TW200827386A - Composites comprising nano-inorganic particles with the organically functional group applied in the manufactures of polyomide film and two-layered flexible copper clad substrate - Google Patents

Abstract

Composites of polyimide film and two-layered flexible copper clad substrate, which comprise nano-inorganic particles modified with coupling agent, and therefore the nano-inorganic particles have the organically functional group to react with modified-bismaleimide. The composites of polyimide (PI) film with semi-interpenetration (semi-IPN) were obtained from, which nano-inorganic particles and modified-bismaleimide were served as reactive additive and formulated in the preparations of PI film and two-layered flexible copper clad substrate. The nano-inorganic particles with organically functional group are incorporated in the composites of PI film and two-layered flexible copper clad substrate, which disperse and distribute well over polyimide substrate to results in even products, therefore, coefficient of thermal expansion (CTE) of PI film is efficiently reduced. Thermal resistance and mechanical property of PI film are improved. The stress of two-layered flexible copper clad substrate resulted from high temperature preparation is also reduced efficiently. Productive rate, yield, and peeling strength of two-layered flexible copper clad substrate between PI/copper are also increased. Therefore, curl of composites may be totally prevented while the composites are applied in the manufacture of two-layered flexible copper clad substrate.

Description

200827386

« I IX, invention description: [Technical field of the invention] The present invention relates to the preparation of a composition and a composite film formed by a particle-free and polyanilin having an organic reactive functional group, The preparation of a ruthenium film comprising a brewed imine and a modified bismaleimide. ~ [Prior Art] Flexible printed circuit board (7) exible Printed as..., (4) Also known as soft (four) substrate, after exposure, development, and (4) processing, the circuit leads of the design can be used as electronic product current signal transmission _ ". The special-purpose printed circuit board is mainly characterized by three-dimensional wiring, and it is also called a flexible printed circuit board. The related products are roughly classified into single-panel, double-panel and multi-layer boards. Because FPC has (four), short, flexible, anti-static, low power consumption and the diversity of the space design, in today's electronic technology and the mouth of the general production, both emphasize the short binding, resistance to tortuosity The trend is that the market for flexible printed circuit boards is increasing and has huge market potential, such as notebook computers, folding mobile phones, LCD flat panel displays, digital cameras, video cameras, CD players, etc., which require the application of soft board materials. The most important raw material for flexible printed circuit boards is FleXlbleC〇PPerClad Laminate (FCCL). The substrate can be divided into three layers of soft flexible copper box substrates (3L-CGL) according to whether it contains an adhesive. There are no (four) two layers of soft (four) substrates (2Lm). The three-layer soft copper matte substrate (3L_ca) has a poor adhesion to some performance items due to the inclusion of an adhesive. It has many applications in the application (IV) such as dimensional stability and heat resistance (2L-FCCL). Not only in the 1 ° hot glue system, two layers of soft copper drop substrate

The preparation ability is both good and heat resistant. "The performance of the fine line...^ A, . is compared with the adhesive substrate, JL 5 := resolution, heat resistance, good dimensional stability , electricity, s ^ knowledge, also enhance the application range of FPC products. q Two-layer U· raw copper substrate is produced by using Poke yimide 'PI) on the surface of the steel raft substrate to form two layers of copper bismuth base. The thermal expansion coefficient of the two-bulk imine is greater than ~ I have a thermal expansion coefficient of about 17 8 _ / t, so it is necessary to introduce a more rigid sub-chain, that is, reduce the difference between the polyimine and the copper collar (10). Although this method reduces the CTE of the 酿τ / , ” 胺 胺 , , 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少Although the 'flatness is improved, but the resulting adhesion between the copper-binder and the copper box is worse, the defects in the preparation process of the line are easy to occur, and the FPC process cannot be met. The Republic of China Patent Announcement 5861 9 "Tiger's "high-drilled polyimine composition", U.S. Patent Publication Nos. 52,474 and 5,372,891 disclose Bamaimide modified with Barbituric Acid (Modified £is)蚪leimide' MBMI) Polyimine composition application. However, this patent does not teach the use of modified inorganic additives and modified bismaleimide and polyimine compositions. SUMMARY OF THE INVENTION In view of the above problems, the main object of the present invention is to provide a 19861, 2008, 2008, 386, *, a low-incremental coefficient of polyimine composition and a composite film made of February - Preparation of a poly-imine composition having a high _ heat and a composite film. Still another object of the present invention is a mustard & alpha system for providing a double layer soft copper foil substrate which can reduce thermal stress and a method for preparing the same. In addition, the object of the present invention is to provide a double-layer flexible copper box substrate capable of avoiding surface warp and a method for preparing the same. ^The purpose of the month is to provide an excellent Cu/PI interface. A double-layered flexible copper foil substrate and a method for preparing the same. > v 2 OBJECTS OF THE INVENTION The present invention provides a composition formed by a machine-reactive functional group of a tearing machine rice granule and a polyimine. Including the inorganic y = yam and yam y5 & imine and the coupling agent modified inorganic neat additive. Since the inorganic nano additive is modified by a coupling agent to have an organic official When the composition is used to make a composite film, the modified inorganic nano-addition, the 3 wood-imine polymer molecular chemical reaction is combined, and then: the enthalpy into the Asian-month female molecular chain forms a semi-interpenetrating network structure. The inorganic reactive agent having the organic reactive functional group of the present invention can be uniformly obtained as a composite material formed by the combination of the Russian water-free particles and the polyimine. It is distributed on the poly-imine soil and has been lowered to reduce the film of the composite material. The expansion coefficient, the heat resistance and mechanical properties of the composite film are improved, and the adhesion between the composite film and the V white substrate is increased, so that it is particularly suitable for the production of a double-layer soft copper matte substrate, which can reduce the high temperature during film preparation. The stress generated by hardening avoids the occurrence of buckling of the composite material. 19861 200827386 The present invention also provides a method for producing a polyimide film, comprising (a) modifying the inorganic nanopowder with a coupling agent, and organically a functional group is introduced into the inorganic nanopowder; (b) a modified inorganic nanopowder prepared in the step (a) is added to a solution of a polylysine composition containing a modified bismaleimide; and (c) Heating and drying the polyphthalic acid composition solution prepared in the step (b), and converting the polyamic acid to a polyimine substrate by high temperature cyclization. The invention further provides a method for manufacturing a double-layer soft copper foil substrate The package includes (a) using a coupling agent to modify the inorganic nano-powder, introducing an organic functional group into the inorganic nano-powder; (b) adding the modified inorganic nano-powder prepared in the step (a) to the modified Bismaleimide a polyamic acid composition solution; and (c) applying a solution of the polyamic acid composition prepared in the step (b) to a copper foil substrate, heating at a high temperature to carry out a cyclization reaction, thereby promoting conversion of the poly-proline to Polyimine, finally obtaining a finished product of a double-layered soft copper junction substrate. [Embodiment] The invention relates to an inorganic nanoparticle having an organic reactive functional group and a composition formed by an amine, including a polyimine, a modified double-maleimide, and a coupling agent-modified inorganic nano-additive; wherein the poly-imine is formed by polyamidating at high temperature cycloheximide. In a specific example, The phthalic anhydride is reacted with a diamine to form a poly-proline. Examples of the dianhydride include, but are not limited to, tetrahydrofuran tetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, bicyclo-[2,2,2]- Octene (7)-2,3,5,6-tetracarboxylic acid-2,3,5,6-dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3, 3', 4 , 4'-diphenyltetracarboxylic acid dianhydride, 1,4,5, 8-naphthalenetetracarboxylic acid dianhydride, pyromellitic anhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, double ( 3,4-dicarbonylphenyl) dianhydride, and bis(3,4-dicarboxyl 198 61 200827386 Phenyl)ether dianhydride. Typical diamines are of the formula H2N_R, _NH2, wherein R, which may be an aryl group, a fatty group, a cyclic aliphatic group, or a decane-containing aliphatic group. In one embodiment, the modified bismaleimide is a barbituric acid or a derivative thereof:

Λ I I

(wherein 1 and R2 are independently selected from _H, _CH3, _C2il5, _CeH5, -chc(ch3)2, -CH2CH(CH〇2, -CH2CH2CH(CH3)2, or -CH(CH〇-( CH2)2-CHs) and bismaleimide as shown by formula (Π):

(Π) A fat-based, cyclic aliphatic group, or a compound containing glycerin (wherein 'R may be an aliphatic group of an aromatic group) is reacted. Examples of bismaleimide include, but are not limited to, hydrazine, Ν'-ethylene-bismaleimide, N,N,-butene-bismaleimide, N,N'-hexamidine --Bismaleimide, N,N,-phenylene-double-malay 醯亚月女Ν'N -4, 4 -diphenyl oxime-shuangma quinone imine, n,n,- 4, 4,- Ben _Bismaleimide, hydrazine, ν'-4,4'-diphenylhydrazine-bis-maleic acid imine, hydrazine, Ν'-4,4'-dicyclohexylmethane- Bismaleimide, anthraquinone, anthraquinone, a 9 19861 200827386. benzodiazepine-bismaleimide, and hydrazine, Ν'-diphenylcyclohexane-bismaleimide. a solution containing a mixture of bismaleimide and polylysine modified with barbituric acid, which is cyclized by polypyridyl acid to a polyimine at a high temperature, and dehydrated and condensed in the cyclization process of ruthenium Under the dual effect of the modified double-maleimide free radical bridging, after uniform mixing and high-temperature cyclization processing, the final solidification forms a semi-interpenetrating cross-linked network structure (semi-ΙΡΝ), such as the structure of Figure 1. The schematic shows. The thermal expansion coefficient of the polysiimide composite film is effectively reduced, and the peeling strength between the polyimide film and the copper foil substrate is enhanced, thereby improving the peel strength between the conventional polyimide resin and the copper foil. Defects. Further, the composition of the present invention is further added with an inorganic nano-additive modified with a coupling agent, particularly an inorganic nano-powder. The organic functional group is introduced into the inorganic nano-powder by the modification of the coupling agent, and the partial free radical ring-opening reaction with the modified bismaleimide is carried out under the addition reaction of the barbituric acid catalyst. Finally, the high temperature bridging reaction and the polyamidene form a semi-interpenetrating network

The nano structure of the A t structure is compounded. The modified inorganic additive used in the present invention has an active organic functional group and can form a semi-interpenetrating network structure with a maleimide oligomer and a polyimine. As shown in the structure diagram of Fig. 2, the polyimine polymer substrate a, the modified maleic imine oligomer b and the coupling agent modified inorganic nano powder c醯 imine are subjected to high temperature cyclization. The quinone imine forms a semi-interpenetrating cross-linked network structure. Since the modified inorganic additive is not randomly or randomly dispersed in the polyimide substrate, it is effective to form a semi-interpenetrating network with the polyimide and the maleimide oligomer. 19861 200827386 Shaped structure, thus promoting the upgrade of the helmet machine, A, ..., the mechanical nai + powder can be evenly distributed in the poly-pick: soil 'no f 杳 giant phase separation and agglomeration phenomenon, can greatly enhance the poly-imine The mechanical properties and heat resistance properties of the composite film. Therefore, only the modified nano-powder of ^ = can be effectively added to the (iv) imine composition, (8) the free-volume relaxation behavior of the polyimine (relaxatlon behaVlor), and then the thermal expansion of the oligomeric quinone imine coefficient. Examples of the coupling agent include a sulphur coupling agent having a vinyl functional group, a money coupling agent having an amino functional group, and an oleic acid coupling agent, and the oleic acid coupling agent has a structure represented by the following formula Eight

CH3-(CH2)n-CH= CH-(CH2)n-c〇〇H

^ where η is an integer from 1 to 14). In the present invention, inorganic nano-powder can be used as an additive. Examples thereof include oxygen cutting, oxidation, tin oxide, lead oxide, selenium oxide, antimony oxide, aluminum oxide, zinc oxide, antimony oxide, oxygen (IV), gallium oxide, and oxidation. Indium, or oxidized M nano powder. In one embodiment, the powdered ceramsite powder is modified using a compound coupling agent having an ethylenic functional group, as schematically illustrated by the chemical mechanism of Figure 3. In order to obtain completely purified dioxonide particles having an organic reactive functional group, it is preferred to select a solvent similar to the coupling agent dissolution parameter for purification to separate the unreacted coupling agent, for example, using an A151 decane coupling agent. (Dissolution parameter is 7) 8 car/2/cra3/2), hexane solvent with a solubility parameter of 7 8 cai]/2/cm3/2 can be used to obtain 1〇0% purified ruthenium dioxide with vinyl functional group at the end. Rice flour. In the composition of the present invention, the inorganic nano-additive modified by the coupling agent may account for 0.5 to 15% by weight of the total solid content, preferably 〇5 to 1%, and further, 19861 11 200827386 * * preferably 0. 5 to 5%; Barbituric acid modified bismaleimide can account for 1 to 10% of the total solid content, and the rest is polyimine. The invention also provides a composite film formed by inorganic nano particles and polyimine having an organic reactive functional group, comprising polyimine, modified bismaleimide, and inorganic modified by a coupling agent. Nano-additive, in which the imine inorganic nano-additive is modified by a coupling agent to have an organic official, an energy group, and is combined with a molecular chemical reaction of a barbituric acid-modified maleic imine oligomer. Thereafter, a semi-interpenetrating network-like structure (semi-IPN) is formed with the polyimine molecular chain, so that the inorganic additive is uniformly distributed on the polyimide substrate. The inorganic nano-additive may be modified using a decane coupling agent having a vinyl functional group, a decane coupling agent having an amine b-mercapto group, or an oleic acid coupling agent. In one embodiment, the cerium oxide coupling is used to modify the cerium oxide nanopowder to carry the vinyl functional group into the cerium oxide nanopowder. Next, the modified oxidized oxidized ceramsite powder was added to a polyamic acid composition solution containing barbituric acid modified bismaleimide. The modified cerium oxide: [the content of the rice powder is 5 5 to 5% of the total weight of the solid content, preferably 〇 5: to 10%, more preferably 0.5 to 5%, The content of the bismaleimide which is modified by the acid is based on the total weight of the solid content to 1%. Heating the solution containing the modified cerium oxide nanometer powder to combine the modified cerium oxide nanometer powder with the barbituric acid modified maleic imine oligomer molecular chemical reaction, and then with high temperature The cyclized polyimine molecular chain forms a semi-interpenetrating crosslinked network structure, and is uniformly distributed on the polyimine substrate, which is the polyaniline composite film of the present invention. The composite film can be applied to produce a double-layer flexible copper foil substrate. First, 19861 12 200827386 . Using a coupling agent to modify the inorganic nano-powder, introducing an organic functional group into the nano-toner powder, for example, using a Shixi sinter coupling agent to modify the cerium oxide cerium powder, and introducing the ethylenic functional group The surface of the silica dioxide glutinous rice powder. Then, the modified oxidized oxidized ceramsite powder is added to a polyamic acid composition solution containing barbituric acid modified / bismaleimide, wherein the content of the modified and glutinous rice powder is occupied. The total weight of solid content is 55. 15i, 0.5 to 10% flatter. 'More preferably 〇5 to 5%. Barbituric acid is modified: ^(4) is the total weight of solid content... (10). Applying the solution of the modified and emulsified emulsified granules to the copper box substrate, and adding the dry residue to cyclize the poly-nitrile acid imide to a polyamicimide at a high temperature. The double-layered soft copper film of the polyamidite composite film is formed on the surface. The underarms 4 further illustrate the features and utilities of the present invention by way of specific examples, but are not intended to limit the scope of the invention. In the embodiment, the coupling is fused with the solvent and the solvent is stirred, and then the granules are mixed with the emulsified glutinous rice powder. The weight ratio of the cerium oxide nanoparticle to the mixture is 1:2. . The reaction was changed by reflux heating at 8 Torr for 4 hours, and the organic functional group was introduced into the cerium oxide powder surface, and the second solution = the solution after the application was taken out. After the immersion gas is cleaned by using the hexahydrate, it is placed in a box for baking for 12 to 16 hours to obtain a white powder, which is a coupling agent-modified cerium oxide powder. 19861 13 200827386 The FTIR functional map is characterized by unmodified silica dioxide Si-〇H (3400 cnT1: 0-H bonding stretching) and coupling agent CH3-CH2 ( 544,470 cm-1 : Deformation vibration) disappeared or not as a reference for the degree of modification and purification. Fig. 4 is a FTIR spectrum showing a coupling agent, an unmodified cerium oxide nanopowder, and a bismuth dioxide nanopowder having a vinyl functional group based on a coupling agent. Si-ΟΗ (3400 cnT1 ·· 0-Η bonding stretching) modified by coupling agent, and coupling agent CH3-CH2 (544,470 cm-1 : deformation vibration ( Deformation vibration)) completely disappeared, indicating that the reaction is completely 100% purified, while =CH2 (2975 cnT1: symmetric stretching vibration) is weakly weakened by Boqin, and after β-modified cerium oxide Rice flour has a vinyl functional group. Thermogravimetric analysis (Ihermo泾ravimetr ic packet analysis: TGA) under a nitrogen atmosphere at a heating rate of 10 ° C / min ° TGA of Figure 5 • The spectrum shows the residual weight during the calculation, after calculation, the vinyl has been modified Guan, the energy-based bismuth dioxide nano-powder, the organic phase content is about 11%, which is consistent with the results of Figure 4, which proves that the coupling agent has effectively modified the cerium oxide nano-powder to have a vinyl functional group. Dynamic laser scattering test using the Photal-Otsuka Electronics LPA-3100 Laser Particle Analyzer for unmodified cerium oxide nanopowder and modified cerium oxide nanopowder with vinyl functional group via coupling agent Laser fatter: DLS). Using N-fluorenylpyrrolidone (NMP) as a solvent, it was confirmed that 14 19861 200827386: the particle size of the cerium oxide nano-powder dissolved in a specific solvent, and the particle size range 丨~2〇^ ^ a ^ r . As shown in Table 1, the coupling agent "I. The particle size of the cerium oxide nano-powder powder of the sulphate 旎 旎 & & 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Maintain its original nanometer size and no particle aggregation.

Qualitative double Malay 醮 convex face table 8.66 g N, N'-4, 4'-diphenyl decane a pair of maleimide dissolved in 20 g of r-butyrolactone, and mixed solution Add i grams of barbituric acid. The mixture was heated and stirred at a temperature of 11 ° C for a few hours to prepare a bismale acid-modified bismaleimide. Synthesis Example 3: Polylysine 17.45 g (0.087 M) of 4,4'-diaminodiphenyl ether (DDE) was placed in a 500 ml four-necked reactor, and 130 ml of N-methylrrolidine was added. Ketone (NMP) and 30 ml of diphenylbenzene were dissolved. Next, add 55 g (0·085 M) of pyromellitic anhydride (PMDA) under nitrogen at room temperature for 3 hours, and then add 436 g (〇·〇2M) of pyromellitic anhydride to continue the reaction. 2小时的聚聚胺酸溶液。 2 hours, a solid content of 18.5% of a polyamic acid solution. 15 19861 200827386 , Example 1 The modified cerium oxide nano powder of Synthesis Example 1 and the bismale acid modified bismaleimide prepared in Synthesis Example 2 were added to the polyaminic acid solution of Synthesis Example 3. Among them, the modified cerium oxide nano-powder system accounts for 1% of the total solid content, and the barbituric acid-modified double-maleimide-based yttrium accounts for 5% of the total solid content, while the poly-proline contains The total weight of the content is 94%. The polyamic acid composition solution was centrifuged to remove the foam, and the polyamic acid composition solution was applied onto a copper foil substrate using a coater, and placed in a high-temperature nitrogen (I) oven to be baked in a stepwise heating manner. . First, bake at 8 (rc for 3 minutes. Then, heat up to 120 ° C, 15 (TC, and 200 ° C for 30 minutes, then 350t for 60 minutes. Finally, get complete cyclization and Dry two layers of soft copper foil substrate (2L-FCCL). Example 2 Two layers of soft copper foil substrate were prepared in the same manner as in Example 1. The modified bismuth oxide nano-powder was changed to the total solid content. Compared with the acid-modified Bismaleimide, it accounts for 5% of her solids, U3, and 5% of heart, and polyamine contains 92% of the total solid content. 3 Two layers of soft copper foil substrate. The total weight is 5%, the barbituric acid is 5% by weight, and the poly-aracine is repeated in the same manner as in Example 1 to prepare the modified cerium oxide nanopowder to change the solid content. The quality of the double-maleimide-based solid content accounts for 90% of the total solid content. 19861 16 200827386 Comparative Example 1 The two-layer soft copper foil was prepared by repeating the method of Example 1 using the polyamic acid solution of Synthesis Example 3. Substrate. The polyamic acid solution is not added with barbituric acid modified bismuth, and the modified oxidized hair is obtained. Example 2 A two-layer flexible copper foil substrate was prepared in the same manner as in Example 1. The polyamic acid solution was not added with barbituric acid-modified bismaleimide, and unmodified cerium oxide was used. For the nano powder, the cerium oxide nano powder accounts for 15% of the total solid content, and the polyamic acid accounts for 85% of the total solid content. Comparative Example 3 The same method as in Example 1 was repeated to prepare a two-layer soft copper foil. Substrate. The polyamic acid solution does not add modified cerium oxide nanopowder, and the barbary soil S is not modified, and the bismuth ylide is the total solid content, and the citric acid accounts for the solid content. The total weight is 95%. m The two layers of soft copper foil substrate prepared in each of the above examples and comparative examples are placed in a 25% ammonium persulfate solution, and the temperature is controlled and set to 6 + 〇C. The copper wire is engraved to obtain a film of polyiminoimide composite material. The carrier is taken out of the polyamidide composite film and washed thoroughly, and placed in an oven at a temperature of 120 (32/R) for 3 minutes. Amine composite film and two layers of soft copper drop substrate are used as test samples, and the characteristics of the following samples are used. In Table 2. Received 19861 17 200827386 This test method of Maoyue, zhongli analysis, peel strength, and thermal expansion coefficient was tested according to the following method: Ihermogjavimetric 卽aiysis: TGA: nitrogen gas was introduced 1 〇 t / min heating rate test sample thermal cracking initiation temperature (by 〇 n - Set temPerature of 5% wt · Loss for comparison and analysis criteria). (2) peel strength: using lpc ΤΜ -65 〇 (2 · 4·9) Test methods a and C, the copper foil substrates of the respective examples and comparative examples were tested, and the test after etching and the surface film were placed at a 90-degree angle peeling jig, and the corresponding tensile force was measured by a universal testing machine. The tensile force per unit width (kgf/cm) at which the copper foil was pulled away from the polyimide film was tested. (3) Coefficient of thermal expansion: measured by a thermomechanical analyzer (l_hermo sub-echanical analysis: TMA), and tested at 1 (rC/min heating rate) in a nitrogen atmosphere and a temperature range of 30 to 300 °C. For example, the length difference of the polyimide film at the unit temperature before and after heating and the ratio of the original length (ppm/°C). Table 2, V-flying heat analysis °C Peel strength (kgf/cm) Thermal expansion Coefficient (ppm/°C) Example 1 585·73 1. 18 24. 65 tjUH 2 587.65 1. 32 22. 15 Example 3 595·96 1. 48 20. 17 Comparative Example 1 555.42 0. 40 35.60 Comparison Example 2 580.78 1. 08 24. 76 Comparative Example 3 585·26 1. 13 26. 48 18 19861 200827386 According to the results of Table 2, it was found that the addition of 1, 3, 5% was modified with a vinyl functional group. The polyimide film formed by the cerium oxide nano-powder combined with the modified bismaleimide oligomer has a remarkable performance improving effect, especially a preferred thermal gravity analysis (TGA), thermal stability, And better peel strength' also exhibits a lower coefficient of thermal expansion. Example 3 • Comparison with Comparative Example 1 without any added additives, The coefficient of expansion of the polyimide film of Example 3 was found to decrease from 35.60 ppm/t to 2 〇. ^ The peel strength of PPm/l was increased from 〇4〇kgf/cm to i48 kg". In Example 2, the polyimide film of the polyimine composite material obtained by adding the conventional second-peroxide nano-nano powder to the weight ratio of the whole composition of 15% has the same thermal expansion and the same as in the comparative example 2. The peel strength of the invention is the same as that of the iJ I, and the mechanical properties of the polyimide film can be effectively used. In the comparative example 3, only the imine oligomer is added. No added modified f-dioxine to find powder, and it can be found that adding a small amount of modified dioxynectin powder. L effectively greatly enhances the mechanical properties of the polyimide film: # by scanning electron microscope (SE Μ Observing the composition of the present invention, the composition of the bismuth imine is in the eve of the day, ^ one, one, the household '% illusion of the organization can be filled with eighteen Γ material Bay film, semi-interpenetrating network Structural knife & 疋 疋 。 。 。 。 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第1% of the 醯 3 ^ ^ ^ sub-microscope (four); (9) off for the example ^ Μ silk made of composite photo. In the 6a picture, alum 1 4 4 only said ..., not modified The sulphur dioxide dissipates the eve of the eve = the particles and pits of the left-level standing, which shows that the uncle of the red king is scattered and has a tendency to condense into larger particles than the 19861 19 200827386. Figure 6b, t, did not find obvious pits and grains. The modified cerium oxide nanopowder, the modified bismaleimide eutrophic polymer and polyamidimide were semi-interpenetrating. The network is interconnected, causing the modified double-maleimide oligomer and the modified cerium oxide to be distributed on the polyimide intermediate substrate, so that there is no obvious pit-aggregated particles. The phenomenon occurs. A singularity of the above-mentioned embodiments is merely illustrative of the principles of the present invention and its efficiencies. It is not intended to limit the invention. Any person skilled in the art will not be obscured by the spirit and scope of the present invention. Repair and change =. Therefore, the scope of protection of the present invention should be as set forth in the scope of the patent as described later. Month [Simple description of the diagram] Figure 1 shows a schematic diagram of the interpenetrating cross-linked network structure of polyimine and modified double Malay; Chengfeng 2 shows polyimine, modified horse Schematic diagram of the semi-interpenetrating cross-linked network structure of inorganic additives modified with hydrazine and coupling agents. Fig. 3 shows the chemical machine intention of coupling/f inorganic additives; ^ Figure 4 shows the coupling agent FTIR spectrum of unmodified dioxonine powder and oxydicarbide powder modified with a vinyl functional group via a coupling agent; Figure 5 shows a coupling agent, unmodified sulphur dioxide The nano-powder and the coupling agent are modified to have a TGA spectrum of the sulphur dioxide sulphate 19861 20 200827386t and its residual weight; the 6a figure is the addition of the traditional unmodified cerium oxide Scanning electron micrograph of rice powder, weight ratio of polyimine film which accounts for the solid content of the whole composition; and Fig. 6b is a composite film electron microscope made of the polyimide composition of Example 3 of the present invention photo. '[Main component symbol description] a Polyimine polymer substrate b Modified maleic imine oligomer c Coupled agent modified inorganic nanopowder A Unmodified copper dioxide Nddong powder B coupling agent C oxidized cerium oxide nano-powder modified by coupling agent 21 19861

Claims (1)

200827386 X. Patent application scope: !. A composition formed of inorganic nanoparticle and polyamidimide having an organic functional group, including: * (A) polyimine; (B) modified double horse Inorganic nano-additives modified with acidimine; and (C) coupling agents. 2· 3· The composition of claim 1, wherein the et 6 coupling agent is selected from the group consisting of a decane coupling agent having a vinyl functional group, a decane coupling agent having an amino functional group, and an oleic acid coupling agent. The group formed. The composition of the second aspect of the patent application scope, wherein the oleic acid coupling agent has a structural port CH3-(CH2)n-CH=CHh(CH2)n-C00H represented by the following formula, wherein n is 1 An integer of up to 14. 4· 5· 6· Such as the scope of patent application. Huan silk, its towel, the inorganic nano-additives, such as antimony oxide, antimony oxide, tin oxide, lead oxide, oxygen: selenium, antimony oxide, aluminum oxide, zinc oxide, antimony oxide, boron oxide, τι gallium A nano-powder composed of a group of emulsified indium and cerium oxide. The composition of claim 1, wherein the inorganic nano-additive is cerium oxide nano-powder. The composition of the first aspect of the invention, wherein the component I (c) is a silica dioxide having a vinyl functional group modified by a decane coupling agent. : The composition of claim 1 of the scope of the patent, wherein the component (c) (d, accounting for the total weight of the solid content of the composition. 5 to j 5%. 19861 22 200827386 8. If the scope of claim 1 a composition in which the octa (B) is a bismaleimide modified by barbituric acid. 9. If the composition of the first item of the patent application has 7 components (Β) k accounted for The composition has a total solid content of 1 to 1% by weight. 10. A composite film of inorganic nanoparticle and polyimine with an organic reactive functional group, including a poly-imine, a modified double horse An inorganic nano-additive modified with an amine and a coupling agent, wherein the poly-imine molecular bond is bonded to an organic polymer substrate, and the two-agent is modified into a 2 inorganic nano-additive and a barbituric acid. Modified Malayia: After the molecular chain of the oligo-polymer is combined, it is bonded to the molecular state of the poly-imine to form a semi-IPN structure. / u·If the patent application is the 10th item The composite film, wherein the modified bismaleimide is a bismaleide modified by barbituric acid. The composite film of the item 10, wherein the coupling j = the inorganic inorganic nano-additive is a cerium oxide nano-powder having a vinyl functional group modified by a decane coupling agent. The composite film of the 帛12 item, wherein the silica-functional sulphur dioxide having a vinyl functional group is uniformly distributed on the polyimine substrate. A double-layered flexible copper substrate comprising a copper foil substrate and a composite film formed on the surface of the foil substrate as claimed in claim 10. 1. A method for producing a polyimide-based composite film comprising the following steps: The use of a coupling agent to modify the inorganic nano-powder, the organic functional group 19861 23 200827386 . base is introduced into the surface of the inorganic neat powder, (b) the modified inorganic nano-powder prepared in the step (a) is added to the modified a solution of a polymulphonic acid composition of bismaleimide; and (c) heating and drying a solution of the polyhedral acid composition prepared in the step (b) to cyclize the polyglycine to a polyimine 1 6. The method of claim 15, wherein the modification is The nano-powder system is a cerium oxide nano-powder having a vinyl functional group modified by a decane coupling agent. The method of claim 15, wherein the modified inorganic nano-powder system has a solid content A total weight of 0.5 to 1 5% is added to a solution of a polyamic acid composition containing barbituric acid modified bismaleimide. 1 8. The method of claim 15, wherein The modified bismaleimide is a bismaleimide modified by barbituric acid. 1 9· A method for manufacturing a double-layered soft copper foil substrate, comprising the following steps: (a) using even The mixture is modified into inorganic nano-powder, and the organic functional group is introduced into the inorganic nano-powder; (b) the modified inorganic nano-powder prepared in the step (a) is added to the polyfluorene containing the modified bismaleimide a solution of the amine acid composition; and (c) applying a solution of the polyamic acid composition prepared in the step (b) to a copper foil substrate, heating and drying to cyclize the polyglycine to a polypyrene amine. The method of claim 19, wherein the modified inorganic nano-powder system is a cerium oxide nano-powder having a vinyl functional group of 24 19861 200827386 modified by a decane coupling agent. 21. The method of claim 19, wherein the modified inorganic nano-powder system is added to a barley-containing acid-modified double-Malaysia with a total solid content of 〇·5 to i 5%. A solution of a polyamic acid composition of an amine. 2 2 . The method of claim 19, wherein the modified bismaleimide is a bismaleimide modified with barbituric acid. 19861 25