CN104893243B - The curing agent and epoxy composite of the phosphorus-nitrogen compound of base containing bisphenol S - Google Patents
The curing agent and epoxy composite of the phosphorus-nitrogen compound of base containing bisphenol S Download PDFInfo
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- CN104893243B CN104893243B CN201510239816.4A CN201510239816A CN104893243B CN 104893243 B CN104893243 B CN 104893243B CN 201510239816 A CN201510239816 A CN 201510239816A CN 104893243 B CN104893243 B CN 104893243B
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Abstract
The invention discloses the curing agent of epoxy resin and compositions.Part or all of the composition of the curing agent is bisphenol S base phosphorus-nitrogen compound, the group (M) for the phosphorus nitrogen skeleton being made of unsaturated phosphorus, nitrogen-atoms comprising the bisphenol S group and band that are connected with each other in the molecular structure of bisphenol S base phosphorus-nitrogen compound, M include the group (M for the cyclic annular phosphorus nitrogen skeleton that at least band of 50wt% is made of three phosphorus, nitrogen-atoms1), the group (M of the chain phosphorus nitrogen skeleton that at most band of 30wt% is made of at most two phosphorus, nitrogen-atoms2) and at most 45wt% the cyclic annular phosphorus nitrogen skeleton being made of at least four phosphorus, nitrogen-atoms group (M3), so that there is the fire-retardant compound good anti-flammability, solidfied material to have good heat resistance, water resistance, cohesiveness and mechanical performance, electrical property.In addition, the composition is applied to composite metal substrate and its anti-flammability, while economy and environmentally friendly friendly can be improved in wiring board.
Description
Technical field
The present invention relates to the technical fields of fire retardant matter, more particularly to the curing agent and ring of the phosphorus-nitrogen compound of base containing bisphenol S
Oxygen composition.
Background technology
Using mobile phone, computer, video camera, electronic game machine as the electronic product of representative, with air-conditioning, refrigerator, television image, sound
The various products that articles for use etc. use for the household of representative, office electric equipment products and other field are rung, for safety, significant portion
Product require that it has different degrees of flame retardant property.
For the flame retardant property or grade for so that product is reached required, traditional technology is usually used to be added into material system
Add the inorganic fire-retarded object of the classes such as such as metal hydroxides of aluminium hydroxide hydrate, magnesium hydroxide hydrate containing the crystallization water
Matter and that such as the brominated amount of brominated bisphenol A, brominated bisphenol a type epoxy resin is added into system material is relatively high or containing halogen
Relatively high organic chemicals is measured, in order to improve the anti-flammability for the organic chemicals that these contain halogen, also usually in body
Such as antimony oxide is added in system to the disagreeableness inorganic chemistry fire retardant substance of environment.
Due to the use of halogen-containing fire retardant matter, no degradability or noxious material difficult to degrade such as two will produce when burning
It dislikes English class organic halogen chemical contamination environment, influence the mankind and animal health.
For the purpose of environmental protection, made instead of halogen contained compound using the compound being halogen-free such as phosphorous, nitrogenous
(there was only one in a molecule using with reactive simple function especially on electronics, electrical, Electric Industrial for fire retardant
A active reactive group) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide hereinafter referred to as DOPO), it is more to use
The derivative compound of DOPO adds as flame-retardant composition or does not add aluminium hydroxide hydrate, magnesium hydroxide hydrate reaches resistance
The effect of combustion.
In electronic field, usually using DOPO and novolac type epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A
The product (abbreviation DOPO epoxy resin) that the high cost such as phenol aldehyde type epoxy resin, polyfunctional epoxy resin are reacted with DOPO is extensive
Using the epoxide resin material as copper-clad plate purposes.
These have a good flame retardant property using the copper-clad plate manufactured by DOPO epoxy resin, but cohesiveness, heat-resisting
Property, processability etc. there are many defects, be not suitable for high multilayer, high reliability, high cohesiveness that manufacture modern communications need, good
The needs of good processing performance, and due to high-cost, it is unfavorable for spreading to the consumption that such as mobile phone requires low cost
The civil goods such as electronics field.
It is anti-usually using the etherate of DOPO and such as bisphenol-A, Bisphenol F, phenolic resin, phenol, o-cresol in electronic field
(being referred to as phosphorus containing phenolic resin) containing phenolic compounds containing DOPO skeletons should be made as epoxy curing agent or anti-flammability object
Matter additive, using the fire retardant of the epoxide resin material as copper-clad plate purposes.
These, as the copper-clad plate obtained by part or all of flame-retardant composition, can be reached fire-retardant using phosphorus-containing phenolic aldehyde
Purpose, but resistance to acid and alkali, chemical resistance, cohesiveness, heat resistance, processability etc. are not suitable for system there are many defects
The high multilayer of modern communications needs, the needs of high reliability, high cohesiveness, good processing performance are made, and due to high cost
The reason of, it is unfavorable for spreading to such as mobile phone and requires the civil goods fields such as the consumer electronics of low cost.
As electronic industry is to short, small, thin, high multiple stratification, the further increasing of high reliability request, civilian consumer electronics
Universal use and the factors such as increasingly severeer pressure of environmental pollution requirement, market there is an urgent need to material have it is good
Anti-flammability, heat resistance, good mechanical performance cheap anti-flammability substance.
Invention content
In view of this, one aspect of the present invention provides a kind of curing agent of epoxy resin, the epoxy obtained using the curing agent
Curing agent of the resin cured matter with good flame-retardance, heat resistance, good mechanical performance.
A kind of curing agent of epoxy resin, includes mainly epoxy resin and curing agent, and part or all of composition is
Bisphenol S base phosphorus-nitrogen compound.
Comprising the bisphenol S group and band being connected with each other by unsaturation in the molecular structure of above-mentioned bisphenol S base phosphorus-nitrogen compound
The group (M) for the phosphorus nitrogen skeleton that phosphorus, nitrogen-atoms are constituted, the group with phosphorus nitrogen skeleton include at least band of 50wt% by three
Group (the M for the cyclic annular phosphorus nitrogen skeleton that a phosphorus, nitrogen-atoms are constituted1), the at most band of 30wt% is by most two phosphorus, nitrogen-atoms institute
Group (the M of the chain phosphorus nitrogen skeleton of composition2) and at most 45wt% the cyclic annular phosphorus being made of at least four phosphorus, nitrogen-atoms
Group (the M of nitrogen skeleton3)
Bisphenol S base phosphorus-nitrogen compound has the molecular structure as shown in formula I：
In formula I, M indicates phosphazenium groups；Mr indicates that aromatic ring or the aromatic ring of non-halogen substitution, R indicate former containing at least one carbon
The aliphatic group or aromatic radical of son.A, b, c are the integer more than or equal to 1, and the sum of b and c are more than or equal to 2, a's and b and c
Be integer more than or equal to zero more than or equal to 6, n.
If M1Content is less than 50wt% or M2More than 30wt%, then the product after being reacted with epoxy resin is in use
Heat resistance, water resistance and mechanical performance etc. will be damaged must performance；M3Content comprise up to the 45% of phosphazenium groups gross mass.
If being more than the content, the product after being reacted with epoxy resin would be possible in use because viscosity is excessive, inconvenient for use, with
And its performance is set the bad result such as to be damaged because molecular weight is excessive.
Method well known in the art can be used to prepare in above-mentioned bisphenol S base phosphorus-nitrogen compound, as phosphorus cyanogen chloride have it is molten
Agent or it is solvent-free under the conditions of, use is with the metal chlorides such as zinc chloride, magnesium chloride, aluminium chloride, boron trifluoride and its complex compound
Deng for catalyst, it is obtained by the reaction under alkaline condition with bisphenol S or its metal salt.These catalyst one or more can mix
It uses, special regulation is had no in the present invention.Here " phosphorus cyanogen chloride " refers to chemical combination made of M groups are connected with Cl in Formulas I
Object, such as hexachlorocyclotriph,sphazene.Well known solvent, catalyst can be used to be closed in well known reaction route as phosphonitrile chloride
At phosphorus pentachloride and ammonium chloride can also being used to be synthesized according to known methods after phosphorus chloride cyanogen compound, by physics
Method processing purification or not direct manufacture, PCl5+NH4Cl → 1/n (NPCl2) n+4HCl is main in the reaction product
It is tripolymer (PNCl2)3(that is, hexachlorocyclotriph,sphazene) and the tetramer (PNCl2)4, reaction product is again by passing through 60 DEG C of vacuum
In slowly distillation can obtain pure hexachlorocyclotriph,sphazene.
The curing agent of the present invention limits bisphenol S base phosphorus-nitrogen compound content without special.Such as bisphenol S base phosphorous nitride closes
Object part forms curing agent.In such cases, by the reactive group equivalents that same epoxy resin reacts in terms of, bisphenol S base phosphorous nitride
It closes object and accounts for 30% or more curing agent, particularly preferably 55%~100%.It is understood that term " is reacted with same epoxy resin
Reactive group equivalents be meter " refer to the relative usage of both bisphenol S base phosphorus-nitrogen compound, curing agent with the two respectively contained by
Reactive group equivalents with epoxy resin reaction is the benchmark calculated.
Certainly in the case of the part composition curing agent of bisphenol S base phosphorus-nitrogen compound, other curing agent of composition
The common curing agent (being named as curing agent B) used with epoxy resin can be used.The specific example of curing agent is B polyphenol base chemical combination
Object, nitrogenous polyphenol based compound, phosphorous polyphenol based compound, nitrogenous phosphorous polyphenol based compound, amine compound, benzoxazine
One kind in resin, acid anhydrides, polyacid and boron trifluoride and its complex compound or at least two.Here, amine compound is fat
Amine or aromatic amine, such as dicyandiamide, diethyl triamine, diaminodiphenylmethane, diaminodiphenylsulfone；Polyphenol based compound is double
Phenol A, Bisphenol F, bisphenol S, linear phenolic resin, o-cresol urea formaldehyde, one kind in bisphenol A phenolic resin or at least two.
Another aspect of the invention provides a kind of epoxy resin with good flame-retardance, heat resistance, good mechanical performance
Composition.
A kind of composition epoxy resin, including epoxy resin, and the solidification as described in claims 1 to 3 any one
Agent.
The present invention provides the specific type of the epoxy resin in epoxy resin ingredient without special, as long as containing epoxy group
Compound, that is, epoxy resin.Can be used epoxy resin generally in the art, for example, with liquid bisphenol A types epoxy resin,
Liquid bisphenol F types epoxy resin, solid-state bisphenol A type epoxy resin resin, solid-state bisphenol f type epoxy resin resin, bisphenol-s epoxy resin,
Biphenyl type epoxy resin is two functional epoxy resins of representative, with solid-state, liquid or semisolid novolac type epoxy resin, neighbour
Cresol novolak epoxy resins, bisphenol-A phenolic epoxy resin, the above epoxy of trifunctional that acyclic isoprenoid type epoxy resin is representative
Resin.Herein, it will be readily appreciated by those skilled in the art that certainly it is necessary to when, can also use alicyclic epoxy resin,
The lower epoxy resin of the ratios of viscosities such as chain type aliphatic type epoxy resin or ester formula epoxy resin, these epoxy resin can be independent
Using can also two or more be used together, the present invention has no this special regulation, and the present invention is to these asphalt mixtures modified by epoxy resin
Fat proportioning amount it is also not specially provided, with reach ensure safe and environment-friendly and required performance under the premise of obtain purpose thing
.
In composition epoxy resin, can also according to actual needs, including curing accelerator, solvent, supporting material and filler,
Auxiliary agent, fire-retarded epoxy resin, bisphenol S base phosphorus nitrogen epoxy resin.
The addition of curing accelerator is for rapid curing.The present invention is to used curing accelerator without special rule
It is fixed, use common epoxy resin curing accelerator, such as imidazoles, triphenylphosphine and its derivative species, tertiary amines, season
The General Catalyst of the epoxy curing agents curing reaction such as amine salt, boron trifluoride and its derivative species, these promotions
Agent both can be used alone, can also two or more be used in mixed way, the number of usage amount can be as needed, with safety, ring
Guarantor obtains subject to purpose thing, and the present invention is simultaneously not specially provided, usually, compares the epoxy resin ingredient in curing system, with
0.001%~2.5% is proper, and more suitably range is between 0.03%~1.2%.
Solvent may make primarily to by the curing agent and epoxy resin in composition epoxy resin using epoxy group
It closes object and obtains the pre-impregnated sheet or bonding sheet of high quality.For using the type and quantity of solvent, the present invention to have no special regulation,
Such as acetone, butanone, DMF, DMAC, ethyl alcohol, methanol, cyclohexanone, 1,4- dioxane, petroleum solvent, toluene, dimethylbenzene, two
The organic solvents such as chloromethanes, dimethyl carbonate, with reach ensure safe and environment-friendly and required performance under the premise of obtain
Purpose thing.Preferably, selecting each ingredient of such as butanone to have, good dissolubility, toxicity is not strong, boiling point is more moderate
Organic solvent；If the substance not readily dissolved containing crystallinity such as dicyandiamides in epoxy resin ingredient, can use a part or
All organic solvents such as nitrogenous class such as DMF, DMAC.It is understood that in solidification process solvent be can by heat come
Improve the speed of volatilization.
Purpose of the supporting material based on the mechanical property for improving final solidfied material, such as glass fibre, carbon fiber and polyester
One kind of fiber or arbitrary two or more combinations.
Filler be in order to increase its certain function, property or reduce cost, can be added into curing system as silica,
The inorganic fillers such as diatomite, kaolin, calcium carbonate, mica, titanium dioxide, magnesium hydroxide, aluminium hydroxide, these inorganic fillers can be with
Be used alone, can also two kinds or it is several be used in mixed way, usage amount is generally advisable with the 500phr no more than epoxy resin ingredient.
Can auxiliary agent be added into system according to actual needs.Auxiliary agent can be it is general or special, as antifoaming agent,
The substances such as coupling agent, toughener, levelling agent, releasing agent, toughener, the present invention are not spy to the type and additive amount of adding auxiliary agent
Other regulation, can be as needed, is subject to and safe and environment-friendly obtains purpose thing.
In order to improve the flame retardant property of composition epoxy resin, bisphenol S base phosphorus can be increased in composition epoxy resin
Nitrogen epoxy resin and fire-retarded epoxy resin.Fire-retarded epoxy resin is DOPO types epoxy resin, resin containing phosphorus type epoxy, nitrogenous
Type epoxy resin, nitrogenous resin containing phosphorus type epoxy, phosphorus-containing phenolic aldehyde epoxy resin, nitrogenous novolac epoxy resin containing phosphorous, silicon-contained type
Epoxy resin and one kind in sulfur-type epoxy resin or at least two.
The product that bisphenol S base phosphorus nitrogen epoxy resin passes through condensation reaction by bisphenol S base phosphorus-nitrogen compound and epoxy resin.
In the polycondensation reaction, the temperature of reaction is generally in 40~250 DEG C of range, and more preferably in 60~180 DEG C of range, the present invention is not
Do special regulation, to ensure safety with environmental protection under the premise of, obtain purpose thing selection subject to.It, can be with as the polycondensation reaction
It is carried out under catalyst or without catalysts conditions.It generally requires and catalyst is added in reaction system, the present invention is to catalyst
Type and addition number have no special regulation, usually as imidazoles, triphenylphosphine and its derivative species, tertiary amines,
The General Catalyst that the epoxy resin such as quaternary ammonium salts are reacted with aldehydes matter can use, these catalyst both can individually make
With, can also two or more be used in mixed way, usage amount generally in comparison system reactive material all 100~
Between 20000ppm, it is more typically between 200~5000ppm.As for the medium of reaction, it can be solvent-free or have a solvent.To anti-
Solvent is answered to have no the ketones solvents such as special regulation, such as acetone, butanone, cyclohexanone, benzene,toluene,xylene, mixed xylenes
Etc. aromatic solvents, dichloromethane, chloroform, chlorobenzene etc. contain chlorinated solvents, the ethers such as ether, butyl ether, glycol monoethyl ether
Class or ether alcohols solvent, petroleum solvent naphtha, alcohols solvents such as butanol, isobutanol etc. can use, these solvents can be single
Solely use, can also two kinds or it is several be used in mixed way, usage amount number, can be determined according to actual conditions, can generally be made
The dosage that fire-retarded epoxy resin solid content is 5~100%, it is particularly preferred for fire-retarded epoxy resin solid content can be made be 20~
100% dosage.Technology is had been known in view of the basic principle of polycondensation reaction, details are not described herein.
A kind of pre-impregnated sheet, is impregnated with by such as above-mentioned fire-retardant combination or is coated on base material and form.Base material can be glass
Fiber base material, polyester base material, polyimide base material, ceramic base material or carbon fiber base material etc..Here, it is impregnated with or is coated with specific
Process conditions are 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 comprising one or more as above-mentioned pre-impregnated sheet carry out successively surface metal-clad overlapping,
It presses.Here, the material of surface metal-clad is aluminium, copper, iron and its alloy arbitrarily combined.The tool of composite metal substrate
Body example has the following copper-clad plate, such as CEM-1 copper-clad plates, CEM-3 copper-clad plates, FR-4 copper-clad plates, FR-5 copper-clad plates, CEM-
1 aluminum substrate, CEM-3 aluminum substrates, FR-4 aluminum substrates or FR-5 aluminum substrates.
A kind of wiring board is formed in the surface processing line of above-mentioned composite metal substrate.The wiring board is produced in such as electronics
Industry, electrical, Electric Industrial, communications and transportation, aerospace, toy industry etc. need the machine of wiring board, equipment, instrument, instrument
Etc. industries extensive use.
Above-mentioned term " ××× base or group ", which refers to, sloughs one or more hydrogen atoms in ××× molecular structure of compounds
Or remaining part after other atoms or atomic group.
The curing agent of the epoxy resin of the present invention, component part or all bisphenol S base phosphorus-nitrogen compounds, bisphenol S base
The phosphorus being made of unsaturated phosphorus, nitrogen-atoms comprising the bisphenol S group and band that are connected with each other in the molecular structure of phosphorus-nitrogen compound
The group (M) of nitrogen skeleton, M include the group for the cyclic annular phosphorus nitrogen skeleton that at least band of 50wt% is made of three phosphorus, nitrogen-atoms
(M1), the group (M of the chain phosphorus nitrogen skeleton that at most band of 30wt% is made of at most two phosphorus, nitrogen-atoms2) and at most
Group (the M for the cyclic annular phosphorus nitrogen skeleton of 45wt% being made of at least four phosphorus, nitrogen-atoms3), so that the anti-flammability
Closing object, there is good anti-flammability, solidfied material to have good heat resistance, water resistance, cohesiveness and mechanical performance, electrical property,
It is a kind of fire retardant matter also with larger economy and environmentally friendly friendly.
Specific implementation mode
The technical solution further illustrated the present invention with reference to embodiment.
Embodiment 1
Put into three mouthfuls of 1000ml glass reactors with agitating device three phosphorus cyanogen 173.83g (0.5mol) of chlordene ring,
Acetone 150ml, phenol 188.0g (2.0mol) and bisphenol S 550.0g (2.2mol), on one side stir, on one side lead to nitrogen, while
52 DEG C are warming up to, 20% sodium hydroxide solution 400g is instilled with 80min, keeps 52 DEG C of temperature, be stirred to react 15 hours.Reaction
Afterwards, with the moisture in physical method removal system, the insoluble matter in removal system is refiltered, solvent in system is distilled, obtains
To flame retardant 804.6g, it is 276.2g/eq to measure its phenolic group equivalent, this purpose product is named as A.
The liquid bisphenol A types that epoxide equivalent is 187g/eq are put into three mouthfuls of 500ml glass reactors with agitating device
The triphenylphosphine of epoxy resin 374g and above-mentioned A substances 52g, 0.1g are warming up to 100 DEG C, react 9.5 hours, obtain epoxy
Equivalent is the purpose thing epoxy resin 437.0g of 247.3g/eq, the epoxy resin solution that acetone is modulated into 60% is added, by this
Purpose thing is named as C.
The solution 100g (solid constituent 60g) for taking above-mentioned C substances adds the dicyandiamide of 3.2g and suitable DMF, stirs
Mix it is uniform after, be added the 2-methylimidazole of 0.08g, then wiring solution-forming is made according to general copper-clad plate production process and meets
The standard copper-clad plate sample of the standards such as national standard, UL is named as a copper-clad plates, tests the performance of a copper-clad plates, result is in table -1
It indicates.
Embodiment 2
Dichloroethanes 180g, phosphorus pentachloride 104.11g are put into three mouthfuls of 2000ml glass reactors with agitating device
(0.5mol), ammonium chloride 26.75g (0.5mol) and magnesium chloride 20g.On one side stirring, be warming up to 52 DEG C while leading to nitrogen, and
After reacting 6 hours under 52 DEG C of temperature conditions, sodium methoxide 108.04g (2.0mol) and bisphenol S 550.0g is added
(2.2mol) the reaction was continued 15 hours, additional solvent 250g are filtered to remove insoluble matter, then evaporate solvent, obtain
To flame retardant 716.2g, it is 210.9g/eq to measure its phenolic group equivalent, this purpose product is named as B.
The liquid bisphenol A types that epoxide equivalent is 187g/eq are put into three mouthfuls of 500ml glass reactors with agitating device
The triphenylphosphine of epoxy resin 374g and above-mentioned B substance 50g and 0.1g are warming up to 100 DEG C, react 9.5 hours, obtain epoxy
Equivalent is the purpose thing epoxy resin 426g of 231.3g/eq, this purpose thing is named as D.
The solution 100g (solid constituent 60g) for taking above-mentioned D substances adds the dicyandiamide of 3.2g and suitable DMF, stirs
Mix it is uniform after, be added the 2-methylimidazole of 0.08g, then wiring solution-forming is made according to general copper-clad plate production process and meets
The standard copper-clad plate sample of the standards such as national standard, UL is named as b copper-clad plates, tests the performance of b copper-clad plates, result is in table -1
It indicates.
Embodiment 3
The use of market epoxide equivalent is 230g/eq, market circulation bisphenol-s epoxy resin 100g, is added as implemented
A substance 71.8g described in example 1 after suitable acetone solution is added, add the 2-methylimidazole wiring solution-forming of 0.08g, then
The standard copper-clad plate sample for meeting the standards such as national standard, UL is made according to general copper-clad plate production process, is named as c copper-clad plates,
The performance of c copper-clad plates is tested, result indicates in table -1.
Comparative example 1
The novolac ring that epoxide equivalent is 178g/eq is put into three mouthfuls of 500ml glass reactors with agitating device
The triphenylphosphine of oxygen resin 374g and DOPO 38g and 0.1g are warming up to 120 DEG C, react 5 hours, obtaining epoxide equivalent is
The purpose thing epoxy resin 412g of 232g/eq, E is named as by this purpose thing.
It takes above-mentioned E substances 100g to add the dicyandiamide of 3.0g and suitable DMF and the 2- of 0.08g is added after stirring is uniform
Then methylimidazole, wiring solution-forming cover copper according to the obtained standard for meeting the standards such as national standard, UL of general copper-clad plate production process
Plate sample is named as d copper-clad plates, tests the performance of d copper-clad plates, and result indicates in table -1.
It (has been people in the art in view of specific test method that test result is as follows for embodiment and comparative example shown in table -1
Known to member, method is no longer described in detail at this)：
The performance of -1 copper-clad plate of table compares
The test data of above table shows that fire-retardant compound and its derivative of the present invention are solid in epoxy resin when use
When in change system and other systems, there is good anti-flammability, solidfied material to have good heat resistance, water resistance, cohesiveness
With mechanical performance, electrical property.The fire-retardant compound of the present invention belongs to low cost, raw material sources enrich, properties are good
The environment-friendly type flame-retardant substance of the novel environmental friendly of energy-saving and emission-reducing.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode all fall within the present invention's
Within protection domain and the open scope.
Claims (33)
1. a kind of curing agent of epoxy resin, which is characterized in that part or all of its composition is that bisphenol S base phosphorous nitride closes
Object；
Comprising the bisphenol S group and band being connected with each other by unsaturated phosphorus, nitrogen in the molecular structure of the bisphenol S base phosphorus-nitrogen compound
The group M for the phosphorus nitrogen skeleton that atom is constituted, the group with phosphorus nitrogen skeleton include at least band of 50wt% by three phosphorus, nitrogen
The group M for the cyclic annular phosphorus nitrogen skeleton that atom is constituted1, the at most band of 30wt% is by chain that at most two phosphorus, nitrogen-atoms are constituted
The group M of shape phosphorus nitrogen skeleton2And the base for the cyclic annular phosphorus nitrogen skeleton of at most 45wt% being made of at least four phosphorus, nitrogen-atoms
Group M3；The bisphenol S base phosphorus-nitrogen compound has the molecular structure as shown in formula I：
In formula I, R indicates aliphatic group or aromatic radical containing at least one carbon atom；A, b, c are the integer more than or equal to 1,
The sum of b and c are greater than or equal to 2, and it is the integer more than zero that the sum of a, b and c three, which is greater than or equal to 6, n,；
By the reactive group equivalents that same epoxy resin reacts in terms of, the bisphenol S base phosphorus-nitrogen compound accounts for 30% or more curing agent.
2. the curing agent of epoxy resin according to claim 1, which is characterized in that the reactive group reacted with same epoxy resin
Equivalents is meter, and the bisphenol S base phosphorus-nitrogen compound accounts for the 55%~100% of curing agent.
3. the curing agent of epoxy resin according to claim 1, which is characterized in that the curing agent also includes curing agent B,
The curing agent B is polyphenol based compound, amine compound, benzoxazine colophony, acid anhydrides, polyacid and boron trifluoride and its network
Close one kind or at least two in object.
4. the curing agent of epoxy resin according to claim 1, which is characterized in that the curing agent also includes curing agent B,
The curing agent B is one kind or at least two in nitrogenous polyphenol based compound, phosphorous polyphenol based compound.
5. the curing agent of epoxy resin according to claim 1, which is characterized in that the curing agent also includes curing agent B,
The curing agent B is nitrogenous phosphorous polyphenol based compound.
6. the curing agent of epoxy resin according to claim 3, which is characterized in that the amine compound be dicyandiamide,
Diethyl triamine, diaminodiphenylmethane, diaminodiphenylsulfone.
7. the curing agent of epoxy resin according to claim 3, which is characterized in that the polyphenol based compound be bisphenol-A,
Bisphenol F, bisphenol S, linear phenolic resin, o-cresol urea formaldehyde, one kind in bisphenol A phenolic resin or at least two.
8. a kind of composition epoxy resin, which is characterized in that include epoxy resin, and such as claim 1~7 any one institute
The curing agent stated.
9. composition epoxy resin according to claim 8, which is characterized in that the epoxy resin is the above ring of two functions
Oxygen resin.
10. composition epoxy resin according to claim 9, which is characterized in that two functional epoxy resins are liquid bisphenol A
Type epoxy resin, liquid bisphenol F types epoxy resin, solid-state bisphenol A type epoxy resin resin, solid-state bisphenol f type epoxy resin resin and bisphenol S
One kind in type epoxy resin, biphenyl type epoxy resin or at least two.
11. composition epoxy resin according to claim 9, which is characterized in that epoxy resin more than two functions is phenol
The one or two of aldehyde type epoxy resin and acyclic isoprenoid type epoxy resin.
12. composition epoxy resin according to claim 9, which is characterized in that epoxy resin more than two functions is neighbour
Cresol novolak epoxy resins or bisphenol-A phenolic epoxy resin.
13. composition epoxy resin according to claim 8, which is characterized in that also include by bisphenol S base phosphorus-nitrogen compound
The bisphenol S base phosphorus nitrogen epoxy resin and other fire-retarded epoxy resins generated by condensation reaction with epoxy resin.
14. composition epoxy resin according to claim 13, which is characterized in that other fire-retarded epoxy resin halogen
Cellulose content is not higher than 0.2%.
15. composition epoxy resin according to claim 13, which is characterized in that other fire-retarded epoxy resins are
Resin containing phosphorus type epoxy, nitrogenous type epoxy resin, silicon-contained type epoxy resin and one kind in sulfur-type epoxy resin or at least two
Kind.
16. composition epoxy resin according to claim 13, which is characterized in that other fire-retarded epoxy resins are
DOPO type epoxy resin.
17. composition epoxy resin according to claim 13, which is characterized in that other fire-retarded epoxy resins are
Nitrogenous resin containing phosphorus type epoxy.
18. composition epoxy resin according to claim 13, which is characterized in that other fire-retarded epoxy resins are
Phosphorus-containing phenolic aldehyde epoxy resin.
19. composition epoxy resin according to claim 13, which is characterized in that other fire-retarded epoxy resins are
Nitrogenous novolac epoxy resin containing phosphorous.
20. composition epoxy resin according to claim 8, which is characterized in that also include curing accelerator；
The curing accelerator be imidazoles, triphenylphosphine and its derivative species, tertiary amines, quaternary ammonium salts and boron trifluoride and its
One kind in derivative species or at least two.
21. composition epoxy resin according to claim 20, which is characterized in that the dosage of the curing accelerator is to account for
The 0.001~2.5% of epoxy resin gross mass.
22. composition epoxy resin according to claim 20, which is characterized in that the dosage of the curing accelerator is to account for
The 0.03~1.2% of epoxy resin gross mass.
23. composition epoxy resin according to claim 8, which is characterized in that also include supporting material and filler.
24. composition epoxy resin according to claim 23, which is characterized in that the supporting material be glass fibre,
One kind in carbon fiber and polyester fiber or at least two.
25. composition epoxy resin according to claim 23, which is characterized in that the filler is silica, diatom
One kind in soil, kaolin, calcium carbonate, mica, titanium dioxide, magnesium hydroxide, aluminium hydroxide or at least two.
26. composition epoxy resin according to claim 23, which is characterized in that the dosage of the filler is no more than ring
The 500phr of oxygen resin gross mass.
27. composition epoxy resin according to claim 8, which is characterized in that also include auxiliary agent, the auxiliary agent is defoaming
One kind in agent, coupling agent, toughener and levelling agent or at least two.
28. a kind of pre-impregnated sheet, which is characterized in that it is contained by the composition epoxy resin as described in any one of claim 8-27
It soaks or is coated on base material and form.
29. pre-impregnated sheet according to claim 28, which is characterized in that the base material be fiberglass substrate, polyester base material,
Polyimide base material, ceramic base material or carbon fiber base material.
30. a kind of composite metal substrate, which is characterized in that it include one or more as described in claim 28 or 29 pre-impregnated sheet according to
Secondary progress surface metal-clad, presses overlapping.
31. composite metal substrate according to claim 30, which is characterized in that the material of the surface metal-clad is
Aluminium, copper, iron and its alloy arbitrarily combined.
32. composite metal substrate according to claim 30, which is characterized in that the composite metal substrate covers for CEM-1
Copper coin, CEM-3 copper-clad plates, FR-4 copper-clad plates, FR-5 copper-clad plates, CEM-1 aluminum substrates, CEM-3 aluminum substrates, FR-4 aluminum substrates or
FR-5 aluminum substrates.
33. a kind of wiring board, which is characterized in that the surface of the composite metal substrate described in any one of claim 30-32
Processing line forms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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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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| Publication Number | Publication Date |
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| CN104893243A CN104893243A (en) | 2015-09-09 |
| CN104893243B true CN104893243B (en) | 2018-07-24 |
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Families Citing this family (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 |
| 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) |
Family Cites Families (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 |
| JP5177730B2 (en) * | 2005-11-30 | 2013-04-10 | 株式会社伏見製薬所 | Hydroxyl group-containing cyclic phosphazene compound and process 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 |
| CN104628997B (en) * | 2015-02-10 | 2017-03-01 | 广东广山新材料有限公司 | Flame retardant with bisphenol S base, fire-retarded epoxy resin and flame-retardant composition |
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