CN107383775A - A kind of bromine phosphorus sulphur synergistic fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate - Google Patents
A kind of bromine phosphorus sulphur synergistic fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The present invention provides a kind of bromine phosphorus sulphur synergistic fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate, it is brominated phenolic compound and its epoxy resin that the fire-retardant combination, which includes brominated flame-retardant, sulfur-bearing fire retardant and phosphonium flame retardant and halogen-free epoxy resin, the brominated flame-retardant,.Brominated flame-retardant and phosphonium flame retardant in the fire-proof resin composition of the present invention have synergy on flame retardant effect, are capable of the fire resistance of reinforced resin composition.It is a kind of fire-retardant combination with larger economy and environmentally friendly friendly and the solidfied material of the fire-proof resin composition has good heat resistance, water resistance, cohesiveness, mechanical performance and electrical property.
Description
Technical field
The invention belongs to fire proofing field, is related to a kind of fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet
And composite metal substrate, more particularly to a kind of bromine phosphorus sulphur synergistic fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and
Composite metal substrate.
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 family expenses of representative, office electric equipment products and other field are rung, for safety, significant portion
Product require that it possesses different degrees of fire resistance.
In order that product reaches required fire resistance or grade, traditional technology usually uses to be added into material system
Add halogen-containing fire retardant matter, such as addition such as brominated bisphenol A, brominated bisphenol a type epoxy resin are brominated into system material
Amount is higher or containing the higher organic chemicals of halogen quantity, although these halogen-containing fire retardant matter anti-flammabilitys are preferable,
But its usage amount is bigger, such as in copper-clad plate preparation, in order to reach preferable flame retardant effect, use brominated fire retardant
When, it is ensured that in the composition of fire retardant and epoxy resin bromine content more than 20%, this cause in product bromo element content compared with
Height, and content of halogen height also brings along some detrimental effects in product, such as difficult degradation can be produced in high temperature or burning
Harmful substance such as dioxin organic halogen chemical contamination environment, influence the mankind and animal health.
Therefore, the usage amount and can for how reducing fire retardant enough ensures the problem of flame retardant effect is this area urgent need to resolve.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of fire-proof resin composition, thermosetting resin
Composition, pre-impregnated sheet and composite metal substrate, it is provided in particular in a kind of bromine phosphorus sulphur synergistic fire-proof resin composition, thermosetting resin
Composition, pre-impregnated sheet and composite metal substrate.
To use following technical scheme up to this purpose, the present invention：
On the one hand, the present invention provides a kind of fire-proof resin composition, and the fire-retardant combination includes brominated flame-retardant, sulfur-bearing
Fire retardant and phosphonium flame retardant and halogen-free epoxy resin, the brominated flame-retardant are brominated phenolic compound and its asphalt mixtures modified by epoxy resin
Fat.
Brominated flame-retardant, sulfur-bearing fire retardant and phosphonium flame retardant composition association are utilized in the fire-proof resin composition of the present invention
Fire retardant is imitated, coordinates halogen-free epoxy resin to make the solidfied material of its composition that there is good anti-flammability, it is heat resistance, water-fast
Property, higher peel strength and heat decomposition temperature.
Preferably, weight percent content shared by bromo element is less than 10% in the fire-proof resin composition, such as
10%th, 9%, 8.5%, 8%, 7%, 7.5%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.3%, 0.1% etc., it is excellent
Select 1-5%.
Preferably, weight percent content shared by element sulphur is more than 0.2% in the fire-proof resin composition, such as
0.2%th, 0.25%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 1.8%, 2% etc.,
It is preferred that 0.2-1%.
Preferably, weight percent content shared by P elements is more than 0.2% in the fire-proof resin composition, such as
0.2%th, 0.25%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 1.8%, 2%,
2.5%th, 3%, 4%, 5% etc., preferably 0.2-2%.
In the range of bromo element, element sulphur and the phosphorus element content that the present invention limits, brominated flame-retardant is fire-retardant with sulfur-bearing
Agent and phosphonium flame retardant are mutually coordinated, cooperate with the fire resistance of reinforced resin composition, can either ensure that resin combination has
There is preferable fire resistance, and can is enough to control bromo element content in relatively low scope, so as to reduce because high temperature produces nuisance
The possibility of matter, and in the content range, the various aspects of performance for the copper-clad plate that fire-proof resin composition is prepared can obtain
To optimization, there is good heat resistance, water resistance, higher heat decomposition temperature etc., be improved the combination property of copper-clad plate.
Traditional brominated flame-retardant will keep bromo element content to be risen more than 20% when being applied in resin combination
To preferable flame retardant effect, to ensure the fire resistance of copper-clad plate, the present invention on the basis of brominated flame-retardant by adding less
Sulfur-bearing fire retardant and phosphonium flame retardant the composition composite flame-retardant agent of amount are applied in resin combination, can make it that three's is fire-retardant
Effect is mutually promoted, and reaches the effect of cooperative flame retardant, while reduces the usage amount of brominated flame-retardant, cost-effective, and energy
Enough ensure that copper-clad plate has good heat resistance, water resistance, higher heat decomposition temperature etc..
In the present invention, bromo element content, sulfur content and phosphorus element content are with fire-retardant in fire-proof resin composition
The weight of resin combination is 100% calculating.
Preferably, the brominated flame-retardant is brominated phenolic resin, bromination novolac epoxy resin, brominated bisphenol A, bromination pair
In phenol A derivatives, brominated bisphenol a type epoxy resin, tetrabromo-bisphenol s, tetrabromobisphenol allyl ether, tribromphenol or pentabromophenol
Any one or at least two combination, preferably brominated bisphenol A, brominated bisphenol A derivatives or brominated bisphenol a type epoxy resin.
Preferably, the sulfur-bearing fire retardant is to diphenyl disulfide phenol and/or 4,4'- diaminourea diphenyl disulfide, preferred pair benzene
Dithiol.
Preferably, the phosphonium flame retardant is that DOPO is etherified bisphenol-A, DOPO modified epoxies, three (2,6- dimethyl benzenes
Base) it is phosphine, four-(2,6- xylyls) resorcinol biphosphonates, resorcinol tetraphenyldiphosphate, triphenyl phosphate, double
Phenol A double (diphenyl phosphoester), phosphonitrile fire retardant, 10- (2,5- dihydroxy phenyls) -10- hydrogen -9- oxa- -10- phosphine phenanthrene -10- oxygen
Compound, 10- (2,5- dihydroxy naphthyl) -10- hydrogen -9- oxa-s -10- phosphines phenanthrene -10- oxides or the miscellaneous -10- of 9,10- dihydro-9-oxies
In phospho hetero phenanthrene -10- oxide fire retardants any one or at least two mixture.
Other fire proofings can be added as needed in the fire-retardant combination of the present invention.
Preferably, other described fire proofings be organic silicon fibre retardant, chloride organic fire-retardant, nitrogenous organic fire-retardant or
In inorganic combustion inhibitor any one or at least two combination.
Preferably, the chloride organic fire-retardant is Dioctyl Tetrachlorophthalate, chlorendic anhydride, chlorine mattress acid or tetrachloro
In bisphenol-A any one or at least two combination.
Preferably, the nitrogenous organic fire-retardant be dicyandiamide, biruea or melamine in any one or at least
Two kinds of combination.
Preferably, the inorganic combustion inhibitor is any one in aluminium hydroxide, magnesium hydroxide, antimony oxide or Firebrake ZB
Kind or at least two combination.
Preferably, the halogen-free epoxy resin is selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol type phenolic aldehyde
Epoxy resin, bisphenol A-type novolac epoxy resin, Study On O-cresol Epoxy Resin, dicyclopentadiene type epoxy resin, isocyanates
In type epoxy resin or biphenyl type epoxy resin at least any one or at least two mixture.
Preferably, the weight/mass percentage composition of epoxy resin described in the fire-proof resin composition is 70-90%, such as
70%th, 73%, 75%, 78%, 80%, 83%, 85%, 88% or 90%.
On the other hand, the present invention provides a kind of compositions of thermosetting resin, and the compositions of thermosetting resin includes as above
Described fire-proof resin composition.
Preferably, the compositions of thermosetting resin also includes curing agent.
Preferably, the curing agent is selected from dicyandiamide, phenolic resin, aromatic amine, acid anhydrides, active esters curing agent or activity
In phenols curing agent any one or at least two combination.
Preferably, the compositions of thermosetting resin also includes curing accelerator；
Preferably, the curing accelerator is imidazoles curing accelerator, organic phosphine curing accelerator or tertiary amine solidification
In accelerator any one or at least two mixture.
Preferably, the glyoxaline compound is selected from 2-methylimidazole, the methylimidazole of 2- ethyls -4,2- phenylimidazoles, 2-
Undecyl imidazole, 1 benzyl 2 methyl imidazole, 2- heptadecyl imidazoles, 2 isopropyl imidazole, 2- phenyl -4-methylimidazole,
In 2- dodecyl imidazoles or 1- 1-cyanoethyl-2-methylimidazoles any one or at least two mixture, preferred 2- methyl
Imidazoles.
On the other hand, the present invention provides a kind of pre-impregnated sheet, and it is impregnated with or be coated with by compositions of thermosetting resin described above
Formed in base material.
Preferably, the base material can be fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon
Fiber base material etc..
In the present invention, the concrete technology condition of its impregnation or coating is not particularly limited." pre-impregnated sheet " is also this area skill
" bonding sheet " known to art personnel.
A kind of composite metal substrate, it carries out surface metal-clad, overlapping, pressure successively by least one such as above-mentioned pre-impregnated sheet
Conjunction forms.
Preferably, the material of the surface metal-clad is the alloy of aluminium, copper, iron and its any combination.
Preferably, the composite metal substrate is that CEM-1 copper-clad plates, CEM-3 copper-clad plates, FR-4 copper-clad plates, FR-5 cover copper
Any one in plate, CEM-1 aluminium bases, CEM-3 aluminium bases, FR-4 aluminium bases or FR-5 aluminium bases.
A kind of wiring board, formed in the Surface Machining circuit of above-mentioned composite metal substrate.
Relative to prior art, the present invention has the advantages that：
Brominated flame-retardant in the fire-proof resin composition of the present invention is with sulfur-bearing fire retardant and phosphonium flame retardant in fire-retardant effect
There is synergy on fruit, be capable of the fire resistance of reinforced resin composition.The solidification of fire-proof resin composition of the present invention
Thing has good heat resistance, water resistance, cohesiveness, mechanical performance and electrical property, is a kind of to have larger economy and ring
Protect the fire-retardant combination of friendly.The heat decomposition temperature (5% is weightless) for the copper-clad plate being prepared by said composition can be up to
More than 385 DEG C, peel strength can reach 2.7kg/mm2More than, T-288 ＞ 100 seconds, wicking heat-resistant limit reaches more than 40 times,
Saturated water absorption can reach less than 0.2%, and flammability (UL-94) reaches V-0 ranks.
Embodiment
Technical scheme is further illustrated below by embodiment.Those skilled in the art should be bright
, the embodiment be only to aid in understand the present invention, be not construed as to the present invention concrete restriction.
Embodiment 1
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, addition epoxide equivalent is 400g/eq, bromine
Brominated bisphenol a type epoxy resin 13.2g and sulfur content that content is 48.5% is 45% diphenyl disulfide phenol 1.43g and phosphorus to be contained
After measuring four for 10.0%-(2,6- xylyls) resorcinol biphosphonate 14.8g mixing, obtain bromine content and contain for 5%, sulphur
The flame-retarded resin mixture for being 1.0% for 0.5%, phosphorus content is measured, appropriate acetone solution is added, adds 6.0g dicyandiamide
After fully being dissolved with 0.1g 2-methylimidazole, it is worth copper-clad plate according to known methods, this copper-clad plate is referred to as copper-clad plate A,
Copper-clad plate A the performance test results are as shown in table 1.
Embodiment 2
Take epoxide equivalent be 186g/eq liquid bisphenol A type epoxy resin 100g, additions phenolic hydroxyl equivalent be 272g/eq,
Brominated bisphenol A11.2g and sulfur content that bromine content is 58.5% is 45% to be to diphenyl disulfide phenol 0.6g and phenolic hydroxyl equivalent
300.0g/eq, after the DOPO that phosphorus content is 10.0% is etherified bisphenol-A 19.8g mixing, obtain bromine content be 5%, sulfur content be
0.2%th, phosphorus content is 1.5% flame-retarded resin mixture, adds appropriate acetone solution, adding phenolic hydroxyl equivalent is
After 105g/eq linear phenol-aldehyde resins 44.3g and 0.1g 2-methylimidazole fully dissolve, it is worth covering copper according to known methods
Plate, this copper-clad plate is referred to as copper-clad plate B, copper-clad plate B the performance test results are as shown in table 1.
Embodiment 3
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, addition epoxide equivalent is 400g/eq, bromine
The 4,4'- diaminourea diphenyl disulfides that the brominated bisphenol a type epoxy resin 7.6g and sulfur content that content is 48.5% are 14.8%
8.4g and phosphorus content are 3.0%, after the universal DOPO modified epoxies 8.3g mixing that epoxide equivalent is 300g/eq, are obtained
To the flame-retarded resin mixture that bromine content is 3%, sulfur content 1%, phosphorus content content are 0.2%, it is molten to add appropriate acetone
Solution, after the 2-methylimidazole of the dicyandiamide and 0.1g that add 5.5g fully dissolves, it is worth copper-clad plate according to known methods, will
This copper-clad plate is referred to as copper-clad plate C, and copper-clad plate C the performance test results are as shown in table 1.
Embodiment 4
Take epoxide equivalent be 186g/eq liquid bisphenol A type epoxy resin 100g, additions phenolic hydroxyl equivalent be 272g/eq,
Brominated bisphenol A1.9g and sulfur content that bromine content is 58.5% is 45% to be to diphenyl disulfide phenol 1.2g and phenolic hydroxyl equivalent
300.0g/eq, after the DOPO that phosphorus content is 10.0% is etherified bisphenol-A 8.9g mixing, obtain bromine content be 1%, sulfur content be
0.5%th, phosphorus content is 0.8% flame-retarded resin mixture, adds appropriate acetone solution, adding phenolic hydroxyl equivalent is
After 105g/eq linear phenol-aldehyde resins 50.8g and 0.1g 2-methylimidazole fully dissolve, it is worth covering copper according to known methods
Plate, this copper-clad plate is referred to as copper-clad plate D, copper-clad plate D the performance test results are as shown in table 1.
Comparative example 1
Take the market circulation standard bromination bisphenol A type epoxy resin 100g that bromine content is 20%, epoxide equivalent is 420g/eq
(solid calculating), dicyandiamide 2.6g and 0.1g 2-methylimidazole are added, after adding appropriate acetone solution, according to known
Copper-clad plate is prepared in method, this copper-clad plate is referred to as into copper-clad plate E, copper-clad plate E the performance test results are as shown in table 2.
Comparative example 2
Take the market circulation standard bromination bisphenol A type epoxy resin that bromine content is 20%, epoxide equivalent is 420g/eq
After 16.7g (solid calculating) and the liquid bisphenol A type epoxy resin 50g that epoxide equivalent is 186g/eq is mixed, obtaining bromine content is
5% composition epoxy resin, appropriate acetone solution is added, it is 105g/eq linear phenol-aldehyde resins to add phenolic hydroxyl equivalent
After 32.4g and 0.1g 2-methylimidazole fully dissolves, copper-clad plate is prepared according to known methods, this copper-clad plate is referred to as
Copper-clad plate F, copper-clad plate F the performance test results are as shown in table 2.
Comparative example 3
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, addition epoxide equivalent is 400g/eq, bromine
The brominated bisphenol a type epoxy resin 14.3g and sulfur content that content is 48.5% be 45% to diphenyl disulfide phenol 1.28g mix after,
The flame-retarded resin mixture that bromine content is 6%, sulfur content is 0.5% is obtained, appropriate acetone solution is added, adds 6.0g's
After dicyandiamide and 0.1g 2-methylimidazole fully dissolve, it is worth copper-clad plate according to known methods, this copper-clad plate is referred to as covering
Copper coin G, copper-clad plate G the performance test results are as shown in table 2.
Comparative example 4
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, addition epoxide equivalent is 400g/eq, bromine
The brominated bisphenol a type epoxy resin 11.8g and sulfur content that content is 48.5% be 45% to diphenyl disulfide phenol 3.85g mix after,
The flame-retarded resin mixture that bromine content is 5%, sulfur content is 1.5% is obtained, appropriate acetone solution is added, adds 5.0g's
After dicyandiamide and 0.1g 2-methylimidazole fully dissolve, it is worth copper-clad plate according to known methods, this copper-clad plate is referred to as covering
Copper coin H, copper-clad plate H the performance test results are as shown in table 2.
Comparative example 5
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, addition epoxide equivalent is 400g/eq, bromine
The brominated bisphenol a type epoxy resin 14.4g that content is 48.5% and four-(2,6- xylyls) isophthalic that phosphorus content is 10.0%
After diphenol biphosphonate 12.7g mixing, the flame-retarded resin mixture that bromine content is 5.5%, phosphorus content is 1.0% is obtained, is added
Appropriate acetone solution, after the 2-methylimidazole of the dicyandiamide and 0.1g that add 6.3g fully dissolves, according to known methods
It is worth copper-clad plate, this copper-clad plate is referred to as copper-clad plate I, copper-clad plate I the performance test results are as shown in table 2.
Comparative example 6
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, addition epoxide equivalent is 400g/eq, bromine
The brominated bisphenol a type epoxy resin 13.8g that content is 48.5% and four-(2,6- xylyls) isophthalic that phosphorus content is 10.0%
After diphenol biphosphonate 20g mixing, the flame-retarded resin mixture that bromine content is 5%, phosphorus content is 1.5% is obtained, is added appropriate
Acetone solution, after the 2-methylimidazole of the dicyandiamide and 0.1g that add 6.2g fully dissolves, be worth according to known methods
Copper-clad plate, this copper-clad plate is referred to as copper-clad plate J, copper-clad plate J the performance test results are as shown in table 2.
Comparative example 7
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, add sulfur content as 45% to benzene two
After thiophenol 15.7g and four-(2,6- xylyl) the resorcinol biphosphonate 12.8g that phosphorus content is 10.0% is mixed, obtain
To the flame-retarded resin mixture that sulfur content is 5.5%, phosphorus content is 1.0%, appropriate acetone solution is added, adds 3.5g's
After dicyandiamide and 0.1g 2-methylimidazole fully dissolve, it is worth copper-clad plate according to known methods, this copper-clad plate is referred to as covering
Copper coin K, copper-clad plate K the performance test results are as shown in table 2.
Comparative example 8
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, add sulfur content as 45% to benzene two
After thiophenol 2.86g and four-(2,6- xylyl) the resorcinol biphosphonate 154.5g that phosphorus content is 10.0% is mixed, obtain
To the flame-retarded resin mixture that sulfur content is 0.5%, phosphorus content is 6%, appropriate acetone solution is added, adds the double of 5.4g
After cyanamide and 0.1g 2-methylimidazole fully dissolve, it is worth copper-clad plate according to known methods, this copper-clad plate is referred to as covering copper
Plate L, copper-clad plate L the performance test results are as shown in table 2.
Table 1
Table 2
It is prepared into it can be seen from the test result of table 1 using bromine phosphorus sulphur synergistic fire-proof resin composition of the present invention
To the heat decomposition temperature (5% weightless) of copper-clad plate more than 385 DEG C can be up to, peel strength can reach 2.7kg/mm2More than,
T-288 ＞ 100 seconds, heat-resistant limit reach more than 40 times, and saturated water absorption can reach less than 0.2%, and flammability (UL-94) reaches
V-0 ranks.When utilizing the market circulation standard bromination bisphenol type epoxy tree that bromine content is 20%, epoxide equivalent is 420g/eq
Fat, and when being added without phosphonium flame retardant and sulfur-bearing fire retardant (comparative example 1), although bromine content is improved to 20%, it is prepared into
Although the copper-clad plate E arrived also has the fire resistance of V-0 ranks, the bromine content of the copper-clad plate is higher, for environmental protection not
Profit, and heat decomposition temperature is relatively low, unstable, its T-288 is only 15 seconds in addition, and heat-resistant limit is only 5 times, saturated water absorption compared with
It is high；And when the market circulation standard bromination bisphenol A type epoxy resin for using bromine content to be 420g/eq for 20%, epoxide equivalent is made
For fire retardant, without using phosphonium flame retardant and sulfur-bearing fire retardant, also truthfully apply example 1 equally and epoxide equivalent is 186g/eq's
Liquid bisphenol A types epoxy resin mixing after keep content of its bromine content in composition epoxy resin be 5% when (comparative example
2), its copper-clad plate F being prepared fire resistance substantially reduces, and its heat-resistant limit is only 8 times, heat decomposition temperature is low,
Peel strength is low, saturated water absorption is high；When without using phosphonium flame retardant, and the amount of brominated flame-retardant is improved with so that bromo element contains
When amount is equal to bromine in embodiment 1 and phosphorus element content sum (comparative example 3), the copper-clad plate being prepared is due in brominated flame-retardant
With although also there is good anti-flammability under the collective effect of sulfur-bearing fire retardant, its heat decomposition temperature and peel strength compare
The heat decomposition temperature and peel strength that the embodiment of the present invention obtains are low, and heat-resistant limit is heat-resisting less than copper-clad plate of the embodiment of the present invention
The limit, and saturated water absorption is higher, equally when without using phosphonium flame retardant, and the dosage of sulfur-bearing fire retardant is improved to cause sulphur
Constituent content is equal in embodiment 1 sulphur and during phosphorus element content sum (comparative example 4), although now with good anti-flammability,
It is resistance to thermoae but the heat decomposition temperature and peel strength that its heat decomposition temperature and peel strength obtain than the embodiment of the present invention are low
Limit is less than the heat-resistant limit of copper-clad plate of the embodiment of the present invention, and saturated water absorption is higher；When without using sulfur-bearing fire retardant, nothing
By being that the dosage for improving brominated flame-retardant makes it equal to bromo element and sulfur content sum (comparative example 5) in embodiment 1, still
Improve phosphonium flame retardant dosage and make it equal to P elements and sulfur content sum (comparative example 6) in embodiment 1, what it was obtained covers
Although copper coin possesses preferable anti-flammability, but its heat decomposition temperature and peel strength are divided than the heat that the embodiment of the present invention obtains
Solve temperature and peel strength it is low, heat-resistant limit be less than copper-clad plate of the embodiment of the present invention heat-resistant limit, and saturated water absorption compared with
It is high；When without using brominated flame-retardant, even if improving sulfur content in composition makes it equal to element sulphur and bromine in embodiment 1
The content of P elements makes it equal to P elements and bromine member in embodiment 1 in constituent content sum (comparative example 7) or raising composition
Cellulose content sum (comparative example 8), the poor flame retardant properties of gained copper-clad plate, other performances compare such as heat resistance, water resistance
Difference.Therefore illustrate that brominated flame-retardant, sulfur-bearing fire retardant have with phosphonium flame retardant in fire resistance in the present invention and cooperate with work
With, and the present invention application brominated phenolic compound and its epoxy resin be used as brominated flame-retardant, coordinate sulfur-bearing fire retardant with
Phosphonium flame retardant and halogen-free epoxy resin so that the copper-clad plate of preparation has good combination property, and the present invention is reducing bromine
It can keep copper-clad plate that there are good flame-retardance energy and heat resistance, water resistance and good mechanical properties while constituent content
Deng.
Applicant states that the present invention illustrates the fire-proof resin composition of the present invention, thermosetting tree by above-described embodiment
Oil/fat composition, pre-impregnated sheet and composite metal substrate, but the invention is not limited in above-described embodiment, that is, do not mean that the present invention must
Above-described embodiment, which must be relied on, to be implemented.Person of ordinary skill in the field is right it will be clearly understood that any improvement in the present invention
The equivalence replacement of each raw material of product of the present invention and the addition of auxiliary element, the selection of concrete mode etc., all fall within the guarantor of the present invention
Protect within the scope of scope and disclosure.
Claims (10)
1. a kind of fire-proof resin composition, it is characterised in that it is fire-retardant that the fire-proof resin composition includes brominated flame-retardant, sulfur-bearing
Agent and phosphonium flame retardant and halogen-free epoxy resin, the brominated flame-retardant are brominated phenolic compound and its epoxy resin.
2. fire-proof resin composition according to claim 1, it is characterised in that bromo element in the fire-proof resin composition
Shared weight percent content is less than 10%, preferably 1-5%；
Preferably, weight percent content shared by element sulphur is more than 0.2% in the fire-proof resin composition, preferably 0.2-
1%；
Preferably, weight percent content shared by P elements is more than 0.2% in the fire-proof resin composition, preferably 0.2-
2%.
3. fire-proof resin composition according to claim 1 or 2, it is characterised in that the brominated flame-retardant is brominated phenols
Urea formaldehyde, bromination novolac epoxy resin, brominated bisphenol A, brominated bisphenol A derivatives, brominated bisphenol a type epoxy resin, tetrabromo are double
In phenol S, tetrabromobisphenol allyl ether, tribromphenol or pentabromophenol any one or at least two combination, preferably bromination is double
Phenol A, brominated bisphenol A derivatives or brominated bisphenol a type epoxy resin；
Preferably, the sulfur-bearing fire retardant is to diphenyl disulfide phenol and/or 4,4'- diaminourea diphenyl disulfide, preferred pair diphenyl disulfide
Phenol；
Preferably, the phosphonium flame retardant is that DOPO is etherified bisphenol-A, DOPO modified epoxies, three (2,6- 3,5-dimethylphenyls)
Phosphine, four-(2,6- xylyls) resorcinol biphosphonates, resorcinol tetraphenyldiphosphate, triphenyl phosphate, bisphenol-A
Double (diphenyl phosphoesters), phosphonitrile fire retardant, 10- (2,5- dihydroxy phenyls) -10- hydrogen -9- oxa- -10- phosphine phenanthrene -10- oxidations
Thing, 10- (2,5- dihydroxy naphthyl) -10- hydrogen -9- oxa-s -10- phosphines phenanthrene -10- oxides or the miscellaneous -10- phosphorus of 9,10- dihydro-9-oxies
In miscellaneous phenanthrene -10- oxide fire retardants any one or at least two mixture.
4. according to the fire-proof resin composition any one of claim 1-3, it is characterised in that the flame-retarded resin combination
Thing can also include other fire proofings；
Preferably, other described fire proofings are organic silicon fibre retardant, chloride organic fire-retardant, nitrogenous organic fire-retardant or inorganic
In fire retardant any one or at least two combination；
Preferably, the chloride organic fire-retardant is Dioctyl Tetrachlorophthalate, chlorendic anhydride, chlorine mattress acid or tetrachlorobisphenol
In A any one or at least two combination；
Preferably, the nitrogenous organic fire-retardant is any one in dicyandiamide, biruea or melamine or at least two
Combination；
Preferably, the inorganic combustion inhibitor be aluminium hydroxide, magnesium hydroxide, antimony oxide or Firebrake ZB in any one or
At least two combination.
5. according to the fire-proof resin composition any one of claim 1-4, it is characterised in that the halogen-free epoxy resin
Selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol type novolac epoxy resin, bisphenol A-type novolac epoxy resin, neighbour
In cresol novolak epoxy, dicyclopentadiene type epoxy resin, isocyanate-based epoxy resin or biphenyl type epoxy resin
At least any one or at least two mixture；
Preferably, the weight/mass percentage composition of halogen-free epoxy resin described in the fire-proof resin composition is 70-90%.
6. a kind of compositions of thermosetting resin, it is characterised in that the compositions of thermosetting resin, which is included in claim 1-5, appoints
Fire-proof resin composition described in one.
7. compositions of thermosetting resin according to claim 6, it is characterised in that the compositions of thermosetting resin also wraps
Containing curing agent；
Preferably, the curing agent is selected from dicyandiamide, phenolic resin, aromatic amine, acid anhydrides, active esters curing agent or reactive phenolic
In curing agent any one or at least two combination；
Preferably, the compositions of thermosetting resin also includes curing accelerator；
Preferably, the curing accelerator is that imidazoles curing accelerator, organic phosphine curing accelerator or tertiary amine solidification promote
In agent any one or at least two mixture；
Preferably, the glyoxaline compound is selected from 2-methylimidazole, the methylimidazole of 2- ethyls -4,2- phenylimidazoles, 2- 11
Alkyl imidazole, 1 benzyl 2 methyl imidazole, 2- heptadecyl imidazoles, 2 isopropyl imidazole, 2- phenyl -4-methylimidazole, 2- ten
In dialkylimidazolium or 1- 1-cyanoethyl-2-methylimidazoles any one or at least two mixture, preferred 2-methylimidazole.
8. a kind of pre-impregnated sheet, it is characterised in that it is impregnated with or applied by compositions of thermosetting resin as claimed in claims 6 or 7
Base material is distributed in form；
Preferably, the base material can be fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiber
Base material etc..
A kind of 9. composite metal substrate, it is characterised in that it is described its by least one pre-impregnated sheet as claimed in claim 8 successively
Carry out surface metal-clad, overlapping, pressing forms；
Preferably, the material of the surface metal-clad is the alloy of aluminium, copper, iron and its any combination；
Preferably, the composite metal substrate be CEM-1 copper-clad plates, CEM-3 copper-clad plates, FR-4 copper-clad plates, FR-5 copper-clad plates,
Any one in CEM-1 aluminium bases, CEM-3 aluminium bases, FR-4 aluminium bases or FR-5 aluminium bases.
10. a kind of wiring board, it is characterised in that formed in the Surface Machining circuit of the composite metal substrate described in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610322024.8A CN107383775A (en) | 2016-05-16 | 2016-05-16 | A kind of bromine phosphorus sulphur synergistic fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610322024.8A CN107383775A (en) | 2016-05-16 | 2016-05-16 | A kind of bromine phosphorus sulphur synergistic fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate |
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| CN107383775A true CN107383775A (en) | 2017-11-24 |
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| CN201610322024.8A Pending CN107383775A (en) | 2016-05-16 | 2016-05-16 | A kind of bromine phosphorus sulphur synergistic fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate |
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| CN107641288A (en) * | 2016-07-21 | 2018-01-30 | 广东广山新材料股份有限公司 | A kind of sulphur phosphorus synergistic fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate |
| CN107641290A (en) * | 2016-07-21 | 2018-01-30 | 广东广山新材料股份有限公司 | A kind of fire-proof resin composition, compositions of thermosetting resin, anti-flammability engineering plastics and composite metal substrate |
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| CN113621230A (en) * | 2021-09-01 | 2021-11-09 | 广东华彩复合材料有限公司 | Epoxy resin composite material for high-transparency prepreg and preparation method thereof |
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Cited By (5)
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| CN107641288A (en) * | 2016-07-21 | 2018-01-30 | 广东广山新材料股份有限公司 | A kind of sulphur phosphorus synergistic fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate |
| CN107641290A (en) * | 2016-07-21 | 2018-01-30 | 广东广山新材料股份有限公司 | A kind of fire-proof resin composition, compositions of thermosetting resin, anti-flammability engineering plastics and composite metal substrate |
| CN109233209A (en) * | 2018-09-30 | 2019-01-18 | 陕西生益科技有限公司 | It is a kind of have halogen without antimony resin combination, using its prepreg, laminate and printed circuit board |
| CN109233209B (en) * | 2018-09-30 | 2021-03-30 | 陕西生益科技有限公司 | Halogen-containing antimony-free resin composition, prepreg using same, laminated board and printed circuit board |
| CN113621230A (en) * | 2021-09-01 | 2021-11-09 | 广东华彩复合材料有限公司 | Epoxy resin composite material for high-transparency prepreg and preparation method thereof |
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Application publication date: 20171124 |