WO2016101497A1 - 环氧树脂组合物以及使用它的预浸料和层压板 - Google Patents

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
WO2016101497A1
WO2016101497A1 PCT/CN2015/078781 CN2015078781W WO2016101497A1 WO 2016101497 A1 WO2016101497 A1 WO 2016101497A1 CN 2015078781 W CN2015078781 W CN 2015078781W WO 2016101497 A1 WO2016101497 A1 WO 2016101497A1
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epoxy resin
component
weight
parts
resin composition
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PCT/CN2015/078781
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English (en)
French (fr)
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何烈相
曾宪平
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广东生益科技股份有限公司
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Publication of WO2016101497A1 publication Critical patent/WO2016101497A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/02—Layered products comprising a layer of natural or synthetic rubber with fibres or particles being present as additives in the layer
    • 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
    • C08G59/62—Alcohols or phenols
    • 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
    • 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
    • C08L63/04—Epoxynovolacs

Definitions

  • the invention belongs to the technical field of copper clad laminates, and in particular relates to an epoxy resin composition and a prepreg and a laminate using the same.
  • the dielectric constant and dielectric loss of the electronic material are relatively low, which is related to the structure of the material, and the low dielectric constant and low dielectric loss resin generally have a structure of large free volume and low polarization. , low water absorption, low dielectric constant structure exists and so on.
  • Phenolic resin curing epoxy resin is a mature technology, but in the reaction process of phenolic resin and epoxy, secondary hydroxyl groups are formed, which leads to poor water absorption and dielectric properties of the system, and has high brittleness.
  • CN101323698A uses bisphenol A type novolac epoxy resin, brominated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin and terminal carbonyl liquid nitrile rubber prepolymer, novolac resin, tetrabromobisphenol A Although it has good toughness, it has high water absorption and poor dielectric properties, and the brominated bisphenol A epoxy resin and the terminal carbonyl liquid nitrile rubber prepolymer are easily separated from each other. The good state results in a decrease in the inherent heat resistance and modulus of elasticity of the epoxy resin, and it is difficult to ensure the improvement of brittleness and impact resistance without sacrificing heat resistance, mechanical strength and chemical resistance.
  • CN103897350A uses o-cresol novolac resin, novolac resin and tetrabromobisphenol A, although It improves the brittleness caused by the curing of o-cresol novolac resin + novolac resin by adding more tetrabromobisphenol A, but excessive introduction of tetrabromobisphenol A leads to heat resistance of the sheet. Deterioration, and resistance to heat and humidity, water absorption and dielectric properties cannot be guaranteed.
  • an object of the present invention to provide an epoxy resin composition and a prepreg and laminate using the same.
  • the laminate produced using the resin composition has advantages of good heat resistance, low dielectric loss value, good heat and humidity resistance, low water absorption, and good toughness.
  • the present inventors conducted intensive studies to achieve the above object, and found that: phenolic epoxy resin, core-shell rubber toughened epoxy resin or / and core-shell rubber, brominated bisphenol A-type epoxy resin, tetrafunctional epoxy
  • phenolic epoxy resin core-shell rubber toughened epoxy resin or / and core-shell rubber
  • brominated bisphenol A-type epoxy resin brominated bisphenol A-type epoxy resin
  • tetrafunctional epoxy phenolic epoxy resin, core-shell rubber toughened epoxy resin or / and core-shell rubber
  • brominated bisphenol A-type epoxy resin brominated bisphenol A-type epoxy resin
  • tetrafunctional epoxy tetrafunctional epoxy
  • An epoxy resin composition comprising the following components:
  • the invention adopts a phenolic epoxy resin to have a high glass transition temperature and low water absorption and excellent dielectric properties; the core-shell rubber toughened epoxy resin and/or core-shell rubber can improve toughness and processing Bismuth brominated bisphenol A epoxy resin provides flame retardancy while increasing the glass transition temperature
  • the four-functional epoxy resin facilitates the AOI detection of subsequent PCB processing and further increases the glass transition temperature of the cured product.
  • the active ester and the novolac resin composite curing agent are beneficial to achieve a balance of heat resistance, dielectric properties and water absorption while reducing costs.
  • the present invention obtains the above epoxy resin composition by utilizing the mutual cooperation and mutual synergistic action between the above five essential components.
  • the prepreg and the laminate prepared by using the epoxy resin composition have better heat resistance, low dielectric loss value, good heat and humidity resistance, low water absorption and good toughness.
  • the addition of the component (A) phenolic epoxy resin is 100 parts by weight of the sum of the addition amounts of the group (A), the component (B), the component (C), and the component (D).
  • the amount is 35 to 65 parts by weight, for example, 35 parts by weight, 38 parts by weight, 46 parts by weight, 49 parts by weight, 50 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 61 parts by weight, 63 Part by weight, 64 parts by weight or 65 parts by weight, preferably 40 to 65 parts by weight.
  • the above-mentioned addition amount of the epoxy resin can significantly increase the glass transition temperature of the cured product, lower the water absorption rate, and improve the toughness.
  • the novolac epoxy resin is bisphenol A type novolac epoxy resin, bisphenol F type novolac epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene- Phenol addition reaction type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol copolycondensation novolak type epoxy resin, naphthol-cresol copolycondensation novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin Any one or a mixture of at least two of a modified phenol resin type epoxy resin or a biphenyl modified novolak type epoxy resin.
  • the novolac epoxy resin is any one or a mixture of at least two epoxy resins having the following structure:
  • R 1 is the same or different and is independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C8 (for example, C2, C3, C4, C5, C6 or C7) alkyl group, and n 1 represents a repeating unit, an integer greater than or equal to 1, such as 5, 8, 10, 13, or 15;
  • R 2 is the same or different and is independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C8 (for example, C2, C3, C4, C5, C6 or C7) alkyl group, and n 2 represents a repeating unit, an integer greater than or equal to 1, such as 5, 8, 10, 13, or 15;
  • R 3 is the same or different and is independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C8 (for example, C2, C3, C4, C5, C6 or C7) alkyl group, and n 3 represents a repeating unit, an integer greater than or equal to 1, such as 5, 8, 10, 13, or 15;
  • n 4 represents a repeating unit, which is an integer greater than or equal to 1, such as 5, 8, 10, 13 or 15;
  • R 5 is the same or different and is independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1-C8 alkyl group, and n 5 represents a repeating unit, and is an integer of 1 or more, for example, 5 or 8. , 10, 13 or 15;
  • n 6 represents a repeating unit, which is an integer greater than or equal to 1, such as 5, 8, 10, 13 or 15;
  • the novolac epoxy resin has a structure represented by the formula (6) in which bisphenol A imparts a large free volume and good toughness, while dicyclopentadiene imparts rigidity and low
  • the water absorption property makes it have high heat resistance, low dielectric property, low water absorption and good toughness.
  • the core-shell rubber toughened epoxy resin or/or the component (A), the component (B), the component (C), and the component (D) are added in an amount of 100 parts by weight.
  • the core shell rubber is added in an amount of 20 to 40 parts by weight, for example, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight or 38 parts by weight. .
  • the core-shell rubber-toughened epoxy resin or/and the core-shell rubber can significantly improve the toughness of the composition by the above-mentioned addition amount, and phase separation and heat resistance are not deteriorated.
  • the core-shell rubber toughened epoxy resin is a toughening agent containing nano-core shell particles dispersed in an epoxy resin, preferably containing 25% by weight of nano-core shell particles dispersed in a brominated bisphenol A type epoxy resin. Or a toughening agent for bisphenol A type phenolic epoxy resin.
  • the sum of the addition amounts of the component (A), the component (B), the component (C) and the component (D) is 100 parts by weight, and the brominated bisphenol A type epoxy resin
  • the amount added is 5 to 15 parts by weight, for example, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight or 14 parts by weight.
  • the brominated bisphenol A type epoxy resin can increase the flame retardancy characteristics of the composition and maintain high heat resistance by the above addition amount.
  • the brominated bisphenol A type epoxy resin has the following structure:
  • n 7 represents a repeating unit, which is an integer greater than or equal to 1, such as 5, 8, 10, 13, or 15.
  • the tetrafunctional epoxy resin is added in an amount of 5 by weight based on 100 parts by weight of the sum of the components (A), the component (B), the component (C), and the component (D). ⁇ 10 parts by weight, for example, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, and 10 parts by weight.
  • the tetrafunctional epoxy resin can increase the glass transition temperature of the composition by the above addition amount, and is favorable for the subsequent AOI detection of the PCB.
  • the tetrafunctional epoxy resin has the following structure:
  • the ester group equivalent of the active ester and the novolac resin are 100 parts by weight of the sum of the addition amounts of the component (A), the component (B), the component (C) and the component (D).
  • the ratio of the hydroxyl equivalents to the epoxy equivalent of the epoxy resin is 1:0.95 to 1.05, for example, 1:0.96, 1:0.97, 1:0.98, 1:0.99, 1:1, 1:1.01, 1:1.02, 1 : 1.03 or 1:1.04.
  • the ester base equivalent of the active ester and the hydroxyl equivalent ratio of the novolac are from 0.25 to 4, such as 0.5, 1, 1.5, 2, 2.5, 3 or 3.5.
  • the equivalent ratio By selecting the equivalent ratio, the dielectric properties and water absorption of the cured product can be improved, and a high glass transition temperature can be maintained to achieve a balance between heat resistance and moist heat resistance.
  • the active ester has the structure:
  • X is a phenyl or naphthyl group
  • j is 0 or 1
  • k is 0 or 1
  • n represents a repeating unit of 0.25 to 1.25. Due to the special structure of the active ester, the rigid structure such as phenyl, naphthyl and cyclopentadiene imparts high heat resistance to the active ester, and also imparts good electrical properties due to the regularity of its structure.
  • the novolac resin is a biphenyl type novolac epoxy resin, a dicyclopentadiene phenol resin, Any one or a mixture of at least two of an alkylphenol phenol resin, a phenol type phenol resin, a bisphenol A type phenol resin, or a bisphenol F type phenol resin.
  • the novolac resin has the following structure:
  • n 8 represents a repeating unit and is an integer of 1 or more, for example, 5, 10, 13, 15, or 18.
  • the epoxy resin composition further includes a curing accelerator which cures the resin and accelerates the curing speed of the resin.
  • the amount of the curing agent accelerator added is 100 parts by weight of the sum of the addition amounts of the component (A), the component (B), the component (C), the component (D), and the component (E).
  • 0.05 to 1 part by weight for example, 0.08 parts by weight, 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight, 0.5 parts by weight, 0.55 parts by weight 0.6 parts by weight, 0.65 parts by weight, 0.7 parts by weight, 0.75 parts by weight, 0.8 parts by weight, 0.85 parts by weight, 0.9 parts by weight or 0.95 parts by weight.
  • the curing accelerator is any one of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl 4-ethylimidazole or 2-phenylimidazole or a mixture of at least two.
  • the epoxy resin composition further comprises a bromine-containing flame retardant.
  • the flame retardant is added in an amount of from 0 to 50 parts by weight and not including 0, based on 100 parts by weight of the sum of the addition amounts of the component (A), the component (B) and the component (C).
  • the flame retardant is added in an amount of from 0 to 50 parts by weight and not including 0, based on 100 parts by weight of the sum of the addition amounts of the component (A), the component (B) and the component (C).
  • the bromine-containing flame retardant is any one or a mixture of at least two of decabromodiphenylethane, brominated polystyrene or ethylene bistetrabromophthalimide.
  • the epoxy resin composition further comprises a filler, which is an organic or/and inorganic filler, which is mainly used to adjust some physical effects of the composition, such as lowering coefficient of thermal expansion (CTE), reducing water absorption and Improve thermal conductivity and so on.
  • a filler which is an organic or/and inorganic filler, which is mainly used to adjust some physical effects of the composition, such as lowering coefficient of thermal expansion (CTE), reducing water absorption and Improve thermal conductivity and so on.
  • the filler is added in an amount of from 0 to 100 parts by weight based on 100 parts by weight of the sum of the components (A), the component (B), the component (C) and the component (D). And does not include 0, preferably 0 to 50 parts by weight and does not include 0.
  • the filler is added in an amount of, for example, 0.5 parts by weight, 1 part by weight, 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, and 45 parts by weight. Parts, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight or 95 parts by weight.
  • the inorganic filler is selected from the group consisting of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, carbonization Any one or a mixture of at least two of silicon, barium sulfate, barium titanate, barium titanate, calcium carbonate, calcium silicate, mica or fiberglass powder.
  • the mixture is, for example, a mixture of fused silica and 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, and nitrided.
  • 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 mixture is, for example, a mixture of polytetrafluoroethylene powder and polyphenylene sulfide, a mixture of polyethersulfone powder and polytetrafluoroethylene powder, a mixture of polyphenylene sulfide and polyethersulfone powder, polytetrafluoroethylene powder, polyphenylene a mixture of thioether and polyethersulfone powder.
  • the filler is silica, and the filler has a median particle diameter of 1 to 15 ⁇ m, and preferably the filler has a median particle diameter of 1 to 10 ⁇ m.
  • 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 conventional preparation method of the resin composition of the present invention taking a container, first putting the solid component, then adding the liquid solvent, stirring until completely dissolved, adding the liquid resin, the filler, the flame retardant, the curing accelerator, and continuing to stir. It can be evenly distributed. Finally, the liquid solid content is adjusted to 60% to 80% with a solvent to prepare a glue.
  • a prepreg comprising a reinforcing material and an 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 ° C for 5 to 10 minutes using the woven fabric or the organic fabric of the impregnated reinforcing material such as glass cloth.
  • a laminate comprising at least one prepreg as described above.
  • a printed circuit board comprising at least one prepreg as described above.
  • the present invention has the following beneficial effects:
  • the invention adopts a phenolic epoxy resin to have a high glass transition temperature and a low water absorption rate and excellent dielectric properties;
  • Core-shell rubber toughened epoxy resin or / and core-shell rubber can improve toughness and processability: improve the end phase carbonyl liquid nitrile rubber prepolymer is easy to phase separation incomplete or non-optimal state, resulting in inherent resistance of epoxy resin The thermal and elastic modulus decreases, and it is difficult to ensure the improvement of brittleness and impact resistance without sacrificing heat resistance, mechanical strength and chemical resistance;
  • the brominated bisphenol A type epoxy resin maintains a high glass transition temperature while providing flame retardant properties
  • the tetrafunctional epoxy resin facilitates the AOI detection of subsequent PCB processing and further increases the glass transition temperature of the cured product
  • the active ester and the linear phenolic resin composite curing agent are beneficial to achieve the balance of heat resistance and dielectric properties, water absorption, and reduce cost;
  • the prepreg, the laminate, and the metal foil-clad laminate produced using the epoxy resin composition have better heat resistance, low dielectric loss value, good moist heat resistance, low water absorption, and good toughness.
  • the glass transition temperature, the dielectric loss factor, the PCT and PCT water absorption, and the drop impact toughness were tested, as described in the following examples.
  • the mass part of the organic resin is based on the mass of the organic solid.
  • the above glue is impregnated with a glass fiber cloth to form a glue.
  • the above glue was impregnated with a glass fiber cloth and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg.
  • the prepregs obtained by using a plurality of sheets are superposed on each other, and a copper foil is respectively pressed on both sides thereof and placed in a heat press to be cured to form the epoxy resin copper clad laminate.
  • the physical property data is shown in Table 1.
  • the production process is the same as that of the implementation column 1.
  • the formulation composition and physical property index are 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.
  • Comparative Example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 Comparative Example 6 164 - - 55 -
  • the table is based on the weight of solid components.
  • NC-3000H a biphenyl type novolac epoxy resin having an epoxy equivalent of 288 g/eq (trade name of a Japanese chemical).
  • NC-2000H an alkylene phenolic epoxy resin having an epoxy equivalent of 273 g/eq (trade name of Nippon Chemical Co., Ltd.).
  • EEPN-501HY a trifunctional epoxy resin having an epoxy equivalent of 166 g/eq (trade name of Nippon Chemical Co., Ltd.).
  • Phenolic epoxy resin of the preparation example an epoxy resin having a structure of a dicyclopentadiene bisphenol A having an epoxy equivalent of 283 g/eq.
  • MX-395 refers to a 25% by weight nano core shell particle dispersed in a brominated bisphenol A type epoxy resin toughening agent having an epoxy equivalent of 433 g/eq (Hexion, USA).
  • HPC-8000-65T Active ester, ester base equivalent of 223 g/eq (Japanese DIC trade name).
  • Resole phenolic resin having a hydroxyl equivalent of 105 g/eq (trade name of Korea Momentive).
  • Tetrabromobisphenol A has a hydroxyl equivalent of 272 g/eq (trade name of Albemarle, USA).
  • Tg Glass transition temperature
  • PCT and PCT water absorption rate after etching the copper foil indicated by the copper clad board, the substrate is evaluated: the substrate is placed in a pressure cooker, and treated at 120 ° C, 150 KPa for two hours: after being immersed in a tin furnace at 288 ° C When the substrate is layered, the corresponding time is recorded: the evaluation can be ended when the substrate has not appeared bubbles or delamination in the tin furnace for more than 5 minutes.
  • Examples 1-8 an active ester and a novolac resin were used as a composite curing agent, and the equivalent ratio thereof was defined, and a core-shell rubber toughened epoxy resin, a brominated bisphenol A-type epoxy resin, and a tetrafunctional epoxy resin were added.
  • the resin has good heat resistance, low dielectric loss value, good heat and humidity resistance, low water absorption and good toughness.
  • the epoxy circuit substrate of the present invention has better heat resistance, low dielectric loss value, good moist heat resistance, low water absorption, and good toughness as compared with a general laminate.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

提供环氧树脂组合物以及使用它的预浸料和层压板。该环氧树脂组合物包括：酚醛环氧树脂；核壳橡胶增韧环氧树脂或/和核壳橡胶；溴化双酚A型环氧树脂：四官能环氧树脂：活性酯及线性酚醛树脂复合固化剂。使用该环氧树脂组合物制成的预浸料和层压板，具有较好耐热性、低介质损耗值、耐湿热性好、低吸水率及良好韧性。

Description

[根据细则37.2由ISA制定的发明名称]　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，具体涉及一种环氧树脂组合物以及使用它的预浸料和层压板。
背景技术
随着电子元器件朝着小型轻量薄型化、高性能化和多功能化的方向发展，随之带来的是高频和高速的信号传输。这就要求电子材料的介电常数和介电损耗比较低，这些与材料的结构有关，而低介电常数、低介电损耗树脂在结构上一般具有：大的自由体积、低的可极化、低吸水率、低介电常数的结构存在等特点。
酚醛树脂固化环氧树脂已是一项成熟技术，但酚醛树脂与环氧反应过程中，有二次羟基的生成，导致体系的吸水性和介电性能较差的问题，且脆性较大。
活性酯与环氧树脂反应过程中，没有二次羟基生成，其具有低吸水性、耐湿热性和介电性能相当好，但其成本较贵，且作为单独固化剂使用会导致体系的玻璃化转变温度较低。
CN101323698A采用双酚A型酚醛环氧树脂、溴化双酚A型环氧树脂、溴化双酚A型环氧树脂和端羰基液体丁腈橡胶预聚物、线性酚醛树脂、四溴双酚A，虽具有较好的韧性，但其存在高吸水性且其介电性能较差，且溴化双酚A型环氧树脂和端羰基液体丁腈橡胶预聚物容易相分离不彻底或非最佳状态，致使环氧树脂固有的耐热性和弹性模量下降，难于保证在改善脆性和耐冲击性能，又不牺牲耐热性、机械强度和耐化学药品性。
CN103897350A采用邻甲酚酚醛树脂、线性酚醛树脂和四溴双酚A，虽然 其通过加入较多的四溴双酚A来改善由邻甲酚酚醛树脂+线性酚醛树脂固化带来的脆性过大的问题，但过多的四溴双酚A引入会导致板材的耐热性变差，且耐湿热性、吸水性和介电性能无法得到保证。
为此，如何解决酚醛树脂固化环氧树脂所带来的高吸水性、耐湿热性差、介电性能差及脆性较差的技术问题，在它们之间找到平衡点，实现耐热性和耐湿热性的平衡成为技术难题之一。
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环氧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造的层压板具有较好耐热性、低介质损耗值、耐湿热性好、低吸水率及良好韧性的优点。
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：酚醛环氧树脂、核壳橡胶增韧环氧树脂或/和核壳橡胶、溴化双酚A型环氧树脂、四官能环氧树脂和活性酯与线性酚醛固化剂，及其他可选地组分适当混合的组合物，可达到上述目的。
一种环氧树脂组合物，其包括如下组分：
(A)酚醛环氧树脂；
(B)核壳橡胶增韧环氧树脂或/和核壳橡胶；
(C)溴化双酚A型环氧树脂；
(D)四官能环氧树脂；
(E)活性酯和线性酚醛树脂复合固化剂。
本发明采用酚醛环氧树脂，使其在拥有较高玻璃化转变温度同时有低吸水率和优异的介电性能；核壳橡胶增韧环氧树脂或/和核壳橡胶可以改善韧性和工艺加工性；溴化双酚A型环氧树脂在提升玻璃化转变温度的同时，提供阻燃特 性；四官能环氧树脂，有利于后续PCB加工的AOI检测，且进一步提升固化物的玻璃化转变温度。活性酯及线性酚醛树脂复合固化剂，有利于实现耐热性、介电性能和吸水率的平衡，同时降低成本。
本发明利用上述五种必要组分之间的相互配合以及相互协同促进作用，得到了如上的环氧树脂组合物。采用该环氧树脂组合物制成的预浸料以及层压板，具有较好耐热性、低介质损耗值、耐湿热性好、低吸水率及良好韧性。
优选地，以组(A)、组分(B)、组分(C)和组分(D)的添加量之和为100重量份计，所述组分(A)酚醛环氧树脂的添加量为35～65重量份，例如35重量份、38重量份、46重量份、49重量份、50重量份、53重量份、54重量份、55重量份、56重量份、61重量份、63重量份、64重量份或65重量份，优选40～65重量份。
在本发明中，环氧树脂采用上述添加量既可以明显提升固化物玻璃化转变温度和降低吸水率，也可以改善韧性。
优选地，所述酚醛环氧树脂为双酚A型酚醛环氧树脂、双酚F型酚醛环氧树脂、苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、双环戊二烯-苯酚加成反应型环氧树脂、萘酚酚醛清漆型环氧树脂、萘酚-苯酚共缩聚酚醛清漆型环氧树脂、萘酚-甲酚共缩聚酚醛清漆型环氧树脂、芳香族烃甲醛树脂改性酚醛树脂型环氧树脂或联苯改性酚醛清漆型环氧树脂中的任意一种或者至少两种的混合物。
优选地，所述酚醛环氧树脂为具有如下结构的环氧树脂中的任意一种或者至少两种的混合物：
Figure PCTCN2015078781-appb-000001
式(1)中，R1相同或不同，独立地为氢原子、卤素原子或取代或未取代的C1～C8(例如C2、C3、C4、C5、C6或C7)的烷基，n1表示重复单元，为大于等于1的整数，例如5、8、10、13或15；
Figure PCTCN2015078781-appb-000002
式(2)中，R2相同或不同，均独立地为氢原子、卤素原子或取代或未取代的C1～C8(例如C2、C3、C4、C5、C6或C7)烷基，n2表示重复单元，为大于等于1的整数，例如5、8、10、13或15；
Figure PCTCN2015078781-appb-000003
式(3)中，R3相同或不同，均独立地为氢原子、卤素原子或取代或未取代的C1～C8(例如C2、C3、C4、C5、C6或C7)烷基，n3表示重复单元，为大于等于1的整数，例如5、8、10、13或15；
Figure PCTCN2015078781-appb-000004
式(4)中，n4表示重复单元，为大于等于1的整数，例如5、8、10、13或15；
Figure PCTCN2015078781-appb-000005
式(5)中，R5相同或不同，均独立地为氢原子、卤素原子或取代或未取代的C1～C8烷基，n5表示重复单元，为大于等于1的整数，例如5、8、10、13或15；
Figure PCTCN2015078781-appb-000006
式(6)中，n6表示重复单元，为大于等于1的整数，例如5、8、10、13或15；
更优选地，所述酚醛环氧树脂具有式(6)所示结构，该结构中的双酚A赋予其大的自由体积和良好的韧性，与此同时双环戊二烯赋予其刚性和低的吸水性，使着其兼具高耐热性、低介电性能、低吸水率及良好的韧性。
优选地，以组分(A)、组分(B)、组分(C)和组分(D)的添加量之和为100重量份计，所述核壳橡胶增韧环氧树脂或/和核壳橡胶的添加量为20～40重量份，例如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、36重量份或38重量份。
在本发明中，核壳橡胶增韧环氧树脂或/和核壳橡胶采用上述添加量既可以明显改善组合物的韧性，且不会出现相分离和耐热性下降。
优选地，所述核壳橡胶增韧环氧树脂为含有纳米核壳粒子分散于环氧树脂的增韧剂，优选为含有25重量％纳米核壳粒子分散于溴化双酚A型环氧树脂或双酚A型酚醛环氧树脂的增韧剂。
优选地，以组分(A)、组分(B)、组分(C)和组分(D)的添加量之和为100重量份计，所述溴化双酚A型环氧树脂的添加量为5～15份重量份，例如6重量份、7重量份、8重量份、9重量份、10重量份、11重量份、12重量份、13重量份或14重量份。
在本发明中，溴化双酚A型环氧树脂采用上述添加量既可以提升组合物的阻燃特性，又可以保持较高的耐热性。
优选地，所述溴化双酚A型环氧树脂具有如下结构：
Figure PCTCN2015078781-appb-000007
n7表示重复单元，为大于等于1整数，例如5、8、10、13或15。
优选地，以组分(A)、组分(B)、组分(C)和组分(D)的添加量之和为100重量份计，所述四官能环氧树脂的添加量为5～10重量份，例如5重量份、6重量份、7重量份、8重量份、9重量份、10重量份。在本发明中，四官能团环氧树脂采用上述添加量既可以提升组合物玻璃化转变温度，又有利于后续的PCB的AOI检测。
优选地，所述四官能环氧树脂具有如下结构：
Figure PCTCN2015078781-appb-000008
优选地，以组分(A)、组分(B)、组分(C)和组分(D)的添加量之和为100重量份计，所述活性酯的酯基当量和线性酚醛树脂羟基当量之和与环氧树脂的环氧当量比值为1∶0.95～1.05，例如1∶0.96、1∶0.97、1∶0.98、1∶0.99、1∶1、1∶1.01、1∶1.02、1∶1.03或1∶1.04。
优选地，活性酯的酯基当量和线性酚醛的羟基当量比为0.25～4，例如0.5、1、1.5、2、2.5、3或3.5。选择该当量比，既能改善固化物的介电性能和吸水率，也可以保持较高的玻璃化转变温度，实现耐热性和耐湿热性的平衡。
优选地，所述活性酯具有如下结构：
Figure PCTCN2015078781-appb-000009
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。由于该活性酯的特殊结构，其中的苯基、萘基和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，也赋予其良好的电性能。
优选地，所述线性酚醛树脂为联苯型酚醛环氧树脂、双环戊二烯酚醛树脂、 烷基酚酚醛树脂、苯酚型酚醛树脂、双酚A型酚醛树脂或双酚F型酚醛树脂中的任意一种或者至少两种的混合物。
优选地，所述线性酚醛树脂具有如下结构：
Figure PCTCN2015078781-appb-000010
式中，n8表示重复单元，为大于等于1的整数，例如5、10、13、15或18。
优选地，所述环氧树脂组合物还包括固化促进剂，其使树脂固化并加快树脂固化速度。以组分(A)、组分(B)、组分(C)、组分(D)和组分(E)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0.08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、0.6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重量份或0.95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-乙基咪唑或2-苯基咪唑中的任意一种或者至少两种的混合物。
优选地，所述环氧树脂组合物还包括含溴阻燃剂。
优选地，以组分(A)、组分(B)和组分(C)的添加量之和为100重量份计，所述阻燃剂的添加量为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，所述含溴阻燃剂为十溴二苯乙烷、溴化聚苯乙烯或乙撑双四溴邻苯二甲酰亚胺中的任意一种或者至少两种的混合物。
优选地，所述环氧树脂组合物还包含填料，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，以组分(A)、组分(B)、组分(C)和组分(D)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。所述填料的添加量例如为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重量份或95重量份。
优选地，所述无机填料选自熔融二氧化硅、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者至少两种的混合物。所述混合物例如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。所述混合物例如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，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。
本发明的树脂组合物的常规制作方法：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、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。
一种预浸料，其包括增强材料及通过含浸干燥后附着其上的如上所述的环氧树脂组合物。
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℃的烘箱中加热干燥5～10分钟即可得到预浸料。
一种层压板，其包括至少一张如上所述的预浸料。
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，本发明具有如下有益效果：
本发明采用酚醛环氧树脂，使其在拥有较高玻璃化转变温度同时有低吸水率和优异的介电性能；
核壳橡胶增韧环氧树脂或/和核壳橡胶可以改善韧性和工艺加工性：改善端羰基液体丁腈橡胶预聚物容易相分离不彻底或非最佳状态，致使环氧树脂固有的耐热性和弹性模量下降，难于保证在改善脆性和耐冲击性能，又不牺牲耐热性、机械强度和耐化学药品性；
溴化双酚A型环氧树脂在提供阻燃特性同时，保持较高的玻璃化转变温度；
四官能环氧树脂，有利于后续PCB加工的AOI检测，且进一步提升固化物的玻璃化转变温度；
活性酯及线性酚醛树脂复合固化剂有利于实现耐热性和介电性能、吸水率的平衡，同时降低成本；
使用该环氧树脂组合物制作的预浸料、层压板和覆金属箔层压板，具有较好耐热性、低介质损耗值、耐湿热性好、低吸水率及良好韧性。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
根据上述所制成的环氧树脂组合物覆金属箔层压板，测试其玻璃化转变温度、介电损耗因子、PCT和PCT吸水率、落锤冲击韧性，如下述实施例加于详细说明与描述，其中有机树脂的质量份按有机固形物质量份计。
制备例：具有式(6)结构的酚醛环氧树脂的合成
在装有搅拌器、温度计、冷凝回流器的四口瓶(500mL)中加入200g双酚A在水浴加热中溶化，称取三氟化硼·乙醚2.0g，加入500mL四口烧瓶中，在滴液漏斗中加入60g双环戊二烯，控制好滴加速度，以便在2h内滴加完所有的双环戊二烯，升温至100℃，保温4h，反应结束，水洗，过滤，重结晶，真空干燥，得到如下结构的酚醛树脂。
Figure PCTCN2015078781-appb-000011
将上一步所得到25g具有双环戊二烯双酚A结构的酚醛树脂放入四口烧瓶中，再称取100.0g环氧氯丙烷缓慢加入，待其溶解后，开始升温，并在滴液漏斗中加入1mol的质量分数为33％的NaOH溶液，控制速度，使其在1h内滴加完，控制反应温度在100℃，滴加完后保温5h，冷却后水洗，再升温至120℃蒸馏，蒸出过量环氧氯丙烷，反应结束，水洗，过滤，重结晶，真空干燥，得如下化学结构式所示的具有双环戊二烯双酚A结构的环氧树脂：
Figure PCTCN2015078781-appb-000012
实施例1
取一容器，加入60重量份的NC-3000H，加入适量的MEK，搅拌溶解后，加入25重量份核壳橡胶增韧环氧树脂MX-395、10重量份四溴双酚A型环氧树脂153、5重量份四官能团改性环氧树脂1031、14重量份活性酯固化HPC-8000-65T和26重量份线性酚醛树脂2812，搅拌，加入适量的固化促进剂4-二甲氨基吡啶和2-甲基-4-乙基咪唑，继续搅拌均匀，最后用溶剂调整液体固含量至60％～80％而制成胶液。用玻璃纤维布浸渍上述胶液，即成胶液。用玻璃纤维布浸渍上述胶液，并控制至适当厚度，然后烘干除去溶剂得到预浸料。使用数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。
实施列2～8
制作工艺和实施列1相同，配方组成及其物性指标如表1所示。
比较例1～6：
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。
表1.各实施例的配方组成及其物性数据。
Figure PCTCN2015078781-appb-000013
表2.各比较例的配方组成及其物性数据。
物质 比较例1 比较例2 比较例3 比较例4 比较例5 比较例6
164 - - 55 -    
627 47 52 - 66 58 58
MX-395         27 27
153         10 10
1031         5 5
HPC-8000-65T 53 - -     88
2812 - 14 13 34 41  
四溴双酚A - 34 32 -    
DMAP 适量 - - -   适量
2E4MI - 适量 适量 适量 适量  
Tg(DSC)/℃ 158 155 162 180 179 156
Df(1GHZ) 0.0100 0.0188 0.0190 0.0220 0.0225 0.0102
PCT吸水率 0.25％ 0.43％ 0.46％ 0.45％ 0.46％ 0.26％
PCT ＞300s ＞300s ＞300s ＞300s ＞300s ＞300s
落锤冲击韧性 △ △ △ △ ◎ ◎
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：
7200-3H：双环戊二烯型酚醛环氧树脂，环氧当量为285g/eq(日本DIC商品名)。
NC-3000H：联苯型酚醛环氧树脂，环氧当量为288g/eq(日本化药商品名)。
NC-2000H：亚烷基酚醛环氧树脂，环氧当量为273g/eq(日本化药商品名)。
627：双酚A型酚醛环氧树脂，环氧当量为205g/eq(美国Hexion商品名)。
EEPN-501HY：三官能环氧树脂，环氧当量为166g/eq(日本化药商品名)。
制备例的酚醛环氧树脂：具有双环戊二烯双酚A结构的环氧树脂，环氧当量为283g/eq。
164：邻甲酚酚醛环氧树脂，环氧当量为225g/eq(韩国Momentive商品名)。
MX-395：指含有25重量％纳米核壳粒子分散于溴化双酚A型环氧树脂增韧剂，环氧当量为433g/eq(美国Hexion商品名)。
153：高溴环氧树脂，环氧当量为400g/eq(无锡迪爱生商品名)。
1031：四官能环氧树脂，环氧当量为400g/eq(韩国Momentive商品名)。
HPC-8000-65T：活性酯，酯基当量为223g/eq(日本DIC商品名)。
2812：线性酚醛树脂，羟基当量为105g/eq(韩国Momentive商品名)。
四溴双酚A，羟基当量为272g/eq(美国雅宝商品名)。
DMAP，4-二甲氨基吡啶(广荣化学商品名)。
2E4MI，2-甲基4-乙基咪唑(日本四国化成商品名)。
以上特性的测试方法如下：
(1)玻璃化转变温度(Tg)：根据差示扫描量热法(DSC)，按照IPC-TM-6502.4.25所规定的DSC方法进行测定。
(2)介电常数和介电损耗因子：按照IPC-TM-6502.5.5.9所规定的方法进行测试，测试频率为1GHZ。
(3)PCT及PCT吸水率：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℃、150KPa条件下，处理两个小时：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)落锤冲击韧性：使用落锤冲击仪，冲击仪落锤高度40cm，下落重锤重量为1Kg，韧性好坏评价：十字架清晰，说明产品韧性越好，以字符◎表示；十字架模糊，说明产品的韧性差、脆性大，以字符△表示；十字架清晰程度介于清晰和模糊之间，说明产品的韧性一般，以字符○表示。
物性分析：
从表1和表2的物性数据可知，比较例中，采用酚醛树脂和四溴双酚A作为复合固化剂，玻璃化转变温度低、电性能差、吸水率高且韧性差，同样的环氧树脂采用活性酯固化时，其介电性能更优，吸水率更低，但其玻璃化转变温 度较低且韧性差，而同样的环氧树脂单独采用酚醛固化时，玻璃化转变温度较高，但其存在介电性能差、吸水率高和韧性差的问题。实施例1～8中采用活性酯和线性酚醛树脂作为复合固化剂，对其当量比进行限定，且加入核壳橡胶增韧环氧树脂、溴化双酚A型环氧树脂和四官能环氧树脂，具有较好耐热性、低介质损耗值、耐湿热性好、低吸水率及良好韧性。
如上所述，与一般的层压板相比，本发明的环氧电路基板具有较好耐热性、低介质损耗值、耐湿热性好、低吸水率及良好韧性。
以上所述，仅为本发明的较佳实施例，对于本领域的普通技术人员来说，可以根据本发明的技术方案和技术构思做出其他各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的范围。
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 (10)

  1. 一种环氧树脂组合物，其特征在于，所述环氧树脂组合物包括如下组分：
    (A)酚醛环氧树脂；
    (B)核壳橡胶增韧环氧树脂或/和核壳橡胶；
    (C)溴化双酚A型环氧树脂；
    (D)四官能环氧树脂；
    (E)活性酯和线性酚醛树脂复合固化剂。
  2. 如权利要求1所述的环氧树脂组合物，其特征在于，以组(A)、组分(B)、组分(C)和组分(D)的添加量之和为100重量份计，所述组分(A)酚醛环氧树脂的添加量为35～65重量份，优选40～65重量份；
    优选地，所述酚醛环氧树脂为具有如下结构的环氧树脂中的任意一种或者至少两种的混合物：
    Figure PCTCN2015078781-appb-100001
    式(1)中，R1相同或不同，独立地为氢原子、卤素原子或取代或未取代的C1～C8的烷基，n1表示重复单元，为大于等于1的整数；
    Figure PCTCN2015078781-appb-100002
    式(2)中，R2相同或不同，均独立地为氢原子、卤素原子或取代或未取代的C1～C8烷基，n2表示重复单元，为大于等于1的整数；
    Figure PCTCN2015078781-appb-100003
    式(3)中，R3相同或不同，均独立地为氢原子、卤素原子或取代或未取代的C1～C8烷基，n3表示重复单元，为大于等于1的整数；
    Figure PCTCN2015078781-appb-100004
    式(4)中，n4表示重复单元，为大于等于1的整数；
    Figure PCTCN2015078781-appb-100005
    式(5)中，R5相同或不同，均独立地为氢原子、卤素原子或取代或未取代的C1～C8烷基，n5表示重复单元，为大于等于1的整数；
    Figure PCTCN2015078781-appb-100006
    式(6)中，n6表示重复单元，为大于等于1的整数；
    更优选地，所述酚醛环氧树脂为具有式(6)所示结构的酚醛环氧树脂。
  3. 如权利要求1或2所述的环氧树脂组合物，其特征在于，以组分(A)、组分(B)、组分(C)和组分(D)的添加量之和为100重量份计，所述核壳橡胶增韧环氧树脂或/和核壳橡胶的添加量为20～40重量份；
    优选地，所述核壳橡胶增韧环氧树脂为含有纳米核壳粒子分散于环氧树脂的增韧剂，优选为含有25重量％纳米核壳粒子分散于溴化双酚A型环氧树脂或双酚A型酚醛环氧树脂的增韧剂；
    优选地，以组分(A)、组分(B)、组分(C)和组分(D)的添加量之和为100重量份计，所述溴化双酚A型环氧树脂的添加量为5～15份重量份；
    优选地，所述溴化双酚A型环氧树脂具有如下结构：
    Figure PCTCN2015078781-appb-100007
    n7表示重复单元，为大于等于1整数。
  4. 如权利要求1-3之一所述的环氧树脂组合物，其特征在于，以组分(A)、组分(B)、组分(C)和组分(D)的添加量之和为100重量份计，所述四官能环氧树脂的添加量为5～10重量份；
    优选地，所述四官能环氧树脂具有如下结构：
    Figure PCTCN2015078781-appb-100008
    优选地，所述活性酯的酯基当量和线性酚醛树脂羟基当量之和与环氧树脂的环氧当量比值为1∶0.95～1.05；
    优选地，活性酯的酯基当量和线性酚醛的羟基当量比为0.25～4；
    优选地，所述活性酯具有如下结构：
    Figure PCTCN2015078781-appb-100009
    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，所述线性酚醛树脂具有如下结构：
    Figure PCTCN2015078781-appb-100010
    式中，n8表示重复单元，为大于等于1的整数。
  5. 如权利要求1-4之一所述的环氧树脂组合物，其特征在于，所述环氧树脂组合物还包括固化促进剂；
    优选地，以组分(A)、组分(B)、组分(C)、组分(D)和组分(E)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-乙基咪唑或2-苯基咪唑中的任意一种或者至少两种的混合物。
  6. 如权利要求1-5之一所述的环氧树脂组合物，其特征在于，所述环氧树 脂组合物还包括含溴阻燃剂；
    优选地，以组分(A)、组分(B)和组分(C)的添加量之和为100重量份计，所述阻燃剂的添加量为0～50重量份且不包括0；
    优选地，所述含溴阻燃剂为十溴二苯乙烷、溴化聚苯乙烯或乙撑双四溴邻苯二甲酰亚胺中的任意一种或者至少两种的混合物。
  7. 如权利要求1-6之一所述的环氧树脂组合物，其特征在于，所述环氧树脂组合物还包含填料，所述填料为有机或/和无机填料；
    优选地，以组分(A)、组分(B)、组分(C)和组分(D)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，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其上的如权利要求1-7之一所述的环氧树脂组合物。
  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。
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CN104177530A (zh) * 2014-08-08 2014-12-03 苏州生益科技有限公司 一种活性酯树脂及其热固性树脂组合物

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CN113493668A (zh) * 2021-08-02 2021-10-12 东莞市邦盛电子材料有限公司 一种具有高韧性且无毒的环氧树脂胶配方及其制备方法
CN114479362A (zh) * 2022-02-09 2022-05-13 建滔电子材料（江阴）有限公司 一种汽车用高caf可靠性fr-4覆铜板的制备方法
CN114479362B (zh) * 2022-02-09 2023-09-15 建滔电子材料（江阴）有限公司 一种汽车用高caf可靠性fr-4覆铜板的制备方法

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