CN104893243A - Bisphenol S-base phosphorus-nitrogen compound containing hardener, and epoxy composition - Google Patents
Bisphenol S-base phosphorus-nitrogen compound containing hardener, and epoxy composition Download PDFInfo
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- CN104893243A CN104893243A CN201510239816.4A CN201510239816A CN104893243A CN 104893243 A CN104893243 A CN 104893243A CN 201510239816 A CN201510239816 A CN 201510239816A CN 104893243 A CN104893243 A CN 104893243A
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Abstract
The present invention discloses an epoxy resin hardener and a composition. The hardener partially or totally consists of a bisphenol S-base phosphorus-nitrogen compound, wherein the molecular structure of the bisphenol S-base phosphorus-nitrogen compound comprises a bisphenol S-base group and a group (M) that contains a phosphorus-nitrogen backbone formed by unsaturated phosphorus and nitrogen atoms, and the two groups are connected with each other. M comprises at least 50 wt% of a group (M1) that contains a cyclic phosphorus-nitrogen backbone formed by three phosphorus and nitrogen atoms, at most 30 wt% of a group (M2) that contains a chain phosphorus-nitrogen backbone formed by at most two phosphorus and nitrogen atoms and at most 45 wt% of a group (M3) that contains a cyclic phosphorus-nitrogen backbone formed by at least four phosphorus and nitrogen atoms, so that the flame-retardant compound has good flame retardancy, and a cured product thereof has good heat resistance, water resistance, and cohesiveness, and a good mechanical property and electric property. In addition, application of the composition in composite metal substrates and circuit boards can improve the flame retardancy of the composite metal substrates and circuit boards, and the composition is economical and environmentally friendly.
Description
Technical field
The present invention relates to the technical field of fire retardant matter, particularly relate to the solidifying agent containing bisphenol S base phosphorus-nitrogen compound and epoxy composite.
Background technology
The electronic product being representative with mobile phone, computer, pick up camera, electronic game machine, the various products used be representative family expenses, office electric equipment products and the other field such as air-conditioning, refrigerator, television image, sound equipment articles for use, in order to safety, very most product all requires that it possesses flame retardant properties in various degree.
Required flame retardant properties or grade is reached in order to make product, traditional technology usually uses adds as aluminium hydroxide hydrate in material system, the inorganic fire-retarded material of the classes such as the metal hydroxides containing crystal water such as magnesium hydroxide hydrate, add as brominated bisphenol A with in system material, the brominated amount such as brominated bisphenol a type epoxy resin higher or organic chemicals that halogen-containing amount is higher, in order to improve the flame retardant resistance that these contain the organic chemicals of halogen, also usually add again in system if antimonous oxide etc. is to environment disagreeableness inorganic chemistry fire retardant material.
Owing to using halogen-containing fire retardant matter, can produce during its burning toxic substance without degradation property or difficult degradation as dioxin organic halogen chemical contamination environment, affect the mankind and animal health.
For the object of protection of the environment; the not halogen-containing compound such as phosphorous, nitrogenous is used to replace halogen contained compound as fire retardant; particularly at electronics, electrically, on Electric Industrial; employing has reactive simple function (only having an active reactive group in a molecule) 9; assorted-10-phospho hetero phenanthrene-10-the oxide compound of 10-dihydro-9-oxy is hereinafter referred to as DOPO); more adopt the derivative compound of DOPO as flame-retardant composition, add or do not add aluminium hydroxide hydrate, magnesium hydroxide hydrate reaches fire-retardant effect.
At electronic applications, resultant (the being called for short DOPO epoxy resin) widespread use usually using high cost, polyfunctional epoxy resin and the DOPO such as DOPO and novolac type epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic type epoxy resin to react is as the epoxide resin material of copper-clad plate purposes.
These use the copper-clad plate manufactured by DOPO epoxy resin, there is good flame retardant properties, but there is many defects in agglutinating value(of coal), thermotolerance, processibility etc., be not suitable for the needs of the high multilayer of manufacture modern communications needs, high reliability, high agglutinating value(of coal), good processing characteristics, and due to high cost, be unfavorable for spreading to and require the civil goods fields such as the consumer electronics of low cost as mobile phone etc.
At electronic applications, usual use DOPO and etherate as dihydroxyphenyl propane, Bisphenol F, resol, phenol, ortho-cresol react obtained contain DOPO skeleton contain phenolic compound (general designation phosphorus containing phenolic resin) as epoxy curing agent or flame retardant resistance material additive, apply the fire retardant of the epoxide resin material as copper-clad plate purposes.
These use phosphorus-containing phenolic aldehydes as flame-retardant composition part or all obtained by copper-clad plate, fire-retardant object can be reached, but there is many defects in resistance to acids and bases, chemical proofing, agglutinating value(of coal), thermotolerance, processibility etc., be not suitable for the needs of the high multilayer of manufacture modern communications needs, high reliability, high agglutinating value(of coal), good processing characteristics, and due to high cost, be unfavorable for spreading to and require the civil goods fields such as the consumer electronics of low cost as mobile phone etc.
Along with electronic industry is to the requirement of the factor such as pressure of the universal use of the further raising of short, little, thin, high multiple stratification, high reliability request, civilian consumer electronics and more and more severeer environmental pollution, market has the cheap flame retardant resistance material of good flame retardant resistance, thermotolerance, good mechanical property in the urgent need to material.
Summary of the invention
In view of this, one aspect of the present invention provides a kind of solidifying agent of epoxy resin, and the epoxy resin cured product using this solidifying agent to obtain has the solidifying agent of good flame-retardance, thermotolerance, good mechanical property.
A solidifying agent for epoxy resin, mainly comprises epoxy resin and solidifying agent, and part or all of its composition is bisphenol S base phosphorus-nitrogen compound.
Comprise the bisphenol S group that is connected with each other in the molecular structure of above-mentioned bisphenol S base phosphorus-nitrogen compound and be with the group (M) of the phosphorus nitrogen skeleton be made up of unsaturated phosphorus, nitrogen-atoms, the group (M of the ring-type phosphorus nitrogen skeleton that the band that the group of described band phosphorus nitrogen skeleton comprises at least 50wt% is made up of three phosphorus, nitrogen-atoms
1), the group (M of chain phosphorus nitrogen skeleton that is made up of two phosphorus, nitrogen-atoms at the most of the band of 30wt% at the most
2) and the group (M of the ring-type phosphorus nitrogen skeleton be made up of at least four phosphorus, nitrogen-atoms of 45wt% at the most
3)
Bisphenol S base phosphorus-nitrogen compound has such as formula the molecular structure shown in I:
In formula I, M represents phosphazenium groups; Mr represents that the aromatic ring that aromatic ring or non-halogen replace, R represent aliphatic group containing at least one carbon atom or aromatic base.A, b, c are the integer being more than or equal to 1, that b and c sum is more than or equal to 2, a and b and c and be more than or equal to 6, n be more than or equal to zero integer.
If M
1content is less than 50wt%, or M
2more than 30wt%, then reacted resultant in use will damage the necessary performance such as thermotolerance, water tolerance and mechanical property with epoxy resin; M
3content account for 45% of phosphazenium groups total mass at the most.If exceed this content, then reacted resultant in use will likely because viscosity is excessive, use inconvenience with epoxy resin, and make the bad results such as its performance suffers damage because molecular weight is excessive.
Above-mentioned bisphenol S base phosphorus-nitrogen compound can adopt method well known in the art to prepare, as phosphorus cyanogen muriate is having under solvent or solvent-free condition, use, is obtained by reacting with bisphenol S or its metal-salt for catalyzer in the basic conditions with the metal chlorides such as zinc chloride, magnesium chloride, aluminum chloride, boron trifluoride and complex compound thereof etc.These catalyzer can one or more be used in combination, there is no special regulation in the present invention.Here " phosphorus cyanogen muriate " refers to the compound that in formula I, M group is connected with Cl, such as hexachlorocyclotriphosphazene.Known solvent, catalyzer can be used to synthesize in known reaction scheme as phosphonitrile chloride, also phosphorus pentachloride and ammonium chloride can be used to be synthesized after phosphorus chloride cyanogen compound according to known method, purify through physical method process or do not purify and directly manufacture, its PCl
5+ NH
4cl → 1/n (NPCl2) n+4HCl is mainly tripolymer (PNCl in this reaction product
2)
3(that is hexachlorocyclotriphosphazene) and the tetramer (PNCl
2)
4, reaction product is again by obtaining pure hexachlorocyclotriphosphazene by slowly distilling in 60 DEG C of vacuum.
Solidifying agent of the present invention to bisphenol S base phosphorus-nitrogen compound content without special restriction.Such as bisphenol S base phosphorus-nitrogen compound part composition solidifying agent.In such cases, in the reactive group equivalents of same epoxy resin reaction for, bisphenol S base phosphorus-nitrogen compound accounts for solidifying agent more than 30%, is particularly preferably 55% ~ 100%.Be understandable that, term " in the reactive group equivalents of same epoxy resin reaction for " refer to that the relative usage of bisphenol S base phosphorus-nitrogen compound, both solidifying agent is all the benchmark of calculating with reactive group equivalents of both same epoxy resin reactions contained separately.
Certainly, in the part composition solidifying agent of bisphenol S base phosphorus-nitrogen compound when, other solidifying agent of its composition can adopt the conventional solidifying agent (called after solidifying agent B) used with epoxy resin.The specific examples of solidifying agent is one in B polyphenol based compound, nitrogenous polyphenol based compound, phosphorous polyphenol based compound, nitrogenous phosphorous polyphenol based compound, amino-complex, benzoxazine colophony, acid anhydrides, polyprotonic acid and boron trifluoride and complex compound thereof or at least two kinds.Here, amino-complex is aliphatic amide or aromatic amine, such as Dyhard RU 100, diethyl triamine, diaminodiphenylmethane, diaminodiphenylsulfone(DDS); Polyphenol based compound is one in dihydroxyphenyl propane, Bisphenol F, bisphenol S, linear phenolic resin, o-cresol urea formaldehyde, bisphenol A phenolic resin or at least two kinds.
Another aspect of the invention provides a kind of composition epoxy resin with good flame-retardance, thermotolerance, good mechanical property.
A kind of composition epoxy resin, comprises epoxy resin, and the solidifying agent as described in claims 1 to 3 any one.
The present invention to the concrete kind of the epoxy resin in epoxy resin ingredient without special regulation, as long as containing the compound of epoxy group(ing) and epoxy resin.The epoxy resin that this area is general can be adopted, such as with the difunctional epoxy resin that liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, solid-state bisphenol A type epoxy resin, solid-state bisphenol f type epoxy resin, bisphenol-s epoxy resin, biphenyl type epoxy resin are representative, the above epoxy resin of trifunctional being representative with solid-state, liquid or semi-solid state novolac type epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, acyclic isoprenoid type epoxy resin.Here, those skilled in the art it is easily understood that, when being certainly necessary, also the epoxy resin that the viscosity ratio such as alicyclic epoxy resin, chain type aliphatics type epoxy resin or ester formula epoxy resin are lower can be used, these epoxy resin can be used alone and also can two or more use together, the present invention there is no special regulation to this, the present invention to the amount of these epoxy resin proportionings also not specially provided for, with reach guarantee safety, environmental protection and required performance prerequisite under obtain object.
In composition epoxy resin, also according to actual needs, curing catalyst, solvent, supporting material and filler, auxiliary agent, fire-retarded epoxy resin, bisphenol S base phosphorus azo-cycle epoxy resins can be comprised.
The interpolation of curing catalyst is in order to fast setting.The present invention to used curing catalyst without special regulation, use common epoxy resin curing accelerator, such as imidazoles, triphenylphosphine and derivatives class thereof, tertiary amines, quaternary ammonium salts, the General Catalyst of the epoxy curing agent such as boron trifluoride and derivatives class thereof curing reaction, these promotor both can be used alone, also can two or more be used in combination, the number of usage quantity, can be as required, with safety, environmental protection obtains object and is as the criterion, the present invention not specially provided for, usually, epoxy resin ingredient in contrast curing system, proper with 0.001% ~ 2.5%, more suitably scope is between 0.03% ~ 1.2%.
Solvent is mainly in order to by the solidifying agent in composition epoxy resin and epoxy resin, and it can make to adopt epoxy composite to obtain high-quality pre-impregnated sheet or bonding sheet.For the kind and the quantity that use solvent, the present invention there is no special regulation, such as acetone, butanone, DMF, DMAC, ethanol, methyl alcohol, pimelinketone, 1, the organic solvents such as 4-dioxane, petroleum solvent, toluene, dimethylbenzene, methylene dichloride, dimethyl carbonate, with reach guarantee safety, environmental protection and required performance prerequisite under obtain object.Preferably, select as each compositions such as butanone have the organic solvent that good solubility, toxicity are not strong, boiling point is more moderate; If containing not diffluent materials of crystallinity such as Dyhard RU 100s in epoxy resin ingredient, part or all nitrogenous class can be used as organic solvents such as DMF, DMAC.Be understandable that, in solidification process, solvent is the speed that can be improved volatilization by heating.
Supporting material based on the object of mechanical property improving final cured article, the one of such as glass fibre, carbon fiber and trevira or any two or more combination.
Filler is to increase its some function, character or reducing costs, can add as mineral fillers such as silicon-dioxide, diatomite, kaolin, calcium carbonate, mica, titanium dioxide, magnesium hydroxide, aluminium hydroxides in curing system, these mineral fillers can be used alone, also can two kinds or several are used in combination, usage quantity is generally advisable with the 500phr being no more than epoxy resin ingredient.
According to actual needs, auxiliary agent can be added in system.Auxiliary agent can be general or special, as materials such as defoamer, coupling agent, toughner, flow agent, releasing agent, toughner, the present invention does not do special regulation to the kind and addition of adding auxiliary agent, as required, can obtain object be as the criterion with safety, environmental protection.
In order to improve the flame retardant properties of composition epoxy resin, bisphenol S base phosphorus azo-cycle epoxy resins and fire-retarded epoxy resin can be increased in composition epoxy resin.Fire-retarded epoxy resin is DOPO type epoxy resin, containing phosphorous epoxy resin, nitrogenous type epoxy resin, nitrogenous containing phosphorous epoxy resin, phosphorus-containing phenolic aldehyde epoxy resin, nitrogenous containing the one in phosphorous novolac epoxy, silicon-contained type epoxy resin and sulfur-type epoxy resin or at least two kinds.
Bisphenol S base phosphorus azo-cycle epoxy resins is by bisphenol S base phosphorus-nitrogen compound and the epoxy resin resultant by condensation reaction.In this polycondensation, the temperature of reaction is generally the scope of 40 ~ 250 DEG C, and be more preferably the scope at 60 ~ 180 DEG C, the present invention does not do special regulation, with under the prerequisite guaranteeing safety and environmental protection, obtains object and selects to be as the criterion.As for this polycondensation, can carry out under catalyzer or catalyst-free condition.General needs add catalyzer in reaction system, the number of the present invention to the kind of catalyzer and add-on there is no special regulation, the General Catalyst usually reacted as the epoxy resin such as imidazoles, triphenylphosphine and derivatives class thereof, tertiary amines, quaternary ammonium salts and aldehydes matter can use, these catalyzer both can be used alone, also can two or more be used in combination, usage quantity is reactive material whole between 100 ~ 20000ppm in contrast system generally, are more typically between 200 ~ 5000ppm.As for the medium of reaction, can be solvent-free or have solvent.Special regulation be there is no to reaction solvent, such as acetone, butanone, the ketones solvents such as pimelinketone, benzene, toluene, dimethylbenzene, the aromatic solvents such as xylol, methylene dichloride, trichloromethane, chlorobenzenes etc. are containing chlorinated solvents, ether, butyl ether, the ethers such as ethylene glycol monomethyl ether or ether alcohol kind solvent, petroleum solvent oil, butanols, the alcoholic solvents etc. such as isopropylcarbinol all can use, these solvents can be used alone, also can two kinds or several are used in combination, the number of usage quantity, can determine according to practical situation, be generally can make fire-retarded epoxy resin solid content be 5 ~ 100% consumption, particularly preferred for can make fire-retarded epoxy resin solid content be 20 ~ 100% consumption.In view of the ultimate principle of polycondensation has been known technology, do not repeat them here.
A kind of pre-impregnated sheet, it is by fire-retardant combination impregnation described above or coat base material and form.Base material can be fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiber base material etc.Here, the concrete technology condition of its impregnation or coating is not particularly limited." bonding sheet " that " pre-impregnated sheet " is also well known to those skilled in the art.
A kind of composite metal substrate, it comprises more than one as above-mentioned pre-impregnated sheet carries out surperficial metal-clad overlap successively, pressing forms.Here, the material of surperficial metal-clad is the alloy of aluminium, copper, iron and arbitrary combination thereof.The specific examples of composite metal substrate has the following copper-clad plate, such as CEM-1 copper-clad plate, CEM-3 copper-clad plate, FR-4 copper-clad plate, FR-5 copper-clad plate, CEM-1 aluminium base, CEM-3 aluminium base, FR-4 aluminium base or FR-5 aluminium base.
A kind of wiring board, the surface working circuit in above-mentioned composite metal substrate forms.This wiring board is in such as electronic industry, electrically, Electric Industrial, communications and transportation, aerospace, toy industry etc. need the widespread use of the industry such as machine, equipment, instrument, instrument of wiring board.
Above-mentioned term " ××× base or group " refers to slough in ××× molecular structure of compounds remaining part after one or more hydrogen atom or other atom or atomic group.
The solidifying agent of epoxy resin of the present invention, its integral part or be all bisphenol S base phosphorus-nitrogen compound, the bisphenol S group be connected with each other and the group (M) being with the phosphorus nitrogen skeleton be made up of unsaturated phosphorus, nitrogen-atoms is comprised, the group (M of the ring-type phosphorus nitrogen skeleton that the band that M comprises at least 50wt% is made up of three phosphorus, nitrogen-atoms in the molecular structure of bisphenol S base phosphorus-nitrogen compound
1), the group (M of chain phosphorus nitrogen skeleton that is made up of two phosphorus, nitrogen-atoms at the most of the band of 30wt% at the most
2) and the group (M of the ring-type phosphorus nitrogen skeleton be made up of at least four phosphorus, nitrogen-atoms of 45wt% at the most
3), make this fire-retardant compound have good flame retardant resistance thus, its cured article has good thermotolerance, water tolerance, agglutinating value(of coal) and mechanical property, electrical property, is a kind of fire retardant matter also with larger economy and environmental protection friendly.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
Chlordene ring three phosphorus cyanogen 173.83g (0.5mol), acetone 150ml, phenol 188.0g (2.0mol) and bisphenol S 550.0g (2.2mol) is dropped into in three mouthfuls of 1000ml glass reactors of whipping appts, stir and lead to nitrogen while be warmed up to 52 DEG C, 20% sodium hydroxide solution 400g is instilled with 80min, keep 52 DEG C of temperature, stirring reaction 15 hours.After reaction, with the moisture in physical method removal system, refilter the insoluble substance in removal system, distill solvent in system, obtain flame retardant 804.6g, recording its phenolic group equivalent is 276.2g/eq, by this object resultant called after A.
With the triphenylphosphine dropping into liquid bisphenol A type epoxy resin 374g that epoxy equivalent (weight) is 187g/eq and above-mentioned A material 52g, 0.1g in three mouthfuls of 500ml glass reactors of whipping appts, be warmed up to 100 DEG C, react 9.5 hours, obtain the object epoxy resin 437.0g that epoxy equivalent (weight) is 247.3g/eq, add the epoxy resin solution that acetone is modulated into 60% again, by this object called after C.
Get the solution 100g (solids component is 60g) of above-mentioned C material, add the Dyhard RU 100 of 3.2g and appropriate DMF again, stir homogeneous after, add the glyoxal ethyline of 0.08g, wiring solution-forming, then obtains the standard copper-clad plate sample meeting the standard such as GB, UL, called after a copper-clad plate according to general copper-clad plate production process, the performance of test a copper-clad plate, its result represents in table-1.
Embodiment 2
Ethylene dichloride 180g, phosphorus pentachloride 104.11g (0.5mol), ammonium chloride 26.75g (0.5mol) and magnesium chloride 20g is dropped into in three mouthfuls of 2000ml glass reactors of whipping appts.Stir and lead to nitrogen while be warmed up to 52 DEG C, and react under 52 DEG C of temperature condition after 6 hours, add sodium methylate 108.04g (2.0mol) again and bisphenol S 550.0g (2.2mol) continues reaction 15 hours, add solvent 250g, cross and filter insoluble substance, then solvent evaporated, obtain flame retardant 716.2g, recording its phenolic group equivalent is 210.9g/eq, by this object resultant called after B.
Be the liquid bisphenol A type epoxy resin 374g of 187g/eq and the triphenylphosphine of above-mentioned B substance 50g and 0.1g with dropping into epoxy equivalent (weight) in three mouthfuls of 500ml glass reactors of whipping appts, be warmed up to 100 DEG C, react 9.5 hours, obtain the object epoxy resin 426g that epoxy equivalent (weight) is 231.3g/eq, by this object called after D.
Get the solution 100g (solids component is 60g) of above-mentioned D material, add the Dyhard RU 100 of 3.2g and appropriate DMF again, stir homogeneous after, add the glyoxal ethyline of 0.08g, wiring solution-forming, then obtains the standard copper-clad plate sample meeting the standard such as GB, UL, called after b copper-clad plate according to general copper-clad plate production process, the performance of test b copper-clad plate, its result represents in table-1.
Embodiment 3
Bisphenol-s epoxy resin 100g that use market epoxy equivalent (weight) to be 230g/eq, market circulation, add A material 71.8g as described in Example 1, after adding appropriate acetone solution, add the glyoxal ethyline wiring solution-forming of 0.08g again, then the standard copper-clad plate sample meeting the standard such as GB, UL is obtained according to general copper-clad plate production process, called after c copper-clad plate, the performance of test c copper-clad plate, its result represents in table-1.
Comparative example 1
Be the linear phenolic epoxy resin 374g of 178g/eq and the triphenylphosphine of DOPO 38g and 0.1g with dropping into epoxy equivalent (weight) in three mouthfuls of 500ml glass reactors of whipping appts, be warmed up to 120 DEG C, react 5 hours, obtain the object epoxy resin 412g that epoxy equivalent (weight) is 232g/eq, by this object called after E.
Get above-mentioned E material 100g and add the Dyhard RU 100 of 3.0g and appropriate DMF again, stir homogeneous after, add the glyoxal ethyline of 0.08g, wiring solution-forming, then the standard copper-clad plate sample meeting the standard such as GB, UL is obtained according to general copper-clad plate production process, called after d copper-clad plate, the performance of test d copper-clad plate, its result represents in table-1.
The test result of embodiment and comparative example is as shown in following table-1 (in view of concrete testing method is well known to those skilled in the art, no longer describing in detail method at this):
The Performance comparision of table-1 copper-clad plate
The test data of above form, show that fire-retardant compound of the present invention and derivative thereof are when being used in epoxy resin solidifying system and other system, have good flame retardant resistance, its cured article has good thermotolerance, water tolerance, agglutinating value(of coal) and mechanical property, electrical property.Fire-retardant compound of the present invention belongs to the environment-friendly type flame-retardant material of novel environmental friendly of low cost, abundant raw material source, energy-saving and emission-reducing that properties is good.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a solidifying agent for epoxy resin, is characterized in that, part or all of its composition is bisphenol S base phosphorus-nitrogen compound;
Comprise the bisphenol S group that is connected with each other in the molecular structure of described bisphenol S base phosphorus-nitrogen compound and be with the group (M) of the phosphorus nitrogen skeleton be made up of unsaturated phosphorus, nitrogen-atoms, the group (M of the ring-type phosphorus nitrogen skeleton that the band that the group of described band phosphorus nitrogen skeleton comprises at least 50wt% is made up of three phosphorus, nitrogen-atoms
1), the group (M of chain phosphorus nitrogen skeleton that is made up of two phosphorus, nitrogen-atoms at the most of the band of 30wt% at the most
2) and the group (M of the ring-type phosphorus nitrogen skeleton be made up of at least four phosphorus, nitrogen-atoms of 45wt% at the most
3).
2. solidifying agent according to claim 1, is characterized in that, described bisphenol S base phosphorus-nitrogen compound has such as formula the molecular structure shown in I:
In formula I, R represents aliphatic group containing at least one carbon atom or aromatic base; A, b, c are the integer being more than or equal to 1, b and c sum is more than or equal to 2, a, b and c three sum be more than or equal to 6, n be more than or equal to zero integer.
3. composition epoxy resin according to claim 1, is characterized in that, in the reactive group equivalents of same epoxy resin reaction for, described bisphenol S base phosphorus-nitrogen compound accounts for solidifying agent more than 30%;
Preferably, in the reactive group equivalents of same epoxy resin reaction for, described solidifying agent A accounts for 55% ~ 100% of solidifying agent;
Preferably, described solidifying agent also comprises solidifying agent B, and described solidifying agent B is one in polyphenol based compound, nitrogenous polyphenol based compound, phosphorous polyphenol based compound, nitrogenous phosphorous polyphenol based compound, amino-complex, benzoxazine colophony, acid anhydrides, polyprotonic acid and boron trifluoride and complex compound thereof or at least two kinds;
Preferably, described amino-complex is Dyhard RU 100, diethyl triamine, diaminodiphenylmethane, diaminodiphenylsulfone(DDS);
Preferably, described polyphenol based compound is one in dihydroxyphenyl propane, Bisphenol F, bisphenol S, linear phenolic resin, o-cresol urea formaldehyde, bisphenol A phenolic resin or at least two kinds.
4. a composition epoxy resin, is characterized in that, comprises epoxy resin, and the solidifying agent as described in claims 1 to 3 any one.
5. composition epoxy resin according to claim 4, is characterized in that, described epoxy resin is two senses or the above epoxy resin of two senses;
Preferably, difunctional epoxy resin is one in liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, solid-state bisphenol A type epoxy resin, solid-state bisphenol f type epoxy resin and bisphenol-s epoxy resin, biphenyl type epoxy resin or at least two kinds;
Preferably, the epoxy resin more than two senses is the one of phenol aldehyde type epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin and acyclic isoprenoid type epoxy resin or at least two kinds.
6. composition epoxy resin according to claim 4, is characterized in that, also comprises the bisphenol S base phosphorus azo-cycle epoxy resins generated by condensation reaction by bisphenol S base phosphorus-nitrogen compound and epoxy resin, and fire-retarded epoxy resin;
Preferably, described fire-retarded epoxy resin content of halogen is not higher than 0.2%;
Preferably, described fire-retarded epoxy resin be DOPO type epoxy resin, containing phosphorous epoxy resin, nitrogenous type epoxy resin, nitrogenous containing phosphorous epoxy resin, phosphorus-containing phenolic aldehyde epoxy resin, nitrogenous containing the one in phosphorous novolac epoxy, silicon-contained type epoxy resin and sulfur-type epoxy resin or at least two kinds.
7. composition epoxy resin according to claim 4, is characterized in that, also comprises curing catalyst;
Described curing catalyst is one in imidazoles, triphenylphosphine and derivatives class thereof, tertiary amines, quaternary ammonium salts and boron trifluoride and derivatives class thereof or at least two kinds;
Preferably, the consumption of described curing catalyst is account for epoxy resin total mass 0.001 ~ 2.5%, more preferably 0.03 ~ 1.2%;
Preferably, supporting material and filler is also comprised;
Preferably, described supporting material is one in glass fibre, carbon fiber and trevira or at least two kinds;
Preferably, described filler is one in silicon-dioxide, diatomite, kaolin, calcium carbonate, mica, titanium dioxide, magnesium hydroxide, aluminium hydroxide or at least two kinds;
Preferably, the consumption of described filler be epoxy resin total mass be no more than 500phr;
Preferably, also comprise auxiliary agent, described auxiliary agent is one in defoamer, coupling agent, toughner and flow agent or at least two kinds
8. a pre-impregnated sheet, is characterized in that, it is by fire-retardant combination impregnation as claimed in claim 7 or coat base material and form;
Preferably, described base material is fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiber base material.
9. a composite metal substrate, is characterized in that, it comprises more than one, and pre-impregnated sheet carries out surperficial metal-clad successively as claimed in claim 8, overlap, pressing form;
Preferably, the material of described surperficial metal-clad is the alloy of aluminium, copper, iron and arbitrary combination thereof;
Preferably, described composite metal substrate is but is not limited to CEM-1 copper-clad plate, CEM-3 copper-clad plate, FR-4 copper-clad plate, FR-5 copper-clad plate, CEM-1 aluminium base, CEM-3 aluminium base, FR-4 aluminium base or FR-5 aluminium base.
10. a wiring board, is characterized in that, the surface working circuit in composite metal substrate according to claim 9 forms.
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| CN201510239816.4A CN104893243B (en) | 2015-05-12 | 2015-05-12 | The curing agent and epoxy composite of the phosphorus-nitrogen compound of base containing bisphenol S |
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| CN201510239816.4A CN104893243B (en) | 2015-05-12 | 2015-05-12 | The curing agent and epoxy composite of the phosphorus-nitrogen compound of base containing bisphenol S |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107254138A (en) * | 2016-05-16 | 2017-10-17 | 广东广山新材料股份有限公司 | A kind of fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate |
| CN110128702A (en) * | 2019-05-05 | 2019-08-16 | 三峡大学 | Benzene sulphones nitrogen phosphorus sulphur synergistic flame retardant containing double DOPO, preparation method and applications |
| CN110435254A (en) * | 2019-08-29 | 2019-11-12 | 山东金宝电子股份有限公司 | A kind of high heat resistance, high CTI CEM-3 copper-clad plate preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4094856A (en) * | 1976-06-15 | 1978-06-13 | E. I. Du Pont De Nemours And Company | Flame retardant polymeric compositions |
| JP2007153747A (en) * | 2005-11-30 | 2007-06-21 | Fushimi Pharm Co Ltd | Hydroxy group-containing cyclic phosphazene compound and method for producing the same |
| CN101092484A (en) * | 2007-06-21 | 2007-12-26 | 上海交通大学 | Surface modified microballons of containing phosphazene, and preparation method |
| CN104530131A (en) * | 2014-12-09 | 2015-04-22 | 广东广山新材料有限公司 | Flame retardant compound, flame retardant epoxy resin and flame retardant composition |
| CN104628997A (en) * | 2015-02-10 | 2015-05-20 | 广东广山新材料有限公司 | Flame-retardant substance with bisphenol S group, flame-retardant epoxy resin and flame-retardant composition |
-
2015
- 2015-05-12 CN CN201510239816.4A patent/CN104893243B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4094856A (en) * | 1976-06-15 | 1978-06-13 | E. I. Du Pont De Nemours And Company | Flame retardant polymeric compositions |
| JP2007153747A (en) * | 2005-11-30 | 2007-06-21 | Fushimi Pharm Co Ltd | Hydroxy group-containing cyclic phosphazene compound and method for producing the same |
| CN101092484A (en) * | 2007-06-21 | 2007-12-26 | 上海交通大学 | Surface modified microballons of containing phosphazene, and preparation method |
| CN104530131A (en) * | 2014-12-09 | 2015-04-22 | 广东广山新材料有限公司 | Flame retardant compound, flame retardant epoxy resin and flame retardant composition |
| CN104628997A (en) * | 2015-02-10 | 2015-05-20 | 广东广山新材料有限公司 | Flame-retardant substance with bisphenol S group, flame-retardant epoxy resin and flame-retardant composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107254138A (en) * | 2016-05-16 | 2017-10-17 | 广东广山新材料股份有限公司 | A kind of fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate |
| CN110128702A (en) * | 2019-05-05 | 2019-08-16 | 三峡大学 | Benzene sulphones nitrogen phosphorus sulphur synergistic flame retardant containing double DOPO, preparation method and applications |
| CN110435254A (en) * | 2019-08-29 | 2019-11-12 | 山东金宝电子股份有限公司 | A kind of high heat resistance, high CTI CEM-3 copper-clad plate preparation method |
| CN110435254B (en) * | 2019-08-29 | 2021-12-03 | 山东金宝电子股份有限公司 | Preparation method of CEM-3 copper-clad plate with high heat resistance and high CTI (comparative tracking index) |
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| CN104893243B (en) | 2018-07-24 |
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