CN101307170A - Fire retardant phosphorus-containing epoxy powder composition - Google Patents
Fire retardant phosphorus-containing epoxy powder composition Download PDFInfo
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- CN101307170A CN101307170A CNA2008100538004A CN200810053800A CN101307170A CN 101307170 A CN101307170 A CN 101307170A CN A2008100538004 A CNA2008100538004 A CN A2008100538004A CN 200810053800 A CN200810053800 A CN 200810053800A CN 101307170 A CN101307170 A CN 101307170A
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Abstract
The invention relates to a fire-retardant phosphoric epoxy powder composition, which is an epoxy powder composition prepared by matching solid phosphoric epoxy resin, general solid epoxy resin, curing agent, pigment, filler, fire retardant and so on. The composition prepared does not contain halogenated and antimonic fire retardant, red phosphorus and so on, can meet the fire-retardant standard of UL94 V0, has superior electroinsulating property, and is widely applied in the electronic component packaging field. The fire-retardant phosphoric epoxy powder composition synthesizes solid phosphoric epoxy resin which is then applied to an epoxy powder system, thereby the problem that liquid phosphoric epoxy resin in the prior art can not be applied to the powder system due to the technological requirements is solved and the technical support is provided for converting the prior halogenated and antimonic fire-retardant system into non-halogenation.
Description
Technical field
The invention belongs to the electronic package field, especially a kind of fire retardant phosphorus-containing epoxy powder composition.
Background technology
Resins, epoxy is a kind of application thermosetting resin more widely, has performances such as excellent physical and mechanical properties, electrical insulation properties, resistance to chemical reagents and low temperature contraction, is widely used in fields such as coating, tackiness agent.The epoxy powder composition that cooperates other suitable color stuffing preparation with solid epoxy resin and solidifying agent; inherited the series of advantages of Resins, epoxy; good processing performances such as excellent thermotolerance, bounding force, solvent resistance, electric insulating quality are arranged; cost is low, is widely used in sealing and the protection field of electron device.
The limiting oxygen index(LOI) of coventional type Resins, epoxy (LOI) is about 19.8, and the volume fraction of oxygen is 21% in the air, and therefore simple Resins, epoxy is than being easier to incendiary.The flame retardant resistance that the employed epoxy powder of general electric elements is sealed material will reach other requirement of UL94V0 level in American insurance merchant laboratory (UL).
Usually, satisfy the requirement of UL94V0 flame-retarded technology in order to ensure this epoxy composite, generally need and contain antimony fire retardant etc. with halogen-containing fire retardant such as decabromodiphenyl oxide, decabromodiphenyl etc. and combine use, this system is less expensive and flame retarding efficiency is very high.But antimonous oxide has been listed in carcinogenic substance at present, the Resins, epoxy that contains halogen can produce in combustion processes has corrosive halogen free radical and hydrogen halide, and the aryl compound of high bromine content more can produce the bromination furans and the bromination Dioxins compound of severe toxicity, has a strong impact on HUMAN HEALTH and harm environment.On February 13rd, 2003, European Union formally announces " about waste electronic andelectrical equipment " (being called for short WEEE) and " using some objectionable impurities about restriction in electronic electric equipment " (being called for short RoHS) two parts of instructions, declaration forbids using Polybrominated biphenyl (PBB) and Poly Brominated Diphenyl Ethers (PBDE) from July 1st, 2006 in electronic electric equipment.
Basic and above-mentioned factor, in today that the environment cry grows to even greater heights, the development and application of novel halogen-free flame-retardant agent seems more and more urgent.At present, more feasible scheme has following several: (1). and utilize phosphorus nitrogen synergistic to realize the good flame effect.Promptly by phosphorus flame retardant addition type or response type, and with contain nitrogen combustion inhibitor and cooperate.(2). utilize the fire-retardant Resins, epoxy of intrinsic to realize that essence is fire-retardant, with phenol-biphenylene type Resins, epoxy and phenol-p-Xylol type Resins, epoxy is that the phenol-aralkyl-type epoxy resin of representative is development in recent years one of fire-retarded epoxy resin the most rapidly, but this kind Resins, epoxy is because the special cost of structure is very high, and this type of more special Resins, epoxy is only produced by several companies of Japan at present.(3). utilize various additive flame retardants and reactive flame retardant to be used, to reach good flame-retardant effect.
Phosphorous reaction-type flame-retarding Resins, epoxy is incorporated into phosphoric in the molecular chain, every performance is better than direct addition type, because the fire retardant of this response type is not easy to move out, good, less with the consistency of matrix to the mechanical property influence of system, become the research focus of Chinese scholars in recent years in view of above-mentioned various advantages.
CN1861682A discloses the halogen-free flameproof epoxy composite of a kind of liquid phosphorous epoxy resin, nbr carboxyl terminal modified epoxy, phenolic mixed curing agent composition, this material main body is the halogen-free flameproof epoxy glue solution, is mainly used in use in printed circuit board copper-clad laminate field.CN1974658A discloses a kind of manufacture method of halogen-free flameproof glue, mainly contains the solution A of triazines solidifying agent and the solution B of liquid phosphorous epoxy and phenolic curing agent thereof and forms, and can be applied in sealing material and the veneer sheet.
By above patent as can be known, present non-halogen scheme mainly concentrates on nitrogen phosphorus synergistic aspect, and is mainly used in semiconductor sealing material such as printed circuit board (PCB), and phosphorous epoxy resin exists with liquid form mostly, because technological requirement, be difficult to it is used among the solid state powder system.In the product of present domestic bigger Resins, epoxy manufacturers, also there is not the solid-state Halogenless fire retarded epoxy resin product that powder systems is used that is applicable to.Therefore, except liquid phosphorous epoxy resin was applied to Halogen copper-clad plate and printed circuit board industry, epoxy powder was sealed the Halogen industrialization of material and must be sought in the preparation production and application of effective fire-retardant approach and solid-state phosphorous epoxy resin.Can learn that by above-mentioned situation at present the halogen-free, flame-retardant composition of material of study on the industrialization seal to(for) epoxy powder yet there are no report.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of fire retardant phosphorus-containing epoxy powder composition is provided, said composition adopts solid-state phosphorous epoxy resin to cooperate with nitrogenous class solidifying agent and the nitrogenous based flame retardant of addition type and obtains, solved liquid phosphorous epoxy resin in the prior art because manufacturability requires to be applied in the problem of powder systems, synthesized solid-state phosphorous epoxy resin, and be applied to the epoxy powder system, for existing halogen antimony flame-retardant system provides technical support to non-halogen switching.
The objective of the invention is to be achieved through the following technical solutions:
A kind of fire retardant phosphorus-containing epoxy powder composition, its material and parts by weight thereof that constitute said composition are respectively:
Common solid-state bisphenol A type epoxy resin: 0～26 weight part
Solid-state phosphorous epoxy resin: 20～50 weight parts
Solidifying agent: 1～8 weight part
Promotor: 0～0.5 weight part
Filler: 30～60 weight parts
Fire retardant: 0～10 weight part
Pigment: 0.1～0.5 weight part.
And the softening temperature of described common solid-state bisphenol A type epoxy resin is 50 ℃～130 ℃, as among E12, E14, CYD011, the CYD012 one or several, and the loop-like epoxy resins kind that limits of non-above trade(brand)name.
And the phosphorus content of described solid-state phosphorous epoxy resin is 1.0%～7.6%, and the step of its synthetic method is:
(1). the Resins, epoxy that will be modified join have Controllable Temperature, vacuum-pumping and can feeding in the reactor of nitrogen, be heated to 100 ℃～180 ℃ and make the abundant fusion of the Resins, epoxy that is modified, be evacuated to the relative vacuum degree afterwards to reach-0.075MPa～-0.099MPa;
(2). add phosphorous-containing monomers and make it and the abundant fusion of Resins, epoxy that is modified, add catalyzer and also feed nitrogen protection, slowly be warming up to 130 ℃～190 ℃, insulation reaction 1.0h～6.0h;
(3). cooling discharge, the cooling compressing tablet can obtain the solid-state phosphorous epoxy resin finished product of yellowish transparent sheet-like.
And, the described Resins, epoxy that is modified is bisphenol A type epoxy resin such as E51, E54, E44, CYD127, CYD128, NPEL127, NPEL128, Epiclon850S, or bisphenol f type epoxy resin such as YDF-162, YDF-165, YDF-170, YDF-175, Epiclon 830, Epiclon 830S, or o-cresol formaldehyde epoxy resin such as CYDCN-100, CYDCN-200, N-670, N-665, NPCN703, NPCN704, CNE195XL2, CNE195XL4, CNE195XL5, or novolac epoxy such as YDPN-631, YDPN636, CYDPN-048, CYDPN-051, NPPN-631, NPPN-638S, PNE-177, PNE-177H, DEN431, DEN438, DEN439, and the non-above loop-like epoxy resins kind that limits.
And described phosphorous-containing monomers is 9, the 10-dihydro-9-oxy is assorted-and the assorted phenanthrene of 10-phosphine-10-oxide compound (DOPO) and derivative thereof such as ODOPB, ODOPM, DOPOMA, DDP, DMSA.
And, adding the catalyzer that is added behind the phosphorous-containing monomers at the Resins, epoxy that is modified is phosphine class material such as triphenylphosphine, perhaps amine substance such as thricyclohexyl amine, dimethyl benzylamine, triphenylamine, triethylamine, Tributylamine, pyridine, quinoline, imidazoles, glyoxal ethyline, 2-phenylimidazole, tetrahydroglyoxaline, perhaps quaternary amines material, the material of phosphorus-containing groups, the addition of catalyzer is 0.01%～5.00% of Resins, epoxy and the phosphorous-containing monomers gross weight that be modified, and the addition of optimization is 0.02%～2.00%.
And, described solidifying agent is anhydrides material such as phthalic anhydride, Tetra Hydro Phthalic Anhydride, trimellitic acid 1,2-anhydride, pyromellitic dianhydride, and nitrogenous amine curing agent is as 4,4 '-diaminodiphenylmethane, to ADP sulfone, Dyhard RU 100, hydrazides class material such as adipic dihydrazide, sebacic dihydrazide, and imidazole curing agent such as imidazoles, glyoxal ethyline, 2-phenylimidazole.
And described promotor is quaternary phosphine salts substances or quaternary ammonium salt material, perhaps imidazoles promotor such as imidazoles, glyoxal ethyline, 2-phenylimidazole.
And described filler is crystalline silica, fused silica, talcum powder, lime carbonate, fused silica powder.
And described fire retardant is trimeric cyanamide or melamine cyanurate and aluminium hydroxide or magnesium hydroxide.
Advantage of the present invention and positively effect are:
(1). synthesized several dissimilar solid-state high phosphorus content Resins, epoxy among the present invention, phosphorus content is 1.0%～7.6%, and synthesis technique is simple, and performance index are stable, conform with the application requiring that solid-state epoxy powder is sealed material;
(2). fire retardant phosphorus-containing epoxy powder composition of the present invention adopts the solid-state high phosphorus content Resins, epoxy that is suitable for powder systems and contains nitrogen combustion inhibitor, the fire retardant of nitrogen-containing hardener and addition type cooperates, prepared the epoxy powder that can reach the fire-retardant requirement of UL94V0 level and sealed material, other performance is all than more excellent.Synthesized solid-state phosphorous epoxy resin, and be applied to the epoxy powder system, solved liquid phosphorous epoxy resin in the prior art because manufacturability requires to be applied in the problem of powder systems, for existing halogen antimony flame-retardant system provides technical support to non-halogen switching.
(3). in fire retardant phosphorus-containing epoxy powder composition of the present invention, do not use virose Sb system fire retardant and the halogenated flame retardant that is easy to generate the carinogenicity material, there are not to adopt the red phosphorus series product of moving out easily and influencing product colour, do not use the heavy metal substance of Rohs management and control, meet the requirement of environmental protection electronic material more, the renewal product that belongs to existing halogen flame retardant system has vast market prospect and potentiality in the application in future and development.
Embodiment
The invention will be further described below in conjunction with specific embodiment, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
Some performance index measuring methods described in the present invention are as follows:
(1). epoxy equivalent (weight): measure according to the method described in the GB4612-84 " mensuration of epoxy compounds epoxy equivalent (weight) ".
(2). melt viscosity: use Brookfield (Brookfield) cone-and-plate viscometer to measure the melt viscosity of synthetic phosphorous epoxy resin under different temperature, general temperature is 150 ℃ or 180 ℃.
(3). softening temperature: measure according to the method described in the GB12007.6-89 " Resins, epoxy softening point measurement method ring and ball method ".
(4). flame retardant resistance is measured: with reference to the testing vertical flammability method among the UL94 " the flammable performance test of equipment and device component material ", determine the flame retardant rating of matrix material.Batten is of a size of: long 125 ± 5mm, wide 13.0 ± 0.5mm, thickness 1.5 ± 0.2mm.
(5). horizontal flow: the measuring method according to the horizontal flow among the GB6554-86 " electric insulation coating powders test method " detects, and design temperature is 150 ℃.
(6). gel time: according to the measuring method of the gel time among the GB6554-86 " electric insulation coating powders test method ", adopt the method for drawing a circle to measure the gel time of epoxy powder, design temperature is 160 ℃.
Essential substance in the fire retardant phosphorus-containing epoxy powder composition of the present invention---details are as follows for solid-state high phosphorus content Resins, epoxy synthetic main component:
(1). phosphorous-containing monomers:
1. .9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound, be called for short DOPO, molecular weight 216, phosphorus content 14.33%;
2. .10-(2, the 5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, DOPO-HQ is called for short ODOPB, molecular weight 324, phosphorus content 9.55%;
3. methyl oneself ring-6-ketone of (1, the 2)-oxygen phospha of .[(6-oxygen-(6H)-dibenzo-(CE))] the Succinic Acid solid, abbreviation DDP, molecular weight 346, phosphorus content 8.96%.
The molecular formula of above-mentioned substance is as follows:
(2). Resins, epoxy is modified:
1.. the o-cresol formaldehyde epoxy resin CYDCN-100 of Resins, epoxy division department of Ba Ling petrochemical complex limited liability company, epoxy equivalent (weight) 195～210g/eq;
2.. the novolac epoxy YDPN631 of national capital chemical industry (Kunshan) company limited, epoxy equivalent (weight) is 165～185g/eq.
3.. the liquid bisphenol A type Resins, epoxy CYD128 of Resins, epoxy division department of Ba Ling petrochemical complex limited liability company, epoxy equivalent (weight) 184～194g/eq;
4.. the liquid bisphenol F type Resins, epoxy YDF-170 of national capital chemical industry (Kunshan) company limited, epoxy equivalent (weight) is 160～180g/eq.
The synthetic method of solid-state high phosphorus content Resins, epoxy provides 6 synthetic embodiment among the present invention, and the solid-state high phosphorus content Resins, epoxy finished product of institute's synthetic marks A, B, C, D, E, F respectively.
Synthetic embodiment 1: the preparation of phosphorous epoxy resin A
Be equipped with electric heater, temperature regulator, electric mixing device, thermometer, nitrogen conduit, vacuumizing and add 144.25g CYDCN-100 in the 500ml four-hole boiling flask of water distilling apparatus, start whipping appts after feeding nitrogen and being heated to 150 ℃, be evacuated to-0.099MPa, remove fugitive constituent residual in the Resins, epoxy; Add 55.75g DOPO then, treat slowly to be warming up to 150 ℃ again after the complete fusion of DOPO powder, add the 0.20g triphenylphosphine as catalyzer, after mixing, feed nitrogen protection, insulation reaction was poured out compressing tablet with melt after 4.0 hours.Finally obtain the transparent lurid chip solid that has a little, be solid-state phosphorous epoxy resin A.
The testing performance index of phosphorous epoxy resin A is as follows: theoretical phosphorus content 4.0%; Theoretical epoxy equivalent (weight) 422g/eq, actual measurement epoxy equivalent (weight) 462g/eq; 114 ℃ of softening temperatures; Melt viscosity in the time of 180 ℃ is 1330mPa.s.
Synthetic embodiment 2: the preparation of phosphorous epoxy resin B
Be equipped with electric heater, temperature regulator, electric mixing device, thermometer, nitrogen conduit, vacuumizing and add 168.51g YDPN631 in the 500ml four-hole boiling flask of water distilling apparatus, start whipping appts after feeding nitrogen and being heated to 150 ℃, be evacuated to-0.099MPa, remove fugitive constituent residual in the Resins, epoxy.Add 121.07g DOPO then, treat slowly to be warming up to 150 ℃ again after the complete fusion of DOPO powder, add the 0.29g triphenylphosphine as catalyzer, after mixing, feed nitrogen protection, insulation reaction was poured out compressing tablet with melt after 3.5 hours.Finally obtain the almost transparent xanchromatic chip solid that has slightly, be solid-state phosphorous epoxy resin B.
The testing performance index of phosphorous epoxy resin B is as follows: theoretical phosphorus content 6.0%; Theoretical epoxy equivalent (weight) 771g/eq, actual measurement epoxy equivalent (weight) 813g/eq; 112 ℃ of softening temperatures; Melt viscosity in the time of 150 ℃ is 5600mPa.s.
Synthetic embodiment 3: the preparation of phosphorous epoxy resin C
Be equipped with electric heater, temperature regulator, electric mixing device, thermometer, nitrogen conduit, vacuumizing and add 231.5g CYD128 in the 500ml four-hole boiling flask of water distilling apparatus, start whipping appts after feeding nitrogen and being heated to 140 ℃, be evacuated to-0.099MPa, remove fugitive constituent residual in the Resins, epoxy.Add 264.6g DOPO then, treat slowly to be warming up to 150 ℃ again after the complete fusion of DOPO powder, feed nitrogen protection, insulation reaction was poured out compressing tablet with melt after 6.0 hours.Finally obtain almost transparent chip solid, be solid-state phosphorous epoxy resin C.
Phosphorous epoxy resin C testing performance index is as follows: theoretical phosphorus content 7.6%; The theoretical epoxy equivalent (weight) of this system is zero, and this resin can be used as the addition type phosphonium flame retardant and comes usefulness, and is relatively good with the consistency of epoxy systems; 86 ℃ of softening temperatures; Melt viscosity in the time of 150 ℃ is 590mPa.s.
Synthetic embodiment 4: the preparation of phosphorous epoxy resin D
164.74g CYD128 joined be equipped with electric heater, temperature regulator, electric mixing device, thermometer, nitrogen conduit, vacuumize in the 500ml four-hole boiling flask of water distilling apparatus, start whipping appts after feeding nitrogen and being heated to 140 ℃, be evacuated to-0.099MPa, remove fugitive constituent residual in the Resins, epoxy.Add 75.25g ODOPB then in four-hole boiling flask, treat the complete fusion of ODOPB powder after, add the 0.18g triphenylamine as catalyzer, mix the back and feed nitrogen protection, slowly be warming up to 170 ℃, insulation reaction was poured out compressing tablet with melt after 4.0 hours.Finally obtain the almost transparent xanchromatic chip solid that has a little, be solid-state phosphorous epoxy resin D.
Phosphorous epoxy resin D testing performance index is as follows: theoretical phosphorus content 3.0%; Theoretical epoxy equivalent (weight) is 590g/eq, and actual epoxy equivalent (weight) is 653g/eq; 117 ℃ of softening temperatures; Melt viscosity in the time of 180 ℃ is 2630mPa.s.
Synthetic embodiment 5: the preparation of phosphorous epoxy resin E
196.54g YDF-170 joined be equipped with electric heater, temperature regulator, electric mixing device, thermometer, nitrogen conduit, vacuumize in the 500ml four-hole boiling flask of water distilling apparatus, start whipping appts after feeding nitrogen and being heated to 140 ℃, be evacuated to-0.099MPa, remove fugitive constituent residual in the Resins, epoxy.Add 89.78g ODOPB then in four-hole boiling flask, treat the complete fusion of ODOPB powder after, add the 0.10g triphenylamine as catalyzer, mix the back and feed nitrogen protection, slowly be warming up to 170 ℃, insulation reaction was poured out compressing tablet with melt after 4.0 hours.Finally obtain the almost transparent xanchromatic chip solid that has a little, be solid-state phosphorous epoxy resin E.
Phosphorous epoxy resin E testing performance index is as follows: theoretical phosphorus content 3.0%; Theoretical epoxy equivalent (weight) is 492g/eq, and actual epoxy equivalent (weight) is 535g/eq; 101 ℃ of softening temperatures; Melt viscosity in the time of 150 ℃ is 4000mPa.s.
Synthetic embodiment 6: the preparation of phosphorous epoxy resin F
In being equipped with electric heater, temperature regulator, electric mixing device, thermometer, nitrogen conduit, vacuumizing and add 253.0g CYD128 in the 500ml four-hole boiling flask of water distilling apparatus, start whipping appts after feeding nitrogen and being heated to 150 ℃, be evacuated to-0.099MPa, remove fugitive constituent residual in the Resins, epoxy.Progressively add 97.91g DDP in four-hole boiling flask, insulation reaction was poured out compressing tablet with melt after 1.0 hours.Finally obtain the yellow transparent chip solid, be solid-state phosphorous epoxy resin F.
Phosphorous epoxy resin F testing performance index is as follows: theoretical phosphorus content 2.5%; Theoretical epoxy equivalent (weight) is 454g/eq, and actual epoxy equivalent (weight) is 492g/eq; Melt viscosity in the time of 150 ℃ is 910mPa.s.
Adopt the prepared fire retardant phosphorus-containing epoxy powder composition of the above-mentioned solid-state phosphorous epoxy resin of institute's synthetic, the present invention provides 10 embodiment altogether:
Embodiment 1: prepare epoxy powder composition according to following material and ratio thereof:
Resins, epoxy E12 22.75 weight parts
Phosphorous epoxy resin A 27.75 weight parts
Tetra hydro Phthalic anhydride 4.63 weight parts
Imidazoles 0.10 weight part
Silicon powder 35.43 weight parts
Melamine cyanurate (MCA) 9.10 weight parts
Phthalocyanine blue 0.24 weight part
Join in the miniature high-speed mixing equipment after the accurate weighing of above-mentioned substance, after fully mixed, use twin screw extruder to melt extrude.Through pulverizing, cross 100 eye mesh screens behind the melt extrusion process cooling compressing tablet, discard the upper strata coarse fodder and can obtain fire retardant phosphorus-containing epoxy powder composition.Then, the epoxy powder that obtains can be carried out performance test.Process mould press strip is made the batten of certain size, behind overcuring, can carry out flame retardant resistance and measure.
The horizontal flow rate of this fire retardant phosphorus-containing epoxy powder composition that records is 12%, and gel time is 174s, and the flame retardant rating of UL94 fire retardancy test evaluation is the V0 level.
Embodiment 2: prepare epoxy powder composition according to following material and ratio thereof:
Phosphorous epoxy resin A 47.73 weight parts
Tetra hydro Phthalic anhydride 6.25 weight parts
Imidazoles 0.15 weight part
Silicon powder 45.68 weight parts
Phthalocyanine blue 0.19 weight part
Above material is mixed, and the operating method processing according to embodiment 1 obtains fire retardant phosphorus-containing epoxy powder composition.
The horizontal flow rate of this fire retardant phosphorus-containing epoxy powder composition that records is 28%, and gel time is 53s, and the flame retardant rating of UL94 fire retardancy test evaluation is the V0 level.
Embodiment 3,4: prepare epoxy powder composition according to following material and ratio thereof:
Table 1
| Embodiment 3 | Embodiment 4 | |
| Resins, epoxy E12 | 22.04 weight part | 23.08 weight part |
| Phosphorous epoxy resin B | 27.04 weight part | 28.08 weight part |
| Dyhard RU 100 (DICY) | 1.96 weight part | 2.05 weight part |
| The 2-phenylimidazole | 0.50 weight part | 0.42 weight part |
| Melamine cyanurate | 0.00 weight part | 4.62 weight part |
| Silicon powder | 48.20 weight part | 41.51 weight part |
| Phthalocyanine blue | 0.26 weight part | 0.24 weight part |
Obtain embodiment 3 and 4 according to the material proportioning in the table 1, above material is processed according to the mode of embodiment 1, obtains fire retardant phosphorus-containing epoxy powder composition.
The horizontal flow rate of the epoxy powder composition that records among the embodiment 3 is 51%, and gel time is 180s, and the flame retardant rating of UL94 fire retardancy test evaluation is the V0 level.Record among the embodiment 4 the horizontal flow rate of epoxy powder composition be 48%, gel time is 127s, the flame retardant rating of UL94 fire retardancy test evaluation is the V0 level.
Embodiment 5: prepare epoxy powder composition according to following material and ratio thereof:
Resins, epoxy E12 22.78 weight parts
Phosphorous epoxy resin B 27.78 weight parts
4,4 '-diaminodiphenylmethane (DDM), 3.44 weight parts
Silicon powder 41.20 weight parts
Melamine cyanurate 4.56 weight parts
Phthalocyanine blue 0.24 weight part
Above material is mixed, and the operating method processing according to embodiment 1 obtains fire retardant phosphorus-containing epoxy powder composition.
The horizontal flow rate of this fire retardant phosphorus-containing epoxy powder composition that records is 29%, and gel time is 153s, and the flame retardant rating of UL94 fire retardancy test evaluation is the V0 level.
Embodiment 6,7: prepare epoxy powder composition according to following material and ratio thereof:
Table 2
| Embodiment 6 | Embodiment 7 | |
| Resins, epoxy E12 | 0.00 weight part | 23.19 weight part |
| Phosphorous epoxy resin B | 47.09 weight part | 28.19 weight part |
| Adipic dihydrazide (AADH) | 1.85 weight part | 2.04 weight part |
| The 2-phenylimidazole | 0.08 weight part | 0.09 weight part |
| Melamine cyanurate | 0.00 weight part | 4.64 weight part |
| Silicon powder | 50.76 weight part | 41.61 weight part |
| Phthalocyanine blue | 0.22 weight part | 0.24 weight part |
Obtain embodiment 6 and 7 according to the material proportioning in the table 2, above material is processed according to the mode of embodiment 1, obtains fire retardant phosphorus-containing epoxy powder composition.The horizontal flow rate of the epoxy powder composition that records among the embodiment 6 is 70%, and gel time is 172s, and the flame retardant rating of UL94 fire retardancy test evaluation is the V0 level.The horizontal flow rate of the epoxy powder composition that records among the embodiment 7 is 33%, and gel time is 328s, and the flame retardant rating of UL94 fire retardancy test evaluation is the V0 level.
Embodiment 8: prepare epoxy powder composition according to following material and ratio thereof:
Phosphorous epoxy resin D 48.96 weight parts
Tetra hydro Phthalic anhydride 3.76 weight parts
Imidazoles 0.12 weight part
Silicon powder 42.12 weight parts
Melamine cyanurate 4.80 weight parts
Phthalocyanine blue 0.24 weight part
Above material is mixed and, obtain fire retardant phosphorus-containing epoxy powder composition according to the method among the embodiment 1 through after melt extruding.The horizontal flow rate of said composition is 18%, and gel time is 94s, and the flame retardant rating of UL94 fire retardancy test evaluation is the V0 level.
Embodiment 9 prepares epoxy powder composition according to following material and ratio thereof:
Phosphorous epoxy resin E 48.43 weight parts
Tetra hydro Phthalic anhydride 4.75 weight parts
Imidazoles 0.12 weight part
Silicon powder 41.92 weight parts
Melamine cyanurate 4.54 weight parts
Phthalocyanine blue 0.24 weight part
Above material is mixed and, obtain fire retardant phosphorus-containing epoxy powder composition according to the method among the embodiment 1 through after melt extruding.The horizontal flow rate of said composition is 30%, and gel time is 163s, and the flame retardant rating of UL94 fire retardancy test evaluation is the V0 level.
Embodiment 10: prepare epoxy powder composition according to following material and ratio thereof:
Resins, epoxy E12 25.20 weight parts
Phosphorous epoxy resin C 16.80 weight parts
Dyhard RU 100 1.01 weight parts
2-phenylimidazole 0.50 weight part
Silicon powder 56.27 weight parts
Phthalocyanine blue 0.22 weight part
Above material is mixed and, obtain fire retardant phosphorus-containing epoxy powder composition according to the method among the embodiment 1 through after melt extruding.The horizontal flow rate of said composition is 45%, and gel time is 212s, and the flame retardant rating of UL94 fire retardancy test evaluation is the V0 level.
The over-all properties of all embodiment sees Table 3.
Table 3
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 |
| Horizontal flow rate (%) | 12 | 28 | 51 | 48 | 29 | 70 | 33 | 18 | 30 | 45 |
| Gel time (Sec) | 174 | 53 | 180 | 127 | 153 | 172 | 328 | 94 | 163 | 212 |
| Flame retardant resistance UL94 | V0 | V0 | V0 | V0 | V0 | V0 | V0 | V0 | V0 | V0 |
Claims (10)
1. fire retardant phosphorus-containing epoxy powder composition is characterized in that: the material and the parts by weight thereof that constitute said composition are respectively:
Common solid-state bisphenol A type epoxy resin: 0～26 weight part
Solid-state phosphorous epoxy resin: 20～50 weight parts
Solidifying agent: 1～8 weight part
Promotor: 0～0.5 weight part
Filler: 30～60 weight parts
Fire retardant: 0～10 weight part
Pigment: 0.1～0.5 weight part.
2. fire retardant phosphorus-containing epoxy powder composition according to claim 1, it is characterized in that: the softening temperature of described common solid-state bisphenol A type epoxy resin is 50 ℃～130 ℃, as among E12, E14, CYD011, the CYD012 one or several, and the loop-like epoxy resins kind that limits of non-above trade(brand)name.
3. fire retardant phosphorus-containing epoxy powder composition according to claim 1 is characterized in that: the phosphorus content of described solid-state phosphorous epoxy resin is 1.0%～7.6%, and the step of its synthetic method is:
(1). the Resins, epoxy that will be modified join have Controllable Temperature, vacuum-pumping and can feeding in the reactor of nitrogen, be heated to 100 ℃～180 ℃ and make the abundant fusion of the Resins, epoxy that is modified, be evacuated to the relative vacuum degree afterwards to reach-0.075MPa～-0.099MPa;
(2). add phosphorous-containing monomers and make it and the abundant fusion of Resins, epoxy that is modified, add catalyzer and also feed nitrogen protection, slowly be warming up to 130 ℃～190 ℃, insulation reaction 1.0h～6.0h;
(3). cooling discharge, the cooling compressing tablet can obtain the solid-state phosphorous epoxy resin finished product of yellowish transparent sheet-like.
4. fire retardant phosphorus-containing epoxy powder composition according to claim 3, it is characterized in that: the described Resins, epoxy that is modified is bisphenol A type epoxy resin such as E51, E54, E44, CYD127, CYD128, NPEL127, NPEL128, Epiclon850S, or bisphenol f type epoxy resin such as YDF-162, YDF-165, YDF-170, YDF-175, Epiclon 830, Epiclon830S, or o-cresol formaldehyde epoxy resin such as CYDCN-100, CYDCN-200, N-670, N-665, NPCN703, NPCN704, CNE195XL2, CNE195XL4, CNE195XL5, or novolac epoxy such as YDPN-631, YDPN636, CYDPN-048, CYDPN-051, NPPN-631, NPPN-638S, PNE-177, PNE-177H, DEN431, DEN438, DEN439, and the non-above loop-like epoxy resins kind that limits.
5. fire retardant phosphorus-containing epoxy powder composition according to claim 3 is characterized in that: described phosphorous-containing monomers is 9, the 10-dihydro-9-oxy is assorted-and the assorted phenanthrene of 10-phosphine-10-oxide compound (DOPO) and derivative thereof such as ODOPB, ODOPM, DOPOMA, DDP, DMSA.
6. fire retardant phosphorus-containing epoxy powder composition according to claim 3, it is characterized in that: adding the catalyzer that is added behind the phosphorous-containing monomers at the Resins, epoxy that is modified is phosphine class material such as triphenylphosphine, perhaps amine substance such as thricyclohexyl amine, dimethyl benzylamine, triphenylamine, triethylamine, Tributylamine, pyridine, quinoline, imidazoles, glyoxal ethyline, the 2-phenylimidazole, tetrahydroglyoxaline, perhaps quaternary amines material, the material of phosphorus-containing groups, the addition of catalyzer is 0.01%～5.00% of Resins, epoxy and the phosphorous-containing monomers gross weight that be modified, and the addition of optimization is 0.02%～2.00%.
7. fire retardant phosphorus-containing epoxy powder composition according to claim 1, it is characterized in that: described solidifying agent is anhydrides material such as phthalic anhydride, Tetra Hydro Phthalic Anhydride, trimellitic acid 1,2-anhydride, pyromellitic dianhydride, and nitrogenous amine curing agent is as 4,4 '-diaminodiphenylmethane, to ADP sulfone, Dyhard RU 100, hydrazides class material such as adipic dihydrazide, sebacic dihydrazide, and imidazole curing agent such as imidazoles, glyoxal ethyline, 2-phenylimidazole.
8. fire retardant phosphorus-containing epoxy powder composition according to claim 1 is characterized in that: described promotor is quaternary phosphine salts substances or quaternary ammonium salt material, perhaps imidazoles promotor such as imidazoles, glyoxal ethyline, 2-phenylimidazole.
9. fire retardant phosphorus-containing epoxy powder composition according to claim 1 is characterized in that: described filler is crystalline silica, fused silica, talcum powder, lime carbonate, fused silica powder.
10. fire retardant phosphorus-containing epoxy powder composition according to claim 1 is characterized in that: described fire retardant is trimeric cyanamide or melamine cyanurate and aluminium hydroxide or magnesium hydroxide.
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