WO2016155263A1 - 一种活性酯以及含有该活性酯的热固性树脂组合物、预浸料和层压板 - Google Patents

一种活性酯以及含有该活性酯的热固性树脂组合物、预浸料和层压板 Download PDF

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Publication number
WO2016155263A1
WO2016155263A1 PCT/CN2015/090080 CN2015090080W WO2016155263A1 WO 2016155263 A1 WO2016155263 A1 WO 2016155263A1 CN 2015090080 W CN2015090080 W CN 2015090080W WO 2016155263 A1 WO2016155263 A1 WO 2016155263A1
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WIPO (PCT)
Prior art keywords
resin composition
thermosetting resin
active ester
prepreg
ppo
Prior art date
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PCT/CN2015/090080
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English (en)
French (fr)
Inventor
罗成
唐国坊
Original Assignee
广东生益科技股份有限公司
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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 US15/563,185 priority Critical patent/US20180050515A1/en
Priority to JP2017535745A priority patent/JP6522760B2/ja
Publication of WO2016155263A1 publication Critical patent/WO2016155263A1/zh

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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
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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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    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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    • H—ELECTRICITY
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Definitions

  • the invention belongs to the technical field of copper clad laminates, and particularly relates to an active ester and a thermosetting resin composition, a prepreg and a laminate containing the active ester.
  • the circuit board is developing in the direction of high multi-layer and high wiring density, which requires that the substrate material not only has good dielectric energy (low dielectric constant and low dielectric loss tangent) to meet the needs of high-frequency transmission of signals, and also requires Has good heat resistance and machinability to meet the requirements of multilayer printed circuit board reliability and processability.
  • Japanese Laid-Open Patent Publication Nos. 2002-012650 and 2003-082063 provide a series of curing esters containing a benzene ring, a naphthalene ring or a biphenyl structure as curing agents for epoxy resins such as IAAN, IABN, TriABN and TAAN, and the resulting cured products and Compared with conventional phenolic, the dielectric constant and dielectric loss value can be significantly reduced.
  • Japanese Patent Laid-Open No. 2003-252958 proposes to use a biphenyl type epoxy and an active ester as a curing agent to obtain a cured product having a reduced dielectric constant and dielectric loss value, but the cured product has low heat resistance and glass. The temperature is low.
  • Japanese Patent Laid-Open No. 2004-155990 uses a reaction of an aromatic carboxylic acid with an aromatic phenol to obtain a polyfunctional active ester curing agent, and curing the phenolic epoxy using the active ester curing agent can obtain higher heat resistance and better dielectric constant. And the cured product of the dielectric loss value.
  • Japanese Patent Laid-Open No. 2009-235165 provides a polyfunctional active ester curing agent containing dicyclopentadiene to cure an epoxy containing an aliphatic structure, which can simultaneously obtain higher heat resistance, better dielectric constant and medium. The cured product of the loss value.
  • Japanese Patent Laid-Open Publication No. 2009-040919 provides a thermosetting resin composition having a stable dielectric constant and excellent electrical continuity properties, and the main components include an epoxy resin, an active ester curing agent, an accelerator, and an organic solvent.
  • the amount of epoxy resin and active ester was studied, and the relationship between the structure and properties of epoxy resin and active ester was not studied.
  • Japanese Patent Laid-Open No. 2009-242559, JP-A-2009-242560, JP-A-2010-077344, and JP-A-2010-077343 respectively propose the use of alkylated phenol or alkylated naphthol novolac type epoxy resin, biphenyl type phenolic ring Oxygen resin, active ester curing agent, can obtain a cured product with low hygroscopicity, low dielectric constant and dielectric loss value.
  • Patent WO2013056411A proposes an epoxy resin containing a naphthol structure, an active ester curing agent containing a dicyclopentadiene structure, and an accelerator, which can simultaneously obtain higher heat resistance, better dielectric constant and dielectric loss value, and good a heat-resistant cured product.
  • Patent CN102504201A proposes cyanate ester, epoxy resin containing naphthol structure, active ester curing agent containing dicyclopentadiene structure, and accelerator, which can obtain excellent heat resistance, dielectric properties, and heat and humidity resistance. Cured product.
  • Patent CN1364821A discloses that by modifying a macromolecular PPO resin to obtain a small molecule polyphenylene ether terminated with a small amount of benzoate, and then capping it with an ester group containing a double bond, the modified product is obtained.
  • the curing crosslinking group of the PPO resin is a double bond, and it is required to be cured and crosslinked under the condition of a radical initiator, and does not react with the epoxy resin at all.
  • Patent CN102354546A discloses that the curable composition comprises a terminal olefin ester-based polyphenylene ether, an epoxy resin and a curing agent, wherein curing of the terminal olefin ester-based polyphenylene ether requires curing crosslinking under the condition of a radical initiator, and The epoxy resin does not react at all. Moreover, the curing of the epoxy resin therein requires a curing agent of an epoxy resin such as polyester or the like.
  • an object of the present invention is to provide a double-end polyfunctional active ester containing a PPO main chain, a thermosetting resin composition containing the active ester, and a prepreg prepared using the above thermosetting resin composition, With a laminate and a copper clad laminate, the thermosetting resin composition can provide excellent dielectric properties, heat and humidity resistance, heat resistance, and extremely low water absorption and high bending strength required for a high-frequency high-speed copper clad laminate.
  • R 1 is R 2 is a substituted or unsubstituted C1-C3 linear alkyl or branched alkyl, allyl or isoallyl group;
  • R 3 is H, allyl or isoallyl;
  • R 4 , R 5 , R 6 And R 7 is independently selected from H, substituted or unsubstituted C1-C3 linear alkyl or branched alkyl, allyl, isoallyl or -OR 8 ;
  • R 8 is substituted or unsubstituted C1 - a linear alkyl or branched alkyl group of C3 or a substituted or unsubstituted phenyl group;
  • N1, n2 are positive integers greater than 0, and satisfy 4 ⁇ n1+n2 ⁇ 25, for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 , 20, 21, 22, 23 or 24; n3, n4 are equal or unequal, independently 1, 2 or 3.
  • n1 + n2 ⁇ 20 Preferably, 6 ⁇ n1 + n2 ⁇ 20, preferably 8 ⁇ n1 + n2 ⁇ 15.
  • n3, n4 are equal or unequal, independently 2 or 3, preferably n3, n4 are equal and independently 2 or 3.
  • the present invention also provides a thermosetting resin composition
  • a thermosetting resin composition comprising an epoxy resin and a double-end polyfunctional active ester resin containing a PPO backbone as described above.
  • the double-end polyfunctional active ester resin containing a PPO main chain accounts for 10 to 80%, for example, 15%, 20%, 25%, based on the total weight of the thermosetting resin composition. 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70% or 75%, preferably 30 to 75%.
  • the epoxy resin accounts for 20 to 50%, for example, 23%, 27%, 31%, 35%, 38%, 40%, 42% of the total weight of the thermosetting resin composition. %, 45% or 48%.
  • the epoxy resin refers to an epoxy resin having two or more epoxy groups in one molecule, specifically a bisphenol A type epoxy resin, Bisphenol F Epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy, naphthalene type epoxy resin, alicyclic epoxy resin, resorcinol type epoxy resin, polyethylene glycol type epoxy resin
  • the trifunctional epoxy resin, the brominated epoxy resin, the tetrafunctional epoxy resin, and the novolac epoxy resin, and other types of epoxy resins are not limited thereto, and may be used alone or in combination of two or more.
  • thermosetting resin composition in addition to the epoxy resin, a cyanate resin, a bismaleimide-triazine resin, a 1,2-polybutadiene resin or a styrene-butadiene resin may be further included. Any one or a mixture of at least two, which accounts for 5 to 40%, such as 10%, 15%, 20%, 25%, 30% or 35%, based on the total weight of the thermosetting resin composition.
  • thermosetting resin composition further contains an organic additive-type flame retardant which is a phosphorus-based flame retardant and/or a halogen-based flame retardant.
  • organic additive-type flame retardant which is a phosphorus-based flame retardant and/or a halogen-based flame retardant.
  • thermosetting resin composition it further contains a filler and/or a curing accelerator.
  • the recommended addition amount of the filler is 0 to 5 times (and excluding 0) of the total mass of the double-end polyfunctional active ester containing the PPO main chain, the epoxy resin, and the above-mentioned optional other thermosetting resin, the curing
  • the promoter is 0.02 to 2% of the total mass of the double-end polyfunctional active ester containing the PPO backbone, the epoxy resin, and optionally other thermosetting resins described above.
  • thermosetting resin composition means that it may include other components in addition to the components, and these other components impart different characteristics to the thermosetting resin composition.
  • the "include” of the present invention may also be replaced by a closed “for” or “consisting of”.
  • thermosetting 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 present invention also provides the use of the thermosetting resin composition as described above in prepregs, laminates, metal foil-clad laminates, and printed wiring boards.
  • a prepreg comprising a reinforcing material and a thermosetting resin composition as described above adhered thereto by dipping and drying.
  • a laminate comprising at least one prepreg as described above.
  • the laminate is obtained by bonding at least one prepreg together by heat and pressure.
  • a metal foil-clad laminate comprising at least one prepreg as described above and a metal foil stamped on one or both sides of the laminated prepreg.
  • a printed wiring board comprising at least one prepreg as described above.
  • the present invention has the following beneficial effects:
  • the double-end polyfunctional active ester resin containing a PPO main chain can ensure a high thermosetting resin composition because of its structure containing a heat-resistant, rigid, toughness, low water absorption, and excellent electrical properties PPO resin. Heat resistance, low water absorption and excellent dielectric properties. Meanwhile, the double-end polyfunctional active ester resin containing a PPO main chain contains an active ester functional group, which can crosslink with an epoxy resin without generating a hydroxyl group, and the hydroxyl group is a highly polar functional group, which is strong. The water absorption rate and poor dielectric properties further ensure the excellent dielectric properties of the thermosetting resin composition and further ensure the low water absorption of the thermosetting resin composition.
  • the structure of the double-end polyfunctional active ester resin containing a PPO main chain contains 4 to 8 active ester functional groups, and has a large crosslinking point, which enables the thermosetting resin composition to have a large crosslinking density, further ensuring Good heat resistance of the thermosetting resin composition.
  • thermosetting resin composition of a double-end polyfunctional active ester containing a PPO main chain, having excellent dielectric properties, heat and humidity resistance, heat resistance and extremely low water absorption Rate and high bending strength.
  • trimesoyl chloride 530 g was placed in a 5000 ml three-necked flask equipped with a stirrer, a thermometer, a condenser (with a drying tube and a gas absorbing device). Start the stirrer and slowly heat it in an oil bath. After the isophthalic acid chloride is melted into a liquid state, 376 g of phenol is slowly added. At this time, the generated gas HCl continuously escapes, and the contents seem to boil. When the reaction is not too intense, gradually increase the reaction temperature to 120 ° C for 1.5 to 2 h (no HCl gas escapes). Then, 1000 g of redistributed difunctional PPO resin was added and heated with stirring.
  • 3600 g of toluene was stirred and heated to 100 ° C in a three-necked flask equipped with a stirrer, a condensing reflux tube, and a thermometer, and then 3600 g of a PPO resin having a number average molecular weight of 20,000 was added, and when it became a homogeneous phase, 540 g of bisphenol A (BPA) was added. ), after being homogenized, stir for another 30 minutes, then add 720g to a concentration of 75%. An aqueous solution of benzoyl (BPO) was oxidized and maintained at a temperature of 100 ° C for 120 min.
  • BPA bisphenol A
  • the reaction was carried out at room temperature for about 13 h, 500 ml of deionized water was added, and after stirring for 30 min, the aqueous layer was removed, and several layers were washed with saturated brine and deionized water, and concentrated to 1000 ml, and then slowly poured into 5000 ml of methanol to precipitate. The precipitate was washed twice with methanol and dried to give 500 g of ANCO-rPPE.
  • the epoxy resin, the double-end polyfunctional active ester resin containing the PPO main chain obtained by the above method, and the curing accelerator are uniformly mixed in a solvent to control the solid content of the glue liquid to be 65%, and the 2116 fiberglass cloth is used. Dipping the above glue, controlling the appropriate thickness, and then baking in an oven at 115-175 ° C for 2-15 minutes to make a prepreg, then stacking several prepregs together, stacking copper foil on both sides,
  • the copper-clad laminate is prepared at a curing temperature of 170 to 250 ° C, a curing pressure of 25 to 60 kg/cm 2 , and a curing time of 60 to 300 min.
  • the sheet properties are as follows:
  • the epoxy resin, the esterified PPO resin, the cyanate resin and the curing accelerator are uniformly mixed in a solvent in a certain ratio, and the solid content of the glue is controlled to be 65%, and the above glue is impregnated with 2116 glass cloth to control the appropriate thickness. Then, it is baked in an oven at 115-175 ° C for 2-15 minutes to make a prepreg, then several prepregs are stacked together, and copper foil is laminated on both sides thereof at a curing temperature of 170-250 ° C to cure.
  • the copper-clad laminate is prepared under the conditions of a pressure of 25 to 60 kg/cm 2 and a curing time of 60 to 300 min.
  • the performance of the sheet is as follows:
  • HPC-8000-65T DIC, DCPD active ester, ester equivalent 223,
  • HP-7200HHH DIC, DCPD type epoxy resin, epoxy equivalent 288,
  • HP-7200H-75M DIC, DCPD type epoxy resin, epoxy equivalent 280,
  • NC-7300L Nippon Chemical, naphthol type novolac epoxy resin, epoxy equivalent 214,
  • SA90 Saberky, small molecule difunctional polyphenylene ether, hydroxyl equivalent 850,
  • SA9000 Saberki
  • the small molecular end group is acrylate-terminated polyphenylene ether
  • CY-40 Wuqiao resin factory
  • DCPD type cyanate resin DCPD type cyanate resin

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Abstract

本发明提供了一种活性酯以及含有该活性酯的热固性树脂组合物、预浸料和层压板。所述活性酯为含有PPO主链的双端基多官能活性酯，所述热固性树脂组合物，其包括环氧树脂和含有PPO主链的双端基多官能活性酯树脂。使用上述含有PPO主链的双端基多官能活性酯的热固性树脂组合物制作的预浸料、层压板及覆铜板，具有优良的介电性能、耐湿热性、耐热性和极低的吸水率以及较高的弯曲强度。

Description

一种活性酯以及含有该活性酯的热固性树脂组合物、预浸料和层压板 技术领域
本发明属于覆铜板技术领域，具体涉及一种活性酯以及含有该活性酯的热固性树脂组合物、预浸料和层压板。
背景技术
近年来，随着信息通讯设备高性能化、高功能化以及网络化的发展，为了高速传及处理大容量信息，操作信号趋向于高频化，同时，为了满足各类电子产品的发展趋势求，电路板向着高多层、高布线密度的方向发展，这就要求基板材料不仅具有良好的介电能(低介电常数和低介质损耗角正切)来满足信号高频传输的需要，而且要求具有良好的耐热性和机械加工性来满足多层印制电路板可靠性和加工性的需求。
然而现有的用于印制电路基板的材料中，广泛使用以环氧树脂为主体的粘结普通的环氧树脂电路基板(FR-4覆铜板)一般介电常数和介质损耗角正切由于在用通用固化剂时会产生大量羟基，导致较高的(介电常数4.4，介质损耗角正切0.02左右)，高频特性不充分，不能适应信号高频化的要求，并且由于羟基的产生，导致板材耐湿热性差。
日本特开2002-012650和2003-082063提供了一系列含有苯环、萘环或联苯结构的活性酯固化剂作为环氧树脂的固化剂如IAAN、IABN、TriABN以及TAAN，得到的固化产物和传统酚醛相比，可以明显降低其介电常数和介质损耗值。
日本专利特开2003-252958提出采用联苯型环氧和活性酯作为固化剂，可以得到降低介电常数和介质损耗值固化产物，但是固化产物耐热性较低，玻璃 化温度低。
日本专利特开2004-155990采用芳香族羧酸与芳香族酚反应得到多官能度活性酯固化剂，使用该活性酯固化剂固化酚醛型环氧可以得到较高耐热性、较好介电常数和介质损耗值的固化产物。
日本专利特开2009-235165提供了含有双环戊二烯的多官能度活性酯固化剂固化一种含有脂肪族结构的环氧，可以得到同时具有较高耐热性、较好介电常数和介质损耗值的固化产物。
日本专利特开2009-040919提供了一种介电常数稳定，导电层接着性能优异的热固性树脂组合物，主要组分包括环氧树脂、活性酯固化剂、促进剂、有机溶剂。对环氧树脂和活性酯的用量做了研究，对环氧树脂和活性酯结构和性能的关系未做研究。
日本专利特开2009-242559、特开2009-242560、特开2010-077344、特开2010-077343分别提出了采用烷基化苯酚或烷基化萘酚酚醛型环氧树脂，联苯型酚醛环氧树脂，活性酯固化剂，可以得到低吸湿性、低介电常数和介质损耗值的固化产物。
专利WO2013056411A中提出用含有萘酚结构的环氧树脂，含有双环戊二烯结构的活性酯固化剂，促进剂，可以得到同时具有较高耐热性、较好介电常数和介质损耗值以及好的耐湿热性的的固化产物。
专利CN102504201A中提出用氰酸酯、含有萘酚结构的环氧树脂，含有双环戊二烯结构的活性酯固化剂，促进剂，可以得到具有优良耐热性、介电性、耐湿热性的的固化产物。
以上现有技术中，都提出了使用活性酯作为环氧树脂的固化剂，可以改善固化产物的耐湿热性、降低吸水率、降低固化产物的介电常数和介质损耗值， 但是其缺点是很难在上述性能之间实现平衡，使其同时具有好的耐热性、介电性能以及低的吸水率，并且其介电性能随频率变化比较稳定。
专利CN1364821A披露了通过将大分子的PPO树脂再分配后得到一种含有少量苯甲酸酯封端的小分子聚苯醚，然后用含有双键的酯基对其封端，得到此种改性的PPO树脂的固化交联基团为双键，需要在自由基引发剂的条件下才能发生固化交联，与环氧树脂根本不会发生反应。
专利CN102354546A披露了可固化组合物包括端烯烃酯基聚苯醚、环氧树脂和固化剂，其中端烯烃酯基聚苯醚的固化需要在自由基引发剂的条件下才能发生固化交联，与环氧树脂根本不会发生反应。而且，其中的环氧树脂的固化需要有环氧树脂的固化剂在其中，比如聚酯等。
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含有PPO主链的双端基多官能活性酯、含有该活性酯的热固性树脂组合物以及使用上述热固性树脂组合物制备的预浸料、层压板以及覆铜板，该热固性树脂组合物能够提供高频高速覆铜板所需的优良的介电性能、耐湿热性、耐热性和极低的吸水率以及较高的弯曲强度。
为了实现上述目的，本发明采用了如下技术方案：
一种含有PPO主链的双端基多官能活性酯树脂，其具有式(1)所示的结构
Figure PCTCN2015090080-appb-000001
其中，R1为
Figure PCTCN2015090080-appb-000002
R2为
Figure PCTCN2015090080-appb-000003
取代或未取代的C1～C3的直链烷基或支链烷基、烯丙基或异烯丙基；R3为H、烯丙基或异烯丙基；R4、R5、R6、R7独立选自H、取代或未取代的C1～C3的直链烷基或支链烷基、烯丙基、异烯丙基或-O-R8；R8为取代或未取代的C1～C3的直链烷基或支链烷基或取代或未取代的苯基；
n1、n2为大于0的正整数，且满足4≤n1+n2≤25，例如5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23或24；n3、n4相等或不等，独立地为1、2或3。
优选地，6≤n1+n2≤20，优选8≤n1+n2≤15。
优选地，n3、n4相等或不等，独立地为2或3，优选n3、n4相等且独立地为2或3。
本发明还提供了一种热固性树脂组合物，其包括环氧树脂和如上所述的含有PPO主链的双端基多官能活性酯树脂。
优选地，在所述热固性树脂组合物中，所述含有PPO主链的双端基多官能活性酯树脂占热固性树脂组合物总重量的10～80％，例如15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％或75％，优选30～75％。
优选地，在所述热固性树脂组合物中，所述环氧树脂占热固性树脂组合物总重量的20～50％，例如23％、27％、31％、35％、38％、40％、42％、45％或48％。
优选地，在所述热固性树脂组合物中，所述环氧树脂是指在1个分子中具有两个或两个以上环氧基团的环氧树脂，具体为双酚A型环氧树脂、双酚F型 环氧树脂、联苯型环氧树脂、双环戊二烯型环氧、萘类环氧树脂、脂环族类环氧树脂、间苯二酚型环氧树脂、聚乙二醇型环氧树脂、三官能团环氧树脂、溴化环氧树脂、四官能团环氧树脂和酚醛型环氧树脂以及其它类型的环氧树脂，但不仅限于此，可以1种或2种以上混合使用。
优选地，在所述热固性树脂组合物中，除环氧树脂以外，还可以包括氰酸酯树脂、双马来酰亚胺-三嗪树脂、1，2-聚丁二烯树脂或丁苯树脂中的任意一种或者至少两种的混合物，其占热固性树脂组合物总重量的5～40％，例如10％、15％、20％、25％、30％或35％。
优选地，在所述热固性树脂组合物中，其进一步包含有机添加型阻燃剂，所述有机添加型阻燃剂为磷系阻燃剂和/或卤系阻燃剂。
优选地，在所述热固性树脂组合物中，其进一步包含填料和/或固化促进剂。
所述填料的建议添加量为含有PPO主链的双端基多官能活性酯、环氧树脂以及上述任选地其他热固性树脂的总质量的0～5倍(且不包括0)，所述固化促进剂为含有PPO主链的双端基多官能活性酯、环氧树脂以及上述任选地其他热固性树脂的总质量的0.02～2％。
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热固性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，所述热固性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。
本发明还提供了如上所述的热固性树脂组合物在预浸料、层压板、覆金属箔层压板和印制线路板中的应用。
一种预浸料，其包括增强材料及通过浸渍干燥后附着在其上的如上所述的热固性树脂组合物。
一种层压板，所述层压板含有至少一张如上所述的预浸料。该层压板通过加热和加压使至少一张以上的预浸料粘合在一起而得到。
一种覆金属箔层压板，其包括至少一张如上所述的预浸料及压覆在叠合的预浸料一侧或两侧的金属箔。
一种印制线路板，其含有至少一张如上所述的预浸料。
与已有技术相比，本发明具有如下有益效果：
所述含有PPO主链的双端基多官能活性酯树脂，因为其结构中含有耐热性好、刚性强、韧性好、吸水率低和电性能优异PPO树脂，可以保证热固性树脂组合物具有高的耐热性、低的吸水率以及优异的介电性能。同时，所述含有PPO主链的双端基多官能活性酯树脂中含有活性酯官能团，能与环氧树脂发生交联反应不会生成羟基，而羟基是极性大的官能基，具有较强的吸水率和较差的介电性能，这样既进一步保证了热固性树脂组合物的优异的介电性能，又进一步保证了热固性树脂组合物的低吸水率。而且，含有PPO主链的双端基多官能活性酯树脂结构中含有4～8活性酯官能基，具有较多的交联点，能使热固性树脂组合物具有较大的交联密度，进一步保证了热固性树脂组合物的好的耐热性。
使用上述含有PPO主链的双端基多官能活性酯的热固性树脂组合物制作的预浸料、层压板及覆铜板，具有优良的介电性能、耐湿热性、耐热性和极低的吸水率以及较高的弯曲强度。
具体实施方式
以下所述是本发明实施例的具体实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改 进和润饰，这些改进和润饰也视为本发明实施例的保护范围。
下面分多个实施例对本发明实施例进行进一步的说明。本发明实施例不限定于以下的具体实施例。在不改变权利要求的范围内，可以适当的进行变更实施。
实施例
(1)PPO的再分配
将4000g甲苯于装有搅拌器、冷凝回流管、温度计的三颈瓶中搅拌加热到100℃，然后加入2000g数均分子量为20000的PPO树脂，当变为均一相后加入600g二烯丙基双酚A(DABPA)，搅拌30min，然后加入溶于甲苯中的150g过氧化苯甲酰(BPO)，并保持温度为92℃，反应360min。然后将产物冷却到室温然后加入4000ml甲醇，并剧烈搅拌，过滤、干燥，得到小分子化的双官能基PPO树脂(A1)2400g。
重复以上操作，改变再分配PPO树脂各种反应物的比例，改变反应温度和反应时间，可以得到不同的数均分子量的双官能基PPO树脂，如下表：
  A1 A2 A3 A4 A5 A6
PPO 2000 2000 2000 2000 2000 2000
DABPA 600 480 360 320 / /
BPA / / / / 300 240
BPO 150 150 150 120 100 80
反应温度/℃ 92 100 90 100 90 92
反应时间/min 360 240 240 240 240 300
Mn 1304 1600 1909 2433 2658 3024
(2)酰化反应
将530g均苯三甲酰氯投入装有搅拌器、温度计、冷凝器(带有干燥管和气体吸收装置)的5000ml三颈瓶中。开动搅拌器，用油浴锅缓缓加热，待均苯三甲酰氯熔成液态，缓慢加入苯酚376g，此时有生成的气体HCl不断逸出，内容物似有沸腾现象。待反应不太激烈时，逐步提高反应温度至120℃，维持1.5～2h(无HCl气体逸出为止)。然后加入再分配的小分子化的双官能基PPO树脂1000g，并搅拌加热，反应2h后，稍冷后，在搅拌下将反应混合物逐步倒入4000ml水中，研细，过滤，用水洗涤、用乙醇洗涤，然后干燥，得产物1345g，为酯当量为332g/mol的含有PPO主链的双端基六官能基的活性酯树脂B4。
重复以上操作，改变不同数均分子量的再分配PPO树脂和酰氯以及酚类，可以得到不同酯官能基数的不同酯当量的含有PPO主链的双端基多官能的活性酯树脂，如下表：
  B1 B2 B3 B4 B5 B6 B7
对苯二甲酰氯/g 203 203          
均苯三甲酰氯/g       530 530    
1，2，4，5-均苯四甲酰氯/g     328     328 328
苯酚/g 94   282 376   282  
对羟基苯甲醚/g   124     496   372
A1/g       1000      
A2/g 700            
A3/g   800 800        
A4/g         2000    
A5/g           1200  
A6/g             1400
酯官能基数 4 4 8 6 6 8 8
酯当量(g/mol) 513 605 354 332 540.5 448.5 517
合成对比例：ANCO-rPPE的合成
将3600g甲苯于装有搅拌器、冷凝回流管、温度计的三颈瓶中搅拌加热到100℃，然后加入3600g数均分子量为20000的PPO树脂，当变为均一相后加入540g双酚A(BPA)，变均一后，再搅拌30min，然后加720g浓度为75％的过 氧化苯甲酰(BPO)水溶液，并保持温度为100℃，反应120min。然后将产物冷却到室温然后加入8000ml甲醇，并剧烈搅拌，过滤、干燥，得到数均分子量为3400的双官能基PPO树脂4000g。
将上述改性PPO树脂500g溶于5000ml二氯甲烷中，并将100g的50wt％氢氧化钠水溶液加入，10min后再加入49.9g硫酸氢根四正丁基铵(TBAHS)，在室温下搅拌10min后，再加入324.5g N，N-二烯丙基-2-氯乙酰胺。于室温下反应约13h，加入去离子水500ml，搅拌30min后，去除水层，有几层用饱和食盐水、去离子水洗涤，并浓缩至1000ml，然后缓慢倒入5000ml甲醇中沉淀，并将沉淀物用甲醇清洗两遍，干燥后得到500gANCO-rPPE。
(3)含有PPO主链的双端基多官能的活性酯树脂与环氧树脂的组合物
将环氧树脂、前述方法得到的含有PPO主链的双端基多官能的活性酯树脂以及固化促进剂按一定比例于溶剂中混合均匀，控制胶液固含量为65％，用2116玻纤布浸渍上述胶液，控制合适厚度，然后在115～175℃的烘箱中烘烤2～15min制成预浸料，然后将数张预浸料叠在一起，在其两侧叠上铜箔，在固化温度为170～250℃，固化压力为25～60kg/cm2，固化时间为60～300min条件下制成覆铜板。如下表：
Figure PCTCN2015090080-appb-000004
Figure PCTCN2015090080-appb-000005
Figure PCTCN2015090080-appb-000006
Figure PCTCN2015090080-appb-000007
板材性能如下表：
Figure PCTCN2015090080-appb-000008
性能分析：
实施例可以看出，活性酯官能基个数是8最优，而对比例1与实施例6比较，得出用同样比例的活性酯固化剂对同种环氧树脂进行固化，由于B4具有PPO主链，其刚性较强，导致其固化体系的耐热性增强。
(4)含有PPO主链的双端基多官能的活性酯树脂、环氧树脂和氰酸酯组合物
将环氧树脂、酯化PPO树脂、氰酸酯树脂和固化促进剂按一定比例于溶剂中混合均匀，控制胶液固含量为65％，用2116玻纤布浸渍上述胶液，控制合适 厚度，然后在115～175℃的烘箱中烘烤2～15min制成预浸料，然后将数张预浸料叠在一起，在其两侧叠上铜箔，在固化温度为170～250℃，固化压力为25～60kg/cm2，固化时间为60～300min条件下制成覆铜板。如下表：
Figure PCTCN2015090080-appb-000009
Figure PCTCN2015090080-appb-000010
Figure PCTCN2015090080-appb-000011
板材性能如下：
Figure PCTCN2015090080-appb-000012
Figure PCTCN2015090080-appb-000013
涉及材料及牌号信息如下：
HPC-8000-65T：DIC，DCPD活性酯，酯当量223，
HP-7200HHH：DIC，DCPD型环氧树脂，环氧当量288，
HP-7200H-75M：DIC，DCPD型环氧树脂，环氧当量280，
NC-7300L：日本化药，萘酚型酚醛环氧树脂，环氧当量214，
SKE-3：尚科特，特种环氧树脂，环氧当量120，
SA90：沙伯基，小分子化双官能基聚苯醚，羟基当量850，
SA9000：沙伯基，小分子化端基为丙烯酸酯封端的聚苯醚，CY-40：吴桥树酯厂，DCPD型氰酸酯树脂，
PT30S：LONCZ，酚醛型氰酸酯树脂，
HF-10：上海慧丰，双酚A型氰酸酯树脂，
DMAP：4-二甲胺基吡啶，
2E4MZ：2-乙基-4甲基咪唑。
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. 一种含有PPO主链的双端基多官能活性酯树脂，其具有式(1)所示的结构：
    Figure PCTCN2015090080-appb-100001
    其中，R1为
    Figure PCTCN2015090080-appb-100002
    R2为
    Figure PCTCN2015090080-appb-100003
    取代或未取代的C1～C3的直链烷基或支链烷基、烯丙基或异烯丙基；R3为H、烯丙基或异烯丙基；R4、R5、R6、R7独立选自H、取代或未取代的C1～C3的直链烷基或支链烷基、烯丙基、异烯丙基或-O-R8；R8为取代或未取代的C1～C3的直链烷基或支链烷基或取代或未取代的苯基；
    n1、n2为大于0的正整数，且满足4≤n1+n2≤25；n3、n4相等或不等，独立地为1、2或3。
  2. 如权利要求1所述的活性酯树脂，其特征在于，6≤n1+n2≤20，优选8≤n1+n2≤15；
    优选地，n3、n4相等或不等，独立地为2或3，优选n3、n4相等且独立地为2或3。
  3. 一种热固性树脂组合物，包括环氧树脂和权利要求1或2所述的含有PPO主链的双端基多官能活性酯树脂。
  4. 如权利要求3所述的热固性树脂组合物，其特征在于，所述含有PPO主链的双端基多官能活性酯树脂占热固性树脂组合物总重量的10～80％，优选 30～75％；
    优选地，所述环氧树脂占热固性树脂组合物总重量的20～50％。
  5. 如权利要求3或4所述的热固性树脂组合物，其特征在于，所述热固性树脂组合物还包括氰酸酯树脂、双马来酰亚胺-三嗪树脂、1，2-聚丁二烯树脂或丁苯树脂中的任意一种或者至少两种的混合物，其占热固性树脂组合物总重量的5～40％。
  6. 如权利要求3-5之一所述的热固性树脂组合物，其特征在于，所述热固性树脂组合物进一步包含有机添加型阻燃剂，所述有机添加型阻燃剂为磷系阻燃剂和/或卤系阻燃剂；
    优选地，所述热固性树脂组合物进一步包含填料和/或固化促进剂。
  7. 一种预浸料，其包括增强材料及通过浸渍干燥后附着在其上的如权利要求3-6之一所述的热固性树脂组合物。
  8. 一种层压板，所述层压板含有至少一张如权利要求7所述的预浸料。
  9. 一种覆金属箔层压板，其包括至少一张如权利要求7所述的预浸料及压覆在叠合的预浸料一侧或两侧的金属箔。
  10. 一种印制线路板，其含有至少一张如权利要求7所述的预浸料。
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CN103842397A (zh) * 2011-09-30 2014-06-04 三菱瓦斯化学株式会社 树脂组合物、预浸料以及覆金属箔层叠板
CN104761719A (zh) * 2015-04-01 2015-07-08 广东生益科技股份有限公司 一种活性酯以及含有该活性酯的热固性树脂组合物、预浸料和层压板

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