WO2018223524A1 - 无卤环氧树脂组合物以及使用它的预浸料和层压板 - Google Patents

无卤环氧树脂组合物以及使用它的预浸料和层压板 Download PDF

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Publication number
WO2018223524A1
WO2018223524A1 PCT/CN2017/097335 CN2017097335W WO2018223524A1 WO 2018223524 A1 WO2018223524 A1 WO 2018223524A1 CN 2017097335 W CN2017097335 W CN 2017097335W WO 2018223524 A1 WO2018223524 A1 WO 2018223524A1
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WIPO (PCT)
Prior art keywords
halogen
epoxy resin
weight
free epoxy
parts
Prior art date
Application number
PCT/CN2017/097335
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English (en)
French (fr)
Inventor
曾宪平
何烈相
Original Assignee
广东生益科技股份有限公司
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Publication date
Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to US15/744,686 priority Critical patent/US10723875B2/en
Publication of WO2018223524A1 publication Critical patent/WO2018223524A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
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    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
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    • C08G59/68—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 catalysts used
    • C08G59/686—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 catalysts used containing nitrogen
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    • H—ELECTRICITY
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    • H—ELECTRICITY
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles

Definitions

  • the invention belongs to the technical field of copper clad laminates, in particular to a halogen-free epoxy resin composition and a prepreg, a laminate and a printed circuit board using the same.
  • halogen flame retardants For a long time, laminates for printed circuit boards usually use halogen flame retardants to achieve flame retardant purposes. However, when halogen flame retardants are burned, not only smoke is large, smell is unpleasant, and highly corrosive hydrogen halide gas is generated. . In other literatures, in recent years, halogen flame retardants produce carcinogens such as dioxins and dibenzofurans during pyrolysis and combustion at high temperatures. Therefore, with the EU Directive on Waste Electrical and Electronic Equipment and on Electrical and Electronic The implementation of the Restriction of Hazardous Substances in Equipment Directive was officially implemented on July 1, 2006, and the development of laminates for halogen-free flame-retardant printed circuit has become the focus of the industry.
  • halogen-free epoxy resin composition and a prepreg and laminate using the same.
  • the laminate produced using the halogen-free epoxy resin composition has the advantages of high-rise adhesion, low coefficient of thermal expansion, and high heat and humidity resistance, and can realize halogen-free flame retardancy.
  • the present inventors conducted intensive studies to achieve the above object, and as a result, found that a halogen-free epoxy resin, an active ester resin, a reactive phosphorus-containing flame retardant, and other optional components are appropriately mixed.
  • the composition can achieve the above purpose.
  • a halogen-free epoxy resin composition comprising the following components:
  • the reactive phosphorus-containing flame retardant has the following structure:
  • R is X is Wherein Y is a substituted phenyl group, an unsubstituted phenyl group, a substituted naphthyl group or an unsubstituted naphthyl group; Z is an unsubstituted group, -CH 2 -, n, m are independently selected from an integer of 0 to 2, such as 0, 1, or 2; and n+m is an integer of ⁇ 1.
  • the invention adopts a reactive phosphorus-containing flame retardant, which has better crosslinkability than ordinary phosphorus-containing phenolic resin, and can improve crosslink density and reactivity.
  • the addition of the halogen-free epoxy resin can significantly improve the curing crosslink density of the cured product;
  • the addition of the ester resin can effectively enhance the crosslinking curing effect of the halogen-free epoxy resin.
  • the present invention obtains the halogen-free epoxy resin composition as described above by utilizing the mutual cooperation and synergistic promotion between the above three essential components.
  • the prepreg and the laminate prepared by using the halogen-free epoxy resin composition have the advantages of high-rise adhesion, low thermal expansion coefficient and high heat and humidity resistance, and the interlayer bonding force can reach 0.45 or more, and the thermal expansion coefficient is 2.10% or less, moisture and heat resistance up to 5min, and can achieve halogen-free flame retardant.
  • the halogen-free epoxy resin is any one or a mixture of at least two of a biphenolic epoxy resin, a DCPD novolac epoxy resin, an alkylene novolac epoxy resin or a bisphenol A type novolac epoxy resin.
  • Typical but non-limiting mixtures are: a mixture of a biphenolic epoxy resin and a DCPD novolac epoxy resin, a mixture of a DCPD novolac epoxy resin and an alkylene novolac epoxy resin, a DCPD novolac epoxy resin, an alkylene group.
  • a mixture of a phenolic epoxy resin and a bisphenol A type phenolic epoxy resin are examples of a phenolic epoxy resin and a bisphenol A type phenolic epoxy resin.
  • the active ester resin is an active ester having a structure in which a rigid structure such as a benzene ring, a naphthalene ring or a cyclopentadiene imparts high heat resistance to the active ester due to the specific structure of the active ester. Due to the regularity of its structure and the absence of secondary hydroxyl groups during the reaction with epoxy resin, it imparts good dielectric properties and heat and humidity resistance.
  • X is phenyl or naphthyl; j is 0 or 1; k is 0 or 1; n represents a repeating unit of 0.25 to 1.25, such as 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65 , 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2 or 1.25.
  • the active ester resin is added in an amount of 11 to 37 parts by weight, for example, 11 parts by weight, 12 parts by weight, 15 parts by weight, 20 parts by weight, based on 100 parts by weight of the halogen-free epoxy resin. 25 The parts by weight, 30 parts by weight, 35 parts by weight or 37 parts by weight, preferably 24 to 37 parts by weight.
  • the reactive phosphorus-containing flame retardant is added in an amount of 40 to 66 parts by weight, for example, 40 parts by weight, 45 parts by weight, 48 parts by weight, based on 100 parts by weight of the halogen-free epoxy resin. 50 parts by weight, 52 parts by weight, 55 parts by weight, 60 parts by weight, 62 parts by weight or 66 parts by weight.
  • the halogen-free epoxy resin composition may further comprise a cyanate ester or a prepolymer thereof, which can increase the glass transition temperature of the composition, and can be realized together with the reactive phosphorus-containing flame retardant.
  • the cyanate ester or a prepolymer thereof is added in an amount of 10 to 20 by weight based on 100 parts by weight of the sum of the halogen-free epoxy resin, the active ester resin, and the reactive phosphorus-containing flame retardant.
  • Parts for example, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight or 20 parts by weight.
  • the cyanate ester may be a cyanate ester compound having at least two cyanooxy groups in a molecule such as a bisphenol A type cyanate ester or a prepolymer thereof, which can better enhance the glass transition of the composition. temperature.
  • the halogen-free epoxy resin composition may further include a curing accelerator which cures the resin and accelerates the curing speed of the resin.
  • the curing agent accelerator is added in an amount of 0.05 to 1 part by weight, for example, 0.05, based on 100 parts by weight of the sum of the halogen-free epoxy resin, the active ester resin, and the reactive phosphorus-containing flame retardant.
  • the curing accelerator is any one or at least two of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl 4-ethylimidazole, 2-phenylimidazole or zinc isooctanoate. a mixture of which is typical but non-limiting: a mixture of 4-dimethylaminopyridine and 2-methylimidazole, 2-methylimidazole and 2-methyl A mixture of 4-ethylimidazole, a mixture of 2-phenylimidazole and zinc isooctylate, a mixture of 2-methylimidazole, 2-methyl 4-ethylimidazole and 2-phenylimidazole.
  • the present invention may optionally additionally add at least one specific flame retardant compound.
  • the flame retardant compound may be selected from, but not limited to, a flame retardant salt such as a phosphate compound or a nitrogen-containing phosphate compound.
  • the flame retardant compound is added in an amount of from 0 to 50 parts by weight, based on 100 parts by weight of the sum of the halogen-free epoxy resin, the active ester resin, and the reactive phosphorus-containing flame retardant. 0, for example, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or 50 parts by weight.
  • the halogen-free epoxy resin composition may further comprise a filler, which is an organic or/and inorganic filler, which is mainly used to adjust some physical properties of the composition, such as lowering coefficient of thermal expansion (CTE), and reducing Water absorption and thermal conductivity increase.
  • a filler which is an organic or/and inorganic filler, which is mainly used to adjust some physical properties of the composition, such as lowering coefficient of thermal expansion (CTE), and reducing Water absorption and thermal conductivity increase.
  • the filler is added in an amount of from 0 to 100 parts by weight and not including 0, based on 100 parts by weight of the sum of the halogen-free epoxy resin, the active ester resin, and the reactive phosphorus-containing flame retardant.
  • the inorganic filler may be selected from the group consisting of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, Any one or a mixture of at least two of silicon carbide, barium sulfate, barium titanate, barium titanate, calcium carbonate, calcium silicate, mica or fiberglass powder, wherein a typical but non-limiting mixture is: molten two Silicon oxide and a mixture of crystalline silica, a mixture of spherical silica and hollow silica, a mixture of aluminum hydroxide and aluminum oxide, a mixture of talc and aluminum nitride, a mixture of boron nitride and silicon carbide, barium sulfate Mixture with barium titanate, mixture of barium titanate and calcium carbonate, mixture of calcium silicate, mica and glass fiber powder, mixture of fused silica
  • the organic filler may be selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide or polyethersulfone powder, wherein a typical but non-limiting mixture is: polytetrafluoroethylene a mixture of ethylene powder and polyphenylene sulfide, a mixture of polyethersulfone powder and polytetrafluoroethylene powder, a mixture of polyphenylene sulfide and polyethersulfone powder, polytetrafluoroethylene powder, polyphenylene sulfide and polyethersulfone powder mixture.
  • the filler is silica, and the filler has a median particle diameter of 1 to 15 ⁇ m, for example, 1 ⁇ m, 2 ⁇ m, 5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m or 15 ⁇ m, preferably in the particle diameter of the filler.
  • the degree is 1 to 10 ⁇ m.
  • the halogen-free 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 halogen-free epoxy resin composition of the present invention is conventionally prepared by taking a container, first putting a solid component, then adding a liquid solvent, stirring until completely dissolved, adding liquid resin, filler, and resistance. The fuel and the curing accelerator are continuously stirred, and finally the solvent is used to adjust the liquid solid content to 60 to 80% to prepare a glue.
  • Another object of the present invention is to provide a prepreg comprising a reinforcing material and a halogen-free epoxy resin composition as described above adhered thereto by impregnation and drying.
  • Exemplary reinforcing materials are nonwoven fabrics and/or other fabrics such as natural fibers, organic synthetic fibers, and inorganic fibers.
  • the prepreg is obtained by heating and drying the impregnated reinforcing material in an oven at 155 to 170 ° C for 5 to 10 minutes by using a woven fabric or an organic fabric such as a glass cloth impregnated reinforcing material.
  • a third object of the present invention is to provide a laminate comprising at least one prepreg as described above.
  • a fourth object of the present invention is to provide a printed circuit board comprising at least one prepreg as described above.
  • the present invention has at least the following beneficial effects:
  • the reactive phosphorus-containing flame retardant can be used as a curing agent for an epoxy resin, and can provide a halogen-free flame retardant property, and is combined with a halogen-free epoxy resin composed of a halogen-free epoxy resin and an active ester resin.
  • the three interact with each other to have a synergistic promoting effect; the prepreg, the laminate and the metal foil-clad laminate produced by the halogen-free epoxy resin composition not only have interlayer adhesion of up to 0.45 or more
  • the force, the thermal expansion coefficient as low as 2.10% and the heat and humidity resistance up to 5 min, and the halogen-free flame retardant can be achieved.
  • the above glue is impregnated with a glass fiber cloth to form a glue.
  • the above-mentioned glue was impregnated with a glass cloth of 2116 size, and controlled to a prepreg having a resin content of 50%, and then the solvent was removed by drying to obtain a prepreg.
  • the prepregs prepared by using 6 sheets are superposed on each other, and a copper foil is respectively pressed on both sides thereof and placed in a hot press.
  • the intermediate layer is cured to form the epoxy resin copper clad laminate.
  • Table 1 The physical property data is shown in Table 1.
  • the manufacturing process was the same as that of Example 1, and the formulation composition and physical property index are shown in Table 2.
  • the table is based on the weight of solid components.
  • R is an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group.
  • NC-3000H Biphenol novolac epoxy resin (trade name of Nippon Chemical Co., Ltd.).
  • HPC-8000-65T Active ester resin (Japanese DIC trade name).
  • CE01PS bisphenol A type cyanate (Yangzhou Tianqi Chemical Trade Name).
  • BYK-W903 filler dispersant (BYK trade name).
  • DMAP curing accelerator, 4-dimethylaminopyridine (Golden Chemical Co., trade name).
  • Zinc isooctanoate curing accelerator (Alfa Aesar trade name).
  • Interlayer adhesion (vertical method): The interlayer adhesion of the composition was tested by the vertical stretching method specified in SYL Enterprise Standard Q/GDSY6052-2016.
  • thermomechanical analysis method TMA
  • the measurement was carried out in accordance with the TMA method specified in IPC-TM-6502.4.24.
  • Example 1 was composed of a halogen-free epoxy resin 7200-H, an active ester resin HPC-8000-65T, and a reactive phosphorus-containing flame retardant B1.
  • a halogen epoxy resin composition which has a laminate having an interlayer adhesion of 0.45 to 0.60 and a coefficient of thermal expansion of 1.90%, and has a heat and humidity resistance of more than 5 minutes as measured by PCT (6h), and can achieve halogen-free flame retardancy.
  • Comparative Examples 1 and 2 a halogen-free epoxy resin, an active ester resin HPC-8000-65T, and a halogen-free epoxy resin composed of a phosphorus-containing phenolic resin 92741 were used, and the interlayer bonding force of the laminate prepared was 0.20. ⁇ 0.30, much lower than Example 1, the coefficient of thermal expansion is 2.70%, which is much larger than that of Example 1, and its heat and humidity resistance is 3s as measured by PCT (6h), which is much lower than the implementation. example 1.
  • Example 1 adopts a halogen-free epoxy resin composition composed of a halogen-free epoxy resin, an active ester resin and a reactive phosphorus-containing flame retardant, and a reactive phosphorus-containing resist is used as compared with Comparative Examples 1 and 2.
  • the flammable agent is replaced with a halogen-free epoxy resin composition containing a phosphorus phenolic resin, and the laminate is made of a higher interlayer adhesion, a lower coefficient of thermal expansion, and more excellent heat and humidity resistance, and can be halogen-free. Flame retardant.
  • Example 2 Comparing Example 2 with Comparative Example 3, the halogen-free ring composed of the halogen-free epoxy resin NC-3000H, the active ester resin HPC-8000-65T, and the reactive phosphorus-containing flame retardant B1 was used in Example 2.
  • the oxyresin composition has a laminate having an interlayer adhesion of 0.60 to 0.80, a thermal expansion coefficient of 2.10%, a heat and humidity resistance of more than 5 minutes, and a halogen-free flame retardant, and a halogen-free method in Comparative Example 3
  • a halogen-free epoxy resin composition composed of epoxy resin NC-3000H, novolac resin 2812 and reactive phosphorus-containing flame retardant B1
  • the interlayer adhesion of the laminate prepared is 0.26 to 0.36, which is much lower than
  • the coefficient of thermal expansion was 2.80%, which was much larger than that of Example 2
  • its heat and humidity resistance was 3 s as measured by PCT (6h), which was much lower than that of Example 2.
  • Example 1 Comparing Example 1 with Comparative Example 4, the halogen-free epoxy resin composition comprising the halogen-free epoxy resin 7200-H, the active ester HPC-8000-65T and the reactive phosphorus-containing flame retardant B2 was used in Example 1.
  • the laminate produced has an interlayer bonding force of 0.45 to 0.60, a thermal expansion coefficient of 1.90%, a heat and humidity resistance of more than 5 minutes, and a halogen-free flame retardant, and a halogen-free epoxy resin 7200 is used in Comparative Example 4.
  • a halogen-free epoxy resin composition composed of -H, a novolac resin 2812 and a reactive phosphorus-containing flame retardant B2, which has a laminate having an interlayer adhesion of 0.27 to 0.37, which is much lower than that of the embodiment 1.
  • the coefficient of thermal expansion was 2.40%, which was much larger than that of Example 1, and its heat and humidity resistance was 3 s as measured by PCT (6h), which was much lower than that of Example 1.
  • Examples 1 and 2 employ a halogen-free epoxy resin composition composed of a halogen-free epoxy resin, an active ester resin, and a reactive phosphorus-containing flame retardant, and an active ester resin is used as compared with Comparative Examples 3 to 4.
  • a halogen-free epoxy resin composition substituted with a novolac resin which has a laminate having a higher interlayer adhesion, a lower coefficient of thermal expansion, and more excellent heat and humidity resistance, and is capable of achieving halogen-free flame retardancy.
  • Example 3 Comparing Examples 3 and 5 with Comparative Example 5, the halogen-free ring composed of epoxy resin NC-3000H, active ester resin HPC-8000-65T and reactive phosphorus-containing flame retardant B1 was used in Example 3.
  • the oxyresin composition has a laminate having an interlayer adhesion of 0.62 to 0.82, a thermal expansion coefficient of 2.00%, a heat and humidity resistance of more than 5 minutes, and a halogen-free flame retardant, and an epoxy resin is used in the embodiment 5.
  • a halogen-free epoxy resin composition comprising NC-3000H, an active ester resin HPC-8000-65T and a reactive phosphorus-containing flame retardant B2, wherein the laminate has a interlayer adhesion of 0.70 to 0.90 and a coefficient of thermal expansion 2.10%, its heat and humidity resistance is greater than 5min, and can achieve halogen-free flame retardant, while in Comparative Example 5, epoxy resin NC-3000H, active ester resin HPC-8000-65T and reactive phosphorus-containing flame retardant B3 are used.
  • a halogen-free epoxy resin composition which has a laminate having an interlayer adhesion of only 0.20 to 0.30, which is much lower than Examples 3 and 5, and has a coefficient of thermal expansion of 2.80%, which is higher than Examples 3 and 5, The heat and humidity resistance is only 3 s, which is much lower than Examples 3 and 5.
  • Examples 3 and 5 employ the halogen-free epoxy resin composition composed of a halogen-free epoxy resin, an active ester resin, and a reactive phosphorus-containing flame retardant B1 or B2, and the present invention is used in comparison with Comparative Example 5.
  • the reactive phosphorus-containing flame retardants B1 and B2 replace the halogen-free epoxy resin composition composed of B3 in CN105906785A, and the laminates thereof have higher interlayer adhesion, lower thermal expansion coefficient and more excellent It is resistant to heat and humidity and can achieve halogen-free flame retardant.
  • the present invention employs a halogen-free epoxy resin, an active ester resin, and a reactive phosphorus-containing flame retardant in a halogen-free epoxy resin composition, the three essential components.
  • the prepreg and the laminate prepared by using the halogen-free epoxy resin composition have the advantages of high-rise adhesion, low thermal expansion coefficient and high heat and humidity resistance, and the layers are inter-layered and synergistically promoted.
  • the bonding force can reach 0.45 or more, the thermal expansion coefficient is less than 2.10%, the heat and humidity resistance is more than 5 minutes, and the halogen-free flame retardant can be realized.
  • the present invention uses a prepreg made of a halogen-free epoxy resin composition composed of a halogen-free epoxy resin, an active ester resin, and a reactive phosphorus-containing flame retardant, compared with a general laminate.
  • Laminate and The metal foil-clad laminate has the advantages of high-rise adhesion, low coefficient of thermal expansion, and high heat and humidity resistance, and can achieve halogen-free flame retardant.
  • the present invention illustrates the detailed process equipment and process flow of the present invention by the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, that is, does not mean that the present invention must rely on the above detailed process equipment and The process can only be implemented. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

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Abstract

无卤环氧树脂组合物以及使用它的预浸料和层压板。该无卤环氧树脂组合物包括：（A）无卤环氧树脂；（B）活性酯树脂；（C）反应型含磷阻燃剂。使用这种无卤环氧树脂组合物制成的预浸料和层压板，具有高层间粘合力、低热膨胀系数和高耐湿热性的优点，且能实现无卤阻燃。

Description

[根据细则37.2由ISA制定的发明名称]　无卤环氧树脂组合物以及使用它的预浸料和层压板 技术领域
本发明属于覆铜板技术领域，尤其涉及一种无卤环氧树脂组合物以及使用它的预浸料、层压板和印制电路板。
背景技术
一直以来，印制电路用层压板通常采用卤素阻燃剂达到阻燃目的，但卤素阻燃剂在燃烧时，不但发烟量大，气味难闻，而且会产生腐蚀性很强的卤化氢气体。另有文献报道，近年来卤素阻燃剂在高温裂解和燃烧时会产生二噁英、二苯并呋喃等致癌物质，因此，随着欧盟《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有害物质指令》于2006年7月1日的正式实施，无卤阻燃型印制电路用层压板的开发成为了业界的重点。
随着电子材料往轻、薄、短、小的方向发展，更低的损耗和更高的耐热可靠性成为未来的方向，这除了要求层压板具有更高的Tg外，还需具有更好地层间粘合力和低热膨胀系数。
如何在保持组合物具有实现无卤阻燃的同时，兼具好的层间粘合力和低热膨胀系数以及高耐湿热性是本领域亟待解决的技术问题。
发明内容
针对已有技术的问题，本发明的目的在于提供一种无卤环氧树脂组合物以及使用它的预浸料和层压板。使用该无卤环氧树脂组合物制造的层压板具有高层间粘合力、低热膨胀系数和高耐湿热性的优点，且能实现无卤阻燃。
本发明人为实现上述目的进行了反复深入的研究，结果发现：通过将无卤环氧树脂、活性酯树脂和反应型含磷阻燃剂，及其他可选地组分适当混合得到 的组合物，可达到上述目的。
一种无卤环氧树脂组合物，其包括如下组分：
(A)无卤环氧树脂；
(B)活性酯树脂；
(C)反应型含磷阻燃剂；
所述反应型含磷阻燃剂具有如下结构：
Figure PCTCN2017097335-appb-000001
其中，R为
Figure PCTCN2017097335-appb-000002
X为
Figure PCTCN2017097335-appb-000003
其中，Y为取代的苯基、未取代的苯基、取代的萘基或未取代的萘基；Z为无取代基，-CH2-，
Figure PCTCN2017097335-appb-000004
n、m独立选自0～2的整数，例如0、1或2；且n+m为≥1的整数。
本发明采用反应型含磷阻燃剂，相较于普通含磷酚醛树脂有较佳的交联性，可提高交联密度和反应性。
在本发明中，无卤环氧树脂的加入可以明显改善固化物固化交联密度；活 性酯树脂的加入可有效提升和无卤环氧树脂的交联固化作用。
本发明利用上述三种必要组分之间的相互配合以及相互协同促进作用，得到了如上所述的无卤环氧树脂组合物。采用该无卤环氧树脂组合物制成的预浸料及层压板，兼具高层间粘合力、低热膨胀系数和高耐湿热性的优点，其层间结合力可达到0.45以上，热膨胀系数在2.10％以下，耐湿热性高达5min以上，且能实现无卤阻燃。
优选地，所述无卤环氧树脂为联苯酚醛环氧树脂、DCPD酚醛环氧树脂、亚烷基酚醛环氧树脂或双酚A型酚醛环氧树脂任意一种或至少两种的混合物，其中典型但非限制性的混合物为：联苯酚醛环氧树脂和DCPD酚醛环氧树脂的混合物，DCPD酚醛环氧树脂和亚烷基酚醛环氧树脂的混合物，DCPD酚醛环氧树脂、亚烷基酚醛环氧树脂和双酚A型酚醛环氧树脂的混合物。
优选地，所述活性酯树脂为具有如下结构的活性酯，由于该活性酯的特殊结构，其中的苯环、萘环、环戊二烯等刚性结构赋予该活性酯高的耐热性，同时由于其结构的规整性及与环氧树脂反应过程中无二次羟基产生，赋予其良好的介电性能和耐湿热性。
Figure PCTCN2017097335-appb-000005
其中，X为苯基或者萘基；j为0或1；k为0或1；n表示重复单元，为0.25～1.25，例如0.25、0.3、0.35、0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9、0.95、1.0、1.05、1.1、1.15、1.2或1.25。
优选地，以无卤环氧树脂的添加量为100重量份计，所述活性酯树脂的添加量为11～37重量份，例如11重量份、12重量份、15重量份、20重量份、25 重量份、30重量份、35重量份或37重量份，优选24～37重量份。
优选地，以无卤环氧树脂的添加量为100重量份计，所述反应型含磷阻燃剂的添加量为40～66重量份，例如40重量份、45重量份、48重量份、50重量份、52重量份、55重量份、60重量份、62重量份或66重量份。
优选地，所述无卤环氧树脂组合物还可进一步包括氰酸酯或其预聚物，该组分可提升组合物的玻璃化转变温度，同时与反应型含磷阻燃剂可共同实现N-P协同阻燃，提高阻燃效率。
优选地，以无卤环氧树脂、活性酯树脂和反应型含磷阻燃剂的添加量之和为100重量份计，所述氰酸酯或其预聚物的添加量为10～20重量份，例如10重量份、12重量份、14重量份、16重量份、18重量份或20重量份。
优选地，所述氰酸酯可以为双酚A型氰酸酯等分子中含有至少2个氰氧基的氰酸酯化合物或其预聚物，其可更好地提升组合物的玻璃化转变温度。
优选地，所述无卤环氧树脂组合物还可进一步包括固化促进剂，其使树脂固化并加快树脂固化速度。
优选地，以无卤环氧树脂、活性酯树脂和反应型含磷阻燃剂的添加量之和为100重量份计，所述固化剂促进剂的添加量为0.05～1重量份，例如0.05重量份、0.08重量份、0.1重量份、0.15重量份、0.2重量份、0.25重量份、0.3重量份、0.35重量份、0.4重量份、0.45重量份、0.5重量份、0.55重量、0.60重量份、0.65重量份、0.7重量份、0.75重量份、0.8重量份、0.85重量份、0.9重量份、0.95重量份或1重量份。
优选地，所述固化促进剂为4-二甲氨基吡啶、2-甲基咪唑、2-甲基4-乙基咪唑、2-苯基咪唑或异辛酸锌中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为：4-二甲氨基吡啶和2-甲基咪唑的混合物，2-甲基咪唑和2-甲基 4-乙基咪唑的混合物，2-苯基咪唑和异辛酸锌的混合物，2-甲基咪唑、2-甲基4-乙基咪唑和2-苯基咪唑的混合物。
为进一步提高无卤环氧树脂组合物的难燃特性，于较佳的情形中，本发明尚可选择性添加至少一种特定的阻燃性化合物。
优选地，所述阻燃性化合物可以选自阻燃性盐类，如磷酸盐化合物或含氮磷酸盐化合物，但并不仅限于此。
优选地，以无卤环氧树脂、活性酯树脂和反应型含磷阻燃剂的添加量之和为100重量份计，所述阻燃性化合物的添加量为0～50重量份且不包括0，例如5重量份、10重量份、15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份或50重量份。
优选地，所述无卤环氧树脂组合物还可进一步包含填料，所述填料为有机或/和无机填料，其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)、降低吸水率和提高热导率等。
优选地，以无卤环氧树脂、活性酯树脂和反应型含磷阻燃剂的添加量之和为100重量份计，所述填料的添加量为0～100重量份且不包括0，例如0.5重量份、1重量份、5重量份、10重量份、15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份、85重量份、90重量份、95重量份或100重量份，优选0～50重量份且不包括0。
优选地，所述无机填料可以选自熔融二氧化硅、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至少两种的混合物，其中典型但非限制性的混合物为：熔融二氧化硅和 结晶型二氧化硅的混合物，球型二氧化硅和空心二氧化硅的混合物，氢氧化铝和氧化铝的混合物，滑石粉和氮化铝的混合物，氮化硼和碳化硅的混合物，硫酸钡和钛酸钡的混合物，钛酸锶和碳酸钙的混合物，硅酸钙、云母和玻璃纤维粉的混合物，熔融二氧化硅、结晶型二氧化硅和球型二氧化硅的混合物，空心二氧化硅、氢氧化铝和氧化铝的混合物，滑石粉、氮化铝和氮化硼的混合物，碳化硅、硫酸钡和钛酸钡的混合物，钛酸锶、碳酸钙、硅酸钙、云母和玻璃纤维粉的混合物。
优选地，所述有机填料可以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至少两种的混合物，其中典型但非限制性的混合物为：聚四氟乙烯粉末和聚苯硫醚的混合物，聚醚砜粉末和聚四氟乙烯粉末的混合物，聚苯硫醚和聚醚砜粉末的混合物，聚四氟乙烯粉末、聚苯硫醚和聚醚砜粉末的混合物。
优选地，所述填料为二氧化硅，填料的粒径中度值为1～15μm，例如1μm、2μm、5μm、8μm、10μm、11μm、12μm、13μm、14μm或15μm，优选填料的粒径中度值为1～10μm。
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环氧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，所述无卤环氧树脂组合物还可以含有各种添加剂，作为具体例，可以举出抗氧剂、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。
本发明的无卤环氧树脂组合物的常规制作方法为：取一容器，先将固体组分放入，然后加入液体溶剂，搅拌直至完全溶解后，加入液体树脂、填料、阻 燃剂和固化促进剂，继续搅拌均匀即可，最后用溶剂调整液体固含量至60～80％而制成胶液。
本发明的目的之二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其上的如上所述的无卤环氧树脂组合物。
示例性的增强材料如无纺织物或/和其他织物，例如天然纤维、有机合成纤维以及无机纤维。
使用该胶液含浸增强材料如玻璃布等织物或有机织物，将含浸好的增强材料在155～170℃的烘箱中加热干燥5～10分钟即可得到预浸料。
本发明的目的之三在于提供一种层压板，其包括至少一张如上所述的预浸料。
本发明的目的之四在于提供一种印制电路板，其包括至少一张如上所述的预浸料。
与现有技术相比，本发明至少具有以下有益效果：
在本发明中，反应型含磷阻燃剂既可作为环氧树脂的固化剂，又能提供无卤阻燃特性，且与无卤环氧树脂和活性酯树脂组成的无卤环氧树脂组合物中，这三者之间相互配合，具有协同促进作用；利用该无卤环氧树脂组合物制作的预浸料、层压板和覆金属箔层压板，不仅具有高达0.45以上的层间粘合力、低至2.10％以下的热膨胀系数以及高达5min以上的耐湿热性，且能实现无卤阻燃。
具体实施方式
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
根据上述所制成的无卤环氧树脂组合物覆金属箔层压板，测试其层间粘合力、热膨胀系数以及燃烧性，如下实施例用于详细说明与描述，其中有机树脂 的质量份按有机固形物质量份计。
制备例1：反应型含磷阻燃剂B1的制备
在反应釜中投490g双酚F、324克甲醛水溶液(质量浓度为37％)和24g氢氧化钠，开启搅拌，将温度加热至40℃，保温3小时；然后升温至65℃，保温3小时后，加入1480g正丁醇，回流12小时；将料温降至55～60℃，并减压蒸馏除去1000g左右的正丁醇，得到中间体。
往中间体中加入1080g DOPO(9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物)，在2小时内将料温从80℃逐步升温至190℃，并在120℃时向体系施加减压以保证正丁醇及时排出体系。在180℃下保温1小时，然后将料温降至135℃，加入900g左右的丙二醇甲醚，继续搅拌0.5小时，放料，得到磷系固化剂A1。
在安装有温度计、滴液漏斗、冷凝管、分馏管、搅拌器的烧瓶中加入1molA2和816g甲基异丁基酮(MIBK)，将体系内减压氮气置换，使其溶解。接着，投入0.9mol对苯二甲酰氯，反应2h，体系内温度控制在60℃以下；然后，向体系中加入1.2mol苯酚，继续反应1h；通氮气条件下，缓慢滴加189g的20％氢氧化钠水溶液；在该条件下继续搅拌1小时。反应结束后，静止分液除去水层。在反应物溶解的MIBK相中投入水，搅拌混合，静止分液，除去水层。重复上述操作直至水层的pH值达到7.0左右。然后通过倾析器脱去水分，接着减压蒸馏脱去MIBK，得到反应型含磷阻燃剂B1，酯基当量为223g/mol。
制备例2：反应型含磷阻燃剂B2的制备
在反应釜中投372g二羟基联苯、324克甲醛水溶液(质量浓度为37％)和24g氢氧化钠，开启搅拌，将温度加热至40℃，保温3小时；然后升温至65℃， 保温3小时后，加入1480g正丁醇，回流12小时；将料温降至55～60℃，并减压蒸馏除去1000g左右的正丁醇，得到中间体。
往中间体中加入1080g DOPO(9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物)，在2小时内将料温从80℃逐步升温至190℃，并在120℃时向体系施加减压以保证正丁醇及时排出体系。在180℃下保温1小时，然后将料温降至135℃，加入900g左右的丙二醇甲醚，继续搅拌0.5小时，放料，得到磷系固化剂A2。
在安装有温度计、滴液漏斗、冷凝管、分馏管、搅拌器的烧瓶中加入1molA2和816g甲基异丁基酮(MIBK)，将体系内减压氮气置换，使其溶解。接着，投入0.9mol对苯二甲酰氯，反应2h，体系内温度控制在60℃以下；然后，向体系中加入1.2mol苯酚，继续反应1h；通氮气条件下，缓慢滴加189g的20％氢氧化钠水溶液；在该条件下继续搅拌1小时。反应结束后，静止分液除去水层。在反应物溶解的MIBK相中投入水，搅拌混合，静止分液，除去水层。重复上述操作直至水层的pH值达到7.0左右。然后通过倾析器脱去水分，接着减压蒸馏脱去MIBK，得到反应型含磷阻燃剂B2，酯基当量为226g/mol。
实施例1
取一容器，加入100重量份的7200-H和适量的MEK，搅拌溶解后，加入37重量份的HPC-8000-65T、40重量份制备例1中的反应型含磷阻燃剂和76重量份的硅微粉525和0.76重量份的BYK-W903，搅拌，加入适量的固化促进剂DMAP，继续搅拌均匀，最后用溶剂调整液体固含量至60～70％而制成胶液。
用玻璃纤维布浸渍上述胶液，即成胶液。用2116规格的玻璃纤维布浸渍上述胶液，并控制至树脂含量为50％的半固化片，然后烘干除去溶剂得到预浸料。使用6张所制得的预浸料相互叠合，在其两侧分别压覆一张铜箔，放进热压机 中固化制成所述的环氧树脂覆铜板层压板。物性数据如表1所示。
实施例2～8：
制作工艺和实施例1相同，配方组成及其物性指标如表1所示。
比较例1～5：
制作工艺与实施例1相同，配方组成及其物性指标如表2所示。
注：表中皆以固体组分重量份计。
表1和表2列举的材料具体如下：
B1：制备例1得到的反应型含磷阻燃剂。
B2：制备例2得到的反应型含磷阻燃剂。
B3：CN105906785A专利中具有如下结构的物质：
Figure PCTCN2017097335-appb-000006
其中R为含有1～8个碳原子的烷基基团或为取代或未取代的苯基。
2812：线性酚醛树脂(韩国Momentive商品名)。
92741：含磷酚醛树脂(DOW商品名)。
NC-3000H：联苯酚醛环氧树脂(日本化药商品名)。
7200-H：DCPD型酚醛环氧树脂(DIC商品名)。
HPC-8000-65T：活性酯树脂(日本DIC商品名)。
CE01PS：双酚A型氰酸酯(扬州天启化学商品名)。
525：二氧化硅填料(矽比科商品名)。
BYK-W903：填料分散剂(BYK商品名)。
DMAP：固化促进剂，4-二甲氨基吡啶(广荣化学商品名)。
异辛酸锌：固化促进剂(阿法埃莎商品名)。
表1
Figure PCTCN2017097335-appb-000007
表2
Figure PCTCN2017097335-appb-000008
Figure PCTCN2017097335-appb-000009
以上特性的测试方法如下：
(1)层间粘合力(垂直法)：采用SYL企业标准Q/GDSY6052-2016所规定的垂直拉伸法测试组合物的层间粘合力。
(2)热膨胀系数：根据热机械分析法(TMA)，按照IPC-TM-6502.4.24所规定的TMA方法进行测定。
(3)PCT(6h)：将覆铜板表明的铜箔蚀刻后，评价基板：将基板放置压力锅中，在120℃、105KPa条件下，处理6个小时：后浸渍于288℃的锡炉中，当基材分层时，记录相应时间：当基板在锡炉中超过5min还没出现气泡或分层时即可结束评价。
(4)燃烧性：依照UL94法规定。
从表1和表2的物性数据可知：
(1)将实施例1与比较例1和2相比，实施例1中采用无卤环氧树脂7200-H、活性酯树脂HPC-8000-65T和反应型含磷阻燃剂B1组成的无卤环氧树脂组合物，其制成的层压板的层间结合力为0.45～0.60，热膨胀系数为1.90％，经PCT(6h)测定，其耐湿热性大于5min，并可实现无卤阻燃，而比较例1和2中采用无卤环氧树脂、活性酯树脂HPC-8000-65T和含磷酚醛树脂92741组成的无卤环氧树脂，其制成的层压板的层间结合力为0.20～0.30，远低于实施例1，热膨胀系数为2.70％，远大于实施例1，经PCT(6h)测定，其耐湿热性为3s，远低于实施 例1。
以上结果说明，实施例1通过采用无卤环氧树脂、活性酯树脂和反应型含磷阻燃剂组成的无卤环氧树脂组合物，相比比较例1～2采用将反应型含磷阻燃剂替换为含磷酚醛树脂的无卤环氧树脂组合物，其制成的层压板具有更高的层间结合力、更低的热膨胀系数以及更优异的耐湿热性，且能实现无卤阻燃。
(2)将实施例2与比较例3相比，实施例2中采用无卤环氧树脂NC-3000H、活性酯树脂HPC-8000-65T和反应型含磷阻燃剂B1组成的无卤环氧树脂组合物，其制成的层压板的层间结合力为0.60～0.80，热膨胀系数为2.10％，其耐湿热性大于5min，并可实现无卤阻燃，而比较例3中采用无卤环氧树脂NC-3000H、线性酚醛树脂2812和反应型含磷阻燃剂B1组成的无卤环氧树脂组合物，其制成的层压板的层间粘合力为0.26～0.36，远低于实施例2，热膨胀系数为2.80％，远大于实施例2，经PCT(6h)测定，其耐湿热性为3s，远低于实施例2。
将实施例1与比较例4相比，实施例1中采用无卤环氧树脂7200-H、活性酯HPC-8000-65T和反应型含磷阻燃剂B2组成的无卤环氧树脂组合物，其制成的层压板的层间结合力为0.45～0.60，热膨胀系数为1.90％，其耐湿热性大于5min，并可实现无卤阻燃，而比较例4中采用无卤环氧树脂7200-H、线性酚醛树脂2812和反应型含磷阻燃剂B2组成的无卤环氧树脂组合物，其制成的层压板的层间粘合力为0.27～0.37，远低于实施例1，热膨胀系数为2.40％，远大于实施例1，经PCT(6h)测定，其耐湿热性为3s，远低于实施例1。
以上结果说明，实施例1和2通过采用无卤环氧树脂、活性酯树脂和反应型含磷阻燃剂组成的无卤环氧树脂组合物，相比比较例3～4采用将活性酯树脂替换为线性酚醛树脂的无卤环氧树脂组合物，其制成的层压板具有更高的层间结合力、更低的热膨胀系数以及更优异的耐湿热性，且能实现无卤阻燃。
(3)将实施例3和5与比较例5相比，实施例3中采用环氧树脂NC-3000H、活性酯树脂HPC-8000-65T和反应型含磷阻燃剂B1组成的无卤环氧树脂组合物，其制成的层压板的层间结合力为0.62～0.82，热膨胀系数为2.00％，其耐湿热性大于5min，并可实现无卤阻燃，实施例5中采用环氧树脂NC-3000H、活性酯树脂HPC-8000-65T和反应型含磷阻燃剂B2组成的无卤环氧树脂组合物，其制成的层压板的层间结合力为0.70～0.90，热膨胀系数为2.10％，其耐湿热性大于5min，并可实现无卤阻燃，而比较例5中采用环氧树脂NC-3000H、活性酯树脂HPC-8000-65T和反应型含磷阻燃剂B3组成的无卤环氧树脂组合物，其制成的层压板的层间结合力仅为0.20～0.30，远低于实施例3和5，热膨胀系数为2.80％，原高于实施例3和5，其耐湿热性仅为3s，远低于实施例3和5。
以上结果说明，实施例3和5通过采用无卤环氧树脂、活性酯树脂和反应型含磷阻燃剂B1或B2组成的无卤环氧树脂组合物，相比比较例5采用将本发明的反应型含磷阻燃剂B1和B2替换CN105906785A中的B3组成的无卤环氧树脂组合物，其制成的层压板具有更高的层间结合力、更低的热膨胀系数以及更优异的耐湿热性，且能实现无卤阻燃。
(4)通过实施例1～8可以看出，本发明采用无卤环氧树脂、活性酯树脂和反应型含磷阻燃剂组成的无卤环氧树脂组合物中，这三种必要组分之间相互配合并具有协同促进作用，采用该无卤环氧树脂组合物制成的预浸料及层压板，兼具高层间粘合力、低热膨胀系数和高耐湿热性的优点，其层间结合力可达到0.45以上，热膨胀系数在2.10％以下，耐湿热性达到5min以上，且能实现无卤阻燃。
综上所述，与一般的层压板相比，本发明采用由无卤环氧树脂、活性酯树脂和反应型含磷阻燃剂组成的无卤环氧树脂组合物而制作的预浸料、层压板和 覆金属箔层压板，具有高层间粘合力、低热膨胀系数以及高耐湿热性的优点，且能实现无卤阻燃。
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。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 (10)

  1. 一种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包括如下组分：
    (A)无卤环氧树脂；
    (B)活性酯树脂；
    (C)反应型含磷阻燃剂；
    所述反应型含磷阻燃剂具有如下结构：
    Figure PCTCN2017097335-appb-100001
    其中，R为
    Figure PCTCN2017097335-appb-100002
    X为
    Figure PCTCN2017097335-appb-100003
    其中，Y为取代的苯基、未取代的苯基、取代的萘基或未取代的萘基；Z为无取代基，
    Figure PCTCN2017097335-appb-100004
    n、m独立选自0～2的整数，且n+m为≥1的整数。
  2. 如权利要求1所述的无卤环氧树脂组合物，其特征在于，所述无卤环氧树脂为联苯酚醛环氧树脂、DCPD型酚醛环氧树脂、亚烷基酚醛环氧树脂或双酚A型酚醛环氧树脂中的任意一种或至少两种的混合物。
  3. 如权利要求1或2所述的无卤环氧树脂组合物，其特征在于，所述活性酯树脂具有如下结构：
    Figure PCTCN2017097335-appb-100005
    其中，X为苯基或者萘基；j为0或1；k为0或1；n表示重复单元，为0.25～1.25；
    优选地，以无卤环氧树脂的添加量为100重量份计，所述活性酯树脂的添加量为11～37重量份，优选24～37重量份；
    优选地，以无卤环氧树脂的添加量为100重量份计，所述反应型含磷阻燃剂的添加量为40～66重量份。
  4. 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氰酸酯或其预聚物；
    优选地，以无卤环氧树脂、活性酯树脂和反应型含磷阻燃剂的添加量之和为100重量份计，所述氰酸酯或其预聚物的添加量为10～20重量份。
  5. 如权利要求1-4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固化促进剂；
    优选地，以无卤环氧树脂、活性酯树脂和反应型含磷阻燃剂的添加量之和为100重量份计，所述固化剂促进剂的添加量为0.05～1重量份；
    优选地，所述固化促进剂为4-二甲氨基吡啶、2-甲基咪唑、2-甲基4-乙基咪唑、2-苯基咪唑或异辛酸锌中的任意一种或至少两种的混合物。
  6. 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，所述无卤环氧树脂组合物还包括阻燃性化合物；
    优选地，所述阻燃性化合物为阻燃性盐类，优选磷酸盐化合物或含氮磷酸 盐化合物；
    优选地，以无卤环氧树脂、活性酯树脂和反应型含磷阻燃剂的添加量之和为100重量份计，所述阻燃性化合物的添加量为0～50重量份且不包括0。
  7. 如权利要求1-6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含填料；
    优选地，所述填料为有机或/和无机填料；
    优选地，以无卤环氧树脂、活性酯树脂和反应型含磷阻燃剂的添加量之和为100重量份计，所述填料的添加量为0～100重量份且不包括0，优选0～50重量份且不包括0；
    优选地，所述无机填料为熔融二氧化硅、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至少两种的混合物；
    优选地，所述有机填料为聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或至少两种的混合物；
    优选地，所述填料为二氧化硅，填料的粒径中度值为1～15μm，优选填料的粒径中度值为1～10μm。
  8. 一种预浸料，其包括增强材料及通过含浸干燥后附着在其上的如权利要求1-7之一所述的无卤环氧树脂组合物。
  9. 一种层压板，其包括至少一张如权利要求8所述的预浸料。
  10. 一种印制电路板，其包括至少一张如权利要求8所述的预浸料。
PCT/CN2017/097335 2017-06-05 2017-08-14 无卤环氧树脂组合物以及使用它的预浸料和层压板 WO2018223524A1 (zh)

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