CN101608019B - Method for preparing maleimide stop end type polyimide resin - Google Patents

Method for preparing maleimide stop end type polyimide resin Download PDF

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CN101608019B
CN101608019B CN 200910148857 CN200910148857A CN101608019B CN 101608019 B CN101608019 B CN 101608019B CN 200910148857 CN200910148857 CN 200910148857 CN 200910148857 A CN200910148857 A CN 200910148857A CN 101608019 B CN101608019 B CN 101608019B
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maleimide
polyimide resin
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庄永兵
范和平
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湖北省化学研究院
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Abstract

The invention relates to a method for preparing maleimide stop end type polyimide resin, comprising the following steps: diamine, maleic anhydride and tetracarboxylic dianhydride are sequentially added to a polar solvent according to a molar ratio of (n+1):2:n to have the solid content of 25 plus or minus 1 percent (gram/milliliter) and then stirred for 8-24 hours at room temperature under the protection of nitrogen to generate intermediate polyamide acid, then a dehydrating agent acetic anhydride, a dehydrating catalytic agent triethylamine and the polar solvent are added into the intermediate polyamide acid so that the solid content is reduced to 15 percent (gram/milliliter) and then chemical imidization for 4-6 hours is conducted under the temperature of 30 DEG C-80 DEG C, then reaction liquid is poured into anhydrous ethanol which is stirred at high speed to obtain deposits, and the deposits are sequentially and sufficiently washed by the anhydrous ethanol and anhydrous ether and then dried in vacuum so as to obtain the maleimide stop end type maleimide polyimide resin, or heat dehydration cyclizing is conducted on the generated intermediate polyamide acid under the action of entrainer ortho-dichlorobenzene and chlorobenzene or methylbenzene to obtain outcomes of the maleimide stop end type maleimide polyimide resin.

Description

一种马来酰亚胺封端型聚酰亚胺树脂的制备方法 A method for preparing a maleimide-terminated polyimide resins

技术领域: FIELD:

[0001] 本发明是申请号为200710053151. 3,申请日为2007年9月6日,发明名称为聚酰亚胺热固树脂的制备和在二层法挠性覆铜板上的应用的分案申请。 [0001] The present invention has application No. 200710053151.3, filed on September 6, 2007, entitled Preparation of a polyimide resin and heat divisional application on a solid two-layer method FCCL Application.

[0002] 本发明涉及挠性印制电路用挠性覆铜板基材及其复合材料领域,包括一种马来酰亚胺封端型聚酰亚胺树脂的制备方法,一种改性马来酰亚胺封端型聚酰亚胺树脂及其制备方法与其在一种无胶型二层法挠性覆铜板上的应用。 [0002] The present invention relates to a method for preparing a copper clad laminate for flexible printed circuits and flexible substrate composite materials comprising a maleimide terminated polyimide resin, a modified maleic imide-terminated polyimide resins and their method of preparation in an application on the gel-type two-layer method FCCL no.

技术背景: technical background:

[0003] 目前生产的挠性印制电路(FPC)基材中,最常见的是使用胶粘剂将聚酰亚胺薄膜和铜箔粘结复合的有胶型三层法产品,如CN1138782A及CN1178237A中所述的使用双马来酰亚胺改性丁腈橡胶配制的胶粘剂用于覆铜板生产。 [0003] The current production of flexible printed circuit (FPC) substrate, the most common is the use of an adhesive to a polyimide film and copper foil are bonded composite three-layer plastic product method, as in CN1138782A and CN1178237A the use nitrile rubber-modified bismaleimide adhesive formulation used for the production of CCL.

[0004] 随着电子工业的快速发展,对电子产品的外观和性能提出了更高要求,短、小、轻、 薄、美及优异的综合性能已成为生产商和消费者的首选。 [0004] With the rapid development of the electronics industry, the appearance and performance of electronic products put a higher demand, short, small, light, thin, beauty and excellent performance has become the first choice for producers and consumers. FPC工业为了满足这种需要,相继研发出了厚度更薄、性能更优的无胶型二层法基材。 To meet this need FPC industry, we have developed a thinner, better performance of the non-gel-type base layer method. 这种无胶型二层法挠性覆铜板基材的生产方法主要有三种:其一是在聚酰亚胺薄膜表面通过化学沉积和电镀的方法形成铜导电层(CN95106677);其二是采用真空溅射技术或蒸发沉淀技术,把铜沉积到绝缘膜上(CN01109402/CN1579754A);其三是将作为聚酰亚胺前体的聚酰胺酸溶液直接涂覆于金属箔上,然后进行梯度升温脱水环化成聚酰亚胺覆金属箔(CN00137383/CN1410471A),此种方法的最大优点是生产成本低、工艺比较简单。 The method of producing such a flexible copper clad laminate substrate without glue type Layer There are three main methods: one is a copper conductive layer (CN95106677) is formed by chemical deposition and electroplating on the polyimide film surface; the other is the use of vacuum sputtering technique or vapor deposition technique, the deposition of copper into the insulating film (CN01109402 / CN1579754A); the third is on the metal foil, and then as a gradient heating the polyamic acid solution is directly coated polyimide precursor dehydration cyclization to polyimide metal-clad (CN00137383 / CN1410471A), the biggest advantage of this method is the low production costs, the process is relatively simple. 但因使用的聚酰亚胺前体溶液——聚酰胺酸极易降解,使其贮存期过短,不能很好地满足大型工业生产的需要,且其热亚胺化过程须在氮气气氛下,在350°C以上的高温下完成,对设备和环境条件的要求极为苛刻。 But the polyimide precursor solution used - polyamic acid degradation easily, so that the storage period is too short, can not satisfy the needs of large-scale industrial production, and its thermal imidization process to be under a nitrogen atmosphere , at a high temperature of 350 ° C or more to complete, equipment requirements and the extremely harsh environmental conditions.

[0005] 在热固性聚酰亚胺树脂分支中,双马来酰亚胺(BMI)除具有一般的热固性聚酰亚胺突出的耐热、耐湿、耐辐射、绝缘及优良的加工性能外,它还具有类似环氧树脂的低固化温度以下),低固化压力(0. 7MPa以下)的特点,可极大程度地降低加工成本和生产过程对设备的要求,因此广泛应用于航空、航天、机械、电子等工业领域中先进复合材料的树脂基体、耐高温绝缘材料和胶粘剂等。 [0005] In the thermosetting polyimide resin branch, bismaleimide (BMI) in addition to a general thermosetting polyimide outstanding heat, external moisture, radiation resistance, insulation and excellent processing performance, it also has a similar low curing temperature of the epoxy resin), low curing pressure (0. 7MPa hereinafter) characteristics, can be reduced to a great extent and the cost of production and processing equipment requirements, it is widely used in aerospace, mechanical , electronics industry and other advanced resin matrix composite materials, high temperature insulation materials and adhesives. 目前,其在电子工业如印制电路板上的应用研究十分活跃。 Currently, its applied research in the electronics industry, such as printed circuit board is very active. 但因传统BMI固化树脂一般较脆,抗冲击性能和抗应力开裂的能力也较差,从而限制了其在无胶型二层法挠性覆铜板上的应用。 But conventional BMI resins are generally cured brittle resistance to impact stress cracking resistance and also poor, thus limiting its application in non-gel-type two-layer method FCCL. 要将双马来酰亚胺类树脂用作无胶型二层法挠性覆铜板生产的基体树脂,必须对其进行改性。 To bismaleimide resin is used as non-gel-type two-layer method FCCL produced matrix resin, it must be modified.

发明内容: SUMMARY:

[0006] 本发明的目的在于提供一种用于无胶型二层法挠性覆铜板生产所需的改性马来酰亚胺封端型聚酰亚胺树脂。 [0006] The object of the present invention is to provide a desired non-gel type Layer FCCL method for producing a modified maleimide terminated polyimide resin type used. 这种树脂具有优异的耐热性、尺寸稳定性、耐弯折性、可加工性和低介电常数、低介电损耗因子。 Such resins have excellent heat resistance, dimensional stability, bending resistance, workability, and low dielectric constant, low dielectric loss factor.

[0007] 本发明的另一目的在于提供一种改性马来酰亚胺封端型聚酰亚胺树脂的制备方法。 [0007] Another object of the present invention to provide a method for preparing a modified maleimide terminated polyimide resin. [0008] 本发明的另一目的在于提供一种改性马来酰亚胺封端型聚酰亚胺树脂在无胶型二层法挠性覆铜板上的应用方法。 [0008] Another object of the present invention is to provide a modified maleimide terminated applications without glue on a resin-type two-layer method FCCL polyimide.

[0009] 为达到目的,本发明采用的技术方案为: [0009] To achieve the object, the technical solution of the present invention is used are:

[0010] 一种改性马来酰亚胺封端型聚酰亚胺树脂,其特殊之处在于:所述的改性马来酰亚胺封端型聚酰亚胺树脂的组成和重量配比为: [0010] A modified maleimide terminated polyimide resin, which is special in that: said modified maleimide terminated polyimide resin composition and weight distribution ratio:

马来酰亚胺封端型聚酰亚胺树脂 100份 100 parts of maleimide terminated polyimide resin

烯丙基化合物 4〜50份 Allyl compounds 4~50 parts

所述的烯丙基化合物为二烯丙基双酚A和二烯丙基双酚S中的一种或二者共混 The allyl compound is blended with one or both of diallyl bisphenol A, diallyl bisphenol S and the

[0011] [0012] [0011] [0012]

[0013]物。 [0013] thereof.

[0014] 在树脂体系的配方中,烯丙基化合物的用量选定为马来酰亚胺封端型聚酰亚胺树脂用量的4%〜50%,若烯丙基化合物的用量小于4%,则体系的韧性较差,若其用量大于50%,则体系的耐热性和介电性能大幅度降低。 [0014] In the formulation of the resin system, the amount of the allyl compound selected is maleimide terminated polyimide resin 4% ~ 50% of the amount, if used in an amount of less than 4% allyl compound , the toughness is poor system, the heat resistance and dielectric properties of the system greatly reduced if the amount is more than 50%.

[0015] 上述的马来酰亚胺封端型聚酰亚胺树脂,其制备过程为:将二元胺、顺丁烯二酸酐和四酸二酐按物质的量比为(n+1) : 2 : η先后加入到极性溶剂中,使其固含量为25士(克/毫升),在氮气保护下,室温下搅拌8〜M小时后,生成中间体聚酰胺酸,随即加入脱水剂乙酸酐和脱水催化剂三乙胺及适量极性溶剂,使其固含量降为15% (克/毫升),再于30°C〜80°C下化学亚胺化反应4〜16小时,将反应液倒入高速搅拌的无水乙醇中,得到沉淀物,所得沉淀物先后用无水乙醇和无水乙醚充分洗涤后,真空干燥即得马来酰亚胺封端型聚酰亚胺树脂;或者将生成的中间体聚酰胺酸在共沸剂邻二氯苯、氯苯或甲苯的作用下, 进行热脱水环化得到马来酰亚胺封端型聚酰亚胺树脂产物,反应过程如式(1)所示, [0015] The maleimide-terminated polyimide resins, their preparation process: the diamine, maleic anhydride and dianhydride by the molar ratio of (n + 1) : 2: η successively added to a polar solvent to a solid content of 25 persons (g / mL), stirred 8~M hours under nitrogen at room temperature, the polyamic acid to form an intermediate, then added a dehydrating agent acetic anhydride and triethylamine dehydration catalyst and the amount of polar solvent, that the solid content is reduced to 15% (g / mL), and then to a chemical imidization reaction at 30 ° C~80 ° C 4~16 hours, the reaction after the solution was poured into absolute ethanol with rapid stirring to give a precipitate resulting precipitate was washed well successively with ethanol and anhydrous ether, and dried in vacuo to yield the maleimide terminated polyimide resin; or the intermediate produced under the action of the polyamic acid in the azeotropic agent o-dichlorobenzene, chlorobenzene, or toluene, thermal dehydration cyclization to give a maleimide-terminated polyimide resin product, such as reaction formula (1),

[0016] [0016]

Figure CN101608019BD00041

[0017] 式中;η为树脂聚合度,1彡η彡20 ;四酸二酐为0 (CO)况(CO) 2 ; 二元胺为 [0017] wherein; [eta] is a degree of polymerization of the resin, 1 [eta] San San 20; tetracarboxylic dianhydride is 0 (CO) condition (CO) 2; diamine is

H2N-R2-NH2 ; H2N-R2-NH2;

[0018] 所选用的四酸二酐单体O(CO)2R1(CO)2,其中适用的可以列举队为如式⑵所示。 [0018] The tetracarboxylic acid dianhydride monomer selected O (CO) 2R1 (CO) 2, where applicable may include teams are as shown in formula ⑵. 其中X为0、S、SO2, CO、CH2、C(CH3)3、CF2、C(CF3)2或者不存在。 Wherein X is 0, S, SO2, CO, CH2, C (CH3) 3, CF2, C (CF3) 2 or absent. 队可以有取代基,但优选没有取代基,或者是C1〜C6低级烷基或低级烷氧基。 Team may have a substituent, but preferably no substituents, or a C1~C6 lower alkyl or lower alkoxy. 在合成马来酰亚胺封端型聚酰亚胺树脂时,可使用单一的四酸二酐,也可选用二种或更多四酸二酐组成的混合物。 In the synthesis of maleimide terminated polyimide resin, may be used a single tetracarboxylic dianhydride can also be used two or more tetracarboxylic acid dianhydride consisting of a mixture. 优选的四酸二酐W -.3, 3' ,4,4'-联苯四酸二酐(BPDA)、3,3' ,4,4' -二苯甲酮四酸二酐(BTDA)、3,3', 4,4' -二苯醚四酸二酐(ODPA)、2,2'-双W-(3,4-二羧苯氧基)苯基]丙烷四酸二酐(BPADA)、2,2'-双(3,4-二羧苯基)六氟丙烷四酸二酐(6FDA)。 Preferred tetracarboxylic dianhydride W -.3, 3 ', 4,4'- biphenyltetracarboxylic dianhydride (BPDA), 3,3', 4,4 '- benzophenone tetracarboxylic dianhydride (BTDA) , 3,3 ', 4,4' - diphenyl ether dianhydride (ODPA), 2,2'- bis W- (3,4- dicarboxyphenyl) phenyl] propane dianhydride ( BPADA), 2,2'- bis (3,4-carboxyphenyl) hexafluoropropane dianhydride (6FDA). 五者的量不能同时为零, 其中任意一种占四酸二酐共混物的物质的量分数为0%〜100% ; An amount of five persons can not be zero, any of which accounts for the amount of substance dianhydride blend fraction is 0% ~ 100%;

[0019] [0019]

Figure CN101608019BD00051

[0020] 所选用的二元胺H2N-R2-NH2,其中适用的可列举&如式(3)所示。 [0020] The choice of a diamine H2N-R2-NH2, where applicable include & as shown in (3). 其中Z为0、S、 SO2, CO、CH2, C (CH3) 3> CF2, C(CF3)2或者不存在出2可以有取代基,但优选没有取代基,或者是C1〜C6低级烷基或低级烷氧基;民是C1〜C12的烃基或烃氧基;在合成马来酰亚胺封端型聚酰亚胺树脂时,可选用其中的一种、二种或多种二胺单体混合物;优选的二元胺有:1, 6-己二胺、1,3_双(3-氨基丙烷基)四甲基二硅氧烷、1,3_双(4-氨基苯氧基甲烷)-1, 1,3,3_四甲基二硅氧烷、3,4' - 二氨基二苯醚(3,4' -0DA)、4,4' - 二氨基二苯醚(4, 4' -0DA)、4,4' - 二氨基二苯砜0,4' -DDS)、1,4-双(4-氨基苯氧基)苯(1,4-BAB)、2, 2-双[(4-氨基苯氧基)苯基]丙烷G-BAPP)、双W-(4-苯氧基)苯基]砜(BAPQ ;九者的量不能同时为零,其中任意一种占二元胺共混物的物质的量分数为0%〜100%。 Wherein Z is 0, S, SO2, CO, CH2, C (CH3) 3> CF2, C (CF3) 2 or a 2 absence may have a substituent, but preferably no substituents, a lower alkyl group or a C1~C6 or lower alkoxy; C1~C12 China is a hydrocarbon group or a hydrocarbon group; when synthetic maleimide terminated polyimide resin, which can choose one of two or more diamines single mixtures thereof; preferred diamines are: 1,6-hexanediamine, 1,3_-bis (3-amino-propane-yl) tetramethyl disiloxane, 1,3_-bis (4-aminophenoxy methane) -1 1,3,3_ tetramethyldisiloxane, 3,4 '- diaminodiphenyl ether (3,4' -0DA), 4,4 '- diaminodiphenyl ether (4 , 4 '-0DA), 4,4' - diaminodiphenyl sulfone, 0,4 '-DDS), 1,4- bis (4-aminophenoxy) benzene (1,4-BAB), 2, 2 - bis [(4-aminophenoxy) phenyl] propane G-BAPP), bis W- (4-aminophenoxy) phenyl] sulfone (BAPQ; nine persons amount can not be zero at the same time, any of which the amount of material accounted diamine blend fraction is 0% ~ 100%.

Figure CN101608019BD00052

[0022] 反应所用的极性溶剂为N-甲基-2-卩比咯烷酮(NMP) ,N, N' -二甲基甲酰胺(DMF)、 N,N' -二甲基乙酰胺(DMAc)、二甲基亚砜(DMSO)、间甲酚、硫酸二甲酯、环丁砜、丁内酯、四氢呋喃等,其中优选N-甲基-2-吡咯烷酮(NMP)、N,N' - 二甲基甲酰胺(DMF)、N,N' -二甲基乙酰胺(DMAc)、二甲基亚砜(DMSO)中的一种或数种混合物。 [0022] The polar solvent used in the reaction of N- methyl-2-Jie-pyrrolidone (NMP), N, N '- dimethylformamide (DMF), N, N' - dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), m-cresol, dimethyl sulfate, sulfolane, butyrolactone, tetrahydrofuran, N- methyl-2-pyrrolidone being preferred (NMP), N, N '- dimethylformamide (DMF), N, N '- dimethylacetamide (DMAc), a medium dimethylsulfoxide (DMSO) or a mixture of several kinds.

[0023] 所述的脱水剂为乙酸酐,用量为二元胺物质的量的2〜4倍;脱水催化剂为三乙胺、吡啶及金属盐如乙酸钠、乙酸镍、乙酸镁、硫酸镁、氯化镁、乙酸钴、硫酸钴、乙酸锰、氯化锰等,其中优选三乙胺,用量为乙酸酐物质的量的0. 2〜1倍。 A dehydrating agent [0023] The acetic anhydride is used in an amount of 2 ~ 4 times the amount of the diamine substance; dehydration catalyst is triethylamine, pyridine, and metal salts such as sodium acetate, nickel acetate, magnesium acetate, magnesium sulfate, magnesium chloride, cobalt acetate, cobalt sulfate, manganese acetate, manganese chloride, etc., where triethylamine is preferred, in an amount of 0.5-fold amount of acetic anhydride 2~1 substance.

[0024] 上述化学亚胺化反应温度优选50°C〜70V ;化学亚胺化反应时间优选6〜8小时。 [0024] The chemical imidization reaction temperature is preferably 50 ° C~70V; chemical imidization reaction time is preferably 6 ~ 8 hours.

[0025] 本发明的改性马来酰亚胺封端型聚酰亚胺树脂在无胶型二层法挠性覆铜板上的应用,其特殊之处在于: [0025] Mid-modified maleimide resin of the present invention is applied on the non-gel-type two-layer method FCCL polyimide, which is special in that:

[0026] 按照上述的马来酰亚胺封端型聚酰亚胺树脂与烯丙基化合物重量份数比称取原料,将二者混合后,溶于极性溶剂中,充分搅拌,形成固含量为10%〜50% (克/毫升)的均相溶液,固含量优选为20%〜30% (克/毫升),将此溶液涂覆到5微米〜35微米厚的铜箔上,控制液膜在溶剂挥发后厚度为10微米〜30微米,于高温烘箱中,在氮气保护下进行梯度升温固化即得。 [0026] According to the above maleimide terminated polyimide resin by weight ratio of the compound with an allyl weighed raw materials, mixing them, in a polar solvent, and thoroughly stirred to form a solid content of 10% ~ 50% (g / ml) homogeneous solution, preferably 20% solids content of ~ 30% (g / mL), this solution was coated on a copper foil of 5 m ~ 35 m thick, control after evaporation of the solvent in a film having a thickness of 10 m ~ 30 microns, in a high temperature oven, heating gradient to yield cured under nitrogen.

[0027] 上述溶解改性马来酰亚胺封端型聚酰亚胺树脂的极性溶剂为N-甲基-2-吡咯烷酮(NMP)、N,N' - 二甲基甲酰胺(DMF)、N,N' - 二甲基乙酰胺(DMAc)、二甲基亚砜(DMSO)、 间甲酚、硫酸二甲酯、环丁砜、丁内酯、四氢呋喃等。 [0027] polar solvent of the dissolution modifying maleimide terminated polyimide resin is N- methyl-2-pyrrolidone (NMP), N, N '- dimethyl formamide (DMF) , N, N '- dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), m-cresol, dimethyl sulfate, sulfolane, butyrolactone, tetrahydrofuran and the like. 其中优选N-甲基-2-吡咯烷酮(NMP)、 N, N' - 二甲基甲酰胺(DMF)、N,N' - 二甲基乙酰胺(DMAc)、二甲基亚砜(DMSO)中的一种或数种混合物。 N- methyl-2-pyrrolidone being preferred (NMP), N, N '- dimethylformamide (DMF), N, N' - dimethylacetamide (DMAc), dimethylsulfoxide (DMSO) one or a mixture of several.

[0028] 上述梯度升温固化工艺为:80°C Xl小时,120°C Xl小时,180°C Xl小时, [0028] The curing process is a gradient of temperature rise: 80 ° C Xl hours, 120 ° C Xl hours, 180 ° C Xl hours,

52600C Xl 小时。 52600C Xl hours.

[0029] 上述所用铜箔的粘结面进行了化学或物理粗糙化处理。 [0029] The adhesive surface of the copper foil was chemically or physically roughening treatment.

[0030] 本发明的主要优点在于: [0030] The main advantage of the present invention is that:

[0031] 合成的改性马来酰亚胺封端型聚酰亚胺树脂具有良好的溶解性,可溶解在选用的极性溶剂中,溶液在室温下稳定性好。 [0031] Synthesis of maleimide terminated modified polyimide resin having good solubility, soluble in a polar solvent of choice, the solution stability at room temperature. 用在无胶型二层法挠性覆铜板上,生产成本低、工艺简单。 Used in the flexible copper clad laminate non-gel-type two-layer method, low production cost and simple process. 其固化温度相对常用聚酰亚胺的前体溶液——聚酰胺酸要低得多,因而在生产过程中对设备和环境条件的要求大大降低。 The curing temperature is relatively common precursor solution of the polyimide - polyamic acid is much lower, thus greatly reducing equipment requirements and environmental conditions during production. 树脂在固化时无小分子挥发物放出,因而可以得到几乎无气孔的综合性能优异的无胶型二层法挠性覆铜板基材。 Resin upon curing no release of volatiles small molecule, it is possible to obtain an excellent overall performance almost no pores of non-gel-type base layer method FCCL. 可广泛应用于高速计算机、 卫星通讯设备、移动电话等高新技术领域。 It can be widely used in high-tech field of high-speed computers, satellite communications equipment, mobile phones and so on.

具体实施方式: detailed description:

[0032] 本发明用以下实例进一步说明,但本发明并不局限于这些实例。 Invention is further illustrated by the following examples [0032] present, but the present invention is not limited to these examples.

[0033] 实施例1 [0033] Example 1

[0034] 将3,4' - 二氨基二苯醚03克(0. 12摩尔)、顺丁烯二酸酐3. 92克(0.04摩尔)和3,3' ,4,4'-联苯四酸二酐四· 42克(0. 10摩尔)先后加入到NMPO^毫升)中, 在氮气保护下,室温下搅拌10小时后,加入脱水剂乙酸酐0. 24摩尔65毫升)、脱水催化剂三乙胺0.M摩尔(33. 47毫升)和NMP 153毫升,于50°C下反应7小时,将其倒入大量高速搅拌的无水乙醇中,得到沉淀物。 [0034] The 3,4 '- diaminodiphenyl ether 03 g (0.12 mol), maleic anhydride 3.92 g (0.04 mol) and 3,3', 4,4'-biphenyltetracarboxylic after tetracarboxylic acid 8.42 g (0.10 moles) were added successively to the NMPO ^ mL), stirred at room temperature for 10 hours under nitrogen, a dehydrating agent is added 0.24 mole of acetic anhydride 65 ml), three dehydration catalyst ethanamine 0.M mole (33.47 ml) and NMP 153 ml reaction at 50 ° C 7 hours, it was poured into a large amount of absolute ethanol with rapid stirring to give a precipitate. 所得沉淀物先后用无水乙醇和无水乙醚充分洗涤后, 真空干燥得47. 16克马来酰亚胺封端型聚酰亚胺树脂。 The resulting precipitate was sufficiently washed successively with anhydrous ethanol and anhydrous diethyl ether, and dried in vacuo to give 47.16 g of maleic imide-terminated polyimide resin.

[0035] 称取上述马来酰亚胺封端型聚酰亚胺树脂30克和二烯丙基双酚A 3克,将二者混合后,溶于NMP(158毫升)中,充分搅拌成均相溶液。 [0035] Weigh the above maleimide terminated polyimide resin and 30 grams diallyl bisphenol A 3 grams, the mixture of the two, was dissolved in NMP (158 ml), stirred well into homogeneous solution. 将此溶液涂覆到35微米厚的经物理粗糙化处理过的铜箔上,控制液膜在溶剂挥发后厚度为10微米〜30微米,于高温烘箱中, 在氮气保护下进行梯度升温,升温过程为:80°C Xl小时,120°C Xl小时,180°C Xl小时, 2600C Xl小时。 This solution was coated onto a 35 micrometer thick on physically roughening treated copper foil, after evaporation of the solvent control film having a thickness of 10 m ~ 30 m, a gradient heated under nitrogen in a high temperature oven, heated process is: 80 ° C Xl hours, 120 ° C Xl hours, 180 ° C Xl hours, 2600C Xl hours. 缓慢冷却至室温即得无胶型二层法挠性覆铜板。 It was slowly cooled to room temperature to obtain the non-gel-type two-layer method FCCL.

[0036] 实施例2 [0036] Example 2

[0037] 将4,4' - 二氨基二苯醚50. 06克(0.25摩尔)、顺丁烯二酸酐9.81克(0. 10摩尔)和3,3' ,4,4' -二苯醚四酸二酐62. 13克(0.20摩尔)先后加入到DMAc 088毫升) 中,在氮气保护下,室温下搅拌12小时后,加入脱水剂乙酸酐0. 75摩尔(70. 77毫升)、脱水催化剂三乙胺0. 50摩尔(69. 73毫升)和DMAc 325毫升,于70°C下反应4小时,将其倒入大量高速搅拌的无水乙醇中,得到沉淀物。 [0037] 4,4 '- diaminodiphenyl ether 50.06 g (0.25 mol), maleic anhydride 9.81 g (0.10 mol) and 3,3', 4,4 '- diphenyl ether after dianhydride 62.13 g (0.20 mol) were added successively to DMAc 088 mL), stirred at room temperature for 12 hours under nitrogen, a dehydrating agent is added 0.75 mole of acetic anhydride (70.77 ml), dehydrated 0.50 mol of the catalyst triethylamine (69.73 ml) and DMAc 325 ml reaction at 70 ° C 4 hours, it was poured into a large amount of absolute ethanol with rapid stirring to give a precipitate. 所得沉淀物先后用无水乙醇和无水乙醚充分洗涤后,真空干燥得99. 26克马来酰亚胺封端型聚酰亚胺树脂。 The resulting precipitate was sufficiently washed successively with anhydrous ethanol and anhydrous diethyl ether, and dried in vacuo to give 99.26 g of maleic imide-terminated polyimide resin.

[0038] 称取上述马来酰亚胺封端型聚酰亚胺树脂80克和二烯丙基双酚A 13克,将二者混合后,溶于DMAc 025毫升)中,充分搅拌成均相溶液。 [0038] Weigh the above maleimide terminated polyimide resin and 80 grams diallyl bisphenol A 13 grams, the mixture of the two, was dissolved in DMAc 025 ml) were stirred well to phase solution. 将此溶液涂覆到35微米厚的铜箔上,控制液膜在溶剂挥发后厚度为10微米〜30微米,于高温烘箱中,在氮气保护下进行梯度升温,升温过程为:80°CX 1小时,1200C X 1小时,1800C X 1小时,260°CX 1小时。 This solution was applied on a copper foil 35 microns thick, after evaporation of the solvent control film having a thickness of 10 m ~ 30 m, a gradient heated under nitrogen in a high temperature oven, the heating process is: 80 ° CX ​​1 hours, 1200C X 1 hour, 1800C X 1 hour, 260 ° CX ​​1 hour. 缓慢冷却至室温即得无胶型二层法挠性覆铜板。 It was slowly cooled to room temperature to obtain the non-gel-type two-layer method FCCL.

[0039] 实施例3 [0039] Example 3

[0040]将 4,4' - 二氨基二苯砜G,4' -DDS) 86. 90 克(0.35 摩尔)、顺丁烯二酸酐9. 81 克(0. 10摩尔)和2,2'-双(3,4-二羧苯基)六氟丙烷四酸二酐133. 27克(0. 30摩尔)先后加入到DMF(920毫升)中,在氮气保护下,室温下搅拌16小时后,加入脱水剂乙酸酐1. 40摩尔(132. 10毫升)、脱水催化剂三乙胺0. 14摩尔(19. 52毫升)和DMF 613毫升,于60°C下反应6小时,将其倒入大量高速搅拌的无水乙醇中,得到沉淀物。 [0040] 4,4 '- diaminodiphenyl sulfone G, 4' -DDS) 86. 90 g (0.35 mol), maleic anhydride 9.81 g (0.10 mol) and 2,2 ' after the bis (3,4-carboxyphenyl) hexafluoropropane dianhydride 133.27 g (0.30 moles) were added successively to DMF (920 mL), stirred at room temperature under nitrogen for 16 hours - , a dehydrating agent is added 1.40 mole of acetic anhydride (132.10 ml), triethylamine dehydration catalyst 0.14 mole (19.52 ml) and DMF 613 mL, reacted at 60 ° C 6 hours, it was poured into a large number of high-speed stirring in anhydrous ethanol to obtain a precipitate. 所得沉淀物先后用无水乙醇和无水乙醚充分洗涤后,真空干燥得200. 00克马来酰亚胺封端型聚酰亚胺树脂。 The resulting precipitate was sufficiently washed successively with anhydrous ethanol and anhydrous diethyl ether, and dried in vacuo to give 200.00 g of maleic imide-terminated polyimide resin.

[0041] 称取上述马来酰亚胺封端型聚酰亚胺树脂100克和二烯丙基双酚A 6克,将二者混合后,溶于DMF 060毫升)中,充分搅拌成均相溶液。 [0041] Weigh the above maleimide terminated polyimide resin and 100 grams diallyl bisphenol A 6 grams, the mixture of the two, was dissolved in DMF 060 ml) were stirred well to phase solution. 将此溶液涂覆到35微米厚的经物理粗糙化处理过的铜箔上,控制液膜在溶剂挥发后厚度为10微米〜30微米,于高温烘箱中, 在氮气保护下进行梯度升温,升温过程为:80°C Xl小时,120°C Xl小时,180°C Xl小时, 2600C Xl小时。 This solution was coated onto a 35 micrometer thick on physically roughening treated copper foil, after evaporation of the solvent control film having a thickness of 10 m ~ 30 m, a gradient heated under nitrogen in a high temperature oven, heated process is: 80 ° C Xl hours, 120 ° C Xl hours, 180 ° C Xl hours, 2600C Xl hours. 缓慢冷却至室温即得无胶型二层法挠性覆铜板。 It was slowly cooled to room temperature to obtain the non-gel-type two-layer method FCCL.

[0042] 实施例4 [0042] Example 4

[0043] 将1,4_双(4-氨基苯氧基)苯58. 47克(0. 20摩尔)、顺丁烯二酸酐19. 61克(0.20摩尔)和3,3' ,4,4' -二苯甲酮四酸二酐32.27克(0.10摩尔)先后加入到DMSO (440毫升)中,在氮气保护下,室温下搅拌18小时后,加入脱水剂乙酸酐0. 50摩尔(47. 18毫升)、脱水催化剂三乙胺0. 10摩尔(13. 95毫升)和DMSO 295毫升,于60°C下反应5小时,将其倒入大量高速搅拌的无水乙醇中,得到沉淀物。 [0043] The 1,4_-bis (4-aminophenoxy) benzene, 58.47 g (0.20 mol), maleic anhydride, 19.61 g (0.20 mol) and 3,3 ', 4, 4 '- benzophenone tetracarboxylic dianhydride 32.27 g (0.10 mol) were added successively to a DMSO (440 mL), under nitrogen, was stirred at room temperature for 18 hours, a dehydrating agent was added 0.50 mole of acetic anhydride (47 . 18 ml), triethylamine dehydration catalyst 0.10 mole (13.95 ml) and DMSO 295 ml of a reaction at 60 ° C 5 hours, it was poured into a large amount of absolute ethanol with rapid stirring to give a precipitate . 所得沉淀物先后用无水乙醇和无水乙醚充分洗涤后,真空干燥得86. 52克马来酰亚胺封端型聚酰亚胺树脂。 The resulting precipitate was sufficiently washed successively with anhydrous ethanol and anhydrous diethyl ether, and dried in vacuo to give 86.52 g of maleic imide-terminated polyimide resin.

[0044] 称取上述马来酰亚胺封端型聚酰亚胺树脂60克和二烯丙基双酚A 18克,将二者混合后,溶于DMSO(355毫升)中,充分搅拌成均相溶液。 [0044] Weigh the above maleimide terminated polyimide resin and 60 grams diallyl bisphenol A 18 grams, the mixture of the two, was dissolved in DMSO (355 mL), stirred well into homogeneous solution. 将此溶液涂覆到35微米厚的铜箔上,控制液膜在溶剂挥发后厚度为10微米〜30微米,于高温烘箱中,在氮气保护下进行梯度升温,升温过程为:80°CX 1小时,1200C X 1小时,1800C X 1小时,260°CX 1小时。 This solution was applied on a copper foil 35 microns thick, after evaporation of the solvent control film having a thickness of 10 m ~ 30 m, a gradient heated under nitrogen in a high temperature oven, the heating process is: 80 ° CX ​​1 hours, 1200C X 1 hour, 1800C X 1 hour, 260 ° CX ​​1 hour. 缓慢冷却至室温即得无胶型二层法挠性覆铜板。 It was slowly cooled to room temperature to obtain the non-gel-type two-layer method FCCL.

[0045] 实施例5 [0045] Example 5

[0046] 将4,4' - 二氨基二苯醚12. 01克(0.06摩尔)、1,3-双(4-氨基苯氧基甲烷)_1, 1,3,3-四甲基二硅氧烷22. 60克(0.06摩尔)、顺丁烯二酸酐3. 92克(0. 04摩尔)和2, 2'-双W-(3,4-二羧苯氧基)苯基]丙烷四酸二酐52. 05克(0.10摩尔)先后加入到NMP(362毫升)中,在氮气保护下,室温下搅拌8小时后,加入脱水剂乙酸酐0. 34摩尔(32. 08毫升)、脱水催化剂三乙胺0. 10摩尔(13. 95毫升)和NMP 242毫升,于60°C下反应4小时,将其倒入大量高速搅拌的无水乙醇中,得到沉淀物。 [0046] 4,4 '- diaminodiphenyl ether 12.01 g (0.06 mol), 1,3-bis (4-aminophenoxy methane) _1, 1,3,3-tetramethyl disilazane siloxane 22.60 g (0.06 mol), maleic anhydride 3.92 g (0.04 mol) and 2, 2'-bis W- (3,4- dicarboxyphenyl) phenyl] propane after dianhydride 52.05 g (0.10 mol) were added successively to NMP (362 mL), stirred at room temperature for 8 hours under nitrogen, a dehydrating agent is added 0.34 mole of acetic anhydride (32.08 ml), the dehydration catalyst 0.10 molar triethylamine (13.95 ml) and NMP 242 ml 4 hours at 60 ° C, it was poured into a large amount of absolute ethanol with rapid stirring to give a precipitate. 所得沉淀物先后用无水乙醇和无水乙醚充分洗涤后,真空干燥得77. 93克马来酰亚胺封端型聚酰亚胺树脂。 The resulting precipitate was sufficiently washed successively with anhydrous ethanol and anhydrous diethyl ether, and dried in vacuo to give 77.93 g of maleic imide-terminated polyimide resin.

[0047] 称取上述马来酰亚胺封端型聚酰亚胺树脂50克和二烯丙基双酚A 4克,将二者混合后,溶于DMAc Q70毫升)中,充分搅拌成均相溶液。 [0047] Weigh the above maleimide terminated polyimide resin and 50 grams diallyl bisphenol A 4 grams, the mixture of the two, was dissolved in DMAc Q70 ml) were stirred well to phase solution. 将此溶液涂覆到35微米厚的铜箔上, 控制液膜在溶剂挥发后厚度为10微米〜30微米,于高温烘箱中,在氮气保护下进行梯度升温,升温过程为:80°CX 1小时,1200C X 1小时,1800C X 1小时,260°CX 1小时。 This solution was applied on a copper foil 35 microns thick, after evaporation of the solvent control film having a thickness of 10 m ~ 30 m, a gradient heated under nitrogen in a high temperature oven, the heating process is: 80 ° CX ​​1 hours, 1200C X 1 hour, 1800C X 1 hour, 260 ° CX ​​1 hour. 缓慢冷却至室温即得无胶型二层法挠性覆铜板。 It was slowly cooled to room temperature to obtain the non-gel-type two-layer method FCCL.

[0048] 实施例6 [0048] Example 6

[0049] 将4,4' - 二氨基二苯砜M.83克(0. 10摩尔)、1,3_双(4-氨基苯氧基甲烷)_1, 1,3,3-四甲基二硅氧烷47. 08克(0. 125摩尔)、顺丁烯二酸酐4. 90克(0. 05摩尔)和3, 3' ,4,4'-联苯四酸二酐58. 84克(0.20摩尔)先后加入到DMF(542毫升)中,在氮气保护下,室温下搅拌4小时后,加入脱水剂乙酸酐0. 85摩尔(80. 21毫升)、脱水催化剂三乙胺0. 77摩尔(107. 40毫升)和DMF362毫升,于60°C下反应4小时,将其倒入大量高速搅拌的无水乙醇中,得到沉淀物。 [0049] 4,4 '- diaminodiphenyl sulfone M.83 g (0.10 mol), 1,3_-bis (4-aminophenoxy methane) _1, 1,3,3-tetramethyl disiloxane 47.08 g (0.125 mol), maleic anhydride 4.90 g (0.05 mol) and 3, 3 ', 4,4'-biphenyl tetracarboxylic dianhydride 58.84 after g (0.20 mol) were added successively to DMF (542 mL), stirred at room temperature for 4 hours under nitrogen, a dehydrating agent is added 0.85 mole of acetic anhydride (80.21 ml), triethylamine 0 dehydration catalyst. 77 molar (107.40 ml) and DMF362 ml, for 4 hours at 60 ° C, it was poured into a large amount of absolute ethanol with rapid stirring to give a precipitate. 所得沉淀物先后用无水乙醇和无水乙醚充分洗涤后,真空干燥得121. 17克马来酰亚胺封端型聚酰亚胺树脂。 The resulting precipitate was sufficiently washed successively with anhydrous ethanol and anhydrous diethyl ether, and dried in vacuo to give 121.17 g of maleic imide-terminated polyimide resin.

[0050] 称取上述马来酰亚胺封端型聚酰亚胺树脂100克和二烯丙基双酚A 5. 80克,将二者混合后,溶于DMF(505毫升)中,充分搅拌成均相溶液。 [0050] Weigh the above maleimide terminated polyimide resin and 100 grams diallyl bisphenol A 5. 80 grams, the mixture of the two, was dissolved in DMF (505 ml), sufficiently stirred into a homogeneous solution. 将此溶液涂覆到35微米厚的铜箔上,控制液膜在溶剂挥发后厚度为10微米〜30微米,于高温烘箱中,在氮气保护下进行梯度升温,升温过程为:80°CX 1小时,1200C X 1小时,1800C X 1小时,260°CX 1小时。 This solution was applied on a copper foil 35 microns thick, after evaporation of the solvent control film having a thickness of 10 m ~ 30 m, a gradient heated under nitrogen in a high temperature oven, the heating process is: 80 ° CX ​​1 hours, 1200C X 1 hour, 1800C X 1 hour, 260 ° CX ​​1 hour. 缓慢冷却至室温即得无胶型二层法挠性覆铜板。 It was slowly cooled to room temperature to obtain the non-gel-type two-layer method FCCL.

[0051] 实施例7 [0051] Example 7

[0052] 将4,4' - 二氨基二苯醚沘· 03克(0.14摩尔)、1,6-己二胺9. 30克(0.08摩尔)、顺丁烯二酸酐3. 92克(0.04摩尔)和3,3' ,4,4'-联苯四酸二酐四.42克(0. 10 摩尔)、3,3' ,4,4' -二苯醚四酸二酐31. 06克(0. 10摩尔)先后加入到NMH407毫升) 中,在氮气保护下,室温下搅拌11小时后,加入脱水剂乙酸酐0. 79摩尔(74. M毫升)、脱水催化剂三乙胺0.63摩尔(87. 86毫升)和NMP 271毫升,于50°C下反应8小时,将其倒入大量高速搅拌的无水乙醇中,得到沉淀物。 [0052] 4,4 '- diaminodiphenyl ether Bi 2.03 g (0.14 mol), 1,6-diamine 9.30 g (0.08 mol), maleic anhydride 3.92 g (0.04 mol) and 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride IV.42 g (0.10 mol), 3,3', 4,4 '- diphenyl ether dianhydride 31.06 after g (0.10 moles) were added successively to the NMH407 mL), stirred at room temperature for 11 hours under nitrogen, a dehydrating agent is added 0.79 mole of acetic anhydride (74. M mL), 0.63 mole of triethylamine dehydration catalyst (87.86 ml) and NMP 271 ml reaction at 50 ° C 8 hours, it was poured into a large amount of absolute ethanol with rapid stirring to give a precipitate. 所得沉淀物先后用无水乙醇和无水乙醚充分洗涤后,真空干燥得85. 21克马来酰亚胺封端型聚酰亚胺树脂。 The resulting precipitate was sufficiently washed successively with anhydrous ethanol and anhydrous diethyl ether, and dried in vacuo to give 85.21 g of maleic imide-terminated polyimide resin.

[0053] 称取上述马来酰亚胺封端型聚酰亚胺树脂50克和二烯丙基双酚A2. 8克,将二者混合后,溶于NMPO70毫升)中,充分搅拌成均相溶液。 [0053] Weigh the above-described maleimide-terminated polyimide resins, and 50 g diallyl bisphenol A2. 8 grams, the mixture of the two, was dissolved NMPO70 ml) were stirred well to phase solution. 将此溶液涂覆到35微米厚的铜箔上,控制液膜在溶剂挥发后厚度为10微米〜30微米,于高温烘箱中,在氮气保护下进行梯度升温,升温过程为:80°CX 1小时,1200C X 1小时,1800C X 1小时,260°CX 1小时。 This solution was applied on a copper foil 35 microns thick, after evaporation of the solvent control film having a thickness of 10 m ~ 30 m, a gradient heated under nitrogen in a high temperature oven, the heating process is: 80 ° CX ​​1 hours, 1200C X 1 hour, 1800C X 1 hour, 260 ° CX ​​1 hour. 缓慢冷却至室温即得无胶型二层法挠性覆铜板。 It was slowly cooled to room temperature to obtain the non-gel-type two-layer method FCCL.

[0054] 实施例8 [0054] Example 8

[0055] 将2,2-双[(4-氨基苯氧基)苯基]丙烷82. 10克(0. 20摩尔)、1,3_双G-氨基苯氧基甲烷)-1,1,3,3_四甲基二硅氧烷94. 15克(0. 25摩尔)、顺丁烯二酸酐9. 81克(0. 10摩尔)和二苯醚四酸二酐62. 13克(0.20摩尔)、3,3' ,4,4' -二苯甲酮四酸二酐64. 53克(0. 20摩尔)先后加入到DMSO (1250毫升)中,在氮气保护下,室温下搅拌16小时后,加入脱水剂乙酸酐1. 53摩尔(144. 37毫升)、脱水催化剂三乙胺1. 07摩尔(149. 22毫升)和DMS0835毫升,于70°C下反应7小时,将其倒入大量高速搅拌的无水乙醇中,得到沉淀物。 [0055] 2,2-bis [(4-aminophenoxy) phenyl] propane 82.10 g (0.20 moles), bis 1,3_ methane G- aminophenoxy) -1,1 , 3,3_ tetramethyldisiloxane 94.15 g (0.25 mol), maleic anhydride 9.81 g (0.10 mol) and diphenyl ether dianhydride 62.13 g (0.20 mol), 3,3 ', 4,4' - benzophenone tetracarboxylic dianhydride 64.53 g (0.20 moles) were added successively to a DMSO (1250 mL), under nitrogen, at room temperature after stirring for 16 hours, a dehydrating agent was added 1.53 mole of acetic anhydride (144.37 ml), triethylamine 1.07 dehydration catalyst molar (149.22 ml) and DMS0835 ml and reacted at 70 ° C 7 hours, it was poured into a large amount of absolute ethanol with rapid stirring to give a precipitate. 所得沉淀物先后用无水乙醇和无水乙醚充分洗涤后,真空干燥得278. 2克马来酰亚胺封端型聚酰亚胺树脂。 The resulting precipitate was sufficiently washed successively with anhydrous ethanol and anhydrous diethyl ether, and dried in vacuo to give 278.2 g of maleic imide-terminated polyimide resin.

[0056] 称取上述马来酰亚胺封端型聚酰亚胺树脂250克和二烯丙基双酚A 13. 0克,将二者混合后,溶于DMF(1120毫升)中,充分搅拌成均相溶液。 [0056] Weigh the above maleimide terminated polyimide resin and 250 grams diallyl bisphenol A 13. 0 grams, the mixture of the two, was dissolved in DMF (1120 ml), sufficient stirred into a homogeneous solution. 将此溶液涂覆到35微米厚的铜箔上,控制液膜在溶剂挥发后厚度为10微米〜30微米,于高温烘箱中,在氮气保护下进行梯度升温,升温过程为:80°CX 1小时,1200C X 1小时,1800C X 1小时,260°CX 1小时。 This solution was applied on a copper foil 35 microns thick, after evaporation of the solvent control film having a thickness of 10 m ~ 30 m, a gradient heated under nitrogen in a high temperature oven, the heating process is: 80 ° CX ​​1 hours, 1200C X 1 hour, 1800C X 1 hour, 260 ° CX ​​1 hour. 缓慢冷却至室温即得无胶型二层法挠性覆铜板。 It was slowly cooled to room temperature to obtain the non-gel-type two-layer method FCCL.

[0057] 实施例9 [0057] Example 9

[0058] 将1,3-双(3-氨基丙烷基)四甲基二硅氧烷49. 70克(0. 20摩尔)、1,4_双氨基苯氧基)苯四.23克(0. 10摩尔)、2,2_双[(4-氨基苯氧基)苯基]丙烷20. 52克(0. 05 摩尔)、顺丁烯二酸酐9.81克(0. 10摩尔)和3,3' ,4,4'-联苯四酸二酐四.42克(0. 10摩尔)、3,3' ,4,4' -二苯甲酮四酸二酐32.¾克(0. 10摩尔)、3,3' ,4,4' -二苯醚四酸二酐31. 06克(0. 10摩尔)先后加入到DMAc (808毫升)中,在氮气保护下,室温下搅拌13 小时后,加入脱水剂乙酸酐1. 05摩尔1 (99. 08毫升)、脱水催化剂三乙胺1. 05摩尔(146. 43 毫升)和DMAc 538毫升,于60°C下反应7小时,将其倒入大量高速搅拌的无水乙醇中,得到沉淀物。 [0058] 1,3-bis (3-amino-propane-yl) tetramethyl disiloxane 49.70 g (0.20 mol), 1,4_ bis aminophenoxy) benzene IV.23 g ( 0.10 mol), 2,2_-bis [(4-aminophenoxy) phenyl] propane 20.52 g (0.05 mol), maleic anhydride 9.81 g (0.10 mol) and 3 , 3 ', 4,4'-biphenyl tetracarboxylic dianhydride IV.42 g (0.10 mol), 3,3', 4,4 '- benzophenone tetracarboxylic dianhydride 32.¾ g (0 . 10 mol), 3,3 ', 4,4' - diphenyl ether dianhydride 31.06 g (0.10 moles) were added successively to a DMAc (808 mL), under nitrogen, stirred at room temperature after 13 hours, a dehydrating agent was added 1.05 moles of an acetic anhydride (99.08 ml), triethylamine 1.05 dehydration catalyst molar (146.43 ml) and DMAc 538 ml of a reaction at 60 ° C 7 hours. poured into a large number of high-speed stirring in anhydrous ethanol to obtain a precipitate. 所得沉淀物先后用无水乙醇和无水乙醚充分洗涤后,真空干燥得147. 52克马来酰亚胺封端型聚酰亚胺树脂。 The resulting precipitate was sufficiently washed successively with anhydrous ethanol and anhydrous diethyl ether, and dried in vacuo to give 147.52 g of maleic imide-terminated polyimide resin.

[0059] 称取上述马来酰亚胺封端型聚酰亚胺树脂120克和二烯丙基双酚AlO克,将二者混合后,溶于DMAc (520毫升)中,充分搅拌成均相溶液。 [0059] Weigh the above maleimide terminated polyimide resin and 120 grams diallyl bisphenol AlO grams, after mixing them, was dissolved in DMAc (520 ml) were stirred well to phase solution. 将此溶液涂覆到35微米厚的铜箔上,控制液膜在溶剂挥发后厚度为10微米〜30微米,于高温烘箱中,在氮气保护下进行梯度升温,升温过程为:80°CX 1小时,1200C X 1小时,1800C X 1小时,260°CX 1小时。 This solution was applied on a copper foil 35 microns thick, after evaporation of the solvent control film having a thickness of 10 m ~ 30 m, a gradient heated under nitrogen in a high temperature oven, the heating process is: 80 ° CX ​​1 hours, 1200C X 1 hour, 1800C X 1 hour, 260 ° CX ​​1 hour. 缓慢冷却至室温即得无胶型二层法挠性覆铜板。 It was slowly cooled to room temperature to obtain the non-gel-type two-layer method FCCL.

[0060] 实施例10 [0060] Example 10

[0061] 将1,6_己二胺11.62克(0. 10摩尔)、1,3_双(4_氨基苯氧基甲烷)_1,1,3, 3-四甲基二硅氧烷75. 32克(0. 20摩尔)、4,4' - 二氨基二苯醚12. 01克(0. 06摩尔)、 双W- (4-苯氧基)苯基]砜32. 03克(0. 08摩尔)、顺丁烯二酸酐7. 85克(0. 08摩尔)和2,2'-双^_(3,4-二羧苯氧基)苯基]丙烷四酸二酐52.05克(0.10摩尔)、3,3',4, 4' -二苯醚四酸二酐62. 13克(0.20摩尔)、3,3',4,4' -二苯甲酮四酸二酐32.洸克(0. 10摩尔)先后加入到NMP (1140毫升)中,在氮气保护下,室温下搅拌15小时后,加入脱水剂乙酸酐1. 50摩尔(141. 54毫升)、脱水催化剂三乙胺0. 90摩尔(125. 51毫升)和NMP 761毫升,于60°C下反应8小时,将其倒入大量高速搅拌的无水乙醇中,得到沉淀物。 [0061] The 1,6_ hexamethylenediamine 11.62 g (0.10 mol), 1,3_-bis (methane 4_ aminophenoxy) _1,1,3, 3- tetramethyldisiloxane 75 32 g (0.20 mol), 4,4 '- diaminodiphenyl ether 12.01 g (0.06 mol), bis W- (4- aminophenoxy) phenyl] sulfone, 32.03 g ( 0.08 mol), maleic anhydride 7.85 g (0.08 mol) and 2,2'-bis ^ _ (3,4-dicarboxyphenyl) phenyl] propane dianhydride 52.05 g (0.10 mol), 3,3 ', 4, 4' - diphenyl ether dianhydride 62.13 g (0.20 mol), 3,3 ', 4,4' - benzophenone tetracarboxylic dianhydride 32. after Guang g (0.10 moles) were added successively to NMP (1140 mL), stirred at room temperature for 15 hours under nitrogen, a dehydrating agent is added 1.50 mole of acetic anhydride (141.54 ml), the dehydration catalyst 0.90 mol of triethylamine (125.51 ml) and NMP 761 ml of a reaction at 60 ° C 8 hours, it was poured into a large amount of absolute ethanol with rapid stirring to give a precipitate. 所得沉淀物先后用无水乙醇和无水乙醚充分洗涤后,真空干燥得255. 66克马来酰亚胺封端型聚酰亚胺树脂。 The resulting precipitate was sufficiently washed successively with anhydrous ethanol and anhydrous diethyl ether, and dried in vacuo to give 255.66 g of maleic imide-terminated polyimide resin.

[0062] 称取上述马来酰亚胺封端型聚酰亚胺树脂200克和二烯丙基双酚A 9克,将二者混合后,溶于DMAc (1040毫升)中,充分搅拌成均相溶液。 [0062] Weigh the above maleimide terminated polyimide resin and 200 grams diallyl bisphenol A 9 grams, the mixture of the two, was dissolved in DMAc (1040 ml), stirred well into homogeneous solution. 将此溶液涂覆到35微米厚的铜箔上,控制液膜在溶剂挥发后厚度为10微米〜30微米,于高温烘箱中,在氮气保护下进行梯度升温,升温过程为:80°CX 1小时,1200C X 1小时,1800C X 1小时,260°CX 1小时。 This solution was applied on a copper foil 35 microns thick, after evaporation of the solvent control film having a thickness of 10 m ~ 30 m, a gradient heated under nitrogen in a high temperature oven, the heating process is: 80 ° CX ​​1 hours, 1200C X 1 hour, 1800C X 1 hour, 260 ° CX ​​1 hour. slow

慢冷却至室温即得无胶型二层法挠性覆铜板。 Slow cooling to room temperature to obtain the non-gel-type two-layer method FCCL.

[0063] 上述实例制备的无胶型二层法挠性覆铜板的测试性能如表1所示。 [0063] Test Performance FCCL non-gel-type two-layer method of preparing the above examples are shown in Table 1.

[0064] [0064]

Figure CN101608019BD00101

Claims (3)

  1. 1. 一种马来酰亚胺封端型聚酰亚胺树脂的制备方法,其特征在于,制备过程为:将二元胺、顺丁烯二酸酐和四酸二酐按物质的量比为(n+1) : 2 : η先后加入到极性溶剂中,使其固含量为25士克/毫升,在氮气保护下,室温下搅拌8〜M小时后,生成中间体聚酰胺酸,随即加入脱水剂乙酸酐和脱水催化剂三乙胺及极性溶剂,使其固含量降为15%克/ 毫升,再于30°C〜80°C下化学亚胺化反应4〜16小时,将反应液倒入高速搅拌的无水乙醇中,得到沉淀物,所得沉淀物先后用无水乙醇和无水乙醚充分洗涤后,真空干燥即得马来酰亚胺封端型聚酰亚胺树脂;反应过程如式(1)所示, 1. A method for preparing a maleimide-terminated polyimide resins, characterized in that the preparation process to: diamine, maleic anhydride and dianhydride by the molar ratio of (n + 1): 2: η successively added to a polar solvent to a solid content of 25 Shike / ml, 8~M hours stirring under nitrogen at room temperature, to form the intermediate polyamic acid, then was added acetic anhydride dehydrating agent and a dehydration catalyst of triethylamine and a polar solvent, so that it is reduced to 15% solids content g / mL, and then the chemical imidization reaction at 30 ° C~80 ° C 4~16 hours, the reaction solution was poured into absolute ethanol with rapid stirring to give a precipitate, the resulting precipitate was sufficiently washed successively with ethanol and anhydrous ether, and dried in vacuo to yield the maleimide terminated polyimide resin; a reaction The process shown in the formula (1),
    Figure CN101608019BC00021
    式中,η为树脂聚合度,1 ≤η ≤20 ;四酸二酐为O(CO)2R1(CO)2 ;二元胺为H2N-R2-NH2 ; 所用四酸二酐为3,3' ,4,4'-联苯四酸二酐、3,3' ,4,4' - 二苯甲酮四酸二酐、3, 3' ,4,4' -二苯醚四酸二酐、2,2'-双^_(3,4_ 二羧苯氧基)苯基]丙烷四酸二酐和2, 2'-双(3,4_ 二羧苯基)六氟丙烷四酸二酐,五者的量不能同时为零,其中任意一种占四酸二酐共混物的物质的量分数为0%〜100% ;所用二元胺为1,6_己二胺、1,3_双(3-氨基丙烷基)四甲基二硅氧烷、1,3_双G-氨基苯氧基甲烷)-1,1,3,3_四甲基二硅氧烷、3,4' -二氨基二苯醚、4,4' -二氨基二苯醚、 4,4' -二氨基二苯砜、1,4_双(4-氨基苯氧基)苯、2,2_双[(4-氨基苯氧基)苯基]丙烷和双苯氧基)苯基]砜,九者的量不能同时为零,其中任意一种占二元胺共混物的物质的量分数为0%〜100% ;反应所用极性溶剂为N-甲基-2-吡 Wherein, η is the degree of polymerization of the resin, 1 ≤η ≤20; tetracarboxylic dianhydride is O (CO) 2R1 (CO) 2; diamine of H2N-R2-NH2; as used tetracarboxylic dianhydride 3,3 ' , 4,4'-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4' - benzophenone tetracarboxylic dianhydride, 3, 3 ', 4,4' - diphenyl ether dianhydride, ^ _ 2,2'-bis (3,4_ dicarboxylic phenoxy) phenyl] propane dianhydride and 2,2'-bis (3,4_-dicarboxyphenyl) hexafluoropropane dianhydride, an amount of five persons can not be zero, any of which accounts for the amount of substance dianhydride blend fraction is 0% ~ 100%; the diamine used is hexamethylenediamine 1,6_, 1,3_ bis (3-amino-propane-yl) tetramethyl disiloxane, bis 1,3_ methane G- aminophenoxy) -1,1,3,3_ tetramethyldisiloxane, 3,4 ' - diaminodiphenyl ether, 4,4 '- diaminodiphenyl ether, 4,4' - diaminodiphenyl sulfone, 1,4_-bis (4-aminophenoxy) benzene, bis 2,2_ [ (4-aminophenoxy) phenyl] propane and bis) phenyl] sulfone, an amount of nine persons can not be zero at the same time, any of which accounts for the amount of substance fraction diamine blend is 0 % ~ 100%; polar solvent used in the reaction of N- methyl-2- 咯烷酮、N,N' -二甲基甲酰胺、N,N' -二甲基乙酰胺、二甲基亚砜中的一种或数种混合物;所述的脱水剂乙酸酐用量为二元胺物质的量的2〜4倍;所述的脱水催化剂三乙胺用量为乙酸酐物质的量的0. 2〜1倍。 Pyrrolidone, N, N '- dimethylformamide, N, N' - dimethylacetamide, dimethyl sulfoxide one kind or a mixture of several; an amount of the dehydrating agent is acetic anhydride is two 2 ~ 4 times the amount of monoamines substance; the amount of dehydration catalyst to 0. triethylamine 2~1-fold amount of acetic anhydride species.
  2. 2.根据权利要求1所述的马来酰亚胺封端型聚酰亚胺树脂的制备方法,其特征在于: 所述的化学亚胺化反应温度为50°C〜70°C。 2. maleimide terminated type according to claim 1 preparing a polyimide resin, wherein: said chemical imidization reaction temperature was 50 ° C~70 ° C.
  3. 3.根据权利要求1所述的马来酰亚胺封端型聚酰亚胺树脂的制备方法,其特征在于: 所述的化学亚胺化反应时间为6〜8小时。 The maleimide terminated according to a type of preparation of the polyimide resin as claimed in claim, wherein: said chemical imidization reaction time was 6 ~ 8 hours.
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