WO2015149449A1 - 一种无卤树脂组合物及其用途 - Google Patents
一种无卤树脂组合物及其用途 Download PDFInfo
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- WO2015149449A1 WO2015149449A1 PCT/CN2014/082419 CN2014082419W WO2015149449A1 WO 2015149449 A1 WO2015149449 A1 WO 2015149449A1 CN 2014082419 W CN2014082419 W CN 2014082419W WO 2015149449 A1 WO2015149449 A1 WO 2015149449A1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
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Classifications
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Definitions
- the present invention relates to a halogen-free resin composition and a prepreg and laminate using the same, which have low dielectric constant, low dielectric loss factor, low water absorption, high dimensional stability, high heat resistance, and Good flame retardancy, processability and chemical resistance.
- BACKGROUND OF THE INVENTION Conventional laminates for printed circuit boards generally use brominated flame retardants to achieve flame retardancy, in particular, tetrabromobisphenol A type epoxy resin, which has good flame retardancy, but It produces hydrogen bromide gas when burned.
- the application frequency is increasing.
- the dielectric constant and dielectric loss values are required to be lower and lower. Reducing Dk/Df has become a hot spot for substrate manufacturers.
- Conventional FR-4 materials use dicyandiamide as a curing agent. This curing agent has a tertiary reaction amine and has good process operability. However, due to its weak CN bond, it is easily cracked at high temperatures, resulting in a cured product. The thermal decomposition temperature is low and cannot meet the heat resistance requirements of the lead-free process.
- phenolic resin was used as a curing agent for epoxy in the industry.
- the phenolic resin has a high-density benzene ring structure, so the heat resistance of the system after curing with epoxy resin Excellent, but at the same time the dielectric properties of the cured product have deteriorated
- Japanese Patent Laid-Open No. 2002-012650, 2003-082063 proposes to synthesize a series of active ester curing agents containing a benzene ring, a naphthalene ring or a biphenyl structure as a curing agent for an epoxy resin such as IAAN, IABN, TriABN, yttrium.
- Japanese Patent Laid-Open No. 2003-252958 proposes that a biphenyl-type epoxy resin cured with an active ester can obtain a cured product having a lower dielectric constant and a dielectric loss value, but since the epoxy resin is a difunctional epoxy resin, with an active ester The crosslink density is low, and the cured product has a low glass transition temperature and poor heat resistance.
- Japanese Patent Laid-Open No. 2004-155990 uses a reaction of an aromatic carboxylic acid with an aromatic phenol to prepare a polyfunctional active ester curing agent. The active ester curing agent can be used to cure the phenolic epoxy to obtain better dielectric properties and higher heat resistance. Sexual cured product.
- Japanese Patent Laid-Open No. 2009-040919 proposes a thermosetting resin composition having excellent adhesion and stable dielectric constant, and the main components include an epoxy resin, an active ester curing agent, a curing accelerator, an organic solvent, and an epoxy resin. The amount of resin and active ester used.
- Japanese Patent Laid-Open No. 2009-242559, JP-A-2009-242560, JP-A-2010-077344, and JP-A-2010-077343 respectively propose to cure an alkylated phenol or an alkylated naphthol novolac type epoxy resin with an active ester, respectively.
- a benzene type epoxy resin can obtain a cured product having low hygroscopicity, low dielectric constant, and dielectric loss.
- the present invention provides a halogen-free resin composition, and a prepreg and a laminate using the same.
- the laminate for printed circuit board prepared using the resin composition has low dielectric constant, low dielectric loss factor, low water absorption, high dimensional stability, high heat resistance, high storage modulus, high bending strength, and high Peel strength as well as good flame retardancy, processability and chemical resistance.
- the present invention adopts the following technical solutions:
- a halogen-free resin composition comprising, based on 100 parts by weight of total organic solids of (A), (B), (C) and (D), comprising:
- the inventors conducted intensive studies and found that: by mixing a dicyclopentadiene type benzoxazine with an epoxy resin, an active ester curing agent, a phosphorus-containing flame retardant, and other optional substances.
- the resulting composition achieves the above object.
- the component (A) in the present invention can provide a low dielectric constant, a low dielectric loss factor, and a moisture resistance required for the cured resin and the laminate thereof.
- Properties, dimensional stability, heat resistance, flame retardancy and mechanical properties preferably used in an amount of 10 to 60 parts by weight, such as 13 parts by weight, 16 parts by weight, 19 parts by weight, 22 parts by weight, 25 parts by weight, 28 parts by weight, 31 parts by weight, 34 parts by weight, 37 parts by weight, 40 parts by weight, 43 parts by weight, 46 parts by weight, 49 parts by weight, 52 parts by weight, 55 parts by weight or 58 parts by weight.
- the content of the component (A) dicyclopentadiene type benzoxazine resin is 10 to 30 parts by weight, for example, 12 parts by weight, 14 parts by weight, 16 Parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight or 28 parts by weight, at this time, component (A) dicyclopentadiene type benzoxazine resin as epoxy resin It is used as a curing agent, which can significantly reduce the dielectric constant and dielectric loss of the cured product and maintain good toughness of the cured product.
- the content of the component (A) dicyclopentadiene type benzoxazine resin is 30 to 60 parts by weight, for example, 32 parts by weight, 34 parts by weight, 36 Weight , 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 54 parts by weight, 56 parts by weight or 58 parts by weight, at this time,
- the (A) dicyclopentadiene type benzoxazine resin is used as a host resin, which can further reduce the dielectric constant, dielectric loss factor and water absorption rate of the cured product and increase the rigidity and storage modulus of the cured product.
- the component (A) dicyclopentadiene type benzoxazine resin has the following structure:
- the epoxy resin of the component (B) is an epoxy resin having an epoxy equivalent of 150 to 550 g/mol, and the epoxy equivalent is, for example, 180 g/mol. 210 g/mol, 240 g/mol, 270 g/mol, 300 g/mol, 330 g/mol, 360 g/mol, 390 g/mol, 420 g/mol, 450 g/mol, 480 g/mol, 510 g/mol or 540 g/mol.
- the component (B) epoxy resin is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol type novolac epoxy resin, double Phenolic A type phenolic epoxy resin, o-cresol novolac epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, phenol aralkyl self-flame retardant epoxy resin (Xylok type epoxy resin) or At least any one or a mixture of at least two of biphenyl type epoxy resins is preferably a dicyclopentadiene type epoxy resin.
- X is a benzene ring or a naphthalene ring
- j is 0 or 1
- k is 0 or 1
- n represents an average repeating unit of 0.25 to 1.25.
- the component (C) active ester curing agent is added in an amount of 5 to 35 parts by weight, for example, 6 parts by weight, 8 parts by weight, 10 parts by weight, and 12 parts by weight.
- the component (D), that is, the phosphorus-containing flame retardant, in the present invention provides the resin composition with flame retardant properties and meets the requirements of UL 94V-0.
- the amount of the flame retardant added is not particularly limited as long as the flame retardancy of the cured product reaches the UL 94V-0 level, and it is preferable that the phosphorus-containing flame retardant is added in the component (A), the component (B), and 5 to 100% by weight of the sum of the addition amounts of the component (C), for example, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, and 45% by weight, 50% by weight, 555% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight or 95% by weight, preferably 5 to 50% by weight.
- the phosphorus-containing flame retardant is tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9 , 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene or 10-phenyl-9,10- Any one or a mixture of at least two of dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenoxyphosphazene compound, phosphate or polyphosphate.
- the resin-free composition further includes
- the curing accelerator which cures the resin and accelerates the curing speed of the resin.
- the curing accelerator is an imidazole curing accelerator or/and a pyridine curing accelerator, and more preferably 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-H ⁇ - Any one or a mixture of at least two of alkylimidazole, triethylamine, benzyldimethylamine or dimethylaminopyridine.
- the curing accelerator is added in an amount of 0.05 to 1% by weight, for example, 0.08 wt%, 0.1 wt%, 0.2 wt%, of the sum of the components (A), (B), (C), and (D). 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight or 0.9% by weight.
- the resin-free composition further includes
- (F) Filler mainly used to adjust some physical properties of the composition, such as lowering the coefficient of thermal expansion (CTE), reducing water absorption, and improving thermal conductivity.
- the filler is an organic or inorganic filler.
- the inorganic filler is selected from the group consisting of silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, and titanic acid.
- 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 is silica.
- the median diameter of the filler is
- the filler located in this particle size segment has good dispersibility.
- the filler is added in an amount of 0 to 300% by weight of the sum of the components (A), ( ⁇ ), (C) and (D), excluding 0, for example, 0.08 wt%, 0.1 wt%, 0.2 wt. %, 0.3% by weight, 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 60% by weight, 90% by weight, 120% by weight, 150% by weight, 180% by weight, 210% by weight, 240% by weight, 260% by weight, 270% by weight, 280% by weight, 290% by weight or 295% by weight, preferably 0 to 50% by weight.
- the halogen-free resin composition may further contain various additives, and specific examples thereof include a flame retardant, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant or a lubricant. Wait. These various additives may be used singly or in combination of two or more kinds.
- Another object of the present invention is to provide a resin glue obtained by dissolving or dispersing a halogen-free resin composition as described above in a solvent.
- the conventional preparation method of the resin composition of the present invention is as follows: first, the solid matter is placed, and then the liquid solution is added. The agent is stirred until the solid matter is completely dissolved, and then the liquid resin and the accelerator are added, and the stirring is continued uniformly. Finally, the solid content of the solution is adjusted to 65 to 75% with a solvent to prepare a glue, that is, the halogen-free resin composition glue. liquid.
- the solvent in the present invention is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, and butyl.
- Ethers such as carbitol, ketones such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and mesitylene, ethoxylate
- An ester such as ethyl acetate or ethyl acetate; a nitrogen-containing solvent such as hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide or hydrazine-methyl-2-pyrrolidone.
- solvents may be used singly or in combination of two or more.
- aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, and acetone, butanone, methyl ethyl ketone, and methyl group.
- a ketone flux such as butyl ketone or cyclohexanone is used in combination.
- a third object of the present invention is to provide a prepreg comprising a reinforcing material and a halogen-free resin composition as described above adhered to the reinforcing material by impregnation and drying.
- the prepreg has low dielectric constant, low dielectric loss factor, low water absorption, high dimensional stability, high heat resistance, high storage modulus, high bending strength, high peel strength, and good flame retardancy. , processability and chemical resistance.
- the prepreg of the present invention is obtained by heat drying using the above halogen-free resin composition, and the reinforcing material used is a non-woven fabric or other fabric such as natural fibers, organic synthetic fibers, and inorganic fibers.
- the prepreg is obtained by heating and drying the impregnated glass cloth in an oven at 155 ° C for 5 to 8 minutes using a fabric or an organic fabric such as a glass cloth impregnated with the above-mentioned glue.
- a fourth object of the present invention is to provide a laminate comprising at least one prepreg as described above.
- the laminate has low dielectric constant, low dielectric loss factor, low water absorption, high dimensional stability, high heat resistance, high storage modulus, high bending strength, high peel strength, and good flame retardancy. Processability and chemical resistance. Compared with the prior art, the present invention has the following beneficial effects:
- the halogen-free resin composition of the present invention employs a dicyclopentadiene type benzoxazine resin having a dicyclopentadiene structure, in addition to having a high glass transition temperature of a conventional benzoxazine
- Tg low water absorption
- high dimensional stability low thermal expansion coefficient
- good heat resistance and flame retardancy etc.
- excellent dielectric properties The inclusion of the benzoxazine resin in the epoxy resin can not only reduce the cured product.
- the dielectric constant, the dielectric loss value, and the water absorption rate can also increase the storage modulus and bending strength of the cured product, and maintain the adhesive strength without decreasing; the benzoxazine and the phosphorus-containing flame retardant have a synergistic flame retardant effect,
- the flame retardancy of the cured product is reduced to the phosphorus content required by UL 94V-0, and the water absorption rate is further reduced.
- the halogen-free resin composition of the present invention uses the active ester as a curing agent to fully exert the reaction of the active ester and the epoxy resin without generating a pole.
- the group has excellent dielectric properties and good heat and humidity resistance.
- the prepreg and printed circuit board made of the resin composition have low dielectric constant, low dielectric loss factor, low water absorption, High heat resistance, high dimensional stability, high peel strength, high storage modulus, high flexural strength, and good flame retardancy, processability, and chemical resistance.
- Spherical silicon micropowder (average particle size 1 to ⁇ , purity 99% or more)
- the resin composition is prepared by first placing the solid matter, then adding the liquid solvent, stirring until the solid matter is completely dissolved, adding the liquid resin and the accelerator, and continuing to stir evenly, and finally adjusting the solid content of the solution with the solvent to 65%-75% is made into a glue, that is, the glue of the halogen-free resin composition is obtained, and the fabric or organic fabric such as glass cloth is impregnated with the glue, and the impregnated glass cloth is dried by heating in an oven at 155 ° C. Prepreg is made in 5-8 minutes.
- the lamination must meet the following requirements Requirements: 1 The heating rate of the lamination should be controlled at 1.5-2.5 °C/min at the material temperature of 80-120 °C ; 2 the pressure setting of the lamination, the outer layer temperature should be applied at 120-150 °C, The full pressure is about 350 psi; 3 When curing, the temperature of the material is controlled at 190 ° C and held for 90 min.
- the metal foil is copper foil, nickel foil, aluminum foil, SUS foil, etc., and the material thereof is not limited.
- the laminate for printed circuit (10 prepregs) prepared above was tested for its glass transition temperature, dielectric constant, dielectric loss factor, water absorption, heat resistance, flame retardancy, etc., as shown in Table 1. Shown.
- Tg Glass transition temperature: Measured according to differential scanning calorimetry (DSC) according to the DSC method specified in IPC-TM-650 2.4.25.
- the dielectric loss and dielectric loss at 1 GHz were measured in accordance with IPC-TM-650 2.5.5.5.
- the measurement was carried out according to the IPC-TM-650 2.4.4 method, and the load was applied to a sample of a predetermined size and shape at room temperature.
- the stratified foaming time was observed in accordance with IPC-TM-650 2.4.13.1.
- Example 1-4 is a laminate obtained by co-curing a dicyclopentadiene-type benzoxazine resin with an epoxy resin or an active ester curing agent, and the resulting dielectric properties and water absorbability of the laminate.
- the storage modulus and flexural strength were greatly improved, and the peel strength did not decrease.
- Comparative Example 1 the dicyclopentadiene type epoxy resin and the active ester curing agent were used for curing, and the peeling strength was high, the dielectric properties were general, the water absorption rate was high, and the storage modulus and bending strength were low; After PPO, the dielectric properties and water absorption were greatly improved, but the peel strength, storage modulus and flexural strength were impaired; in Comparative Example 3, bisphenol A type oxazine was used as the main resin, and in Comparative Example 4, bisphenol was used.
- a type of oxazine and an active ester co-cured epoxy resin in Comparative Example 5, a linear phenolic resin was used instead of an active ester to cure a dicyclopentadiene type benzoxazine and an epoxy resin, and in Comparative Example 6, dicyandiamide was used instead of an active ester to cure.
- Dicyclopentadiene type benzoxazine and epoxy resin the dielectric properties of the board were significantly deteriorated, and the water absorption, storage modulus and heat resistance of Comparative Example 6 also deteriorated; Comparative Examples 7 and 8 respectively used nitrogen.
- the flame retardancy of the plate is poor, only V-1 grade; Comparative Example 9 uses biscyclopentadiene benzoxazine and active ester co-cured epoxy tree
- the grease has no filler, and the peel strength of the sheet is improved, but the storage modulus and flame retardancy are poor.
- the laminate for printed circuit of the present invention has superior dielectric properties, moisture resistance, dimensional stability, and peel strength as compared with a general halogen-free laminate, and is suitable for use in a high-density interconnection field.
- the invention fully utilizes the synergistic properties of the benzoxazine resin and the phosphorus-containing flame retardant, and the halogen content can reach the V-0 standard in the flame retardancy test UL94 within the requirements of the JPCA halogen-free standard, and has an environmental protection effect.
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Abstract
本发明公开了一种无卤树脂组合物，以（A）、（B）、（C）和（D）总有机固形物总量100重量份计，其包含（A）双环戊二烯型苯并噁嗪树脂，10～60 重量份；（B）环氧树脂；（C）活性酯固化剂；（D）含磷阻燃剂。采用上述无卤树脂组合物制成的预浸料及层压板，具有低介电常数、低介电损耗因素、低吸水率、高尺寸稳定性、高耐热性以及良好的阻燃性、加工性能、耐化学性。
Description
说 明 书 一种无卤树脂组合物及其用途
技术领域 本发明涉及一种无卤树脂组合物以及使用它的预浸料和层压板， 其具有低 介电常数、 低介电损耗因素、 低吸水率、 高尺寸稳定性、 高耐热性以及良好的 阻燃性、 加工性能、 耐化学性。 背景技术 传统的印制电路用层压板通常采用溴系阻燃剂来实现阻燃， 特别是采用四 溴双酚 A型环氧树脂， 这种溴化环氧树脂具有良好的阻燃性， 但它在燃烧时会 产生溴化氢气体。 此外， 近年来在含溴、 氯等卤素的电子电气设备废弃物的燃 烧产物中已检测出二噁英、 二苯并呋喃等致癌物质， 因此溴化环氧树脂的应用 受到限制。 2006年 7月 1 日， 欧盟的两份环保指令《关于报废电气电子设备指 令》 和 《关于在电气电子设备中限制使用某些有害物质指令》 正式实施， 无卤 阻燃覆铜箔层压板的开发成为业界的热点， 各覆铜箔层压板厂家都纷纷推出自 己的无卤阻燃覆铜箔层压板。
随着电子产品信息处理的高速化和多功能化， 应用频率不断提高， 除了对 层压板材料的耐热性有更高的要求外， 要求介电常数和介电损耗值越来越低， 因此降低 Dk/Df已成为基板业者的追逐热点。 传统的 FR-4材料多采用双氰胺作 为固化剂， 这种固化剂具有三级反应胺， 具有良好的工艺操作性， 但由于其 C-N键较弱， 在高温下容易裂解， 导致固化物的热分解温度较低， 无法满足无 铅制程的耐热要求。 在此背景下， 随着 2006 年无铅工艺的大范围实施， 行内 开始采用酚醛树脂作为环氧的固化剂， 酚醛树脂具有高密度的苯环结构， 所以 和环氧树脂固化后体系的耐热性优异， 但同时固化物的介电性能有被恶化的趋
日本专利特开 2002-012650， 2003-082063提出了合成一系列含有苯环、 萘 环或联苯结构的活性酯固化剂作为环氧树脂的固化剂如 IAAN、 IABN、 TriABN、 ΤΑΑΝ, 得到的固化物与传统酚醛相比有较低的介电常数和介电损耗 值。 日本专利特开 2003-252958提出用活性酯固化联苯型环氧树脂可以得到介 电常数和介电损耗值较低的固化物， 但由于环氧树脂为二官能环氧树脂， 与活 性酯的交联密度低， 固化物的玻璃化转变温度较低、 耐热性较差。 日本专利特 开 2004-155990采用芳香羧酸与芳香酚反应制得一种多官能的活性酯固化剂， 使用该活性酯固化剂固化酚醛型环氧可以得到较好介电性能、 较高耐热性的固 化物。 日本专利特开 2009-040919提出一种粘合力优异、 介电常数稳定的热固 性树脂组合物， 主要组分包括环氧树脂、 活性酯固化剂、 固化促进剂、 有机溶 剂， 并研究了环氧树脂和活性酯的用量。 此外， 日本专利特开 2009-242559、 特开 2009-242560、 特开 2010-077344、 特开 2010-077343分别提出用活性酯固 化烷基化苯酚或烷基化萘酚酚醛型环氧树脂、 联苯型环氧树脂， 可以得到低吸 湿性、 低介电常数和介电损耗的固化物。
以上现有专利都提出了使用活性酯固化剂固化环氧树脂可以降低固化物介 电常数、 介电损耗因素、 吸水率， 其缺点是难在保持粘合力不下降的前提下进 一步降低介电常数、 介电损耗值和吸水率并提高储能模量和弯曲强度。
发明内容
针对已有技术中的问题， 本发明的目的在于提供一种无卤树脂组合物， 以 及使用它的预浸料和层压板。 使用该树脂组合物制备的印制电路用层压板具有 低介电常数、 低介电损耗因素、 低吸水率、 高尺寸稳定性、 高耐热性、 高储能 模量、 高弯曲强度、 高剥离强度以及良好的阻燃性、 加工性能和耐化学性。
为了达到上述目的， 本发明采用了如下技术方案：
一种无卤树脂组合物， 以 （A) 、 (B ) 、 (C ) 和 （D ) 总有机固形物总 量 100重量份计， 其包含：
(A) 双环戊二烯型苯并噁嗪树脂， 10到 60重量份；
(B ) 环氧树脂；
(C) 活性酯固化剂；
(D) 含磷阻燃剂。
为实现上述目的， 本发明人进行了反复深入的研究， 结果发现： 通过将双 环戊二烯型苯并噁嗪与环氧树脂、 活性酯固化剂、 含磷阻燃剂及其他可选物质 混合得到的组合物， 可达到上述目的。
本发明中的组分 （A) ， 即双环戊二烯型苯并噁嗪树脂， 其可以提供固化 后树脂及其制成的层压板所需的低介电常数、 低介电损耗因素、 耐湿性、 尺寸 稳定性、 耐热性、 阻燃性能以及力学性能， 使用量建议为 10 到 60 重量份为 宜， 例如 13重量份、 16重量份、 19重量份、 22重量份、 25重量份、 28重量 份、 31重量份、 34重量份、 37重量份、 40重量份、 43重量份、 46重量份、 49 重量份、 52重量份、 55重量份或 58重量份。
优选地， 在本发明提供的技术方案的基础上， 所述组分 （A) 双环戊二烯 型苯并噁嗪树脂的含量为 10〜30重量份， 例如 12重量份、 14重量份、 16重量 份、 18重量份、 20重量份、 22重量份、 24重量份、 26重量份或 28重量份， 此时， 组分 （A) 双环戊二烯型苯并噁嗪树脂作为环氧树脂的固化剂使用， 其 能明显降低固化物介电常数、 介电损耗因素并使固化物保持较好的韧性。
优选地， 在本发明提供的技术方案的基础上， 所述组分 （A) 双环戊二烯 型苯并噁嗪树脂的含量为 30〜60重量份， 例如 32重量份、 34重量份、 36重量
份、 38重量份、 40重量份、 42重量份、 44重量份、 46重量份、 48重量份、 50 重量份、 52重量份、 54重量份、 56重量份或 58重量份， 此时， 组分 （A) 双 环戊二烯型苯并噁嗪树脂作为主体树脂使用， 能进一步降低固化物介电常数、 介电损耗因素及吸水率并提高固化物的刚性和储能模量。
优选地， 在本发明提供的技术方案的基础上， 所述组分 （A) 双环戊二烯 型苯并噁嗪树脂具有如下结构：
优选地， 在本发明提供的技术方案的基础上， 所述组分（B )环氧树脂为环 氧当量为 150〜550g/mol 的环氧树脂， 所述环氧当量例如为 180g/mol、 210g/mol、 240g/mol、 270g/mol、 300g/mol、 330g/mol、 360g/mol、 390g/mol、 420g/mol、 450g/mol、 480g/mol、 510g/mol或 540g/mol。
优选地， 在本发明提供的技术方案的基础上， 所述组分（B )环氧树脂选自 双酚 A型环氧树脂、 双酚 F型环氧树脂、 苯酚型酚醛环氧树脂、 双酚 A型酚酸 环氧树脂、 邻甲酚酚醛环氧树脂、 双环戊二烯型环氧树脂、 异氰酸酯型环氧树 脂、 苯酚芳烷基自阻燃环氧树脂 （Xylok型环氧树脂） 或联苯型环氧树脂中的 至少任意一种或者至少两种的混合物， 优选双环戊二烯型环氧树脂。
其中， X为苯环或萘环， j为 0或 1， k为 0或 1， n表示平均重复单元为 0.25〜1.25。
优选地， 在本发明提供的技术方案的基础上， 所述组分（C)活性酯固化剂 的添加量为 5〜35重量份， 例如 6重量份、 8重量份、 10重量份、 12重量份、 14重量份、 16重量份、 18重量份、 20重量份、 22重量份、 24重量份、 26重 量份、 28重量份、 30重量份、 32重量份、 34重量份。
优选地， 在本发明提供的技术方案的基础上， 本发明中所述组分 （D ) ， 即含磷阻燃剂， 使树脂组合物具有阻燃特性， 符合 UL 94V-0要求。 阻燃剂的 添加量根据固化物阻燃性达到 UL 94V-0级别要求而定， 并没有特别的限制， 优选含磷阻燃剂的添加量是组分 （A) 、 组分 （B ) 和组分 （C) 的添加量之和 的 5〜100重量％， 例如 10重量％、 15重量％、 20重量％、 25重量％、 30重 量％、 35重量％、 40重量％、 45重量％、 50重量％、 55重量％、 60重量％、 65 重量％、 70重量％、 75重量％、 80重量％、 85重量％、 90重量％或95重量％， 优选 5〜50重量％。
优选地， 在本发明提供的技术方案的基础上， 所述含磷阻燃剂为三 (2， 6- 二甲基苯基)膦、 10-(2,5-二羟基苯基) -9,10-二氢 -9-氧杂 -10-膦菲 -10-氧化物、 2,6-二 (2,6-二甲基苯基)膦基苯或 10-苯基 -9,10-二氢 -9-氧杂 -10-膦菲 -10-氧化物、 苯氧基磷腈化合物、 磷酸酯或聚磷酸酯中的任意一种或者至少两种的混合物。
优选地， 在本发明提供的技术方案的基础上， 所述无 ^树脂组合物还包括
(E)固化促进剂， 其可以使树脂固化并加快树脂固化速度。 所述固化促进剂为 咪唑类固化促进剂或 /和吡啶类固化促进剂， 进一步优选 2-甲基咪唑、 2-乙基 —4-甲基咪唑、 2-苯基咪唑、 2-H ^—烷基咪唑、 三乙胺、 苄基二甲胺或二甲氨基 吡啶中的任意一种或者至少两种的混合物。
所述固化促进剂的添加量为组分 （A) 、 (B ) 、 (C) 和 （D) 添加量之 和的 0.05〜1重量％， 例如 0.08重量％、 0.1重量％、 0.2重量％、 0.3重量％、 0.4 重量％、 0.5重量％、 0.6重量％、 0.7重量％、 0.8重量％或0.9重量％。
优选地， 在本发明提供的技术方案的基础上， 所述无 ^树脂组合物还包括
(F)填料， 主要用来调整组合物的一些物性效果， 如降低热膨胀系数（CTE)、 降低吸水率、 提高热导率等。
优选地， 在本发明提供的技术方案的基础上， 所述填料为有机或无机填 料。
优选地， 在本发明提供的技术方案的基础上， 所述无机填料选自二氧化 硅、 氢氧化铝、 氧化铝、 滑石粉、 氮化铝、 氮化硼、 碳化硅、 硫酸钡、 钛酸 钡、 钛酸锶、 碳酸钙、 硅酸钙、 云母或玻璃纤维粉中的任意一种或者至少两种 的混合物， 优选熔融二氧化硅、 结晶型二氧化硅、 球型二氧化硅、 空心二氧化 硅、 氢氧化铝、 氧化铝、 滑石粉、 氮化铝、 氮化硼、 碳化硅、 硫酸钡、 钛酸 钡、 钛酸锶、 碳酸钙、 硅酸钙、 云母或玻璃纤维粉中的任意一种或者至少两种 的混合物， 所述混合物例如结晶型二氧化硅和无定形二氧化硅的混合物， 球形 二氧化硅和二氧化钛的混合物， 钛酸锶和钛酸钡的混合物， 氮化硼和氮化的混 合物， 碳化硅和氧化铝的混合物， 结晶型二氧化硅、 无定形二氧化硅和球形二 氧化硅的混合物， 二氧化钛、 钛酸锶和钛酸钡的混合物， 氮化硼、 氮化铝、 碳
化硅和氧化铝的混合物。
优选地， 在本发明提供的技术方案的基础上， 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， 在本发明提供的技术方案的基础上， 所述填料为二氧化硅。
优选地， 在本发明提供的技术方案的基础上， 所述填料的粒径中度值为
1〜15μηι， 例如 2μιτι、 3μιτι、 4μιτι、 5μιτι、 6μιτι、 7μιτι、 8μιτι、 9μιτι、 10μηι、 11μηι、 12μηι、 13μηι或 14μηι， 优选 1〜10μηι， 位于此粒径段的填料具有良好的 分散性。
所述填料的添加量为组分（A)、 (Β )、 (C)和（D)添加量之和的 0〜300 重量％， 不包括 0， 例如 0.08重量％、 0.1重量％、 0.2重量％、 0.3重量％、 5重 量％、 10重量％、 15重量％、 20重量％、 25重量％、 30重量％、 35重量％、 40 重量％、 45 重量％、 60重量％、 90重量％、 120重量％、 150重量％、 180重 量％、 210重量％、 240重量％、 260重量％、 270重量％、 280重量％、 290重 量％或295重量％， 优选 0〜50重量％。
本发明所述的 "包括"， 意指其除所述组份外， 还可以包括其他组份， 这些 其他组份赋予所述无卤树脂组合物不同的特性。 除此之外， 本发明所述的 "包 括"， 还可以替换为封闭式的 "为"或 "由……组成"。
例如， 所述无卤树脂组合物还可以含有各种添加剂， 作为具体例， 可以举 出阻燃剂、 抗氧剂、 热稳定剂、 抗静电剂、 紫外线吸收剂、 颜料、 着色剂或润 滑剂等。 这些各种添加剂可以单独使用， 也可以两种或者两种以上混合使用。
本发明的目的之二在于提供一种树脂胶液， 其是将如上所述的无卤树脂组 合物溶解或分散在溶剂中得到。
本发明树脂组合物的常规制备方法为： 先将固形物放入， 然后加入液态溶
剂， 搅拌至固形物完全溶解后， 再加入液态树脂和促进剂， 继续搅拌均匀即可， 最后用溶剂调整溶液固体含量至 65〜75%而制成胶液， 即本无卤树脂组合物胶 液。
作为本发明中的溶剂， 没有特别限定， 作为具体例， 可以举出甲醇、 乙醇、 丁醇等醇类， 乙基溶纤剂、 丁基溶纤剂、 乙二醇-甲醚、 卡必醇、 丁基卡必醇等 醚类， 丙酮、 丁酮、 甲基乙基甲酮、 甲基异丁基甲酮、 环己酮等酮类， 甲苯、 二甲苯、 均三甲苯等芳香族烃类， 乙氧基乙基乙酸酯、 醋酸乙酯等酯类， Ν,Ν- 二甲基甲酰胺、 Ν,Ν-二甲基乙酰胺、 Ν-甲基 -2-吡咯烷酮等含氮类溶剂。 上述溶 剂可以单独使用一种， 也可以两种或者两种以上混合使用， 优选甲苯、 二甲苯、 均三甲苯等芳香族烃类溶剂与丙酮、 丁酮、 甲基乙基甲酮、 甲基异丁基甲酮、 环己酮等酮类熔剂混合使用。
本发明的目的之三在于提供一种预浸料， 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上所述的无卤树脂组合物。 所述预浸料具有低介电常 数、 低介电损耗因素、 低吸水率、 高尺寸稳定性、 高耐热性、 高储能模量、 高 弯曲强度、 高剥离强度以及良好的阻燃性、 加工性能和耐化学性。
本发明的预浸料是使用上述的无卤树脂组合物加热干燥制得的， 所使用的 增强材料为无纺织物或其它织物， 例如天然纤维、有机合成纤维以及无机纤维。 使用上述胶液含浸玻璃布等织物或有机织物， 将含浸好的玻璃布在 155°C的烘 箱中加热干燥 5〜8分钟即可得到预浸料。
本发明的目的之四在于提供一种层压板， 所述层压板含有至少一张如上所 述的预浸料。 所述层压板具有低介电常数、 低介电损耗因素、 低吸水率、 高尺 寸稳定性、 高耐热性、 高储能模量、 高弯曲强度、 高剥离强度以及良好的阻燃 性、 加工性能和耐化学性。
与已有技术相比， 本发明具有如下有益效果：
①本发明涉及的无卤树脂组合物采用了双环戊二烯型苯并噁嗪树脂， 该苯 并噁嗪树脂含双环戊二烯结构， 除了拥有传统苯并噁嗪高玻璃化转变温度
(Tg) 、 吸水率低、 尺寸稳定性高、 低热膨胀系数、 耐热阻燃好等优点外还有 着优异的介电性能， 在环氧树脂中混入该苯并噁嗪树脂不仅可以降低固化物介 电常数、 介电损耗值、 吸水率还可提高固化物储能模量、 弯曲强度， 并保持粘 合力不下降； 该苯并噁嗪与含磷阻燃剂有协同阻燃效果， 能减少固化物阻燃性 达到 UL 94V-0所需磷含量， 进一步降低吸水率； ②本发明的无卤树脂组合物 以活性酯为固化剂， 充分发挥了活性酯与环氧树脂反应不生成极性基团从而介 电性能优异耐湿热性能好的优势， ③使用该树脂组合物制成的预浸料、 印制电 路用层压板具有低介电常数、 低介电损耗因素、 低吸水率、 高耐热性、 高尺寸 稳定性、 高剥离强度、 高储能模量、 高弯曲强度以及良好的阻燃性、 加工性 能、 耐化学性。
具体实舫式
下面通过具体实施方式来进一步说明本发明的技术方案。
兹将本发明实施例详细说明如下， 但本发明并非局限在实施例范围。 下文 中无特别说明， 其份代表重量份， 其％代表 "重量％" 。
(A-1 ) 双环戊二烯型苯并噁嗪树脂
LZ 8260N70 (HUNTSMAN商品名）
(A-2) 改性 PPO
PP-403 (台湾晋一化工商品名）
(A-3 ) 双酚 A型苯并噁嗪
LZ 8290H62 (HUNTSMAN商品名）
(B) 环氧树脂
(B-l ) HP-7200H (大日本油墨， 双环戊二烯型环氧树脂）
(B-2) NC-3000 (日本化药， 联苯型环氧树脂）
(C) 固化剂
(C-1 ) HPC-8000-65T (大日本油墨， 活性酯固化剂）
(C-2) 2812 (韩国 MOMENTIVE, 线性酚醛固化剂）
(C-3 ) DICY (宁夏大荣， 双氰胺固化剂）
(D) 阻燃剂
(D-1 ) 含磷阻燃剂
SPB-100 (日本大塚化学株式会社， 苯氧基磷腈化合物）
(D-2) 含氮阻燃剂
MCA (山东寿光， 三聚氰胺尿酸盐）
(E) 2-苯基咪唑 （日本四国化成）
(F) 填料
球型硅微粉 （平均粒径为 1至 ΙΟμηι, 纯度 99%以上）
树脂组合物的制备方法为： 先将固形物放入， 然后加入液态溶剂， 搅拌至 固形物完全溶解后， 再加入液态树脂和促进剂， 继续搅拌均匀即可， 最后用溶 剂调整溶液固体含量至 65%-75%而制成胶液， 即得到本无卤树脂组合物胶液， 使用该胶液含浸玻璃布等织物或有机织物， 将含浸好的玻璃布在 155°C的烘箱 中加热干燥 5-8分钟制成预浸料。
使用上述的预浸料 10片和 2片 1盎司（35μη厚度）的金属箔叠合在一起， 通过热压机层压， 从而压制成双面金属箔的层压板。 所述的层压须满足以下要
求： ①层压的升温速率通常在料温 80-120°C时应控制在 1.5-2.5 °C/min; ②层压 的压力设置， 外层料温在 120-150°C施加满压， 满压压力为 350psi左右； ③固 化时， 控制料温在 190°C， 并保温 90min。 所述的金属箔为铜箔、 镍箔、 铝箔 及 SUS箔等， 其材质不限。
针对上述制成的印制电路用层压板（10片预浸料)测试其玻璃化转变温度、 介电常数、 介电损耗因素、 吸水性、 耐热性、 阻燃性等性能， 如表 1所示。
表 1、 各实施例比较例的配方组成及其物性数据 1
实施例 实施例 实施例 实施例 比较例 比较例
1 2 3 4 1 2
A-1 10 30 60 30 ― ―
A-2 ― ― ― ― ― 30
A-3 ― ― ― ― ― ―
B-1 43 31 14 ― 49 31
B-2 ― ― ― 31 ― ―
C-1 32 24 11 24 36 24
C-2 ― ― ― ― ― ―
C-3 ― ― ― ― ― ―
D-1 15 15 15 15 15 15
D-2 ― ― ― ― ― ―
E 适量 适量 适量 适量 适量 适量
F 40 40 40 40 40 40
玻璃化转变温 153 158 165 172 150 160
/乂
(DSC) °C
介电常数 3.64 3.61 3.58 3.59 3.92 3.65 ( 1GHz)
介电损耗 0.0078 0.0075 0.0070 0.0072 0.0100 0.0070 ( 1GHz)
剥离强度 1.47 1.45 1.41 1.43 1.43 1.12 (N/mm)
储能模量 2068 3231 4215 4585 1748 1535 (MPa)
弯曲强度 495 540 592 615 413 387 (N/mm2)
吸水性 （％) 0.10 0.07 0.06 0.06 0.19 0.12 耐浸焊 288 °C， >120 >120 >120 >120 >120 >120 s
难燃烧性 V-0 V-0 V-0 V-0 V-0 V-0 表 2、 各实施例比较例的配方组成及其物性数据 2
比较例 比较例 比较例 比较例 比较例 比较例 比较例 3 4 5 6 7 8 9
A-1 ― ― 30 30 30 30 30
A-2 ― ― ― ― ― ― ―
A-3 60 10 ― ― ― ― ―
B-l 14 43 37 51 31 42 31
B-2 ― ― ― ― ― ― ―
C-l 11 32 ― ― 24 28 24
C-2 ― ― 18 ― ― ― ―
C-3 ― ― ― 4 ― ― ―
D-l 15 15 15 15 ― ― 15
D-2 ― ― ― ― 15 ― ―
E 适量 适量 适量 适量 适量 适量 适量
F 40 40 40 40 40 40 ― 玻璃化转变温 167 151 161 152 155 167 158
(DSC) °C
介电常数 3.80 3.79 3.87 3.81 3.67 3.65 3.70 ( 1GHz)
介电损耗 0.0110 0.0098 0.0135 0.0103 0.0095 0.0079 0.0082
( 1GHz)
剥离强度 1.39 1.44 1.48 1.41 1.45 1.46 1.58 (N/mm)
储能模量 4420 2120 3563 2612 3380 3080 2651 (MPa)
弯曲强度 585 480 560 425 521 475 461 (N/mm2)
吸水性 （％) 0.06 0.10 0.08 0.15 0.09 0.08 0.09 耐浸焊 >120 >120 >120 85 >120 >120 >120 288 °C， s
难燃烧性 V-0 V-0 V-0 V-0 V-1 V-1 V-1
以上特性的测试方法如下：
(a)玻璃化转变温度 (Tg): 根据差示扫描量热法 (DSC)， 按照 IPC-TM-650 2.4.25 所规定的 DSC方法进行测定。
(b ) 介电常数、 介电损耗因素
根据使用条状线的共振法， 按照 IPC-TM-650 2.5.5.5测定 1GHz下的介电损 耗、 介电损耗因素。
( c ) 剥离强度
按照 IPC-TM-650 2.4.8方法中的 "热应力后" 的实验条件， 测试金属盖层 的剥离强度。
( d ) 储能模量
按照 IPC-TM-650 2.4.24.4方法进行测定。
(e) 弯曲强度
按照 IPC-TM-650 2.4.4方法进行， 在室温下把负载施加于规定尺寸和形状 的试样上进行测定。
(0 吸水性
按照 IPC-TM-650 2.6.2.1方法进行测定。
(g) 耐浸焊性
按照 IPC-TM-650 2.4.13.1观察分层起泡时间。
(h) 难燃烧性
依据 UL 94垂直燃烧法测定。
从表 1 的物性数据可知， 实施例 1-4是使用了双环戊二烯型苯并噁嗪树脂 与环氧树脂、 活性酯固化剂共固化后， 得到的层压板介电性能、 吸水性、 储能 模量以及弯曲强度大有改善， 而且剥离强度没有下降。 比较例 1 中使用双环戊 二烯型环氧树脂与活性酯固化剂固化时剥离强度较高， 介电性能一般， 吸水率 高同时储能模量和弯曲强度较低； 比较例 2中加入改性 PPO之后介电性能和吸 水性有较大改善， 但有损剥离强度、 储能模量和弯曲强度； 比较例 3中使用双 酚 A型噁嗪作为主体树脂， 比较例 4中采用双酚 A型噁嗪与活性酯共固化环氧 树脂， 比较例 5中采用线性酚醛代替活性酯固化双环戊二烯型苯并噁嗪和环氧 树脂， 比较例 6中使用双氰胺代替活性酯固化双环戊二烯型苯并噁嗪和环氧树 脂， 板材介电性能均明显恶化， 其中比较例 6吸水率、 储能模量和耐热性也有 所恶化； 比较例 7和 8分别采用含氮阻燃剂和不加阻燃剂， 板材阻燃性较差， 只能达到 V-1级； 比较例 9采用双环戊二烯型苯并噁嗪和活性酯共固化环氧树
脂但不加填料， 板材剥离强度有所改善， 但储能模量、 阻燃性较差。 如上所述， 与一般的无卤层压板相比， 本发明的印制电路用层压板在具有 更优异的介电性能、 耐湿性、 尺寸稳定性和剥离强度， 适用于高密度互联领 域。 另外本发明充分利用了苯并噁嗪树脂与含磷阻燃剂的协同特性， 卤素含量 在 JPCA无卤标准要求范围内能达到难燃性试验 UL94中的 V-0标准， 有环保的 功效。 申请人声明， 本发明通过上述实施例来说明本发明的详细方法， 但本发明 并不局限于上述详细方法， 即不意味着本发明必须依赖上述详细方法才能实 施。 所属技术领域的技术人员应该明了， 对本发明的任何改进， 对本发明产品 各原料的等效替换及辅助成分的添加、 具体方式的选择等， 均落在本发明的保 护范围和公开范围之内。
Claims
1、 一种无卤树脂组合物， 其特征在于， 以 （A) 、 (B) 、 (C) 和 （D) 总有机固形物总量 100重量份计， 其包含：
(A) 双环戊二烯型苯并噁嗪树脂， 10到 60重量份；
(B) 环氧树脂；
(C) 活性酯固化剂；
(D) 含磷阻燃剂。
2、 如权利要求 1 所述的无卤树脂组合物， 其特征在于， 所述双环戊二烯 型苯并噁嗪树脂的含量为 10〜30重量份。
3、 如权利要求 1 所述的无卤树脂组合物， 其特征在于， 所述双环戊二烯 型苯并噁嗪树脂的含量为 30〜60重量份。
4、 如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 所述双环戊二 烯型苯并噁嗪树脂具有如下结构：
5、如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 所述组分（B) 环氧树脂为环氧当量为 150〜550g/mol的环氧树脂。
6、如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 所述组分（B) 环氧树脂添加量为 10-60重量份。
7、如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 所述组分（B) 环氧树脂选自双酚 A型环氧树脂、 双酚 F型环氧树脂、 苯酚型酚醛环氧树脂、 双酚 A型酚醛环氧树脂、 邻甲酚酚醛环氧树脂、 双环戊二烯型环氧树脂、 异氰
酸酯型环氧树脂、 苯酚芳烷基自阻燃环氧树脂或联苯型环氧树脂中的至少任 一种或者至少两种的混合物， 优选双环戊二烯型环氧树脂。
8、 如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 所述活性酯 化剂包括下述结构的活性酯：
其中， X为苯环或萘环， j为 0或 1， k为 0或 1， n表示平均重复单元为
0.25〜1.25 ,
9、如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 所述组分（C ) 活性酯固化剂的添加量为 5〜35重量份。
10、 如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 所述含磷阻 燃剂的添加量是组分 （A) 、 组分 （B ) 和组分 （C ) 的添加量之和的 5〜100重 量％， 优选 5〜50重量％。
11、 如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 所述含磷阻 燃剂为三 (2， 6-二甲基苯基)膦、 10-(2,5-二羟基苯基) -9,10-二氢 -9-氧杂 -10-膦菲 -10-氧化物、 2,6-二 (2,6-二甲基苯基)膦基苯或 10-苯基 -9,10-二氢 -9-氧杂 -10-膦菲 -10-氧化物、 苯氧基磷腈化合物、 磷酸酯或聚磷酸酯中的任意一种或者至少两 种的混合物。
12、 如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 所述无卤树 脂组合物还包括 （E) 固化促进剂。
13、如权利要求 12所述的无卤树脂组合物， 其特征在于， 所述固化促进剂 为咪唑类固化促进剂或 /和吡啶类固化促进剂， 进一步优选 2-甲基咪唑、 2-乙基
-4-甲基咪唑、 2-苯基咪唑、 2-H ^—烷基咪唑、 三乙胺、 苄基二甲胺或二甲氨基 吡啶中的任意一种或者至少两种的混合物。
14、如权利要求 12所述的无卤树脂组合物， 其特征在于， 所述固化促进剂 的添加量为组分 （A) 、 (B) 、 (C) 和 （D) 添加量之和的 0.05〜1重量％。
15、 如权利要求 1或 2所述的无卤树脂组合物， 其特征在于， 所述无卤树 脂组合物还包括 （F) 填料。
16、如权利要求 15所述的无卤树脂组合物， 其特征在于， 所述填料为有机 或无机填料。
17、如权利要求 16所述的无卤树脂组合物， 其特征在于， 所述无机填料选 自二氧化硅、 氢氧化铝、 氧化铝、 滑石粉、 氮化铝、 氮化硼、 碳化硅、 硫酸 钡、 钛酸钡、 钛酸锶、 碳酸钙、 硅酸钙、 云母或玻璃纤维粉中的任意一种或者 至少两种的混合物， 优选熔融二氧化硅、 结晶型二氧化硅、 球型二氧化硅、 空 心二氧化硅、 氢氧化铝、 氧化铝、 滑石粉、 氮化铝、 氮化硼、 碳化硅、 硫酸 钡、 钛酸钡、 钛酸锶、 碳酸钙、 硅酸钙、 云母或玻璃纤维粉中的任意一种或者 至少两种的混合物。
18、如权利要求 16所述的无卤树脂组合物， 其特征在于， 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。
19、如权利要求 15所述的无卤树脂组合物， 其特征在于， 所述填料为二氧 化硅。
20、如权利要求 15所述的无卤树脂组合物， 其特征在于， 所述填料的粒径 中度值为 1〜15μηι， 优选 1〜10μηι。
21、如权利要求 15所述的无卤树脂组合物， 其特征在于， 所述填料的添加
量为组分（A)、 (B)、 (C)和（D)添加量之和的 0〜300重量％， 不包括 0， 优选 0〜50重量％。
22、 一种树脂胶液， 其特征在于， 其是将如权利要求 1-21之一所述的无卤 树脂组合物溶解或分散在溶剂中得到。
23、 一种预浸料， 其特征在于， 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 1-21之一所述的无卤树脂组合物。
24、 一种层压板， 其特征在于， 所述层压板含有至少一张如权利要求 23 所述的预浸料。
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| EP14888197.2A EP3053963B1 (en) | 2014-04-02 | 2014-07-17 | Halogen-free resin composition and uses thereof |
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| WO2018223524A1 (zh) * | 2017-06-05 | 2018-12-13 | 广东生益科技股份有限公司 | 无卤环氧树脂组合物以及使用它的预浸料和层压板 |
| US10723875B2 (en) | 2017-06-05 | 2020-07-28 | Shengyi Technology Co., Ltd. | Halogen-free epoxy resin composition and a prepreg and a laminate using the same |
| US11319406B2 (en) | 2017-11-14 | 2022-05-03 | Eneos Corporation | Prepreg, fiber-reinforced composite material, and molded article |
| EP3919566A4 (en) * | 2019-01-30 | 2022-12-07 | Shengyi Technology Co., Ltd. | COMPOSITION OF THERMOSETTING RESIN, PREPREGNATED CONTAINING THE SAME, LAMINATE COVERED WITH A METALLIC FOIL AND PRINTED CIRCUIT BOARD |
Also Published As
| Publication number | Publication date |
|---|---|
| US20160272808A1 (en) | 2016-09-22 |
| EP3053963A4 (en) | 2017-06-14 |
| TW201538615A (zh) | 2015-10-16 |
| CN104974520B (zh) | 2017-11-03 |
| JP2016536403A (ja) | 2016-11-24 |
| CN104974520A (zh) | 2015-10-14 |
| JP6294478B2 (ja) | 2018-03-14 |
| TWI532784B (zh) | 2016-05-11 |
| EP3053963A1 (en) | 2016-08-10 |
| EP3053963B1 (en) | 2018-09-19 |
| KR101596591B1 (ko) | 2016-02-22 |
| KR20150114872A (ko) | 2015-10-13 |
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