CN102977551A - Halogen-free resin composition and method for preparing copper-clad plate from the halogen-free resin composition - Google Patents
Halogen-free resin composition and method for preparing copper-clad plate from the halogen-free resin composition Download PDFInfo
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- CN102977551A CN102977551A CN2011102579301A CN201110257930A CN102977551A CN 102977551 A CN102977551 A CN 102977551A CN 2011102579301 A CN2011102579301 A CN 2011102579301A CN 201110257930 A CN201110257930 A CN 201110257930A CN 102977551 A CN102977551 A CN 102977551A
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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
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
Abstract
The invention discloses a halogen-free resin composition and a method for preparing a copper-clad plate from the halogen-free resin composition. Based on the total weight part of solid ingredients of the halogen-free resin composition, the halogen-free resin composition comprises, by weight, 5 to 50 parts of reaction-type allylphenoxycyclotriphosphazene or vinylphenoxycyclotriphosphazene, 15 to 85 parts of a thermosetting resin, 1 to 35 parts of a crosslinking curing agent, 0 to 5 parts of a crosslinking curing accelerator and 0 to 100 parts of a filling material. Through introduction of reaction-type allylphenoxycyclotriphosphazene or vinylphenoxycyclotriphosphazene having very low water absorbency into the thermosetting resin, the halogen-free resin composition can satisfy halogen-free flame-retardation requirements, improve system electrical properties, and realize non-halogenation of a high-frequency high-speed substrate material. The copper-clad plate prepared from the halogen-free resin composition satisfies halogen-free requirements, has excellent heat resistance and moisture resistance and has a low dielectric loss.
Description
Technical field
The present invention relates to a kind of resin combination, relate in particular to a kind of halogen-free resin composition and use it to make the method for copper-clad plate.
Background technology
In recent years, development along with integrated technology, joining technique and the mounting technology of the semiconducter device of using in electronics, high-density electronic package and the high density printed circuit board wiring, electronics has obtained continuous progress, especially uses the electronics in broadband such as mobile communications device that fast development has been arranged at those.
Printed-wiring board (PWB) is as a formation of this electronics, more accurate wiring development in the time of towards the multilayer printed circuit board of higher degree.For signaling rate being brought up to the needed level of information processing of accelerating, effective ways are the specific inductivity that reduce the material that uses, and in order to reduce transmission loss, effective way is the material that uses than low-dielectric loss tangent (dielectric loss).
When electronic technology develops rapidly, people also more and more ask most environment protection, but traditional high-frequency high-speed material is to reach fire-retardant purpose with halogenide, stibnide etc. basically, during the copper-clad plate ignition of halide, not only the amount of being fuming is large, and the smell is awful, and can emit the hydrogen halide that toxicity is large, corrodibility is strong, not only contaminate environment also is detrimental to health; At present industrial generally have luxuriant and rich with fragrance type Compound D OPO or Resins, epoxy corresponding to ODOPB to realize that common FR-4 reaches fire-retardant with phosphorous, but phosphorous have luxuriant and rich with fragrance type Compound D OPO or ODOPB that larger water-intake rate is still arranged, and specific inductivity, the dielectric loss angle tangent of high-frequency high-speed material had great impact.
Summary of the invention
The object of the present invention is to provide a kind of halogen-free resin composition, by in thermosetting resin, introducing extremely low response type allyl group phenoxy cyclotriphosphazene or the vinyl phenoxy cyclotriphosphazene of water-intake rate, the halogen-free flameproof requirement can be satisfied, the system electrical property can be improved again.
The advantages such as another object of the present invention is to provide a kind of method of using above-mentioned halogen-free resin composition to make copper-clad plate, simple, Halogen-free requirement is satisfied in prepared copper-clad plate, has excellent thermotolerance and wet fastness, and dielectric loss is low.
For achieving the above object, the invention provides a kind of halogen-free resin composition, calculate with the solid ingredient total weight parts, it comprises that component and content thereof are: response type allyl group phenoxy cyclotriphosphazene or vinyl phenoxy cyclotriphosphazene 5-50 part, thermosetting resin 15-85 part, crosslinking and curing agent 1-35 part, crosslinking curing promotor 0-5 part, and filler 0-100 part.
The chemical structural formula of described response type allyl group phenoxy cyclotriphosphazene or vinyl phenoxy cyclotriphosphazene is as follows:
M represents the integer of 3-25 in the formula, and X is phenoxy group:
X quantity is 0～2m-1, and Y is selected from the allyl group phenoxy group:
Between the allyl group phenoxy group:
O-allyl oxygen base:
To the vinyl phenoxy group:
Vinyl phenoxy group between reaching:
Y quantity is 1～2m, X+Y=2m.
Described thermosetting resin comprises one or more in the following resin:
Resins, epoxy, it comprises bisphenol A epoxide resin, bisphenol F epoxy resin, DCPD-containing epoxy resin, triphenol epoxy, biphenyl epoxy, naphthols epoxy and phosphorous epoxy resin;
Benzoxazine colophony, it comprises bisphenol A-type benzoxazine colophony, Bisphenol F type benzoxazine colophony, dicyclopentadiene type benzoxazine colophony, reaches the phenolphthalein type benzoxazine resin;
Cyanate ester resin, it comprises bisphenol A cyanate ester resin, dicyclopentadiene type ethylene rhodanate resin, reaches Novolac Cyanate Ester Resins;
Bimaleimide resin, it comprises 4,4 '-diphenyl methane dimaleimide and allyl group modified diphenylmethane bismaleimides;
Number-average molecular weight is the response type polyphenylene oxide resin of 1000-7000, and its reactive group is hydroxyl or two key; And
Hydrocarbon resin is by the vinyl butadiene styrene resin of molecular weight below 11000, form with the vinyl polybutadiene resin of polar group and maleic anhydride graft divinyl and cinnamic multipolymer.
Described crosslinking and curing agent is selected from one or more mixing in Dyhard RU 100, aromatic amine, acid anhydrides, phenolic compound, tricarbimide triolefin ester and the phosphorus-containing phenolic aldehyde.
Described crosslinking curing promotor is glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, DMP-30 (three-(dimethylamino methyl)), hexamethylenetetramine, dicumyl peroxide, peroxidized t-butyl perbenzoate, 2,5-two (2-ethyl hexanoyl peroxide)-2,5-dimethylhexane, acetyl pyruvate, and zincate in one or more mixture.
Described filler is selected from one or more in aluminium hydroxide, magnesium hydroxide, zeolite, wollastonite, silicon-dioxide, magnesium oxide, Calucium Silicate powder, calcium carbonate, clay, talcum and the mica.
Further, the present invention also provides a kind of method of using above-mentioned halogen-free resin composition to make copper-clad plate, comprises the steps:
Step 1, get 5～50 parts of response type allyl group phenoxy cyclotriphosphazene or vinyl phenoxy cyclotriphosphazenes, be dissolved in the solvent fully dissolving under normal temperature or medium temperature condition;
Step 2, get 0～100 part of 15～85 parts of corresponding thermosetting resins, 1～35 part of crosslinking and curing agent, 0～5 part of crosslinking curing promotor and filler and add in the above-mentioned gained solution, stirring obtains glue;
Step 3, choose the E-glass-fiber-fabric of surfacing, evenly apply above-mentioned glue, then smoke into B-rank prepreg;
Step 4, big or small according to press is cut into suitable size with B-rank prepreg, several neat stacks, and respectively put up and down a Copper Foil, and place vacuum hotpressing machine to suppress, obtain copper-clad plate.
Described solvent is one or more in benzene class and the ketones solvent; Described middle temperature is≤80 ℃.
Described step 3 is smoked in the process of B-rank prepreg, and temperature arranges according to the boiling point of glue solvent for use, and temperature range is 85～175 ℃, and the baking sheet time is 5～20 minutes.
In the described step 4, pressing process adopts staged compacting (substep heats up and boosts) method, and concrete steps are: rising to 150 ℃ from room temperature in 15 minutes kept 30 minutes, then rose to 180 ℃ in 5 minutes and kept 2 hours, was cooled to room temperature in last 30 minutes; Pressure 1 minute rose to the 0.6Mpa pressurize 20 minutes from zero, then rose to 1.0Mpa pressurize 2.5 hours in 1 minute; Post-treatment condition is 200～245 ℃ and kept 1～5 hour.
Beneficial effect of the present invention: the present invention is by introducing extremely low response type allyl group phenoxy cyclotriphosphazene or the vinyl phenoxy cyclotriphosphazene of water-intake rate in thermosetting resin, can satisfy the halogen-free flameproof requirement, can improve the system electrical property again: reduce, stablize Dk (specific inductivity) and Df (dielectric dissipation factor), so that the non-halogen possibility that becomes of high-frequency high-speed baseplate material, Halogen-free requirement is satisfied in prepared copper-clad plate, have excellent thermotolerance and wet fastness, the advantage such as dielectric loss is low.
Embodiment
Halogen-free resin composition provided by the invention, calculate with total weight of solids part, it comprises that component and content thereof are: response type allyl group phenoxy cyclotriphosphazene or vinyl phenoxy cyclotriphosphazene 5-50 part, thermosetting resin 15-85 part, crosslinking and curing agent 1-35 part, crosslinking curing promotor 0-5 part, and filler 0-100 part.
The chemical structural formula of described response type allyl group phenoxy cyclotriphosphazene or vinyl phenoxy cyclotriphosphazene is as follows:
M represents the integer of 3-25 in the formula, and X is phenoxy group:
X quantity is 0～2m-1, and Y is selected from the allyl group phenoxy group:
Between the allyl group phenoxy group:
O-allyl oxygen base:
To the vinyl phenoxy group:
Vinyl phenoxy group between reaching:
Y quantity is 1～2m; Described X+Y=2m.
Above-mentioned response type allyl group phenoxy cyclotriphosphazene and vinyl phenoxy cyclotriphosphazene are phosphazene compound, water-intake rate is extremely low, the present invention utilize its with response type group and specific thermosetting resin reaction, high-frequency high-speed material halogen-free flameproof be can realize, and its good specific inductivity and dielectric loss angle tangent performance do not affected.
Described thermosetting resin comprises one or more in the following resin: Resins, epoxy, and it comprises bisphenol A epoxide resin, bisphenol F epoxy resin, dicyclopentadiene (DCPD) Resins, epoxy, triphenol epoxy, biphenyl epoxy, naphthols epoxy and phosphorous epoxy resin etc.; Benzoxazine colophony, it comprises bisphenol A-type benzoxazine colophony, Bisphenol F type benzoxazine colophony, dicyclopentadiene type benzoxazine colophony, phenolphthalein type benzoxazine resin etc.; Cyanate ester resin, it comprises bisphenol A cyanate ester resin, dicyclopentadiene type ethylene rhodanate resin, Novolac Cyanate Ester Resins etc.; Bimaleimide resin, it comprises 4,4 '-diphenyl methane dimaleimide and allyl group modified diphenylmethane bismaleimides etc.; Reactive polyphenylene oxide resin; And hydrocarbon resin.Wherein said reactive polyphenylene oxide resin number-average molecular weight is 1000-7000, and reactive group is hydroxyl, two keys etc.; Hydrocarbon resin is by the vinyl butadiene styrene resin of molecular weight below 11000, form with the vinyl polybutadiene resin of polar group and maleic anhydride graft divinyl and cinnamic multipolymer.
Described crosslinking and curing agent is selected from one or more mixing in Dyhard RU 100, aromatic amine, acid anhydrides, phenolic compound, tricarbimide triolefin ester and the phosphorus-containing phenolic aldehyde.
Described crosslinking curing promotor is glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, DMP-30 (three-(dimethylamino methyl)), hexamethylenetetramine, dicumyl peroxide, peroxidized t-butyl perbenzoate, 2,5-two (2-ethyl hexanoyl peroxide)-2,5-dimethylhexane, acetyl pyruvate, and zincate in one or more mixture.
Described filler is selected from: one or more in the general mineral filler such as aluminium hydroxide, magnesium hydroxide, zeolite, wollastonite, silicon-dioxide, magnesium oxide, Calucium Silicate powder, calcium carbonate, clay, talcum and mica, this mineral filler can be made suitable dose titration with application target, its consumption is with organic total solid 100 listed as parts by weight of the component in the above-mentioned halogen-free resin composition, be advisable with the 0-100 weight part, best with the 25-100 weight part.
Adopt above-mentioned halogen-free resin composition to make prepreg and copper-clad plate etc., the prepreg of its made comprises: base-material and apply halogen-free resin composition on it, and base-material is glass-fiber-fabric etc., preferably the E-glass-fiber-fabric; The copper-clad plate of its made comprises: several superimposed prepregs and be located at Copper Foil on the one or both sides of the prepreg after superimposed.The advantages such as Halogen-free requirement is satisfied in prepared copper-clad plate, has excellent thermotolerance and wet fastness, and dielectric loss is low.
Use above-mentioned halogen-free resin composition to make the method for copper-clad plate, comprise the steps:
Step 1, get 5～50 parts of response type allyl group phenoxy cyclotriphosphazene or vinyl phenoxy cyclotriphosphazenes, be dissolved in the solvent of benzene class, ketone etc. fully dissolving under normal temperature or medium temperature condition; Solvent can be one or more in benzene class and the ketones solvent, and normal temperature is normal temperature of the prior art, and middle temperature refers to≤80 ℃ temperature range.
Step 2, get 0～100 part of 15～85 parts of corresponding thermosetting resins, 1～35 part of crosslinking and curing agent, 0～5 part of crosslinking curing promotor and filler and add in the above-mentioned gained solution, stirring obtains glue;
Step 3, choose the E-glass-fiber-fabric of surfacing, evenly apply above-mentioned glue, then smoke into B-rank prepreg; Smoke in the process of B-rank prepreg, temperature arranges according to the boiling point of glue solvent for use, and temperature range is 85～175 ℃, and the baking sheet time is 5～20 minutes (min).
Step 4, big or small according to press is cut into suitable size with B-rank prepreg, several neat stacks, and respectively put up and down a Copper Foil, and place vacuum hotpressing machine to suppress, obtain copper-clad plate.In this step, pressing process adopts staged compacting (substep heats up and boosts) method, and concrete steps are: rising to 150 ℃ from room temperature in 15 minutes kept 30 minutes, then rose to 180 ℃ in 5 minutes and kept 2 hours (hr), was cooled to room temperature in last 30 minutes; Pressure 1 minute rose to the 0.6Mpa pressurize 20 minutes from zero, then rose to 1.0Mpa pressurize 2.5 hours in 1 minute; Post-treatment condition is 200～245 ℃ and kept 1～5 hour.
Survey its specific inductivity, second-order transition temperature, stripping strength, resistance to flame, water-absorbent, punching etc. for above-mentioned copper-clad plate of making, further give to illustrate in detail and describe such as following embodiment.
Hereby the embodiment of the invention is described in detail as follows, but the present invention is confined to scope of embodiments.
Embodiment 1:
Solvent, hexachlorocyclotriphosphazene, chavicol (take o-allyl phenol as main component), acid binding agent are added in the reaction unit; stir; pass into nitrogen protection; be heated to 50～120 ℃, in reaction unit, add catalyzer again, react and be cooled to room temperature after 5～16 hours; suction filtration; filtrate is carried out pressure distillation, and evaporating solvent obtains brown ceramic powder or thick product.After getting above-mentioned product 30g and being dissolved in organic solvent, (selected DCPD Resins, epoxy is HP-7200H (DIC) to add DCPD Resins, epoxy 50g, equivalent 275-280), DCPD resol 20g (selected DCPD resol is Nihon Petro-chemical DPP-600M), an amount of imidazoles and 2,5-two (2-ethyl hexanoyl peroxide) mixes and obtains glue.Choose 300 * 300cm, any surface finish, smooth E-glass-fiber-fabric, evenly apply above-mentioned glue, 155 ℃ of lower baking 7min make prepreg in baking oven.With 5 prepreg stacks of cutting out deflashing, enclose up and down the Copper Foil of 35 μ m, place the vacuum hotpressing machine compacting to obtain copper-clad plate.Adopt the compacting of staged (substep heats up and boosts) program, wherein, rose to 150 ℃ from room temperature in 15 minutes and keep 30min, then 5min rises to 180 ℃ and keeps 2hr, last 30min cooling room temperature; Pressure 1min rises to 0.6Mpa pressurize 20min from zero, and then 1min rises to 1.0Mpa pressurize 2.5hr.Prepared copper-clad plate fundamental property such as table one.
Embodiment 2:
Solvent, hexachlorocyclotriphosphazene, chavicol (take o-allyl phenol as main component), acid binding agent are added in the reaction unit; stir; pass into nitrogen protection; be heated to 50～120 ℃, in reaction unit, add catalyzer again, react and be cooled to room temperature after 5～16 hours; suction filtration; filtrate is carried out pressure distillation, and evaporating solvent obtains brown ceramic powder or thick product.After getting above-mentioned product 30g and being dissolved in organic solvent, add DCPD benzoxazine 40g (selected DCPD benzoxazine is MT36000 (Huntsman)), (selected DCPD Resins, epoxy is HP-7200H (DIC) to DCPD Resins, epoxy 20g, equivalent 275-280), (selected acid anhydrides is EF-30 to vinylbenzene/MALEIC ANHYDRIDE 10g, Sartomer), an amount of imidazoles and 2,5-two (2-ethyl hexanoyl peroxide) mixes and obtains glue.Choose 300 * 300cm, any surface finish, smooth E-glass-fiber-fabric, evenly apply above-mentioned glue, 155 ℃ of lower baking 7min make prepreg in baking oven.With 5 prepreg stacks of cutting out deflashing, enclose up and down the Copper Foil of 35 μ m, place the vacuum hotpressing machine compacting to obtain copper-clad plate.Adopt the compacting of staged (substep heats up and boosts) program, wherein, rose to 150 ℃ from room temperature in 15 minutes and keep 30min, then 5min rises to 190 ℃ and keeps 2hr, last 30min cooling room temperature; Pressure 1min rises to 0.6Mpa pressurize 20min from zero, and then 1min rises to 1.0Mpa pressurize 2.5hr.Prepared copper-clad plate fundamental property such as table one.
Embodiment 3:
Solvent, hexachlorocyclotriphosphazene, chavicol (take o-allyl phenol as main component), acid binding agent are added in the reaction unit; stir; pass into nitrogen protection; be heated to 50～120 ℃, in reaction unit, add catalyzer again, react and be cooled to room temperature after 5～16 hours; suction filtration; filtrate is carried out pressure distillation, and evaporating solvent obtains brown ceramic powder or thick product.After getting above-mentioned product 30g and being dissolved in organic solvent, add DCPD cyanate 30g (selected DCPD cyanate is LONZA-Primaset BADCy), 4,4 '-(selected DCPD Resins, epoxy is HP-7200H (DIC) for diphenyl methane dimaleimide 20g, DCPD Resins, epoxy 20g, equivalent 275-280), an amount of acetopyruvic acid aluminium, mix and obtain glue.Choose 300 * 300cm, any surface finish, smooth E-glass-fiber-fabric, evenly apply above-mentioned glue, 155 ℃ of lower baking 7min make prepreg in baking oven.With 5 prepreg stacks of cutting out deflashing, enclose up and down the Copper Foil of 35 μ m, place the vacuum hotpressing machine compacting to obtain copper-clad plate.Adopt the compacting of staged (substep heats up and boosts) program, wherein, rose to 150 ℃ from room temperature in 15 minutes and keep 30min, then 5min rises to 210 ℃ and keeps 2hr, last 30min cooling room temperature; Pressure 1min rises to 0.6Mpa pressurize 20min from zero, and then 1min rises to 1.0Mpa pressurize 2.5hr.Prepared copper-clad plate fundamental property such as table one.
Embodiment 4:
Solvent, hexachlorocyclotriphosphazene, chavicol (take o-allyl phenol as main component), acid binding agent are added in the reaction unit; stir; pass into nitrogen protection; be heated to 50～120 ℃, in reaction unit, add catalyzer again, react and be cooled to room temperature after 5～16 hours; suction filtration; filtrate is carried out pressure distillation, and evaporating solvent obtains brown ceramic powder or thick product.After getting above-mentioned product 30g and being dissolved in organic solvent, add reactive polyphenylene oxide resin 50g (selected reactive polyphenylene oxide resin MX9000, SABIC), (selected DCPD Resins, epoxy is HP-7200H (DIC) to DCPD Resins, epoxy 20g, equivalent 275-280), an amount of imidazoles and 2,5-two (2-ethyl hexanoyl peroxide) mixes and obtains glue.Choose 300 * 300cm, any surface finish, smooth E-glass-fiber-fabric, evenly apply above-mentioned glue, 155 ℃ of lower baking 7min make prepreg in baking oven.With 5 prepreg stacks of cutting out deflashing, enclose up and down the Copper Foil of 35 μ m, place the vacuum hotpressing machine compacting to obtain copper-clad plate.Adopt the compacting of staged (substep heats up and boosts) program, wherein, rose to 150 ℃ from room temperature in 15 minutes and keep 30min, then 5min rises to 190 ℃ and keeps 2hr, last 30min cooling room temperature; Pressure 1min rises to 0.6Mpa pressurize 20min from zero, and then 1min rises to 1.0Mpa pressurize 2.5hr.Prepared copper-clad plate fundamental property such as table one.
Comparative example 1:
Solvent, hexachlorocyclotriphosphazene, vinylphenol (4-Vinyl phenol and a vinylphenol 50/50 mixture), acid binding agent are added in the reaction unit; stir; pass into nitrogen protection; be heated to 50～120 ℃, in reaction unit, add catalyzer again, react and be cooled to room temperature after 5～16 hours; suction filtration; filtrate is carried out pressure distillation, and evaporating solvent obtains brown ceramic powder or thick product.After getting above-mentioned product 30g and being dissolved in organic solvent, add DCPD cyanate 30g (selected DCPD cyanate is LONZA-Primaset BADCy), 4,4 '-(selected DCPD Resins, epoxy is HP-7200H (DIC) for diphenyl methane dimaleimide 20g, DCPD Resins, epoxy 20g, prepreg stack when the limit, enclose up and down the Copper Foil of 35 μ m, place the vacuum hotpressing machine compacting to obtain copper-clad plate.Adopt the compacting of staged (substep heats up and boosts) program, wherein, rose to 150 ℃ from room temperature in 15 minutes and keep 30min, then 5min rises to 190 ℃ and keeps 2hr, last 30min cooling room temperature; Pressure 1min rises to 0.6Mpa pressurize 20min from zero, and then 1min rises to 1.0Mpa pressurize 2.5hr.Prepared copper-clad plate fundamental property such as table one.
Comparative example 2:
Solvent, hexachlorocyclotriphosphazene, vinylphenol (4-Vinyl phenol and a vinylphenol 50/50 mixture), acid binding agent are added in the reaction unit; stir; pass into nitrogen protection; be heated to 50～120 ℃, in reaction unit, add catalyzer again, react and be cooled to room temperature after 5～16 hours; suction filtration; filtrate is carried out pressure distillation, and evaporating solvent obtains brown ceramic powder or thick product.After getting above-mentioned product 30g and being dissolved in organic solvent, add reactive polyphenylene oxide resin 50g (selected reactive polyphenylene oxide resin MX9000, SABIC), (selected DCPD Resins, epoxy is HP-7200H (DIC) to DCPD Resins, epoxy 20g, equivalent 275-280), an amount of imidazoles and 2,5-two (2-ethyl hexanoyl peroxide) mixes and obtains glue.Choose 300 * 300cm, any surface finish, smooth E-glass-fiber-fabric, evenly apply above-mentioned glue, 155 ℃ of lower baking 7min make prepreg in baking oven.With 5 prepreg stacks of cutting out deflashing, enclose up and down the Copper Foil of 35 μ m, place the vacuum hotpressing machine compacting to obtain copper-clad plate.Adopt the compacting of staged (substep heats up and boosts) program, wherein, rose to 150 ℃ from room temperature in 15 minutes and keep 30min, then 5min rises to 190 ℃ and keeps 2hr, last 30min cooling room temperature; Pressure 1min rises to 0.6Mpa pressurize 20min from zero, and then 1min rises to 1.0Mpa pressurize 2.5hr.Prepared copper-clad plate fundamental property such as table one.
Table one, characteristic evaluation
The testing method of above characteristic is as follows:
(1), second-order transition temperature (Tg): according to dsc (DSC), measure according to the DSC method of IPC-TM-650 2.4.25 defined.
(2), resistance to flame (flame retardancy): measure according to UL 94 methods.
(3), anti-immersed solder: the sample (base material of 100 * 100mm) after will keeping 2 hours in 121 ℃, the pressure cooking treatment unit of 105Kpa is immersed in 20 seconds in the solder bath that is heated to 260 ℃, (h1) has or not layering with visual inspection, (h2) have or not generation hickie or wrinkling, symbol zero in the table shows unchanged, △ shows the generation hickie, * show the generation layering.
(4), water-absorbent: measure according to IPC-TM-650 2.6.2.1 method.
(5), dielectric dissipation factor: according to the resonant method of using stripline runs, according to the dielectric dissipation factor under the IPC-TM-650 2.5.5.5 mensuration 1GHz.
(6), punching: the base material that 1.60mm is thick is put on the punch die of certain figure and carries out punching, Kong Bianwu encloses in vain with visual inspection (h1), (h2) Kong Bianyou Bai Quan, (h3) split in the limit, hole, in the table respectively with symbol zero, △, * expression.
By the above results as can be known, can reach according to the present invention and to reach halogen-free flameproof (content of halogen is in JPCA Halogen standard-required scope) on the basis that does not reduce dielectric properties, and have excellent thermotolerance, also have preferably workability simultaneously.
Above embodiment, be not that content to composition of the present invention imposes any restrictions, every foundation technical spirit of the present invention or composition composition or content all still belong in the scope of technical solution of the present invention any trickle modification, equivalent variations and modification that above embodiment does.
Claims (10)
1. halogen-free resin composition, it is characterized in that, calculate with the solid ingredient total weight parts, it comprises that component and content thereof are: response type allyl group phenoxy cyclotriphosphazene or vinyl phenoxy cyclotriphosphazene 5-50 part, thermosetting resin 15-85 part, crosslinking and curing agent 1-35 part, crosslinking curing promotor 0-5 part, and filler 0-100 part.
2. halogen-free resin composition as claimed in claim 1 is characterized in that, the chemical structural formula of described response type allyl group phenoxy cyclotriphosphazene or vinyl phenoxy cyclotriphosphazene is as follows:
M represents the integer of 3-25 in the formula, and X is phenoxy group:
X quantity is 0～2m-1, and Y is selected from the allyl group phenoxy group:
Between the allyl group phenoxy group:
O-allyl oxygen base:
To the vinyl phenoxy group:
Vinyl phenoxy group between reaching:
Y quantity is 1～2m, X+Y=2m.
3. halogen-free resin composition as claimed in claim 1 is characterized in that, described thermosetting resin comprises one or more in the following resin:
Resins, epoxy, it comprises bisphenol A epoxide resin, bisphenol F epoxy resin, DCPD-containing epoxy resin, triphenol epoxy, biphenyl epoxy, naphthols epoxy and phosphorous epoxy resin;
Benzoxazine colophony, it comprises bisphenol A-type benzoxazine colophony, Bisphenol F type benzoxazine colophony, dicyclopentadiene type benzoxazine colophony, reaches the phenolphthalein type benzoxazine resin;
Cyanate ester resin, it comprises bisphenol A cyanate ester resin, dicyclopentadiene type ethylene rhodanate resin, reaches Novolac Cyanate Ester Resins;
Bimaleimide resin, it comprises 4,4 '-diphenyl methane dimaleimide and allyl group modified diphenylmethane bismaleimides;
Number-average molecular weight is the response type polyphenylene oxide resin of 1000-7000, and its reactive group is hydroxyl or two key; And
Hydrocarbon resin is by the vinyl butadiene styrene resin of molecular weight below 11000, form with the vinyl polybutadiene resin of polar group and maleic anhydride graft divinyl and cinnamic multipolymer.
4. halogen-free resin composition as claimed in claim 1 is characterized in that, described crosslinking and curing agent is selected from one or more mixing in Dyhard RU 100, aromatic amine, acid anhydrides, phenolic compound, tricarbimide triolefin ester and the phosphorus-containing phenolic aldehyde.
5. halogen-free resin composition as claimed in claim 1, it is characterized in that, described crosslinking curing promotor is glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, three-(dimethylamino methyl), hexamethylenetetramine, dicumyl peroxide, peroxidized t-butyl perbenzoate, 2,5-two (2-ethyl hexanoyl peroxide)-2,5-dimethylhexane, acetyl pyruvate, and zincate in one or more mixture.
6. halogen-free resin composition as claimed in claim 1 is characterized in that, described filler is selected from one or more in aluminium hydroxide, magnesium hydroxide, zeolite, wollastonite, silicon-dioxide, magnesium oxide, Calucium Silicate powder, calcium carbonate, clay, talcum and the mica.
7. a method of using halogen-free resin composition as claimed in claim 1 to make copper-clad plate is characterized in that, comprises the steps:
Step 1, get 5～50 parts of response type allyl group phenoxy cyclotriphosphazene or vinyl phenoxy cyclotriphosphazenes, be dissolved in the solvent fully dissolving under normal temperature or medium temperature condition;
Step 2, get 0～100 part of 15～85 parts of corresponding thermosetting resins, 1～35 part of crosslinking and curing agent, 0～5 part of crosslinking curing promotor and filler and add in the above-mentioned gained solution, stirring obtains glue;
Step 3, choose the E-glass-fiber-fabric of surfacing, evenly apply above-mentioned glue, then smoke into B-rank prepreg;
Step 4, big or small according to press is cut into suitable size with B-rank prepreg, several neat stacks, and respectively put up and down a Copper Foil, and place vacuum hotpressing machine to suppress, obtain copper-clad plate.
8. the making method of copper-clad plate as claimed in claim 7 is characterized in that, described solvent is one or more in benzene class and the ketones solvent; Described middle temperature is≤80 ℃.
9. the making method of copper-clad plate as claimed in claim 7 is characterized in that, described step 3 is smoked in the process of B-rank prepreg, and temperature arranges according to the boiling point of glue solvent for use, and temperature range is 85～175 ℃, and the baking sheet time is 5～20 minutes.
10. the making method of copper-clad plate as claimed in claim 7 is characterized in that, in the described step 4, pressing process adopts the staged pressing, concrete steps are: rising to 150 ℃ from room temperature in 15 minutes kept 30 minutes, then rose to 180 ℃ in 5 minutes and kept 2 hours, was cooled to room temperature in last 30 minutes; Pressure 1 minute rose to the 0.6Mpa pressurize 20 minutes from zero, then rose to 1.0Mpa pressurize 2.5 hours in 1 minute; Post-treatment condition is 200～245 ℃ and kept 1～5 hour.
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