CN100400592C - Fire tetardant no-halogen epoxy resin glue and its prepn process and use - Google Patents
Fire tetardant no-halogen epoxy resin glue and its prepn process and use Download PDFInfo
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- CN100400592C CN100400592C CNB200610155095XA CN200610155095A CN100400592C CN 100400592 C CN100400592 C CN 100400592C CN B200610155095X A CNB200610155095X A CN B200610155095XA CN 200610155095 A CN200610155095 A CN 200610155095A CN 100400592 C CN100400592 C CN 100400592C
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- epoxy resin
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- tetardant
- halogen
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Abstract
The present invention relates to one kind of fire retardant no-halogen epoxy resin glue comprising solution A and solution B. solution A consists of triazine compound with general expression as shown, organic acid and water; and solution B consists of epoxy resin, curing agent, coupler, curing promoter, fire retardant and solvent. The fire retardant no-halogen epoxy resin thus prepared has excellent heat resisting performance and excellent fire retarding performance, and may be used in sealing material and laminated plate.
Description
Technical field
The present invention relates to the technology of a kind of fire tetardant no-halogen epoxy resin glue and application thereof.Be specifically related to adopt simple fabrication process that ignition-proof element nitrogen is incorporated in the Resins, epoxy, high heat-resisting, high initial heat decomposition temperature of realization and excellent flame retardancy, the matrix resin that can be used as sealing material and veneer sheet in the electric field, and their manufacture method.
Background technology
Thermostability, insulativity, cohesiveness, good mechanical performance, good building-up properties reach lower advantages such as cost to epoxy resin cured product owing to have preferably, be widely used in bonding, the encapsulation of electronic devices and components and the manufacturing of printed circuit board (PCB), be one of present of paramount importance electron chemistry material, become the mainstay that supports electric industry already.Yet the same with most of macromolecular materials, the curable epoxide thing is inflammable, and the fire that the annual whole world therefore causes has caused huge loss of life and personal injury and property damage, therefore necessary the curable epoxide thing that is applied in electric field is carried out fire-retardant finish.
In recent decades, widely used in electric field is to be monomeric brominated Resins, epoxy with tetrabromo-bisphenol, with bromine flame retardant epoxy cured article.Yet brominated flame-retardant discharges toxic substance in burning or waste treatment, as produce a large amount of dense smokes and irritating toxic gas, (PBDF), dioxin (dioxin) etc. are carcinogenic probably and cause animal body odd-shaped Toxic, and it is also quite difficult to handle or reclaim brominated waste material in addition also may to produce many bromines diphenylene-oxide.Can predict that harm humans halogen fire retardant healthy and environmental safety can be forbidden by countries in the world gradually, needs to seek the environment friendly flame retardant that substitutes bromine.
The Resins, epoxy that is used for electric field at present also suffers from another predicament.Because plumbous baneful influence to environment and human health, traditional leaded weldprocedure will be eliminated." electric and electronics offal treatment method (Waste Electricaland Electronic Equipment; WEEE) " of European Union and " in the electronic electric equipment restriction use some objectionable impurities instruction (Restrictionof certain Hazardous Substances; RoHS) " draft for amendments, to Halogen, unleaded environmental protection electronic material standard in addition.Clearly regulation lead, mercury, cadmium, chromium (6 valency), Polybrominated biphenyl (PBB) and six kinds of chemical substances of polybromodiphenyl ether (PBDE) forbade using in electronic and electrical equipment from July 1st, 2006.This means and in various electronic products, must use leadless process that base material is processed from now on, work the mischief to avoid lead is incorporated in the product.Because the welding temperature of lead-free solder has the welding temperature of lead solder apparently higher than tradition, so require the thermosetting resin base material of carrying electric elements to have higher thermostability.This regulation has proposed the thermostability of more strict performance requriements, particularly material to the curable epoxide thing that is used for electronic substrate.Satisfy application requiring of " Halogen " fire-retardant and " unleaded " welding, be actually the preparation problem that has proposed the curable epoxide thing material that a halogen-free flameproof and thermotolerance have both.
For tackling these requirements, the phosphorous epoxy resin system of flame retardant properties excellence just is widely studied since the middle and later periods nineties in last century as the principal item of " Halogen " Resins, epoxy, as patent US6403220, US6500546 and EP1312638 etc.But it is big more that the shortcoming of this resinoid system is phosphorus content, and the thermal characteristics of material is just poor more, and complicated process of preparation, cost are higher, and industrialization is difficulty relatively, and the phosphate ester structure of facile hydrolysis also threatens its stable use in the product in addition.Phosphorus content in the reduction resin system helps promoting the thermal characteristics of material.Utilize the principle of phosphorus nitrogen cooperative flame retardant, can reduce the phosphorus consumption largely, also the characteristics of nitrogen flame retardant excellent heat resistance can be incorporated in the epoxy resin cured product simultaneously, thereby reach " Halogen " fire-retardant application requiring that welds with " unleaded ".But present most nitrogen flame retardant is an additive flame retardant, and is poor with the epoxy systems consistency, is difficult to be widely used in electric field.To contain N structure is the optimum method that solves both compatibility problems by covalent linkage form introducing epoxy systems.As patent US20030099839, US6617029 etc. triazine structure is introduced in the epoxy-resin systems with the solidifying agent form, obtained better result, but relate to limited than the nitrogen content of complicated resin manufacture technology and introducing; Our last patent ZL200410053181.0 has obviously improved flame retardant resistance and thermotolerance by introducing isocyanurate structure for another example, but owing to introduced the structure of portion of hot poor performance simultaneously, and be difficult to adapt to " unleaded " welding requirements.
Summary of the invention
The purpose of this invention is to provide a kind of safe, fire-retardant, excellent heat resistance, the simple fire tetardant no-halogen epoxy resin glue of preparation technology and purposes.
For achieving the above object, take following technical scheme: a kind of halogen-free flameproof epoxy glue solution is characterized in that the mixture by solution A and solution B.
Wherein solution A is made up of contain triazine ring structure compound, organic acid and the water of general formula (1) expression.
R wherein
1Expression alkyl, phenyl, fragrant phenyl or N (CH
2OR
2)
2, be preferably phenyl and N (CH
2OR
2)
2
R
2Expression hydrogen atom, straight or branched alkyl are preferably methyl and butyl.
Wherein organic acid is to the acid of methylbenzene semi-annular jade pendant, oxalic acid, formic acid etc., is preferably oxalic acid and to the acid of methylbenzene semi-annular jade pendant.The organic acid consumption is generally the 0.005-5wt.% that contains the triazine ring compound, is preferably 0.01-2wt.%; The consumption of water is generally the 0.1-20wt.% that contains the triazine ring compound, is preferably 0.1-5wt.%.
Wherein solution B is by Resins, epoxy, solidifying agent, coupling agent, curing catalyst, fire retardant and solvent composition.
Described Resins, epoxy comprises: phosphorous epoxy resin, be preferably contain annular phosphate group (as following formula 2-5) and contain phosphine structure (as following formula 6-7) phosphorous epoxy resin:
Or general commercial Resins, epoxy such as bisphenol type epoxy, Bisphenol F type epoxy, bisphenol S type epoxy, biphenyl type epoxy, naphthalene type epoxy, ortho-cresol type phenolic aldehyde epoxy, phenol type phenolic aldehyde epoxy, bisphenol A-type phenolic aldehyde epoxy.The use of above-mentioned Resins, epoxy is not particularly limited, as required also can be from wherein several mixing uses.
Described solidifying agent can use all materials well known in the art.Particularly: aromatic amine such as mphenylenediamine, Ursol D, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide, 4,4 '-diamino diphenyl sulfone etc., phenolic solidifying agent such as phenol molded lines resol, cresols molded lines resol and bisphenol A-type linear phenolic resin, and Dyhard RU 100, cyanurotriamide modified novolac phenolic aldehyde etc.Above-mentioned solidifying agent can be used alone, but also also mix together.The epoxy equivalent (weight) equivalent adding that the usage quantity of described solidifying agent is preferably total with Resins, epoxy.
Described coupling agent can use all materials well known in the art.Be preferably silane coupling agent, as γ-epoxy silanes such as Racemic glycidol oxygen propyl trimethoxy silicane, perhaps N-phenyl-aminosilanes such as gamma-amino propyl trimethoxy etc.
Described curing catalyst can use all materials well known in the art.Be preferably glyoxaline compounds such as glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and triphenyl phosphorus etc.
Described fire retardant uses all materials well known in the art, is preferably hydrated metal oxide, as aluminium hydroxide, magnesium hydroxide and nitrogenous or phosphorus type flame retardant, as melamine derivative, phosphoric acid ester derivant, ammonium polyphosphate.
Described solvent is: dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl ethyl ketone, acetone, pimelinketone, Propylene Glycol Dimethyl Ether etc., these solvents of tetrahydrofuran (THF) can use separately also and can mix use.
The preparation method's of fire tetardant no-halogen epoxy resin glue provided by the invention feature is: prepare described solution A, and make it to mix, be generally colourless viscous liquid; Preparing described solution B, is Resins, epoxy, solidifying agent or curing catalyst to be dissolved in the solvent mix, and is generally transparent and homogeneous solution.Then solution A and solution B are directly mixed under stirring and heating condition.The consumption that wherein contains the triazine structure compound is the 1-50wt.% of solution B solid content, is preferably 5-30wt.%, and mixing temperature is 20-100 ℃, is preferably 40-80 ℃, and churning time is 1-24 hour, is preferably 1-6 hour.
When using fire retarding epoxide resin glue provided by the invention to use as the sealing resin of sealing material, can be as required, in the mixture of solution A and B, add releasing agent, tinting material, anti-stressed agent or inorganic filler etc., these materials can use all materials well known in the art, list no longer one by one.Mixture should be vacuumized then and eliminate moisture and solvent.Solidify according to different forming methods and program curing, be not particularly limited.
Fire retarding epoxide resin glue provided by the invention can also be as the making of veneer sheet.After the fire-retarded epoxy resin glue removed moisture, adding solvent again and be mixed with the epoxy resin adhesive liquid that solid content is 40-85%, is strongthener with the alkali-free glass cloth, by impregnation, semicure and heat pressing process compacting, obtain woven fiber glass enhanced epoxy matrix composite, i.e. veneer sheet.Wherein said solvent is toluene, dimethylbenzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl ethyl ketone, acetone and pimelinketone etc., and these solvents can use separately also can mix use.
Remarkable advantage of the present invention and effect:
The present invention is a nitrogenous source with the triaizine compounds of height alkyl etherificate, prepared fire tetardant no-halogen epoxy resin glue nitrogenous, the phosphorus ignition-proof element by simple solution blending mode (being called the hydridization method), when improving flame retardant resistance and thermostability, greatly reduced the phosphorus consumption, can be used as the matrix resin of sealing material and veneer sheet in the electric field.
Embodiment
Embodiment 1:
Solution A: height methyl-etherified melamine formaldehyde resin (HM
3, commercially available product) and 0.42g, oxalic acid 0.003g and water (0.042g) mixes at normal temperatures; Solution B is that (solvent is a tetrahydrofuran (THF) to bisphenol A type epoxy resin, mixes under the normal temperature for E51,0.52mol/100g) 2.0g, phosphorous phenol type novolac epoxy 3.0g, the linear phenolic aldehyde 3.0g of solidifying agent, silane coupling agent (KH560) 0.2g.A and B are mixed under 60 ℃ of conditions, stir and obtain clear solution.Except that desolvating, get transparent viscous solution in 60 ℃ of following vacuum-dryings.Be cured according to 100 ℃/1 hour+130 ℃/1 hour+185 ℃/2 hours, obtain the transparent cured thing.
Embodiment 2:
Solution A: height methyl-etherified melamine formaldehyde resin (HM
3, commercially available product) and 0.90g, oxalic acid 0.009g and water (0.09g) mixes at normal temperatures; Solution B is with embodiment 1.Other step is with embodiment 1.
Embodiment 3:
Solution A: height methyl-etherified melamine formaldehyde resin (HM
3, commercially available product) 2.0g, methylbenzene semi-annular jade pendant acid 0.02g and water (0.2g) are mixed at normal temperatures; Solution B is with embodiment 1.Other step is with embodiment 1.
Embodiment 4:
Solution A: height methyl-etherified melamine formaldehyde resin (HM
3, commercially available product) 3.43g, methylbenzene semi-annular jade pendant acid 0.034g and water (0.34g) are mixed at normal temperatures; Solution B is with embodiment 1.Other step is with embodiment 1.
Embodiment 5:
Solution A: height methyl-etherified melamine formaldehyde resin (HM
3, commercially available product) 5.33g, methylbenzene semi-annular jade pendant acid 0.053g and water (0.53g) are mixed at normal temperatures; Solution B is with embodiment 1.Other step is with embodiment 1.
Comparative example 1 ':
Solution B obtains cured article according to solidifying according to 100 ℃/1 hour+130 ℃/1 hour+185 ℃/2 hours among the embodiment 1.
The correlated results of the foregoing description is listed in table 1:
Table 1
Embodiment 6:
Solution A: height methyl-etherified melamine formaldehyde resin (HM
3, commercially available product) 4.2g, methylbenzene semi-annular jade pendant acid 0.04g and water (0.42g) are mixed at normal temperatures; Solution B is the linear phenolic aldehyde 30g of phosphorous ortho-cresol type novolac epoxy 40g, bisphenol A type epoxy resin 10g, solidifying agent, silane coupling agent (KH560) 0.2g, and solvent is an acetone, mixes under the normal temperature.A and B are mixed under 60 ℃ of conditions, stir and obtain clear solution.Except that desolvating and moisture, get transparent viscous solution in 60 ℃ of following vacuum-dryings.Add butanone and be made into the glue that solid content is 60wt.%.
Embodiment 7:
Solution A: height methyl-etherified melamine formaldehyde resin (HM
3, commercially available product) 9.0g, methylbenzene semi-annular jade pendant acid 0.09g and water (0.9g) are mixed at normal temperatures; Solution B is the linear phenolic aldehyde 30g of phosphorous phenol type novolac epoxy 35g, bisphenol A type epoxy resin 15g, solidifying agent, silane coupling agent (KH560) 0.2g, and solvent is an acetone, mixes under the normal temperature.Other step is with embodiment 6.
Embodiment 8:
Solution A: height methyl-etherified melamine formaldehyde resin (HM
3, commercially available product) 20g, methylbenzene semi-annular jade pendant acid 0.2g and water (2.0g) are mixed at normal temperatures; Solution B is with embodiment 7.Solution A and solution B mix final vacuum and remove moisture, add acetone then, are made into the glue that solid content is 55wt.%.
Embodiment 9:
Solution A: height methyl-etherified melamine formaldehyde resin (HM
3, commercially available product) 34g, methylbenzene semi-annular jade pendant acid 0.34g and water (3.4g) are mixed at normal temperatures; Solution B is phosphorous phenol type novolac epoxy 20g, bisphenol A type epoxy resin 30g, lacquer resin 30g, silane coupling agent (KH560) 0.2g, and solvent is an acetone, mixes under the normal temperature.Other step is with embodiment 9.
To the foregoing description 6-9 by behind the formulated glue, with alkali-free 7628 type woven fiber glass is strongthener, (the prepreg solid content is controlled at 38～45wt.%), in 175 ℃ of compacting 2.0h, obtains woven fiber glass enhanced epoxy matrix composite in the vacuum hotpressing machine by impregnation, semicure.The naturally cooling depanning obtains the sample of long 130mm * wide * 13mm * thick 1.6mm after cutting out, carry out tests such as oxygen index and vertical combustion, utilizes the second-order transition temperature (T of DSC method test cured article
g), utilization TMA method is measured thermal linear expansion coefficient.The results are shown in Table 2.By the result of embodiment 6-9 as seen, they all have excellent heat resisting (high T
g), high initial heat decomposition temperature, low coefficient of linear thermal expansion and excellent flame.
Table 2
Claims (10)
1. fire tetardant no-halogen epoxy resin glue, it is characterized in that mixed by solution A and solution B, wherein solution A is made up of contain triazine structure compound, organic acid and the water of general formula (1) expression, and solution B is by Resins, epoxy, solidifying agent, coupling agent, curing catalyst, fire retardant and solvent composition
(1) R in
1Expression alkyl, phenyl, fragrant phenyl or N (CH
2OR
2)
2R
2Expression hydrogen atom, methyl or butyl.
2. fire tetardant no-halogen epoxy resin glue according to claim 1, wherein Resins, epoxy is phosphorous epoxy resin, nitrogen-containing epoxy thermoset, halogen-free epoxy resin or the mixture of two or more Resins, epoxy arbitrarily wherein.
3. fire tetardant no-halogen epoxy resin glue according to claim 1, described solidifying agent are aromatic amine, aliphatics amine, resol class and anhydrides.
4. fire tetardant no-halogen epoxy resin glue according to claim 1, wherein coupling agent is a silane coupling agent.
5. fire tetardant no-halogen epoxy resin glue according to claim 1, wherein fire retardant is hydrated metal oxide class, nitrogenous based flame retardant, contains phosphorus type flame retardant or nitrogenous phosphorus type flame retardant.
6. the preparation method of the described halogen-free flameproof epoxy glue solution of claim 1, it is characterized in that: the consumption of contained triazine structure compound is the 1-50wt.% of solution B solid content in the described solution A, solution A and B directly mix stirring, and mixing temperature is 20-100 ℃, and churning time is 1-24 hour.
7. the application of the described fire tetardant no-halogen epoxy resin glue of claim 1 is used to make sealing material.
8. by the application of the described fire tetardant no-halogen epoxy resin glue of claim 7, it is characterized in that in the mixture of solution A and B, add releasing agent, tinting material, anti-stressed agent or inorganic filler, vacuumize after stirring and eliminate moisture and solvent, curing molding.
9. the application of the described fire tetardant no-halogen epoxy resin glue of claim 1 is used for the making layer pressing plate.
10. press the application of the described fire tetardant no-halogen epoxy resin glue of claim 9, it is characterized in that vacuumizing in the mixture with solution A and B eliminate moisture and solvent after, add solvent again and be mixed with the epoxy resin adhesive liquid that solid content is 40-85%, with the alkali-free glass cloth is strongthener, by obtaining veneer sheet after impregnation, semicure and the hot pressing.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206401A (en) * | 2011-04-14 | 2011-10-05 | 北京理工大学 | Halogen-free flame-retardant epoxy resin composition and preparation method thereof |
| CN102276961A (en) * | 2011-07-22 | 2011-12-14 | 苏州生益科技有限公司 | Halogen-free phosphorus-free epoxy resin composition, and semi-curing sheet and laminated sheet manufactured thereby |
| CN108215247A (en) * | 2018-01-11 | 2018-06-29 | 惠州市纵胜电子材料有限公司 | A kind of preparation method of moulded board |
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Assignee: Kingboard Chemical Holdings Ltd. Assignor: Zhejiang University Contract fulfillment period: 2008.8.1 to 2013.7.31 contract change Contract record no.: 2009320001060 Denomination of invention: Fire tetardant no-halogen epoxy resin glue and its prepn process and use Granted publication date: 20080709 License type: Exclusive license Record date: 2009.7.7 |
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