CN1167732C - Resin firming agent containing phosphorus and nitrogen and fireproof resin composition containing said firming agent - Google Patents
Resin firming agent containing phosphorus and nitrogen and fireproof resin composition containing said firming agent Download PDFInfo
- Publication number
- CN1167732C CN1167732C CNB001235257A CN00123525A CN1167732C CN 1167732 C CN1167732 C CN 1167732C CN B001235257 A CNB001235257 A CN B001235257A CN 00123525 A CN00123525 A CN 00123525A CN 1167732 C CN1167732 C CN 1167732C
- Authority
- CN
- China
- Prior art keywords
- epoxy
- epoxy resin
- resin composition
- groups
- formula
- 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.)
- Expired - Fee Related
Links
Landscapes
- Epoxy Resins (AREA)
Abstract
The present invention relates to a resin curing agent containing phosphorus and nitrogen. The chemical formula of the present invention is shown in the drawing, R<2> in a formula I stands for a formula II or hydrogen atoms, and at least one R<2> is not a hydrogen atom; R<1> stands for NHR<2>, C<1-6> alkyl groups or phenyl groups, and n stands for an integer from 0 to 20; furthermore, R stands for the groups of phenylene and naphthylidene or the groups of the formula I, and A in the formula stands for the groups of-O-,-S-,-SO2-,-CO-,-CH2-, C (CH3) 2-or the groups of the formula 2. In addition, in the groups represented by R and A, aryl groups can be substituted by one or a plurality of substituting groups selected from hydroxyl groups, amino groups, carboxyl groups and the C<1-6> alkyl groups. The present invention also relates to a fire resistant resin combination which contains the curing agent and has the advantages of excellent heat resistance and fire resistance.
Description
Technical field
The present invention relates to a kind of resin curing agent of novelty, particularly relate to phosphorous and resin curing agent nitrogen, the invention still further relates to the difficult combustible epoxy resin composition that contains this solidifying agent.
The not halogen-containing and antimonous oxide of difficult combustible epoxy resin composition of the present invention, have the difficulty combustion characteristic that reaches UL94V-0 and have high heat resistance, and can be used as adhesive sheet (bonding sheet or prepreg), matrix material (composite), laminated plates (laminate), printed circuit board (PCB) (printedcircuit board), Layer increasing method substrate (build-up, Resin Coated Copper), semiconductor sealing material (Epoxy Molding Compound) etc.
Background technology
Matrix material, especially epoxy resin composite material, with the security of its easy processibility, height, excellent mechanical properties and chemical property, be applied to widely among every field such as application, electric insulation, building building materials, tackiness agent and the lamination product etc.Wherein, laminated plates with the Resins, epoxy manufacturing, because of Resins, epoxy strong to the clinging power of reinforcement materials such as glasscloth, do not produce fugitive constituent during curing, mould shrinkage is little, therefore resulting laminated plates has advantages such as use range is wide, physical strength is excellent, electric insulating quality is good, chemical proofing is good, has improved the reliability of lamination sheet material greatly, makes the Resins, epoxy laminated plates use in a large number in what electricity oxygen and the electronic product.
Yet in order to adapt to improved day by day fine rule road and highdensity requirement in the printed circuit board (PCB), laminated plates also is required to have more excellent electrical properties, mechanical properties and heat-resisting processibility.With present general FR4 laminated plates of seeing, second-order transition temperature after the curing is mostly about 130 ℃, for the cutting and the boring processing that surpass 200 ℃ in the printed circuit board (PCB) processing procedure, even welding sequence more than 270 ℃, so the laminated plates material might break or plate bursting in the manufacturing and the course of processing.Therefore, the various laminated plates materials of high heat-resistant quality, high glass-transition temperature of emphasizing just are developed successively energetically.In addition, for laminated plates, another important properties is its difficult combustion characteristic.In the occasion of some use, for example the vehicles such as aircraft, automobile and public transportation directly threaten for the person and life security because of burning.Therefore, the difficulty of printed circuit board (PCB) combustion characteristic is absolute necessary.
Introduce among the laminated plates material for difficulty being fired characteristic, must use some to have the material of isolation flame reduction ignition quality.Laminated plates for Resins, epoxy/glass fibre class (or organic fibre), use halogen contained compound, particularly bromated Resins, epoxy and solidifying agent, and cooperation is as the difficulty combustion auxiliary agent of antimonous oxide and so on, in the hope of reaching the harsh requirement (as UL 94V-0 grade) to the difficult combustion of laminated plates characteristic.Usually, Resins, epoxy need contain the bromine content up to 17% to 21%, and is used antimonous oxide or other incombustible agent, just can reach the level of UL 94V-0.Yet, use high bromine content Resins, epoxy or antimonous oxide, will bring a little danger to the mankind far and away.
At first, antimonous oxide has been listed in carcinogenic substance; On the other hand, bromine just can not produce mordant bromine free radical and hydrogen bromide in the middle of the incendiary process, and the aromatic substance of high bromine content more can produce the bromination furans and the bromine dioxin-like compound of severe toxicity, badly influences people's health and environment.Therefore, seeking a kind of new nonflammable material and difficult burning method, improve the pollution and the environmental issue of present laminated plates because of using brominated epoxy resin to cause, is instant thing.Especially, the epoxy glass laminated plates usage quantity of FR-4 class is big, and then demand is stronger.
The incombustible agent that Phosphorus compound has the environmental protection notion as a new generation is studied widely and is used.For example directly use the organic compound (for example triphenylphosphine acid esters, trityl phosphonic acid ester, carbonic acid etc.) of red phosphorus or phosphorus to wait and replace halogen compounds, to improve the combustioncharacteristics of macromolecular material or gel-type resin as incombustible agent.Yet, directly add these compounds among resin, not only need bigger addition because of the difficulty combustion efficient that is subject to these compounds, and because of its lower molecular weight, high transport property (migration) will directly have influence on the characteristic of resin base material: as electrical properties, adhesion strength etc., cause practical difficulty.
In recent years, cooperate the consideration of environmental protection and safety with the idea of response type incombustible agent, phosphatization Resins, epoxy has been used to replace brominated epoxy resin, as the prescription of difficulty combustion laminated plates, for example United States Patent (USP) 5,376, No. 453, use the phosphoric acid ester of band epoxy group(ing) to cooperate nitrogenous ring-type solidifying agent to make laminated plates, but be difficult to reach the shortcoming that UL 94V-0 requires, added multiple phosphoric acid ester epoxide in order to remedy the phosphorus content deficiency; United States Patent (USP) 5,458 then utilizes for No. 978 epoxy phosphate ester to cooperate nitrogenous Resins, epoxy and metal composite as solidifying agent, about 175 ℃ of its finished glass transition temperature, and flame retardancy matter then reaches in the UL94V-0 edge (42 seconds with respect to threshold value 50 seconds).United States Patent (USP) 4,973, the trihydrocarbyl phosphine muriate that No. 631 and the U.S. is special to make apparatus active hydrogen substituting group (as amino) for 5,086, No. 156 separately or cooperate other Ammonia solidifying agent are used for the curing of Resins, epoxy; In resin, have the low shortcoming of phosphorus content yet use solidifying agent to introduce phosphorus, also do not have the measurement of actual difficulty combustion effect in these two parts of patents.
Goal of the invention
The present invention improves the shortcoming in the existing technology promptly at above-mentioned, and improving electric and mechanical essential property and to reduce cost be target, thereby finish the present invention.
Therefore, primary and foremost purpose of the present invention is to provide a kind of resin curing agent of phosphorous and nitrogen;
Another object of the present invention is to provide a kind of difficult combustible epoxy resin composition that contains described solidifying agent;
Of the present invention in addition again a purpose provide described difficult combustible epoxy resin composition and use being used for making substrate and the semiconductor sealing material that adhesive sheet, matrix material, laminated plates, printed circuit board (PCB), Layer increasing method use.
The present invention relates to a kind of resin curing agent of phosphorous and nitrogen, it has following formula:
Or hydrogen atom
R
1Expression NHR
2, C
1-6Alkyl or phenyl;
N represents 0 to 20 integer;
-R-represents the group of penylene, naphthylene or following formula:
-Ph-A-Ph-
Ph represents phenyl in the formula, A represents-O-,-S-,-SO
2-,-CO-,-CH
2-, C (CH
3)
2-or the group of following formula:
In the group shown in above-mentioned R and the A, the hydrogen atom of aryl is selected from hydroxyl, amino, carboxyl and C by one or more
1-6The substituting group of alkyl replaces or is not substituted.
The invention still further relates to a kind of difficult combustible epoxy resin composition, it comprises (A) Resins, epoxy, and (B) resin curing agent of above-mentioned phosphorous and nitrogen reaches (C) curing catalyst.
In difficult combustible epoxy resin composition of the present invention, contained Resins, epoxy can be any Resins, epoxy, and it is selected from glycidyl ether, phenolic aldehyde polyglycidyl ether and the polyhydroxy phenol polyglycidyl ether etc. of bis-phenol glycidyl ether, two diphenol glycidyl ether, dihydroxy-benzene glycidyl ether, the glycidyl ether that contains azo-cycle, dihydroxy naphthlene.
The glycidyl ether of bis-phenol comprises: for example dihydroxyphenyl propane glycidyl ether, Bisphenol F glycidyl ether, dihydroxyphenyl propane D glycidyl ether, bisphenol S glycidyl ether, tetramethyl-dihydroxyphenyl propane glycidyl ether, tetramethyl-Bisphenol F glycidyl ether, tetramethyl-dihydroxyphenyl propane D glycidyl ether, tetramethyl-bisphenol S glycidyl ether.
Two diphenol glycidyl ethers comprise: for example 4, and 4 '-diphenol glycidyl ether, 3,3 '-dimethyl-4,4 '-diphenol glycidyl ether, 3,3 ', 5,5 '-tetramethyl--4,4 '-diphenol glycidyl ether.
The dihydroxy-benzene glycidyl ether comprises: for example dihydroxy-benzene glycidyl ether, Resorcinol glycidyl ether, isobutyl-Resorcinol glycidyl ether.
The phenolic aldehyde polyglycidyl ether comprises: for example phenolic aldehyde polyglycidyl ether, cresols phenolic aldehyde polyglycidyl ether, bisphenol-A phenolic polyglycidyl ether.
Phenyl polyhydroxy phenol polyglycidyl ether comprises; Three (4-hydroxy phenyl) methane polyglycidyl ether, three (4-hydroxy phenyl) ethane polyglycidyl ether, three (4-hydroxy phenyl) propane polyglycidyl ether, three (4-hydroxy phenyl) butane polyglycidyl ether, three (3-methyl-4-hydroxy phenyl) methane polyglycidyl ether, three (3 for example, 5-dimethyl-4-hydroxy phenyl) methane polyglycidyl ether, four (4-hydroxy phenyl) ethane polyglycidyl ether, four (3,5-dimethyl-4-hydroxy phenyl) ethane polyglycidyl ether, dicyclo amylene-phenolic aldehyde polyglycidyl ether.
The glycidyl ether that contains azo-cycle comprises: the triglycidyl ether of the triglycidyl ether of chlorinated isocyanurates and cyanurate for example.
The glycidyl ether of dihydroxy naphthlene comprises: for example 1, and 6-dihydroxy naphthlene diglycidylether and 2,6-dihydroxy naphthlene diglycidylether.
These Resins, epoxy can use separately or use with two or more form of mixtures.
Wherein be preferably four (phenyl-4-hydroxyl) ethane polyglycidyl ether or its mixture of polymer with bis phenol A glycidyl ether, phenolic aldehyde polyglycidyl ether, three (4-hydroxy phenyl) methane polyglycidyl ether, dicyclo amylene-phenolic aldehyde polyglycidyl ether and four functional groups.
Epoxy curing agent in the difficult combustible epoxy resin composition of the present invention is preferably following formula: compound:
B is 0 to 20 integer in the formula.
Difficult combustible epoxy resin composition of the present invention except the resin curing agent of phosphorous and nitrogen of the present invention, also can further comprise other not halogen-containing solidifying agent.These other not halogen-containing solidifying agent comprises amine, bis-phenol resin, dihydroxy-benzene, polyhydroxy phenol resin and phenolic etc.
Amine comprises: for example dicyan diamide, diaminodiphenyl-methane.
Bisphenol resin, (wherein Ph represents phenylene, X=CH for example to comprise formula HO-Ph-X-Ph-OH
2-C (CH
3)
2,-O-,-S-,-CO-and-SO
2-) shown in compound, for example: dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, tetramethyl-dihydroxyphenyl propane, tetramethyl-Bisphenol F, tetramethyl-dihydroxyphenyl propane D, tetramethyl-bisphenol S, 4,4 ' diphenol, 3,3 '-dimethyl-4,4 ' diphenol, 3,3 ', 5,5 '-tetramethyl--4,4 ' diphenol.
Dihydroxy-benzene comprises: for example Resorcinol, Resorcinol, isobutyl-Resorcinol.
Many (hydroxyl phenol) resin comprises: three (4-hydroxy phenyl) methane, three (4-hydroxy phenyl) ethane, three (4-hydroxy phenyl) propane, three (4-hydroxy phenyl) butane, three (3-methyl-4-hydroxy phenyl) methane, three (3 for example, 5-dimethyl-4-hydroxy phenyl) methane, four (4-hydroxy phenyl) ethane, four (3,5-dimethyl-4-hydroxy phenyl) ethane.
The phenolic that is fit to is for example: phenol formaldehyde condensate, cresols phenolic condensation compound, bisphenol-A phenolic condenses, dicyclo amylene-phenolic condensation compound.
In difficult combustible epoxy resin composition of the present invention, the addition of solidifying agent is decided according to the epoxy equivalent (weight) of the reactive behavior hydrogen equivalent of each solidifying agent and Resins, epoxy, the equivalence ratio that is fit to is the epoxy equivalent (weight) 100% to Resins, epoxy, the reactive behavior hydrogen equivalent of solidifying agent is 20 to 140%, the equivalence ratio that is more suitable for is the epoxy equivalent (weight) 100% to Resins, epoxy, the reactive behavior hydrogen equivalent of solidifying agent is 40 to 95%, the equivalence ratio that is more suitable for again is the epoxy equivalent (weight) 100% to Resins, epoxy, and the reactive behavior hydrogen equivalent of solidifying agent is 50 to 95%.
In difficult combustible epoxy resin composition of the present invention, if when using other not halogen-containing solidifying agent, the epoxy curing agent of phosphorous and nitrogen of the present invention and these other not the usage ratio of halogen-containing solidifying agent be 5: 95 to 100: 0, be preferably 20: 80 to 100: 0, more preferably 25: 75 to 100: 0.If of the present invention phosphorous low excessively, then easily cause flame retardancy and thermotolerance deficiency with epoxy curing agent content nitrogen.
Curing catalyst in the difficult combustible epoxy resin composition of the present invention, it is selected from tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt, boron trifluoride complex, lithiumation thing and imidazolium compoundss and composition thereof.
Tertiary amine is triethylamine, tributylamine, dimethyl amine ethanol, 3,5-dimethylphenyl amine, three (N, N-dimethyl-amino methyl) phenol, N for example, N-dimethyl-amino methyl phenol.
Three grades of phosphines are triphenylphosphine for example.
Quaternary ammonium salt is tetramethyl-ammonium muriate, tetramethyl-ammonium bromide, tetramethyl-ammonium iodide, triethylbenzene ammonium methyl muriate, triethylbenzene ammonium methyl bromide, triethylbenzene ammonium methyl iodide for example.
Quaternary alkylphosphonium salt is the 4-butyl-phosphonium muriate for example, the 4-butyl-phosphonium bromide, the 4-butyl-phosphonium iodide, 4-butyl-phosphonium acid ester salt acetic acid title complex, the tetraphenylphosphoniphenolate muriate, the tetraphenylphosphoniphenolate bromide, the tetraphenylphosphoniphenolate iodide, Yi base triphenyl phosphonium muriate, Yi base triphenyl phosphonium bromide, Yi base triphenyl phosphonium iodide, Yi base triphenyl phosphonium acid ester salt acetic acid title complex, Yi base triphenyl phosphonium acid ester salt phosphorylated ligand compound, propyl group triphenyl phosphonium muriate, propyl group triphenyl phosphonium bromide, propyl group triphenyl phosphonium iodide, Ding base triphenyl phosphonium muriate, Ding base triphenyl phosphonium bromide, Ding base triphenyl phosphonium iodide etc.
Imidazolium compounds is glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole etc. for example.
Described curing catalyst two or more forms alone or in combination uses.
Preferable curing catalyst is tertiary amine and imidazolium compounds, especially xylidine, glyoxal ethyline, 2-phenylimidazole and 2-ethyl-4-methylimidazole etc.
The usage quantity of curing catalyst is generally 50 to 50 of composition epoxy resin weight, and 000ppm is preferably 100 to 30000ppm, and more preferably 200 to 10000ppm, most preferably is 500 to 2000ppm.If the amount of curing catalyst surpasses 50,000ppm though can shorten the reaction times, generates and subsequently application such as board layer zoarium etc. is produced detrimentally affect to electrical properties, moisture resistance, suction character by product, if addition is too little, then speed of reaction is crossed slow and inefficiency.
If difficult combustible epoxy resin composition of the present invention can add solvent to adjust viscosity when being modulated into varnish (vanish).Suitable solvent comprises organic aromatic species, ketone, protonic solvent, ethers, ester class etc.
The organic aromatic species solvent that is fit to is for example: toluene, dimethylbenzene.
The ketones solvent that is fit to is for example: acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK).
The protonic solvent that is fit to is for example: N, dinethylformamide, N, N-diethylformamide, dimethyl sulfoxide (DMSO).
The ether solvent that is fit to is for example: ethylene glycol monomethyl ether, propylene glycol monomethyl ether.
The esters solvent that is fit to is for example: ethyl acetate, isopropyl acid ethyl ester, propylene glycol monomethyl ether ethyl ester.
Viscosity transfers to 20 to 500cps/25 ℃ scope usually.
Decide on end-use, difficult combustible epoxy resin composition of the present invention also can add general additive or properties-correcting agent, as thermo-stabilizer, photostabilizer, ultraviolet absorbers and plasticizer etc.
The invention further relates to described flame retardancy composition and be used for making the substrate that adhesive sheet, matrix material, laminated plates, printed circuit board (PCB), Layer increasing method use and the application of semiconductor sealing material.
Difficult combustible epoxy resin composition of the present invention can utilize the known method of general industry, makes the laminate of Copper Foil, fiber support thing and difficult combustible epoxy resin composition of the present invention.
Use difficult combustible epoxy resin composition of the present invention to be modulated into varnish, impregnation fiber base material such as organic or inorganic fibre base material for example glass fibre, steel fiber, carbon fiber, aramid fiber, boron and Mierocrystalline cellulose etc. will contain impregnated fiber base material heat drying, and the prepreg that obtains doing (prepreg).This prepreg can plasticly further be made the matrix material laminated plates, or be used in the bonding coat of other film separately, or with its one or more combinations, one side or upper and lower faces are placed Copper Foil thereon, depress heating this prepreg or its composition adding, resulting laminated plates matrix material all surpasses the standard of present product on dimensional stability, chemical proof, erosion resistance, water absorbability and electrical properties, be suitable for making the electric product that is used in electronics, space, traffic etc., as be used to make printed circuit board (PCB) and multilayer circuit board etc.
Also difficult combustible epoxy resin composition of the present invention can be modulated into varnish, and on the coating what Copper Foil, be heated drying, and the Copper Foil tackiness agent that obtains doing (RCC, Resin Coated Copper).This Copper Foil tackiness agent can be preserved the several months long under room temperature, has good storage stability.This RCC moulding further makes the matrix material laminated plates, or be used in the bonding coat of other film separately, or with its one or more combinations, one side or upper and lower faces in layer add lamination one by one and close (build-up) thereon, resulting laminated plates matrix material all surpasses the standard of present product on dimensional stability, chemical proof, erosion resistance, water absorbability and electrical properties, be suitable for making the multilayer printed circuit board that is used in electronics, space, traffic etc.
The suitable sclerous reaction temperature of difficult combustible epoxy resin composition of the present invention is generally 20 to 350 ℃, is preferably 50 to 300 ℃, more preferably is 100 to 250 ℃, most preferably is 120 to 220 ℃.The too high easy generation side reaction of temperature and difficult its speed of response of control, and may impel the speed of resin deterioration to speed; Temperature is crossed low except that the efficient difference, the difficult demand that meets the high temperature use of the resin properties that is produced.
According to the difficult combustible epoxy resin composition that the present invention formed, do not need to add other processing aids and difficult combustion additive, can improve the flame retardancy and the heat-resisting character of Resins, epoxy simultaneously.
Embodiment
To further specify the present invention with following synthesis example and embodiment, but therefore not limit the scope of the invention.
Details are as follows for used each composition among synthesis example and the embodiment:
Resins, epoxy 1:Represent Changchun artificial resin factory to produce, the diglycidylether of the dihydroxyphenyl propane of selling with trade(brand)name BE188EL, its epoxy equivalent (weight) are between 185 to 195g/eq, and hydrolyzable chlorine is below the 200ppm, and viscosity is between 11000 to 15000cps/25 ℃.
Resins, epoxy 2:Represent Changchun artificial resin factory to produce, the polyglycidyl ether of cresols-aldehyde condensate of selling with trade(brand)name CNE200ELD, its epoxy equivalent (weight) between 190 to 210g/eq.
Resins, epoxy 3:Represent Changchun artificial resin factory to produce, with the phenolic aldehyde polyglycidyl ether that trade(brand)name PNE177 sells, its epoxy equivalent (weight) between 170 to 190g/eq.
Resins, epoxy 4:Represent Changchun artificial resin factory to produce, the diglycidylether of the tetrabromo-bisphenol of selling with trade(brand)name BEB530A80, its epoxy equivalent (weight) be between 430 to 450g/eq, bromine content between 18.5 to 20.5wt%.
Resins, epoxy 5:Represent Changchun artificial resin factory to produce, trade(brand)name BE501, its epoxy equivalent (weight) between 490 to 510g/eq.
Solidifying agent A:Represent the dicyan diamide, 10% molten what dimethyl formamide.
Solidifying agent B:Represent the epoxy curing agent of the phosphorous and nitrogen shown in the following formula of the present invention.
B is 0 to 20 integer in the formula.
Solidifying agent C:Represent Changchun artificial resin factory to produce, commodity are called BEH510, Ahew between 105 to 110g/eg.
Curing catalyst A:Represent glyoxal ethyline (2MI), 10% molten what methyl ethyl ketone.
Relevant epoxy equivalent (weight) used herein (EEW, Epoxy Equivalent Weight), varnish viscosity (Viscosity), solid content (Solid content) are to test according to following method of testing:
(1) epoxy equivalent (weight): make Resins, epoxy dissolving what chlorobenzene: in the solvent of chloroform=1: 1, carry out titration with the HBr/ Glacial acetic acid, record according to the method for ASTM D1652, wherein indicator is a Viola crystallina.
(2) viscosity: phosphorous epoxy resin varnish was placed 25 ℃ of thermostatic baths 4 hours, use Brookfield (Brookfield) viscometer in 25 ℃ of measurements.
(3) solid content: get the varnish sample that contains phosphorous epoxy resin of the present invention of 1 gram, in 60 minutes non-volatile part measured weight percents of 150 ℃ of bakings.
Synthesis example 1: the resin curing agent (solidifying agent B) of phosphorous and nitrogen synthetic:
Be equipped with the electrically heated cover, temperature regulator electric blender and stirring rod, nitrogen inlet, thermopair, water cooled condenser, insert phenol 1410 grams (15mole) in the 3000ml five neck glass reaction stills of feed hopper, 92% polyoxymethylene, 244.7 grams (7.5mole), benzoguanamine (benzoguanamine) 337 grams (1.8mole), 9, the 10-dihydro-9-oxy is mixed-10-phosphorus anthracene-10-oxide compound (HCA) 259 grams (1.2mole), oxalic acid 11.2 grams, after the fusion, vacuumize and make above raw material drying, and then feeding nitrogen, heavily cover and vacuumize and feed the nitrogen program twice.Be warming up to 100 to 110 ℃, reacted 3 hours.Be warming up to 120 to 125 ℃ of reactions 2 hours again.Phenol and reaction condensation water slowly that unreacted is intact after reaction is finished are removed with the normal pressure steaming, at last with 180 ℃, keep 1 hour under the vacuum.The product of gained is the resin curing agent (solidifying agent B) of phosphorous and nitrogen of the present invention.
By analysis, softening temperature is 161 ℃, and theoretical nitrogen content is that 10.0wt%, phosphorus content are that 2.93wt%, Ahew are 210g/eq.
Embodiment 1 to b and comparative example 1
In being equipped with under the room temperature in the container of agitator and condenser, 1 synthetic solidifying agent of synthesis example B, other solidifying agent, Resins, epoxy, curing catalyst and solvent are modulated into epoxy resin varnish according to ratio shown in the table 1.
Table 1
With modulated epoxy resin varnish of making and glasscloth impregnation, through 180 ℃ of dryings after 120 minutes, after becoming prepreg, the prepreg of gained is through DSC (Differential ScanCalorimeter, TA2910) (temperature range is 50 to 250 ℃ to test its second-order transition temperature, heat-up rate is 20 ℃/minute), survey its flame retardancy through combustion test, it is the method according to UL746,5 of 12.5mm * 1.3mm size are cut in the prepreg test piece, every burning 2 times, 10 times the burning summation is no more than 50 seconds, single is the highest to be no more than 10 seconds, represents that promptly combustion test passes through.The result is as shown in table 2:
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 | |
| Combustion testing | By | By | By | By | By | By | By |
| Tg(℃) | 163 | 160 | 151 | 148 | 158 | 144 | 132 |
Superimposed with eight prepregs, it respectively places the Copper Foil of a slice 35 μ m up and down, through 185 ℃, 25kg/cm
2Pressure pressing and become the laminate of Resins, epoxy and glasscloth, the rerum natura result who analyzes each laminate is as shown in table 3
Table 3
| Analysis project | Condition and specification | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| Soldering resistance | 288 ℃ of specification＞300 second | By | By | Failure |
| Stripping strength | Specification＞8lb/in | 8.92 | 8.56 | 9.25 |
| The surface resistance | Specification＞10 12 | 2.5*10 15 | 3.3*10 15 | 2.9*10 15 |
| The volume resistance | Specification＞10 10 | 11*10 13 | 2.0*10 13 | 1.2*10 14 |
| Specific inductivity | Specification＜5.4 | 4.45 | 4.81 | 4.72 |
| The loss factor | -- | 0.021 | 0.023 | 0.022 |
Embodiment 7 to 10 and comparative example 2
In being equipped with under the room temperature in the container of agitator and condenser, composition shown in the table 4 is modulated into epoxy resin varnish according to ratio shown in the table 4.
Table 4
The foregoing description 7,8 and 10 and the composition epoxy resin of comparative example 2 gained coat on the 18 micron copper foil uneven surfaces with 80 micron thickness, in 150 ℃ of oven dry.The Copper Foil of the epoxy resin coating of gained is added in the aforementioned prepreg of being made by the composition epoxy resin of embodiment 1 both sides up and down, through 185 ℃ of temperature and 25kg/cm
2The pressure pressing makes multi-ply wood.Analyze this multiple-plate rerum natura, the result is as shown in table 5.
Table 5
| Analysis project | Condition and specification | Embodiment 7 | Embodiment 8 | Embodiment 10 | Comparative example 2 |
| Combustion testing | UL 94-V0 | By | By | By | By |
| Soldering resistance | 288 ℃ of specification＞300 second | By | By | By | Failure |
| Stripping strength | IPC specification＞6lb/in (18 μ m) | 7.3 | 7.9 | 8.1 | 8.4 |
Can find out that by The above results phosphorous solidifying agent more not phosphorous with resin curing agent nitrogen and nitrogen of the present invention shows better combustion testing and soldering resistance, but stripping strength is not also seen reduction.
Claims (8)
1. the resin curing agent of a phosphorous and nitrogen, it has following formula:
In the formula
Or hydrogen atom
But at least one R
2It is not hydrogen atom;
R
1Expression NHR
2, C
1-6Alkyl or phenyl;
N represents 0 to 20 integer;
-R-represents the group of penylene, naphthylene or following formula:
-Ph-A-Ph-
Ph represents phenyl in the formula, A represents-O-,-S-,-SO
2-,-CO-,-CH
2-,-C (CH
3)
2-or the group of following formula:
In the represented group of above-mentioned R and A, the hydrogen atom of aryl is selected from hydroxyl, amino, carboxyl and C by one or more
1-6The substituting group of alkyl replaces or is not substituted.
2. the resin curing agent of phosphorous and nitrogen as claimed in claim 1, it has following formula:
B is 0 to 20 integer in the formula.
3. a difficult combustible epoxy resin composition comprises (A) Resins, epoxy, (B) resin curing agent of claim 1 or 2 described phosphorous and nitrogen, and (C) curing catalyst;
Wherein said Resins, epoxy is selected from glycidyl ether, phenolic aldehyde polyglycidyl ether and the polyhydroxy phenol polyglycidyl ether of bis-phenol glycidyl ether, two diphenol glycidyl ether, dihydroxy-benzene glycidyl ether, the glycidyl ether that contains azo-cycle, dihydroxy naphthlene.
4. difficult combustible epoxy resin composition as claimed in claim 3, wherein this curing catalyst is selected from tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt, boron trifluoride complex, lithiumation thing and imidazolium compoundss.
5. difficult combustible epoxy resin composition as claimed in claim 3, wherein the Resins, epoxy epoxy equivalent (weight) in composition (A) is 100%, the hardener dose of composition (B) counts 20 to 140% with its reactive behavior hydrogen equivalent.
6. difficult combustible epoxy resin composition as claimed in claim 3, wherein the curing catalyst consumption of composition (C) is 50 to 50 of a composition epoxy resin gross weight, 000ppm.
7. difficult combustible epoxy resin composition as claimed in claim 3, it can further comprise the solidifying agent of amine, bisphenol resin, dihydroxy-benzene, polyhydroxy phenol resin and phenolic.
8. the described difficult combustible epoxy resin composition of claim 3 is being used for making the substrate that adhesive sheet, matrix material, laminated plates, printed circuit board (PCB), Layer increasing method use and the application of semiconductor sealing material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001235257A CN1167732C (en) | 2000-08-18 | 2000-08-18 | Resin firming agent containing phosphorus and nitrogen and fireproof resin composition containing said firming agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001235257A CN1167732C (en) | 2000-08-18 | 2000-08-18 | Resin firming agent containing phosphorus and nitrogen and fireproof resin composition containing said firming agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1339525A CN1339525A (en) | 2002-03-13 |
| CN1167732C true CN1167732C (en) | 2004-09-22 |
Family
ID=4589931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001235257A Expired - Fee Related CN1167732C (en) | 2000-08-18 | 2000-08-18 | Resin firming agent containing phosphorus and nitrogen and fireproof resin composition containing said firming agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1167732C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005015605B4 (en) * | 2005-04-05 | 2008-04-17 | Schill + Seilacher "Struktol" Aktiengesellschaft | Organophosphorus-containing prepolymers and uses therefor |
| CN104017327B (en) * | 2013-02-28 | 2017-08-01 | 宏泰电工股份有限公司 | The resistance to combustion resin combination of phosphorus-nitrogen type halogen-free, prepreg and film, copper foil laminates and its printed circuit board (PCB) |
-
2000
- 2000-08-18 CN CNB001235257A patent/CN1167732C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1339525A (en) | 2002-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10189988B2 (en) | High-CTI and halogen-free epoxy resin composition for copper-clad plates and use thereof | |
| EP1814949B1 (en) | Non-halogen flame retardant epoxy resin composition, and prepreg and copper-clad laminate using the same | |
| EP2818487B1 (en) | Phosphor-containing phenol formaldhyde resin and flame-retardant epoxy resin hardener containing thereof | |
| CN1423678A (en) | Flame retardant phosphorus element-containing epoxy resin compositions | |
| EP2896653B1 (en) | Epoxy resin composition, and, prepreg and copper clad laminate manufactured using the composition | |
| CN1788053A (en) | Flame-retarded epoxy resin composition, prepregs containing the same, laminated sheets and printed wiring boards | |
| CN1239609C (en) | Resin composition and its use and production process thereof | |
| CZ70597A3 (en) | Mixtures of expoxy resins for prepregs and sandwiches | |
| CN1238422C (en) | Halogen-free flame-retarding epoxy resin composition containing phosphor and nitrogen and preimpregnated material and laminate containing same | |
| JP3906961B2 (en) | Resin curing agent containing phosphorus and nitrogen and flame retardant resin composition containing the curing agent | |
| CN1249128C (en) | Phosphorous resin and fire retarded resin composition containing said resin | |
| JP4259031B2 (en) | Resin composition, prepreg and paper base phenolic resin laminate | |
| CN1167732C (en) | Resin firming agent containing phosphorus and nitrogen and fireproof resin composition containing said firming agent | |
| JP3659908B2 (en) | Flame retardant resin composition containing phosphorus-containing resin | |
| CN1156539C (en) | Fire-retarded resin and fire-retardedresin composition containing said resin | |
| CN1145677C (en) | Resin composition with phosphorous compound having epoxy radical and its use | |
| CN101061127A (en) | 1,4-hydroquinone functionalized phosphinates and phosphonates | |
| US20030073781A1 (en) | Phosphorus-containing resin and flame retardant resin composition containing the same | |
| CN1350030A (en) | Fireproof epoxy resin composite and its application | |
| US6432539B1 (en) | Phosphorus-containing polymer having phenolic units and uses thereof | |
| CN1333014C (en) | Halogen-free resin composition | |
| CN100489027C (en) | Flame-retarded epoxy resin composition and phosphorous compound | |
| CN1339518A (en) | Phosphorous polymer having phenolic structure and its use | |
| KR101468005B1 (en) | High heat-resistance flame retardant compounds and Manufacturing method thereof | |
| CN100475912C (en) | Halogen-free resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1044163 Country of ref document: HK |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040922 Termination date: 20150818 |
|
| EXPY | Termination of patent right or utility model |