CN107254138A - A kind of fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate - Google Patents
A kind of fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate Download PDFInfo
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- CN107254138A CN107254138A CN201610325626.9A CN201610325626A CN107254138A CN 107254138 A CN107254138 A CN 107254138A CN 201610325626 A CN201610325626 A CN 201610325626A CN 107254138 A CN107254138 A CN 107254138A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/136—Phenols containing halogens
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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
- B32B15/08—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 of 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/095—Carboxylic acids containing halogens
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
- C08K5/3155—Dicyandiamide
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- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
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- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
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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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- 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
- B32B2307/70—Other properties
- B32B2307/73—Hydrophobic
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
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- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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Abstract
The present invention provides a kind of fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate, and the fire-proof resin composition includes brominated flame-retardant, sulfur-bearing fire retardant and/or phosphonium flame retardant, and halogen-free epoxy resin；The brominated flame-retardant is brominated phenolic compound and its epoxy resin.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, it is related to a kind of fire-proof resin composition, thermosetting resin combination
Thing, pre-impregnated sheet and composite metal substrate.
Background technology
Using mobile phone, computer, video camera, electronic game machine as representative electronic product, with air-conditioning, refrigerator,
Television image, sound equipment articles for use etc. for representative family expenses, office electric equipment products and other field use it is various
Product, for safety, significant portion of product requires that it possesses different degrees of fire resistance.
In order that product reaches required fire resistance or grade, traditional technology is usually used to material bodies
Halogen-containing fire retardant matter is added in system, such as addition such as brominated bisphenol A, brominated bisphenol into system material
The brominated amounts such as A type epoxy resin are higher or containing the higher organic chemicals of halogen quantity, and these are halogen
Although the fire retardant matter anti-flammability of element is preferably, its usage amount is than larger, such as in copper-clad plate preparation,
In order to reach preferable flame retardant effect, during using brominated fire retardant, it is ensured that fire retardant and epoxy resin
Bromine content is more than 20% in composition, and this causes bromo element content in product higher, and halogen contains in product
Amount height also brings along some detrimental effects, for example, the harmful substance of difficult degradation can be produced in high temperature or burning
Such as dioxin organic halogen chemical contamination environment, the influence mankind and animal health.
Therefore, the usage amount for how reducing fire retardant ensure that flame retardant effect is this area urgent need to resolve again
Problem.
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
Property resin combination, pre-impregnated sheet and composite metal substrate.
For up to this purpose, the present invention uses following technical scheme：
On the one hand, the present invention provides a kind of fire-proof resin composition, and the fire-proof resin composition is comprising brominated
Fire retardant, sulfur-bearing fire retardant and/or phosphonium flame retardant, and halogen-free epoxy resin；The brominated flame-retardant
For brominated phenolic compound and its epoxy resin.
Coordinate sulfur-bearing fire retardant and/or phosphorous using brominated flame-retardant in the fire-proof resin composition of the present invention
Fire retardant constitutes synergistic flame retardant, then to coordinate halogen-free epoxy resin to have the solidfied material of its composition good
Good anti-flammability, heat resistance, water resistance, higher peel strength and heat decomposition temperature.
Must include brominated flame-retardant in the fire-proof resin composition of the present invention, and for sulfur-bearing fire retardant and
Phosphonium flame retardant can comprising one of which can also the two be included in fire-proof resin composition, preferably
Ground, the fire-proof resin composition includes brominated flame-retardant, sulfur-bearing fire retardant and phosphonium flame retardant and Halogen
Epoxy resin, the brominated flame-retardant is brominated phenolic compound and its epoxy resin.
Preferably, weight percent content shared by bromo element is less than 10% in the fire-proof resin composition,
Such as 10%, 9%, 8.5%, 8%, 7%, 7.5%, 6%, 5%, 4%, 3%, 2%, 1%,
0.5%th, 0.3%, 0.1% etc., preferably 1-10%.
Preferably, weight percent content shared by element sulphur is more than 0.2% in the fire-proof resin composition,
Such as 0.2%, 0.25%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%,
1.5%th, 1.8%, 2% etc., preferably 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%, 0.25%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%,
1.5%th, 1.8%, 2%, 2.5%, 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 is limited, brominated flame-retardant is with containing
Sulphur fire retardant and/or phosphonium flame retardant are mutually coordinated, cooperate with the fire resistance of reinforced resin composition, can
Enough ensure that resin combination has preferable fire resistance, again can be by the control of bromo element content in relatively low model
Enclose, so as to reduce because high temperature produces the possibility of harmful substance, and in the content range, flame-retarded resin
The various aspects of performance for the copper-clad plate that composition is prepared can be optimized, with good heat resistance, resistance to
Aqueous, higher heat decomposition temperature etc., is improved the combination property of copper-clad plate.
Traditional brominated flame-retardant will keep bromo element content ability more than 20% when being applied in resin combination
Preferable flame retardant effect can be played, to ensure the fire resistance of copper-clad plate, the present invention is by brominated flame-retardant
On the basis of add a small amount of sulfur-bearing fire retardant and/or phosphonium flame retardant composition composite flame-retardant agent is applied to resin
In composition, the flame retardant effect phase of brominated flame-retardant and sulfur-bearing fire retardant and/or phosphonium flame retardant can be caused
Mutually promote, reach the effect of cooperative flame retardant, while the usage amount of brominated flame-retardant is reduced, it is cost-effective,
And it 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 in fire-proof resin composition
Calculated using the weight of fire-proof resin composition as 100%.
Preferably, the brominated flame-retardant is brominated phenolic resin, bromination novolac epoxy resin, brominated bisphenol
A, brominated bisphenol A derivatives, brominated bisphenol a type epoxy resin, tetrabromo-bisphenol s, tetrabromobisphenol allyl
In 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, preferably
To diphenyl disulfide phenol.
Preferably, the phosphonium flame retardant is DOPO etherificates bisphenol-A, DOPO modified epoxies, three
(2,6- 3,5-dimethylphenyls) phosphine, four-(2,6- xylyls) resorcinol biphosphonates, resorcinol tetraphenyl
Bisphosphate, triphenyl phosphate, bisphenol-A double (diphenyl phosphoester), phosphonitrile fire retardant, 10- (2,5-
Dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phosphine phenanthrene -10- oxides, 10- (2,5- dihydroxy naphthyl) -10- hydrogen -9-
Appointing in oxa- -10- phosphines phenanthrene -10- oxides or the miscellaneous -10- phospho hetero phenanthrenes -10- oxide fire retardants of 9,10- dihydro-9-oxies
Meaning it is a kind of or at least two mixtures.
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, it is chloride organic fire-retardant, nitrogenous organic
In fire retardant or 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 tetrachlorobisphenol A in 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 is in aluminium hydroxide, magnesium hydroxide, antimony oxide or Firebrake ZB
Any one or at least two combination.
Preferably, the halogen-free epoxy resin be selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin,
Phenol type novolac epoxy resin, bisphenol A-type novolac epoxy resin, Study On O-cresol Epoxy Resin, bicyclic penta
In diene type epoxy resin, isocyanate-based epoxy resin or biphenyl type epoxy resin at least any one or
The mixture of person at least two.
Preferably, the weight/mass percentage composition of epoxy resin is described in the fire-proof resin composition
70-90%, such as 70%, 73%, 75%, 78%, 80%, 83%, 85%, 88% or 90%.
On the other hand, the present invention provides a kind of compositions of thermosetting resin, the compositions of thermosetting resin bag
Containing fire-proof resin composition as described above.
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 and consolidated
In agent or reactive phenolic 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 three-level
In amine curing accelerator any one or at least two mixture.
Preferably, the glyoxaline compound is selected from 2-methylimidazole, the methylimidazole of 2- ethyls -4,2- phenyl
Imidazoles, 2- undecyl imidazoles, 1 benzyl 2 methyl imidazole, 2- heptadecyl imidazoles, 2- isopropyl miaows
Any one in azoles, 2- phenyl -4-methylimidazole, 2- dodecyl imidazoles or 1- 1-cyanoethyl-2-methylimidazoles
Or at least two mixture, preferred 2-methylimidazole.
On the other hand, the present invention provides a kind of pre-impregnated sheet, and it is impregnated with by compositions of thermosetting resin described above
Or be coated on base material and form.
Preferably, the base material can be fiberglass substrate, polyester base material, polyimide base material, ceramics
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
" bonding sheet " well-known to those skilled in the art.
A kind of composite metal substrate, its by least one as above-mentioned pre-impregnated sheet carry out successively surface metal-clad,
Overlapping, pressing is formed.
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 cover copper
Plate, FR-5 copper-clad plates, CEM-1 aluminium bases, CEM-3 aluminium bases, FR-4 aluminium bases or FR-5 aluminium bases
In any one.
A kind of wiring board, is 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 and sulfur-bearing fire retardant and/or phosphonium flame retardant in the fire-proof resin composition of the present invention
There is synergy on flame retardant effect, be capable of the fire resistance of reinforced resin composition.Resistance of the present invention
The solidfied material of retardant resin composition have good heat resistance, water resistance, cohesiveness, mechanical performance and electrically
Can, it is a kind of fire-retardant combination with larger economy and environmentally friendly friendly.It is prepared into by said composition
To the heat decomposition temperature (5% weightless) of copper-clad plate more than 353 DEG C can be up to, peel strength can reach 1.8
kg/mm2More than, T-288 ＞ 100 seconds, wicking heat-resistant limit reaches that saturated water absorption is reachable more than 31 times
To less than 0.35%, flammability (UL-94) reaches V-0 ranks.
Embodiment
Technical scheme is further illustrated below by embodiment.Those skilled in the art
It will be clearly understood that the embodiment is only to aid in understanding the present invention, the specific limit to the present invention is not construed as
System.
Embodiment 1
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, adding epoxide equivalent is
Pair that the brominated bisphenol a type epoxy resin 26.4g and sulfur content that 400g/eq, bromine content are 48.5% are 45%
After diphenyl disulfide phenol 1.42g mixing, it is the flame-retarded resin mixture that 10%, sulfur content is 0.5% to obtain bromine content,
Appropriate acetone solution is added, 6.4g dicyandiamide and 0.1g 2-methylimidazole is added, fully after dissolving,
Copper is covered according to the obtained standard for meeting the standards such as national standard, UL of general copper-clad plate production process using said composition
Plate, is referred to as copper-clad plate A by this copper-clad plate, and copper-clad plate A the performance test results are as shown in table 1.
Embodiment 2
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, adding phenolic hydroxyl equivalent is
The brominated bisphenol A20.8g and sulfur content that 272g/eq, bromine content are 58.5% are 45% to diphenyl disulfide phenol
After 0.68g mixing, it is the resin compound that 10%, sulfur content is 0.25% to obtain bromine content, is added in right amount
Acetone solution, adds the 2- methyl miaows that phenolic hydroxyl equivalent is 105g/eq linear phenol-aldehyde resins 47.4g and 0.1g
Azoles, fully dissolving after, using said composition according to general copper-clad plate production process be made meet national standard,
The standard copper-clad plate of the standards such as UL, is referred to as copper-clad plate B, copper-clad plate B the performance test results by this copper-clad plate
As shown in table 1.
Embodiment 3
Take epoxide equivalent be 200g/eq o-cresol formaldehyde epoxy resin 100g, additions epoxide equivalent be 400g/eq,
The 4,4'- diaminos that the brominated bisphenol a type epoxy resin 11.9g and sulfur content that bromine content is 48.5% are 14.8%
Base diphenyl disulfide 2.1g, it is the resin combination that 5%, sulfur content is 0.25% to obtain bromine content, is added suitable
The acetone solution of amount, add phenolic hydroxyl equivalent be 105g/eq linear phenol-aldehyde resin curing agent 59.7g and
After 0.1g 2-methylimidazole, fully dissolving, using said composition according to general copper-clad plate production process system
The standard copper-clad plate of the standards such as national standard, UL must be met, this copper-clad plate is referred to as copper-clad plate C, copper-clad plate C's
The performance test results are as shown in table 1.
Embodiment 4
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, adding epoxide equivalent is
Brominated bisphenol a type epoxy resin 31.0g that 400g/eq, bromine content are 48.5% and phosphorus content is 9.0% four
After-(2,6- xylyl) resorcinol biphosphonate 14g mixing, it is that 10%, phosphorus content is to obtain bromine content
1.0% flame-retarded resin mixture, add appropriate acetone solution, adds 6.7g dicyandiamide and 0.1g
After 2-methylimidazole fully dissolves, copper-clad plate is worth according to known methods, 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.
Embodiment 5
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, adding phenolic hydroxyl equivalent is
The brominated bisphenol A 25.5g and phenolic hydroxyl equivalent that 272g/eq, bromine content are 58.5% are 300.0g/eq, and phosphorus contains
Measure after the DOPO etherificate bisphenol-A 23.0g mixing for 10.0%, it is that 10%, phosphorus content is to obtain bromine content
1.5% flame-retarded resin mixture, adds appropriate acetone solution, adds phenolic hydroxyl equivalent for 105g/eq
After linear phenol-aldehyde resin 38.6g and 0.1g 2-methylimidazole fully dissolve, it is worth covering according to known methods
Copper coin, is referred to as copper-clad plate E by this copper-clad plate, and copper-clad plate E the performance test results are as shown in table 1.
Embodiment 6
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, adding epoxide equivalent is
The brominated bisphenol a type epoxy resin 44.8g and phosphorus content that 400g/eq, bromine content are 48.5% are 3.0%, ring
After oxygen equivalent is 300g/eq universal DOPO modified epoxies 72.5g mixing, obtaining bromine content is
10%th, phosphorus content content is 1.0% flame-retarded resin mixture, adds appropriate acetone solution, adds 9.7g
Dicyandiamide and 0.1g 2-methylimidazole fully dissolve after, according to known methods be worth copper-clad plate, by this
Copper-clad plate is referred to as copper-clad plate F, and copper-clad plate F the performance test results are as shown in table 1.
Embodiment 7
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, adding phenolic hydroxyl equivalent is
The brominated bisphenol A9.3g and phenolic hydroxyl equivalent that 272g/eq, bromine content are 58.5% are 300.0g/eq, phosphorus content
After 10.0% DOPO etherificate bisphenol-A 5.7g mixing, it is that 5%, phosphorus content is 0.5% to obtain bromine content
Flame-retarded resin mixture, add appropriate acetone solution, add phenolic hydroxyl equivalent for 105g/eq line styles
After phenolic resin 50.9g and 0.1g 2-methylimidazole fully dissolve, copper-clad plate is worth according to known methods,
This copper-clad plate is referred to as copper-clad plate G, copper-clad plate G the performance test results are as shown in table 1.
Embodiment 8
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, adding epoxide equivalent is
Pair that the brominated bisphenol a type epoxy resin 13.2g and sulfur content that 400g/eq, bromine content are 48.5% are 45%
Diphenyl disulfide phenol 1.43g and four-(2,6- xylyls) the resorcinol biphosphonates that phosphorus content is 10.0%
After 14.8g mixing, it is that 5%, sulfur content is the flame-retarded resin that 0.5%, phosphorus content is 1.0% to obtain bromine content
Mixture, adds appropriate acetone solution, add 6.0g dicyandiamide and 0.1g 2-methylimidazole it is abundant
After dissolving, copper-clad plate is worth according to known methods, this copper-clad plate is referred to as copper-clad plate H, copper-clad plate H's
The performance test results are as shown in table 1.
Embodiment 9
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, adding phenolic hydroxyl equivalent is
The brominated bisphenol A 11.2g and sulfur content that 272g/eq, bromine content are 58.5% are 45% to diphenyl disulfide phenol 0.6g
And phenolic hydroxyl equivalent is 300.0g/eq, phosphorus content mixes for 10.0% DOPO etherificate bisphenol-As 19.8g
Afterwards, it is that 5%, sulfur content is the flame-retarded resin mixture that 0.2%, phosphorus content is 1.5% to obtain bromine content, plus
Enter appropriate acetone solution, add phenolic hydroxyl equivalent for 105g/eq linear phenol-aldehyde resins 44.3g and 0.1g
2-methylimidazole fully dissolve after, according to known methods be worth copper-clad plate, this copper-clad plate is referred to as covering copper
Plate J, copper-clad plate J the performance test results are as shown in table 1.
Embodiment 10
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, adding epoxide equivalent is
The 4,4'- that the brominated bisphenol a type epoxy resin 7.6g and sulfur content that 400g/eq, bromine content are 48.5% are 14.8%
Diaminourea diphenyl disulfide 8.4g and phosphorus content are 3.0%, and epoxide equivalent is universal for 300g/eq's
After DOPO modified epoxies 8.3g mixing, it is that 3%, sulfur content is that 1%, phosphorus content contains to obtain bromine content
Measure the flame-retarded resin mixture for 0.2%, add appropriate acetone solution, add 5.5g dicyandiamide and
After 0.1g 2-methylimidazole fully dissolves, copper-clad plate is worth according to known methods, this copper-clad plate is referred to as
Copper-clad plate K, copper-clad plate K the performance test results are as shown in table 1.
Embodiment 11
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, adding phenolic hydroxyl equivalent is
The brominated bisphenol A 1.9g and sulfur content that 272g/eq, bromine content are 58.5% are 45% to diphenyl disulfide phenol 1.2g
And phenolic hydroxyl equivalent is 300.0g/eq, after phosphorus content is 10.0% DOPO etherificate bisphenol-A 8.9g mixing,
It is that 1%, sulfur content is the flame-retarded resin mixture that 0.5%, phosphorus content is 0.8% to obtain bromine content, is added suitable
The acetone solution of amount, adds the 2- that phenolic hydroxyl equivalent is 105g/eq linear phenol-aldehyde resins 50.8g and 0.1g
After methylimidazole fully dissolves, copper-clad plate is worth according to known methods, this copper-clad plate is referred to as copper-clad plate L,
Copper-clad plate L the performance test results are as shown in table 2.
Comparative example 1
It is the market circulation standard bromination bisphenol type epoxy that 20%, epoxide equivalent is 420g/eq to take bromine content
Resin 100g (solid calculating), adds dicyandiamide 2.6g and 0.1g 2-methylimidazole, adds appropriate
After acetone solution, copper-clad plate is prepared according to known methods, and this copper-clad plate is referred to as copper-clad plate M, covered
Copper coin M the performance test results are as shown in table 2.
Comparative example 2
It is the market circulation standard bromination bisphenol type epoxy that 20%, epoxide equivalent is 420g/eq to take bromine content
Resin 16.7g (solid calculating) and the liquid bisphenol A type epoxy resin 50g that epoxide equivalent is 186g/eq
After mixing, the composition epoxy resin that bromine content is 5% is obtained, appropriate acetone solution is added, adds phenol
After hydroxyl equivalent fully dissolves for 105g/eq linear phenol-aldehyde resins 32.4g and 0.1g 2-methylimidazole, press
Copper-clad plate is prepared according to known method, this copper-clad plate is referred to as copper-clad plate N, copper-clad plate N performance is surveyed
Test result is as shown in table 2.
Comparative example 3
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, adding epoxide equivalent is
400g/eq, bromine content are 48.5% brominated bisphenol a type epoxy resin 27.6g, after mixing, obtain bromine and contain
Measure the flame-retarded resin mixture for 10.5%, add appropriate acetone solution, add 6.4g dicyandiamide and
After 0.1g 2-methylimidazole, fully dissolving, using said composition according to general copper-clad plate production process system
The standard copper-clad plate of the standards such as national standard, UL must be met, this copper-clad plate is referred to as copper-clad plate P, copper-clad plate P's
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, it is 45% to add sulfur content
Diphenyl disulfide phenol 30.4g is mixed after, obtain the flame-retarded resin mixture that sulfur content is 10.5%, add appropriate
Acetone solution, add 6.4g dicyandiamide and 0.1g 2-methylimidazole, fully dissolving after, using this
The standard copper-clad plate for meeting the standards such as national standard, UL is made according to general copper-clad plate production process for composition, will
This copper-clad plate is referred to as copper-clad plate Q, and copper-clad plate Q 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, adding epoxide equivalent is
400g/eq, bromine content are 48.5% brominated bisphenol a type epoxy resin 29.3g, after mixing, obtain bromine and contain
The flame-retarded resin mixture for 11% is measured, appropriate acetone solution is added, adds 6.7g dicyandiamide and 0.1g
2-methylimidazole fully dissolve after, according to known methods be worth copper-clad plate, this copper-clad plate is referred to as covering copper
Plate R, copper-clad plate R 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, adding phenolic hydroxyl equivalent is
After 300.0g/eq, phosphorus content is 10.0% DOPO etherificate bisphenol-A 122g mixing, it is 5.5% to obtain phosphorus content
Flame-retarded resin mixture, add appropriate acetone solution, add phenolic hydroxyl equivalent for 105g/eq line styles
After phenolic resin 13.7g and 0.1g 2-methylimidazole fully dissolve, copper-clad plate is worth according to known methods,
This copper-clad plate is referred to as copper-clad plate S, copper-clad plate S 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, it is 45% to add sulfur content
To four-(2,6- xylyls) resorcinol biphosphonates that diphenyl disulfide phenol 15.7g and phosphorus content are 10.0%
After 12.8g mixing, it is the flame-retarded resin mixture that 5.5%, phosphorus content is 1.0% to obtain sulfur content, is added suitable
The acetone solution of amount, after the 2-methylimidazole of the dicyandiamide and 0.1g that add 3.5g fully dissolves, according to public affairs
The method known is worth copper-clad plate, this copper-clad plate is referred to as into copper-clad plate T, copper-clad plate T the performance test results are such as
Shown in table 2.
Comparative example 8
The liquid bisphenol A type epoxy resin 100g that epoxide equivalent is 186g/eq are taken, it is 45% to add sulfur content
To four-(2,6- xylyls) resorcinol biphosphonates that diphenyl disulfide phenol 2.86g and phosphorus content are 10.0%
After 154.5g mixing, it is the flame-retarded resin mixture that 0.5%, phosphorus content is 6% to obtain sulfur content, is added suitable
The acetone solution of amount, after the 2-methylimidazole of the dicyandiamide and 0.1g that add 5.4g fully dissolves, according to public affairs
The method known is worth copper-clad plate, this copper-clad plate is referred to as into copper-clad plate U, copper-clad plate U the performance test results are such as
Shown in table 2.
Table 1
Table 2
Prepared it can be seen from the test result of table 1 using fire-proof resin composition of the present invention
The heat decomposition temperature (5% is weightless) of copper-clad plate can be up to more than 353 DEG C, and peel strength can reach
1.8kg/mm2More than, T-288 ＞ 100 seconds, heat-resistant limit reaches that saturated water absorption can reach more than 31 times
Less than 0.35%, flammability (UL-94) reaches V-0 ranks.
When being market circulation standard bromination bisphenol A-type that 20%, epoxide equivalent is 420g/eq using bromine content
Epoxy resin, and when being added without sulfur-bearing fire retardant (comparative example 1), although bromine content is improved to 20%,
Although its copper-clad plate D prepared also has the fire resistance of V-0 ranks, the heat point of the copper-clad plate
Solution temperature is relatively low, and unstable, its T-288 is only 15 seconds in addition, and heat-resistant limit is only 5 times, saturation water suction
Rate is higher；And work as and use the market circulation standard bromination that bromine content is 420g/eq for 20%, epoxide equivalent double
Phenol A types epoxy resin is as fire retardant, without using sulfur-bearing fire retardant, also truthfully applies that example 1 is the same and epoxy
Equivalent keeps its bromine content in epoxy composite after being mixed for 186g/eq liquid bisphenol A types epoxy resin
When content in thing is 10% (comparative example 2), its copper-clad plate E prepared fire resistance drops significantly
It is low, and its heat-resistant limit is only 8 times, and heat decomposition temperature is low, peel strength is low, saturated water absorption is high.
Compared with Example 1, when without using sulfur-bearing fire retardant, and improve the amount of brominated flame-retardant to cause bromine
When constituent content is equal to bromine in embodiment 1 and sulfur content sum (comparative example 3), what is prepared covers
Copper coin is poor in anti-flammability and other performances, equally works as without using brominated flame-retardant, and improves and contain
The amount of sulphur fire retardant is to cause sulfur content to be equal in embodiment 1 bromine and (compare during sulfur content sum
Example 4), the copper-clad plate prepared is also performed poor in anti-flammability and other performances, therefore is illustrated
Brominated flame-retardant has synergy with sulfur-bearing fire retardant in fire resistance in the present invention, and in composition
Minimal amount of element sulphur can just coordinate with brominated phenolic compound and its epoxy resin increases substantially preparation
The fire resistance of obtained copper-clad plate, the present invention brominated phenolic compound of application and its epoxy resin as containing
Bromine flame retardant, coordinates sulfur-bearing fire retardant and halogen-free epoxy resin so that the copper-clad plate of preparation has good
Combination property.
Compared with Example 4, when without using phosphonium flame retardant, and improve the amount of brominated flame-retardant to cause bromine
When constituent content is equal to bromine in embodiment 4 and phosphorus element content sum (comparative example 5), what is prepared covers
Copper coin is poor in anti-flammability and other performances；Compared with Example 7, when without using brominated fire-retardant
Agent, and improve the amount of phosphonium flame retardant to cause phosphorus element content to be equal to bromine and phosphorus element content in embodiment 7
During sum (comparative example 6), the copper-clad plate prepared is also performed poor in anti-flammability and other performances,
Therefore brominated flame-retardant has synergy to explanation with phosphonium flame retardant in fire resistance in the present invention, and
And the brominated phenolic compound of present invention application and its epoxy resin coordinate phosphor-containing flame-proof as brominated flame-retardant
Agent and halogen-free epoxy resin so that the copper-clad plate of preparation has good combination property.
Compared with Example 8, when without using brominated flame-retardant, even if improving sulfur content in composition
Make it equal to element sulphur and phosphorus in bromo element content sum (comparative example 7) or raising composition in embodiment 8
The content of element makes it equal to P elements and bromo element content sum (comparative example 8), gained in embodiment 8
The poor flame retardant properties of copper-clad plate, other performances are poor such as heat resistance, water resistance.
Therefore, brominated flame-retardant can be cooperateed with sulfur-bearing fire retardant and/or phosphonium flame retardant composition in the present invention
Fire retardant, the brominated phenolic compound of present invention application and its epoxy resin are as brominated flame-retardant, and cooperation contains
Sulphur fire retardant and/or phosphonium flame retardant and halogen-free epoxy resin so that the copper-clad plate of preparation has good
Combination property, the present invention can keep copper-clad plate to have good flame-retardance energy while bromo element content is reduced
And heat resistance, water resistance and good mechanical properties etc..
Applicant states that the present invention illustrates the fire-proof resin composition of the present invention, heat by above-described embodiment
Thermosetting resin composition, pre-impregnated sheet and composite metal substrate, but the invention is not limited in above-described embodiment,
Do not mean that the present invention has to rely on above-described embodiment and could implemented.Person of ordinary skill in the field should
This is clear, any improvement in the present invention, the equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (10)
1. a kind of fire-proof resin composition, it is characterised in that the fire-proof resin composition includes brominated resistance
Fire agent, sulfur-bearing fire retardant and/or phosphonium flame retardant, and halogen-free epoxy resin；The brominated flame-retardant is
Brominated phenolic compound and its epoxy resin.
2. fire-proof resin composition according to claim 1, it is characterised in that the flame-retarded resin
Weight percent content shared by bromo element is less than 10%, preferably 1-10% in composition；
Preferably, weight percent content shared by element sulphur is more than 0.2% in the fire-proof resin composition,
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,
It is preferred that 0.2-2%.
3. fire-proof resin composition according to claim 1 or 2, it is characterised in that the brominated resistance
Combustion agent be brominated phenolic resin, bromination novolac epoxy resin, brominated bisphenol A, brominated bisphenol A derivatives,
Brominated bisphenol a type epoxy resin, tetrabromo-bisphenol s, tetrabromobisphenol allyl ether, tribromphenol or pentabromophenol
In any one or at least two combination, preferably brominated bisphenol A, brominated bisphenol A derivatives or bromination
Bisphenol A type epoxy resin；
Preferably, the sulfur-bearing fire retardant is to diphenyl disulfide phenol and/or 4,4'- diaminourea diphenyl disulfide, preferably
To diphenyl disulfide phenol；
Preferably, the phosphonium flame retardant is DOPO etherificates bisphenol-A, DOPO modified epoxies, three
(2,6- 3,5-dimethylphenyls) phosphine, four-(2,6- xylyls) resorcinol biphosphonates, resorcinol tetraphenyl
Bisphosphate, triphenyl phosphate, bisphenol-A double (diphenyl phosphoester), phosphonitrile fire retardant, 10- (2,5-
Dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phosphine phenanthrene -10- oxides, 10- (2,5- dihydroxy naphthyl) -10- hydrogen -9-
Appointing in oxa- -10- phosphines phenanthrene -10- oxides or the miscellaneous -10- phospho hetero phenanthrenes -10- oxide fire retardants of 9,10- dihydro-9-oxies
Meaning it is a kind of or at least two mixtures.
4. the fire-proof resin composition according to any one of claim 1-3, it is characterised in that described
Fire-proof resin composition can also include other fire proofings；
Preferably, other described fire proofings be organic silicon fibre retardant, it is chloride organic fire-retardant, nitrogenous organic
In fire retardant or 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 tetrachlorobisphenol A in 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 is in aluminium hydroxide, magnesium hydroxide, antimony oxide or Firebrake ZB
Any one or at least two combination.
5. the fire-proof resin composition according to any one of claim 1-4, it is characterised in that described
Halogen-free epoxy resin is selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol type epoxy novolac tree
Fat, bisphenol A-type novolac epoxy resin, Study On O-cresol Epoxy Resin, dicyclopentadiene type epoxy resin,
In isocyanate-based epoxy resin or biphenyl type epoxy resin at least any one or at least two mixing
Thing；
Preferably, the weight/mass percentage composition of halogen-free epoxy resin is described in the fire-proof resin composition
70-90%.
6. a kind of compositions of thermosetting resin, it is characterised in that the compositions of thermosetting resin includes power
Profit requires the fire-proof resin composition any one of 1-5.
7. compositions of thermosetting resin according to claim 6, it is characterised in that the thermosetting
Resin combination also includes curing agent；
Preferably, the curing agent is selected from dicyandiamide, phenolic resin, aromatic amine, acid anhydrides, active esters and consolidated
In agent or reactive phenolic 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 three-level
In amine curing accelerator any one or at least two mixture；
Preferably, the glyoxaline compound is selected from 2-methylimidazole, the methylimidazole of 2- ethyls -4,2- phenyl
Imidazoles, 2- undecyl imidazoles, 1 benzyl 2 methyl imidazole, 2- heptadecyl imidazoles, 2- isopropyl miaows
Any one in azoles, 2- phenyl -4-methylimidazole, 2- dodecyl imidazoles or 1- 1-cyanoethyl-2-methylimidazoles
Or at least two mixture, preferred 2-methylimidazole.
8. a kind of pre-impregnated sheet, it is characterised in that it is by thermosetting resin group as claimed in claims 6 or 7
Compound is impregnated with or is coated on base material and forms；
Preferably, the base material can be fiberglass substrate, polyester base material, polyimide base material, ceramics
Base material or carbon fiber base material etc..
9. a kind of composite metal substrate, it is characterised in that it is described its by least one such as claim 8 institute
The pre-impregnated sheet stated carries out surface metal-clad, overlapping, pressing and formed successively；
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 cover copper
Plate, FR-5 copper-clad plates, CEM-1 aluminium bases, CEM-3 aluminium bases, FR-4 aluminium bases or FR-5 aluminium bases
In any one.
10. a kind of wiring board, it is characterised in that in the surface of the composite metal substrate described in claim 9
Processing line is formed.
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| CN201610325626.9A CN107254138A (en) | 2016-05-16 | 2016-05-16 | A kind of fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate |
| TW105128532A TWI609916B (en) | 2016-05-16 | 2016-09-02 | Flame retardant resin composition, thermosetting resin composition, prepreg and composite metal substrate |
| KR1020160151262A KR101830539B1 (en) | 2016-05-16 | 2016-11-14 | Flame retardant resin composition, the thermosetting resin compositions, prepreg and composite metal substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| CN107815066A (en) * | 2016-09-14 | 2018-03-20 | 广东广山新材料股份有限公司 | A kind of composite flame-retardant agent, fire-proof resin composition, composite metal substrate, anti-flammability electronic material and anti-flammability engineering plastics |
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| CN115651366B (en) * | 2022-11-18 | 2023-09-12 | 江苏耀鸿电子有限公司 | Alumina-containing resin glue solution for copper-clad plate and preparation method thereof |
| CN116218180B (en) * | 2023-05-09 | 2023-10-10 | 北京微构工场生物技术有限公司 | Flame-retardant material |
| CN116515244B (en) * | 2023-05-10 | 2024-01-23 | 江苏耀鸿电子有限公司 | Phosphorus-nitrogen composite modified epoxy resin and copper-clad plate prepared from same |
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| CN104893243A (en) * | 2015-05-12 | 2015-09-09 | 广东广山新材料有限公司 | Bisphenol S-base phosphorus-nitrogen compound containing hardener, and epoxy composition |
| CN105175995A (en) * | 2015-08-03 | 2015-12-23 | 广东生益科技股份有限公司 | Epoxy resin composition for copper-clad plate and application thereof |
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| TW201741387A (en) | 2017-12-01 |
| KR101830539B1 (en) | 2018-03-29 |
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Application publication date: 20171017 |