WO2022052106A1 - 无卤热固性树脂组成物及其用途 - Google Patents
无卤热固性树脂组成物及其用途 Download PDFInfo
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- WO2022052106A1 WO2022052106A1 PCT/CN2020/115085 CN2020115085W WO2022052106A1 WO 2022052106 A1 WO2022052106 A1 WO 2022052106A1 CN 2020115085 W CN2020115085 W CN 2020115085W WO 2022052106 A1 WO2022052106 A1 WO 2022052106A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
- C08G59/60—Amines together with other curing agents with amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- the present invention relates to a thermosetting resin composition and use thereof, in particular to a halogen-free thermosetting resin composition and use thereof.
- the present invention provides a halogen-free thermosetting resin composition, the resin does not contain halogen, has low dielectric constant and low dielectric loss characteristics, and still has high Tg (glass transition temperature), high heat resistance, and can be Used in copper foil substrates and printed circuit boards.
- the halogen-free thermosetting resin composition of the present invention includes a halogen-free epoxy resin, a styrene maleic anhydride copolymer, a cyanate resin, a maleimide resin, and a flame retardant.
- the content of the styrene maleic anhydride copolymer is 40 to 90 parts by weight, and the content of the cyanate ester resin is 30 to 90 parts by weight 120 parts by weight, the content of the maleimide resin is 20 to 70 parts by weight, and the content of the flame retardant is 20 to 70 parts by weight.
- the epoxy resin includes novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene epoxy resin (DCPD), bisphenol epoxy resin, phosphorus-containing epoxy resin Epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, naphthalene ring epoxy resin, isocyanate modified epoxy resin, biphenyl epoxy resin, triazine-containing structure Epoxy resin (triazine), fulorene-containing epoxy resin (fulorene), or a combination thereof.
- DCPD dicyclopentadiene epoxy resin
- bisphenol epoxy resin phosphorus-containing epoxy resin Epoxy resin
- o-cresol novolac epoxy resin bisphenol A novolac epoxy resin
- phenol novolac epoxy resin phenol novolac epoxy resin
- naphthalene ring epoxy resin isocyanate modified epoxy resin
- biphenyl epoxy resin triazine-containing structure Epoxy resin (triazine), fulor
- the molecular weight of the styrene maleic anhydride copolymer is 3000 to 10000, and the molar ratio of styrene:maleic anhydride is 1 to 8:1.
- the cyanate ester resin includes bisphenol A type cyanate ester resin, dicyclopentadiene type (DCPD) cyanate ester resin, bisphenol F type cyanate ester resin, and novolac type cyanate ester resin or a combination thereof.
- the maleimide resin includes 4,4'-diphenylmethanebismaleimide, phenylmethanemaleimide oligomer, m-phenylenebismaleimide Imide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide Amine, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, or a combination thereof.
- the flame retardant is a halogen-free flame retardant.
- the flame retardant includes a phosphorus-containing flame retardant.
- the phosphorus-containing flame retardant includes a phosphazene compound, a phosphoric acid ester compound, a phosphorus-containing epoxy resin, a phosphorus-containing phenolic resin, a phosphorus-containing cyanate resin, or a combination thereof.
- the present invention provides a prepreg made of the above-mentioned halogen-free thermosetting resin composition, wherein the impregnated or coated base material is produced by impregnating or coating a base material with the halogen-free thermosetting resin composition and drying the impregnated or coated base material .
- the present invention provides a halogen-free thermosetting resin composition, including a halogen-free epoxy resin, which has the characteristics of low dielectric constant and low dielectric loss, and still has high Tg (glass transition temperature), high Heat resistance, and can be used in copper foil substrates and printed circuit boards.
- a range represented by "one value to another value” is a general representation that avoids listing all the values in the range in the specification. Accordingly, the recitation of a particular numerical range includes any numerical value within that numerical range and a smaller numerical range bounded by any numerical value within that numerical range, as if the arbitrary numerical value and the smaller numerical value were written in the description in the specification same range.
- the present invention provides a halogen-free thermosetting resin composition, which comprises a halogen-free epoxy resin, a styrene maleic anhydride copolymer, a cyanate ester resin, a maleimide resin and a flame retardant.
- a halogen-free epoxy resin based on 100 parts by weight of the epoxy resin, the content of the styrene maleic anhydride copolymer is, for example, 40 to 90 parts by weight, and the content of the cyanate resin is, for example, 30 to 120 parts by weight.
- the content of the maleimide resin is, for example, 20 to 70 parts by weight, and the content of the flame retardant is, for example, 20 to 70 parts by weight.
- the epoxy resin of the present invention does not contain halogen, and can mainly include novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene epoxy resin (DCPD), bisphenol epoxy resin, phosphorus-containing epoxy resin Epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, naphthalene ring epoxy resin, isocyanate modified epoxy resin, biphenyl epoxy resin, triazine-containing structure Epoxy resin (triazine), fulorene-containing epoxy resin (fulorene), or a combination thereof.
- novolac epoxy resin trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene epoxy resin (DCPD), bisphenol epoxy resin, phosphorus-containing epoxy resin Epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, naphthalene ring epoxy resin, isocyanate modified epoxy resin,
- the molecular weight of the styrene maleic anhydride copolymer of the present invention is, for example, 3,000 to 10,000, and the molar ratio of styrene:maleic anhydride is, for example, 1 to 8:1.
- the cyanate resin of the present invention may include a bisphenol A type cyanate resin, a dicyclopentadiene type (DCPD) cyanate resin, a bisphenol F type cyanate resin, a novolac type cyanate resin, or a combination thereof.
- DCPD dicyclopentadiene type
- the maleimide resin of the present invention may include 4,4'-diphenylmethanebismaleimide, phenylmethanemaleimide oligomer, m-phenylenebismaleimide, bismaleimide Phenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl 1,3-phenylenebismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, or a combination thereof.
- the flame retardant of the present invention is a halogen-free flame retardant
- the halogen-free flame retardant may include, but is not limited to, nitrogen-containing compounds, phosphorus-containing compounds or metal hypophosphorous acid salts, preferably phosphorus-containing compounds.
- the phosphorus-containing flame retardant may include a phosphazene compound, a phosphoric acid ester compound, a phosphorus-containing epoxy resin, a phosphorus-containing phenolic resin, a phosphorus-containing cyanate resin, or a combination thereof.
- the halogen-free thermosetting resin composition of the present invention may further include at least one of the following additives: a crosslinking agent, a filler, a catalyst and a solvent.
- the crosslinking agent of the present invention may include 2,2'-diallyl bisphenol A, triallyl isocyanurate, bis(3-allyl-4-hydroxyphenyl) sulfone, active ester ( For example: DIC's HPC-8000-65T), hydroquinone or a combination thereof.
- Fillers of the present invention may include silica, alumina, magnesia, magnesium hydroxide, calcium carbonate, talc, clay, aluminum nitride, boron nitride, aluminum hydroxide, aluminum silicon carbide, silicon carbide, sodium carbonate, titanium dioxide , Zinc oxide, zirconia, quartz, diamond, diamond-like, graphite, calcined kaolin, kaolin, mica, hydrotalcite, hollow silica, polytetrafluoroethylene (PTFE) powder, glass beads, nano carbon Tubes, nanoscale inorganic powders, or combinations thereof.
- PTFE polytetrafluoroethylene
- the type of the catalyst of the present invention is not particularly limited as long as it can promote ring-opening of epoxy functional groups and lower the curing reaction temperature of the resin composition.
- the catalyst can be selected from the following: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, dimethylbenzylamine, 2-(dimethylaminomethyl)phenol, 2 ,4,6-Tris(dimethylaminomethyl)phenol, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,6-diaminopyridine, 4-dimethylaminopyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-3-nitropyridine, zinc oxide and combinations thereof.
- the type of the solvent in the present invention is not particularly limited, as long as it can make the viscosity of the resin composition moderate, and is convenient for operation and curing, which is not limited in the present invention.
- the present invention also provides a prepreg made of the above-mentioned halogen-free thermosetting resin composition, wherein the prepreg is prepared by impregnating or coating a base material with the halogen-free thermosetting resin composition, and drying the impregnated or coated base material become.
- the base material may include glass fiber reinforcing materials (glass fiber fabric or non-woven fabric, cellophane, glass mat, etc.), kraft paper, cotton paper, natural fiber cloth, organic fiber cloth, liquid crystal polymer fiber mat, etc. .
- 2116 glass fiber cloth can be used as a reinforcing material (substrate), and the semi-cured pre-impregnated sheet can be prepared by heating and drying at a temperature of 130° C. to 200° C. for 2 minutes to 10 minutes. Take several semi-cured pre-impregnated sheets and stack them in a hot press for high temperature curing.
- thermosetting resin composition proposed by the present invention will be described in detail through experimental examples. However, the following experimental examples are not intended to limit the present invention.
- thermosetting resin composition proposed by the present invention has low dielectric constant, low dielectric loss, and at the same time still has high glass transition temperature (Tg) and high heat resistance
- Tg glass transition temperature
- Resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were prepared according to the composition ratios listed in Table 1 below.
- the substrate is impregnated or coated with a resin composition, and heated and dried at a temperature of 130°C to 200°C for 2 minutes to 10 minutes to prepare a semi-cured pre-impregnation piece.
- a resin composition Using 2116 glass fiber cloth as a reinforcing material (substrate), the substrate is impregnated or coated with a resin composition, and heated and dried at a temperature of 130°C to 200°C for 2 minutes to 10 minutes to prepare a semi-cured pre-impregnation piece. Take several semi-cured pre-impregnated sheets and stack them in a hot press for high temperature curing. After that, the electrothermal properties of the test pieces were tested, and the test results are listed in Table 1 below.
- the epoxy resins are trifunctional epoxy resins, dicyclopentadiene epoxy resins, and bisphenol-type epoxy resins.
- the styrene maleic anhydride copolymer is in a molar ratio of styrene:maleic anhydride from 3:1 to 6:1.
- the cyanate resin is a bisphenol A type cyanate resin.
- the maleimide resin is 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide.
- the crosslinking agent is an active ester.
- the flame retardant is a phosphazene compound.
- the filler is silica.
- the catalyst is 2-methylimidazole.
- the present invention provides a halogen-free thermosetting resin composition, comprising a halogen-free epoxy resin, a styrene maleic anhydride copolymer, a cyanate ester resin, a maleimide resin and a flame retardant, And the above composition is added in a specific proportion range, so it has low dielectric constant, low dielectric loss, and still has high glass transition temperature (Tg) and high heat resistance, and the glass transition temperature (Tg) can reach 200 °C The above, and can be applied to copper foil substrates and printed circuit boards.
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Abstract
一种无卤热固性树脂组成物及其用途，所述无卤热固性树脂组成物包括不含有卤素的环氧树脂、苯乙烯马来酸酐共聚物、氰酸酯树脂、马来酰亚胺树脂以及阻燃剂。
Description
本发明涉及一种热固性树脂组成物及其用途，尤其涉及一种无卤热固性树脂组成物及其用途。
近年来，随着通讯技术的高速发展，电子产品在轻量化与高密度化方面的需求与日俱增。电子产品在使用过程中的消耗功率将产生大量热能，导致电子产品温度升高，进而使基板容易损毁。同时，随着环保意识逐渐提高，各项环保法规愈加严苛，材料的无卤化成为势在必行的趋势。因此，在树脂组成物开发方面，无卤化且具有优良电气性能的同时，还具有良好的耐热性，为本领域技术人员亟欲发展的目标。
发明内容
本发明提供一种无卤热固性树脂组成物，树脂中不含有卤素，具有低介电常数、低介电损耗特性的同时，仍具有高Tg(玻璃化转变温度)、高耐热性，并且可应用在铜箔基板与印刷电路板中。
本发明的无卤热固性树脂组成物包括不含有卤素的环氧树脂、苯乙烯马来酸酐共聚物、氰酸酯树脂、马来酰亚胺树脂以及阻燃剂。
在本发明的一实施例中，以环氧树脂的含量为100重量份计，苯乙烯马来酸酐共聚物的含量为40重量份至90重量份，氰酸酯树脂的含量为30重量份至120重量份，马来酰亚胺树脂的含量为20重量份至70重量份，阻燃剂的含量为20重量份至70重量份。
在本发明的一实施例中，环氧树脂包括酚醛环氧树脂、三官能环氧树脂、四官能环氧树脂、双环戊二烯环氧树脂(DCPD)、双酚型环氧树脂、含磷环氧树脂、邻甲酚醛环氧树脂、双酚A酚醛环氧树脂、苯酚酚醛环氧树脂、萘环型环氧树脂、异氰酸酯改性环氧树脂、联苯型环氧树脂、含三嗪结构环氧树脂(triazine)、含茀结构脂环氧树脂(fulorene)或其组合。
在本发明的一实施例中，苯乙烯马来酸酐共聚物的分子量为3000至10000，且苯乙烯:马来酸酐的摩尔比为1至8:1。
在本发明的一实施例中，氰酸酯树脂包括双酚A型氰酸酯树脂、双环戊二烯型(DCPD)氰酸酯树脂、双酚F型氰酸酯树脂、酚醛型氰酸酯树脂或其组合。
在本发明的一实施例中，马来酰亚胺树脂包括4,4’-二苯甲烷双马来酰亚胺、苯甲烷马来酰亚胺寡聚物、间-亚苯基双马来酰亚胺、双酚A二苯基醚双马来酰亚胺、3,3’-二甲基-5,5’-二乙基-4,4’-二苯基甲烷双马来酰亚胺、4-甲基-1,3-亚苯基双马来酰亚胺、1,6-双马来酰亚胺-(2,2,4-三甲基)己烷或其组合。
在本发明的一实施例中，阻燃剂为无卤阻燃剂。
在本发明的一实施例中，阻燃剂包括含磷阻燃剂。
在本发明的一实施例中，含磷阻燃剂包括磷腈化合物、磷酸酯化合物、含磷环氧树脂、含磷酚醛树脂、含磷氰酸酯树脂或其组合。
本发明提供一种预浸渍片，由上述无卤热固性树脂组成物所制成，其中通过将基材含浸或涂布无卤热固性树脂组成物，并干燥经含浸或涂布的基材而制成。
基于上述，本发明提供一种无卤热固性树脂组成物，包括不含有卤素的环氧树脂，具有低介电常数、低介电损耗特性的同时，仍具有高Tg(玻璃化转变温度)、高耐热性，并且可应用在铜箔基板与印刷电路板中。
以下，将详细描述本发明的实施例。然而，这些实施例为例示性，且本发明揭示不限于此。
在本文中，由“一数值至另一数值”表示的范围，是一种避免在说明书中一一列举该范围中的所有数值的概要性表示方式。因此，某一特定数值范围的记载，涵盖该数值范围内的任意数值以及由该数值范围内的任意数值界定出的较小数值范围，如同在说明书中说明文写出该任意数值和该较小数值范围一样。
本发明提出一种无卤热固性树脂组成物，包括不含有卤素的环氧树脂、 苯乙烯马来酸酐共聚物、氰酸酯树脂、马来酰亚胺树脂以及阻燃剂。更详细而言，以环氧树脂的含量为100重量份计，苯乙烯马来酸酐共聚物的含量例如是40重量份至90重量份，氰酸酯树脂的含量例如是30重量份至120重量份，马来酰亚胺树脂的含量例如是20重量份至70重量份，阻燃剂的含量例如是20重量份至70重量份。以下，将对上述各种组分进行详细说明。
<环氧树脂>
本发明的环氧树脂不含有卤素，主要可包括酚醛环氧树脂、三官能环氧树脂、四官能环氧树脂、双环戊二烯环氧树脂(DCPD)、双酚型环氧树脂、含磷环氧树脂、邻甲酚醛环氧树脂、双酚A酚醛环氧树脂、苯酚酚醛环氧树脂、萘环型环氧树脂、异氰酸酯改性环氧树脂、联苯型环氧树脂、含三嗪结构环氧树脂(triazine)、含茀结构脂环氧树脂(fulorene)或其组合。
<苯乙烯马来酸酐共聚物>
本发明的苯乙烯马来酸酐共聚物的分子量例如是3000至10000，且苯乙烯:马来酸酐的摩尔比例如是1至8:1。
<氰酸酯树脂>.
本发明的氰酸酯树脂可包括双酚A型氰酸酯树脂、双环戊二烯型(DCPD)氰酸酯树脂、双酚F型氰酸酯树脂、酚醛型氰酸酯树脂或其组合。
<马来酰亚胺树脂>
本发明的马来酰亚胺树脂可包括4,4’-二苯甲烷双马来酰亚胺、苯甲烷马来酰亚胺寡聚物、间-亚苯基双马来酰亚胺、双酚A二苯基醚双马来酰亚胺、3,3’-二甲基-5,5’-二乙基-4,4’-二苯基甲烷双马来酰亚胺、4-甲基-1,3-亚苯基双马来酰亚胺、1,6-双马来酰亚胺-(2,2,4-三甲基)己烷或其组合。
<阻燃剂>
本发明的阻燃剂为无卤阻燃剂，无卤阻燃剂可包括但不限于含氮化合物、含磷化合物或次磷酸金属盐，较佳例如是含磷化合物。含磷阻燃剂可包括磷腈化合物、磷酸酯化合物、含磷环氧树脂、含磷酚醛树脂、含磷氰酸酯树脂或其组合。
<其他添加剂>
本发明的无卤热固性树脂组成物可进一步包括以下添加剂的至少一种：交联剂、填料、催化剂及溶剂。
本发明的交联剂可包括2,2'-二烯丙基双酚A、三烯丙基异氰脲酸酯、双(3-烯丙基-4-羟苯基)砜、活性酯(例如:DIC的HPC-8000-65T)、对苯二酚或其组合。
本发明的填料可包括二氧化硅、氧化铝、氧化镁、氢氧化镁、碳酸钙、滑石、黏土、氮化铝、氮化硼、氢氧化铝、碳化铝硅、碳化硅、碳酸钠、二氧化钛、氧化锌、氧化锆、石英、钻石、类钻石、石墨、锻烧高岭土、白岭土、云母、水滑石、中空二氧化硅、聚四氟乙烯(polytetrafluoroethylene，PTFE)粉末、玻璃珠、纳米碳管、纳米级无机粉体或其组合。
本发明催化剂的种类并无特殊限制，只要其能促进环氧官能基开环、并降低树脂组成物的固化反应温度即可。具体而言，催化剂可选择自以下：2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、二甲芐胺、2-(二甲胺甲基)苯酚、2,4,6-三(二甲胺甲基)苯酚、2,3-二胺基吡啶、2,5-二胺基吡啶、2,6-二胺基吡啶、4-二甲基氨基吡啶、2-胺基-3-甲基吡啶、2-胺基-4-甲基吡啶、2-胺基-3-硝基吡啶、氧化锌及其组合物。
本发明的溶剂的种类并无特殊限制，只要其能使树脂组合物的黏度适中，便于操作、固化即可，本发明对此不加以限定。
本发明也提供一种预浸渍片，由上述无卤热固性树脂组成物所制成，其中通过将基材含浸或涂布无卤热固性树脂组成物，并干燥经含浸或涂布的基材而制成。更详细而言，基材可包括玻璃纤维补强材料(玻璃纤维织物或不织物、玻璃纸、玻璃毡等)、牛皮纸、短绒棉纸、天然纤维布、有机纤维布、液晶高分子纤维毡等。在本实施例中，例如可使用2116玻璃纤维布作为补强材(基材)，并在温度130℃至200℃下加热干燥2分钟至10分钟，从而制得半固化的预含浸片。取数片半固化的预含浸片堆栈于热压机中进行高温固化，固化条件例如是在温度160℃至280℃下固化1小时至4小时。
以下，通过实验例来详细说明上述本发明所提出的无卤热固性树脂组成物。然而，下述实验例并非用以限制本发明。
实验例
为了证明本发明所提出的无卤热固性树脂组成物具有低介电常数、低介电损耗，同时仍具有高玻璃化转变温度(Tg)及高耐热性，以下特别作此实 验例。
依据以下表1所列出的组成比例，制备实例1至实例4以及比较例1至比较例4的树脂组成物。使用2116玻璃纤维布作为补强材(基材)，将基材含浸或涂布树脂组成物，并在温度130℃至200℃下加热干燥2分钟至10分钟，从而制得半固化的预含浸片。取数片半固化的预含浸片堆栈于热压机中进行高温固化，固化条件例如是在温度160℃至280℃下固化1小时至4小时。之后，测试试片的电热性质，并将测试结果列于以下表1中。
在以下表1中，环氧树脂为三官能环氧树脂、双环戊二烯环氧树脂、双酚型环氧树脂。苯乙烯马来酸酐共聚物为苯乙烯:马来酸酐的摩尔比例3:1至6:1。氰酸酯树脂为双酚A型氰酸酯树脂。马来酰亚胺树脂为3,3’-二甲基-5,5’-二乙基-4,4’-二苯基甲烷双马来酰亚胺。交联剂为活性酯。阻燃剂为磷腈化合物。填料为二氧化硅。催化剂为2-甲基咪唑。
表1
(单位：重量份)
如表1所示，从实例1至实例4可以得知，当树脂组成物的组成及含量符合本发明所提出的范围时，固化后的树脂组合物具有优良的热性质与电器性质。从比较例1可以得知，未添加氰酸酯树脂会使树脂组合物整体性质大幅降低。从比较例2可以得知，当马来酰亚胺树脂添加量过高时(超出本发明所提出的范围)，会使Dk提高。从比较例3可以得知，当氰酸酯树脂及马来酰亚胺树脂的含量超出本发明所提出的范围时，会使Df提高。从比较例4 可以得知，当马来酰亚胺树脂添加量过低时(超出本发明所提出的范围)，会使Dk提高。如此一来，可得知当树脂组成物的组成比例符合本发明所提出的范围时，固化后的树脂组合物Tg可达到200℃以上高温，且具有较佳的Dk/Df值(Dk<4.0、Df<0.010)。
综上所述，本发明提供一种无卤热固性树脂组成物，包括不含有卤素的环氧树脂、苯乙烯马来酸酐共聚物、氰酸酯树脂、马来酰亚胺树脂以及阻燃剂，且上述组成以特定比例范围添加，因此，具有低介电常数、低介电损耗，同时仍具有高玻璃化转变温度(Tg)及高耐热性，玻璃化转变温度(Tg)可达到200℃以上，且可应用于铜箔基板与印刷电路板。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (10)
- 一种无卤热固性树脂组成物，包括：环氧树脂，其中不含有卤素；苯乙烯马来酸酐共聚物；氰酸酯树脂；马来酰亚胺树脂；以及阻燃剂。
- 根据权利要求1所述的无卤热固性树脂组成物，其中以所述环氧树脂的含量为100重量份计，所述苯乙烯马来酸酐共聚物的含量为40重量份至90重量份，所述氰酸酯树脂的含量为30重量份至120重量份，所述马来酰亚胺树脂的含量为20重量份至70重量份，所述阻燃剂的含量为20重量份至70重量份。
- 根据权利要求1所述的无卤热固性树脂组成物，其中所述环氧树脂包括酚醛环氧树脂、三官能环氧树脂、四官能环氧树脂、双环戊二烯环氧树脂、双酚型环氧树脂、含磷环氧树脂、邻甲酚醛环氧树脂、双酚A酚醛环氧树脂、苯酚酚醛环氧树脂、萘环型环氧树脂、异氰酸酯改性环氧树脂、联苯型环氧树脂、含三嗪结构环氧树脂、含茀结构脂环氧树脂或其组合。
- 根据权利要求1所述的无卤热固性树脂组成物，其中所述苯乙烯马来酸酐共聚物的分子量为3000至10000，且苯乙烯:马来酸酐的摩尔比为1至8:1。
- 根据权利要求1所述的无卤热固性树脂组成物，其中所述氰酸酯树脂包括双酚A型氰酸酯树脂、双环戊二烯型氰酸酯树脂、双酚F型氰酸酯树脂、酚醛型氰酸酯树脂或其组合。
- 根据权利要求1所述的无卤热固性树脂组成物，其中所述马来酰亚胺树脂包括4,4’-二苯甲烷双马来酰亚胺、苯甲烷马来酰亚胺寡聚物、间-亚苯基双马来酰亚胺、双酚A二苯基醚双马来酰亚胺、3,3’-二甲基-5,5’-二乙基-4,4’-二苯基甲烷双马来酰亚胺、4-甲基-1,3-亚苯基双马来酰亚胺、1,6-双马来酰亚胺-(2,2,4-三甲基)己烷或其组合。
- 根据权利要求1所述的无卤热固性树脂组成物，其中所述阻燃剂为无卤阻燃剂。
- 根据权利要求1所述的无卤热固性树脂组成物，其中所述阻燃剂包括含磷阻燃剂。
- 根据权利要求8所述的无卤热固性树脂组成物，其中所述含磷阻燃剂包括磷腈化合物、磷酸酯化合物、含磷环氧树脂、含磷酚醛树脂、含磷氰酸酯树脂或其组合。
- 一种预浸渍片，由如权利要求1至9中任一项所述的无卤热固性树脂组成物所制成，其中通过将基材含浸或涂布所述无卤热固性树脂组成物，并干燥经含浸或涂布的所述基材而制成。
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