CN104945601A - Curing agent and epoxy composition containing bisphenol-A-base phosphorus nitrogen compounds - Google Patents
Curing agent and epoxy composition containing bisphenol-A-base phosphorus nitrogen compounds Download PDFInfo
- Publication number
- CN104945601A CN104945601A CN201510240709.3A CN201510240709A CN104945601A CN 104945601 A CN104945601 A CN 104945601A CN 201510240709 A CN201510240709 A CN 201510240709A CN 104945601 A CN104945601 A CN 104945601A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- phosphorus
- nitrogen
- bisphenol
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Epoxy Resins (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a curing agent and composition of epoxy resins. The curing agent is partially or completely composed of bisphenol-A-base phosphorus nitrogen compounds; the molecular structure of the bisphenol-A-base phosphorus nitrogen compounds comprises a bisphenol A group and a group (M) with a phosphorus nitrogen framework composed of unsaturated phosphorus and nitrogen atoms, wherein M comprises at least 50 wt% of group (M1) with a cyclic phosphorus nitrogen framework composed of three phosphorus and nitrogen atoms, at most 30 wt% of group (M2) with a chain phosphorus nitrogen framework composed of at most two phosphorus and nitrogen atoms, and at most 45 wt% of group (M3) with a cyclic phosphorus nitrogen framework composed of at least four phosphorus and nitrogen atoms; and thus, the flame-retardant compounds have favorable flame retardancy, and the curing product has the advantages of favorable heat resistance, favorable water resistance, favorable adhesiveness, favorable mechanical properties and favorable electric properties. Besides, the composition can enhance the flame retardancy, economical efficiency and environment friendliness when being used in composite metal substrates and circuit boards.
Description
Technical field
The present invention relates to the technical field of fire retardant matter, particularly relate to the solidifying agent containing dihydroxyphenyl propane 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 dihydroxyphenyl propane base phosphorus-nitrogen compound.
Comprise the dihydroxyphenyl propane group that is connected with each other in the molecular structure of above-mentioned dihydroxyphenyl propane 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)
Dihydroxyphenyl propane 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 dihydroxyphenyl propane 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 dihydroxyphenyl propane 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 dihydroxyphenyl propane base phosphorus-nitrogen compound content without special restriction.Such as dihydroxyphenyl propane base phosphorus-nitrogen compound part composition solidifying agent.In such cases, in the reactive group equivalents of same epoxy resin reaction for, dihydroxyphenyl propane 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 dihydroxyphenyl propane 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 dihydroxyphenyl propane 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, dihydroxyphenyl propane 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, 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, dihydroxyphenyl propane 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.
Dihydroxyphenyl propane base phosphorus azo-cycle epoxy resins is by dihydroxyphenyl propane 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.
In above-mentioned fire-retardant combination, can be according to actual needs, some are added general in or special materials such as defoamer, coupling agent, toughner, flow agents in system, the present invention does not do special regulation to the kind and addition of adding auxiliary agent, as required, object can be obtained with safety, environmental protection and is as the criterion.
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 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 dihydroxyphenyl propane base phosphorus-nitrogen compound, the dihydroxyphenyl propane 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 dihydroxyphenyl propane 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
With dropping into chlordene ring three phosphorus cyanogen 86.9g in three mouthfuls of 2000ml glass reactors of whipping appts, acetone 200ml, phenol 94.0g and dihydroxyphenyl propane 250.8g (, stir and lead to nitrogen while be warmed up to 45 DEG C, 20% sodium hydroxide solution 200.0g is instilled with 60min, keep 45 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 374.5g, recording its phenolic group equivalent is 220.1g/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 125g and 0.05g in three mouthfuls of 500ml glass reactors of whipping appts, be warmed up to 100 DEG C, react 8 hours, obtain the object epoxy resin 499.0g that epoxy equivalent (weight) is 350.1g/eq, add the epoxy resin solution that acetone is modulated into 60% again, by this object called after B.
Get the solution 100g (solids component is 60g) of above-mentioned B substance, add the Dyhard RU 100 of 3.1g 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, ammonium chloride 26.75g is dropped into in three mouthfuls of 2000ml glass reactors of whipping appts, and magnesium chloride 20g.Stir and lead to nitrogen while be warmed up to 50 DEG C, and react under 50 DEG C of temperature condition after 8 hours, add sodium methylate 54.02g, phenol 94.0g and dihydroxyphenyl propane 501.6g again, continue reaction 12 hours, add solvent 300g, cross and filter insoluble substance, then solvent evaporated, obtain flame retardant 689.3g, recording its phenolic group equivalent is 203.2g/eq, by this object resultant called after C.
Be the liquid bisphenol A type epoxy resin 374g of 187g/eq and the triphenylphosphine of above-mentioned B substance 110g and 0.05g with dropping into epoxy equivalent (weight) in three mouthfuls of 500ml glass reactors of whipping appts, be warmed up to 100 DEG C, react 10 hours, obtain the object epoxy resin 484.0g that epoxy equivalent (weight) is 331.2g/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 2.85g 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
Chlordene ring three phosphorus cyanogen 173.83g (0.5mol), acetone 250ml, sodium methylate 108.04g and dihydroxyphenyl propane 501.6g is dropped into in three mouthfuls of 2000ml glass reactors of whipping appts, stir and lead to nitrogen while be warmed up to 40 DEG C, 20% sodium hydroxide solution 400g is instilled with 60min, keep 45 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 667.0g, recording its phenolic group equivalent is 196.2g/eq, by this object resultant called after E.
With the triphenylphosphine dropping into liquid bisphenol A type epoxy resin 374g that epoxy equivalent (weight) is 187g/eq and above-mentioned A material 120g and 0.08g in three mouthfuls of 500ml glass reactors of whipping appts, be warmed up to 100 DEG C, react 8 hours, obtain the object epoxy resin 494.0g that epoxy equivalent (weight) is 356.2g/eq, add the epoxy resin solution that acetone is modulated into 60% again, by this object called after F.
Get the solution 100g (solids component is 60g) of above-mentioned F material, add linear phenolic resin and appropriate acetone that 16.7g phenolic hydroxyl equivalent is 105g/eq again, after linear phenolic resin is dissolved completely, 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 c copper-clad plate according to general copper-clad plate production process, 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 G.
The solution (solids component is 60g) getting above-mentioned G material adds 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.
Comparative example 2
Get above-mentioned G substance solution 100g (solids component 60g), add the glyoxal ethyline that phenolic hydroxyl equivalent is lacquer resins 27.1g and 0.05g of 105g/eq, add the homogeneous rear wiring solution-forming of suitable acetone solution, 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 dihydroxyphenyl propane base phosphorus-nitrogen compound;
The dihydroxyphenyl propane 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 described dihydroxyphenyl propane 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).
2. solidifying agent according to claim 1, is characterized in that, described dihydroxyphenyl propane 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 dihydroxyphenyl propane 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 dihydroxyphenyl propane base phosphorus azo-cycle epoxy resins generated by condensation reaction by dihydroxyphenyl propane 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510240709.3A CN104945601A (en) | 2015-05-12 | 2015-05-12 | Curing agent and epoxy composition containing bisphenol-A-base phosphorus nitrogen compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510240709.3A CN104945601A (en) | 2015-05-12 | 2015-05-12 | Curing agent and epoxy composition containing bisphenol-A-base phosphorus nitrogen compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104945601A true CN104945601A (en) | 2015-09-30 |
Family
ID=54160708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510240709.3A Pending CN104945601A (en) | 2015-05-12 | 2015-05-12 | Curing agent and epoxy composition containing bisphenol-A-base phosphorus nitrogen compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104945601A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916281A (en) * | 2015-12-28 | 2017-07-04 | 广东广山新材料股份有限公司 | Flame-retardant compound, curing agent and polyphenol base epoxy |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1449427A (en) * | 2000-07-18 | 2003-10-15 | 京瓷化成株式会社 | Halogen-free nonflammable epoxy resin composition, halogen-free nonfammable epoxy resin composition for build-up type multi-layer board |
| TW200927809A (en) * | 2007-10-11 | 2009-07-01 | Fushimi Pharmaceutical Co Ltd | Epoxy compound composition |
-
2015
- 2015-05-12 CN CN201510240709.3A patent/CN104945601A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1449427A (en) * | 2000-07-18 | 2003-10-15 | 京瓷化成株式会社 | Halogen-free nonflammable epoxy resin composition, halogen-free nonfammable epoxy resin composition for build-up type multi-layer board |
| TW200927809A (en) * | 2007-10-11 | 2009-07-01 | Fushimi Pharmaceutical Co Ltd | Epoxy compound composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916281A (en) * | 2015-12-28 | 2017-07-04 | 广东广山新材料股份有限公司 | Flame-retardant compound, curing agent and polyphenol base epoxy |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6318191B2 (en) | Flame retardant compounds, curing agents and polyphenolic epoxy resins | |
| CN104530131A (en) | Flame retardant compound, flame retardant epoxy resin and flame retardant composition | |
| CN104892898A (en) | Phosphorus-nitrogen epoxy resin with bisphenol S radicals, flame-retardant composition, composite metal substrate | |
| CN102369227B (en) | Phosphorus-containing phenol novolac resin, hardener comprising the same and epoxy resin composition | |
| US20020032279A1 (en) | Flame retardant resin and flame retardant composition containing the same | |
| US8362116B2 (en) | Low dielectric resin varnish composition for laminates and the preparation thereof | |
| CN104610530A (en) | Flame retardant with bisphenol A groups, flame-retardant epoxy resin and flame-retardant composition | |
| CN107337694A (en) | A kind of phosphazene compound with silanol, fire retardant, composition epoxy resin and composite metal substrate | |
| CN104628996A (en) | Flame retardant with bisphenol F group, flame-retardant epoxy resin and flame-retardant composition | |
| EP3190119A1 (en) | Phosphazene compound comprising cyano group, preparation method and uses thereof | |
| CN106916281A (en) | Flame-retardant compound, curing agent and polyphenol base epoxy | |
| US6548627B1 (en) | Flame-retardant phosphorus-modified epoxy resins | |
| CN104893243A (en) | Bisphenol S-base phosphorus-nitrogen compound containing hardener, and epoxy composition | |
| EP3187501B1 (en) | A phosphazene compound, and a composition, a prepreg and a wiring board comprising the same | |
| CN104628997A (en) | Flame-retardant substance with bisphenol S group, flame-retardant epoxy resin and flame-retardant composition | |
| CN104892906A (en) | Single aromatic ring phenol based phosphorus-nitrogen compound containing hardener, and epoxy composition | |
| CN104892900A (en) | Bisphenol A group containing phosphorus-nitrogen epoxy resin, flame retardant composition, and composite metal substrate | |
| CN104892899A (en) | Phosphorus-nitrogen epoxy resin with bisphenol F radicals, flame-retardant composition, composite metal substrate | |
| TWI617614B (en) | Epoxy resin composition and prepreg and copper clad laminate prepared using same | |
| CN107337696A (en) | Phosphazene compound, curing agent, phosphonitrile epoxy resin and composite metal substrate and plastic packaging material with aldehyde radical | |
| CN104945601A (en) | Curing agent and epoxy composition containing bisphenol-A-base phosphorus nitrogen compounds | |
| CN104892907A (en) | Curing agent of phosphorus-nitrogen compound with bisphenol F groups, and epoxy composition | |
| CN103333464B (en) | A kind of phosphor-containing halogen-free fire retarded epoxy resin composition and application | |
| CN104892901A (en) | Phosphorus-nitrogen epoxy resin with single aromatic ring phenolic groups, flame-retardant combination, and composite metal substrate | |
| US20130025916A1 (en) | Flame retardant epoxy laminate containing metal phosphonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 523000 Dongguan Port Road, Guangdong (Sha Tianduan) Humen port service center, Humen port service building on the third floor Applicant after: Guangdong Guang Shan new materials Limited by Share Ltd Address before: 523990 Dongguan Port Road, Guangdong (Sha Tianduan) Humen port service center, Humen port service building 3F Applicant before: GUANG SHAN NEW MATERIALS CO., LTD. |
|
| CB02 | Change of applicant information | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150930 |
|
| RJ01 | Rejection of invention patent application after publication |