CN101307155A - Fire retardant crosslinking agent and halogen free, non-phosphate and fire retardant epoxy resin composition - Google Patents
Fire retardant crosslinking agent and halogen free, non-phosphate and fire retardant epoxy resin composition Download PDFInfo
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- CN101307155A CN101307155A CNA2007101039901A CN200710103990A CN101307155A CN 101307155 A CN101307155 A CN 101307155A CN A2007101039901 A CNA2007101039901 A CN A2007101039901A CN 200710103990 A CN200710103990 A CN 200710103990A CN 101307155 A CN101307155 A CN 101307155A
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Abstract
The invention provides fire-retardant crosslinking agent, which does not contain halogen and phosphide, can be applied to macromolecular composite material compositions such as epoxy resin and so on, and achieves the effect of fire resistance grade V0 under the UL-94 standard. The structure of the crosslinking agent takes a phenolic aldehyde structure with high fire resistance as priority and nitrogenous and/or siliceous compound as decoration, and simultaneously can be matched and added with inorganic powder to make compositions after hot curing have the characteristics of fire resistance, low swelling property, low water absorbability, high glass-transition temperature and so on. The compositions can be applied to films and copper coil laminate.
Description
Technical field
The present invention relates to the composition epoxy resin of halogen-free phosphorus-free inflaming retarding, relate more specifically to the flame-retardant agent that said composition comprises.
Background technology
Resins, epoxy has excellent electric characteristics, dimensional stability, high thermal resistance, chemical resistant properties, reaches high-adhesiveness, therefore is widely used in industrial.For instance, Resins, epoxy can be used as coating, the tackiness agent of protection usefulness, the packaged material or the matrix material of unicircuit.Copper clad laminate (copper clad laminate) with electronic material is an example, and Resins, epoxy is one of important composition.In the sixties, improve the flame resistant practice of Resins, epoxy for add halogen compounds such as tetrabromo-bisphenol type compound (tetra-bromo-bisphenol A, TBBA).Though halogen compounds can effectively increase the flame resistivity of Resins, epoxy, can discharge dioxin/furans objectionable impuritiess such as (dioxin/furan) in combustion processes, therefore by other not halogen-containing fire retardant replace.
Except adding halogenide, also can add phosphide as fire retardant.For instance, at United States Patent (USP) the 6646064th, 6645631,679821,6291626,6291627,6900269,6524709,6645631, in No. 6645630, adopt phosphide as 9, the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthryl-10-oxide compound (9,10-dihydro-9-oxa-10-phosphahenanthrene-10-oxide, DOPO), 10-(2,5,-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-and (10-(2 ' for 10-phosphorus phenanthryl-10-oxide compound, 5 '-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphahenanthrene-10-oxide, DOPO-HQ), or above-mentioned derivative replaces halogen compounds.DOPO or DOPO-HQ can be earlier and the Resins, epoxy reaction form bifunctional or multi-functional Resins, epoxy.The structural formula of DOPO and DOPO-HQ is as follows respectively:
In European patent the 0384940th and No. 0408990, also adopt the reaction of phosphorus compound and Resins, epoxy, form bifunctional or multi-functional Resins, epoxy.The cost of these phosphorated modified epoxies is quite high, also mentions this problem in US 6353080.In No. the 6534601st, United States Patent (USP), after the Resins, epoxy reaction with DOPO-HQ and bifunctional, import silicone resin (siliconeresin) again with the increase flame resistivity, but equally have expensive problem.Except expensive problem, rerum naturas such as the water-absorbent (water uptake) of the interpolation regular meeting of phosphide reduction composition or sheet material tolerance, waste can the polluted water resource simultaneously.Therefore the replacement scheme of fire retardant is a high proportion of inorganic fire-retarded thing of interpolation at present.
Though inorganics and organic matrix material have been widely used in fields such as high molecule nano composite material, in thermosetting macromolecule such as printed circuit board material, add a large amount of inorganic fire-retarded things and will produce many problems.These problems comprise that processibility is bad, and flowability is poor, the sheet material uniformity coefficient is poor, back segment is holed yield (drill yield) etc.For instance, in No. the 2002226558th, Japanese Patent, finish the non-halogen non-phosphate substrate of anti-the combustion in the mode of adding aluminium hydroxide.Under the standard of UL-94V0, the substrate flame resistivity can reach V0.PCT test (121 ℃ 2atm) after 2 hours, can tolerate 180 seconds at 260 ℃.Yet this substrate second-order transition temperature, water absorption character, and test such as tin stove high temperature tolerance in can only meet the FR-4 level.
Summary of the invention
The invention provides a kind of flame-retardant agent, its structure is as follows:
N wherein
1Integer for 1-15; R
1Be selected from phenolic group, phenyl, naphthols base or xenyl; R
2Be selected from hydrogen or trimeric cyanamide; R
3Be selected from
R wherein
5Comprise OH, COOH, CN, NO
2, OCN or NH
2, n
2Integer for 1-3; And R
4For
R wherein
6Comprise OH, COOH, CN, NO
2, OCN or NH
2, n
3Integer for 1-3.
The present invention also provides a kind of composition epoxy resin of halogen-free phosphorus-free inflaming retarding, comprises the above-mentioned flame-retardant agent of 10-30 weight part, 30-50 weight part Resins, epoxy, 20-40 weight part stiffening agent, 20-40 weight part inorganic powder and 0.01-0.1 weight part catalyzer.
Embodiment
In order to improve the defective of flame-retardant agent of the prior art, the invention provides a kind of flame-retardant agent, its structure is suc as formula 3.
Formula 3 is resol, wherein n
1Integer for 1-15; R
1Be selected from phenolic group, phenyl, naphthols base or xenyl; R
2Be selected from hydrogen or trimeric cyanamide.For improve limited oxygen index (Limited Oxygen Index, LOI), become the carbon contribution margin (char-formation tendency, CFT) and when burning, emit fire-retardant gas, R
3Be selected from
Above-mentioned R
5Comprise OH, COOH, CN, NO
2, OCN or NH
2, n
2Integer for 1-3; And R
4For
R wherein
6Comprise OH, COOH, CN, NO
2, OCN or NH
2, n
3Integer for 1-3.
Get the composition epoxy resin that promptly forms halogen-free phosphorus-free inflaming retarding after the above-mentioned flame-retardant agent of 10-30 weight part, 30-50 weight part Resins, epoxy, 20-40 weight part stiffening agent, 20-40 weight part inorganic powder, the 0.01-0.1 weight part catalyst mix.
It is Resins, epoxy that above-mentioned Resins, epoxy can be dihydroxyphenyl propane, Bisphenol F is a Resins, epoxy, cresylol formaldehyde novolac epoxy (cresol-formaldehyde novolac resin), phenol formaldehyde novolac epoxy (phenol-formaldehyde novolac resin), phenol biphenylcarboxaldehyde novolac epoxy (phenol biphenyl-formaldehyde novolac resin), phenol p-Xylol formaldehyde novolac epoxy (phenol p-xylene formaldehyde novolac resin), the two benzene cyclohexene carboxaldehyde novolac epoxys (phenol biphenylene formaldehyde novolac resin) of phenol, phenol Dicyclopentadiene (DCPD) formaldehyde novolac epoxy (phenol dicyclopentadiene formaldehydenovolac resin), or above-mentioned combination, and at least a be novolac epoxy.In an embodiment of the present invention, Resins, epoxy has the phenol formaldehyde novolac epoxy of 60-80 weight %, and the dihydroxyphenyl propane of 20-40 weight % is a Resins, epoxy.
Above-mentioned stiffening agent is the degree of crosslinking in order to functional group in the further increase composition epoxy resin, can be cresylol formaldehyde phenolic resin, phenol biphenylcarboxaldehyde resol, the two benzene cyclohexene carboxaldehyde resol of phenol, phenol Dicyclopentadiene (DCPD) formaldehyde phenolic resin, trimeric cyanamide phenol formaldehyde phenolic resin (melaminephenol-formaldehyde novolac resin) or above-mentioned combination.In an embodiment of the present invention, the mol ratio of the epoxy group(ing) of the phenolic group of stiffening agent and Resins, epoxy is 0.8-1.2.
Catalyzer system comprises methylimidazole, diethyl tetramethyl-imidazoles, diphenyl-imidazole, dimethylamino ethyl phenol, three (dimethylamino methyl) phenol or benzyl dimethyl amine in order to increase rate of crosslinking.
Inorganic powder can further increase the flame retardant resistance of composition epoxy resin, comprises barium titanium oxide, silicon-dioxide, titanium dioxide, aluminium hydroxide, magnesium hydroxide or zinc carbonate.
Except above-mentioned composition, composition epoxy resin of the present invention can further comprise the coupler of 0.5-3.0 weight part, comprises amine coupler or the silicane coupler compatibility and dispersiveness to increase inorganic powder.
Second-order transition temperature after the Halogen flame resistant material of the prior art sclerosis is about 130 ℃, and of the prior art phosphorous/second-order transition temperature after the nitrogenous mixing fire retardant material sclerosis is about 140-160 ℃.Composition epoxy resin of the present invention, the second-order transition temperature after sclerosis are approximately between 180-220 ℃, and the flame retardant rating after the sclerosis reaches the V0 standard of UL-94 test.On the other hand, compare the phenolic group that flame-retardant agent of the present invention has, COOH base, CN base, NO as the composition epoxy resin of fire retardant with simple employing inorganic powder
2The base, OCN is basic or NH
2Can carry out crosslinking reaction with the epoxy group(ing) of Resins, epoxy Deng functional group, can avoid processibility bad, mobile poor, problem such as the sheet material uniformity coefficient is poor, back segment is holed yield is not good.Flame-retardant agent of the present invention and Resins, epoxy are organic compound, therefore the situation that is separated for the unlikely generation of homophase (homogeneous).Except flame retardant resistance and high glass-transition temperature, flame-retardant agent of the present invention also has advantages such as low bulk and low water absorbable.Under the situation of collocation small amounts of inorganic powder, composition epoxy resin of the present invention can stop heat transmission, reduce inflammable gas and penetrate under the surface of composition, produce non-flammable gases with the oxygen in the diluent air, and can form non-flame properties coke layer and be covered in the combustionmaterial surface.
In an embodiment of the present invention, getting 20-40 weight part inorganic powder inserts in the bottle, after the coupler of adding acetone and above-mentioned 0.5-3.0 weight part stirs, add 20-40 weight part phenol formaldehyde novolac epoxy (NPCN-704, available from South Asia resin limited-liability company), 30-50 weight part dihydroxyphenyl propane is that (Epikote 828 for Resins, epoxy, available from Shell), phenol formaldehyde phenolic resin (6000IZ is available from Bakelite) as stiffening agent, 10-30 weight part flame-retardant agent of the present invention, and the 0.01-0.1 weight part promptly gets rubber water (varnish) after stirring as the imidazoles catalyzer (available from Aldrich) of catalyzer.The gel time of rubber water is 200 ± 10 seconds after tested.Gel time is defined as mixture and finishes the required time of crosslinking reaction.After mixing the back, the validity period of rubber water (pot life) is 7 days.
Then, glasscloth can be immersed in the rubber water about 20 minutes, make the impregnation amount be about 45-55%.Send into 170 ℃ of Hotaircirculatingovens baking several minutes after the taking-up, control crosslinking reaction ratio is about 50%, promptly gets film.
After getting five film storehouses, respectively place up and down teflon separate-type paper (teflon release paper), mirror steel plate, and kraft paper after, insert in 200 ℃ the vacuum press molding machine and carried out hot pressing 2 hours, promptly get the substrate that thickness is 1.0 ± 0.05mm.Change steel plate into Copper Foil and can form so-called copper clad laminate.
In order to make the clearer feature of the present invention of those skilled in the art, the spy is schematically illustrated in following preferred embodiment.
The used Resins, epoxy of the present invention is mixture, and the title and the source of its composition are listed below:
Phenol formaldehyde novolac epoxy (NPCN-704, available from South Asia resin limited-liability company), dihydroxyphenyl propane is that (Epikote 828 for Resins, epoxy, available from Shell), as the phenol formaldehyde phenolic resin (6000IZ of stiffening agent, available from Bakelite) and as the 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole is available from Aldrich) of catalyzer.
Embodiment 1
Get 100 gram phenol formaldehyde novolac epoxy (NPCN-704; available from South Asia resin limited-liability company) with dihydroxyphenyl propane be that (Epikote 828 for Resins, epoxy; available from Shell) epoxy resin composition and 30 gram flame-retardant agent uniform mixing after; at room temperature remove earlier partly solvent; remove residual solvent with vacuum-drying again; then insert in 200 ℃ the vacuum press molding machine and carried out hot pressing 2 hours; carrying out the back with hot-air oven with 220 ℃ again bakes; promptly get the bulk that thickness is 1.0 ± 0.05mm; and measure into carbon contribution margin (CFT%), its observed value such as table 1 in air under 800 ℃ or the nitrogen atmosphere.
Embodiment 2
Get 100 gram phenol formaldehyde novolac epoxy (NPCN-704; available from South Asia resin limited-liability company) with dihydroxyphenyl propane be that (Epikote 828 for Resins, epoxy; available from Shell) epoxy resin composition and 50 gram flame-retardant agent uniform mixing after; at room temperature remove earlier partly solvent; remove residual solvent with vacuum-drying again; then insert in 200 ℃ the vacuum press molding machine and carried out hot pressing 2 hours; carrying out the back with hot-air oven with 220 ℃ again bakes; promptly get the bulk that thickness is 1.0 ± 0.05mm; and measure into carbon contribution margin (CFT%), its observed value such as table 1 in air under 800 ℃ or the nitrogen atmosphere.
Embodiment 3
Get 100 gram phenol formaldehyde novolac epoxy (NPCN-704; available from South Asia resin limited-liability company) with dihydroxyphenyl propane be that (Epikote 828 for Resins, epoxy; available from Shell) epoxy resin composition and 80 gram flame-retardant agent uniform mixing after; at room temperature remove earlier partly solvent; remove residual solvent with vacuum-drying again; then insert in 200 ℃ the vacuum press molding machine and carried out hot pressing 2 hours; carrying out the back with hot-air oven with 220 ℃ again bakes; promptly get the bulk that thickness is 1.0 ± 0.05mm; and measure into carbon contribution margin (CFT%), its observed value such as table 1 in air under 800 ℃ or the nitrogen atmosphere.
Embodiment 4
Get 100 gram phenol formaldehyde novolac epoxy (NPCN-704; available from South Asia resin limited-liability company) with dihydroxyphenyl propane be that (Epikote 828 for Resins, epoxy; available from Shell) epoxy resin composition and 100 gram flame-retardant agent uniform mixing after; at room temperature remove earlier partly solvent; remove residual solvent with vacuum-drying again; then insert in 200 ℃ the vacuum press molding machine and carried out hot pressing 2 hours; carrying out the back with hot-air oven with 220 ℃ again bakes; promptly get the bulk that thickness is 1.0 ± 0.05mm; and measure into carbon contribution margin (CFT%), its observed value such as table 1 in air under 800 ℃ or the nitrogen atmosphere.
Comparative example 1
Get 100 gram phenol formaldehyde novolac epoxy (NPCN-704; available from South Asia resin limited-liability company) with dihydroxyphenyl propane be that (Epikote 828 for Resins, epoxy; available from Shell) epoxy resin composition and phenol formaldehyde phenolic resin (6000IZ; available from Bakelite); and as the 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole of catalyzer; available from Aldrich); at room temperature remove earlier partly solvent behind the uniform mixing; remove residual solvent with vacuum-drying again; then insert in 200 ℃ the vacuum press molding machine and carried out hot pressing 2 hours; carrying out the back with hot-air oven with 220 ℃ again bakes; promptly get the bulk that thickness is 1.0 ± 0.05mm; and measure into carbon contribution margin (CFT%), its observed value such as table 1 in air under 800 ℃ or the nitrogen atmosphere.
Table 1
| Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| The Resins, epoxy ratio | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| The linking agent ratio | 0 | 0.3 | 0.5 | 0.8 | 1.0 |
| Tg | 155 | 167 | 183 | 184 | 184 |
| CFT (air, %) | 0 | 16.3 | 25 | 28 | 30 |
| CFT(N 2，％) | 32 | 35 | 39 | 43 | 48 |
Can know discovery by table 1, the one-tenth carbon contribution margin (CFT) and the second-order transition temperature of the embodiment of the invention all are higher than comparative example.This obvious difference comes from composition epoxy resin of the present invention and contains flame-retardant agent.
Embodiment 5
Get 100 gram 4-benzaminic acid (4-amino benzoic acid, available from aldrich) add in the mixed liquid of deionized water/hydrochloric acid, slowly splash into the mixed solution of 53 gram Sodium Nitrite (sodium nitrite)/deionized waters again, with mixed solution at low temperatures (0～5 ℃) stir companion 4 hours after, slowly pour 130 gram phenol formaldehyde phenolic resin (6000IZ again into, available from Bakelite)/60 gram sodium-acetate (sodium acetate is available from aldrich)/180 gram ammonia soln (NH
4OH is available from aldrich) mixed solution in, mixed solution (0～5 ℃) at low temperatures stirred the companion after 4 hours, with 0.1N sulfuric acid stopped reaction, through filtering and drying course, can obtain flame-retardant agent a again, productive rate is 90%.
Get 100 gram phenol formaldehyde novolac epoxy (NPCN-704, available from South Asia resin limited-liability company) with dihydroxyphenyl propane be that (Epikote 828 for Resins, epoxy, available from Shell) epoxy resin composition and the flame-retardant agent a of 50 grams, and 45 gram inorganic powder (aluminium hydroxides, aluminum trihydroxide), promptly get rubber water after stirring.The gel time of rubber water is 170 ± 10 seconds after tested.Gel time is defined as mixture and finishes the required time of crosslinking reaction.After the mixing, the validity period of rubber water is 7 days.
Then glasscloth can be immersed rubber water about 20 minutes, make the impregnation amount be about 45-55%.Send into 170 ℃ of Hotaircirculatingovens baking several minutes after the taking-up, control crosslinking reaction ratio is about 50%, promptly gets film.
After getting five film storehouses, after respectively placing teflon separate-type paper, mirror steel plate and kraft paper up and down, insert in 200 ℃ the vacuum press molding machine and carried out hot pressing 2 hours, promptly get the substrate that thickness is 1.0 ± 0.05mm.Change steel plate into Copper Foil and can form so-called copper clad laminate.
Then measure substrate second-order transition temperature, thermal expansivity (Z-axis, %), flame retardant rating and the water-absorbent (water uptake, the suction % of PCT condition after following 1 hour) of UL-94, its observed value such as table 2.
Embodiment 6
Get 125 gram 4-aminophenyl sulfone (4-amino phenyl sulfone, available from aldrich) add in the mixed liquid of deionized water/hydrochloric acid, slowly splash into the mixed solution of the Sodium Nitrite/deionized water of 80 grams again, mixed solution (0～5 ℃) at low temperatures stirred the companion after 4 hours, slowly pour 130 gram phenol formaldehyde phenolic resin (6000IZ is available from Bakelite)/60 gram sodium-acetate (available from aldrich)/250 gram ammonia soln (NH again into
4OH is available from aldrich) mixed solution in, mixed solution (0～5 ℃) at low temperatures stirred the companion after 4 hours, with 0.1N sulfuric acid stopped reaction, through filtering and drying course, can obtain flame-retardant agent b again, productive rate is 85%.
Get 100 gram phenol formaldehyde novolac epoxy (NPCN-704, available from South Asia resin limited-liability company) with dihydroxyphenyl propane be that (Epikote 828 for Resins, epoxy, available from Shell) epoxy resin composition and 50 the gram flame-retardant agent b, and 45 the gram inorganic powders (aluminium hydroxide), promptly get rubber water after stirring.The gel time of rubber water is 170 ± 10 seconds after tested.Gel time is defined as mixture and finishes the required time of crosslinking reaction.After mixing the back, the validity period of rubber water is 7 days.
Then glasscloth can be immersed rubber water about 20 minutes, make the impregnation amount be about 45-55%.Send into 170 ℃ of Hotaircirculatingovens baking several minutes after the taking-up, control crosslinking reaction ratio is about 50%, promptly gets film.
After getting five film storehouses, in respectively place up and down teflon separate-type paper, mirror steel plate, and kraft paper after, insert in 200 ℃ the vacuum press molding machine and carried out hot pressing 2 hours, promptly get the substrate that thickness is 1.0 ± 0.05mm.Change steel plate into Copper Foil and can form so-called copper clad laminate.
Then measure substrate second-order transition temperature, thermal expansivity (Z-axis, %), the flame retardant rating of UL-94, and water-absorbent (water uptake, the suction % of PCT condition after following 1 hour), its observed value such as table 2.
Embodiment 7
Getting 100 gram 4-benzaminic acid (available from aldrich) adds in the mixed liquid of deionized water/hydrochloric acid, slowly splash into the mixed solution of the Sodium Nitrite/deionized water of 53 grams again, mixed solution (0～5 ℃) at low temperatures stirred the companion after 4 hours, slowly poured 85 gram phenol (available from aldrich)/120 gram sodium-acetate (available from aldrich)/200 gram ammonia soln (NH again into
4OH is available from aldrich) mixed solution in, mixed solution (0～5 ℃) at low temperatures stirred the companion after 4 hours, with 0.1N sulfuric acid stopped reaction, through filtering and drying course, can obtain flame-retardant agent precursor c-1 again, productive rate is 95%.
Other gets 100 gram 4-benzaminic acid (available from aldrich) and adds in the mixed liquid of deionized water/hydrochloric acid, slowly splash into the mixed solution of the Sodium Nitrite/deionized water of 53 grams again, mixed solution (0～5 ℃) at low temperatures stirred the companion after 4 hours, slowly pour 130 gram phenol formaldehyde phenolic resin (6000IZ is available from Bakelite)/60 gram sodium-acetate (available from aldrich)/180 gram ammonia soln (NH again into
4OH is available from aldrich) mixed solution in, mixed solution (0～5 ℃) at low temperatures stirred the companion after 4 hours, with 0.1N sulfuric acid stopped reaction, through filtering and drying course, can obtain flame-retardant agent c-2 again, productive rate is 90%.
Get 50 gram flame-retardant agent precursor b-1/ thionyl chloride (thionyl chloride), 210 grams stopped reaction after refluxed under nitrogen is reacted 4 hours, and with the rotation concentrating instrument remove thionyl chloride, the THF dissolving that adds 200 milliliters again, under nitrogen, add in the mixed solution of 40 gram flame-retardant agent b-2/300 milliliter THF/25 gram pyridines (Pyridine) under the environment, continue to stir stopped reaction after 12 hours, pour in 2 literss of water and produce precipitated product, with the product filtration and with behind the oven drying, can obtain flame-retardant agent c.
Get 100 gram phenol formaldehyde novolac epoxy (NPCN-704, available from South Asia resin limited-liability company) with dihydroxyphenyl propane be that (Epikote 828 for Resins, epoxy, available from Shell) epoxy resin composition and 50 the gram flame-retardant agent c, promptly get rubber water after stirring.The gel time of rubber water is 170 ± 10 seconds after tested.Gel time is defined as mixture and finishes the required time of crosslinking reaction.After mixing the back, the validity period of rubber water is 7 days.
Then glasscloth can be immersed rubber water about 20 minutes, make the impregnation amount be about 45-55%.Send into 170 ℃ of Hotaircirculatingovens baking several minutes after the taking-up, control crosslinking reaction ratio is about 50%, promptly gets film.
After getting five film storehouses, in respectively place up and down teflon separate-type paper, mirror steel plate, and kraft paper after, insert in 200 ℃ the vacuum press molding machine and carried out hot pressing 2 hours, promptly get the substrate that thickness is 1.0 ± 0.05mm.Change steel plate into Copper Foil and can form so-called copper clad laminate.
Then measure substrate second-order transition temperature, thermal expansivity (Z-axis, %), the flame retardant rating of UL-94, and water-absorbent (water uptake, the suction % of PCT condition after following 1 hour), its observed value such as table 2.
Embodiment 8
Get 100 gram phenol formaldehyde novolac epoxy (NPCN-704, available from South Asia resin limited-liability company) with dihydroxyphenyl propane be that (Epikote 828 for Resins, epoxy, available from Shell) epoxy resin composition and 30 gram flame-retardant agent c, and 45 gram inorganic powder (aluminium hydroxides, aluminum trihydroxide), promptly get rubber water after stirring.The gel time of rubber water is 170 ± 10 seconds after tested.Gel time is defined as mixture and finishes the required time of crosslinking reaction.After mixing the back, the validity period of rubber water is 7 days.
Then glasscloth can be immersed rubber water about 20 minutes, make the impregnation amount be about 45-55%.Send into 170 ℃ of Hotaircirculatingovens baking several minutes after the taking-up, control crosslinking reaction ratio is about 50%, promptly gets film.
After getting five film storehouses, in respectively place up and down teflon separate-type paper, mirror steel plate, and kraft paper after, insert in 200 ℃ the vacuum press molding machine and carried out hot pressing 2 hours, promptly get the substrate that thickness is 1.0 ± 0.05mm.Change steel plate into Copper Foil and can form so-called copper clad laminate.
Then measure substrate second-order transition temperature, thermal expansivity (Z-axis, %), the flame retardant rating of UL-94, and water-absorbent (water uptake, the suction % of PCT condition after following 1 hour), its observed value such as table 2.
Comparative example 2
Get 100 gram phenol formaldehyde novolac epoxy (NPCN-704, available from South Asia resin limited-liability company) with dihydroxyphenyl propane be that (Epikote 828 for Resins, epoxy, available from Shell) epoxy resin composition and 300 the gram inorganic powders (aluminium hydroxide), promptly get rubber water after stirring.The gel time of rubber water is 170 ± 10 seconds after tested.Gel time is defined as mixture and finishes the required time of crosslinking reaction.After mixing the back, the validity period of rubber water is 7 days.
Then glasscloth can be immersed rubber water about 20 minutes, make the impregnation amount be about 45-55%.Send into 170 ℃ of Hotaircirculatingovens baking several minutes after the taking-up, control crosslinking reaction ratio is about 50%, promptly gets film.
After getting five film storehouses, after respectively placing teflon separate-type paper, mirror steel plate and kraft paper up and down, insert in 200 ℃ the vacuum press molding machine and carried out hot pressing 2 hours, promptly get the substrate that thickness is 1.0 ± 0.05mm.Change steel plate into Copper Foil and can form so-called copper clad laminate.
Then measure the second-order transition temperature of substrate MEASUREMENTS OF THIN and flame retardant rating, its observed value such as table 2 of UL-94.
Table 2
| Comparative example 2 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Weight epoxy part | 100 | 100 | 100 | 100 | 100 |
| The flame-retardant agent weight part | 0 | 50 a | 50 b | 50 c | 50 c |
| The inorganic powder weight part | 300 | 30-50 | 35-50 | -- | 20-35 |
| Second-order transition temperature | 150 | 160 | 190 | 170 | 180 |
| Thermal expansivity | -- | 2.5 | 2.5 | 2.9 | 2.7 |
| The UL-94 flame retardant test | V0 | V0 | V0 | V1 | V0 |
| Water-absorbent (%) | -- | 0.5-0.6 | 0.2-0.3 | 0.3-0.4 | 0.4-0.5 |
Annotate: a: contain azo-benzoic linking agent; B: the linking agent that contains sulfuryl-xenyl; C: the linking agent that contains azo.
Can know discovery by table 2, the present invention can reduce the consumption of inorganic powder significantly after adding flame-retardant agent.In addition, composition epoxy resin of the present invention all meets the standard that industry is utilized in character such as the flame retardant test of UL-94, thermal expansivity, water-absorbent, second-order transition temperatures.
Though the present invention discloses as above with a plurality of preferred embodiments; right its is not in order to limit the present invention; any person of ordinary skill in the field; without departing from the spirit and scope of the present invention; Ying Kezuo at random changes and retouches, so protection scope of the present invention should be as the criterion with appended claims institute restricted portion.
Claims (11)
1. flame-retardant agent, its structure is as follows:
N wherein
1Integer for 1-15;
R
1Be selected from phenolic group, phenyl, naphthols base or xenyl;
R
2Be selected from hydrogen or trimeric cyanamide;
R
3Be selected from
R
4For
R wherein
6Comprise OH, COOH, CN, NO
2, OCN or NH
2, n
3Integer for 1-3.
2. the composition epoxy resin of a halogen-free phosphorus-free inflaming retarding comprises:
The described flame-retardant agent of 10-30 weight part claim 1;
30-50 weight part Resins, epoxy;
20-40 weight part stiffening agent;
20-40 weight part inorganic powder; And
0.01-0.1 weight part catalyzer.
3. the composition epoxy resin of halogen-free phosphorus-free inflaming retarding as claimed in claim 2, wherein this Resins, epoxy comprises that dihydroxyphenyl propane is that Resins, epoxy, Bisphenol F are the two benzene cyclohexene carboxaldehyde novolac epoxys of Resins, epoxy, cresylol formaldehyde novolac epoxy, phenol formaldehyde novolac epoxy, phenol biphenylcarboxaldehyde novolac epoxy, phenol p-Xylol formaldehyde novolac epoxy, phenol, phenol Dicyclopentadiene (DCPD) formaldehyde novolac epoxy or above-mentioned combination, and at least a be novolac epoxy.
4. the composition epoxy resin of halogen-free phosphorus-free inflaming retarding as claimed in claim 2, wherein this Resins, epoxy comprises that the phenol formaldehyde novolac epoxy of 60-80 weight % and the dihydroxyphenyl propane of 20-40 weight % are Resins, epoxy.
5. the composition epoxy resin of halogen-free phosphorus-free inflaming retarding as claimed in claim 2, wherein this stiffening agent comprises cresylol formaldehyde phenolic resin, phenol biphenylcarboxaldehyde resol, the two benzene cyclohexene carboxaldehyde resol of phenol, phenol Dicyclopentadiene (DCPD) formaldehyde phenolic resin, trimeric cyanamide phenol formaldehyde phenolic resin or above-mentioned combination.
6. the composition epoxy resin of halogen-free phosphorus-free inflaming retarding as claimed in claim 5, wherein the mol ratio of the epoxy group(ing) of the phenolic group of this stiffening agent and this Resins, epoxy is 0.8-1.2.
7. the composition epoxy resin of halogen-free phosphorus-free inflaming retarding as claimed in claim 2, wherein this catalyzer comprises methylimidazole, diethyl tetramethyl-imidazoles, diphenyl-imidazole, dimethylamino ethyl phenol, three (dimethylamino methyl) phenol or benzyl dimethyl amine.
8. the composition epoxy resin of halogen-free phosphorus-free inflaming retarding as claimed in claim 2, wherein this inorganic powder comprises barium titanium oxide, silicon-dioxide, titanium dioxide, magnesium hydroxide, aluminium hydroxide or zinc carbonate.
9. the composition epoxy resin of halogen-free phosphorus-free inflaming retarding as claimed in claim 2 also comprises the coupler of 0.5～3.0 weight part comprising amine coupler, silicane coupler or above-mentioned combination.
10. the composition epoxy resin of halogen-free phosphorus-free inflaming retarding as claimed in claim 2, the second-order transition temperature after its sclerosis is about 180 ℃～220 ℃.
11. the composition epoxy resin of halogen-free phosphorus-free inflaming retarding as claimed in claim 2, the flame retardant rating after its sclerosis is V0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101039901A CN101307155A (en) | 2007-05-17 | 2007-05-17 | Fire retardant crosslinking agent and halogen free, non-phosphate and fire retardant epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101039901A CN101307155A (en) | 2007-05-17 | 2007-05-17 | Fire retardant crosslinking agent and halogen free, non-phosphate and fire retardant epoxy resin composition |
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| Publication Number | Publication Date |
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| CN101307155A true CN101307155A (en) | 2008-11-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101039901A Pending CN101307155A (en) | 2007-05-17 | 2007-05-17 | Fire retardant crosslinking agent and halogen free, non-phosphate and fire retardant epoxy resin composition |
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| CN (1) | CN101307155A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701058B (en) * | 2009-11-19 | 2011-10-26 | 中国科学院广州化学研究所 | Epoxy resin containing melamine-organic silicon hybrid structure and preparation method and application thereof |
-
2007
- 2007-05-17 CN CNA2007101039901A patent/CN101307155A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701058B (en) * | 2009-11-19 | 2011-10-26 | 中国科学院广州化学研究所 | Epoxy resin containing melamine-organic silicon hybrid structure and preparation method and application thereof |
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Application publication date: 20081119 |