TWI243186B - Polyimide film, manufacturing method of same, and usage of same - Google Patents

Abstract

This invention relates to a kind of polyimide film, which comprises 3,3',4,4'-benzophenonetetracarboxylic dianhydride and can satisfy physical properties such as mean linear expansion coefficient between 100 and 200 DEG C being above 18 ppm/DEG C and below 28 ppm/DEG C, elastic modulus being greater than 4.5 GPa, and coefficient of expansion caused by moisture absorption being below 13 ppm. Due to fulfilling all of the three physical property requirements, the polyimide film which prevents warping or curling from occurring in the TAB tape and flexile printed circuit board processing steps can be realized.

Description

1243186 发明 Description of the invention: [Technical field to which the invention belongs] With the lightweight and miniaturization of various electronic devices, polyimide film hanging is used as an insulating material. The present invention relates to polyimide film, A representative example of a method for producing the polyfluoreneimide film and its use. In particular, a polyimide film used for processing into a flexible printed wiring board (Fiexible printed wiring board) and a base film with a Tape Automated Bonding (TAB) tape, a method for manufacturing the same, and an example of use . [Previous technology] Previously, flexible printed circuit boards (WFPC) used its flexibility and were mainly referred to as ® used in narrow spaces inside cameras. However, in recent years, FPC has been widely used in the drive parts of flexible disk drives (FDD), hard disk drives (HDD), photocopiers, printing machines, etc., and it is sought to further improve the flexural bending characteristics of FPC. FPC resin film is used as a base, and this resin film is also called a base film. As the base film, a polyimide film composed of polyimide having high chemical flexibility and high f-flexibility may be used for the purpose of improving the flexibility and bendability. Here, as the above polyimide film, various physical properties have been developed, especially in the processing steps of FPC by using the automatic bonding technology method (TAB method is abbreviated), as a polymer film used as a base film. The imine film is sought for those who have the following three physical properties. (1) Moderate thermal expansion Polyimide with high flexibility is generally high in thermal expansion, that is, it has a large linear expansion coefficient. 'FPC using polyimide film as the base film has bending and curling.

O: \ 87 \ 87969-940216.DOC -6-1243186. In addition, if polyimide with a small linear expansion coefficient is selected in turn to form a yew film, and this film is used as a base film, the base film becomes very fragile due to the loss of the flexibility of the belt itself, resulting in continuous income. The disadvantage of FPC is that the flexibility is also reduced. However, in recent years, the above-mentioned TAB method has attracted attention as a technology capable of supporting the versatility, miniaturization, and high-density packaging of semiconductor devices. In the tab method, a hole (instrument hole) for mounting a semiconductor wafer such as an LSI on a continuously formed resin film is formed, and a very thin copper foil wire is formed thereon, and the copper foil wire is connected to the LSI and the printed circuit board. Wait. In the TAB method, a flip-chip bonding tape (abbreviated as an FC tape) composed of a three-layer structure of a protective layer, an adhesive layer, and an organic insulating film layer (substrate layer) is generally used. The TAB method is used to process the above-mentioned FC tape, and the processing steps are generally composed of the next 8 steps. That is, ① the step of forming a sprocket hole and a semiconductor wafer for carrying the tape on the FC tape according to the perforation, ② a step of removing the adhesion layer copper foil and then hardening the adhesive (copper foil lamination step), ③ according to the coating The step of etching the insulating coating and peeling the insulating coating to form a predetermined pattern (configuration pattern) of the copper foil (configuration pattern forming step), ④ metal plating processing step, ⑤ semiconductor bonding step, ⑥ resin packaging step, ⑦ perforation step, and各 Each step of the outer pin bonding step. After such processing, the γ step is used to package the LSI in TAB. In addition, the layer to be paid after the above step ② is called an adhesive-soft copper foil laminated board (abbreviated as FCcl). In the above processing steps, bending and curling of the FCCL or TAB tape is generated, and such bending and curling becomes one of the major causes of poor packaging when the TAB tape is used to package the LSI. That is, such bending and curling, in seeking the ruler

〇 Λ87 \ 87969-940216.DOC 1243186 inch precision steps cause all kinds of defects. With West? The main country / β 耶 ⑶ in the--pattern formation step, caused by the formation of the pattern formation of copper foil defective formation ⑤ in the semiconductor bonding step or ⑥ outer pin bonding step, 彡 | from the V-body connection Bad etc. In addition, since the actual step is performed by the separation element (reeU0_reei), the longer direction of the TAB band is full of tension. Therefore, the offender can correct the bending and curling in the long direction, but cannot correct the bending and curling of the web width. In this way, it can be said that the polyimide film used for TAB tape and FPC has a moderate thermal expansion property, and the degree of bending and curling of its linear expansion coefficient is not large. Within a small range is necessary. As such a range of the linear expansion coefficient, specifically 18 ppm / r or more and ^ ppm / ° C or less is preferable. (2) In the case where the water absorption rate of the base film is small and the water absorption rate of the base film is large, after the above-mentioned ② copper foil lamination step, the problem of accumulating internal stress in the adhesive layer sandwiched between the base film and the copper foil occurs. This internal α 卩 stress is accumulated as it is below. That is, in the step ② copper foil lamination, the hardening reaction of the adhesive is ended, and the base film is dried after being taken out from the hardening heating furnace, and the base film is fixed to the copper foil without skewing. Here, if the copper foil is placed in a bonded state, the base film swells with time with moisture absorption. On the other hand, copper foil does not absorb moisture and swell, and the expansion of a rigid band has almost no dimensional change due to the reason. Therefore, internal stress is accumulated in the adhesive layer sandwiched between the base film and the copper foil. Therefore, if the configuration pattern forming step is performed in this situation, it will become repeated drying and moisture absorption. Once the wiring pattern is formed on the copper foil by etching, O: \ 87 \ 87969-940216.DOC -8- 1243186 Then the stress of the removed part of the copper flute is released to produce a dimensional change. Therefore, even if a photomask is used to form a wiring pattern, a pattern larger than the size of the photomask is formed, and bending and curling are also generated. As a result, a poor connection with the semiconductor device occurred. Such a dimensional change causes a reduction in the yield of the TAB processing step.

In this way, the base film is required to have low water absorption and moisture absorption. Therefore, in order to prevent the above-mentioned bending and curling discomfort during processing of TAB tapes and FPCs, a base film with a small linear expansion coefficient and a low hygroscopic expansion coefficient in a moderate range is necessary. (3) Elastic modulus And the elastic modulus of the base film is small, that is, the elasticity is weak, and there may be a case where the base film has a dimensional change. This is because the tension is applied in the longer direction in the manufacturing step of the separation element tape. This dimensional change has an adverse effect on the processing steps and becomes the cause of 'curving and curling.' Therefore, for example, a polyimide film 'used in a TAB tape has a large elastic modulus. However, if the elastic modulus of the base film becomes large, a problem arises that the coefficient of linear expansion is small. This is because the modulus of elasticity and the coefficient of linear expansion greatly depend on the chemical structure of the human being (the structure of the repeated unit). That is, the primary chemical structure of polyimide, which has a large number of elastic branches, is generally selected, the linear expansion coefficient is small, the flexibility of the polyimide film is lost, and the flexibility is reduced. As above, in order to avoid bending and curling in the process of FPC by TAB method, seek to obtain 3 physical properties of (1) thermal expansion and (2) water and moisture absorption and (3) elastic modulus. Polyimide film. Here, in Japanese Patent Laid-Open Publication No. Hei 9-328544 "(publication: 〇: \ 87 \ 87969-940216.D0C -9-1243186 December 22, 1997), the polyimide film was explicitly instructed by The polyimide film composed of polyimide obtained by using 3,3f, 4,4 ^ benzophenonetetracarboxylic dianhydride as the acid component is reported to have a "slightly lower water absorption, slightly lower Moisture expansion coefficient, high elastic modulus "and" low thermal expansion coefficient "(for example, refer to paragraph number [0059]). The polyimide film reported in this bulletin uses pyromellitic dianhydride or 3,31,4,4'-dibenzo-tetraweilic acid monoanhydride as the acid component, and p-phenylenediamine as the diamine component. 4,4'-oxybisaniline is used; polyimide is used to copolymerize the acid component and the diamine component. However, even if the polyimide film reported in the above publication is used, (1) the combination of thermal expansion properties and (3) the elastic modulus can still cause (2) the problem of poor water and moisture absorption. Specifically, the examples described in the above-mentioned publications have extremely large water absorption ratios ranging from 2.62 to 3.69% and hygroscopic expansion coefficients ranging from 16 · 8 to 29 · 8 ppm. Furthermore, in Japanese Published Patent Publication "Japanese Patent Laid-Open No. 235373" (publication: September 9, 1997), "the block component of polyimide is composed of an aromatic mono-aminated compound and an aromatic tetracarboxylic compound having a rigid structure. Composition of acid compounds and copolymerization of any component of polyimine, which is composed of an aromatic diamine compound with a flexible structure and up to 2 kinds of aromatic tetracarboxylic acid compounds, and is a copolymerization effect of the molecular combination "It is clearly instructed that the use of 3,3,4,4, _dibenzylidene tetrapic acid dianhydride as an acid component is clearly instructed (refer to Example 5 of the same publication). ^ In the A report, as a "resin-formed product, it has both high elasticity, low thermal expansion, and low absorption". Indeed using 3,3,, 44, _ two stupid armor 'four ... liver Example 11, the elastic modulus is 4: 3' GPa (440 g), the linear inflation coefficient is 16.7 Ppm / ° C, the water absorption rate becomes 2.4%, indeed

O: \ 87 \ 87969-940216.DOC -10- 1243186 Although the physical properties of ⑴- (3) are improved, the above-mentioned M-side & FPCH is used as Comparative Example 8 described below, which cannot be called full. In this way, 3,3 ', 4, _benzophenone tetra is used as an acid component of polyimide.

In the case of polyimide properties transmitted by hydrazone-anhydride, the use of FPC (TAB tape, etc.) by the TAB method has previously been achieved. At the same time, it can achieve the so-called due to thermal expansion, water absorption and moisture absorption, and elastic modulus. Those whose physical properties are better are those who know. However, when evaluating the above-mentioned physical properties, rather than using the linear expansion coefficient, hygroscopic expansion coefficient, and sunny modulus, it is better to use specific parameters, such as parameters, as the values of all the ideal ranges. It is known that it is very difficult to adjust the numerical values of the parameters (1) to (3) as the values of all the ideal ranges. [Summary of the Invention] The present invention was made based on the above-mentioned problems, and its purpose is particularly as a base film for TAB tape and FPC, using 3,3, obtained from dibenzoyltetracarboxylic acid dianhydride. In the case of Yalai, it is possible to fully obtain the reconciliation of thermal expansion, (2) water absorption and moisture absorption, and (3) elastic modulus, and provide polyimide film and A typical example of its production method and its use. μ Here, in view of the results of the intensive discussion in view of the above-mentioned problems, the inventors have used a hygroscopic expansion coefficient in particular to evaluate the hygroscopicity and hygroscopicity, and have sufficiently obtained (1) thermal expansion properties, (2) hydroscopic properties and ( 3) The adjustment of the various physical properties of the elastic modulus is &, and the result satisfies that it is possible to manufacture a polyimide film which can more effectively avoid the occurrence of bending and curling, and complete the present invention. The polyimide film obtained by blending each of these physical properties (ι) to (3) is used as a representative example: O: \ 87 \ 87969-940216.DOC -11-1243186 TAB tape is of course applied to a variety of Fpc for the purpose can also be used suitably. That is, in order to solve the above-mentioned problems, the ammonium imine film of the present invention is a hydroimide film obtained from polyammonium amine mainly composed of an aromatic diamine and an aromatic tetracarboxylic dianhydride. 100〇_2〇〇. . The average linear expansion coefficient is ppm 'The elastic modulus is 4.5 or more, and the hygroscopic expansion coefficient is ^ ppm or less. As the aromatic tetracarboxylic dianhydride, 3,3,, 4,4, _benzoyl Ketone tetracarboxylic dianhydride is constituted as an essential component. In the polyimide according to the present invention, when the content of the diliverium tetrametanoic acid dihepatic acid component is 100 mol%, 3,3,, 4,4, _benzophenonetetracarboxylic dianhydride is used as 20 A range of ~ 60 mol% is preferred. In addition, as the acid component used in the polyfluorene imide film of the present invention, it is preferable to use the compound shown next. #, It is preferable to use an aromatic ester acid dianhydride as the aromatic tetracarboxylic dianhydride component. When (II) the total aromatic tetracarboxylic dianhydride component is 100 mol%, it is preferable to use the aromatic ester acid dianhydride in the range of 10 to 60 mol%. Furthermore, as (III) the aromatic ester acid dianhydride, p-phenylene bis (trimellitic acid monoester anhydride) is preferably used. As the diamine component used in the polyfluorene imine film of the present invention, it is preferable to use at least one of each of a linear diamine and a flexible diamine. At this time, when the wholly aromatic diamine component is 100 mol%, the linear diamine and the flexible diamine described above are each used in the range of 20 to 80 mol% and 80 to 20 mol%. Within the range is better. (Π) As the linear diamine, p-phenylenediamine is preferably used. (II) As the flexible diamine, 4,4'-oxybisaniline is preferably used. O: \ 87 \ 87969-940216.DOC -12-1243186 In the polyimide film of the present invention, the above-mentioned linear diamine and bendable monoamine are distributed in the polyimide molecule, and the arbitrary distribution is better. . With regard to the method for producing a fluorene imine film according to the present invention, the structure of the fluorene imine film includes at least a) an organic solvent and reacting an aromatic diamine and an aromatic tetracarboxylic dianhydride polyfluorinated acid to obtain polyfluorene. Steps of amino acid solution, ... washing on the support #including the steps of film forming adhesive agent containing ㈣amine 酉 mann solution, c) after heating the film forming viscosity agent on the support, detaching the coagulation from the support The step of the gel film, d) heating the gel film, and the step of drying the imine remaining amine acid and drying it. In the method for manufacturing the polyfluorine film of the present invention, at least a dehydrating agent and An imidization catalyst is preferred. As an example of the use of the polyfluorene imide film of the present invention, an iFc band formed by providing an adhesive layer and a protective layer on the polyfluorine imide film, and at least a layer composed of the polyfluorine imide film may be mentioned. And a flexible printed circuit board with a metal conductive layer. According to the above structure, especially as a base film for a TAB tape, that is, a polyimide film obtained by using 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride as an essential component In this case, it is possible to provide a polyimide film having no linear expansion coefficient and elastic modulus at the same time as no bending and curling, and no bending or curling due to dimensional changes in moisture absorption. Still other objects, features, and advantages of the present invention will be fully understood from the following description. [Embodiment] If one embodiment of the present invention is described, it is the same as the following. O: \ 87 \ 87969-940216.DOC -13-1243186, the present invention is not limited to this. In the following, the details of the present invention, the polyimide film, its manufacturing method, and its use will be described in detail in the order of specific examples. (1) Polyimide film of the present invention < Physical properties of polyimide film > About the polyimide film of the present invention is mainly amidated by aromatic tetracarboxylic dianhydride and aromatic dicarboxylic acid. Polyacrylic acid synthesized by amines (caffeic acid), produced using polyimide. During this period, at least 3 of the aromatic tetracarboxylic dianhydrides mentioned above had 3,3,4,4-benzophenone tetra Carboxylic dianhydride, the polyimide film thus obtained meets the following three requirements. Condition (1): Within the range of an average linear expansion coefficient from 100C to 200 ° C is 18 to 28 ppmrc. Conditions ( 2) The elastic modulus is 4.5 GPa or more. Condition (3): The coefficient of hygroscopic expansion is 13 ppm or less. When the S & imine film is used as FPC and tab tape according to the condition (i), The occurrence of bending and curling is prevented. According to this, at the same time of high bending property, the linear expansion coefficient is also high, and it is possible to supply polyimide film within the range that does not cause bending and curling. Furthermore, compared with the above-mentioned polyimide The ideal linear expansion coefficient of the amine film from 100 C to 200 ° C is in the range of 18 ρριη ~ 25 ppm / ° C, and more The ideal range is within the range of 20 to 25 ppm / tt. At the same time, according to the above condition (2), the polyimide film has a dimensional change in the manufacturing step of the separation device tape type, thereby preventing bending of the FPC and TAB tapes. And the occurrence of curling. Furthermore, the elastic modulus of the polyimide film is more ideal than O: \ 87 \ 87969-940216.DOC -14-1243186 in the range of 4.5 0? &Amp; ~ 8.0 0? 3 A more desirable range is 50 GPa to 7.5 GPa. In addition, the polyimide film satisfies the condition (3), and the dimensional change of internal stress between copper cancers is prevented by hygroscopic expansion according to the condition (3). Furthermore, The ideal range for the hygroscopic expansion coefficient of the polyimide film is 12 ppm or less, and the more desirable fe range is 11 ppm or less. Regarding the polyimide film of the present invention, according to the above three conditions, It has the general thermal expansion properties and elastic modulus without bending and curling, and it is possible to reduce the water absorption and moisture absorption, and it is possible to provide a polyimide film that does not bend and curl due to the dimensional change of moisture absorption. ≪ For the synthesis of polyimide Body composition > on polyimide film of the present invention, mainly using the polyamide acid of the acid (PEI) synthesis from an aromatic tetracarboxylic dianhydride and aromatic diamine) of the resulting polyimide. That is, after the polyimide used in the present invention is polymerized (synthesized) with the polyamic acid of the precursor, it can be obtained by the imidization. Here, the so-called "polyamino acid mainly composed of aromatic diamine and aromatic tetracarboxylic dianhydride" refers to the aromatic four Carboxylic dianhydride has the largest content ratio, and among the diamines, the aromatic diamine has the largest content ratio. In other words, in the present invention, in the polymerization of polyamic acid as a precursor, an aromatic tetracarboxylic dianhydride is contained as an acid component, and an aromatic diamine is contained as a diamine component. It is also good to use other acid components and diamine components. O: \ 87 \ 87969-940216.DOC -15-1243186 The following specifically describes the acid component and diamine component as raw materials (monomer components) of polyamic acid. < Acid component (acid dianhydride component) > Regarding the polyimide film in the present invention, among the raw materials of polyimide of the precursor of polyimide, at least 3,3f can be used as the acid component. 4,4, -benzophenone tetracarboxylic dianhydride. The 3,3,4,4, -benzophenone tetracarboxylic dianhydride is included in the category of the aromatic tetracarboxylic dianhydride. In the case of polymerizing polyamic acid, the specific amount (dose used) in the case of using the above 3,3,4,4, -diphenylphosphonium tetracarboxylic dianhydride as the acid component is not particularly limited, but all When the aromatic tetracarboxylic dianhydride component is 100 mol%, it is better to use it within the range of 20 to 60 mol%, and it is more desirable to use it within the range of 25 to 60 mol%. 25 to 55 mol% is more desirable. In other words, the upper limit of the amount of 3,3,4,4'-benzophenonetetracarboxylic dianhydride is 60 mol% or less, and more preferably 55 mol% or less. Meanwhile, the lower limit is preferably 20 mol% or more, and more preferably 25 mol% or more. According to the usage of 3,3,4,4, -benzophenonetetracarboxylic dianhydride within this range, it is possible to obtain a blend of linear expansion coefficient and elastic modulus, and according to this range, it is below the upper limit. This makes it possible to have a small moisture absorption swelling coefficient. Dan Kao, as the above-mentioned aromatic tetracarboxylic dianhydride used in the present invention, 2 and the above 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, and further added " Acid dianhydride is preferred. The so-called "aromatic lysine dianhydride" refers to an aromatic tetracarboxylic acid dianhydride containing an ester in the structure. The above-mentioned aromatic acetic dianhydride is not a specific one—for example, p-phenylene bis ( Trimellitic acid monoester ^ ethyl ^

O: \ 87 \ 87969-940216_DOC -16-1243186 trimellitic acid monoester anhydride), bis-carbonic acid A bis (trimellitic acid monoester anhydride), etc. The use amount of the above-mentioned aromatic ester acid dianhydride is not particularly limited, but if the total aromatic tetracarboxylic dianhydride component is 100 mol%, it is preferably in the range of 10 to 60 mol%. For example, a range of 20 to 55 md% is more desirable, and a range of 25 to 50 ml% is more desirable. In other words, the upper limit of the amount of the aromatic ester pentane anhydride is preferably 60% or less, more preferably 55% or less, and still more preferably 50% or less. Meanwhile, the lower limit is preferably 10 mol. /. The above 'is more preferably 20 mol% or more, and even more preferably 25 mol% or more. According to the use amount of the above-mentioned aromatic ester acid dianhydride not less than this range, the effect of improving the elastic modulus and the coefficient of hygroscopic expansion is not great, and it is possible to obtain a soft band if it exceeds this range. In the present invention ', even among the above-mentioned aromatic S-acid diliver, p-phenylene bis (trimellitic acid monoester anhydride) is particularly preferably used. According to this, it is possible to obtain an improvement in mechanical strength, moisture absorption, and expansion coefficient, and a suitable polyimide from the viewpoint of thermal behavior. The use amount of phenylbenzylbis (monobenzyltriacid monoester anhydride) is not particularly limited, but when the total aromatic tetracarboxylic dianhydride component is 100%, 1 ％ A range of from 60 to 60% is more preferred, a range of from 20 to 55 mol% is more preferred, and a range of from 25 to 50% is more desirable. In other words, the upper limit of the amount of p-phenylene bis (trimellitic acid monoester anhydride) used is preferably 60 m% or less, more preferably 55 mol% or less, and more preferably 50 m. 〇1% or less. At the same time, the lower limit is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 25 mol% or more.

O: \ 87 \ 87969-940216.DOC -17-1243186 Furthermore, as the above-mentioned aromatic tetracarboxylic dianhydride used in the present invention, the above-mentioned 3,3,, 4,4, -dibenzone ketone is used Carboxylic dianhydride or 3,3,4,4, _dibenzidine_tetracarboxylic dianhydride and the above aromatic ester acid dianhydride, in addition to other aromatic tetracarboxylic dianhydride can. The so-called "other than aromatic tetracarboxylic dianhydride" mentioned here does not conform to the above 3,3,, 4,4, _dibenzoyl tetrakidic acid dianhydride and the above-mentioned aromatic dicarboxylic acid dianhydride Aromatic tetracarboxylic acid dianhydride. The above-mentioned other aromatic tetracarboxylic dianhydrides are not particularly limited, and specific examples include pyromellitic dianhydride, 2,3,6,7_tetracarboxylic dianhydride, 3, 3 ', 4,4'_biphenyltetracarboxylic dianhydride, ^^, tetracarboxylic dianhydride, 2,2', 3,3'_biphenyltetracarboxylic dianhydride, 2, into bis ( 3,4_bicarboxyphenyl) propane dianhydride, 3,4,9,10_peryiene tetracarboxylic dianhydride, bis [3,4_bicarboxyphenyl] propane dianhydride, 1,1-bis ( 2,3-dicarboxyphenyl) ethane dianhydride, 込 ^ bis ^; bicarboxyphenyl) ethane dianhydride, bis (2,3_dicarboxyphenyl) biogas dianhydride, bis (3,4_ Bis (phenylphenyl) ethane dianhydride, oxydibenzyl dianhydride, bis (3, 'dicarboxybenzyl) polysulfone dianhydride, ethylene bis (trimellitic acid monoester anhydride), biscarbohydrate A bis ( Trimellitic acid monoacetic anhydride) and so on. These may be used alone or in combination of two or more. Among the other aromatic tetracarboxylic dianhydrides mentioned above, pyromellitic dianhydride is more preferable than 3,3f, 4,4f-biphenyltetracarboxylic dianhydride. The use amount of the other aromatic tetracarboxylic dianhydrides is not particularly limited. However, when the total aromatic tetracarboxylic dianhydride component is 100 mol%, 50 mol% or less is preferred, 45 mol. % Is more preferable, and 40 mol% is more preferable. In other words, the upper limit of the use of other aromatic tetraweilic acid dianhydrides is preferably 50 mol% or less, more preferably 45 mol% or less, O: \ 87 \ 87969-940216.DOC -18- 1243186 is more preferably 40 mol% or less. Five soils. Above 丨% is sufficient. Moreover, the lower limit is not particularly limited.: According to the death: the amount of other aromatic tetracarboxylic acid dianhydrous is within this range, hunting by using 3,3,, 4,4, _ 二 芏 田 ⑽ 1 In this case, when the tetracarboxylic dianhydride and / or aromatic acid bis is used, the amount of polyimide film can be increased. According to the present invention, the physical properties of the polyimide film required by the present invention, as the above-mentioned acid component, aromatic tetramethylene dianhydride (other acid dianhydrides) can also be used. The amount used is not particularly limited either. < Monoamine component > In the polyimide film of the present invention, among the raw materials of the polyamic acid precursor of the polyimide precursor, as a diamine component, at least an aromatic diamine can be produced. Specific examples of the aromatic diamine include p-phenylenediamine and its nuclear replacement compound, benzidine and its nuclear replacement compound, 4,4, · oxybisaniline, and I, 3 · bis (cardiamine benzene). Oxygen) benzene, bis (3-aminephenoxy) benzene, 4,4, bis (3 only phenoxy) biphenyl, 4,4, bis (4-aminebenzyloxy) biphenyl, bis (4_ (cardiamine) benzene Oxygen) benzyl) polylithic wind, bis (4- (3-aminephenoxy) phenyl) polysulfone, 4,4, _diaminediphenylpropane, 4, diaminediphenylmethane, 4,4, -Diamine diphenyl sulfide, 3,3, _diamine diphenyl polyfluorene, 4,4'-diamine diphenyl polysulfone, 3,3, _oxybisaniline, 3,4, _oxy Diphenylamine, 2,4'-oxybisaniline, 4,4, -diamine diphenyloxybisaniline and 4,4, _diamine dibenzylsilylmethane, 4,4'-diamine diphenylethyl ring Phosphine oxide, 4,4, _diaminediphenyl N · fluorenylamine, 4,4'-diaminediphenylphenylamine, ipdiaminebenzyl, I] -diaminebenzine, etc., but it is not Specially restricted person. In the present invention ', the aromatic diamine component includes at least linearity

O: \ 87 \ 87969-940216.DOC -19-1243186 and one of the flexible diamines are preferred. Here, the so-called "linear diamine" does not contain in the main chain t such as ethyl ether, propyl, hexafluoro, propyl, acetyl, polyfluorenyl, sulfur, etc. In general, the 'f-curved group' refers to a diamine compound in which the nitrogen atom pointing to two amino groups and the combined counter atoms are arranged in a straight line. Specific examples of the linear diamine include p-phenylenediamine and its nuclear-substituted compounds, benzidine and its nuclear-substituted compounds, but they are not particularly limited. These linear diamines may be used singly or in combination of two or more kinds as appropriate. Of these, p-phenylenediamine is particularly preferred. According to this, a polyimide film is excellent in terms of treatment, characteristics, and characteristics. In addition, the so-called "flexible diamine" contains one of the four bent groups such as ether group, methylenyl propyl group, /, fluoro block propyl group, several groups, minus group, and sulfide group in the main chain. An amine, or a case where it does not include a bending group, is a diamine compound having a structure in which a nitrogen atom having 2 amino groups and a carbon atom bonded thereto are not arranged in a straight line. Specific examples of the flexible diamine include 4,4, -oxybisaniline, 1,3-bis (4-aminephenoxy) benzene, n-bis (3-aminephenoxy) benzene, and 4 , 4, -bis (3_aminophenoxy) biphenyl, 4,4, -bis (cardioaminophenoxy) biphenyl, bis (4- (4-aminephenoxy) phenyl) polysulfone, bis (4- (3-Aminophenoxy) phenyl) polyfluorene, 4,4, _diaminediphenylpropane, 4,4, _diaminediphenylmethane, 4,4, -diaminediphenylsulfide, 3,3, diamine diphenyl polyhard, 4,4'-diamine dibenzyl polysulfone, 3,3, _oxodianiline, 3,4, _oxodiphenylamine, 2,4'_oxodi Aniline, 4,4, _diaminediphenyldiethyl and 4,4, _diaminediphenyldisulfide, 4,4, diaminediphenylethyl phosphine, 4,4, -di Amine diphenyl

O: \ 87 \ 87969-940216.D0C -20-1243186 N methylamine, 4,4'-diamine diphenyl N-phenylamine, 13-diaminobenzene, n-diaminobenzene, etc., however It is not particularly limited. The bendable diamine may be used alone or in combination of two or more of them. Among these, 4,4'-oxybisaniline is particularly preferred. Accordingly, a polyimide film excellent in blending with various physical properties can be obtained. Among the above-mentioned aromatic diamines, the amount of linear diamine and bendable diamine used is not particularly limited. When the total aromatic diamine component is 100% ^ 1%, the linear diamine is used at 20 to A range of 80 m% is better, a range of 30 to 70 mol% is more preferred, and a range of 35 to 65 m% is more preferred. In addition, when Wang aromatic has no monoamine component as 100 mol%, the flexible diamine is preferably in the range of 20 to 80 mol%, and is used in the range of 30 mol% to 70 mol%. Those within the range are more ideal, and those that can be used within the range of 35 to 65 m% are more ideal. In other words, the upper limit of the amount of linear diamine and bendable diamine used is preferably 80 mol% or less, more preferably 70 mol% or less, and more preferably 65 mol% or less. . Furthermore, the lower limit is preferably at least 20 mol%, more preferably at least 30 mol%, and even more preferably at least 35 mol%. In addition, when the amounts of linear diamine and bendable diamine are compared, when the total aromatic diamine content is 100 ml%, use each within the range of 20 to 80 ml% and 80%. It is better to be in the range of ~ 2,111,01%, more preferably in the range of 30 to 7,101,01%, and 70 to 30 mol%, and the range of 35 to 65 mol% is used. And the range of 65 ~ 35 mol% is more desirable. According to the amount of linear diamine used and the amount of bendable diamine within the above range of O: \ 87 \ 87969-940216.DOC -21-1243186, the blending of the "secret modulus and linear expansion point" is maintained, and the improvement The bending characteristics of the flexible copper foil laminate or TAB tape become easy. The distribution of the linear diamine and the curved diamine is not particularly limited to the polyimide molecules (polyamic acid molecules), but arbitrary distributions are preferred. According to this, the high elastic modulus and the coefficient of linear expansion are large: it becomes easy. ^ In addition, in the present invention, for the physical properties required for the obtained polyimide film, etc., as the diamine component, a diamine other than an aromatic diamine (an other amine) may be used. The amount of other diamines is not particularly limited. (2) Production method of polyimide film of the present invention The production method of polyimide film of the present invention is described below. The method for polymerizing (synthesizing) the amino acid is not particularly limited, and a method known in the art can be used. In an organic solvent, it appears to be approximately the same molar amount (substantially equal to the molar amount). In an organic solvent, the acid component and the monoamine component are dissolved and reacted to prepare a polymer as a precursor of polyimide. An organic solvent solution of phosphonic acid (hereinafter referred to as a polyphosphonic acid solution) is sufficient. The conditions under which the reaction is performed are not particularly limited, but a reaction temperature in the range of -20 ° C to 90 ° C is preferred, and a reaction time in the range of 30 minutes to 24 hours is preferred. By. In addition, as the atmosphere during the reaction, an inert atmosphere such as argon or nitrogen is preferred. For the polymerization of the polyamic acid, a plurality of types of polymerization methods different from the method of reacting the acid component and the diamine component are used. Specifically, general polymerization methods such as those shown in 1) to 5) below can be suitably used. 1) Dissolve the aromatic diamine in an organic solvent, and make the aromatic diamine and

O: \ 87 \ 87969-940216.DOC -22-! 243186 A method for the reaction polymerization of Moore's aromatic tetrakistic dianhydride. 2) The Fangxiang Wuquan acid second field is reacted with the aromatic diamine sigma ^ organic solvent with an excessively small molar amount to obtain a prepolymer having acid anhydride groups at both ends _ only in the entire step Aromatic tetracarboxylic diamino and aromatic diamine compounds become substantially the same as Mol, and a method of polymerizing them using an aromatic diamine is used. " 3) Aromatic tetramethylene di liver reacts with the excess molar amount of the aromatic diamine compound in an organic solvent to obtain a prepolymer having amino groups at both ends. Continuing, after the aromatic diamine compound is added here, the aromatic tetraamine diamino compound and the aromatic diamine compound become substantially the same as Moore in the entire step, and the aromatic tetrakidic acid difield is used for polymerization. method. ,) Make aromatic bismuth tetracarboxylic dianhydride dissolve and / or disperse in organic solvent = become a minus the same as Moore-using 'aromatic diamine compounds to make it 5) the same as Moore's aromatic A method of polymerizing a mixture of diene tetradicarboxylic acid and aromatic diamine in an organic solvent. The organic solvent used for the production of the polyamic acid solution is not particularly limited even if it has a solvent for dissolving the polyamic acid, even if it is a polymerization solvent used for the polymerization of the polyamic acid. As a specific one you! Examples include N, N-dimethylformamide, N, N_: methylacetamide, N_methyl-2-tonamidine, and the like, among which amine-based solvents are N, N_: methylformamide Sterile amine and N, N-dimethyl ^ acetamide are preferred. These organic solvents are usually used alone, but two or more of them may be used in combination as appropriate. In addition, the composition of the above-mentioned polyamic acid solution is not particularly limited. O: \ 87 \ 87969-940216.DOC -23-1243186 Anyone, however, the polyamic acid is in the range of 5 to 35% by weight in the organic solvent. It is more preferable to be reduced to '10 to 30% by weight. It is possible to obtain an appropriate molecular weight and solution viscosity according to the relationship. The polyimide film 'may be added with a filler for the purpose of improving various properties such as sliding properties, thermal conductivity, electrical conductivity, and resistance to electric power. The filler 'is not particularly limited, but specific examples of preferred ones include% dioxide, titanium oxide, oxygen charm, nitrogen cutting, nitrogen oxide, calcium dihydrogenate, calcium phosphate, mica, and the like. In addition, the particle diameter of the filler mentioned above is obtained according to the characteristics of the reforming belt and the type of filler added, which is not particularly limited, but generally the average particle diameter is in the range of 0.05 to 100 μπχ. 〇 ″ ~ ”μπ is more desirable, 0el ~ 50 μιη is more desirable, and 〇J ~ 25 μιη is particularly desirable. If the particle diameter is within this range, weight is likely to appear in the polyimide film. If the mass effect does not exceed this range, good surface properties and mechanical properties can be obtained in the polyimide film. In addition, the amount of the filler added above is also based on the characteristics of the reforming belt and the filler particles. Those with changes in diameter are not particularly limited. The addition amount of the general filler is preferably within the range of 0.001 to 100 parts by weight based on 100 parts by weight of polyimide, 0.01 to 90 parts by weight. It is more ideal within the range of 0.02 to 80 parts by weight. If the amount of filler added is not less than this range, the reforming effect of the filler is likely to occur. If it does not exceed this range, Polyurethane can be maintained amine Good mechanical properties. The method of adding filler is not particularly limited, but specifically, for example, the method of adding to the polymerization reaction solution before or during polymerization, poly O: \ 87 \ 87969-940216. DOC -24-1243186 A method of kneading a filler using 3 rolls after the completion of polymerization of amidine, a method of preparing a dispersion containing a filler and mixing it in a polyamic acid solution, etc. Among them, a preparation containing a filler is also prepared. The method of mixing the dispersant of the agent in the polyamic acid solution, especially the method immediately before the production of the film is preferred. According to this, the pollution energy of the manufacturing line through the filler is the least. Prepare the filler When dispersing liquid, it is better to use polyamic acid polymerization solvent and the same solvent. Furthermore, "The dispersion of fillers is well dispersed, and the dispersion state of the magicians is stabilized, which does not affect the physical properties of the tape. It is also possible to use fener powder, viscosity-increasing agent, etc. in the scope. In the present invention, the method for producing a polyimide film from the polyamic acid solution is not particularly limited, and a conventionally known method can be used. As Examples of the method of fluoridation include thermal fluoridation and chemical fluoridation. However, it is more preferable to use chemical fluoridation. Based on this, a polymer having excellent thermal dimensional stability and mechanical strength can be obtained.醯 imine film. Next, an ideal example for explaining the method for producing a polyimide film of the present invention will be described, but of course, the method of producing the present invention is not limited thereto. About the production of a polyimide film of the present invention Method, a) the step of reacting an aromatic diamine with an aromatic tetracarboxylic dianhydride in an organic solvent to obtain a polyamic acid solution 'b) a film-forming viscose containing the above polyamino acid solution is flowed on a support Step 'c) After the above film-forming viscose is heated on the support, the step of detaching the gel film from the support, changing the gel film and heating the gel film, and drying the remaining imine acid to dry it The step, including at least 4 steps thereof, is the better one. In the above-mentioned production, a dehydrating agent may also be used in combination with a curing agent containing a sulfonium imidization catalyst. 0: \ 87 \ 87969-940216.D0C -25-1243186 Take one of the ideal forms of the present invention as an example, and explain it by the manufacturing steps of chemically brewed polyimide film using a hardener. Chemical ammonium imidization method, for polyacrylic acid solution, any dehydrating agent representing anhydride of anhydrous acetic acid, etc., and tertiary amines representing isoquinoline, β-methyl eσdine, < σdine etc. A similar method of imidization catalyst to make it work. The chemical amidine method may be used in combination with the thermal amidine method. The heating conditions can be changed according to the type and film thickness of the polyamic acid. a) The aromatic diamine is reacted with the aromatic tetrahydroacid di-field in an organic solvent to obtain a polyamic acid solution. b) The dehydrating agent and the ammonium imidization catalyst are mixed in the polyamino acid solution at low temperature. Film-forming viscose is cast into a film on a support such as glass plate, aluminum foil, ring-shaped stainless steel strip, stainless steel roller, etc. C) 80 on the support. (: ~ 200 ° C, preferably 10 (TC ~ i8 (rc temperature heating 'according to the hardening and / or drying of the activated dehydrating agent and the imidization catalyst' after being detached from the support to obtain the polymer Amino acid film (hereinafter referred to as gel film). The gel film is a self-supporting intermediate stage from the curing of polyacrylic acid to polyimide, with the formula 1 (AB) x100 / B ···· 1 In formula 1, A and B represent the following: A: the weight of the gel film B: the volatile content calculated from the weight of the gel film after heating at 450 ° C for 20 minutes is in the range of 5 to 500/0, It is preferably 5 to 100%, more preferably 10 to 80%, and most preferably 30 to 60%. The use of a film in this range is suitable, and once the deviation has a mechanical strength of O: \ 87 \ 87969-940216.DOC -26- 1243186 lowered, etc. d) Fix the end of the gel film to avoid shrinkage and drying during hardening, and remove the residual solvent, additives and catalysts in the water, and the residual ammonium acid is completely The polyimide film of the present invention can be obtained by amidine imidization. At this time, it is better to finally heat at a temperature of 400 to 58 ° C. for 5 to 400 seconds. If it is higher than this temperature and / or time long, The thermal degradation of the green film causes problems. On the contrary, if the temperature is lower than the temperature and / or the time is short, the predetermined effect cannot be achieved. The thickness of the obtained polyimide film is not particularly limited, but it is especially used as a TAB tape and FPC. In the case of a base film, the thickness of the belt is preferably in the range of 10-125, more preferably in the range of 2 μm, more preferably in the range of 25-90, and particularly desirable in the range of 40-80 μm. In this way, as for the polyimide film of the present invention, as described above, the average linear expansion coefficient of loot: 20 to 20 (TC is 18 to 28 ppmrc), and the elastic modulus is 4.5 GPa or more. The condition for the wet expansion coefficient to be i3 ppm or less. (3) Applications of the present invention (usefulness of the present invention) The polyimide film of the present invention can be used in various applications depending on its physical properties, and is particularly suitable for Use of FC (Film Loading Assistance) for FPC, TAB tape, etc. Regarding the FC tape of the present invention, an adhesive layer is provided on the polyimide film of the present invention, and a protective layer is provided on the adhesive layer as three layers. The so-called f of the structure is used as the material f of the adhesive layer. Epoxy purpose tree months, nylon Pangshu green gun-based resins, acrylic resin, polyimide resin, carbolic acid-based tree May said carbolic acid modified epoxy resin, polyamide-imide-based resin,

O: \ 87 \ 87969-940216.DOC -27-1243186 However, it is not limited to these. Furthermore, the materials used as the protective layer include, for example, PET and EVA, but they are not particularly limited to these. Furthermore, regarding the FPC and TAB tapes of the present invention, and on at least one side of the polyimide film of the present invention, it is not particularly limited if the metal conductive layer is formed with or without the adhesive layer. In other words, in the Fpc and TAB pages of the present invention, it is preferable to have at least a constitution of an adhesive between a layer composed of the above polyimide film and a metal conductive layer. # 纟 Even if the metal conductive layer is laminated only on one side of the layer (base film) composed of the polyimide film, it is also preferable to laminate on both sides of the metal conductive layer. Therefore, in the present invention, a laminate including a two-layer structure composed of a polyimide film / metal conductive layer; a laminate having a three-layer structure composed of a metal conductive layer / polyimide film / metal conductive layer; Polyimide film / adhesive layer / metal conductive layered structure; 3-layer structure consisting of metal conductive layer / adhesive layer / polyimide film / adhesive layer / metal conductive layer The laminated body is used as the material of the adhesive layer. For example, epoxy-based resin, 8.4% oxygen-based resin, propylene-based resin, polyimide-based resin, and stone force: the tree moon and the sun; "Ethylene-based epoxy resins, amines, and imine-based trees" are not particularly limited to these. Examples of the metal used for the metal conductive layer include copper, but are not particularly limited to these. These, = 'Using the polyimide film of the present invention, when bonding Quye, FPC, and TAB tapes with an adhesive, the spotting agent is completely hardened and collapsed at 60% humidity in 100% * ^, For the small amount of bending after cyclic wetness, add the adhesive surface as the side material, and the "surface w material is reduced =

O: \ 87 \ 87969-940216.DOC -28-1243186 is as follows. In the state where copper is not subjected to the engraving method, the bending amount is preferably 0.5 mm or less, more preferably 0 mm or less, and particularly preferably _0.5 mm or less. In addition, in a state where the copper foil is completely removed by an etching method, the bending amount is preferably 30 mm or less, more preferably 2.5 mm or less, and particularly preferably 2.0 mm or less. The bending amount in the state of the steel foil and the copper foil attached is completely removed by the last name engraving method. If the same percentages satisfy these ranges, the discomfort caused by the bending of the processing and packaging steps can be eliminated. (4) Specific examples Hereinafter, the present invention will be described more specifically based on examples and comparative examples. The present invention is not limited to these. Moreover, the measurement of the elastic modulus of the polyimide film obtained in the examples or comparative examples is based on ASTM D882. The linear expansion coefficient and the hygroscopic expansion coefficient of the polyimide film obtained are based on ASTM D882. The next general measurement. [Measurement of linear expansion coefficient] Measurement of the average linear expansion coefficient from 100 ° C to 200 ° C was performed using TMA120C manufactured by Seiko Instruments Inc. The sample size is taken as a width of 3 mm and a length of 10 mm. Load a 3g load to 10%. 〇 / 11 ^ 11 to 10t > c to 40,000c Once the temperature rises, it is cooled to 10 ° C. 〇. Furthermore, the temperature was raised at 10 t: / min, so as to be 100 at the second temperature increase. (: And the thermal expansion coefficient of 2001 are calculated as the average value. [Measurement of the hygroscopic expansion coefficient] The measured film is left for 24 hours at 5 (rc, relative humidity of 30% in an environmental testing machine to measure the film size ( L1). Secondly, the film is placed in an environmental testing machine with a relative humidity of 80% for 24 hours. The measured film size (L2) is calculated by the following formula: O: \ 87 \ 87969-940216.DOC -29-1243186 Coefficient of wet expansion and coefficient of wet expansion (ppm) = (L1_L2) + L 1+ (80-30) χ106 Furthermore, from the obtained polyimide film, a TAB tape is generally produced as follows, and the bending is measured. [TAB tape Production] Here, polyamidoamine resin (bonding material M1276, manufactured by Nippon Lekko Corporation) was mixed with 50 weight parts, and bis-carbonic acid A-type epoxy resin was mixed (Eplcoat828, manufactured by Petrochemical Shell Epoxy Co., Ltd.) 30 parts by weight. Cresol novolac epoxy resin 10 weight percent, toluene / isopropanol 1/1 mixed solution 15 weight parts of the solution, to prepare the mixed reset part diamine diphenyl polysulfone / dicyandiamide 4/1 2 % Glycol Methyl Ether Solution 4 5 Adhesive solution. On a 25 μm thick PET film, it looks like u μηι after drying. The cloth was dried at 120 ° C for 2 minutes. The obtained B-stage adhesive was attached to the PET film and separated by a width of 26 mm. The above B (^ 丨 adhesive was attached to the pet film and the center of the polyimide film with a width of 35 mm. Adhesion, pressing at 90 ° C, 1 kg / cm2 pressure. Detach pET film, copper box (Mitsui metal, thickness VLP18 μm) with a roll adhesion method and the surface of the polyimide film of the pET film (Taf β tape without etching method). The bonding temperature is 120 C, and the pressure is 2 kg / cm2. The above copper-bonded composite product is 50 C for 3 hours, 30 ° C for 3 hours, 12 0.03 hours, 14 ( After heating at TC for 3 hours and 160 ° C for 4 hours, it is slowly cooled to harden the adhesive. The resulting tape is referred to as a "copper adhesive tape". After the adhesive is hardened, the copper box is completely removed according to the etching method. The resulting ▼ is used as "Bronze full surname carving method." O: \ 87 \ 87969-940216.DOC -30- 1243186 [Measurement of Bending Amount] The value of the bending amount is a TAB tape made in the above order and cut to a length of 40 mm X width 35 mm square The test piece was placed in a room with a relative humidity of 60% and a temperature of 23 ° C for 72, and then it was allowed to stand on a flat surface. Measure the height of the four corners. The value of the amount of bending is expressed as the average of 4 pieces of data. [Example 1] 4,7.5'-oxygen was dissolved in 407.5 g of N, N-dimethylformamide (DMF). 21.98 g of diphenylamine (ODA) and 7.91 g of p-phenylenediamine dissolution (PDA). Keep the solution at 0 ° C. Here, 29.47 g of 3,3 ', 4,4L benzophenonetetracarboxylic dianhydride (BTDA) was added slowly, and the mixture was stirred for 1 hour to completely dissolve the BTDA. To this solution was slowly added 25.15 g of p-phenylene bis (trimellitic acid monoester anhydride) (TMHQ), and after stirring for 1 hour, 7.98 g of pyromellitic dianhydride (PMDA) was added and stirred for 1 hour to obtain The solution at 23 ° C has a viscosity of 3000 poise and a solid concentration of 18.5% by weight. The mol% of the monomer component added at this time is shown in Table 1. In addition, in Table 1 and Table 3 described later, the monomer composition is described from the top stage to the next stage in the order of adding monomers. 100 g of the polyamic acid solution was mixed and stirred to contain 11.4 g of anhydrous acetic acid, 4.8 g of isoquinine, and 33.8 g of DMF as a hardener. The obtained solution was degassed by centrifugation, and then cast and coated on an aluminum foil. From stirring to degassing, cooling was performed simultaneously to 0 ° C. The laminated body of the aluminum foil and the polyamic acid solution was heated at 90 ° C for 600 seconds to obtain a self-supporting gel tape. The gel tape was detached from the aluminum foil and fixed to the frame. The gel strip was heated at 120 ° C, 250 ° C, 350 ° C, 450 ° C for 180 seconds each, and then heated in a far-infrared oven at 400 ° C for 180 seconds. Using this method, a 50 μm thick Polyurethane O: \ 87 \ 87969-940216.DOC -31-1243186 amine film was used to make a TAB tape according to the method described above. The elastic modulus, average linear expansion coefficient, hygroscopic expansion coefficient, and bending amount of the TAB tape of the polyimide film measured for the "copper tape" and "copper fully etched tape". The measurement results are shown in Table 2. [Example 2] 〇] 7.5 407.5 8 dissolves 00 八 17.9 008 and? 0-89.678, keep the solution at 0 ° C. Here, 28.81 g of BTDA was slowly added and stirred for 1 hour to completely dissolve the BTDA. To this solution was slowly added 24.59 g of TMHQ, and after stirring for 1 hour, 11.52 g of BTDA was added and stirred for 1 hour to obtain a polyamic acid solution having a solution viscosity of 2800 poise and a solid content concentration of 18.5 wt% at 23 ° C. The mol% of the monomer component added at this time is shown in Table 1. In addition, the mol% of BTDA in Table 1 is 50 and 20, which represent the amount of BPDA added initially and BPDA added later. A polyimide film and a TAB tape having a thickness of 50 µm were obtained in the same manner as in Example 1 except that the polyamic acid solution was used. The properties of the polyimide film and TAB tape are shown in Table 2. [Example 3] Dissolve 17.90 g of ODA and 9.67 g of PDA in 407.5 g of DMF, and keep the solution at 0 ° C. Here, 8.61 g of BTDA 3 was slowly added and stirred for 1 hour to completely dissolve the BTDA. To this solution, slowly add 24.59 g of TMHQ, and after stirring for 1 hour, add 1.73 g of BTDA and stir for 1 hour to obtain a polyamic acid solution with a viscosity of 3 10,000 poise and a solid concentration of 18.5 wt% at 23 ° C. . The mol% of the monomer component added at this time is shown in Table 1. Furthermore, the mol% of BTDA in Table 1 is 50 and 20, which represent the amount of BPDA added at the beginning of O: \ 87 \ 87969-9402t6.DOC -32-1243186 added afterwards. A polyimide film and a TAB tape having a thickness of 50 µm were obtained in the same manner as in Example 1 except that the polyamic acid solution was used. The properties of the polyimide film and TAB tape are shown in Table 2. [Example 4] 19.86 g of ODA and 8.77 g of PDA were dissolved in 407.5 g of DMF, and the solution was kept at 0 ° C. Here, 29.04 g of BTDA was slowly added and stirred for 1 hour to completely dissolve the BTDA. 28.92 g of TMHQ was slowly added to the solution, and after stirring for 1 hour, 5.90 g of PMDA was added, and the mixture was stirred for 1 hour to obtain a polyamic acid solution having a solution viscosity of 2900 poise and a solid content concentration of 18.5 wt% at 23 ° C. The mol% of the monomer component added at this time is shown in Table 1. A polyimide film and a TAB tape having a thickness of 50 µm were obtained in the same manner as in Example 1 except that the polyamic acid solution was used. The properties of the polyimide film and TAB tape are shown in Table 2. [Example 5] Dissolve 18.66 g of ODA and 10.07 g of PDA in 407.5 g of DMF, and keep the solution at 0 ° C. Here, 0.02 g of BTDA 3 was slowly added and stirred for 1 hour to completely dissolve the BTDA. 25.62 g of TMHQ was slowly added to the solution, and after stirring for 1 hour, 8.13 g of PMDA was added and stirred for 1 hour to obtain a polyamic acid solution having a viscosity of 3200 poise at 23 ° C and a solid content concentration of 18.5 wt%. The mol% of the monomer component added at this time is shown in Table 1. A polyimide film and a TAB tape having a thickness of 50 μm were obtained in the same manner as in Example 1 except that the polyamic acid solution was used. The properties of the polyimide film and TAB tape are shown in Table 2. O: \ 87 \ 87969-940216.DOC -33-1243186 [Example 6] Dissolve ODA 22.92 g and PDA 8.25 g in DMF 407.5 g, and keep the solution at 0 ° C. Here, 18.44 g of BTDA was slowly added and stirred for 1 hour to completely dissolve the BTDA. To this solution was slowly added 26.23 g of TMHQ, and after stirring for 1 hour, 16.65 g of PMDA was added and stirred for 1 hour to obtain a polyamic acid solution having a viscosity of 3000 poise and a solid content concentration of 18.5% by weight at 23 ° C. The monomer component mo 1 added at this time was 1 ° /. Shown in Table 1. A polyimide film and a TAB tape having a thickness of 50 μm were obtained in the same manner as in Example 1 except that the polyamic acid solution was used. The properties of the polyimide film and TAB tape are shown in Table 2. [Example 7] In DMF 407.5 g, 25.13 g of ODA and 7.31 g of PDA were dissolved, and the solution was kept at 0 ° C. Here, 12.44 g of BTDA was slowly added and stirred for 1 hour to completely dissolve the BTDA. To this solution was slowly added 26.55 g of TMHQ, and after stirring for 1 hour, 21.06 g of PMDA was added and stirred for 1 hour to obtain a polyamic acid solution having a viscosity of 3000 poise in 23 ^: and a solid content concentration of 18.5 wt%. The mol% of the monomer component added at this time is shown in Table 1. A polyimide film and a TAB tape having a thickness of 50 µm were obtained in the same manner as in Example 1 except that the polyamic acid solution was used. The properties of the polyimide film and TAB tape are shown in Table 2. [Example 8] Dissolve 18.86 g of ODA and 10.19 g of PDA in 407.5 g of DMF, and keep the solution at 0 ° C. Here, 11.09 g of 3,3f, 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was slowly added and stirred for 1 hour to completely dissolve the BPDA. In this solution, O: \ 87 \ 87969-940216.DOC -34-1243186 was added with BTDA 18.22 g, and after stirring for 1 hour, TMHQ 25.91 g was added, stirred for 1 hour, and then PMDA 8.22 g was added. The solution has a viscosity of 2700 poise and a solid concentration of 18.5% by weight. The mol% of the monomer component added at this time is shown in Table 1. A polyimide film and a TAB tape having a thickness of 50 µm were obtained in the same manner as in Example 1 except that the polyamic acid solution was used. The properties of the polyimide film and TAB tape are shown in Table 2. [Comparative Example 1] Dissolve 21.48 g of ODA and 11.06 g of PDA in 407.5 g of DMF, and keep the solution at 0 ° C. Here, 31.56 g of BPDA was slowly added and stirred for 2 hours to completely dissolve the BPDA. 14.04 g of PMDA was slowly added to the solution, and after stirring for 1 hour, 13.83 g of BTDA was added and stirred for 1 hour to obtain a polyamic acid solution having a solution viscosity of 2800 poise and a solid content concentration of 18.5 wt% at 23 ° C. The mol% of the monomer component added at this time is shown in Table 3. A polyimide film and a TAB tape having a thickness of 50 µm were obtained in the same manner as in Example 1 except that the polyamic acid solution was used. The characteristics of the polyimide film and TAB tape are shown in Table 4. [Comparative Example 2] Dissolve 19.20 g of ODA and 10.37 g of PDA in 407.5 g of DMF, and keep the solution at 0 ° C. Here, slowly add 28.21 g of BPDA, for example, stir for 2 hours to completely dissolve the BPDA. To this solution, TMHQ 26.3 6 g was slowly added, and after stirring for 1 hour, 8.36 g of PMDA was added, and the mixture was stirred for 1 hour to obtain a polyamic acid solution having a solution viscosity of 2800 poise and a solid content concentration of 18.5% by weight at 23 ° C. The mol% of the monomer component added at this time is shown in Table 3. 〇: \ 87 \ 87969-940216. DOC -35-1243186 The polyimide film and TAB tape having a thickness of 50 µm were obtained in the same manner as in Example 1 except that this polyamic acid solution was used. The characteristics of the polyimide film and TAB tape are shown in Table 4. [Comparative Example 3] 19.92 g of ODA was dissolved in 407.5 g of DMF, and the solution was kept at 0 ° C. Here, 16.49 g of PMDA was slowly added and stirred for 1 hour to completely dissolve the PMDA. After dissolving 10.76 g of PDA in this solution, slowly add 17.57 g of BPDA and stir for 2 hours to completely dissolve BPDA. Furthermore, slowly add 26.45 g of TMHQ, stir for 1 hour, and then add 1.30 g of PMDA, and stir for 1 hour to obtain a polyamic acid with a viscosity of 3 100 poise at 23 ° C and a solid concentration of 18.5 wt% Solution. The mol% of the monomer component added at this time is shown in Table 3. And, the mol% of PMDA in Table 3 is 50 and 20, which represent the amount of PMDA added initially and BPDA added later. A polyimide film and a TAB tape having a thickness of 50 µm were obtained in the same manner as in Example 1 except that the polyamic acid solution was used. The characteristics of the polyimide film and TAB tape are shown in Table 4. [Comparative Example 4] 0.21 g of ODA3 and 5.15 g of PDA were dissolved in 407.5 g of DMF, and the solution was kept at 0 ° C. Here, TMHQ 26.39 g was slowly added, and after stirring for 1 hour, PMDA 3 0.75 g was added, and the mixture was stirred for 1 hour to obtain a polyamic acid solution having a solution viscosity of 2900 poise and a solid content concentration of 18.5 wt% at 23 ° C. . The mol% of the monomer component added at this time is shown in Table 3. A polyimide film and a TAB tape having a thickness of 50 µm were obtained in the same manner as in Example 1 except that the polyamic acid solution was used. The characteristics of polyimide film and TAB tape are shown in Table 4: O: \ 87 \ 87969-940216.DOC -36-1243186. [Comparative Example 5] 44.27 g of ODA was dissolved in 407.5 g of DMF, and the solution was kept at 0 ° C. Here, 48.23 g of PMDA was slowly added and stirred for 2 hours to completely dissolve the PMDA to obtain a polyamic acid solution having a viscosity of 2800 poise and a solid content concentration of 18.5% by weight in a solution at 23 ° C. The mol% of the monomer component added at this time is shown in Table 3. A polyimide film and a TAB tape having a thickness of 50 µm were obtained in the same manner as in Example 1 except that the polyamic acid solution was used. The characteristics of the polyimide film and TAB tape are shown in Table 4. [Comparative Example 6] Dissolve 24.87 g of ODA and 13.43 g of PDA in 407.5 g of DMF, and keep the solution at 0 ° C. Here, 54.19 g of PMDA was slowly added and stirred for 2 hours to completely dissolve the PMDA to obtain a polyamic acid solution having a viscosity of 2900 poise and a solid content concentration of 18.5 wt% in 231. The mol% of the monomer component added at this time is shown in Table 3. A polyimide film and a TAB tape having a thickness of 50 µm were obtained in the same manner as in Example 1 except that the polyamic acid solution was used. The characteristics of the polyimide film and TAB tape are shown in Table 4. [Comparative Example 7] Dissolve 26.19 g of ODA and 14.14 g of PDA in 489 g of DMF, and keep the solution at 0 ° C. At this point, 42.14 g of BTDA was slowly added, and after stirring for 1 hour, 28.53 g of PMDA was added slowly, and stirred for 2 hours to completely dissolve PMDA. The solution viscosity at 3,000 poise at 23 ° C and a solid concentration of 18.5 wt. % 〇: \ 87 \ 87969-940216.DOC -37-1243186 Polyamine solution. The mol% of the monomer component added at this time is shown in Table 3. A polyimide film and a TAB tape having a thickness of 50 µm were obtained in the same manner as in Example 1 except that the polyamic acid solution was used. The characteristics of the polyimide film and TAB tape are shown in Table 4. [Comparative Example 8] It is disclosed in the aforementioned Japanese Patent Application Publication No. 9-235373. The use of 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride as the acid component is the same as in Example 11. It is composed of monomers to obtain polyamic acid. The added weight of each monomer is 5.93 g of PPD, 11.64 g of PMDA, 2.97 g of ODA 3, 17.68 g of BTDA, and 24.28 g of PMDA. 〇The thickness of 50 μm was obtained in the same manner as in Example 1 except that the polyamic acid solution was used. When measuring the coefficient of hygroscopic expansion of a polyimide film, it is 18 ppm, which is a very large value. Therefore, the technique described in the above publication has not achieved a reduction in the coefficient of hygroscopic expansion. O: \ 87 \ 87969-940216.DOC 38-1243186 [Table 1] Example monomer composition (mol%) ODA PDA TMHQ BTDA PMDA BPDA 1 60 40 30 50 20 2 50 50 30 50 20 3 50 50 30 67 3 4 55 45 35 50 15 5 50 50 30 50 20 6 60 40 30 30 40 7 65 35 30 20 50 8 60 50 30 30 20 20 O: \ 87 \ 87969-940216.DOC -39- 1243186

The average linear expansion coefficient of the imine film from 100 ° C to 20 ° t is 18 ppm / t: above, 28 ppm / ° C; the elastic modulus is above 4.5 GPa; and the coefficient of hygroscopic expansion is below 13 ppm 'As the polyimide film of the present invention, it has excellent physical properties. In addition, the bending amount in the "attached copper strip" is all below -0.5 mm, and the bending amount in "full etching" is all below 2.0 mm. It shows that it can be solved in the processing and packaging steps. Discomfort from bending. O: \ 87 \ 87969-940216.DOC -40-1243186 [Table 3] Comparative Example Monomer Composition (mol%) ODA PDA TMHQ BTDA PMDA BPDA 1 50 50 20 30 50 2 50 50 30 20 50 3 50 50 29 38 3 30 4 76 24 29 71 5 100 100 6 50 50 100 7 50 50 50 50 [Table 4] Comparative Example Gel Modulus CTE CHE Bend, mm Volatile GPa ppm ppm Full Copper Etching 1 40 5.6 19 14 1.0 1.7 2 55 Film melted during calcination 3 52 Film bubbled during calcination 4 52 4.3 25 10 -2.5 2.4 5 47 3.1 32 12 -3.2 4.5 6 50 5.7 13 15 -2.7 1.6 7 50 5.7 13 15 -2.7 1.6 In this regard, as shown in Table 4, the average linear expansion coefficient, elastic modulus, and hygroscopic expansion coefficient of the polyfluorene imine film evaluated at 100 ° C to 200 ° C were produced in Comparative Examples 1 to 7. One of them does not satisfy the conditions (1) to (3) above. O: \ 87 \ 87969-940216.DOC -41-1243186 Compared with the polyimide film of the present invention, the physical properties are obviously inferior. In addition, the amount of bending in "copper tape" is in a comparative example! , 4, and 7 are 5 or more, and the bending amount in "full etching" is 3111111 or more in Comparative Example 6. Compared with the polyimide film of the present invention, the physical properties are poor. As for the polyimide film of the present invention, as described above, a polyimide film obtained from a polyimide acid synthesized from an aromatic diamine and an aromatic tetracarboxylic dianhydride is mainly used as the aromatic tetracarboxylic acid. The dianhydride system contains 3,3,4,4, _benzophenonetetracarboxylic acid dianhydride, while the average linear expansion coefficient in RC is 18 ppm / t: above, 28 ppm / t: below; one with a modulus of elasticity of 4 5 or more and a coefficient of hygroscopic expansion of 13 ppm or less. Thus, it has both a coefficient of linear expansion and a modulus of elasticity that prevent bending and curling from occurring. Provides a polyimide film that does not undergo bending and curling due to dimensional changes due to moisture absorption. Therefore, it can prevent defective packaging during the processing steps of FPC and TAB tapes used in various electronic devices The so-called effect of the cause of bending and curling works. Therefore, the present invention is not only the chemical industry and resin industry for manufacturing polyimide film, the electronic component industry using FPC and TAB tape, etc., but also the electrical, Electronic equipment industry can also be used appropriately. The specific implementation form or embodiment made in the item of the detailed description 'Although the technical content of the present invention is clear, it should not be limited to these specific examples and should be interpreted narrowly. Within the scope of the patent, it can be changed and implemented by diversity. O: \ 87 \ 87969-940216.DOC -42-

Claims (1)

1243186 Fanyuan Garden: A polyimide film, which is mainly obtained by using polyamino acid synthesized from aromatic diamine and aromatic quaternary acid dianhydride. The average value at 100 ~ 200 ° c The linear expansion coefficient is ^ ~ ", the elastic modulus is 4.5 GPa or more, and the hygroscopic expansion coefficient is 13 ppm or less. As the aromatic tetracarboxylic dianhydride, 3,3,, 4,4, _dibenzene is used. Formic acid tetracarboxylic dianhydride is an essential component. 2. The polyimide film according to item 1 of the scope of patent application, in which the total aromatic tetracarboxylic monoanhydride component is set to 100 m0 / 0, Use 3,3,4,4'-Dibenzoyl-tetraweilic acid diliver in the range of 20 to 60. 3. The polyimide film according to item 2 of the patent application, wherein aromatics are further used. Sg acid mono-gf is used as the above-mentioned aromatic tetramethylene acid two-field component. 4. The polyimide film according to item 3 of the patent application scope, wherein when the wholly aromatic tetracarboxylic dianhydride component is set to 1000 m01 %, The above-mentioned aromatic ester acid dianhydride in the range of 10 to 60 is used. 5. The polyimide film according to item 3 of the patent application, wherein (Trimellitic acid monoester anhydride) as the above-mentioned aromatic ester acid dianhydride. 6. The polyimide film according to item 丨 of the application, wherein at least one linear diamine and flexible diamine are used as each. The above aromatic diamine component is the polyimide film according to item 6 of the patent application, wherein when the total aromatic diamine component is set to 100 mol%, each is used at 20 to 8 The above-mentioned linear diamine and flexible diamine in the range of 〇 and in one or more ranges of 80 to 20 mol%. O: \ 87 \ 87969-940216.DOC 1243186 imine film, in which terephthalic acid 8 · For example, the polyamine in the scope of the application for the patent No. 6 is used as the above-mentioned linear diamine. 9 · The polyaniline in the scope of the patent application for the No. 6 is used as the above-mentioned flexible diamine. The imine film, which uses 4,4,- Oxygen carbamide 0 10 · As for the polyimide film of scope 6 of the patent application Imine molecule. The step of obtaining a polyamino acid solution accordingly, b) casting the imine film of the film-forming paste containing the polyamino acid solution on a support, the card linear manufacturing method described above, including at least: Amine and aromatic tetracarboxylic dianhydride reverse steps, c) the step of detaching the gel film from the support after heating the film-forming glue on the support, d) heating the weight film to make the remaining amidine A step of imidizing and drying the acid, and using 3,3 ', 4,4, benzophenone tetracarboxylic dianhydride and an aromatic ester acid dianhydride as the aromatic tetracarboxylic dianhydride, When the total aromatic tetracarboxylic dianhydride component is set to 100 mol%, 3,3 », 4,4'-benzophenone tetracarboxylic dianhydride in the range of 20-60 m% is used. Aromatic ester dianhydride in the range of 10-60 mol%. 12. The method for producing a polyimide film according to item u of the application, wherein p-phenylene bis (trimellitic acid monoester anhydride) is used as the aromatic ester acid dianhydride. 13. A method for manufacturing a polyimide film according to item u of the application, wherein O: \ 87 \ 87969-940216.DOC-2-1243186 uses at least one of linear diamine and flexible diamine, respectively. The aromatic diamine component. 14. The method for manufacturing a polyimide film according to item 13 of the scope of the patent of claim 4, wherein when the composition of Wangyao Fangya Monoamine is set to 100%, use each of 20 ~ 80m. The above-mentioned linear diamine and flexible diamine in the range of 1% and in the range of 80 to 20 mol%. 15. A method for manufacturing a polyimide film as described in item u of the Shenqing patent, wherein at least a dehydrating agent and an imidization catalyst are used in combination. 16. · A type of FC tape, which is formed by providing an adhesive layer and a protective layer on a polyimide film, wherein the polyimide film is obtained by subjecting a polyimide to a polyimide It is made of polyimide, and the S component and the diamine component as the raw material of the polyamic acid are the aromatic tetracarboxylic acid component and the aromatic two The amine component, in addition, the aromatic tetracarboxylic acid used as the raw material of the polyamic acid is a knife, and at least benzophenone tetracarboxylic dianhydride is used as an essential component. The average linear expansion coefficient at 200 times is 18 ~ 28 卯 111, the hygroscopic expansion coefficient is 13 卯 111 or less, and the elastic modulus is 4.5 GPa or more. 1 ·· A flexible printed circuit board comprising at least a layer composed of a polyimide film and a metal conductive layer. The polyimide film is obtained by subjecting a polyimide to a polyimide. Those obtained from polyimide, and the acid component and diamine component of the raw material of polyamidic acid, respectively, use an aromatic tetracarboxylic acid component and an aromatic diamine component containing an aromatic ring structure in the structure. , O: \ 87 \ 87969-940216.DOC -3- 1243186 In addition, as the aromatic tetracarboxylic acid component in the raw material of the above polyamic acid, at least 3,3,4,4, -dibenzene is used. Methyl ketone tetracarboxylic dianhydride is an essential component. The average linear expansion coefficient of the polyimide film at 100 to 20 (rc is 18 to 28 Ppm, the coefficient of hygroscopic expansion is less than or equal to, and the elastic modulus is 4.5. GPa or higher. O: \ 87 \ 87969-940216.DOC 4-