CN103232705B - High-frequency resin composition as well as semi-cured sheet and laminated board manufactured by high-frequency resin composition - Google Patents
High-frequency resin composition as well as semi-cured sheet and laminated board manufactured by high-frequency resin composition Download PDFInfo
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Abstract
The invention discloses a high-frequency resin composition. The high-frequency resin composition comprises the following components in parts by weight: (a), 15-80 parts of anhydride-modified benzoxazine resin prepolymer, (b),10-60 parts of halogen-free epoxy resins, (c), 5-40 parts of fire retardant, (d), 0.001-2 parts of accelerant and (e), 0-70 parts of inorganic fillers, wherein the number-average molecular weight of the anhydride-modified benzoxazine resin prepolymer is 400-20000. The preparation method of the anhydride-modified benzoxazine resin prepolymer comprises the following steps of: getting and placing benzoxazine and anhydride compounds in a reaction bottle, heating up to 60 DEG C to 200 DEG C, adding a catalyst which is 0%-2% of the total weight of the reactants, and reacting for 10minutes-150minutes to obtain uniform and transparent anhydride-modified benzoxazine resin prepolymer. According to the high-frequency resin composition as well as a semi-cured sheet and a laminated board manufactured by the high-frequency resin composition, the anhydride-modified benzoxazine resin prepolymer is used for lowering concentration of hydroxyl groups generated by the epoxy resin curing process by the anhydride, so that the content of benzene ring is relatively improved, and the dielectric constant and the dielectric loss of the product are greatly lowered.
Description
Technical field
The invention belongs to technical field of electronic materials, relate to a kind of high frequency resin composition and the prepreg using it to make and veneer sheet, can be applicable to the fields such as integrated antenna package, high-frequency high-speed and high density interconnect.
Background technology
For a long time, epoxy resin, owing to having the comprehensive advantages such as raw material sources is extensive, processibility good, cost is lower, obtains and applies in a large number and widely in FR-4 veneer sheet.But, along with the high-speed high frequency of information processing in recent years and information transmission, veneer sheet used for printed circuit is had higher requirement in dielectric properties.In simple terms, namely laminate sheet material need possess low specific inductivity and dielectric loss, the delay of signal during to reduce high-speed transfer, distortion and loss, and the interference between signal.But, common epoxy resin specific inductivity and dielectric loss higher, be difficult to the application meeting high frequency aspect.
In recent years, in order to reduce copper-clad plate product dielectric constant and dielectric loss, domestic and international researchist carries out many-sided trial, as adopted the existing research of teflon resin, bismaleimide-triazine resin, thermosetting polyphenylene ether resin, cyanate ester resin, polyimide, the contour performance resins of polyether-ether-ketone, but the factor such as processing characteristics, price limits their application.
What current report was more selects styrene-maleic anhydride oligopolymer to carry out cured epoxy resin in addition, as United States Patent (USP) 6534181B2,6509414B2 etc., and Chinese invention patent application CN101684191A discloses a kind of halogen-less high frequency resin composition and with its prepreg made and veneer sheet, introduces the problem that benzoxazine solves moisture absorption in its resin combination.But all there are the following problems for such scheme: (1), because of the constructional feature of styrene-maleic anhydride, its polar group is few, can cause bad adhesion, poor in processability; And bad adhesion just easily cause downstream line to come off, hole difficult, hole wall quality is poor and the problem such as plate bursting; (2) acid anhydrides in resin combination easily and water react and generate free acid, acid anhydrides containing free acid can hinder and react with epoxide group, make it fully to be solidified, although the method for adding benzoxazine can reduce water absorbability, but the generation of free acid cannot be avoided, thus have impact on the stability of product wet fastness.
Summary of the invention
The object of the invention is to provide a kind of high frequency resin composition and the prepreg using it to make and veneer sheet.
For achieving the above object, the technical solution used in the present invention is: a kind of high frequency resin composition, with solid weight meter, comprising:
(a) anhydride modified benzoxazine resin performed polymer: 15 ~ 80 parts;
(b) halogen-free epoxy resin: 10 ~ 60 parts;
(c) fire retardant: 5 ~ 40 parts;
(d) promotor: 0.001 ~ 2 part;
(e) mineral filler: 0 ~ 70 part;
The number-average molecular weight of described anhydride modified benzoxazine resin performed polymer is 400 ~ 20000, obtain in the following manner: in mass ratio, benzoxazine: anhydride compound=100:15 ~ 130; get benzoxazine, anhydride compound in reaction flask; be heated to 60 ~ 200 DEG C; and under keeping the condition stirred; add catalyzer; catalyst levels is 0 ~ 2% of reactant total mass;, reaction 10 ~ 150 min obtain that number-average molecular weight is 400 ~ 20000, gelation time be temperature at the 210 DEG C anhydride modified benzoxazine resin prepolymer of homogeneous transparent of 200 ~ 2000 seconds;
Wherein, described benzoxazine is selected from bisphenol A-type benzoxazine resin, bisphenol-f type benzoxazine resin, 4, one or more in 4 ' diaminodiphenylmethane benzoxazine resin, diaminodiphenyl oxide benzoxazine resin, diaminodiphenylsulfone(DDS) benzoxazine resin, dicyclopentadiene type benzoxazine resin, phenolphthalein type benzoxazine, allyl group bisphenol A benzoxazine resin;
Described anhydride compound is selected from styrene-maleic anhydride, 3, and 3 ', 4,4 '-oxydiphthalic, 2,3,3', 4'-diphenyl ether tetraformic dianhydride, 3,3', 4,4'-bibenzene tetracarboxylic dianhydride, 2,3,3', 4'-bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, Bisphenol A Type Diether Dianhydride, 1, one or more in 2,4,5-pyromellitic acid dianhydride.
Above, described gelation time is that temperature is tested at 210 DEG C; The result that gelation time is tested under condition of different temperatures is different, as long as but the scope of testing under meeting temperature condition given to this invention all belong in protection scope of the present invention.
In technique scheme, described halogen-free epoxy resin is selected from one or more the mixture in diglycidyl ether type epoxy resin, glycidyl amine type epoxy resin and glycidyl ester type epoxy resin.
In technique scheme, described fire retardant is selected from one or more in phosphonium flame retardant and brominated flame-retardant.
In technique scheme, described mineral filler is selected from one or more mixture of silicon-dioxide, boron nitride, aluminium hydroxide, boehmite, talcum, clay, mica, kaolin, barium sulfate, calcium carbonate, magnesium hydroxide and zinc borate.
In technique scheme, described promotor is imidazoles, organic metal salt or its mixture, and wherein, imidazoles is selected from glyoxal ethyline, 2-phenylimidazole or 2-ethyl-4 Methylimidazole; Organic metal salt is selected from zinc octoate, isocaprylic acid zinc, stannous octoate, dibutyl tin laurate, zinc naphthenate, cobalt naphthenate, aluminium acetylacetonate, acetylacetone cobalt or acetylacetone copper.
The present invention asks to protect the prepreg adopting above-mentioned high frequency resin composition to make simultaneously, above-mentioned high frequency resin composition dissolution with solvents is made glue, is then immersed in by strongthener in above-mentioned glue; After flooding, strongthener is after heat drying, can obtain described prepreg.
One or more mixture of described solvent selected from acetone, butanone, toluene, mibk, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, propylene glycol monomethyl ether.
The present invention asks to protect the veneer sheet adopting above-mentioned high frequency resin composition to make simultaneously; be covered with tinsel at the single or double of a prepreg, or by after at least 2 prepregs superpositions, be covered with tinsel at its single or double; hot compacting, can obtain described veneer sheet.
The quantity of described prepreg determines according to the laminate thickness of customer requirement, available one or more.Described tinsel can be Copper Foil, and also can be aluminium foil, their thickness be not particularly limited.
The present invention asks to protect a kind of anhydride modified benzoxazine resin performed polymer for high frequency resin composition simultaneously, obtain as follows: in mass ratio, benzoxazine resin: anhydride compound=100:15 ~ 130, get benzoxazine, anhydride compound is in reaction flask, be heated to 60 ~ 200 DEG C, and under keeping the condition stirred, add catalyzer, catalyst levels is 0 ~ 2% of reactant total mass, it is 400 ~ 20000 that reaction 10 ~ 150 min obtain number-average molecular weight, gelation time is temperature at the 210 DEG C anhydride modified benzoxazine resin prepolymer of homogeneous transparent of 200 ~ 2000 seconds,
Wherein, described benzoxazine is selected from bisphenol A-type benzoxazine resin, bisphenol-f type benzoxazine resin, 4, one or more in 4 ' diaminodiphenylmethane benzoxazine resin, diaminodiphenyl oxide benzoxazine resin, diaminodiphenylsulfone(DDS) benzoxazine resin, dicyclopentadiene type benzoxazine resin, phenolphthalein type benzoxazine, allyl group bisphenol A benzoxazine resin;
Described anhydride compound is selected from styrene-maleic anhydride, 3, and 3 ', 4,4 '-oxydiphthalic, 2,3,3', 4'-diphenyl ether tetraformic dianhydride, 3,3', 4,4'-bibenzene tetracarboxylic dianhydride, 2,3,3', 4'-bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, Bisphenol A Type Diether Dianhydride, 1, one or more in 2,4,5-pyromellitic acid dianhydride.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the present invention's configuration obtains a kind of resin combination, select anhydride modified benzoxazine performed polymer, make part anhydride group and the raw pre-open loop of benzoxazine oxazine environment-development, greatly reduce acid anhydrides, benzoxazine and solidify separately temperature required and heat, improve curing efficiency, part acid anhydrides and the pre-open loop of benzoxazine ring-type group it also avoid because using acid anhydrides, benzoxazine that cross-linking density that cured epoxy resin produces is large, cause the phenomenon that product fragility increases; Eliminate micromolecular existence, make the arrangement can optimizing molecule, increase the concentration degree of molecular weight distribution, be more prone to the activity controlling to react with epoxy resin, reduce the poor heat resistance, the dielectric properties difference equivalent risk that cause because of molecular chain easy fracture after small molecules solidification.
2. the present invention selects anhydride modified benzoxazine performed polymer, the hydroxyl group concentration produced when reducing acid anhydride curable epoxy resin, relatively improves the content of phenyl ring, the specific inductivity of the product greatly reduced and dielectric loss; And because there is a large amount of hydrogen bond action bodies in performed polymer, avoid the existing acid anhydride curable epoxy resin technology being applied to printed electronic circuit veneer sheet, because of problems such as polar group also bring bad adhesion less, poor toughness, significantly improve cohesiveness and the toughness of product.
3. adopt the printed wiring veneer sheet prepared of the present composition, the resistance to water soak ability brought not only solving acid anhydride curable epoxy resin be poor, the problem such as bad adhesion, poor toughness.And there is excellent peel strength of copper foil and thermotolerance, there is the more low-k under high frequency condition and low dielectric loss simultaneously.
4. the present invention adopts anhydride modified benzoxazine performed polymer can avoid the generation of free acid, greatly improves the moisture resistance of product, avoid because of its with the reduction of electrical performance issues, particularly dielectric properties.
Embodiment
Below in conjunction with embodiment, the invention will be further described: hereinafter without special instruction, " part " representative " weight part ", " % " representative " % by weight ":
Synthesis example:
The synthesis preparation method of anhydride modified benzoxazine performed polymer: be 100 parts with the weight of benzoxazine, according to weight ratio benzoxazine: anhydride compound=100:15 ~ 130, get benzoxazine, anhydride compound is in reaction flask, slowly be heated to 60 ~ 200 DEG C, and under keeping the condition stirred, add catalyzer, catalyst levels is 0% ~ 2% of reactant total mass, reaction 10 ~ 150min obtains the anhydride modified benzoxazine prepolymer of homogeneous transparent, its molecular weight ranges is 400 ~ 20000, gelation time controls in 200s ~ 2000 second temperature 210 DEG C, room temperature is cooled to after having reacted, stand-by.
Embodiment one:
According to the method in synthesis example, obtain diaminodiphenylmethane type benzoxazine at 140 DEG C of reaction 60min: the performed polymer 60g of styrene-maleic anhydride=100:36, gelation time controls at 500 ~ 550 seconds temperature 210 DEG C, adds appropriate butanone and dissolves; After anhydride modified benzoxazine performed polymer dissolves completely, add 23g phosphorous epoxy resin (XZ92530, DOW Chemical), 17g phosphonium flame retardant (XZ92741, DOW Chemical), 0.01g 2-ethyl-4 Methylimidazole, 40g preparing spherical SiO 2, appropriate butanone solvent, be uniformly mixed the glue obtaining 60% solids content.
This glue is flooded and is coated on E glass-fiber-fabric (2116, substance is 104g/m
2) on, and in 135 DEG C of baking ovens, dry the prepreg that 5min obtains resin content 50%.
By the prepreg of this obtained resin content 50%, respectively put a metal copper foil up and down, be placed in vacuum hotpressing machine compacting and obtain copper-clad plate.Concrete process for pressing is at 1.5Mpa pressure, and 195 DEG C of temperatures close 2 hours.
The copper clad laminate performance obtained is as shown in table 1.
Embodiment two
According to the method in synthesis example, obtain bisphenol-f type benzoxazine at 130 DEG C of reaction 40min: the performed polymer 60g of 3,3', 4,4'-bibenzene tetracarboxylic dianhydride=100:100, gelation time controls at 700 ~ 750 seconds temperature 210 DEG C, adds appropriate butanone and dissolves; After anhydride modified benzoxazine performed polymer dissolves completely, add 25g phosphorous epoxy resin (XZ92530, DOW Chemical), 15g phosphonium flame retardant (XZ92741, DOW Chemical), 0.05g stannous octoate, 40g preparing spherical SiO 2, appropriate butanone solvent, be uniformly mixed the glue obtaining 60% solids content.
Prepreg, copper clad laminate preparation method are with embodiment one.
The copper clad laminate performance obtained is as shown in table 1.
Embodiment three
According to the method in synthesis example, obtain bisphenol A-type benzoxazine at 150 DEG C of reaction 50min: 3,3 ', 4, the performed polymer 55g of 4 '-oxydiphthalic=100:70, gelation time controls at 1000 ~ 1100 seconds temperature 210 DEG C, adds appropriate butanone and dissolves; After anhydride modified benzoxazine performed polymer dissolves completely, add 25g naphthalene nucleus type epoxy resin (NC-7300, Japan chemical drug), 20g phosphonium flame retardant (XZ92741, DOW Chemical), 0.05g 2-ethyl-4 Methylimidazole, 40g preparing spherical SiO 2, appropriate butanone solvent, be uniformly mixed the glue obtaining 60% solids content.
Prepreg, copper clad laminate preparation method are with embodiment one.
The copper clad laminate performance obtained is as shown in table 1.
Embodiment four
According to the method in synthesis example, obtain bisphenol A-type benzoxazine at 150 DEG C of reaction 50min: the performed polymer 40g of styrene-maleic anhydride=100:30, gelation time controls at 400 ~ 450 seconds temperature 210 DEG C, adds appropriate butanone and dissolves; After anhydride modified benzoxazine performed polymer dissolves completely, add 43g bisphenol A-type novolac epoxy (EPON 627, HEXION), 17g phosphonium flame retardant (XZ92741, DOW Chemical), 0.02g 2-ethyl-4 Methylimidazole, 40g preparing spherical SiO 2, appropriate butanone solvent, be uniformly mixed the glue obtaining 60% solids content.
Prepreg, copper clad laminate preparation method are with embodiment one.
The copper clad laminate performance obtained is as shown in table 1.
Embodiment five
According to the method in synthesis example, dicyclopentadiene type benzoxazine is obtained: styrene-maleic anhydride: 2 at 80 DEG C of reaction 100min, 3,3', the performed polymer 50g of 4'-bibenzene tetracarboxylic dianhydride=100:20:10, gelation time controls at 500 ~ 550 seconds temperature 210 DEG C, adds appropriate butanone and dissolves; After anhydride modified benzoxazine performed polymer dissolves completely, add 30g bisphenol A-type novolac epoxy (EPON 627, HEXION), 20g phosphonium flame retardant (XZ92741, DOW Chemical), 0.01g 2-ethyl-4 Methylimidazole, 40g preparing spherical SiO 2, appropriate butanone solvent, be uniformly mixed the glue obtaining 60% solids content.
Prepreg, copper clad laminate preparation method are with embodiment one.
The copper clad laminate performance obtained is as shown in table 1
Embodiment six
According to the method in synthesis example, allyl group bisphenol A benzoxazine is obtained: styrene-maleic anhydride: the performed polymer 50g of Bisphenol A Type Diether Dianhydride=100:20:10 at 60 DEG C of reaction 130min, gelation time controls at 350 ~ 400 seconds temperature 210 DEG C, adds appropriate butanone and dissolves; After anhydride modified benzoxazine performed polymer dissolves completely, add 35g biphenyl type epoxy resin (NC-3000, Japan chemical drug), 15g phosphonium flame retardant (XZ92741, DOW Chemical), 0.01g 2-phenylimidazole, 40g fusion silicon-dioxide, appropriate butanone solvent, be uniformly mixed the glue obtaining 60% solids content.
Prepreg, copper clad laminate preparation method are with embodiment one.
The copper clad laminate performance obtained is as shown in table 1
Embodiment seven
According to the method in synthesis example, obtain Bisphenol F benzoxazine at 60 DEG C of reaction 130min: styrene-maleic anhydride: 1,2,4, the performed polymer 45g of 5-pyromellitic acid dianhydride=100:35:15, gelation time controls at 200 ~ 250 seconds temperature 210 DEG C, adds appropriate butanone and dissolves; After anhydride modified benzoxazine performed polymer dissolves completely, add 45g phosphorous epoxy resin (KDP555, Korea S national capital), 10g phosphonium flame retardant (XZ92741, DOW Chemical), 0.005g 2-phenylimidazole, 40g fusion silicon-dioxide, appropriate butanone solvent, be uniformly mixed the glue obtaining 60% solids content.
Prepreg, copper clad laminate preparation method are with embodiment one.
The copper clad laminate performance obtained is as shown in table 1.
Embodiment eight
According to the method in synthesis example, obtain Bisphenol F benzoxazine at 60 DEG C of reaction 130min: the performed polymer 50g of styrene-maleic anhydride=100:30, gelation time controls at 300 ~ 350 seconds temperature 210 DEG C, adds appropriate butanone and dissolves; After anhydride modified benzoxazine performed polymer dissolves completely, add 30g dicyclopentadiene type epoxy resin (XD-1000, Japan chemical drug), 20g phosphonium flame retardant (XZ92741, DOW Chemical), 0.005g 2-phenylimidazole, 40g fusion silicon-dioxide, appropriate butanone solvent, be uniformly mixed the glue obtaining 60% solids content.
Prepreg, copper clad laminate preparation method are with embodiment one.
The copper clad laminate performance obtained is as shown in table 1.
Comparative example one
Get 16g SMA-EF40 (U.S. Sartomer trade(brand)name) and 44g diaminodiphenylmethane type benzoxazine (D125 Sichuan Dong Cai scientific & technical corporation), add suitable acetone, after dissolving completely, add 23g phosphorous epoxy resin (XZ92530, DOW Chemical), 17g phosphonium flame retardant (XZ92741, DOW Chemical), 0.05g 2-ethyl-4 Methylimidazole, 40g preparing spherical SiO 2, appropriate butanone solvent, be uniformly mixed the glue obtaining 60% solids content.
This glue is flooded and is coated on E glass-fiber-fabric (2116, substance is 104g/m
2) on, and in 135 DEG C of baking ovens, dry the prepreg that 5min obtains resin content 50%.
By the prepreg of this obtained resin content 50%, respectively put a metal copper foil up and down, be placed in vacuum hotpressing machine compacting and obtain copper-clad plate.Concrete process for pressing is at 1.5Mpa pressure, and 220 DEG C of temperatures close 2 hours.
The copper clad laminate performance obtained is as shown in table 1.
Comparative example two
Get 11.5g SMA-EF40 (U.S. Sartomer trade(brand)name) and 38.5g bisphenol A-type benzoxazine (the graceful advanced material of Hensel), add suitable acetone, after dissolving completely, add 30g dicyclopentadiene type epoxy resin (XD-1000, Japan chemical drug), 20g phosphonium flame retardant (XZ92741, DOW Chemical), 0.02g 2-phenylimidazole, 40g preparing spherical SiO 2, appropriate butanone solvent, be uniformly mixed the glue obtaining 60% solids content.
Prepreg, copper clad laminate preparation method are with comparative example one.
The copper clad laminate performance obtained is as shown in table 1.
Comparative example three
Get 30g bisphenol-f type benzoxazine and 30g3,3', 4,4'-bibenzene tetracarboxylic dianhydride, adds suitable acetone, after dissolving completely, add 25g phosphorous epoxy resin (XZ92530, DOW Chemical), 15g phosphonium flame retardant (XZ92741, DOW Chemical), 0.05g stannous octoate, 40g preparing spherical SiO 2, appropriate butanone solvent, be uniformly mixed the glue obtaining 60% solids content.
Prepreg, copper clad laminate preparation method are with comparative example one.
The copper clad laminate performance obtained is as shown in table 1.
Table 1 adopts the copper clad laminate performance of different embodiment gained
In upper table, the testing method of characteristic is as follows:
(1) second-order transition temperature (Tg DEG C):
According to dsc, measure according to the DSC method of IPC-TM-650 2.4.25 defined.
(2) stripping strength (PS):
According to " after the thermal stresses " experiment condition in IPC-TM-650 2.4.8 method, the stripping strength of test metallic cover layer.
(3) internal layer stripping strength:
Use 1.6mm veneer sheet, peeled off the batten that test layer is shown in cohesive strength, recording materials tensiometer pull-up batten masterpiece is veneer sheet internal layer stripping strength (N/mm).
(4) resistance to flame (flame retardancy):
Measure according to UV94 method.
(5) specific inductivity:
Use flat band method according to IPC-TM-650 2.5.5.9, measure the specific inductivity under 1GHz.
(6) dielectric loss angle tangent:
Use flat band method according to IPC-TM-650 2.5.5.9, measure the dielectric loss factor under 1GHz.
(7) drop impact toughness (veneer sheet fragility):
Use Apparatus for Impacting at low-temp, Apparatus for Impacting at low-temp height of the fall 45cm, whereabouts weight weight 1kg.
The judge that toughness is good and bad: cross bar is clear, illustrates that the toughness of product is better, represents with character ☆; Cross bar is fuzzy, illustrates that the poor toughness of product, fragility are large, represents with character ◎; Cross bar readability illustrates that toughness of products is general between clear and fuzzy, represents with character ◇.
(8) wicking thermotolerance after wet heat treatment:
Get 3 pieces of 10cm × 10cm, thickness is 0.80mm, two sides removes the sample of tinsel, 100 DEG C of dryings 5 hours, then test (Pressure Cooker test) machine is pressure-cooked, process 1 hour under 121 DEG C, 2 normal atmosphere after, wicking 20s in the tin stove of 288 DEG C, whether visual observations has demixing phenomenon.If any 0 in 3 pieces, 1,2,3 pieces of demixing phenomenons are designated as 0/3,1/3,2/3,3/3 respectively.
To sum up result is known, and the product of embodiment is compared with the product of comparative example: stripping strength and splitting are significantly increased about more than 20%; Thermotolerance after moisture absorption is also obvious, and specific inductivity and dielectric loss are all reduced; Can find out that the toughness tool of embodiment improves significantly by falling weight impact test, thus veneer sheet has good processibility.
Claims (8)
1. a high frequency resin composition, is characterized in that, with solid weight meter, comprising:
(a) anhydride modified benzoxazine resin performed polymer: 15 ~ 80 parts;
(b) halogen-free epoxy resin: 10 ~ 60 parts;
(c) fire retardant: 5 ~ 40 parts;
(d) promotor: 0.001 ~ 2 part;
(e) mineral filler: 0 ~ 70 part;
The number-average molecular weight of described anhydride modified benzoxazine resin performed polymer is 400 ~ 20000, obtain in the following manner: in mass ratio, benzoxazine: anhydride compound=100:15 ~ 130, get benzoxazine, anhydride compound is in reaction flask, be heated to 60 ~ 200 DEG C, and under keeping the condition stirred, add catalyzer, catalyst levels is 0 ~ 2% of reactant total mass and is not 0, it is 400 ~ 20000 that reaction 10 ~ 150 min obtain number-average molecular weight, gelation time is temperature at the 210 DEG C anhydride modified benzoxazine resin prepolymer of homogeneous transparent of 200 ~ 2000 seconds,
Wherein, described benzoxazine is selected from bisphenol A-type benzoxazine resin, bisphenol-f type benzoxazine resin, 4, one or more in 4 ' diaminodiphenylmethane benzoxazine resin, diaminodiphenyl oxide benzoxazine resin, diaminodiphenylsulfone(DDS) benzoxazine resin, dicyclopentadiene type benzoxazine resin, phenolphthalein type benzoxazine, allyl group bisphenol A benzoxazine resin;
Described anhydride compound is selected from styrene-maleic anhydride, 3, and 3 ', 4,4 '-oxydiphthalic, 2,3,3', 4'-diphenyl ether tetraformic dianhydride, 3,3', 4,4'-bibenzene tetracarboxylic dianhydride, 2,3,3', 4'-bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, Bisphenol A Type Diether Dianhydride, 1, one or more in 2,4,5-pyromellitic acid dianhydride.
2. high frequency resin composition according to claim 1, is characterized in that: described halogen-free epoxy resin is selected from one or more the mixture in diglycidyl ether type epoxy resin, glycidyl amine type epoxy resin and glycidyl ester type epoxy resin.
3. high frequency resin composition according to claim 1, is characterized in that: described fire retardant is selected from one or more in phosphonium flame retardant and brominated flame-retardant.
4. high frequency resin composition according to claim 1, is characterized in that: described mineral filler is selected from one or more mixture of silicon-dioxide, boron nitride, aluminium hydroxide, boehmite, talcum, clay, mica, kaolin, barium sulfate, calcium carbonate, magnesium hydroxide and zinc borate.
5. high frequency resin composition according to claim 1, is characterized in that: described promotor is imidazoles, organic metal salt or its mixture, and wherein, imidazoles is selected from glyoxal ethyline, 2-phenylimidazole or 2-ethyl-4 Methylimidazole; Organic metal salt is selected from zinc octoate, isocaprylic acid zinc, stannous octoate, dibutyl tin laurate, zinc naphthenate, cobalt naphthenate, aluminium acetylacetonate, acetylacetone cobalt or acetylacetone copper.
6. the prepreg adopting high frequency resin composition as claimed in claim 1 to make, is characterized in that: high frequency resin composition dissolution with solvents according to claim 1 is made glue, is then immersed in by strongthener in above-mentioned glue; After flooding, strongthener is after heat drying, can obtain described prepreg.
7. the veneer sheet adopting high frequency resin composition as claimed in claim 1 to make, it is characterized in that: be covered with tinsel at the single or double of a prepreg obtained by claim 6, or after the prepreg superposition that at least 2 are obtained by claim 6, tinsel is covered with at its single or double, hot compacting, can obtain described veneer sheet.
8. the anhydride modified benzoxazine resin performed polymer for high frequency resin composition, it is characterized in that, obtain as follows: in mass ratio, benzoxazine resin: anhydride compound=100:15 ~ 130, get benzoxazine, anhydride compound is in reaction flask, be heated to 60 ~ 200 DEG C, and under keeping the condition stirred, add catalyzer, catalyst levels is 0 ~ 2% of reactant total mass and is not 0, it is 400 ~ 20000 that reaction 10 ~ 150 min obtain number-average molecular weight, gelation time is temperature at the 210 DEG C anhydride modified benzoxazine resin prepolymer of homogeneous transparent of 200 ~ 2000 seconds,
Wherein, described benzoxazine is selected from bisphenol A-type benzoxazine resin, bisphenol-f type benzoxazine resin, 4, one or more in 4 ' diaminodiphenylmethane benzoxazine resin, diaminodiphenyl oxide benzoxazine resin, diaminodiphenylsulfone(DDS) benzoxazine resin, dicyclopentadiene type benzoxazine resin, phenolphthalein type benzoxazine, allyl group bisphenol A benzoxazine resin;
Described anhydride compound is selected from styrene-maleic anhydride, 3, and 3 ', 4,4 '-oxydiphthalic, 2,3,3', 4'-diphenyl ether tetraformic dianhydride, 3,3', 4,4'-bibenzene tetracarboxylic dianhydride, 2,3,3', 4'-bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, Bisphenol A Type Diether Dianhydride, 1, one or more in 2,4,5-pyromellitic acid dianhydride.
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Cited By (1)
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|---|---|---|---|---|
| WO2020180973A1 (en) * | 2019-03-04 | 2020-09-10 | Sabic Global Technologies B.V. | Metal-clad laminate including thermoset epoxy composition |
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| CN104371276A (en) * | 2014-11-21 | 2015-02-25 | 芜湖市宝艺游乐科技设备有限公司 | High-temperature-resistant epoxy resin composite material and preparation method thereof |
| CN104531008B (en) * | 2014-12-23 | 2016-10-05 | 上海南亚覆铜箔板有限公司 | A kind of binding agent being applicable to high Tg Halogen low dielectric type copper coated foil plate laminated substrate material and preparation method thereof |
| CN104987667B (en) * | 2015-07-03 | 2018-03-20 | 苏州生益科技有限公司 | A kind of resin combination and the prepreg and laminate using its making |
| CN105199384B (en) * | 2015-09-21 | 2017-10-27 | 四川天策聚材科技有限公司 | Fire-retardant benzoxazine nano composite material of transparent type and preparation method thereof |
| CN112608582A (en) * | 2020-11-02 | 2021-04-06 | 建滔（江苏）化工有限公司 | Resin composition and preparation method and application thereof |
| CN117261378B (en) * | 2023-11-23 | 2024-01-23 | 四川烈火胜服科技有限公司 | Fireproof heat-insulating composite fabric and application thereof in firefighter uniform |
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