CN101302327B - Halogen-free fire-resistant epoxy resin composition, film and copper clad laminate - Google Patents
Halogen-free fire-resistant epoxy resin composition, film and copper clad laminate Download PDFInfo
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- CN101302327B CN101302327B CN2007101049706A CN200710104970A CN101302327B CN 101302327 B CN101302327 B CN 101302327B CN 2007101049706 A CN2007101049706 A CN 2007101049706A CN 200710104970 A CN200710104970 A CN 200710104970A CN 101302327 B CN101302327 B CN 101302327B
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Abstract
The invention relates to an epoxy resin composition, which is characterized in that: phosphate esters which are provided with phenolic groups or benzoxazinyl are added into the epoxy resin composition to improve the flame resistance of the epoxy resin composition, and the molecular weight and the viscosity of the epoxy resin composition are higher than those of the prior phosphate esters. Because the phosphate esters can react with epoxy resins, the addition is higher than that of general flame retardant and the viscosity applied to a film of a copper foil substrate or a printed circuit board can be further improved.
Description
Technical field
The present invention relates to a kind of composition epoxy resin that can be used for copper clad laminate, relate in particular to a kind of composition epoxy resin of halogen-free flame-retardant, its contain can with the phosphate flame retardant of epoxy reaction.
Background technology
Resins, epoxy has excellent electric characteristics, dimensional stability, high thermal resistance, chemical resistant properties and high tackyness, therefore is widely used in industrial.For instance, Resins, epoxy can be used as coating, the solid of protection usefulness, the packaged material or the matrix material of unicircuit.Copper foil layer substrate (copperclad laminate) with electronic material is an example, and Resins, epoxy is one of important composition.In generation nineteen sixty, improve the flame resistant practice of Resins, epoxy for adding halogen compounds, 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.
Announce the 6th, 646 at United States Patent (USP), 064,6,645,631,6,679,821,6,291,626,6,291,627,6,900,269,6,524,709,6,645,631, in 6,645, No. 630, adopt phosphide as 9,10-dihydro-9-dislikes base-10-phosphorus phenanthryl-10-oxide compound (9,10-dihydro-9-oxa-10-phosphahenanthrene-10-oxide is hereinafter to be referred as DOPO), 10-(2,5,-dihydroxy phenyl)-9, the 10-dihydro-base-(10-(2 ', 5 '-dihydroxyphenyl)-9 for 10-phosphorus phenanthryl-10-oxide compound for 9-evil, 10-dihydro-9-oxa-10-phosphahenanthrene-10-oxide is hereinafter to be referred as DOPO-HQ), or above-mentioned derivative replaces halogen compounds.DOPO or DOPO-HQ can be earlier and the Resins, epoxy reaction form the Resins, epoxy of difunctionality base or multiple functional radical.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 the Resins, epoxy of difunctionality base or multiple functional radical.The cost of these phosphorated upgrading Resins, epoxy is quite high, at United States Patent (USP) the 6th, 353, also mentions this problem in No. 080.At United States Patent (USP) the 6th, 534, in No. 601, after the Resins, epoxy reaction with DOPO-HQ and difunctionality base, import silicone resin (silicone resin) again increasing flame resistivity, but equally have expensive problem.
Another kind improves the flame resistant method of Resins, epoxy, and phosphide and nitride as importing stiffening agent, are got stiffening agent and Resins, epoxy again and reacted.At United States Patent (USP) the 6th, 613, in No. 848, utilize DOPO derivative and resol (phenol novolac) reaction to form the phosphorated phenol resin, or utilize DOPO derivative and melamine resin (melamine phenol novolac) reaction to form nitrogenous phenol resin as stiffening agent as stiffening agent.At United States Patent (USP) the 6th, 797, in No. 821 patents, with the phosphide that contains active hydrogen or nitride (active-hydrogen containing phosphorus and nitrogen compound) stiffening agent, in order to increase the flame resistivity of Resins, epoxy as Resins, epoxy.
In order to reduce cost, can adopt commercially available phosphate compound to replace DOPO, DOPO-HQ or other phosphorous epoxy resin.Announce the 6th, 500 at United States Patent (USP), in No. 546, its prescription has comprised the phosphoric acid ester EXOLIT OP910 (CLARIANT sells) of DOPO and special construction to improve the Resins, epoxy flame resistivity, and its structure is as follows:
The multipolymer of polystyrene (polystyrene) and toxilic acid or acid anhydrides (maleic acid or anhydride) also can be used as stiffening agent.At United States Patent (USP) the 6th, 353, in No. 080, utilize phosphoric acid ester, as commercially available Amgard
TMP45 or Amgard
TMV19 (Albright and Wilson ltd sells) and nitrogenous novolac epoxy reaction, the nitrogenous linking agent that importing simultaneously contains two above amidos increases the flame resistivity of Resins, epoxy as stiffening agent.
At United States Patent (USP) the 5th, 955,184 and 6,214, in No. 455, adopt nitrogenous phenol resin or phosphorous nitrogenous phenol resin as stiffening agent, and the collocation inorganic filler, as aluminium hydroxide, magnesium hydroxide, talcum powder, silicon-dioxide or aforesaid combination.After the above-mentioned composition sclerosis, can reach the anti-combustion standard of UL94V0 grade.
Phosphoric acid ester is common fire retardant, except aforesaid EXOLIT OP910, Amgard
TMP45, and Amgard
TMOutside the V19, also have the two diphenyl phosphoesters (resorcinol bis-diphenylphosphate is hereinafter to be referred as RDP) of Resorcinol, the Fyrolflex RDP that is sold as AKZO Nobel; The two diphenyl phosphoesters (bisphenol A bis-diphenyl phosphate is hereinafter to be referred as BDP) of bisphenol A-type are as the Fyrolflex BDP that AKZONobel sold; And triphenyl (triphenyl phosphate is hereinafter to be referred as TPP), the Fyrolflex TPP that is sold as AKZO Nobel.Except TPP, commercially available RDP and BDP all are thick liquids.In addition, the flame resistivity of RDP is better than BDP, but the hydrolytic resistance of BDP then is better than RDP.Yet RDP, BDP or TPP all with Resins, epoxy reaction, the viscosity of Resins, epoxy that therefore contains above-mentioned fire retardant is lower.Be dipped in this kind Resins, epoxy if woven fiber glass contained, its viscosity of film (prepreg) that the oven dry back forms is lower, and the solation amount is big when pressing plate, causes pressing window narrows and control to be difficult for, and makes pressing substrate thickness inequality, thickness deficiency and produce white edge all around.On the other hand, the flame retardant effect of RDP, BDP or TPP and thermotolerance not as traditional Halogen Resins, epoxy or expensive phosphorous/and or nitrogen-containing epoxy thermoset.
In sum, need the composition epoxy resin of new halogen-free fire-resistant at present badly to address the above problem.
Summary of the invention
In order to improve the flame resistivity of Resins, epoxy, the invention provides phosphoric acid ester, the BDP height that its molecular weight and ratio of viscosities are commercially available with phenolic group or benzoxazinyl-.Because phosphoric acid ester of the present invention at high temperature can be reacted with Resins, epoxy, so the comparable general flame retardant height of addition, can further improve the viscosity of the film that is applied to copper clad laminate or printed circuit board (PCB).
The invention provides a kind of composition epoxy resin of halogen-free fire-resistant, it comprises the novolac epoxy of (a) 25-45%; (b) phosphate compound of 18-35%; (c) the nitrogenous phenol resin of 10-20% comprises amido triazine resol, benzoxazinyl-resin or its combination; And (d) inorganic filler of 20%-45%; Wherein phosphate compound comprises:
Wherein, n is the integer of 4-10; Each R
1Independent separately, be hydrogen or methyl; Each R
2Independent separately, be sec.-propyl or sulfuryl; Each X is independent separately, is oxygen or singly-bound.
The present invention also provides a kind of film, is that a woven fiber glass contains the composition epoxy resin that is dipped in above-mentioned halogen-free fire-resistant.
The present invention more provides a kind of copper clad laminate, and it is formed by Copper Foil and above-mentioned film pressing.
Embodiment
The invention provides a kind of composition epoxy resin of halogen-free fire-resistant, it comprises the novolac epoxy of (a) 25%-45%; (b) phosphate compound of 18%-35%; (c) the nitrogenous phenol resin of 10%-20% comprises amido triazine resol, benzoxazinyl-resin or its combination; And (d) inorganic filler of 20%-45%; Wherein, phosphate compound comprises:
Wherein, n is the integer of 4-10; Each R
1Independent separately, comprise hydrogen or methyl; Each R
2Independent separately, comprise sec.-propyl or sulfuryl; Each X is independent separately, comprises oxygen or singly-bound.
(a) of the present invention novolac epoxy is mainly formed by resol and epoxy chloropropane (epichlorohydrin) reaction, and the commercial goods comprises the D.E.N. that DOW Chemical is sold
TMThe CNE200ELF that series, Changchun chemical industry are sold, the NPCN-703 that CNE series product such as 202ELF, South Asia plastics are sold, 704 series product such as NPCN such as grade, its structural formula is as follows:
R in the formula 7 is independent separately, can be hydrogen or methyl.
The softening temperature of general novolac epoxy is approximately between 70 ℃ to 130 ℃, and the softening temperature of the novolac epoxy of preferred embodiment of the present invention is approximately between 75 ℃ to 100 ℃, and epoxy equivalent (weight) is approximately between 190 to 240, account for halogen-free fire-resistant the composition epoxy resin gross weight 25% to 45%, preferably can account for halogen-free fire-resistant the composition epoxy resin gross weight 30% to 40%.
(b) of the present invention phosphate compound is suc as formula 4, shown in the formula 5, its synthetic method is, utilizes derivative such as dihydroxyphenyl propane or bis-phenol sulfuryl and the two chlorine phosphoric acid ester (phenoxy dichlorophosphate) of phenoxy group or benzenephosphonic acid dichloro (phenyl phosphonic dichloride) to carry out the copolymerization condensation and forms.The formula 4 of the embodiment of the invention, the phosphoric acid ester of formula 5 are with general commercially available BDP difference: (1) contains the terminal functional group of phenolic group, can react with Resins, epoxy when high temperature; (2) be solid, thermotolerance is better than BDP; (3) viscosity is than the BDP height, and at 100 ℃, commercially available BDP viscosity is 40-100cps, and the terminal functional group BDP of phenolic group that contains used in the present invention is 20000-25000cps at 100 ℃ viscosity.Above-mentioned difference makes the comparable general BDP of addition of phosphoric acid ester of formula 4 of the present invention, formula 5 many.
In addition, (b) of the present invention phosphate compound also can have benzoxazinyl-(benzoxazine) suc as formula 6, and it is mainly by phenolic group compound, formaldehyde or Paraformaldehyde 96 (paraformaldehyde), and aniline reaction and getting.Benzoxazinyl-can carry out ring-opening polymerization after being heated, form polyphenyl and oxazines (polybenzoxazine).The ring-opening polymerization of formula 6 is suc as formula 8, and the phenolic group that forms after open loop can react with Resins, epoxy.
The phosphoric acid ester of formula 4, formula 5, formula 6 both can be used alone, but also also mix together, phosphorus content account for halogen-free fire-resistant the composition epoxy resin gross weight 1.40% to 2.73%, preferably between 1.40% to 2.34%.
(c) of the present invention nitrogenous phenol resin can be amido triazine resol (amino triazine novolac, ATN), benzoxazinyl-resin or its combination, its nitrogen content account for halogen-free fire-resistant the composition epoxy resin gross weight 1.40% to 2.80%.Amido triazine resol can be by phenol, trimeric cyanamide (melamine) or benzoguanamine (benzoguanamine) and formaldehyde copolymerization condensation and is got.Commercially available nitrogenous phenol resin comprises LA-7751, LA-1356 that big Japanese ink sells, and LA-1398.The structure of amido triazine resol is suc as formula 9:
With LA7751 is example, and its nitrogen content is 14%, and hydroxyl equivalent is 135, solids content is 57-61%, and solvent is a methylethylketone.
Except above-mentioned amido triazine resol, (c) of the present invention nitrogenous phenol resin also can be the benzoxazinyl-resin, as benzoxazinyl-bisphenol A-type resin, benzoxazinyl-Bisphenol F type resin, benzoxazinyl-bis-phenol sulfuryl resin, benzoxazinyl-resol or its combination.Above-mentioned benzoxazinyl-can form nitrogenous phenol resin after being heated.
In preferred embodiment of the present invention, (c) content of nitrogenous phenol resin is to calculate and get according to the epoxy group(ing) of the composition epoxy resin of halogen-free fire-resistant and the hydroxyl ratio of nitrogenous phenol resin.The proportional range of epoxy group(ing) and hydroxyl is preferable between between the 1:0.3 to 1:1.1, and is better between the 1:0.4 to 1:0.8.The nitrogen content of nitrogenous phenol resin is preferable account for halogen-free fire-resistant the composition epoxy resin gross weight 1.40% to 2.80% between, better between 1.50% to 2.52%.
(d) of the present invention inorganic filler comprises silicon-dioxide, aluminium hydroxide, magnesium hydroxide, aluminum oxide, clay or mica powder.Inorganic filler account for halogen-free fire-resistant the composition epoxy resin gross weight 20% to 45% between, better between 25% to 36%.
Except above-mentioned composition, the present invention can add bisphenol A type epoxy resin according to circumstances, and its structural formula is as follows:
Commercially available bisphenol A type epoxy resin comprises the NPES-301 series that DER-331 series that DOW Chemical sold, Epikote828 series that ShellChemical Company is sold, BE-188 series that Changchun chemical company is sold or South Asia plastics are sold.In preferred embodiment of the present invention, the epoxy equivalent (weight) of bisphenol A type epoxy resin is less than 1000.Preferable below 5% of composition epoxy resin gross weight that accounts for halogen-free fire-resistant of bisphenol A type epoxy resin, bisphenol A type epoxy resin can be the combination of the resin or the different epoxy equivalent (weight) resins of single epoxy equivalent (weight).
After the dilution of above-mentioned composition epoxy resin, soak into or be applied to woven fiber glass rebake, the film that can obtain doing.Thinner can be 1-Methoxy-2-propyl acetate (propylene glycol monomethyl etheracetate, abbreviation PMA), propylene glycol monomethyl ether (propylene glycol monomethyl ether is called for short PM), methylethylketone, acetone or above-mentioned mixing.If composition epoxy resin adds inorganic filler, then need inorganic filler to be dispersed in the resin with violent stirring or other suitable dispersing mode, will disperse uneven particulate filter to fall with filter screen (100-200mesh) again.Between 170 ℃ to 220 ℃, storing time is about 3-5 minute to the storing temperature of woven fiber glass after infiltration or coating approximately.After above-mentioned baking, get final product film.
But above-mentioned film storehouse pressing forms laminated plates (laminated sheet), and between 140 ℃ to 200 ℃, pressing pressure is approximately between between the 200psi to 450psi approximately for pressing-in temp.The generation type of copper clad laminate (copper clad laminate) is similar to laminated plates, just carries out pressing after the one-sided or bilateral of storehouse film is put Copper Foil again.In addition, also the circuit card of patterning can be located between the film, Copper Foil be placed outside the film again, then carry out pressing to form multilayer laminated boards plate (multi laminated sheet), pressing-in temp is approximately between 160 ℃ to 190 ℃.
In order to make those of ordinary skill in the art more be expressly understood feature of the present invention, now enumerate following preferred embodiment.
Nomenclature of drug and source that the present invention is used are listed below:
(1) bisphenol A type epoxy resin (bisphenel Atype Epoxy)
The BE-188L that the Changchun chemical industry is sold, its epoxy equivalent (weight) be between 185-195, solid content 100%.
(2) novolac epoxy (Novalac Epoxy Resin)
The CNE-200ELF that the Changchun chemical industry is sold, its epoxy equivalent (weight) be between 190-210, and softening temperature is between 76-82 ℃, solid content 100%.
(3) two diphenyl phosphoester (the bisphenol A bis (diphenyl phosphate) of bisphenol A-type
The Fyrolflex BDP that AKZO Nobel is sold, the liquid of phosphorus content 9.0%, its structural formula is suc as formula 11:
(4) two diphenyl phosphoester (the resorcinol bis (diphenyl phosphate) of Resorcinol
The Fyrolflex RDP that AKZO Nobel is sold, the liquid of phosphorus content 10.9%, its structural formula is suc as formula 12:
(5) triphenyl (Triphenyl Phosphate)
The Fyrolflex TPP that AKZO Nobel is sold, the solid of phosphorus content 9.5%, its structural formula is suc as formula 13:
(6) can with the poly phosphate (PBDP1) of Resins, epoxy reaction
The poly phosphate (PBDP1) that skill source science and technology (China) limited-liability company (TSI (China) company Limited) is sold, the solid of phosphorus content 7.8%, its structural formula is suc as formula 14:
(formula 14)
(7) phosphoric acid ester (BDP1) of the terminal phenolic group of tool
Skill source science and technology (China) phosphoric acid ester (BDP1) that limited-liability company sold, the solid of phosphorus content 5.2%, its structural formula is suc as formula 15:
(8) amido triazine resol (amino triazine novalic, ATN)
Big Japanese ink (Dai Nippon Ink Chemical Co., the Ltd.) LA-7751 that is sold, nitrogen content 14%, solid content 57-61%, hydroxyl equivalent are 135.
(9) benzoxazinyl-bisphenol A-type resin
The BZ-4 that gold Longhua Industries, Inc (Taiwan) is sold, solid.
(10) aluminium hydroxide
(SUMITOMO CHEMICAL CO., the LTD.) CL-303 that is sold, particle diameter are 2.5 μ m to the Sumitomo chemical industry.
(11) silicon-dioxide
(BAO-Lin Industrial Co., the Ltd) SilverBond925 that is sold, particle diameter are 3 μ m in Po Lam industry.
Synthesizing of benzoxazinyl-phosphate compound
Get the BDP1 of 180g, the Paraformaldehyde 96 of 38.3g (paraformaldehyde), 55.9g aniline (aniline), and the methylethylketone of 92g place reaction flask under the nitrogen, 80-90 ℃ of following back flow reaction 8 hours.Remove unreacted Paraformaldehyde 96, aniline, reach methylethylketone with concentrating instrument after having reacted, obtain the benzoxazinyl-phosphate compound suc as formula 16.The methylethylketone that adds 114g at last is used as solvent, will consolidate part and be adjusted to 70%.
Embodiment 1
Get the PBDP1 (70% solid content is in methylethylketone) of BE-188,2800g of CNE-200ELF (70% solid content is in PMA), the 330g of 4270g, the BZ-4 (60% solid content is in methylethylketone) of the methylethylketone of 1000g, the LA-7751 of 1300g (59% solid content is in methylethylketone), 930g, and the aluminium hydroxide (CL-303) of 2400g mix that the back is powerful stirred 6 hours, will consolidate with PMA again and part be diluted to 65%.Then filter, utilize impregnation machine (treater) to carry out the impregnation of woven fiber glass, make film through baking procedure again with screen cloth (100-200mesh).
Embodiment 2
Get the BZ-4 (60% solid content is in methylethylketone), the benzoxazinyl-phosphoric acid ester (formula 16 of 600g of LA-7751 (59% solid content is in methylethylketone), 930g of PBDP1 (70% solid content is in methylethylketone), 1000g methylethylketone, 1600g of BE-188,2800g of CNE-200ELF (70% solid content is in PMA), the 330g of 4270g, 70% solid content is in methylethylketone), and the silicon-dioxide (SilverBond925) of 2700g mix that the back is powerful stirred 6 hours, will consolidate with PMA again and part be diluted to 65%.Then filter, utilize impregnation machine to carry out the impregnation of woven fiber glass, make film through baking procedure again with screen cloth (100-200mesh).
Embodiment 3
Get the PBDP1 (70% solid content is in methylethylketone) of CNE-200ELF (70% solid content is in PMA), the 3930g of 4500g, the aluminium hydroxide (CL303) of LA-7751 (59% solid content is in methylethylketone), the 1400g of the methylethylketone of 1000g, the BZ-4 of 830g (60% solid content is in methylethylketone), 1570g, the silicon-dioxide (SilverBond925) of 1400g mix the powerful stirring in back 6 hours, will consolidate part with PMA again and be diluted to 65%.Then filter, utilize impregnation machine to carry out the impregnation of woven fiber glass, make film through baking procedure again with screen cloth (100-200mesh).
Embodiment 4
Get 4500g CNE-200ELF (70% solid content is in PMA), 2800g PBDP1 (70% solid content is in methylethylketone), 1070g methylethylketone, 1105g BZ-4 (60% solid content is in methylethylketone), 1600g LA-7751 (59% solid content is in methylethylketone), 1155g aluminium hydroxide (CL303), and the silicon-dioxide (SilverBond925) of 2310g mix that the back is powerful stirred 6 hours, will consolidate with PMA again and part be diluted to 65%.Then filter, utilize impregnation machine to carry out the impregnation of woven fiber glass, make film through baking procedure again with screen cloth (100-200mesh).
Comparative Example A An
Get 4270g CNE-200ELF (70% solid content is in PMA), 596g BE-188,1240g Fyroflex RDP, 1670g methylethylketone, 100g BZ-4 (60% solid content is in methylethylketone), 1184g LA-7751 (59% solid content is in methylethylketone), 1260g aluminium hydroxide (CL303), and the silicon-dioxide (SilverBond925) of 1260g mix that the back is powerful stirred 6 hours, will consolidate with PMA again and part be diluted to 65%.Then filter, utilize impregnation machine to carry out the impregnation of woven fiber glass, make film through baking procedure again with screen cloth (100-200mesh).
Comparative Examples B
Get the CNE-200ELF (70% solid content is in PMA) of 4270g, the BE-188 of 596g, the LA-7751 (59% solid content is in methylethylketone) of the methylethylketone of Fyroflex RDP, the 1670g of 1240g, the BZ-4 of 100g (60% solid content is in methylethylketone), 1184g, and the aluminium hydroxide (CL303) of 2520g mix that the back is powerful stirred 6 hours, will consolidate with PMA again and part be diluted to 65%.Then filter, utilize impregnation machine to carry out the impregnation of woven fiber glass, make film through baking procedure again with screen cloth (100-200mesh).
Comparing embodiment C
The aluminium hydroxide (CL303) of LA-7751 (59% solid content is in methylethylketone), 2530g of methylethylketone, 1256g of Fyroflex TPP, 1300g of getting CNE-200ELF (70% solid content is in PMA), the 937g of 4270g mixes that the back is powerful stirred 6 hours, will consolidate with PMA part to be diluted to 65% again.Then filter, utilize impregnation machine to carry out the impregnation of woven fiber glass, make film through baking procedure again with screen cloth (100-200mesh).
Comparing embodiment D
The aluminium hydroxide (CL303) of LA-7751 (59% solid content is in methylethylketone), 2700g of BZ-4 (60% solid content is in methylethylketone), 1256g of methylethylketone, 100g of Fyroflex BDP, 1490g of getting CNE-200ELF (70% solid content is in PMA), the 1240g of 4270g mixes that the back is powerful stirred 6 hours, will consolidate with PMA part to be diluted to 65% again.Then filter, utilize impregnation machine to carry out the impregnation of woven fiber glass, make film through baking procedure again with screen cloth (100-200mesh).
The making of copper clad laminate
Get 8 films from each embodiment 1-4 and each Comparative Example A An-D respectively, respectively put a Copper Foil behind the storehouse up and down again with the pressing of pressing machine.Pressing-in temp is 190 ℃, and pressing pressure is for being 400psi, and pressing time is 90 minutes.
First table is the prescription of embodiment 1-4 and Comparative Example A An-D and the rerum natura table of the copper clad laminate that film forms thereof.In first table, most rerum natura is measured as U.S.'s electronic circuit moulding standard (IPC standard), and its testing method number is shown in second table.
First table
Second table
| Method | IPC testing method number: |
| 171 ± 0.5 ℃ varnish gel time | IPC-TM-650-2.3.18 |
| 171 ± 0.5 ℃ semicure film resin gel time | IPC-TM-650-2.3.18 |
| The Copper Foil peel strength | IPC-TM-650-2.4.8 |
| The flame resistivity test of UL94 | IPC-TM-650-2.3.10 |
Except with the IPC canonical measure, the present invention also can adopt other testing method as follows:
288 ℃ of tin stove thermotolerance tests (at288 ℃ of Solder bath resistance)
With the copper clad laminate of 50mmx100mm size, be immersed in 288 ℃ tin stove, record plate bursting or the time that has bubble to produce.
288 ℃ of thermotolerances test (thermomechanical analyzer) (Heat resistance at288 ℃ (TMA))
The copper clad laminate of 1mmx1mm size is placed thermomechanical analyzer, temperature is maintained 288 ℃ after room temperature is warming up to 288 ℃ with the heating rate of 10 ℃/min.Observation dimensional change (having big variation to represent plate bursting) also writes down the time that plate bursting produces after 288 ℃.
Can know discovery by first table, adopt the embodiment of the phosphoric acid ester that contains phenolic group and/or benzoxazinyl-, compare with the comparing embodiment that adopts existing phosphoric acid ester, the film that embodiments of the invention form has than high viscosity.In addition, the copper clad laminate of the embodiment of the invention and the copper clad laminate of comparing embodiment are compared, and have high glass transition (Tg), thicker degree, reach preferable thermotolerance.
Though the present invention discloses as above by embodiment, it is not in order to limit the present invention.Any those of ordinary skill in the art without departing from the spirit and scope of the present invention, can carry out other change and retouching.Therefore, protection scope of the present invention should be as the criterion with defining of claim.
Claims (21)
1. the composition epoxy resin of a halogen-free fire-resistant, it comprises:
(a) novolac epoxy of 25 weight % to 45 weight %;
(b) phosphate compound of 18 weight % to 35 weight %;
(c) the nitrogenous phenol resin of 10 weight % to 20 weight % comprises amido triazine resol, benzoxazinyl-resin or its combination; And
(d) inorganic filler of 20 weight % to 45 weight %;
Wherein, phosphate compound is:
Wherein:
N is the integer of 4-10;
Each R
1Independent separately, be hydrogen or methyl;
Each R
2Solely sharp separately, be sec.-propyl or sulfuryl;
Each X is an oxygen.
2. the composition epoxy resin of halogen-free fire-resistant according to claim 1 is characterized in that: described novolac epoxy account for halogen-free fire-resistant the composition epoxy resin gross weight 30% to 40%.
3. the composition epoxy resin of halogen-free fire-resistant according to claim 1 is characterized in that: the phosphorus content of described phosphate compound account for halogen-free fire-resistant the composition epoxy resin gross weight 1.40% to 2.73%.
4. the composition epoxy resin of halogen-free fire-resistant according to claim 1 is characterized in that: the phosphorus content of described phosphate compound account for halogen-free fire-resistant the composition epoxy resin gross weight 1.40% to 2.34%.
5. the composition epoxy resin of halogen-free fire-resistant according to claim 1 is characterized in that: the nitrogen content of described nitrogenous phenol resin account for halogen-free fire-resistant the composition epoxy resin gross weight 1.40% to 2.80%.
6. the composition epoxy resin of halogen-free fire-resistant according to claim 1 is characterized in that: the nitrogen content of described nitrogenous phenol resin account for halogen-free fire-resistant the composition epoxy resin gross weight 1.50% to 2.52%.
7. the composition epoxy resin of halogen-free fire-resistant according to claim 1 is characterized in that: described inorganic filler account for halogen-free fire-resistant the composition epoxy resin gross weight 25% to 36%.
8. the composition epoxy resin of halogen-free fire-resistant according to claim 1, it is characterized in that: described inorganic filler comprises silicon-dioxide, aluminium hydroxide, magnesium hydroxide, aluminum oxide, clay or mica powder.
9. the composition epoxy resin of halogen-free fire-resistant according to claim 1, it is characterized in that: it further comprises a bisphenol A type epoxy resin, accounts for below 5% of composition epoxy resin gross weight of halogen-free fire-resistant.
10. the composition epoxy resin of halogen-free fire-resistant according to claim 9, it is characterized in that: the epoxide equivalent of described bisphenol A type epoxy resin is smaller or equal to 1000.
11. the composition epoxy resin of halogen-free fire-resistant according to claim 1 is characterized in that: the softening temperature of described novolac epoxy is between 70 ℃ to 130 ℃.
12. the composition epoxy resin of halogen-free fire-resistant according to claim 1 is characterized in that: the softening temperature of described novolac epoxy is between 75 ℃ to 100 ℃.
13. the composition epoxy resin of halogen-free fire-resistant according to claim 1 is characterized in that: the hydroxyl ratio of the epoxy group(ing) of the composition epoxy resin of described halogen-free fire-resistant and described nitrogenous phenol resin is between 1: 0.3 to 1: 1.1.
14. the composition epoxy resin of halogen-free fire-resistant according to claim 1 is characterized in that: the hydroxyl ratio of the epoxy group(ing) of the composition epoxy resin of described halogen-free fire-resistant and described nitrogenous phenol resin is between 1: 0.4 to 1: 0.8.
15. the composition epoxy resin of halogen-free fire-resistant according to claim 1 is characterized in that: described benzoxazinyl-resin comprises benzoxazinyl-bisphenol A-type resin, benzoxazinyl-Bisphenol F type resin, benzoxazinyl-bis-phenol sulfuryl resin, benzoxazinyl-resol or aforesaid combination.
16. the composition epoxy resin of halogen-free fire-resistant according to claim 1 is characterized in that: the viscosity of described phosphate compound in the time of 100 ℃ is 20000-25000cps.
17. the composition epoxy resin of halogen-free fire-resistant according to claim 1 is characterized in that: described phosphate compound comprises:
18. the composition epoxy resin of halogen-free fire-resistant according to claim 1 is characterized in that: described phosphate compound comprises:
19. the composition epoxy resin of halogen-free fire-resistant according to claim 1 is characterized in that: described phosphate compound comprises:
20. a film is to be contained by a woven fiber glass that the composition epoxy resin that is dipped in the described halogen-free fire-resistant of claim 1 is prepared to form.
21. a copper clad laminate is to be formed by a Copper Foil and the described film pressing of claim 20.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007101049706A CN101302327B (en) | 2007-05-10 | 2007-05-10 | Halogen-free fire-resistant epoxy resin composition, film and copper clad laminate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007101049706A CN101302327B (en) | 2007-05-10 | 2007-05-10 | Halogen-free fire-resistant epoxy resin composition, film and copper clad laminate |
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| CN101302327A CN101302327A (en) | 2008-11-12 |
| CN101302327B true CN101302327B (en) | 2011-05-04 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102002235B (en) * | 2010-11-15 | 2012-07-25 | 烟台德邦电子材料有限公司 | Method for reducing thermal expansion coefficient of polybenzoxazine-based underfill |
| CN103724936B (en) * | 2012-10-10 | 2016-08-03 | 慧智科技（中国）有限公司 | Improve the Halogen-free low dielectric epoxy resin composition of shock resistance |
| CN105295308B (en) * | 2015-12-14 | 2017-12-12 | 南安市鑫灿品牌运营有限公司 | A kind of printed circuit board base board and preparation method thereof |
| CN113372385B (en) * | 2021-06-07 | 2022-04-19 | 珠海宏昌电子材料有限公司 | Phosphorus-benzene bisphenol polymer and preparation method and application thereof |
| CN113292852B (en) * | 2021-06-07 | 2023-06-20 | 珠海宏昌电子材料有限公司 | Resin composition containing phosphorus-benzene bisphenol polymer, preparation method and application thereof |
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| CN1138602A (en) * | 1995-04-10 | 1996-12-25 | 信越化学工业株式会社 | Semiconductor encapsulating epoxy resin compositions and semiconductor devices encapsulated therewith |
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| JP2000336248A (en) * | 1999-05-27 | 2000-12-05 | Dainippon Ink & Chem Inc | Epoxy resin composition and electrical laminate sheet |
| JP2002284963A (en) * | 2001-03-26 | 2002-10-03 | Nippon Kayaku Co Ltd | Flame-retardant epoxy resin composition and use thereof |
| CN1599775A (en) * | 2001-11-30 | 2005-03-23 | 宝理塑料株式会社 | Flame-retardant resin composition |
| CN1621444A (en) * | 2004-10-11 | 2005-06-01 | 广东生益科技股份有限公司 | Thermosetting resin composition, presoaking materials and laminated sheet for printed circuit using same |
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2007
- 2007-05-10 CN CN2007101049706A patent/CN101302327B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1138602A (en) * | 1995-04-10 | 1996-12-25 | 信越化学工业株式会社 | Semiconductor encapsulating epoxy resin compositions and semiconductor devices encapsulated therewith |
| CN1167495A (en) * | 1995-09-29 | 1997-12-10 | 东芝化学株式会社 | Hologen-free flame-retardant epoxy resin composition, and prepreg and laminate containing the same |
| JP2000336248A (en) * | 1999-05-27 | 2000-12-05 | Dainippon Ink & Chem Inc | Epoxy resin composition and electrical laminate sheet |
| JP2002284963A (en) * | 2001-03-26 | 2002-10-03 | Nippon Kayaku Co Ltd | Flame-retardant epoxy resin composition and use thereof |
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| CN1621444A (en) * | 2004-10-11 | 2005-06-01 | 广东生益科技股份有限公司 | Thermosetting resin composition, presoaking materials and laminated sheet for printed circuit using same |
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|---|---|
| CN101302327A (en) | 2008-11-12 |
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