CN102250447A - Halogen-free fire resistance epoxy resin composite as well as prepreg material and printed circuit board therefrom - Google Patents
Halogen-free fire resistance epoxy resin composite as well as prepreg material and printed circuit board therefrom Download PDFInfo
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- CN102250447A CN102250447A CN 201010184744 CN201010184744A CN102250447A CN 102250447 A CN102250447 A CN 102250447A CN 201010184744 CN201010184744 CN 201010184744 CN 201010184744 A CN201010184744 A CN 201010184744A CN 102250447 A CN102250447 A CN 102250447A
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Abstract
The invention discloses a halogen-free fire resistance epoxy resin composite comprising halogen-free epoxy resin (a), styrene-maleic anhydride copolymer (b) serving as a hardening agent, polymethyl methacrylate phosphoric acid 1,3-phenylene ester (c) serving as a fire retardant, a hardening accelerator (d) and an inorganic filling agent (e).
Description
Technical field
The present invention is relevant a kind of composition epoxy resin, and especially a kind of flame-retardant epoxy resin omposition of halogen reaches by its preimpregnation material (Prepreg) and printed circuit board (PCB) of making.In the course of processing that this preimpregnation material is cut or this printed circuit board (PCB) holed etc., the amount of dropping of buffings or dust obviously reduces.
Background technology
Consideration along with the electronic material flame retardant resistance, the known electronic element can utilize brominated raw material to increase its flame retardant effect, but along with the new line of industry environmental consciousness, materials of electronic components also begins requirement and adopts the halogen environment-friendly materials, and the resin raw material that for example is used to make printed circuit board (PCB) has changed into nitrogenous by bromated Resins, epoxy or phosphorated Resins, epoxy.
The main substrate of general printed circuit board (PCB) is Copper Foil coating substrate (Copper clad laminate, be called for short CCL), and Copper Foil coating substrate is to make base material with reinforcement materials such as fibrous paper or woven fiber glass, and in this base material impregnation resol or Resins, epoxy, and through toast, cut, laminated, hot pressing forms laminated board, single or double at this laminated board is covered with Copper Foil then, is shaped under the heating and pressurizing condition and makes.Follow scientific and technological evolution, print circuit plates making is complicated, demand for preimpregnation material that can improve thermotolerance or glass tansition temperature (Tg) or laminated board product is urgent day by day, and be the glass tansition temperature that improves the preimpregnation material, containing on the prescription of resin pickup, known novolac epoxy is collocation styrene-maleic anhydride copolymer (Styrene-Maleic anhydride Copolymer further, be called for short SMA), for example No. the 455613rd, the Taiwan patent, to improve the glass tansition temperature of the made preimpregnation material of this class novolac epoxy, but easily some shortcoming existence of the product of the high glass tansition temperature of this class, need further to improve, wherein for example fragility uprises, and in the course of processing that the preimpregnation material is cut or printed circuit board (PCB) holed etc., easily produce the problem that buffings or filling powder etc. drop, therefore all easily pollute and be badly in need of and will improve for processing procedure or product.
Be known as and solve substrate and for example cutting, taking place in the course of processing such as boring the problem that buffings or filling powder drop, a kind of practice is further to add macromolecular thermoplastic resin (molecular weight is greater than 5000) in containing resin pickup, nbr carboxyl terminal (Carboxyl-terminated butadiene acrylonitrile for example, CTBN) or phenoxy resin (Phenoxy) etc., improving the generation of buffings or dust, and the toughness of the material of preimpregnation simultaneously also is improved.But add the anti-immersed solder that this type of macromolecular thermoplastic resin can reduce made substrate significantly, and for example dissipation factor of electrical specification (Df), specific inductivity (Dk) etc. is all had bad influence, Copper Foil is reduced the sticking power of base material.
How to solve known easy the to be crisp problem that in the course of processing, is produced during as epoxy resin hardener with styrene-maleic anhydride copolymer, and avoid the known problems that macromolecular thermoplastic resin produced of in this resin, adding, then become research topic of the present invention.
Summary of the invention
In view of the above, the objective of the invention is is providing a kind of flame-retardant epoxy resin omposition of halogen, can produce preimpregnation material or printed circuit board (PCB) by this composition epoxy resin with good anti-immersed solder, mechanicalness, toughness and electrical insulating property, and the problem of generations such as buffings or dust more can be improved in the course of processing (for example the preimpregnation material is cut or printed circuit board (PCB) is holed), and made laminated board also can reach the fire-retardant specification of V-0 level simultaneously.
Another object of the present invention is that a kind of preimpregnation material is being provided, it is in solvent, dissolving or disperse the flame-retardant epoxy resin omposition of above-mentioned halogen and make composition epoxy resin varnish, the above-mentioned composition epoxy resin varnish of impregnation in the reinforcement material of glass fabric etc. then bakes and makes.
Another purpose of the present invention is that a kind of printed circuit board (PCB) is being provided, it is to utilize following method and make, this method comprises: give the above-mentioned preimpregnation material of certain number of plies laminated, and in the laminated tinsel of outermost layer of at least one side of this preimpregnation material and form metal coating laminated board, and to this metal coating laminated board pressurized, heated shaping, remove the tinsel of the part on above-mentioned metal coating laminated board surface then,, so can obtain printed circuit board (PCB) to form certain circuit pattern.
In order to achieve the above object, the invention provides a kind of composition epoxy resin, comprising: (a) halogen-free epoxy resin; (b) styrene-maleic anhydride copolymer is as stiffening agent; (c) poly-methyl acid phosphate 1,3-are stretched phenylester (Poly (1,3-phenylene methylphosphonate) is called for short PMP) as fire retardant; (d) hardening accelerator; And (e) inorganic filler, wherein, poly-methyl acid phosphate 1, the ratio that 3-stretches phenylester and styrene-maleic anhydride copolymer is 2.0: 1 to 4.0: 1 by weight, and is preferably 2.7: 1.0.
The present invention is as stiffening agent and with poly-methyl acid phosphate 1 with styrene-maleic anhydride copolymer, 3-stretches phenylester as fire retardant, and with above-mentioned both carry out crosslinking reaction according to specified proportion and Resins, epoxy, can obtain the epoxy composite material of the high glass transition temp of tool, especially preimpregnation material of making or printed circuit board (PCB) have good anti-immersed solder, mechanicalness, toughness and electrical specification (for example Dk, Df), easy the to be crisp problem that is produced in the course of processing in the time of can avoiding simultaneously with styrene-maleic anhydride copolymer as the hardening of resin agent.
For make above and other objects of the present invention, feature and advantage can be more clear, hereinafter will be described in detail below especially exemplified by preferred embodiment.
Embodiment
Composition epoxy resin of the present invention comprises: (a) halogen-free epoxy resin of 100 weight parts; (b) styrene-maleic anhydride copolymer of 10.0～20.0 weight parts is as stiffening agent; (c) the poly-methyl acid phosphate 1 of 25.0～70.0 weight parts, 3-stretches phenylester as fire retardant; (d) hardening accelerator of 0.01～1.0 weight part; And (e) inorganic filler of 5.0～30.0 weight parts, it is that halogen-free epoxy resin with 100 weight parts is a benchmark that each composition weight part constitutes, and poly-methyl acid phosphate 1 wherein, the ratio that 3-stretches phenylester and styrene-maleic anhydride copolymer is 2.0: 1 to 4.0: 1 by weight, and is preferably 2.7: 1.0.
Composition in the flame-retardant epoxy resin omposition of halogen of the present invention (a) is a halogen-free epoxy resin, comprise (1) nitrogen-containing epoxy thermoset, benzoxazine (Benzoxazine, be called for short BZ)/phenol aldehyde type epoxy resin multipolymer or contain the novolac epoxy of triazine ring structure for example; And (2) phosphorous epoxy resin, phosphorus-containing phenolic aldehyde type Resins, epoxy for example, it is the phosphorus-containing phenolic aldehyde type Resins, epoxy for a kind of side chain type, and above-mentioned resin can use separately or can make up simultaneously that the person uses jointly more than two kinds.In this specific embodiment, this phenol aldehyde type epoxy resin is to be o-cresol formaldehyde type Resins, epoxy (o-Cresol Novolac Epoxy Resin, be called for short CNE) (label CCP330), and with organic ring-type phosphide, for example 9, the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-10-oxide compound (9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, be called for short DOPO, label Kolon5138), be directed in the structure of this o-cresol formaldehyde type Resins, epoxy, the o-cresol formaldehyde type Resins, epoxy of phosphorous to form (DOPO) (it is a kind of phosphorus-containing phenolic aldehyde type Resins, epoxy of side chain type), the DOPO structure is then as follows:
The composition of the flame-retardant epoxy resin omposition of halogen of the present invention (b) is a stiffening agent, for example be styrene-maleic anhydride copolymer (label Sartomer EF40), it can further mix supports by the arm for example one-level amine type hardeners of other stiffening agent, as Dicyanodiamide (Dicyandiamide, be called for short DICY), two amido sulfobenzides (Diamino diphenyl sulfone is called for short DDS) etc.The molecular weight of employed styrene-maleic anhydride copolymer can be between 1400 to 50,000, and its structural formula is as follows:
Wherein, m is 1 to 6 integer, and n is 2 to 12 integer.
Composition in the flame-retardant epoxy resin omposition of halogen of the present invention (c) flame retardant for example is poly-methyl acid phosphate 1, and 3-stretches phenylester.The molecular weight that employed poly-methyl acid phosphate 1,3-are stretched phenylester is less than 1000, and its structural formula is as follows:
Wherein, m=0 or 1, n=0 or 1, p are integer.
The ratio that poly-methyl acid phosphate 1 of the present invention, 3-are stretched phenylester and styrene-maleic anhydride copolymer is 2.0: 1 to 4.0: 1 by weight, and is preferably 2.7: 1.0.
Composition in the flame-retardant epoxy resin omposition of halogen of the present invention (d) is a hardening accelerator, comprise glyoxal ethyline (2-Methyl-Imidazole, 2MI), 2-ethyl-4-methylimidazole (2-Ethyl-4-Methyl-Imidazole, 2E4MI), 2-phenylimidazole (2-Phenyl-Imidazole, 2PI), N, N-dimethyl benzene methylamine (Benzyldimethylamine, and above-mentioned hardening accelerator can use separately or can make up simultaneously that the person uses jointly more than two kinds BDMA) and 3,5-dimethylphenyl amine.Those hardening accelerators can quicken the setting time of preimpregnation material.
Added ingredients in the composition epoxy resin of the present invention (e) inorganic filler comprises lime carbonate (CaCO
3), talcum (Mg
3Si
4O
10(OH)
2), glass powder, silicon-dioxide, kaolin, mica, aluminium hydroxide and aluminium sesquioxide, and above-mentioned inorganic filler can use separately or can make up simultaneously that the person uses jointly more than two kinds.Those inorganic fillers can be given characteristics such as Resins, epoxy workability, flame retardant resistance, thermotolerance or wet fastness.
The solvent that the flame-retardant epoxy resin omposition varnish of halogen of the present invention is used comprises acetone (Acetone), methylethylketone (MEK), propylene glycol monomethyl ether (PM), pimelinketone, 1-Methoxy-2-propyl acetate (Propylene GlycolMethyl Ether Acetate, PMA) and dimethyl formamide (Dimethyl Formamide, and above-mentioned solvent can use separately or can make up simultaneously that the person uses jointly more than two kinds DMF).Halogen-free epoxy resin with 100 weight parts is a benchmark, and the consumption of solvent is 20～50 weight parts.
The flame-retardant epoxy resin omposition of halogen of the present invention is can be by mentioned component (a) and (b), (c), (d) are reached and (e) modulate with agitator (mixer) uniform mixing.Then, by the synthetic composition epoxy resin of institute is dissolved or dispersed in the solvent, and adjust the viscosity of Resins, epoxy slurry, and make the flame-retardant epoxy resin omposition varnish of halogen.
Then, the above-mentioned made varnish of impregnation in being used to form the reinforcement material of preimpregnation material, and in drying machine, carried out drying and reaction in 2～10 minutes with 150～180 ℃ of heating, made thereby goes out the preimpregnation material of semi-harden state.Wherein, employed reinforcement material for example is the glasscloth of glass fabric, glassine paper, glassmat etc., in addition also can use kraft paper, short flannel cotton paper, natural fiber cloth, organic fibre cloth etc.
The preimpregnation material that obtains according to this is laminated and form laminated board with certain number of plies, more at the laminated Copper Foil of the outermost layer of at least one side of this laminated board, and its pressurized, heated is shaped, obtain the laminated board of Copper Foil coating whereby.Then,, make the part of the only residual formation circuit pattern of Copper Foil on the laminated board surface of Copper Foil coating, and the part of removing other so just can obtain to have the printed circuit board (PCB) of circuit to form circuit pattern by subtractive process such as etchings.
Hereinafter the embodiment that is provided setting forth technique means of the present invention, is not in order to limit technology category of the present invention only.
Embodiment one to six and comparative example one to two are to be 100 parts with halogen-free epoxy resin weight, and other each composition is all represented with relative parts by weight.
Embodiment one
The o-cresol formaldehyde type Resins, epoxy of phosphorous (DOPO) of 100 weight parts, the styrene-maleic anhydride copolymer of 15 weight parts, the poly-methyl acid phosphate 1 of 40 weight parts, 3-stretches the glyoxal ethyline of phenylester, 0.5 weight part and the silicon-dioxide of 15 weight parts, under room temperature, use agitator to mix 60 minutes, add the methylethylketone of 30 weight parts again.Above-mentioned material after stirring 120 minutes under the room temperature, is formed the flame-retardant epoxy resin omposition varnish of halogen.
Embodiment two
The o-cresol formaldehyde type Resins, epoxy of phosphorous (DOPO) of 100 weight parts, the styrene-maleic anhydride copolymer of 15 weight parts, the poly-methyl acid phosphate 1 of 30 weight parts, 3-stretches the glyoxal ethyline of phenylester, 0.5 weight part and the silicon-dioxide of 15 weight parts, under room temperature, use agitator to mix 60 minutes, add the methylethylketone of 30 weight parts again.Above-mentioned material after stirring 120 minutes under the room temperature, is formed the flame-retardant epoxy resin omposition varnish of halogen.
Embodiment three
The o-cresol formaldehyde type Resins, epoxy of phosphorous (DOPO) of 100 weight parts, the styrene-maleic anhydride copolymer of 15 weight parts, the poly-methyl acid phosphate 1 of 60 weight parts, 3-stretches the glyoxal ethyline of phenylester, 0.5 weight part and the silicon-dioxide of 15 weight parts, under room temperature, use agitator to mix 60 minutes, add the methylethylketone of 30 weight parts again.Above-mentioned material after stirring 120 minutes under the room temperature, is formed the flame-retardant epoxy resin omposition varnish of halogen.
Embodiment four
Two amido sulfobenzides (DDS) of the o-cresol formaldehyde type Resins, epoxy of phosphorous (DOPO) of 100 weight parts, the styrene-maleic anhydride copolymer of 20 weight parts, 10 weight parts, the poly-methyl acid phosphate 1 of 54 weight parts, 3-stretches the glyoxal ethyline of phenylester, 0.5 weight part and the silicon-dioxide of 15 weight parts, under room temperature, use agitator to mix 60 minutes, add the methylethylketone of 30 weight parts again.Above-mentioned material after stirring 120 minutes under the room temperature, is formed the flame-retardant epoxy resin omposition varnish of halogen.
Embodiment five
The o-cresol formaldehyde type Resins, epoxy of phosphorous (DOPO) of 100 weight parts, the styrene-maleic anhydride copolymer of 10 weight parts, the poly-methyl acid phosphate 1 of 27 weight parts, 3-stretches the glyoxal ethyline of phenylester, 0.25 weight part and the silicon-dioxide of 15 weight parts, under room temperature, use agitator to mix 60 minutes, add the methylethylketone of 30 weight parts again.Above-mentioned material after stirring 120 minutes under the room temperature, is formed the flame-retardant epoxy resin omposition varnish of halogen.
Embodiment six
Two amido sulfobenzides (DDS) of the o-cresol formaldehyde type Resins, epoxy of phosphorous (DOPO) of 100 weight parts, the styrene-maleic anhydride copolymer of 10 weight parts, 5 weight parts, the poly-methyl acid phosphate 1 of 30 weight parts, 3-stretches the glyoxal ethyline of phenylester, 0.5 weight part and the silicon-dioxide of 15 weight parts, under room temperature, use agitator to mix 60 minutes, add the methylethylketone of 30 weight parts again.Above-mentioned material after stirring 120 minutes under the room temperature, is formed the flame-retardant epoxy resin omposition varnish of halogen.
Comparative example one
The o-cresol formaldehyde type Resins, epoxy of phosphorous (DOPO) of 100 weight parts, the styrene-maleic anhydride copolymer of 15 weight parts, the glyoxal ethyline of 0.5 weight part and the silicon-dioxide of 15 weight parts, under room temperature, use agitator to mix 60 minutes, add the methylethylketone of 30 weight parts again.Above-mentioned material after stirring 120 minutes under the room temperature, is formed the flame-retardant epoxy resin omposition varnish of halogen.
Comparative example two
The o-cresol formaldehyde type Resins, epoxy of phosphorous (DOPO) of 100 weight parts, the styrene-maleic anhydride copolymer of 15 weight parts, the poly-methyl acid phosphate 1 of 70 weight parts, 3-stretches the glyoxal ethyline of phenylester, 0.5 weight part and the silicon-dioxide of 15 weight parts, under room temperature, use agitator to mix 60 minutes, add the methylethylketone of 30 weight parts again.Above-mentioned material after stirring 120 minutes under the room temperature, is formed the flame-retardant epoxy resin omposition varnish of halogen.
Utilize the cylinder coating machine, the flame-retardant epoxy resin omposition varnish of embodiment one to six and comparative example one to two prepared halogen is coated on 7628 (R/C:43%) glasscloth, then, be placed in the drying machine, and 180 ℃ of following heat dryings 2～10 minutes, made thereby went out the preimpregnation material of semi-harden state.Then four preimpregnation materials are given laminated, and at the Copper Foil of each laminated loz of outermost layer of its both sides.Then, its pressurized, heated is carried out pressing, obtain Copper Foil coating laminated board whereby, wherein the condition of pressurized, heated is the heat-up rate with 2.0 ℃/minute, reaches 180 ℃, and at 180 ℃, total head 15kg/cm
2(first pressing 8kg/cm
2) descended pressurized, heated 60 minutes, and make Copper Foil coating laminated board.Then, by subtractive process such as etchings, make the part of the only residual formation circuit pattern of Copper Foil on Copper Foil coating laminated board surface, and remove other part, form circuit pattern whereby.According to this, just can obtain to have the printed circuit board (PCB) of circuit on the top layer.
Anti-immersed solder (Solder Floating), tearing strength (Peeling Strength), glass transfer temperature (Glass Transition Temperature to prepared Copper Foil coating laminated board, Tg), heat decomposition temperature (Tg (5%)), flame retardancy, toughness, specific inductivity, the dissipation factor and the amount of dropping measure, and the flame-retardant epoxy resin omposition of the halogen of embodiment one to six and comparative example one to two and evaluation result thereof are as shown in Table 1.
Property detection:
[property testing of anti-immersed solder]
Whether the laminated board that drying is crossed behind the immersion certain hour, is observed defective and occurred in 288 ℃ soldering is bathed, for example determine with the layering or the puff of laminated board.
[tearing strength test]
Tearing strength is meant the sticking power of Copper Foil for base material, and the Copper Foil with per inch (25.4mm) width vertically tears up on the plate face usually, expresses the power of sticking power with the size of its required strength.Its qualifying standard of substrate of MIL-P-55110E regulation loz Copper Foil is 4lb/in.
[glass transfer temperature test]
Utilize dynamic mechanical analysis instrument (DMA) to measure glass transfer temperature (Tg).The test specification of glass transfer temperature is interconnected and encapsulation association (The Institute for Interconnecting and PackagingElectronic Circuits, IPC-TM-650.2.4.25C IPC) and a 24C detection method of electronic circuit.
[heat decomposition temperature test]
Utilize thermogravimetric analyzer (TGA) to measure and compare with the initial stage quality, the temperature when quality reduces 5% is heat decomposition temperature.
[flame retardancy test]
Utilize UL 94V: the vertical combustion testing method, laminated board is fixed with the vertical position, with the Bunsen burner burning, relatively its spontaneous combustion is extinguished and combustion-supporting characteristic, and its result's report is divided into UL 94V-0 (the best) to the anti-combustion grade of UL94V-2.
[toughness test]
Laminated board is lain against on the tool of plane, vertically contact with cross metal fixture with the laminated board surface, grant vertical pressure again, after remove this cross tool, observe cross shape vestige on the substrate, inspect this laminate surface, do not have white scrimp and take place then to be judged to be good, show slightly lineae ablicantes for general, it is bad that crackle or fracture person are taken place.[specific inductivity and the dissipation factor measure]
According to ASTM D150 standard, under operating frequency 1GHz, calculate the specific inductivity (Dk) and the dissipation factor (Df).
[drop and measure examination]
After getting the laminated board weighing of 4 inches squared magnitude, form 3.192 inches squares circle with the stamping machine punching press, remove the formed break flour of punching press weighing again, so the weight loss amount is the break flour amount of dropping.
Lower molecular weight used in the present invention is gathered methyl acid phosphate 1,3-stretches phenylester synthetic advantage on processing procedure: molecular weight is lower than 1000 poly-methyl acid phosphate 1,3-stretch phenylester be in a liquid state and be easy to the modulation, do not influence the sclerous reaction time of styrene-maleic anhydride copolymer and halogen-free epoxy resin, resin combination varnish is concocted easily.The condition of embodiment one is best.Embodiment two, three represents poly-methyl acid phosphate 1 respectively, and the ratio that 3-stretches phenylester and styrene-maleic anhydride copolymer is the enforcement aspect of 2.0: 1 and 4.0: 1 by weight.Embodiment four, five is illustrated in poly-methyl acid phosphate 1, the ratio that 3-stretches phenylester and styrene-maleic anhydride copolymer is under 2.7: 1 the condition by weight, adopt higher amount and the enforcement aspect of hanging down the styrene-maleic anhydride copolymer of amount respectively, wherein, embodiment four and embodiment six employed stiffening agents are not single styrene-maleic anhydride copolymer composition, and being to use the composite hardener that is combined by styrene-maleic anhydride copolymer and two amido sulfobenzides to come and poly-methyl acid phosphate 1,3-stretches phenylester collocation modulation.As shown in Table 1, embodiment one to six and comparative example one to two show, flame-retardant epoxy resin omposition (poly-methyl acid phosphate 1 wherein by halogen of the present invention, the ratio that 3-stretches phenylester and styrene-maleic anhydride copolymer is 2.0: 1 to 4.0: 1 by weight) made laminated board meets the specification that printed circuit board (PCB) requires, and especially embodiment one, two, three, five, six more is presented at the effect that the thing that drops that produces when cutting has obvious minimizing.Embodiment four and embodiment six expressions still meet the specification that printed circuit board (PCB) requires by the made laminated board of flame-retardant epoxy resin omposition that the present invention contains the halogen of composite hardener (for example styrene-maleic anhydride copolymer is further mixed and support by the arm other one-level amine).And with reference to comparative example one, its fragility that shows made laminated board is bigger, and toughness is not good, cut the Shi Yiyou thing that drops, and with reference to comparative example two, it shows anti-immersed solder, the equal variation of tearing strength specific inductivity of made laminated board.
The present invention is with the styrene-maleic anhydride copolymer of specified proportion and low-molecular-weight poly-methyl acid phosphate 1, the combination that 3-stretches phenylester is applied to halogen-free epoxy resin composition, to make preimpregnation material or printed circuit board (PCB), easy the to be crisp problem that in the course of processing, is produced when improving with styrene-maleic anhydride copolymer whereby as epoxy resin hardener, for example can increase at the thing that cuts, drops when holing, simultaneously on the heat-resistant quality of laminated board or electrical specification such as Dk, Df etc., all be not subjected to adding the influence of fire retardant, and can promote the flame-retarding characteristic of made laminated board.
For all those of skill in the art, the present invention can make various modifications and changes significantly and not break away from the spirit and scope of the present invention.Therefore, the present invention includes those modifications and variation, and it is included in down all in attached the claim scope and impartial person thereof.
Claims (10)
1. the flame-retardant epoxy resin omposition of a halogen comprises:
(a) halogen-free epoxy resin of 100 weight parts;
(b) styrene-maleic anhydride copolymer (Styrene-Maleic anhydride Copolymer) is as stiffening agent, halogen-free epoxy resin with 100 weight parts is a benchmark, the content of this styrene-maleic anhydride copolymer is 10.0 to 20.0 weight parts, and its structural formula is as follows:
Wherein, m is 1 to 6 integer, and n is 2 to 12 integer; And
(c) poly-methyl acid phosphate 1,3-stretches phenylester (Poly (1,3-phenylene methylphosphonate)) as fire retardant, halogen-free epoxy resin with 100 weight parts is a benchmark, should gather methyl acid phosphate 1, the content that 3-stretches phenylester is 25.0 to 70.0 weight parts, and its structural formula is as follows:
M=0 or 1, n=0 or 1, p are integer,
Wherein, this poly-methyl acid phosphate 1, the molecular weight that 3-stretches phenylester is less than 1000, and should gather methyl acid phosphate 1, the ratio that 3-stretches phenylester and this styrene-maleic anhydride copolymer is 2.0: 1 to 4.0: 1 by weight.
2. the flame-retardant epoxy resin omposition of halogen as claimed in claim 1, wherein, the ratio that this poly-methyl acid phosphate 1,3-are stretched phenylester and this styrene-maleic anhydride copolymer is 2.7: 1.0 by weight.
3. as the flame-retardant epoxy resin omposition of claim 1 a described halogen, wherein, this halogen-free epoxy resin is phosphorous epoxy resin or nitrogen-containing epoxy thermoset.
4. as the flame-retardant epoxy resin omposition of claim 3 a described halogen, wherein, this phosphorous epoxy resin is with 9, and the 10-dihydro-9-oxy is assorted-and 10-phosphorus phenanthrene-10-oxide compound imports in the o-cresol formaldehyde type epoxy resin structural and the o-cresol formaldehyde type Resins, epoxy of phosphorous (DOPO) that form.
5. as the flame-retardant epoxy resin omposition of claim 1 a described halogen, wherein, this styrene-maleic anhydride copolymer is to mix with the one-level amine to support by the arm together as stiffening agent.
6. as the flame-retardant epoxy resin omposition of claim 1 a described halogen, more comprising a hardening accelerator, is benchmark with the halogen-free epoxy resin of 100 weight parts, and the content of this hardening accelerator is 0.01 to 1.0 weight part.
7. as the flame-retardant epoxy resin omposition of claim 6 a described halogen, wherein, this hardening accelerator is an imidazole compound.
8. as the flame-retardant epoxy resin omposition of claim 1 a described halogen, more comprising an inorganic filler, is benchmark with the halogen-free epoxy resin of 100 weight parts, and the content of this inorganic filler is 5.0 to 30.0 weight parts.
9. preimpregnation material is the flame-retardant epoxy resin omposition of impregnation such as claim 1,2,5,6 or 8 described halogen in the reinforcement material, and carries out drying and make.
10. printed circuit board (PCB), be by will be laminated and form laminated board with certain number of plies as claim 9 a described preimpregnation material, and obtain metal coating laminated board, and on this tinsel on this metal coating laminated board surface, form certain circuit pattern and make in the laminated tinsel of the outermost layer of this one of them side of laminated board.
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| CN201010184744.5A CN102250447B (en) | 2010-05-21 | 2010-05-21 | Halogen-free fire resistance epoxy resin composite as well as prepreg material and printed circuit board therefrom |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724936A (en) * | 2012-10-10 | 2014-04-16 | 慧智科技（中国）有限公司 | Low-dielectric halogen-free epoxy resin composite with improved impact resistance property |
| CN103881059A (en) * | 2012-12-21 | 2014-06-25 | 台光电子材料(昆山)有限公司 | Low dielectric resin composition and application thereof |
| CN109790358A (en) * | 2016-07-25 | 2019-05-21 | 伊索拉美国有限公司 | Improved SMA resin formulation |
| CN109929219A (en) * | 2017-12-19 | 2019-06-25 | 洛阳尖端技术研究院 | Modified flame-retardant epoxy resin, prepreg and respective preparation method |
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| CN1317031A (en) * | 1998-08-28 | 2001-10-10 | 陶氏化学公司 | Fire resistant styrene polymer foams with reduced brominated fire ratartant |
| CN1423678A (en) * | 1999-12-13 | 2003-06-11 | 陶氏环球技术公司 | Flame retardant phosphorus element-containing epoxy resin compositions |
| CN101679675A (en) * | 2007-06-14 | 2010-03-24 | 巴斯夫欧洲公司 | Flame retardant compositions |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724936A (en) * | 2012-10-10 | 2014-04-16 | 慧智科技（中国）有限公司 | Low-dielectric halogen-free epoxy resin composite with improved impact resistance property |
| CN103724936B (en) * | 2012-10-10 | 2016-08-03 | 慧智科技（中国）有限公司 | Improve the Halogen-free low dielectric epoxy resin composition of shock resistance |
| CN103881059A (en) * | 2012-12-21 | 2014-06-25 | 台光电子材料(昆山)有限公司 | Low dielectric resin composition and application thereof |
| CN109790358A (en) * | 2016-07-25 | 2019-05-21 | 伊索拉美国有限公司 | Improved SMA resin formulation |
| CN109790358B (en) * | 2016-07-25 | 2022-06-17 | 伊索拉美国有限公司 | Improved SMA resin formulation |
| CN115340737A (en) * | 2016-07-25 | 2022-11-15 | 伊索拉美国有限公司 | Improved SMA resin formulation |
| CN109929219A (en) * | 2017-12-19 | 2019-06-25 | 洛阳尖端技术研究院 | Modified flame-retardant epoxy resin, prepreg and respective preparation method |
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