CN102002235B - Method for reducing thermal expansion coefficient of polybenzoxazine-based underfill - Google Patents

Method for reducing thermal expansion coefficient of polybenzoxazine-based underfill Download PDF

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CN102002235B
CN102002235B CN 201010543815 CN201010543815A CN102002235B CN 102002235 B CN102002235 B CN 102002235B CN 201010543815 CN201010543815 CN 201010543815 CN 201010543815 A CN201010543815 A CN 201010543815A CN 102002235 B CN102002235 B CN 102002235B
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thermal expansion
mixture
expansion coefficient
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CN102002235A (en )
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吴波
王建斌
陈田安
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烟台德邦电子材料有限公司
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Abstract

The invention relates to a method for reducing thermal expansion coefficient of a polybenzoxazine-based underfill. The method comprises the following steps of: preparing a resin mixture containing benzoxazine; adding 10 to 60 parts of negative thermal expansion coefficient filler into 25 to 60 parts of resin mixture containing benzoxazine, and mixing the filler and the resin mixture uniformly; adding 10 to 25 parts of curing agent, 0 to 2 parts of catalyst and 0.1 to 3 parts of coupling agent into the mixture of the resin mixture containing benzoxazine and the negative thermal expansion coefficient filler, and mixing the components uniformly; and putting the mixture into a reaction kettle, pumping air from the reaction kettle, and then curing the mixture. The method for reducing the thermal expansion coefficient of the polybenzoxazine-based underfill by adding the negative thermal expansion coefficient material reduces the thermal expansion coefficient of the polybenzoxazine-based underfill to approach the thermal expansion coefficient of an FR-4 substrate, and does not affect the fluidity of the system.

Description

一种降低聚苯并恶嗪基底部填充胶的热膨胀系数的方法 A method for reducing the thermal expansion coefficient of polybenzoxazine-yl underfill

技术领域 FIELD

[0001] 本发明涉及一种降低底部填充胶的热膨胀系数的方法,尤其涉及一种降低聚苯并恶嗪基底部填充胶的热膨胀系数的方法。 [0001] The present invention relates to a method for the thermal expansion coefficient of the underfill is reduced, particularly to a method of thermal expansion coefficient polybenzoxazine yl underfill decreases.

背景技术 Background technique

[0002] 底部填充工艺是随着高密度电子封装技术的迅速发展而产生的附加工艺,其目的是为了解决集成电路元件、互连材料和衬底之间的热膨胀系数的失配问题,以延长焊接点的使用寿命,提高电子产品的热可靠性。 [0002] The underfill process is an additional process with the rapid development of high-density electronic packaging technology is generated, its purpose is to solve the problem of mismatch between the thermal expansion coefficient of the integrated circuit elements, the interconnect material and the substrate, to extend welds life, improve thermal reliability of electronic products. 因此对底部填充胶的热膨胀系数提出了更高的要求。 Thus the thermal expansion coefficient of the underfill is a higher requirement. 目前市场上的底部填充胶以环氧类为主,存在固化收缩率大(3%〜4%),热膨胀系数高(65ppm/°C〜75ppm/°C)等缺点,难以满足高端电子产品封装的使用要求。 Filling the bottom of the current market in epoxy based glue, there is a large cure shrinkage (3% ~ 4%), high thermal coefficient of expansion disadvantages (65ppm / ° C~75ppm / ° C), it is difficult to meet the high-end electronics package use requirements. 针对于这种情况,目前基本上是通过加入填料来降低固化物的热膨胀系数。 For in this case, it is essentially to reduce the thermal expansion coefficient of the cured by the addition of filler. 有研究报道,将热膨胀系数为75ppm/°C的聚合物体系降至20ppm/°C需要添加70%的硅微粉,同时体系的粘度剧增,影响了胶水的流动性,这对毛细流底部填充效果影响非常大。 Studies have reported that the thermal expansion coefficient is 75ppm / ° C of the polymer system down to 20ppm / ° C to add 70% of microsilica, while the sharp increase in viscosity of the system, affecting the flow of the glue, which filled the bottom of the capillary flow the effect of the impact is very large. 因此可以考虑采用本身具有低膨胀系数的聚合物。 Thus the polymer itself can be considered having a low coefficient of expansion. 但是现有的聚苯并恶嗪基底部填充胶的热膨胀系数与FR-4衬底的热膨胀系数(18ppm/°C〜25ppm/°C)还是差距较大的;双环苯并恶嗪在二羧酸催化剂作用下,加热固化后再加入SiO2可降低热膨胀系数,使其与FR-4衬底的热膨胀系数相近,但填料含量过大会造成体系粘度太大,流动性不够。 However, the conventional thermal expansion coefficient of polybenzoxazine FR-4 substrate with a thermal expansion coefficient (18ppm / ° C~25ppm / ° C) or big gap between the underfill piperazinyl; bicyclic dicarboxylic benzoxazine acid catalyst, and then heating and curing may be added to lower the thermal expansion coefficient of SiO2, so that a thermal expansion coefficient similar to the FR-4 substrate, but cause the filler content is too Assembly system viscosity is too large, insufficient flowability.

发明内容 SUMMARY

[0003] 本发明针对现有聚苯并恶嗪基底部填充胶的热膨胀系数和衬底的热膨胀系数差距较大,以及填充填料后体系粘度太大,流动性不够的不足,提供一种降低聚苯并恶嗪基底部填充胶的热膨胀系数的方法。 [0003] The present invention is directed to the prior polybenzoxazine yl gap thermal expansion coefficient of the underfill coefficient of thermal expansion and the substrate is large, and the viscosity after filling the filler is too large, insufficient flowability insufficient, there is provided a method of reducing a poly the method of thermal expansion coefficient of the bottom-benzoxazin-filled gum base.

[0004] 本发明解决上述技术问题的技术方案如下:一种降低聚苯并恶嗪基底部填充胶的热膨胀系数的方法包括以下步骤:首先,制备包含苯并恶嗪的树脂混合物;接着,在25份〜 60份的包含苯并恶嗪的树脂混合物内加入10份〜60份的负热膨胀系数的填料,并混合均匀;然后,在包含苯并恶嗪的树脂混合物和负热膨胀系数的填料的混合物内加入10份〜25 份的固化剂、O份〜2份的催化剂和O. I份〜3份的偶联剂,并混合均匀后;最后,将混合物放入反应釜中抽真空再进行固化即可。 [0004] The present invention solves the above technical problem the following technical solution: A method for reducing the thermal expansion coefficient and the polyphenylene underfill oxazinyl method comprising the following steps: First, a resin mixture comprising a benzoxazine; Next, in benzoxazine resin mixture comprising 25 parts to 60 parts of a filler added to the ~ 60 parts 10 parts of a negative thermal expansion coefficient, and mixed well; and then a filler containing benzoxazine resin mixture and a negative thermal expansion coefficient ~ 25 parts 10 parts was added to the mixture of a curing agent, O ~ 2 parts parts parts catalyst and O. I ~ 3 parts coupling agent, and uniformly mixed; Finally, the mixture was placed in the reaction vessel was evacuated then It can be cured.

[0005] 所述制备包含苯并恶嗪的树脂混合物即将苯并恶嗪和除苯并恶嗪以外的其他树脂组分混合均匀,混合的温度为50°C〜80°C,混合的时间为30分钟,所述50°C〜80°C的温度为苯并恶嗪的熔点。 [0005] The resin mixture was prepared containing benzoxazine coming benzoxazine resin and other components other than the benzoxazine mixed uniformly, the mixing temperature of 50 ° C~80 ° C, mixing time 30 minutes, 50 ° C~80 ° C the temperature of the melting point of the benzoxazine.

[0006] 所述将混合物放入反应釜中,并在反应釜中抽真空的压力-O. IMpa,抽真空的时间为45分钟,所述抽真空45分钟为了把混合物中的气泡抽干净,然后使其各组分混合均匀。 [0006] The mixture was placed in the autoclave, and the autoclave evacuated pressure -O. IMpa, evacuation time of 45 minutes, 45 minutes the vacuum in order to draw a clean air bubbles in the mixture, then allowed the components mixed.

[0007] 所述抽真空后再进行固化的温度为150°C〜175°C,固化的时间为3小时〜4小时,可以逐步升温固化,也可以在一个温度下固化。 [0007] The vacuumed curing temperature of 150 ° C~175 ° C, the curing time of 3 hours ~ 4 hours, gradually warming can be cured may be cured at a temperature. 所述逐步升温固化可以降低热应力。 The curing can be raised stepwise reduce thermal stress.

[0008] 本发明的有益效果是:本发明降低聚苯并恶嗪基底部填充胶的热膨胀系数的方法通过加入具有负热膨胀系数材料的方法,以达到降低聚苯并恶嗪基底部填充胶的热膨胀系数使其和FR-4衬底的热膨胀系数相接近,同时不影响体系流动性;采用该方法所得到的底部填充胶的热膨胀系数低,与FR-4衬底匹配;采用该方法所得到的底部填充胶的Cl—,K+, Na+浓度在5ppm以下;采用该方法所得到的底部填充胶的吸湿性低,常低温储存性好;采用该方法所得到的底部填充胶的玻璃化转变温度高,力学性能好;还可用于制备其他低热膨胀系数的电子封装材料,如灌封胶,芯片粘接胶,(非)导电胶等。 [0008] Advantageous effects of the present invention are: the present invention reduces the polybenzoxazole method coefficient of thermal expansion oxazinyl underfill by adding method has a negative thermal expansion coefficient of the material, in order to reduce polybenzoxazine yl underfill coefficient of thermal expansion so that thermal expansion coefficient of the FR-4 substrate close, without affecting the fluidity of the system; using a bottom obtained by the method of a low thermal expansion coefficient of the underfill, and FR-4 substrate match; by this method to obtain the underfill Cl-, K +, Na + concentration of 5ppm or less; lower using a bottom obtained by the method of the underfill hygroscopic, normal and low temperature storage stability is good; vitrification obtained by the method of the underfill transition temperature high mechanical performance; electronic packaging materials may also be used to prepare other low thermal expansion coefficient, such as encapsulants, die attach adhesive, (non) conductive paste and the like.

[0009] 在上述技术方案的基础上,本发明还可以做如下改进。 [0009] Based on the foregoing technical solution, the present invention may be modified as follows.

[0010] 进一步,所述苯并恶嗪为单环苯并恶嗪和双环苯并恶嗪中一种或两种的混合物。 [0010] Further, the benzoxazine monocyclic and bicyclic benzoxazine benzoxazine one or mixture of the two.

[0011] 所述苯并恶嗪的结构通式为: [0011] The benzoxazine structural formula is:

[0012] [0012]

Figure CN102002235BD00041

[0013] 其中:R1和R2可以是氧原子、脂肪烧基或芳香基,也可以是苯并恶嚷结构,Rl和R2可以相同,也可以不同。 [0013] wherein: R1 and R2 may be an oxygen atom, aliphatic group or an aromatic group burning, may be cried benzoxazine structure, Rl and R2 may be the same or different.

[0014] 进一步,所述包含苯并恶嗪的树脂混合物还包括环氧树脂、酚醛树脂、氰酸酯树脂、双马来酰亚胺树脂和丙烯酸酯树脂中的一种或几种的混合物。 The resin mixture [0014] Further, the benzoxazine comprises further include epoxy resins, phenolic resins, cyanate ester resin, a mixture of one or more bismaleimide resins and acrylate resins.

[0015] 进一步,所述苯并恶嗪的质量占包含苯并恶嗪的树脂混合物质量的80%〜90%。 [0015] Further, the quality of the benzoxazine comprises 80% ~ 90% of the mass of the benzoxazine resin mixture.

[0016] 进一步,所述负热膨胀系数的填料为锆化物和钨化物中的一种或两种的混合物。 [0016] Further, the negative thermal expansion coefficient of the filler is a mixture of zirconium compound and a tungsten compound of one or two.

[0017] 所述锆化物和钨化物的细度为5 μ m〜10 μ m。 The [0017] The zirconium compound and a tungsten compound fineness of 5 μ m~10 μ m.

[0018]进一步,所述锆化物为 ZrO(NO3)2、Zr (NO3)4、Zr (OH)4、Zr (SO4)2、Zr(O(CH2)3CH3)4' Zr (OC(CH3) 3)4> Zr(OC2H5)4, Zr (CF3⑶CH⑶CF3) 4、Zr (CH3⑶CH⑶CH3) 4、Zr (OCH (CH3) 2) 4、 Zr (O (CH2) 2CH3) 4和Zr3 (C6H5O7) 4中的一种或几种的混合物。 [0018] Further, the zirconium compound as ZrO (NO3) 2, Zr (NO3) 4, Zr (OH) 4, Zr (SO4) 2, Zr (O (CH2) 3CH3) 4 'Zr (OC (CH3) 3) 4> Zr (OC2H5) 4, Zr (CF3⑶CH⑶CF3) 4, Zr (CH3⑶CH⑶CH3) 4, Zr (OCH (CH3) 2) 4, the Zr (O (CH2) 2CH3) 4 and Zr3 (C6H5O7) 4 a or a mixture of several kinds.

[0019]进一步,所述钨化物为 H2WO12, H2W4O12, W (OC2H5) 6、W (OCH (CH3) 2) 6、ZrffO4 和Zrff2O8 中的一种或几种的混合物。 [0019] Further, as H2WO12, H2W4O12, 6, (2 OCH (CH3)) 6, a mixture of one or more of the Zrff2O8 ZrffO4 and tungsten compound W (OC2H5) W.

[0020] 优选地,所述钨化物为ZrWO4或者ZrW2O8。 [0020] Preferably, the tungsten compound is ZrWO4 or ZrW2O8.

[0021] 进一步,所述固化剂为改性胺类、酸酐和酚醛树脂中的一种或几种的混合物。 [0021] Further, the curing agent is a mixture of one or more modified amines, anhydride and phenolic resin.

[0022] 当使用酚醛树脂做固化剂时,前述树脂混合物中的其他树脂一般就不再选用酚醛树脂了。 [0022] When the phenolic resin as a curing agent is used, the resin mixture of other resins is generally no longer the selected phenol resin.

[0023] 所述改性胺类可以是日本味之素的PN23,所述酸酐可以是甲基纳迪克酸酐,所述酌·醒树脂可以是Schenectady International 的HRJ1166。 [0023] The modified amine may be PN23 Ajinomoto, which may be an acid anhydride methylnadic anhydride, the resin may be a wake-discretion Schenectady International of HRJ1166.

[0024] 进一步,所述催化剂为改性咪唑及其衍生物。 [0024] Further, the catalyst is a modified imidazole and derivatives thereof.

[0025] 所述催化剂可以选用Aldrich的I-苯甲基_2_甲基咪唑,I-氰乙基_2_甲基咪唑,I-氰基-乙基-2-乙基-4-甲基咪唑,I-氰乙基-2-苯基咪唑,Shikoku化学的2PHZ、 2E4MZ-CN、日本味之素的PN-H,其中PN-H为优选。 [0025] The catalyst may be selected from Aldrich _2_ I- benzyl-methylimidazole, I- cyanoethyl _2_ methylimidazole, I- cyano - 2-ethyl-4-carboxylic acid imidazole, I- cyanoethyl-2-phenylimidazole, Shikoku chemical 2PHZ, 2E4MZ-CN, Japan pigment Ajinomoto PN-H, PN-H wherein preferred.

[0026] 进一步,所述偶联剂为钛酸四丁酯、氨丙基三乙氧基硅烷(KH-550)、Y -环氧丙基氧丙基三甲氧基硅烷(KH-560)和Y -甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)中的一种或几种的混合物。 [0026] Further, the coupling agent is tetrabutyl titanate, aminopropyl triethoxysilane (KH-550), Y - epoxypropyl trimethoxy silane (KH-560) and Y - a mixture of one or more of methacryloxypropyl trimethoxy silane (KH-570) in the. 具体实施方式 Detailed ways

[0027] 以下对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。 [0027] hereinafter be described principles and features of the present invention, The examples only serve to explain the present invention and are not intended to limit the scope of the invention.

[0028] 实施例I [0028] Example I

[0029] 称取单环苯并恶嗪和环氧树脂(828EL)的混合物40份,混合重量比为9:1,在50°C下混合半小时后加入ZrWO4 47份,细度10 μ m,经三辊机混合均匀后加入固化剂酚醛树脂(HRJ1166) 10份,催化剂改性咪唑(PN-H) O. 5份,偶联剂钛酸四丁酯O. 5份,Y -环氧丙基氧丙基三甲氧基硅烷(KH-560)0. 5份,混匀后加入到反应釜中,在压力为-O. IMPa下抽真空45分钟。 [0029] Weigh monocyclic benzoxazine and epoxy resin (828EL) 40 parts of a mixture, the mixing weight ratio of 9: 1, mixed at 50 ° C for half an hour was added ZrWO4 47 parts, fineness of 10 μ m , three-roll mill by addition of the phenol resin curing agent (HRJ1166) after uniformly mixing 10 parts, a modified imidazole catalyst (PN-H) O. 5 parts of tetrabutyl titanate coupling parts O. 5, Y - epoxy propyl trimethoxy silane (KH-560) 0. 5 parts, after mixing added to the reaction vessel, the pressure is -O. evacuated under IMPa 45 minutes. 取试样按照150°C /I h — 160°C /Ih — 170°C /2 h的升温过程分级固化,所得固化物的热膨胀系数(Coefficient of thermal expansion,简称CTE)为18. 3 ppm/。 Take samples according to 150 ° C / I h - 160 ° C / Ih - 170 ° C / 2 h of heating fractionation curing process, the thermal expansion coefficient of the resulting cured product (Coefficient of thermal expansion, referred to as CTE) of 18. 3 ppm / . . .

[0030] 实施例2 [0030] Example 2

[0031] 称取双环苯并恶嗪和酚醛树脂(HRJ1166)的混合物35份,混合重量比为9:1,在80°C下混合半小时后加入ZrWO4 37份,细度10 μ m。 [0031] The said mixture was taken bicyclic benzoxazine and phenolic resin (HRJ1166) 35 parts by weight of mixing ratio of 9: 1, mixed at 80 ° C for half an hour was added ZrWO4 37 parts, fineness of 10 μ m. 经三辊机混合均匀后加入固化剂双氰胺25份,偶联剂钛酸四丁酯O. 5份,Y -甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)2份, 混匀后加入到反应釜中,在压力为-O. IMPa下抽真空45分钟。 Was added after the three-roll mill mixed 25 parts of a dicyandiamide curing agent, tetrabutyl titanate coupling parts O. 5, Y - methacryloxypropyl trimethoxy silane (KH-570) 2 parts after the reaction mix was added to the autoclave at a pressure of -O. evacuated under IMPa 45 minutes. 取试样在150°C下固化4小时,所得固化物的CTE为20. 2 ppm/°C。 Take a sample cured for 4 hours at 150 ° C, CTE of the resulting cured product 20. 2 ppm / ° C.

[0032] 实施例3 [0032] Example 3

[0033] 称取双环苯并恶嗪和环氧树脂(EP0N825)的混合物55份,混合重量比为9:1,在70°C下混合半小时后加入ZrW2O8 27份,细度5μπι。 [0033] The said mixture was taken bicyclic benzoxazine and epoxy resins (EP0N825) 55 parts by weight of mixing ratio of 9: 1, mixed at 70 ° C for half an hour was added ZrW2O8 27 parts, fineness 5μπι. 经三辊机混合均匀后加入固化剂甲基纳迪克酸酐15份,催化剂改性咪唑(2ΡΗΖ)1份,偶联剂钛酸四丁酯O. 5份,氨丙基三乙氧基硅烷(ΚΗ-550)1. 5份。 After three roll mill after adding the curing agent mixed 15 parts of methylnadic anhydride, the modified imidazole catalysts (2ΡΗΖ) 1 parts of tetrabutyl titanate coupling agent O. 5 parts of aminopropyl triethoxysilane ( ΚΗ-550) 1. 5 parts. 混匀后加入到反应釜中,在压力为-O. IMPa下抽真空45分钟。 After mixing was added to the autoclave at a pressure of -O. Evacuated under IMPa 45 minutes. 取试样在170°C下固化4小时,所得固化物的CTE为22. 7 ppm/°C。 Take a sample cured for 4 hours at 170 ° C, CTE of the resulting cured product 22. 7 ppm / ° C.

[0034] 实施例4 [0034] Example 4

[0035] 称取单环苯并恶嗪、双环苯并恶嗪和环氧树脂(830LVP)的混合物25份,混合重量比为6:3:1,在75°C下混合半小时后加入ZrWO4和ZrW2O8混合物60份,细度5 μ m。 [0035] Weigh benzoxazine monocyclic, bicyclic benzoxazine mixture of an epoxy resin and (830LVP) 25 parts by weight of mixing ratio of 6: 3: 1, mixed at 75 ° C for half an hour was added ZrWO4 and a mixture of 60 parts of ZrW2O8 fineness of 5 μ m. 经三辊机混合均匀后加入改性胺类固化剂(PN23) 10份,催化剂改性咪唑(PN-H) 2份,偶联剂钛酸四丁酯O. 5份,Y-环氧丙基氧丙基三甲氧基硅烷(KH-560) 2. 5份。 After three-roll mill by mixing uniformly modified amine hardener was added (PN23) 10 parts, a modified imidazole catalyst (PN-H) 2 parts of tetrabutyl titanate coupling agent O. 5 parts, Y- glycidoxy yl trimethoxy silane (KH-560) 2. 5 parts. 混匀后加入到反应釜中,在压力为-O. IMPa下抽真空45分钟。 After mixing was added to the autoclave at a pressure of -O. Evacuated under IMPa 45 minutes. 取试样在160°C下固化3小时,所得固化物的CTE 为12. 5 ppm/°C ο Take sample was cured for 3 hours at 160 ° C, CTE of the resulting cured product 12. 5 ppm / ° C ο

[0036] 实施例5 [0036] Example 5

[0037] 称取双环苯并恶嗪、环氧树脂(830LVP)和酚醛树脂(HRJ1166)的混合物55份,混合重量比为8:1: 1,在65°C下混合半小时后加入ZrWO4和ZrW2O8混合物23份,细度5 μ m。 [0037] Weigh bicyclic benzoxazine, epoxy resin mixture (830LVP) and the phenolic resin (HRJ1166) 55 parts by weight mixing ratio of 8: 1: 1, was added at 65 ° C and half an hour after mixing ZrWO4 23 parts of a mixture of ZrW2O8 fineness of 5 μ m. 经三辊机混合均匀后加入改性胺类固化剂(PN23) 20份,催化剂改性咪唑(2E4MZ-CN) O. 5 份,Y-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570) O. 5份,Y-环氧丙基氧丙基三甲氧基硅烷(KH-560)2. O份。 After three-roll mill by mixing uniformly modified amine hardener was added (PN23) 20 parts, a modified imidazole catalyst (2E4MZ-CN) O. 5 parts, Y- methacryloxypropyl trimethoxy silane (KH -570) O. 5 parts, Y- epoxypropyl trimethoxy silane (KH-560) 2. O parts. 混匀后加入到反应釜中,在压力为-O. IMPa下抽真空45分钟。 After mixing was added to the autoclave at a pressure of -O. Evacuated under IMPa 45 minutes. 取试样在170°C下固化4小时,所得固化物的CTE为23. 6 ppm/°C。 Take a sample cured for 4 hours at 170 ° C, CTE of the resulting cured product 23. 6 ppm / ° C.

[0038] 实施例6 [0038] Example 6

[0039] 称取单环苯并恶嗪、环氧树脂(828EL)和酚醛树脂(HRJ1166)的混合物60份,混合重量比为8:1:1,在60°C下混合半小时后加入ZrW04和ZrW208混合物10份,细度5μπι。 [0039] Weigh monocyclic benzoxazine, mixture of epoxy resin (828EL) and the phenolic resin (HRJ1166) 60 parts by weight mixing ratio of 8: 1: 1, mixed at 60 ° C for half an hour was added ZrW04 and a mixture of 10 parts of ZrW208, fineness 5μπι. 经三辊机混合均匀后加入固化剂双氰胺25份,催化剂改性咪唑(PN-H) 2份,氨丙基三乙氧基硅烷(ΚΗ-550) I份,Y -环氧丙基氧丙基三甲氧基硅烷(ΚΗ-560)2. O份,混匀后加入到反应釜中,在压力为-O. IMPa下抽真空45分钟。 After three-roll mill by mixing uniformly 25 parts of a dicyandiamide curing agent was added, the modified imidazole catalysts (PN-H) 2 parts of aminopropyl triethoxysilane (ΚΗ-550) I parts, Y - epoxypropyl trimethoxy silane (ΚΗ-560) 2. O parts, after mixing added to the reaction vessel at a pressure of -O. evacuated under IMPa 45 minutes. 取试样在175°C下固化4小时,所得固化物的CTE 为27. 3 ppm/。 Take a sample cured for 4 hours at 175 ° C, CTE of the resulting cured product 27. 3 ppm /. . .

[0040] 以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。 [0040] The foregoing is only preferred embodiments of the present invention, not intended to limit the present invention within the spirit and principle of the present invention, any modification, equivalent replacement, or improvement, it should be included in the present within the scope of the invention.

Claims (6)

1. 一种降低聚苯并恶嗪基底部填充胶的热膨胀系数的方法,其特征在于,所述方法包括以下步骤:首先,制备包含苯并恶嗪的树脂混合物,其中,所述苯并恶嗪的质量占包含苯并恶嗪的树脂混合物质量的80%〜90% ;接着,在25份〜60份的包含苯并恶嗪的树脂混合物内加入10份〜60份的负热膨胀系数的填料,并混合均匀,其中,所述负热膨胀系数的填料为锆化物和钨化物中的一种或两种的混合物,所述锆化物为ZrO (NO3) 2、Zr (NO3) 4、 Zr(OH)4, Zr (SO4) 2、Zr (O (CH2) 3CH3) 4、Zr (0C (CH3) 3) 4、Zr (OC2H5) 4、Zr (CF3⑶CH⑶CF3) 4、 Zr (CH3C0CHC0CH3) 4、Zr (OCH (CH3) 2) 4、Zr (O (CH2) 2CH3) 4 和Zr3 (C6H5O7) 4 中的一种或几种的混合物,所述钨化物为H2TO12、H2W4O12、W (OC2H5) 6、W (OCH (CH3) 2) 6、ZrffO4 和Zrff2O8 中的一种或几种的混合物;然后,在包含苯并恶嗪的树脂混合物和负热膨胀系数的填料的混合物 CLAIMS 1. A method of reducing the thermal expansion coefficient and the polyphenylene underfill oxazine group, characterized in that the method comprises the following steps: firstly, preparing a benzoxazine resin mixture, wherein said benzoxazin Next filler, ~ 60 parts in 25 parts of ~ 60 parts 10 parts comprises a negative coefficient of thermal expansion of the resin mixture of benzoxazine; piperazine mass comprising 80% accounted for ~ 90% of the mass of the benzoxazine resin mixture , and uniformly mixed, wherein the negative thermal expansion coefficient of the filler is a mixture of zirconium compound and a tungsten compound of one or both of the zirconium compound as ZrO (NO3) 2, Zr (NO3) 4, Zr (OH ) 4, Zr (SO4) 2, Zr (O (CH2) 3CH3) 4, Zr (0C (CH3) 3) 4, Zr (OC2H5) 4, Zr (CF3⑶CH⑶CF3) 4, Zr (CH3C0CHC0CH3) 4, Zr (OCH 2) 4, a mixture of (CH3) Zr (O (CH2) 2CH3) 4 and Zr3 (C6H5O7) one or more of the 4, the tungsten compound is H2TO12, H2W4O12, W (OC2H5) 6, W (OCH (CH3) 2) 6, ZrffO4 and Zrff2O8 or a mixture of several; then, the mixture comprising the filler benzoxazine resin mixture and a negative thermal expansion coefficient 加入10 份〜25份的固化剂、O份〜2份的催化剂和O. I份〜3份的偶联剂,并混合均匀后;最后, 将混合物放入反应釜中抽真空再进行固化即可。 Was added 10 parts of ~ 25 parts curing agent, O ~ 2 parts parts parts catalyst and O. I ~ 3 parts coupling agent, and uniformly mixed; Finally, the mixture was placed in the reaction vessel was evacuated and then cured i.e. can.
2.根据权利要求I所述的降低聚苯并恶嗪基底部填充胶的热膨胀系数的方法,其特征在于,所述苯并恶嗪为单环苯并恶嗪和双环苯并恶嗪中一种或两种的混合物。 A method according to claim I and a polyphenylene bottom oxazinyl underfill coefficient of thermal expansion of the reduction, wherein the benzoxazine monocyclic and bicyclic benzoxazine in a benzoxazine or a mixture of two kinds.
3.根据权利要求I所述的降低聚苯并恶嗪基底部填充胶的热膨胀系数的方法,其特征在于,所述包含苯并恶嗪的树脂混合物还包括环氧树脂、酚醛树脂、氰酸酯树脂、双马来酰亚胺树脂和丙烯酸酯树脂中的一种或几种的混合物。 I 3. The method of claim polybenzoxazole reducing the thermal expansion coefficient of the underfill oxazinyl, characterized in that said resin comprises a mixture of benzoxazine further comprising an epoxy resin, a phenolic resin as claimed in claim cyanate ester resins, bismaleimide resins, and a mixture of one or more acrylate resin.
4.根据权利要求I所述的降低聚苯并恶嗪基底部填充胶的热膨胀系数的方法,其特征在于,所述固化剂为改性胺类、酸酐和酚醛树脂中的一种或几种的混合物。 I 4. The method of claim polybenzoxazole reducing the thermal expansion coefficient of the underfill oxazine group, wherein the curing agent is one or more modified amines, anhydride and phenolic resin as claimed in claim mixture.
5.根据权利要求I所述的降低聚苯并恶嗪基底部填充胶的热膨胀系数的方法,其特征在于,所述催化剂为改性咪唑及其衍生物。 I 5. The method of claim polybenzoxazole reducing the thermal expansion coefficient of the underfill oxazinyl, characterized in that the catalyst is a modified imidazole and derivatives thereof as claimed in claim.
6.根据权利要求I所述的降低聚苯并恶嗪基底部填充胶的热膨胀系数的方法,其特征在于,所述偶联剂为钛酸四丁酯、氨丙基三乙氧基硅烷、Y-环氧丙基氧丙基三甲氧基硅烷和Y-甲基丙烯酰氧基丙基三甲氧基硅烷中的一种或几种的混合物。 According to claim I and a method according to the polyphenylene reducing the thermal expansion coefficient of the underfill oxazinyl, characterized in that the coupling agent is tetrabutyl titanate, aminopropyl triethoxysilane, the mixture Y- epoxypropyl trimethoxy silane and one or more of Y- methacryloxy propyl trimethoxy silane.
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WO2000027921A1 (en) 1998-11-10 2000-05-18 Edison Polymer Innovation Corporation Ternary systems of benzoxazine, epoxy, and phenolic resins
CN101302327A (en) 2007-05-10 2008-11-12 广科工业股份有限公司 Halogen-free fire-resistant epoxy resin composition, film and copper clad laminate
CN101613530A (en) 2008-06-23 2009-12-30 联茂电子股份有限公司 The resin composition and its application

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WO2000027921A1 (en) 1998-11-10 2000-05-18 Edison Polymer Innovation Corporation Ternary systems of benzoxazine, epoxy, and phenolic resins
CN101302327A (en) 2007-05-10 2008-11-12 广科工业股份有限公司 Halogen-free fire-resistant epoxy resin composition, film and copper clad laminate
CN101613530A (en) 2008-06-23 2009-12-30 联茂电子股份有限公司 The resin composition and its application

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叶朝阳 等.苯并口恶嗪树脂插层蛭石纳米复合材料的制备与表征.《四川大学学报(工程科学版)》.2002,第34卷(第4期),

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