V0 | ?V0 |
*1. use Tianjin, island shimazuCFT-100 Flowmeter to test minimum melting viscosity, temperature rise rate=1.75 ℃/min.
*2. use elementary errors to scan thermal analyzer (DSC).
*3. sample heating 30 minutes in 120 ℃ and 2atm pressure cooker.
*4. 288 ℃ of solder furnace are immersed in sample heating in 120 ℃ and 2atm pressure cooker after 30 minutes, record sample plate bursting layering required time.
By table 1, table 2 as can be known (1) when adjusting varnish gel time=300 seconds ± 15 seconds, by promotor usage quantity number, the reactive speed of brominated epoxy resin as can be known, so show embodiment: phenol-phenyl aldehyde polyfunctional epoxy resin synthetic brominated resins (" EP-1 ", " EP-2 ", " EP-3 ") than comparative example: with ortho-cresol phenolic aldehyde polyfunctional epoxy resin and phenolic aldehyde polyfunctional epoxy resin institute synthetic brominated resins (" EP-4 ", " EP-5 ", " EP-6 ") reactivity is slow.When (2) the minimum kinematic viscosity of resin being controlled in the 5000poise left and right sides, with embodiment: phenol-phenyl aldehyde polyfunctional epoxy resin synthetic brominated resins (" EP-1 ", " EP-2 ", " EP-3 "), its prepreg gel time is longer than comparative example: with ortho-cresol phenolic aldehyde polyfunctional epoxy resin institute's synthetic brominated resins (" EP-4 ", " EP-5 ", " EP-6 "), and be close with basic model difunctionality basic ring epoxy resins (brominated resins " EP-7 "), show that phenol-phenyl aldehyde polyfunctional epoxy resin synthetic brominated resins has broad pressing processing interval.(3) with phenol-phenyl aldehyde polyfunctional epoxy resin synthetic brominated resins, have high Tg and good thermotolerance.
Measure explanation
1, varnish gel time (Varnish gel time)
The reactive test of varnish is for (to be dissolved in solvent DMF with epoxy resin solution and stiffening agent Dyhard RU 100 solution, strength of solution=13.3%), promotor 2-phenylimidazole or glyoxal ethyline solution (are dissolved in solvent DMF, strength of solution=14.28%) preparation varnish mixed solution, this varnish mixture drips about 0.3ml in hot plate, hot plate temperature=170 ℃ are recorded to the gel required time.
2, dipping body gel time (Prepreg gel time)
The prepreg testing method is, takes by weighing prepreg powder 0.2mg and places hot plate, and hot plate temperature=170 ℃ are recorded to the required time of gel.
3, the minimum melting viscosity of prepreg
It is Tianjin, island CFT-100flowmeter that the minimum kinematic viscosity testing method of prepreg is to use the instrument label, 1.8g prepreg powder is played ingot become cylindric, temperature test scope=80～130 ℃, temperature rise rate=1.75 ℃/min.
4, water-intake rate test
The water-intake rate testing method is that the etching metacoxa is cut into 5cm
2The square test piece behind the baking 2hr, is put in test piece in the pressure cooker in 105 ℃ of baking ovens, and the pressure cooker condition is 2atm * 120 ℃, and behind pressure cooker 30min, record test piece weight difference before and after pressure cooker is water-intake rate divided by the test piece initial weight.
5,288 ℃ of anti-scolding tin thermotolerances
Testing method then is to immerse 288 ℃ of solder furnace with above-mentioned through the pressure cooker test piece, record test piece plate bursting layering required time.
Claims (5)
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| CNB011397713A CN1159363C (en) | 2001-11-30 | 2001-11-30 | High glass transition temperature brominated epoxy resin for glass fiber laminated plate |
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| CNB011397713A CN1159363C (en) | 2001-11-30 | 2001-11-30 | High glass transition temperature brominated epoxy resin for glass fiber laminated plate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591465B (en) * | 2008-05-27 | 2011-06-22 | 台燿科技股份有限公司 | Improved composition of printed circuit substrate materials |
| CN103819655A (en) * | 2006-06-07 | 2014-05-28 | 陶氏环球技术有限责任公司 | Oligomeric halogenated chain extenders for preparing epoxy resins |
| CN106279704A (en) * | 2015-05-27 | 2017-01-04 | 南亚塑胶工业股份有限公司 | Polyphenyl ether modified phenol-benzaldehyde polyfunctional epoxy resin and purposes |
-
2001
- 2001-11-30 CN CNB011397713A patent/CN1159363C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819655A (en) * | 2006-06-07 | 2014-05-28 | 陶氏环球技术有限责任公司 | Oligomeric halogenated chain extenders for preparing epoxy resins |
| CN103819655B (en) * | 2006-06-07 | 2016-09-28 | 兰科知识产权有限责任公司 | For preparing the oligomeric halogenated chain extenders of epoxy resin |
| CN101591465B (en) * | 2008-05-27 | 2011-06-22 | 台燿科技股份有限公司 | Improved composition of printed circuit substrate materials |
| CN106279704A (en) * | 2015-05-27 | 2017-01-04 | 南亚塑胶工业股份有限公司 | Polyphenyl ether modified phenol-benzaldehyde polyfunctional epoxy resin and purposes |
| CN106279704B (en) * | 2015-05-27 | 2020-10-27 | 南亚塑胶工业股份有限公司 | Polyphenyl ether modified phenol-benzaldehyde multifunctional epoxy resin and application |
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