CN1159363C - Epoxy resin bromide with high glass transfusion temp. for glass fibre laminated board - Google Patents
Epoxy resin bromide with high glass transfusion temp. for glass fibre laminated board Download PDFInfo
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- CN1159363C CN1159363C CNB011397713A CN01139771A CN1159363C CN 1159363 C CN1159363 C CN 1159363C CN B011397713 A CNB011397713 A CN B011397713A CN 01139771 A CN01139771 A CN 01139771A CN 1159363 C CN1159363 C CN 1159363C
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Abstract
The present invention relates to epoxy resin bromide with high glass transition temperature for a glass fiber laminated board, which is obtained in a synthesizing method that (A) 10 to 70 weight percent of phenol-benzaldehyde polyfunctional epoxy resin (formula I), (B) 0 to 55 weight percent of double-functional base epoxy resin, (C) 0 to 20 weight percent of bromine-containing double-functional base epoxy resin and (D) 15 to 40 weight percent of tetrabromo bisphenol A. The structural formula of the present invention is shown in a formula right; when the present invention is synthesized, after the reaction between the (D) 15 to 40 weight percent of tetrabromo bisphenol A and at least one of (A), (B) and (C) is carried out, the rest parts of the three kinds of the epoxy resin (A), (B) and (C) are added, and the novel epoxy resin bromide is obtained after uniformly mixing. The novel epoxy resin bromide can be used in the glass fiber laminated board for providing appropriate reactivity and broad processing space of pressing, and the pressed glass fiber laminated board which has high glass transition temperature (Tg) and good heat resistance 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 formaldehyde novolac 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 reach (D) tetrabromo third diphenol 15～40 weight %, form via synthesis mode by (A) phenol-phenyl aldehyde polyfunctional epoxy resin 10～70 weight %, (B) difunctionality basic ring epoxy resins 0～55 weight %, (C) brominated difunctionality basic ring epoxy resins 0～20 weight %.Earlier will (D) and (A), (B), (C) three at least a (containing a kind of) Resins, epoxy reacts, and then add (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, and glass tansition temperature (Tg) is 150～190 ℃ of brominated epoxy resins.
Wherein (A) composition phenol-phenyl aldehyde polyfunctional epoxy resin structural formula is as follows
Wherein (A) is phenol-phenyl aldehyde polyfunctional epoxy resin, and its epoxy equivalent (weight) (EEW) is 210～260g/eq, and average sense radix is 2～6, and molecular-weight average (Mw) is 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 (diglycidyl 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, and (imidazole) Lei is Ji Benzyl base 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 cools off
And must 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
| 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 |
Annotate:
*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)
1, a kind of fiberglass layer plywood is with the brominated epoxy resin of high glass tansition temperature, be by:
(A) phenol-phenyl aldehyde polyfunctional epoxy resin 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 %;
Form via synthesis mode;
Wherein, (A) phenol-phenyl aldehyde polyfunctional epoxy resin structure is as follows
Earlier D and A, B, at least a Resins, epoxy of C three are reacted, and then add A, B, remaining part of C, mixing and getting weight average molecular weight Mw is 1500～4000, the ratio of the dispersed index M w/Mn of molecular weight distribution is 1.5～4.0, epoxy equivalent (weight) EEW is 300～450 gram/equivalents, and glass tansition temperature Tg is 150～190 ℃ of brominated epoxy resins.
2, fiberglass layer plywood as claimed in claim 1 is with the brominated epoxy resin of high glass tansition temperature, it is characterized in that, wherein A is phenol-phenyl aldehyde polyfunctional epoxy resin, its epoxy equivalent (weight) EEW is 210～260 gram/equivalents, average sense radix is 2～6, and average molecular weight Mw is 400～2500.
3, fiberglass layer plywood as claimed in claim 1 is with the brominated epoxy resin of high glass tansition temperature, it is characterized in that, wherein B is that difunctionality basic ring epoxy resins comprises bisphenol A epoxide resin, bisphenol F epoxy resin, and the epoxy equivalent (weight) EEW scope of B is 170～500 gram/equivalents.
4, fiberglass layer plywood as claimed in claim 1 is with the brominated epoxy resin of high glass tansition temperature, it is characterized in that, wherein C is that brominated difunctionality basic ring epoxy resins is a tetrabromo bisphenol-a epoxy resin, and the epoxy equivalent (weight) EEW of this brominated difunctionality basic ring epoxy resins is 300～500 gram/equivalents, and brominated amount is 30～55%.
5, fiberglass layer plywood as claimed in claim 1 is characterized in that with the brominated epoxy resin of high glass tansition temperature, and wherein D is 544 tetrabromo-bisphenol for molecular weight Mw.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011397713A CN1159363C (en) | 2001-11-30 | 2001-11-30 | Epoxy resin bromide with high glass transfusion temp. for glass fibre laminated board |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011397713A CN1159363C (en) | 2001-11-30 | 2001-11-30 | Epoxy resin bromide with high glass transfusion temp. for glass fibre laminated board |
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| Publication Number | Publication Date |
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| CN1358780A CN1358780A (en) | 2002-07-17 |
| CN1159363C true CN1159363C (en) | 2004-07-28 |
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| CNB011397713A Expired - Fee Related CN1159363C (en) | 2001-11-30 | 2001-11-30 | Epoxy resin bromide with high glass transfusion temp. for glass fibre laminated board |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20080039595A1 (en) * | 2006-06-07 | 2008-02-14 | Joseph Gan | Oligomeric halogenated chain extenders for preparing epoxy resins |
| CN101591465B (en) * | 2008-05-27 | 2011-06-22 | 台燿科技股份有限公司 | Composition for improving tellite material |
| 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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Assignee: South Epoxy Resin (Kunshan) Co.,Ltd. Assignor: Nanya Plastics Industry Co., Ltd. Contract fulfillment period: 2006.1.1 to 2015.12.31 contract change Contract record no.: 2009990000539 Denomination of invention: Epoxy resin bromide with high glass transfusion temp. for glass fibre laminated board Granted publication date: 20040728 License type: Exclusive license Record date: 2009.5.22 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2006.1.1 TO 2015.12.31; CHANGE OF CONTRACT Name of requester: NAN YA EPOXY (KUNSHAN) CO., LTD. Effective date: 20090522 |
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