WO2017092482A1 - 无卤环氧树脂组合物以及含有它的预浸料、层压板和印制电路板 - Google Patents
无卤环氧树脂组合物以及含有它的预浸料、层压板和印制电路板 Download PDFInfo
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- WO2017092482A1 WO2017092482A1 PCT/CN2016/099121 CN2016099121W WO2017092482A1 WO 2017092482 A1 WO2017092482 A1 WO 2017092482A1 CN 2016099121 W CN2016099121 W CN 2016099121W WO 2017092482 A1 WO2017092482 A1 WO 2017092482A1
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- epoxy resin
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- halogen
- resin composition
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Definitions
- the invention belongs to the technical field of copper clad laminates, and particularly relates to a halogen-free epoxy resin composition and a prepreg, a laminate and a printed circuit board containing the same.
- halogen-containing flame retardants especially bromine-based flame retardants
- polymer flame retardant materials have a good flame retardant effect.
- halogen-free flame-retardant printed circuit boards has become the focus of development work in the industry.
- Manufacturers of copper-clad laminates have launched their own halogen-free flame retardants. Copper clad laminate.
- Phosphorus-containing resins are commonly used in the industry to achieve flame retardant effects, but the introduction of excessive phosphorus causes problems such as high water absorption and poor chemical resistance of the substrate.
- Benzooxazine is a kind of benzo six-membered heterocyclic ring system composed of oxygen atom and nitrogen atom. It has the characteristics of ring-opening polymerization, no small molecule release during polymerization, and forms a network structure similar to phenolic resin after polymerization. Low cure shrinkage, low porosity, excellent mechanical, electrical and flame retardant properties.
- CN101684191B proposes to obtain a cured product of lower dielectric constant and dielectric loss by using benzoxazine, styrene-maleic anhydride (SMA), and phosphorus-containing curing agent composite curing epoxy resin, SMA.
- SMA styrene-maleic anhydride
- SMA phosphorus-containing curing agent composite curing epoxy resin
- the polarity of the modified matrix resin weakens the interaction between the resin and the copper foil; meanwhile, because the large amount of benzene ring structure in the SMA increases the brittleness of the resin crosslinked network, it also adversely affects the bonding properties under dynamic conditions. The effect is to reduce the bonding strength between the substrates and the substrate and the copper foil, and with the development of the electronics industry, higher requirements are placed on the heat resistance of the substrate.
- CN100523081C proposes to use a benzoxazine, styrene-maleic anhydride and other curing agents to cure a phosphorus-containing and halogen-free phosphorus-free epoxy composition to obtain a cured product having a lower dielectric constant and dielectric loss, but Phosphorus-containing epoxy as the main resin, although excellent flame retardancy can be achieved, the excessive introduction of phosphorus will inevitably have a great influence on the water absorption of the substrate, which will inevitably have a negative impact on many properties of the substrate.
- CN103131131A proposes a composite curing epoxy resin using benzoxazine, styrene-maleic anhydride and an amine curing agent, which can obtain a cured product having a lower dielectric constant and dielectric loss, and the introduction of an amine curing agent can be Improve the adhesion of the substrate, but it will inevitably lead to a decrease in the heat resistance of the substrate, making it difficult to meet the needs of high-multilayer applications.
- CN 103881302 A provides a resin composition and a copper foil substrate and a printed circuit board using the same.
- the resin composition comprises an epoxy resin, a benzoxazine resin, a styrene maleic anhydride copolymer, And polyester, although polyester has good dielectric properties, polyester is expensive, and the resin composition uses a large amount of benzoxazine, which increases the brittleness of the substrate.
- a halogen-free epoxy resin composition which is controlled in an appropriate range by controlling the amount of benzoxazine and styrene-maleic anhydride (SMA). While maintaining a low dielectric constant and low dielectric loss, the stability of the Df value of the prepreg under different curing temperatures is ensured, and the current benzoxazine and styrene-maleic anhydride cured epoxy resin system Df is overcome. The disadvantage of changing with curing temperature.
- a halogen-free epoxy resin composition comprising the following components in parts by weight:
- Styrene-maleic anhydride 10 to 20 parts by weight 10 to 20 parts by weight.
- the present invention can maintain a low dielectric constant and a low dielectric loss while selecting 15 to 28 parts by weight of a benzoxazine resin and 10 to 20 parts by weight of styrene-maleic anhydride to cure 60 parts by weight of an epoxy resin. It ensures the stability of Df value of prepreg under different curing temperature conditions, and overcomes the shortcomings of current benzoxazine resin and styrene-maleic anhydride curing epoxy resin system Df with curing temperature.
- the benzoxazine resin is useful for improving the flame retardancy, hygroscopicity, heat resistance, mechanical properties and dielectric properties of the cured resin and the substrate it is made of.
- the invention makes the selection of the amount by adding Under the premise of the above properties, the stability of the Df value of the prepreg under different curing temperatures is also ensured, and the current benzoxazine and styrene-maleic anhydride cured epoxy resin system Df is cured. The disadvantage of temperature changes.
- the content of the benzoxazine resin is, for example, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight. Parts, 25 parts by weight, 26 parts by weight, 27 parts by weight or 28 parts by weight.
- the amount of the benzoxazine resin added is less than 15 parts by weight, the Tg and the dielectric properties are not good.
- the amount exceeds 28 parts by weight the brittleness of the substrate increases and the Df value changes depending on the curing temperature, and the stability of the Df value decreases.
- the benzoxazine resin is added in an amount of 20 to 25 parts by weight.
- the styrene-maleic anhydride is added in an amount of, for example, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight or 20 parts by weight.
- styrene-maleic anhydride is advantageous for improving the dielectric properties of the substrate, and the content of styrene-maleic anhydride in the range of 10 to 20 parts by weight allows the halogen-free epoxy resin composition to have Better overall performance.
- the content of the styrene-maleic anhydride is less than 10 parts by weight, the Tg is low and the effect of improving the dielectric properties is not obtained, and if it exceeds 20 parts by weight, the adhesion and flame retardancy of the substrate are deteriorated on the one hand.
- the Df value of the substrate also changes with the curing temperature, and the stability of the Df value decreases.
- the styrene-maleic anhydride is added in an amount of 15 to 18 parts by weight.
- the halogen-free epoxy resin composition comprises the following components in parts by weight:
- Styrene-maleic anhydride 15 to 18 parts by weight.
- the substrate obtained by using the preferred halogen-free epoxy resin composition has a lower Df value and a higher Tg in addition to the above properties.
- the halogen-free epoxy resin composition further comprises a phosphorus-containing flame retardant.
- the phosphorus-containing flame retardant is a phosphorus-containing phenolic aldehyde and a phosphorus-nitrogen based compound.
- the phosphorus-containing flame retardant is 10 to 40 parts by weight of a phosphorus-containing phenolic aldehyde and 10 to 50 parts by weight of a phosphorus-nitrogen-based compound.
- the content of the phosphorus-containing phenolic aldehyde is, for example, 10 parts by weight, 11 parts by weight, 14 parts by weight, 17 parts by weight, 20 parts by weight, 23 parts by weight, 26 parts by weight, 29 parts by weight, 32 parts by weight, 35 parts by weight or 38 parts by weight.
- the phosphorus-containing phenolic aldehyde is less than 10 parts by weight, the flame retardancy is less than the V-0 grade, and when it is more than 40 parts by weight, although the flame retardancy can be ensured, the water absorption of the substrate increases, the Tg decreases, and the base is affected. PCT performance of the material.
- the content of the phosphorus-nitrogen-based compound is, for example, 10 parts by weight, 11 parts by weight, 14 parts by weight, 17 parts by weight, 20 parts by weight, 23 parts by weight, 26 parts by weight, 29 parts by weight, and 32 parts by weight. 35 parts by weight, 38 parts by weight, 41 parts by weight, 44 parts by weight, 47 parts by weight or 49 parts by weight.
- the amount of the phosphorus-nitrogen-based compound added is less than 10 parts by weight, the flame retardancy is not good, and when it exceeds 50 parts by weight, the cost increases, and the glass transition temperature of the substrate decreases.
- the epoxy resin comprises a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a biphenyl epoxy resin, an alkyl novolac epoxy resin, a dicyclopentadiene epoxy resin.
- the benzoxazine resin is selected from any one or a combination of at least two of benzoxazine resins having the following structure:
- R 2 and R 3 are mono- or poly-substituted, R 2 and R 3 are each independently hydrogen, methyl, allyl or aldehyde, and R 1 is -CH 2 -, -O-, -C ( CH 3 ) 2 -, -SO 2 -, -C(CF 3 ) 2 -, -CH 2 CH 2 - or biscyclopentadienyl, or a combination of at least two, each of R 4 and R 5 Independently an allyl group, an unsubstituted or substituted phenyl group, an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms or an unsubstituted or substituted cycloalkyl group or a combination of at least two .
- the styrene-maleic anhydride structural formula is:
- x:n 0.8 to 19:1, preferably 1 to 15:1, further preferably 1 to 12:1.
- the styrene maleic anhydride copolymer has a number average molecular weight of from 1,000 to 50,000, preferably from 1,500 to 45,000, more preferably from 2,000 to 40,000.
- Exemplary styrene-maleic anhydrides are maleic anhydrides such as the trade names SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60, and EF-80.
- the phosphorus-containing phenolic aldehyde is selected from the group consisting of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) modified phenolic resin, 10-(2,5-dihydroxybenzene) 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ) modified phenolic resin or 10-(2,9-dihydroxynaphthyl) 9,10- Any one or a mixture of at least two dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-NQ) modified phenolic resins.
- DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
- the phosphorus-nitrogen-based compound is a compound containing phosphorus and a nitrogen atom, and is preferably a phosphorus-nitrogen-based compound having a structure having a flame retarding function.
- the phosphorus atom of the phosphorus-nitrogen compound forms coke-like phosphoric acid covering the surface of the substrate and blocks air from entering to block combustion.
- n is a positive integer greater than one.
- the addition of the phosphorus-nitrogen-based compound has an advantage in that the flame retardancy of the halogen-free epoxy resin composition and the cured product thereof can be increased.
- the main advantage of the present invention using a phosphorus-nitrogen-based compound as a flame retardant is that the phosphorus-nitrogen-based compound does not have a free hydroxyl group (OH group), and thus addition to the resin composition does not adversely affect the dielectric properties of the resin composition. influences.
- the phosphorus-nitrogen compound also has a high phosphorus content (13%), a thermal cracking temperature of more than 350 ° C, good moisture resistance stability and low moisture absorption. Sexuality is better than the general use of phosphorus-containing flame retardants.
- the present invention may optionally further add a halogen-free flame retardant, which may be a poly Ammonium phosphate, tris(2-carboxyethyl)phosphine, tris(isopropyl chloride) phosphate, trimethyl phosphate, dimethyl-methyl phosphate, resorcinol bis-xylyl phosphate, poly Any one or a combination of at least two of melamine phosphate, melamine cyanurate or tris-hydroxyethyl isocyanurate.
- a halogen-free flame retardant which may be a poly Ammonium phosphate, tris(2-carboxyethyl)phosphine, tris(isopropyl chloride) phosphate, trimethyl phosphate, dimethyl-methyl phosphate, resorcinol bis-xylyl phosphate, poly Any one or a combination of at least two of melamine phosphate, melamine cyanurate or tris-hydroxye
- the halogen-free epoxy resin composition further comprises 20 to 100 parts by weight of a filler.
- the content of the filler is, for example, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, and 75 parts by weight. 80 parts by weight, 85 parts by weight, 90 parts by weight or 95 parts by weight.
- the filler is an organic or/and inorganic filler, which mainly serves to improve dielectric properties, lower thermal expansion coefficient, improve thermal conductivity, and reduce cost.
- the inorganic filler is selected from the group consisting of aluminum hydroxide, aluminum oxide, magnesium hydroxide, magnesium oxide, aluminum oxide, silicon dioxide (including crystalline, molten, spherical silica), calcium carbonate, and nitriding. Any one or a mixture of at least two of aluminum, boron nitride, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite, calcined talc, talc, silicon nitride or calcined kaolin.
- the organic filler is selected from any one of a polytetrafluoroethylene powder, a polyphenylene sulfide or a polyethersulfone powder or a mixture of at least two.
- the filler has a particle diameter of 0.01 to 50 ⁇ m.
- a dispersing agent may be added, and the dispersing agent used is an aminosilane coupling agent or/and an epoxy silane coupling agent for improving inorganic and weaving.
- the bonding property between the reinforcing materials such as glass cloth is achieved, and the purpose of uniform dispersion is achieved.
- such coupling agents are free of heavy metals and do not adversely affect the human body, and are used in an amount of 0.5 to 2% by weight of the filler. If If the amount used is too high, the reaction is accelerated, and the storage time is affected. When the amount is too small, the effect of improving the binding stability is not significantly improved.
- the halogen-free epoxy resin composition further comprises a curing accelerator selected from the group consisting of imidazole accelerators, preferably from 2-methylimidazole, undecylimidazole, 2-ethyl-4- Any one or a combination of at least two of methylimidazole, 2-phenylimidazole or 1-cyanoethyl substituted imidazole.
- a curing accelerator selected from the group consisting of imidazole accelerators, preferably from 2-methylimidazole, undecylimidazole, 2-ethyl-4- Any one or a combination of at least two of methylimidazole, 2-phenylimidazole or 1-cyanoethyl substituted imidazole.
- Comprising as used herein means that in addition to the components, it may include other components which impart different characteristics to the epoxy resin composition.
- the "include” of the present invention may also be replaced by a closed “for” or “consisting of”.
- the epoxy resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These various additives may be used singly or in combination of two or more kinds.
- the epoxy resin composition does not include an amine curing agent. This is mainly because the introduction of the amine curing agent can improve the adhesion of the substrate, but it causes a decrease in the heat resistance of the substrate, and it is difficult to meet the demand for high multi-layer applications.
- a second object of the present invention is to provide a prepreg prepared using the halogen-free epoxy resin composition, the prepreg comprising a reinforcing material and adhering to the reinforcing material by impregnation and drying as described above.
- Halogen free epoxy resin composition is to provide a prepreg prepared using the halogen-free epoxy resin composition, the prepreg comprising a reinforcing material and adhering to the reinforcing material by impregnation and drying as described above.
- the reinforcing material is a non-woven or woven fiberglass cloth or the like.
- a third object of the present invention is to provide a printed circuit board comprising at least one laminated prepreg as described above.
- the present invention also provides a copper clad laminate produced using the prepreg, the copper clad laminate comprising at least one laminated prepreg and a prepreg laminated to the laminate Copper foil on one or both sides.
- Each prepreg includes a reinforcing material and a halogen-free ring attached to the reinforcing material after being impregnated and dried. Oxygen resin composition.
- the present invention has the following beneficial effects:
- the present invention can maintain a low dielectric constant and a low dielectric loss by selecting 15 to 28 parts by weight of a benzoxazine resin and 10 to 20 parts by weight of styrene-maleic anhydride to cure 60 parts by weight of an epoxy resin. At the same time, the stability of the Df value of the prepreg under different curing temperature conditions is ensured, and the shortcomings of the current benzoxazine resin and the styrene-maleic anhydride curing epoxy resin system Df change with the curing temperature are overcome.
- the invention uses a benzoxazine resin having a flame retarding function as a curing agent, and simultaneously adding a phosphorus-containing phenolic aldehyde and a phosphorus-nitrogen compound having a low water absorption rate to achieve a synergistic flame-retarding effect of phosphorus and nitrogen, and simultaneously improving the phosphorus content of the component while greatly reducing The flame retardancy of the substrate is improved, and the substrate has good moisture resistance.
- Prepreg and laminate prepared using the resin composition having a low dielectric constant (1 GHz, ⁇ 3.9), low dielectric loss, excellent flame retardancy (V-0 or V-1), heat resistance (Tg , DSC, ⁇ 178 ° C), adhesion (peel strength ⁇ 1.25 N / mm), low water absorption ( ⁇ 0.36%) and excellent moisture resistance and other comprehensive properties, overcoming the current halogen-free laminate dielectric constant bias Low heat resistance, poor heat resistance and poor moisture resistance are suitable for use in halogen-free high-multilayer boards.
- the peel strength, glass transition temperature, flame retardancy, wettability resistance, water absorption rate, and water absorption rate of the cured substrate under the 200 ° C curing process for 120 min were tested.
- the electrical constants were tested for dielectric loss performance at different curing temperatures, as further illustrated and described in the following examples.
- the epoxy resin, benzoxazine, styrene-maleic anhydride, phosphorus-containing phenolic aldehyde, phosphorus-nitrogen-based compound, filler and other auxiliary agents are placed in a container, stirred and uniformly mixed to prepare a glue, and adjusted with a solvent.
- the solution solid content is from 60% by weight to 70% by weight to prepare a glue, that is, the resin composition of the present invention is obtained.
- the electronic grade fiberglass cloth is impregnated with glue, baked into a prepreg through an oven, and 6 sheets of 2116 prepreg are taken, and double-sided 35 ⁇ m thick electrolytic copper foil is applied on the hot press for vacuum lamination, and the selected curing procedures are respectively
- the copper clad laminate was prepared by curing at 190 ° C, 200 ° C and 210 ° C for 120 min.
- Example 1 It can be seen from Example 1 and Examples 2, 7, and 8 that the curing agent optimized formulation has a lower Df value and a higher Tg.
- the curing agent-optimized formulation has a lower Tg but a higher peel strength and a lower water absorption ratio, that is, from Examples 1-3, 7, and 8. It can be seen that the curing agent optimized formulation has better overall performance.
- Example 2 By comparing Example 2 and Examples 4 and 9, it can be seen that although the Tg is slightly decreased after the addition of the phosphorus-containing phenolic aldehyde and the phosphorus-nitrogen-based compound, the flame retardancy can be ensured to be V-0 and has little effect on other properties, and the filler is added. Base Material performance has little effect.
- Example 4 and Comparative Example 1-2 that the benzoxazine has a low Tg at less than 15 parts by weight and a poor dielectric property, and a higher Tg than 28 parts by weight.
- the processability is poor and Df is unstable, and increases as the curing temperature increases.
- Example 5 it can be seen from Example 5 and Comparative Examples 3-4 that when the styrene-maleic anhydride is less than 10 parts by weight, the Tg is insufficient, the dielectric loss performance is poor, and the workability of the substrate is affected, and when it is more than 20 parts by weight, Although the Tg can be increased but the flame retardancy is insufficient, the water absorption rate increases and the Df is unstable, and increases as the curing temperature increases.
- Example 6 It can be seen from Example 6 and Comparative Examples 5-6 that the flame retardancy of the phosphorus-containing phenolic aldehyde is less than the V-0 grade when it is less than 10 parts by weight, and the flame retardancy is ensured when it is more than 40 parts by weight, but it is based on The water absorption of the material increases, the Tg decreases, and the PCT properties of the substrate are affected.
- Example 5 and Comparative Examples 7-8 that the flame retardancy of the phosphorus-nitrogen compound is less than V-0 when it is less than 10 parts by weight, and the flame retardancy is ensured when it is more than 50 parts by weight, but it will be The substrate Tg is lowered and affects the PCT properties and processability of the substrate.
- Comparative Example 9 is Example 4 disclosed in CN 101684191B.
- Comparative Example 10 is Example 1 disclosed in CN103131131A.
- Comparative Example 11 is Example 2 disclosed in CN 103881302A.
- the laminate prepared by using the halogen-free resin composition of the present invention has good dielectric properties, and the dielectric loss value does not change with the increase of the curing temperature, and the flame retardancy test is achieved.
- the V-0 standard in UL-94 therefore, the laminate has a low dielectric constant, low dielectric loss, excellent heat resistance, adhesion and moisture resistance while ensuring halogen-free flame retardant.
- the combined performance overcomes the shortcomings of the current halogen-free laminates such as high dielectric constant, insufficient heat resistance and poor moisture resistance, and is suitable for use in a halogen-free high-multilayer circuit board.
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Abstract
Description
Claims (12)
- 一种无卤环氧树脂组合物,其按重量份数包括如下组分:环氧树脂 60重量份苯并噁嗪树脂 15~28重量份苯乙烯-马来酸酐 10~20重量份。
- 如权利要求1所述的无卤环氧树脂组合物,其特征在于,所述苯并噁嗪树脂的添加量为20-25重量份。
- 如权利要求1所述的无卤环氧树脂组合物,其特征在于,所述苯乙烯-马来酸酐的添加量为15~18重量份。
- 如权利要求1所述的无卤环氧树脂组合物,其特征在于,所述无卤环氧树脂组合物,其按重量份数包括如下组分:环氧树脂 60重量份苯并噁嗪树脂 20~25重量份苯乙烯-马来酸酐 15~18重量份;
- 如权利要求1-3之一所述的无卤环氧树脂组合物,其特征在于,所述无卤环氧树脂组合物还包括含磷阻燃剂;优选地,所述含磷阻燃剂为含磷酚醛和磷氮基化合物;优选地,所述含磷阻燃剂为10~40重量份的含磷酚醛和10~50重量份的磷氮基化合物。
- 如权利要求1-5之一所述的无卤环氧树脂组合物,其特征在于,所述环氧树脂包括双酚A型环氧树脂、双酚F型环氧树脂、联苯环氧树脂、烷基酚醛环氧树脂、双环戊二烯环氧树脂、双酚A型酚醛环氧树脂、邻甲酚型酚醛环氧树脂、苯酚型酚醛环氧树脂、四官能环氧树脂、异氰酸酯改性环氧树脂、萘型环氧树脂或含磷环氧树脂中的任意一种或者至少两种的混合物;优选地,所述苯并噁嗪树脂选自具有如下结构的苯并噁嗪树脂中的任意一种或者至少两种的组合:其中,R2和R3为单取代或多取代,R2和R3各自独立地为氢、甲基、烯丙基或醛基,R1为-CH2-、-O-、-C(CH3)2-、-SO2-、-C(CF3)2-、-CH2CH2-或双环戊二烯基中的任意一种或者至少两种的组合,R4和R5各自独立地为烯丙基、未取代或取代的苯基、未取代或取代的碳原子数为1-8的烷基或未取代或取代的环烷基中的任意一种或者至少两种的组合;优选地,所述苯乙烯-马来酸酐结构式为:其中,x∶n=0.8~19∶1,优选1~15∶1,进一步优选1~12∶1;优选地,所述苯乙烯马来酸酐共聚物的数均分子量为1000~50000,优选1500~45000,进一步优选2000~40000。
- 如权利要求1-7之一所述的无卤环氧树脂组合物,其特征在于,所述无卤环氧树脂组合物还包括无卤阻燃剂,所述无卤阻燃剂为聚磷酸铵、三(2-羧乙基)膦、三(异丙基氯)磷酸盐、三甲基磷酸盐、二甲基-甲基磷酸盐、间苯二酚双二甲苯基磷酸盐、聚磷酸三聚氰胺、三聚氰胺氰尿酸酯或三-羟乙基异氰尿酸酯中的任意一种或者至少两种的组合。
- 如权利要求1-8之一所述的无卤环氧树脂组合物,其特征在于,所述无卤环氧树脂组合物还包括20~100重量份的填料;优选地,所述填料为有机或/和无机填料;优选地,所述无机填料选自氢氧化铝、氧化铝、氢氧化镁、氧化镁、三氧化二铝、二氧化硅、碳酸钙、氮化铝、氮化硼、碳化硅、二氧化钛、氧化锌、氧化锆、云母、勃姆石、煅烧滑石、滑石粉、氮化硅或煅烧高岭土中的任意一种或者至少两种的混合物;优选地,所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少两种的混合物;优选地,填料的粒径为0.01~50μm;优选地,所述无卤环氧树脂组合物包含固化促进剂,所述固化促进剂选自咪唑类促进剂,优选自2-甲基咪唑、十一烷基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或1-氰乙基取代咪唑中的任意一种或者至少两种的组合。
- 一种预浸料,其包括增强材料及通过含浸干燥后附着在增强材料上的如权利要求1-9之一所述的无卤环氧树脂组合物。
- 一种层压板,其包括至少一张叠合的如权利要求10所述的预浸料。
- 一种印制电路板,其包括至少一张叠合的如权利要求10所述的预浸料。
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