CN103435973B - A kind of halogen-free epoxy resin composition and the prepreg using it to make and veneer sheet - Google Patents
A kind of halogen-free epoxy resin composition and the prepreg using it to make and veneer sheet Download PDFInfo
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- CN103435973B CN103435973B CN201310404011.1A CN201310404011A CN103435973B CN 103435973 B CN103435973 B CN 103435973B CN 201310404011 A CN201310404011 A CN 201310404011A CN 103435973 B CN103435973 B CN 103435973B
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Abstract
The invention discloses a kind of halogen-free epoxy resin composition, with solid weight meter, comprising: (a) epoxy resin: 50 ~ 97 parts; (b) solidifying agent: 3 ~ 50 parts; (c) phosphonium flame retardant: 1 ~ 45 part; (d) imidazoles promotor: 0.05 ~ 1 part; (e) phenylo boric acid: 0.1 ~ 10 part.Resin system of the present invention not only has good flame retardant resistance, and in copper-clad plate production process, and low temperature (less than 170 DEG C) inhibition system reacts, accelerated reaction during high temperature, can remarkable faster production efficiency, reduction product cost.
Description
Technical field
The invention belongs to technical field of electronic materials, relate to a kind of halogen-free epoxy resin composition and the prepreg using it to make and veneer sheet.
Background technology
Along with European RoHS and WEEE instruction (about restriction some Hazardous Substances Directive of use in electrical and electronic product with about scrapping electrical and electronic product instruction) implementing in full on July 1st, 2006, the non-halogen of electronic product has been trend of the times, and the copper-clad plate (i.e. veneer sheet) as baseplate material then stands in the breach.Traditional copper-clad plate material generally adopts brominated flame retardant (as brominated epoxy resin, tetrabromo-bisphenol etc.) to ensure that flame retardant resistance reaches UL94V-0 grade.But correlative study shows, during bromide burning, carcinogenic dioxin can be generated, serious harm HUMAN HEALTH, and contaminate environment.Therefore, in order to meet non-halogen requirement, need to seek a kind of brand-new and effective fire-retardant approach.
For the problems referred to above, the method generally adopted in industry is the bromide fire retardant that use phosphorous epoxy resin substitutes in the past, but its goods also exist, and wicking thermotolerance is not enough, easily the moisture absorption, humidity process the problems such as rear wicking thermotolerance is not enough.
On the other hand, epoxy resin refers to the family macromolecule compound in the molecular structure containing more than 2 or 2 epoxy group(ing).Because it has the cost of excellent processing performance, mechanical property, electrical property, physicals and relative moderate, for a long time in the application of printed wiring plate substrate in occupation of dominant position.Further, in the classification suggestion that industrial security certification authority UL is up-to-date, the composition of copper-clad plate FR-4 being defined as epoxy resin ratio needs to be greater than 50%, more enhances the dominant position of copper-clad plate base material epoxy resin.During PCB in copper-clad plate production and downstream produces, all require that the solidification value of prepreg in the process of pressing sheet material is low, set time is short, to enhance productivity, reduces product cost.This just needs the promotor containing more high-content in the composition epoxy resin making prepreg.Regrettably, simple increase accelerator level, not only accurately can not control curing reaction, and in prepreg making processes, understands initial ring epoxy resins premature reaction and retain solvent, make dissolvent residual in final copper-clad plate sheet material, thus final performance is had a negative impact.
Therefore, develop and a kind of not only there is good flame retardant resistance, and the halogen-free environment-friendly type composition epoxy resin of curing reaction can be accelerated, there are market outlook.
Summary of the invention
The object of the invention is to provide a kind of halogen-free epoxy resin composition and the prepreg using it to make and veneer sheet.
For achieving the above object, the technical solution used in the present invention is: a kind of halogen-free epoxy resin composition, with solid weight meter, comprising:
(a) epoxy resin: 50 ~ 97 parts;
(b) solidifying agent: 3 ~ 50 parts;
(c) phosphonium flame retardant: 1 ~ 45 part;
(d) imidazoles promotor: 0.05 ~ 1 part;
(e) phenylo boric acid: 0.1 ~ 10 part.
Above, the content range of described phenylo boric acid is 0.1 ~ 10 part, if more than 10 parts, there will be solidifying agent excessive, the problem of the degradation such as second-order transition temperature, thermotolerance of sheet material, if lower than 0.1 part, does not just accelerate the effect of solidifying.
Simultaneously, above-mentioned composition can need according to practical application the filler adding 0 ~ 100 part, described filler be selected from aluminium hydroxide, magnesium hydroxide, wollastonite, silicon-dioxide, magnesium oxide, Calucium Silicate powder, calcium carbonate, clay, kaolin, glass powder, mica powder, titanium dioxide one or more.
In technique scheme, described epoxy resin is selected from one or more in bisphenol A epoxide resin, bisphenol F epoxy resin, phosphorous epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol novolac epoxy resins, trifunctional phenol-type epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl novolac epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin.
In technique scheme, described solidifying agent is selected from one or more in Dyhard RU 100, line style phenolic aldehyde, phosphorus-containing phenolic aldehyde, diaminodiphenylsulfone(DDS), diaminodiphenyl oxide, diaminodiphenylmethane.
In technique scheme, described phosphonium flame retardant is selected from phosphazene compound, phosphate compound, 9,10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound, 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, phosphorous cyanate, one or more in phosphorous bismaleimides.
In technique scheme, described curing catalyst is selected from one or more in glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-cyanoethyl-2 Methylimidazole.
In technique scheme, described phenylo boric acid be selected from 4-fluorobenzoic boric acid, 4-(trifluoromethyl) phenylo boric acid, 4-cyanophenylboronic acid, 4-formylphenylboronic acid, to one or more in methylphenylboronic acid, 4-(4-pyridyl) phenylo boric acid.
In technique scheme, the mol ratio of described curing catalyst and phenylo boric acid is 1:2 ~ 5.
The present invention asks the prepreg protected as above-mentioned halogen-free epoxy resin composition makes simultaneously, above-mentioned halogen-free epoxy resin composition dissolution with solvents is made glue, is then immersed in by strongthener in above-mentioned glue; After flooding after strongthener baking, described prepreg can be obtained.
Described solvent can select the mixture of one or more in acetone, butanone, mibk, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, propylene glycol monomethyl ether.Described strongthener can adopt natural fiber, organic synthetic fibers, organic fabric or inorganic fabric.
The present invention asks to protect a kind of veneer sheet adopting above-mentioned halogen-free epoxy resin composition to make simultaneously; tinsel is covered with by the single or double of above-mentioned prepreg at one; or after at least 2 are superposed by above-mentioned prepreg; tinsel is covered with at its single or double; compacting, can obtain described veneer sheet.
The quantity of described prepreg determines according to the laminate thickness of customer requirement, available one or more.Described tinsel can be Copper Foil, and also can be aluminium foil, their thickness be not particularly limited.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the present invention devises a kind of new compositions of thermosetting resin, utilize phosphorus boron cooperative flame retardant, while reducing the phosphorus content in epoxy-resin systems, ensure that the flame retardant resistance of epoxy-resin systems reaches UL94V-0 grade, improve product moisture-resistant and thermotolerance simultaneously, and improve toughness and the processibility of product.
2. resin system of the present invention not only has good flame retardant resistance, and in copper-clad plate production process, and low temperature (less than 170 DEG C) inhibition system reacts, accelerated reaction during high temperature, can remarkable faster production efficiency, reduction product cost.
3. present invention employs phenylo boric acid as boron source, meet environmental requirement, and contain certain crosslinked action due to phenylo boric acid, and chemical structure contains the phenyl ring of rigidity, certain help is also had to the Tg of cured article, and the thermotolerance of quick-setting goods is also unaffected.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
A kind of halogen-free epoxy resin composition, with solid weight meter, comprises following component, shown in seeing table:
Table 1 resin composition formula
Wherein, phosphorous epoxy resin, XZ92530, Dow Chemical is produced; Bisphenol A type epoxy resin, YDB128, Guktoh Chemical Co., Ltd. produces; Biphenyl type epoxy resin, NC-3000, Nippon Kayaku K. K produces; Trifunctional phenol-type epoxy resin, KDB1065, Guktoh Chemical Co., Ltd. produces; Dyhard RU 100, Qingdao is converged and Chemical Co., Ltd.; Lacquer resins, TD2091, Dainippon Ink Chemicals produces; Phosphorus containing phenolic resin, P Modification class phenolic compound, XZ9271, Dow Chemical is produced; Phosphate compound, Guangzhou Zhen Yuanyang company limited; 2-ethyl-4-methylimidazole, glyoxal ethyline, Japanese four countries change into production; 4-cyanophenylboronic acid, 4-formylphenylboronic acid, Lu Xing bio tech ltd, Changsha.
Table 2 is the performance test carried out embodiment one to three and comparative example one to four respectively, and result is as shown in the table:
The performance data of table 2 embodiment one to five and comparative example one to four
In table, the testing method of characteristic is as follows:
(1) the hydrogel time (second): gelation tester is set to l71 ± 0.5 DEG C, 0.5 to 0.7mL glue is dripped on the heating plate of gelation tester, open timing register, one end of toothpick point is aimed at the surface of heating plate, with the circumferential motion agitating resin of diameter 10-13mm.During stirring, circumferential motion should make the resin of middle portion stir outer each time, and the resin of peripheral rim portion stirs centre.Toothpick should always with resin with solidify panel surface and contact.When resin retrogradation, being not easy to external resin and internal resin are exchanged, but must continuing to stir, and making when not making toothpick stir disconnected resin exchange as far as possible.When being separated with solidification dish by the resin mass stirred, stop timing immediately, this time is gel time.
(2) flame resistivity: (flame retardancy): measure according to UL94 method.
(3) heat decomposition temperature Td: measure according to IPC-TM-6502.4.26 method.
(4) thermal expansivity Z axis CTE (TMA): measure according to IPC-TM-6502.4.24 method.
(5) wicking thermotolerance (second): the two sides band copper sample using 50 × 50mm, immerses in the soldering of 288 DEG C, the time that the layering of record sample is bubbled.
(6) humidity resistance: by (base material of 100 × 100cm) sample 121 DEG C, keep 1 hour in the pressure cooking treatment unit of 105kpa after, record is immersed in certain hour in the soldering groove of 288 DEG C and observes sample whether layering, foaming.
(7) glass transition temperature Tg (DEG C): according to dsc, tests according to the DSC method of IPC-TM-6502.4.25 defined.
As seen from the above table, the glue system that composition epoxy resin of the present invention is made can ensure suitable gelation time, is applicable to the complete processing of prepreg.Bonding processes can accelerate again solidification, sheet material can be made to solidify completely in the short period, can faster production efficiency in copper-clad plate and PCB bonding processes, reduces production cost.Further, because phenylo boric acid contains certain crosslinked action, and chemical structure contains the phenyl ring of rigidity, also have certain help, and the thermotolerance of quick-setting goods is also unaffected to the Tg of cured article.
Claims (8)
1. a halogen-free epoxy resin composition, is characterized in that, with solid weight meter, comprising:
(a) epoxy resin: 50 ~ 97 parts;
(b) solidifying agent: 3 ~ 50 parts;
(c) phosphonium flame retardant: 1 ~ 45 part;
(d) imidazoles promotor: 0.05 ~ 1 part;
(e) phenylo boric acid: 0.1 ~ 10 part;
Described phenylo boric acid be selected from 4-fluorobenzoic boric acid, 4-(trifluoromethyl) phenylo boric acid, 4-cyanophenylboronic acid, 4-formylphenylboronic acid, to one or more in methylphenylboronic acid, 4-(4-pyridyl) phenylo boric acid.
2. halogen-free epoxy resin composition according to claim 1, is characterized in that: described epoxy resin is selected from one or more in bisphenol A epoxide resin, bisphenol F epoxy resin, phosphorous epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol novolac epoxy resins, trifunctional phenol-type epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl novolac epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin.
3. halogen-free epoxy resin composition according to claim 1, is characterized in that: described solidifying agent is selected from one or more in Dyhard RU 100, line style phenolic aldehyde, phosphorus-containing phenolic aldehyde, diaminodiphenylsulfone(DDS), diaminodiphenyl oxide, diaminodiphenylmethane.
4. halogen-free epoxy resin composition according to claim 1, it is characterized in that: described phosphonium flame retardant is selected from phosphazene compound, phosphate compound, 9,10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound, 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, phosphorous cyanate, one or more in phosphorous bismaleimides.
5. halogen-free epoxy resin composition according to claim 1, is characterized in that: described imidazoles promotor is selected from one or more in glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-cyanoethyl-2 Methylimidazole.
6. halogen-free epoxy resin composition according to claim 1, is characterized in that: the mol ratio of described imidazoles promotor and phenylo boric acid is 1:2 ~ 5.
7. the prepreg adopting halogen-free epoxy resin composition as claimed in claim 1 to make, is characterized in that: halogen-free epoxy resin composition dissolution with solvents according to claim 1 is made glue, is then immersed in by strongthener in above-mentioned glue; After flooding after strongthener baking, described prepreg can be obtained.
8. the veneer sheet adopting halogen-free epoxy resin composition as claimed in claim 1 to make, it is characterized in that: be covered with tinsel at one by the single or double of prepreg according to claim 7, or after at least 2 are superposed by prepreg according to claim 7, tinsel is covered with at its single or double, compacting, can obtain described veneer sheet.
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| CN105316936B (en) * | 2014-06-06 | 2017-10-24 | 戴李宗 | A kind of anti-flammability finishing agent and its application |
| CN104497493A (en) * | 2015-01-15 | 2015-04-08 | 江苏恒神纤维材料有限公司 | Formula for pollution-free organic fertilizer and preparation method thereof |
| CN106146803B (en) * | 2015-04-02 | 2019-09-27 | 南亚塑胶工业股份有限公司 | Low dielectric phosphor-containing flame-proof curing agent and its application |
| CN105237950B (en) * | 2015-09-24 | 2017-11-28 | 苏州宽温电子科技有限公司 | A kind of copper-clad plate environment friendly halogen-free fireproof epoxy resin and preparation method thereof |
| CN106496950A (en) * | 2016-11-11 | 2017-03-15 | 惠柏新材料科技（上海）股份有限公司 | A kind of low smoke combustion-proof epoxide resin composition |
| CN106832781A (en) * | 2017-02-17 | 2017-06-13 | 南通苏源化纤有限公司 | Novel nano high fire-retardance thermosetting resin based composites |
| GB2568727B (en) * | 2017-11-24 | 2020-06-24 | Gurit Uk Ltd | Fire-retardant composite materials |
| CN109810504A (en) * | 2019-01-24 | 2019-05-28 | 江苏澳盛复合材料科技有限公司 | A kind of bismaleimide resin composition and its solidfied material and composite material |
| DE102019121195A1 (en) * | 2019-08-06 | 2021-02-11 | Alzchem Trostberg Gmbh | Storage-stable epoxy resin composition |
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| CN102276959A (en) * | 2011-06-22 | 2011-12-14 | 天津市凯华绝缘材料有限公司 | Halogen-free non-phosphorization flame-retardant epoxy resin composition and preparation method thereof |
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| US6872762B2 (en) * | 2000-07-13 | 2005-03-29 | Loctite (R&D) Limited | Epoxy resin composition with solid organic acid |
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| CN102276959A (en) * | 2011-06-22 | 2011-12-14 | 天津市凯华绝缘材料有限公司 | Halogen-free non-phosphorization flame-retardant epoxy resin composition and preparation method thereof |
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