TW200948862A - Polyester-imide precursor and polyester-imide - Google Patents

Abstract

A polyester-imide precursor characterized by having repeating units represented by the following formula (1). (In the formula (1), Ar is the tetravalent aromatic group represented by the formula (2) and B1 is an ester structure having a specific structure.)

Description

。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 48 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯Polyimine is widely used in FPC (Flexible Printed Circuit) because it has excellent heat and chemical resistance, radiation resistance, electrical insulation, and excellent mechanical properties. In various electronic devices such as a substrate, a substrate for TAB (Tape Automated Bonding), a protective film for a semiconductor element, and an interlayer insulating film for an integrated circuit. Further, in addition to these properties, polyimine has an increase in the importance of the production method and extremely high film purity. As electronic devices tend to be lighter and shorter, the characteristics of the poly-imine are also stricter year after year. "Therefore, the industry is looking for a solder heat resistance that is not only 0, but also meets the thermal cycle of the polyimide film. A multifunctional versatile polyimide material having a plurality of properties such as dimensional stability, transparency, adhesion strength to a metal substrate, moldability, and fine workability such as through-hole. In recent years, the demand for polyimine as an FPC substrate has rapidly increased. The steel foil laminated sheets of the original FPC and the F::CL (Flexible Copper Clad Laminate 'soft copper foil substrate) are mainly classified into three types. In other words, a three-layer type in which a polyimide layer (hereinafter also referred to as "polyimine film") and a copper foil are attached by an epoxy-based adhesive or the like is known, and 2) is in the direction of 134489. Doc 200948862 Copper foil coated with polyimide solution, dried or coated with polyimide precursor solution, dried, yttrium imidized, or formed by copper ore and sputtered to form copper on the polyimide layer The layer has no adhesive 2 layer type, and 3) a thermoplastic polyimide is used as the pseudo 2-layer type of the adhesive layer. If the polyimine layer is required to have a high dimensional stability, it is advantageous to use a two-layer FCCL without an adhesive. The size of the polyienimine as an FPC substrate is caused by exposure to various thermal cycles in the encapsulation step. In order to suppress this phenomenon as much as possible, it is preferred that the glass transition temperature (Tg) of the polyimide is higher than the step temperature, and further, the linear thermal expansion coefficient of the polyimine at a glass transition temperature is as low as possible and the polyimine Matches the coefficient of thermal expansion of the metal foil. As described below, it is also important to control the linear thermal expansion coefficient of the polyimide layer in terms of reducing the residual stress generated in the 2-layer FCCL manufacturing step. Further, from the viewpoint of safety, the industry has hoped to develop a highly flame-retardant polyimine for use in an FPC substrate. Since most of the polyimine is insoluble in an organic solvent and does not melt even above the glass transition temperature, it is generally not easy to form the polyimine itself. Therefore, 'polyimine is usually an aromatic tetracarboxylic dianhydride such as equimolar pyromellitic dianhydride (PMDA) and an aromatic diamine such as 4,4,-diaminodiphenyl (ODA). Reacting in an aprotic polar organic solvent such as dimercaptoacetamide (DMAc), preliminarily polymerizing a solution of a high degree of polymerization of a polyamidene precursor, and then applying the solution of the polyimide precursor to the metal foil For example, on steel shovel, at 2501:~40 (heating under TC for dehydration ring closure (醯imination), 臈 臈 134489.doc 200948862 Residual stress is caused by yttrium imidization at high temperature, making metal / The polyimide polyimide laminate is produced during the process of cooling to room temperature, which often causes serious problems such as FCCL cracking. X, in the case of using the brewing solution, 'in the drying-cooling step, It also causes residual stress problems when using a polyimide precursor solution. As a measure to reduce residual stress, an effective method is to reduce the linear thermal expansion coefficient of the polyaniline itself as an insulating film. The linear thermal expansion coefficient of ruthenium is 40 ppm/t~1〇 In the range of ppm/t, which is much larger than the linear thermal expansion coefficient of metal foil such as copper foil of 17 ppm/〇c, the industry is investigating the development of linear thermal expansion coefficient close to the value of copper foil showing linear thermal expansion of about 20 ppm/°C or less. Copolyimine of the coefficient. At present, as a practical polyimine material, a polyimine formed from 3,3,4,4,4-biphenyltetracarboxylic dianhydride and p-phenylenediamine is well known. The polyimine film also exhibits a very low linear thermal expansion coefficient of 5 ppm/° C. to 10 ppm/° C. depending on the film thickness or the production conditions, but does not exhibit a low hygroscopic expansion coefficient (see Non-Patent Document 1). Polyimine is required to have dimensional stability not only for thermal cycling but also dimensional stability for moisture absorption. Previous polybenzamine also absorbs 2% by mass to 3% by mass of water. The resulting circuit position shift occurs at the same time, which is a serious problem for high-density wiring or multilayer wiring. Due to the decrease in electrical characteristics, it causes rosin (Corrosion) on the polyimide/conductor interface. Ion migration, insulation damage, etc. are more stringent Therefore, the hygroscopic expansion coefficient of the polyimide layer as the insulating film is required to be as low as possible. 134489.doc 200948862 In order to achieve a low hygroscopic expansion coefficient, for example, the report is expressed by the formula (20). The polyester bismuth imino group having an acid dianhydride having a vinegar structure is effective (see Patent Document 1): [Chemical Formula 1]

<20) 0 ❹ However, it is generally considered that a polyester quinone imine prepared by using the formula (20) as an acid dianhydride and using the formula (21) to the formula (23) as a diamine in order to achieve a low moisture absorption coefficient is considered. Since the film has a highly curved structure, the film has not only a high coefficient of thermal expansion but also a polyester phthalimide film composed of these combinations as a flammable film: [Chemical 2]

[化3] ❹

(2 2) [Chemical 4]

(23) Here, if a diamine having a rigid structure such as formula (24) is used as the diamine, it has a low coefficient of thermal expansion, but has a high elasticity due to its rigidity, and is therefore not suitable for the requirement. For the use of low repellency, it is presumed that the adhesion (peeling strength with metal foil) will decrease: [Chem. 5] W (24). Therefore, a polyester phthalimide using an acid dianhydride represented by the formula (19) (hereinafter referred to as TABP) has been reported (refer to Patent Document 2): [Chemical Formula 6] ❹ ❹

(19) 聚 The polyacetamide obtained by using the diamine and the acid dianhydride disclosed in Patent Document 2 simultaneously exhibits a low coefficient of thermal expansion and a low water absorption (1.2% to 1.9%). However, it is generally considered that a polyesterimine film having a water absorption of 12% is difficult to satisfy the requirement of a low hygroscopic expansion coefficient (below 8 ppm/% RH, 3 〇〇/0 RH to 70% RH). Further, in the processing step of the FPC substrate composed of the thin film polyimide film, in order to avoid a decrease in yield due to cracking of the polyimide film, the polyimide film is required to have high tear strength, but The above documents do not disclose the tear strength. Further, it is considered that the composition of the polyester phthalimide described above cannot achieve high tear strength. Further, it is generally considered that the glass transition temperature is also low due to the use of a bending molecule such as the formula (21) or the formula (25): [Chem. 7] 134489.doc (21) • 10- 200948862 [Chem. 8] In the aspect, a compound having an ester structure in a diamine is also reported. Polyacetal imine (see Patent Document 3). However, it is still considered that this situation is also incapable of obtaining high tear strength as described above. Also, it is also possible to generate anomalies caused by the use of TABP. A general method for producing an acid dianhydride having an ester structure is known as a method for reacting diol or toluene to dimethyl alcohol (trime(1) tic anhydride chloride) with a diol (Patent Document 4), or a phenol. The vinegar exchange reaction of the lower alkanoate with trimellitic anhydride (Patent Document 5); the crude crystal of TABP can be obtained by these methods. However, if the obtained crude crystal is used to copolymerize with an aromatic monoamine, a part of the obtained polyimine precursor solution may be gelated, and if the polyimine precursor solution is used to prepare a poly In the case of the quinone imine film, there is a possibility that the mechanical properties of the polyimide film are significantly lowered. In this way, it is difficult to obtain a low linear thermal expansion coefficient, a high flame retardancy, and a low hygroscopic expansion coefficient (8 ppm/% RH or less) equivalent to copper drop in the state of maintaining polymerization reactivity or film forming workability. , 3〇% RH7〇% RH), flexibility, solder heat resistance, high glass transition temperature, high adhesion, low modulus of elasticity and high tear strength of the brewed imine, so far no known to meet this Practical materials that require characteristics. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 4] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei 7-41472 (Non-Patent Document 1) Macr〇molecules, 29,7897 (1996) [Summary of the Invention] [Problems to be Solved by the Invention] The present invention has been completed in view of the above problems, and an object of the present invention is to provide a low-line thermal expansion coefficient which is high in flame retardancy, low in hygroscopic expansion coefficient, and equivalent to copper foil. High glass transition temperature, high adhesion, low modulus of elasticity, and local tear strength of the polyacetal. [Technical means for solving the problem] The polyester quinone imine precursor of the present invention has a repeating unit represented by the following formula (1): [Chemical 9]

L 8

(1) In the formula (1), Ar is a tetravalent aromatic group represented by the formula (2), and B! is a divalent aromatic group derived from at least one of the formulae (3) to (9): 10]

134489.doc (2) -12· 200948862 [化η] [Chemical 12] ❹ [Chem. 13] [Chem. 14] [Chem. 15] [Chem. 16] 134489.doc (9) 200948862 [Chem. 17]

A represents a carbon number of 1 to 6 and a base of a carbon number of 6 represents a carbon number of 6 and a hydrogen atom. The distance is independently independent, and may be the same or different; &amp; represents an alkyl group having a carbon number of 1 to 6, r6~ R4 represents an alkyl group of a carbon number of 6, and a hydrogen atom). ❹

In the poly(tetra)imine precursor of the present invention, the B1 in the formula (1) in the poly(tetra)imine precursor is preferably a repeating unit represented by the formula (3) or the formula (4), and further preferably (4) The repeating unit represented, in particular, the formula (1〇) in which R 2 to 4 in formula (4) selects a hydrogen atom: [Chem. 18]

(1〇) The polyester-bromide precursor of the present invention, which has a repeating unit represented by the following formulas (11) and (12), and a moie of the formula (n) and the formula (12) The ratio of the formula (11) / formula (12) = 20 / 80 ~ 80 / 20: [Chem. 19]

(Π)

Ar

ύ rH (12) 134489.doc -14- 200948862 (In the formulas (11) and (12), Ar is a tetravalent aromatic group represented by the formula (2); in the formula (12), ugly 2 is selected a divalent aromatic group of at least one of the formula (13) to the formula (17): [Chem. 20] (2) [Chem. 21]

[Chem. 23]

❹ (13) (14) (15)

134489.doc -15- (16) 200948862 [Chem. 25]

(17); R1Q to Ru represent an alkyl group having a carbon number of i to 6 and a hydrogen atom, and these may be independently and may be the same or different). In the polyester quinone imine precursor of the present invention, β2 in the formula (12) in the above polyester quinone imine precursor is preferably represented by the formula (16), the formula (17) or the formula (1)). The repeating unit is further preferably a repeating unit represented by the formula: 6): (18) In the polyester quinone imine precursor of the present invention, the weight average molecular weight Mw is preferably 3 More than 10,000, less than 400,000. In the polyester quinone imine precursor of the present invention, the ester group-containing tetracarboxylic dianhydride represented by the formula (19) used in obtaining the polyester quinone imine precursor is characterized in that a differential scanning is performed. The calorific value of the heat of fusion shown by the calorimeter (DSC) is (a) ° C, and the temperature at which the temperature toward the peak of the melting heat wave and the peak of the peak are kept constant as the intersection of the tangent to the joint point is set to (brc) And when the set temperature is wide, it satisfies (a)g 322 ° C and 5 ° C ·· 134489.doc -16 - 200948862 [化27]

The polyester quinone imine of the present invention is characterized in that it is obtained by imidating the above polyester quinone precursor quinone. The method for producing a polyester quinone imine according to the present invention is characterized in that the polyester acrylonitrile precursor is heated or a dehydrating reagent is used to make an imine oxime to obtain a polyester quinone. The laminated board of the present invention is characterized in that it has a polyester quinone imine layer and a metal layer. The polyacetal layer is composed of the above-mentioned polyacetamide. The laminated board of the present invention is characterized in that it is obtained by applying a polyesterimide precursor to a metal, smelting, drying it, heating it, or imidating the hydrazine using a dehydrating agent. The switchable printed wiring board of the present invention is characterized in that the metal layer of the laminated board is patterned by wiring. [Effect of the Invention] The polyester quinone imine obtained from the polyester quinone imine precursor of the present invention has a high flame retardancy, a low hygroscopic expansion coefficient, a low linear thermal expansion coefficient equivalent to that of a copper foil, and a glass. The effect of transfer temperature, high adhesion, low modulus of elasticity, and high tear strength. [Embodiment] As a molecular design for thermally expanding a polyimine at a low line, it is necessary to make the main chain skeleton linear and rigid as much as possible (it is difficult to obtain various configurations by internal rotation) (conformati〇n) ). However, on the other hand, due to 134489.doc 200948862, there is a entanglement of the polymer chain and the film becomes weak. Further, excessive introduction of a flexible unit such as an ether structure into the polyimine skeleton can contribute to a large improvement in film affinity or an increase in adhesion strength to a metal foil, but it is presumed to hinder low-line thermal expansion characteristics. Performance.

The ester structure of interest in the present invention is more resistant to internal rotation than the ether structure, and the configuration change is relatively more hindered, so that it can be expected to function as a rigid structural unit and also impart polyimine. The main chain provides a flexible film with a degree of softness. Moreover, since the ester structure has a lower polarizability than the guanamine structure or the quinone imine structure, the introduction of the vinegar structure into the polyimine is also advantageous for reducing the hygroscopic expansion coefficient. The aromatic skeleton and the monovalent monomer are introduced into a polyaromatic imine into a specific aromatic skeleton and a (tetra) structure to obtain a polysiloxane having a repeating saponin represented by the following formula (1). Brewed imine precursors. Thereby, the polyacetal imide precursor of the present invention can simultaneously achieve high flame retardancy, low moisture absorption expansion coefficient, low linear thermal expansion coefficient equivalent to copper foil, high glass transition temperature, high adhesion, low modulus of elasticity, And high tear strength: [Chem. 28] 0) .Ύ V _

Bj is a divalent aromatic group selected from = (1) where 'Ar is a tetravalent aromatic represented by the formula (2) and is at least one of the formula (9): 134489.doc (2) 200948862 [Chemical 29 ] [Chem. 30]

[化31]

(3)

(4) [Chem. 32]

(5)

[化33]

(6) [34]

(7) 134489.doc •19- (8) 200948862 [Chem. 35]

[化36]

;Ri represents an alkyl group having 1 to 6 carbon atoms; R2 to R4 represents an alkyl group having 1 to 6 carbon atoms, and an argon φ atom' is independently independent and may be the same or different; R5 represents an alkyl group having 1 to 6 carbon atoms; Base; ruler 6 to rule 9 represents an alkyl group having 1 to 6 carbon atoms and a hydrogen atom. The polyester-bromide precursor of the present invention is produced by using a tetracarboxylic dianhydride monomer containing an ester group and a diamine monomer containing an ester group. It is generally believed that there are four isomers depending on the reaction position of the diamine and the acid dianhydride, but the same product can be obtained from the four isomers after the imidization of the hydrazine. Thus, the obtained polyacetal precursor precursor system has the general formula (1) to indicate. When the polyester quinone imine precursor of the present invention is polymerized, a tetracarboxylic dianhydride (hereinafter referred to as TABP) having an ester structure represented by the formula (19) as a monomer having a vinegar group is used as an essential component. At least one diamine selected from the group consisting of the formulae (26) to (33) is used. &amp; represents an alkyl group having 1 to 6 carbon atoms. ～1 represents an alkyl group having 1 to 6 carbon atoms and a hydrogen atom, and these are independently independent and may be the same or different. R5 represents an alkyl group having 1 to 6 carbon atoms. 〜 represents an alkyl group having a carbon number of 66 and a hydrogen atom. Here, from the viewpoint of low modulus of elasticity and adhesion, it is preferred that the formula (26), the formula (27), and further preferably the formula (27), particularly preferably (33): 134489.doc • 20- (19). 200948862 [化37]

[化38]

[40] (26) (27)

[化43] (28) (29) (30)

( 3 1 134489.doc -21 - 200948862 [化 44] [化 45] (3 2 ) (3 3 ) Ο

Further, from the viewpoint of warpage of the laminated sheet after curing and tear strength of the obtained polyester-imide film, when the polyester quinone imine precursor of the present invention is polymerized, it is preferable to use hydrazine and (33) a diamine having an ester structure (hereinafter referred to as hydrazine) as an essential component, and further using at least one diamine selected from the group consisting of the formula (34) to the formula (39); further preferably Formula (37), formula (38), and formula (39); from the viewpoint of the tear strength of the obtained polyester quinone film, L' is particularly preferable to the formula (37): [Chem. 46]

(34) (35) [Chem. 48]

(36) 134489.doc -22- 200948862 [Chem. 49]

[化 50] [化 51]

Here, R1G to Rls represent an alkyl group having 1 to 6 carbon atoms and a hydrogen atom, and these are independently independent and may be the same or different. It is known that a poly-stained imine film having a linear thermal expansion coefficient equivalent to that of a copper foil generally has a small amount of enchantment after curing, but it has been found that it cannot be judged only by linear thermal expansion coefficient. Warped insight, with copper

The equivalent thermal expansion coefficient of the foil and the smaller amount of warpage are more suitable for the processing steps of the Fpc substrate. Here, 'in order to set the molar ratio to the ratio of the general formula (11) / general formula (12) = 2 〇 / 8 〇 80 80 / 20, TABP and the total diamine are mixed at a ratio of about 1: 丨'To treat the total diamine as 1〇〇m〇l〇/. When using a diamine molar number of 2〇mol%~80 mol% of BPIP, and further using a diamine molar number of 2〇m〇m~8〇mol% selected from the general formula (34) to the general formula (39) At least one diamine having an ester structure. Here, in terms of the linear thermal expansion coefficient, the warpage of the laminated plate after curing, and the tear strength of the obtained film, the molar is preferably a formula 〇1) / 134489.doc • 23· 200948862 The ratio of the formula (12) = 20/80 to 80/20 is more preferably the ratio of the formula (11) / formula (12) = 30/70 to 70/30. Further, in view of the adhesion strength of the polyimine precursor/valley solution of the bismuth molecular weight body having no gel component and the metal/polyimine laminate, the tear strength of the polyimide film, The TABp used as an essential component is preferably a high purity one. Specifically, it is preferable that in the graph of FIG. 1 displayed by the differential scanning calorimeter, the peak temperature of the heat of fusion is (a) C, and the temperature at which the peak toward the melting heat wave starts is used as a connection point. False β sets the temperature at the intersection of the tangent line and the straight line along the substantially straight line portion of the melting heat peak as (b) °c, and satisfies (a) when the set temperature is wide Δ丁=(〇5)_(hook)〇 g 322 C and TABP of ΔΤ$ 5 °C, and further preferably TABP satisfying (a) g 325β (: and ΔΤ$ 4 ° C. The present inventors focused on purifying TABp in order to make TABP high purity. The process 'and found the following. The inventors found that by re-crusting with a specific solvent, "degree, temperature conditions, the effective removal of the mixed enthalpy is represented by the formula (40). 4,4,_bisphenol derivative, or a polymer obtained by a ring-opening reaction of 4,4i_bisphenol and trimellitic anhydride helium represented by the formula (4D), and then dried by anhydrous drying Processing, and removing the adhering water and crystal water of the R-day towel, thereby re-crystallizing a part of the crystallization - 胄 occurs The ring-opened tetracarboxylic anhydride is acidified to obtain a high purity ΤΑΒρ: [Chem. 52] 134489.doc •24- (40) 200948862 [Chem. 53]

- TABP with the increase in purity, the melting heat peak temperature indicated by the differential scanning calorimeter (DSC) moves to the high temperature side, and the melting heat peak temperature is taken as (a) ° C, which will start to rise toward the melting heat peak. The temperature difference between (a) and (b) becomes small when the temperature at the intersection of the line and the line along the line of the melting line of the melting heat peak is assumed to be (b) °C. TABP can be obtained by reacting phthalic anhydride helium with a diol in an organic solvent or transesterifying a lower alkanoate of a phenol with trimellitic acid or an anhydride thereof. The reaction product is recrystallized under specific solvent, concentration, and temperature conditions, and then subjected to anhydrous heating and drying treatment. As a solvent used for recrystallization in order to obtain high-purity TABP, it is preferable to have a cyclic S structure, a solvent, a cyclic fluorene structure or a cyclic carbonate structure or a cyclic sulfone structure. Solvent. For example, α_=methyl-γ-valerolactone, α-methylene_γ-butyrolactone, γ-methylene_丫_丁内· cis-lactone, γ-butyrolactone, cyclopentane Ketone, propylene carbonate, ethylene carbonate: sulfolane. These may be used alone or in combination of two or more. Among these, 'in terms of solubility, recrystallization yield or economy. Preferably, butyrolactone, γ-valerolactone, and cyclobutyl hydrazine are used. The phase: the amount of the mixture used 'If the impurity is removed, the recrystallization yield is taken, 1 part by weight of the product obtained by the reaction, i parts by weight I34489.doc •25·200948862~1〇〇 parts by weight . When the concentration of the solid content of the tetracarboxylic acid containing diester containing the ester group is preferably 20% or less. ～150 parts by weight, particularly preferably 4 parts by weight of the ester group, the concentration of the anhydride in the solution of the tetracarboxylic dianhydride and the solvent is 50% or less as the solid content concentration, and when recrystallization is better from the viewpoint of the yield Mixing the carboxylic acid-containing tetracarboxylic acid anhydride with a specific amount of solvent to achieve the above concentration', and heating the mixed solution to 150 c~30 (TC' to completely dissolve it. Thereafter) by placing the solution To the room

Get the precipitation out of the temperature, and then the precipitation. By this step, the 4 4 bisphenol derivative represented by the formula (40) or the 4′ bis(tetra) represented by the formula (1)” generated by the reaction is opened to cause ring-opening of the trimellitic anhydride gas. The oligomer or the like obtained by the reaction remains in the filtration and liquid towel, whereby it can be removed efficiently: [54] (40)

(41) (here, 'η is 1~5). In an inert gas atmosphere such as nitrogen, helium or argon, at 1 ° C / min to 2 Torr under atmospheric pressure or reduced pressure. The temperature increase rate of 〇/min is carried out at a temperature of 2 ° C to 300 ° C, and the precipitate obtained by filtration is subjected to an anhydrous heat treatment for 3 hours or more to remove the adhered water adhering to the crystal and Crystal water, 134489.doc -26 - 200948862 and a portion of the ring-opening tetracarboxylic acid anhydride formed upon recrystallization. In order to efficiently remove the adhering water and the crystal water adhering to the crystal, it is more preferably maintained at a temperature of 100 C to 130 C for 30 minutes to 1 hour, and then at a temperature of 2 ° C to 300 C for 3 hours. The above anhydrous heating (dehydration ring closure reaction). Further, from the viewpoint of uniformly heating the crystallized material to prevent the crystal from being locally heated to a high temperature to cause a decomposition reaction such as decarboxylation, the temperature increase rate is preferably 2 ° C / min or less. The melting heat peak temperature (a) 〇c & shown by the differential scanning calorimeter (DSC) is the melting point (mp) of the substance, preferably from 325 〇c to 405 from the 325 charge to the high temperature side, When the temperature at which the temperature toward the melting heat wave peak rises is taken as the intersection of the hypothetical tangent to the connecting point and the straight line along the substantially straight portion of the melting heat peak is (b) ° C, the temperature difference between (a) and (b) is Preferably, 5 〇 c, the temperature difference of less than 4 ° C is associated with an increase in the purity of TABP. By satisfying these conditions, polymerization of a high molecular weight, gel-free polyester quinone imine precursor can be carried out. Further, in order to obtain a low hygroscopic expansion coefficient without using a high-priced monomer such as a fluorinated monomer (a monomer containing a fluorine atom), a polyimine having the above characteristics can be produced at low cost. Hereinafter, the embodiments of the present invention will be described in detail, but these are examples of the embodiments of the present invention. The present invention is not limited to the above. In the present invention, a material having physical properties which cannot be obtained by a prior material, that is, a structural property such as rigidity and hydrophobicity of a monomer having an ester structure and having a specific aromatic structure, can be obtained. Adding moderate flexibility, it has high flame retardancy and low moisture absorption coefficient when it is made into laminate of 134489.doc •27· 200948862 and polyester yttrium imide. The low linear thermal expansion coefficient, high glass transition temperature, flexibility, high adhesion, low modulus of elasticity, and high tear strength equivalent to copper foil. &lt;Production Method of Polyester Iridium Imine Precursor&gt; The method for producing the polyester quinone imine precursor of the present invention is not particularly limited, and a known method can be employed. More specifically, it can be obtained by the following method. First, the diamine is dissolved in the reaction solvent, and the tetracarboxylic dianhydride powder is slowly added thereto, using a mechanical stirrer, at 〇»c~1〇〇〇c, preferably 2〇°C~90°C. The stirring is carried out for 0.5 hour to 100 hours, preferably 1 hour to 24 hours. In this case, the monomer concentration is preferably from 5% by mass to 50% by mass, and more preferably from 10% by mass, from the viewpoint of the degree of polymerization and the solubility of the monomer or the polymer to be produced. /. ～40% by mass, particularly preferably 10% by mass to 25% by mass. A polyester quinone imine precursor solution which is uniform and has a high degree of polymerization can be obtained by carrying out polymerization within this monomer concentration range. Here, the obtained polyester phthalimide precursor solution is the same as the polyester oxime imide described in the patent application. The weight average molecular weight (Mw) of the polystyrene film is preferably from 30,000 to 40,000, and more preferably from 30,000 to 300,000. Further, particularly preferably from 50,000 to 20,000. Here, from the viewpoint of toughness, it is preferably 30,000 or more, and more preferably 50,000 or more. Further, from the viewpoint of adhesion and applicability, the weight average knife amount (Mw) is preferably 40,000 or less, and more preferably less than 10,000, and particularly preferably 200,000 or less. As for the aromatic 134489.doc -28- 200948862 tetracarboxylic dianhydride which can be used together with TABp within the range which does not impair the required properties of the polyesterimide film and the polymerization reactivity of the polyester quinone imide. , may be mentioned: 3,3,,4,4,_biphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3,,4,4, -diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, p-phenylene bis(p-trimellitic acid monoester anhydride), p-methylphenylene Bis(trimellitic acid monoester anhydride), 3,3',4,4'-biphenylfluorene tetraphthalic acid dianhydride, 2,2,_bis(3,4-dicarboxyphenyl)hexafluoropropionic acid Monoanhydride, 2,2'-bis(3,4-dicarboxyphenyl)propionic acid dianhydride, naphthalene tetracarboxylic dianhydride, and the like. Further, two or more of these may be used in combination. The aliphatic tetracarboxylic acid monoanhydride which can be used in combination with TABp in a range which does not impair the required properties of the polyester quinone imine film and the polymerization reactivity of the polyester quinone imine precursor is not particularly limited, and examples thereof include a double ring. [2 2·2]octyl-7-ene-2,3,5,6-tetracarboxylic dianhydride, 5-(dioxotetrahydrofuranyl_3_methyl_3·cyclohexene-1,2-dicarboxylate Anhydride, 4-(2,5-dioxatetrahydrofuran-3-yl)-tetrahydronaphthalene-1,2- bis-anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, bicyclo _ 3, 3', 4, 4'-tetradecanoic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetraphthalic acid dianhydride, etc. Two or more of these may be used in combination. As far as the polymerization reactivity of the polyester quin The aromatic diamine used in combination with the diamine having an ester structure represented by the formula (39) is not particularly limited, and examples thereof include p-phenylenediamine, m-phenylenediamine, and 2,4-diaminotoluene. 2,5-Diaminotoluene, 2,4-diaminoxylene, 2,4-diaminotetraphenyl, 4,4,-diamine Methane, 4,4'-fluorenylene bis(2-methylaniline), 4,4,_methylenebis(2-ethylaniline), 4,4'-methylenebis (2,6 -dimercaptoaniline), 4,4,-indenylbis(2,6-diethylaniline), 4,4,-diamine 134489.doc • 29- 200948862 phenyldiphenyl ether, 3,4, -diaminodiphenyl ether, 3,3,-diaminodiphenyl ether, 2,4,-diaminodiphenyl ether, 4,4,-diaminodiphenyl hydrazine, 3,3,-di Aminobiphenyl, 4,4 diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone, 4,4,-diaminophenyl anilide, benzidine, 3,3 ,-dihydroxybenzidine, 3,3,-dimethoxybenzidine, o-toluidine, m-toluidine, 2,2'-bis(trifluoromethyl)benzidine, 1,4-double ( 4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4,-bis (4 -aminophenoxy)biphenyl, bis(4-(3-aminophenoxy)phenyl)anthracene, bis(4-(4-aminophenoxy)phenyl), 2,2- Bis(4-(4-aminophenoxy)phenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4- amine Phenyl) hexafluoropropane, p-terphenyldiamine, etc. Further, two or more of these may be used in combination, and the polymerization reactivity of the polyester quinone imine precursor of the present invention is not significantly impaired. The aliphatic diamine which can be used in combination with the diamine having an ester structure represented by the general formulae (26) to (39) in the range of the desired properties of the polyester quinone is not particularly limited, and examples thereof include, for example, 4,4,_-indenyl bis(cyclohexylamine), isophorone diamine, trans-1,4-diaminocyclohexane, cis-indole-diaminocyclohexane, 1,4 - cyclohexane bis(methylamine), 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)bicyclo[2 21]heptane, 3,8_ bis(aminomethyl)tricyclo[5.2.1.0]decane, hydrazine, % diamine, adamantane, 22_bis(4-aminocyclohexyl)propane, 2,2-bis(4-amine Hexafluoropropane, 1,3-propanol diamine, 1&gt;4_tetramethylenediamine, 1&gt;5_pentamethylenediamine, 1,6-hexamethylenediamine, 17•seven-decyldiamine, 18-octadecyldiamine, anthracene, 9·nonamethylenediamine. Further, two or more of these may be used in combination. 134489.doc -30- 200948862 Ο ❹ As a solvent to be used in the polymerization reaction, there is no problem if the raw material monomer and the produced (IV)-bromide precursor are dissolved, and there is no particular limitation. Ammine amine, hydrazine; = amine solvent such as acetalamine or hydrazine methylpyrrolidone; 丫-butyrolactone, 丫_ 戊内知, δ-valerolactone, γ_hexine Ε-caprolactone, methyl-butane S: a cyclic solvent such as a solvent; a carbonate-based refrigerant such as ethylene carbonate or propylene carbonate; an alcohol solvent such as diethylene glycol; Phenolic solvents such as cresol, p-cresol, 3· chlorophenol, 4- phenol, etc.; acetophenone, anthracene, 3 • dimethyl miso bite _, cyclobutyrate, dimethyl sulphate, and the like. From the viewpoint of solubility, ruthenium, dimethyl dimethyl amide, hydrazine, hydrazine dimethyl ethanoamine, ν_methyl _2 _ _, dimethyl arylene, 1 is preferred. , 3-dimethyl-2" aprotic polar solvent such as mowolinone. Also 'other common organic solvents can be added, butyl acetate, acetic acid, isobutyl acetonate, propylene glycol monomethyl = acid ester, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol methyl ether acetate, ethylene glycol acetate, ethylene glycol butyrate, tetrahydrogen, dimethoxy Ethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl bond, methyl isobutyl hydrazine, diisobutyl butyl, cyclohexyl, methyl ethyl hydrazine, acetone, butanol, Ethanol, xylene, toluene, gas benzene, turpentine, mineral spirits, petroleum essence solvent, etc. The polyacetate imine precursor of the present invention may also be added dropwise to a large amount of water or methanol. It is well-dissolved, filtered, dried, and separated as a powder. &lt;Method for producing polyester quinone imine&gt; 134489.doc • 31 - 200948862 Polyester quinone imine of the present invention It can be produced by subjecting the polyester quinone imine precursor obtained by the above method to a dehydration ring-closure reaction (oxime imidization reaction). At this time, the form of the polyester quinone imide can be used as a film or a metal foil/ a laminate of polyacetal imide, powder, a shaped body and a solution. The polyester phthalimide precursor solution is cast onto a metal pavilion such as copper foil or aluminum crucible in an oven at 40 ° C to 180 ° C, It is preferred to carry out drying at 5 ° C to 150 ° C. The obtained metal/polyimide precursor laminate is adhered to a metal plate made of SUS using a tape, and is inert in a vacuum or a nitrogen atmosphere. Heating in a gas or air at a temperature of from 200 ° C to 430 ° C, preferably from 250 ° C to 400 ° C, thereby obtaining a metal/polyimine laminate. The metal layer of the laminate is # The polyester-imide film of the present invention can be produced by the engraving. Further, there is also a method of obtaining a polyester bismuth imide film by using a metal-plated substrate of a metal ore. The precursor solution is cast onto a substrate on which a metal layer is evaporated, and dried and heated in the above manner to obtain The steamed ore has a metal layer dream/polyester phthalimide layer laminated plate. Thereafter, the metal layer of the laminated body is etched, and the polyester bismuth layer is peeled off from the shixi substrate (polyester yttrium imide film) Therefore, the target object can be obtained. Further, there is a method of obtaining a polyester phthalimide film using a glass substrate. The polyester phthalimide precursor solution is cast onto a glass substrate at 40 ° C in an oven. ~18 (TC is preferably dried at 50 ° c to 15 ° t to obtain a laminate of a glass substrate / polyester phthalimide precursor layer. Thereafter, the polyester bismuth imide precursor is stripped from the laminate. The polyester layer (polyester phthalimide precursor film) was fixed on a metal frame using a tape, and heated by the above method, whereby a polyester phthalimide film was obtained. 134489.doc -32- 200948862 From the viewpoint of the ring closure reaction of the imidization, the reaction temperature is preferably 200 ° C or more, from the viewpoint of the thermal stability of the produced polyester ruthenium film. The reaction temperature is preferably 43 (TC or less. The ruthenium imidization is preferably carried out in a vacuum or in an inert gas, but if the imidization temperature is not excessively high, it can also be carried out in the air. Instead of heat treatment, the ruthenium imidization reaction can also be carried out by adding a tertiary amine such as pyridine or triethylamine to a polyester phthalimide precursor solution to prepare a polyester phthalimide precursor film, one side at 200 The chemical oxime imidization is carried out while heating at a temperature of ° C to 3 00 ° C; or the polyester yttrium imide film is impregnated with a dehydrating reagent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine. Here, a method of producing a polyester phthalimide film from a polyester quinone imine precursor solution will be described, but it is not limited thereto, and it may be heated or used as a dehydrating agent. Heat dried polyester yttrium imide precursor film or separated polyester yam The precursor is subjected to a cyclization reaction or the like to produce a polyester quinone imine. When the polyester quinone imine is insoluble in a solvent, a crystalline polyester quinone imine powder as a precipitate can be obtained. The powder is preferably subjected to heating and compression at 200 ° C to 450 ° C at 25 (TC to 430 ° C), whereby a molded body of polyester quinone imine can be produced. Further, in a polyester phthalimide precursor solution A dehydrating agent such as N,N'-dicyclohexylcarbodiimide or trifluoroacetic anhydride is added and stirred, and the reaction is carried out at a temperature of from 0 ° C to 100 ° C, preferably from 0 ° C to 60 ° C. Thereby, a polyisoimide which is an isomer of polyester quinone imine is produced, and a polyisocyanine solution is formed into a film in the same procedure as above, and is then heated at 250 ° C to 450 ° C. : preferably 134489.doc •33· 200948862 is 27 (TC~40 (heat treatment under TC, which can be easily converted into polyester quinone imine. Iso-imidization reaction, polyester The quinone imine precursor film is impregnated in the above solution containing the dehydrating agent. When the polyacetal is dissolved in the solvent, the poly-bromide is directly The solution may be appropriately diluted with the same solvent and then heated to 15 〇 to 200 ° C, whereby the polyester quinone solution can be easily produced. At this time, the acetaminin is removed for azeotropic distillation. The product may be water or the like, and may be added with toluene or xylene, etc. Further, a base such as γ-mercaptopurine may be added as a catalyst. The obtained polyester phthalimide solution may also be added dropwise to a large amount of water or methanol. Further, the solvent is further filtered to separate the polyester quinone imide as a powder. Further, the polyester quinone imine powder can be redissolved in the solvent to form a polyester quinone imine solution. The imine is obtained by imidating the polyester-bromide precursor of the present invention. Generally, the molecular weight or terminal structure of the resulting polyester quinone imine can be adjusted by adjusting the ratio of the input of the tetracarboxylic dianhydride to the diamine compound in the manufacture. Preferably, the molar ratio of total tetracarboxylic dianhydride to total diamine is 0.90 to 1 · ΐ〇. The terminal structure of the obtained polyester quinone is an amine or anhydride structure depending on the molar ratio of total tetradecanoic dianhydride to total diamine at the time of production. In the case where the terminal structure is an amine, the carboxylic acid anhydride can be used for terminal sealing. As such examples, phthalic anhydride, 4-phenylene o-formic acid if, 4-phenoxy phthalic acid, 4, phenyl phenyl phthalic anhydride, 4- Phenylsulfonyl phthalic anhydride or the like, but is not limited thereto. These carboxylic anhydrides may be used singly or in combination of two or more. 134489.doc -34- 200948862 Further, in the case where the terminal structure is an acid anhydride, a monoamine can be used for terminal sealing. Specific examples thereof include aniline, indolediamine, amine hydrazine, aminobiphenyl, aminodiphenyl ketone, and naphthylamine. These monoamines may be used singly or in combination of two or more. The addition polymerization conditions can be carried out in accordance with the addition polymerization conditions of the previously performed polyamic acid. Specifically, the aromatic diamine is first dissolved in a solvent at 0 ° C to 80 ° C under an inert atmosphere such as nitrogen, helium or argon. 〇~1〇〇. The tetracarboxylic acid dianhydride was rapidly added to the underside to carry out addition polymerization for 4 hours to 8 hours. Thereby, the polyester quinone imine precursor 0 is obtained. The polyester bis-imine solution is applied to the substrate at 4 (TC to 400. (: preferably 10 (TC~30 (drying under TC) A polyester bismuth imide film can also be formed. The polyester bismuth imide precursor solution is applied onto a metal foil such as copper ruthenium and dried, and then yttrium imidized under the above conditions, whereby the original plate of the FPC substrate can be obtained. a laminate of a metal layer and a polyesterimine layer (FCCL). Here, 'a copper foil is used as a metal foil, and a polyester phthalimide precursor solution is directly coated on the copper foil, whereby a copper foil can be obtained. A non-adhesive two-layer laminate formed of a polyester quinone layer. In contrast, a polyester bismuth layer and a copper foil are attached by using an epoxy-based adhesive or a thermoplastic polyimide. It is also known as the composition of FCCL, but it must be thermoplastic. Therefore, the constituent elements of the adhesive must contain a bending component, resulting in a high coefficient of hygroscopic expansion. , glass transition temperature and heat resistance are reduced. Therefore, in 3 layers, pseudo 2 Type of laminate 134489.doc -35- 200948862 In the board 'caused by the thermoplastic adhesive layer', it will inevitably lead to high hygroscopic expansion coefficient, low glass transition temperature, and low heat resistance. On the other hand, the polyss of the present invention The amine has high adhesion, so that a two-layer type laminate can be obtained without the interlayer, and the polyesterimine itself has non-thermoplasticity. Therefore, it can also have high glass transition temperature, high heat resistance and low suction. Wet expansion coefficient. Various metal foils can be used as the metal foil of the FPC board, but aluminum bobbin, copper foil, and stainless steel foil are preferable, and copper foil is especially preferable. These metal 4 can also be roughened, The thickness of the surface treatment β metal box such as electroplating treatment, chromate treatment, aluminum alcoholate treatment, aluminum chelate treatment, and decane coupling agent treatment is not particularly limited, but is preferably 35 μηι or less. More preferably, it is 1 8 μηη or less. FCCL can be produced, for example, in the following manner: First, a polyester bismuth imide precursor solution is applied by using a knife coater or a belt coater or a gravure coater. On the metal foil, it is then dried to form a polyester phthalimide precursor layer (hereinafter also referred to as "polyester phthalimide precursor film"). The coating thickness is affected by the polyester quinone imine precursor solution. The influence of the concentration of the solid component is in the inert environment such as nitrogen, helium or argon, at 200. (:~4〇〇. (:: the thermal imidization of the polyester ylide precursor layer, borrowing This can form a polyester quinone layer. The thickness of the polyester quinone layer is 1 〇〇μΠ1 or less, preferably 50 μπι or less, more preferably 30 μηη or less. The peel strength of the layer and the metal foil is preferably 0.8 N/mm or more, and more preferably 丨〇N/mm or more. The warpage amount is preferably 134489.doc -36- 200948862 It is 10 water-soluble with ferric chloride. It is less than mm, and more preferably 3 or less. At room temperature or under heating conditions of 5 (TC or less), the liquid (manufactured by Tsurumi #达股份有限公司, 40 Baume (the specific gravity unit has a content of 37% or more) is used as the surname solution to describe the above fccl. By engraving, the metal layer of the laminate is engraved into a desired circuit shape, whereby a non-adhesive type flexible printed wiring board can be manufactured.

Further, the tear strength of the polyimide film is preferably 50 mN or more, more preferably 6 〇 mN or more, and particularly preferably 80 mN or more in the polyimide film of 26 μm. The elastic modulus is preferably 4 〇 Gpa~6 5 Gpa. The moisture absorption coefficient is preferably 7 ppm/% RH or less. The linear thermal expansion coefficient is preferably 16 PPm/°C~25 ppm, and the glass transition temperature is preferably 35〇〇ca. In the polyester quinone imine and its precursor solution, an additive such as an oxidative stabilizer, a filler, an adhesion promoter, a smectic coupling agent, a sensitizer, a photopolymerization initiator, and a sensitizer may be added as needed. The polyester quinone imine of the present invention has high flame retardancy, low hygroscopic expansion coefficient, low linear thermal expansion coefficient equivalent to copper foil, high glass transition temperature, high adhesion strength, low modulus of elasticity, and high tear strength. The electric insulating film, the flexible printed wiring board, the display substrate, the electronic paper substrate, the solar cell substrate, and the like in various electronic devices can be used as a substrate for a flexible printed wiring board. Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. Further, the physical property values in the following examples were measured by the methods shown below. 134489.doc •37· 200948862 &lt;polyester phthalimide precursor solution&gt; Firstly, the diamine containing an ester structure was dissolved in N_mercapto-2-pyrrolidone, and the ester-containing structure was slowly added thereto. The tetracarboxylic dianhydride powder was passed through a mechanical stirrer at 80. (: stirring under heating for 3 to 5 hours. At this time, polymerization is carried out in a monomer concentration range in which the monomer concentration is 10% by mass to 2% by mass, thereby obtaining a uniform and high polymerization degree polyester hydrazine. Imine precursor solution. &lt;Copper foil/polyester phthalimide laminated plate&gt; The copper foil of 1 2 μm thick (Nippon Electrolytic Co., Ltd.: USLp • Pavilion) was allowed to stand on the surface of the roughened surface. On the metal coating table, the surface temperature of the coating table was set to 90 ° C, and the polyester-imide precursor solution obtained above was applied onto the roughened surface of the copper foil by a doctor blade. Thereafter, on the coating table. After standing for 30 minutes, and then in a desiccator for 3 minutes after standing at rc, a non-adhesive copper ruthenium/polyacetate precursor film laminate (polyacetate yttrium imide) was obtained. The thickness of the layer is 47 μm and 24 μm. Then, the laminate of the copper foil/polyester ylide precursor is adhered to the metal plate of SUS by a tape, in a nitrogen atmosphere, in a hot air dryer. The yttrium imidization was carried out at 150 ° C for 30 minutes at a heating rate of 5 ° C / min, at 200 ° (: After 1 hour, the imidization was carried out at 4 Torr. (: 1 hour of hydrazine imidization was carried out. Thereafter, the SUS metal plate was removed to obtain a copper foil/polyester phthalimide laminated plate. &lt;Polyester醢imine film&gt; At room temperature or under heating conditions of 5 (TC or less, using a three-iron solution (manufactured by Zhenda Caoda Co., Ltd., 40 Baume, three-ironized iron content of 370/. or more) The above-obtained copper foil/polyester phthalimide laminate steel 134489.doc -38 - 200948862 is etched to obtain a polyacetal oxime having a film thickness of 26 μm and 12 μηι. Average molecular weight: Mw> The polyester yttrium imide precursor solution of o. oi g was measured using a precision balance, and dissolved in 10 g of a developing solvent. The solvent was developed by using 2.61 g of lithium bromide (manufactured by Aldrich Co., Ltd.). 5.88 g of an aqueous phosphoric acid solution (manufactured by Wako Pure Chemical Industries, Ltd., 'purity of 85%) was dissolved in 1 L of dimethyl ketoamine (manufactured by Wako Pure Chemical Industries, Ltd., liquid chromatography). The solution is filtered through a 10 μηη filter. Thereafter, the use will serve as a protective column. TSK guard column Super Η-Η (trade name, manufactured by Tosoh Soda Co., Ltd.) and GPC (colloid permeable layer) connected in series with TSK-GEL SUPER HM-H (trade name, manufactured by Tosoh Corporation) as a separation column The analyzer was used to produce a molecular weight at a flow rate of 〇5 ml/min using the developing solvent. The molecular weight was converted by polystyrene. &lt;Glass transfer temperature: Tg&gt; The heat produced by Shimadzu Corporation was used. Mechanical analysis device (TMA_5〇), by thermomechanical analysis, at a load of 5 g, a heating rate of 1 〇〇 c / min, a nitrogen atmosphere (flow of 20 ml / min), a temperature of 5 ° ° C ~ 450 ° Within the range of C, the elongation of the vinegar-coated imine film with a width of 3 mm, a length of 18 mm (the length between the chucks is 15〇1111), and a thickness of 26 μm is measured, and the inflection point of the obtained curve is obtained. Glass transition temperature of polyester yttrium imide film (26 μm thick). &lt;Line thermal expansion coefficient: CTE&gt; Using a thermomechanical analysis device (ΤΜΑ_5〇) manufactured by Shimadzu Corporation, by thermomechanical analysis, the load was 5 g, the heating rate was thief/min, and the gas ring 134489.doc -39· 200948862 In the environment (flow rate 20 ml / min), temperature in the range of 50 ° C ~ 450 ° C, for a width of 3 mm, length 18 mm (central _ disk length of 15 mm), thickness of 26 μηι polyester 醢The elongation of the imine film was measured, and the linear thermal expansion coefficient of the polyester bismuth imide film (26 μm thick) was determined by the average of the film elongations in the range of 50 ° C to 200 ° C. &lt;Moisture absorption coefficient: CHE&gt; Using a thermomechanical branching device (TM-9400) and a humidity environment adjusting device (HC-1) manufactured by ULVAC Technology Co., Ltd., at 23 C, Elongation of polyester yttrium imide film with a width of 3 mm, a length of 30 mm (with a length between chucks of 15 mm) and a thickness of 26 μm under the condition of 5 g, when the humidity changes from 30 〇/〇RH to 70% RH The hygroscopic expansion coefficient of the polyester yttrium imide film was determined by the average value of the elongation of the film in 3% by RH to 7〇% RH. &lt;Flame-retardant&gt; A polyester quinone imine film having a thickness of 12 μm was prepared into a test piece having a size of 2 〇 ^ and a length of X 5 cm. The sheet in the 4-inch test piece was placed on the η, the relative humidity of 50% of the core i was placed on 48 small (four) upper &lt;receiving state&gt;, and the remaining piece was subjected to aging for 168 hours at a ship degree of 7 gc at a temperature. It was cooled in a drier of m and a relative humidity of 20% or less for 4 hours. Five pieces of each of the polyimidine imines were used, and the flammability test was carried out according to the evaluation method of the UL94VTM test at 23 C and the relative humidity of the environment. ^^ The flame used in the evaluation at this time Blue flame of 20 mm size, steel slag seconds. The heating time of 9 100 C to 700 °C is 42.9 &lt;Evaluation of heat resistance of welding kick&gt; 134489.doc 200948862 ❹ 切割 The laminate of copper foil/polyester phthalimide is cut to a size of 3 cm x width 3 cm. Using a masking tape to shield the center portion by 2.5 cm x 2.5 cm. Under the same conditions as above, using a three-gas iron solution (manufactured by Tsurumi Soda Co., Ltd., 40 Bomei, three gas iron) The content of the steel foil was etched to obtain a test piece. The obtained test piece was allowed to stand in a desiccator at 100 ° C for 1 hour or more, and then dried, and then placed in a solder bath set at 3 ° C in a contact with the copper foil side. The surface of the solder bath was allowed to stand for 2 minutes, and the appearance change such as the occurrence of bulging or wrinkles in the copper foil and the polyester yttrium imide film was visually evaluated, and the appearance change was not observed as a good result (〇). &lt;Evaluation of Heat Resistance of Boiler Solder&gt; 'The test piece was produced in the same manner as the evaluation of the solder heat resistance, and the purified water was placed in a container equipped with a reflux cooler to impregnate the obtained test piece' (4) 下t Set for 2 hours. Thereafter, the test piece was placed in normal temperature purified water, and each piece of the test piece was taken out, and the water on both sides was wiped off with a paper towel. After that, it is set to ·. In the solder bath of C, the test pieces were placed on the surface of the soldering bath for 2 minutes in contact with the side of the copper box, and the _ _ 醋 酿 酿 酿 酿 是否 是否 是否 是否 是否 是否 」 」 」 」 」 」 A good result (〇) is expected in the case where the change is not observed. &lt;Bound strength of copper foil and polyester quinone layer&gt;^Test; ^ method was carried out based on the nsc647i specification. Copper polyacetate-based imide laminate cutting growth 15 - 2 = cover tape to a central portion width 3_ covered with the same conditions as above to inhibit ferric chloride 134489.doc 200948862 obtained test piece in a desiccator Place H at 1〇5&lt;t and dry it, then fix it on a 3 mmiFR_4* plate with double-sided tape. A conductor having a width of 3 mm was peeled off from the interface with the polythene imide film, and attached to an aluminum belt as a gripping portion to prepare a sample. The obtained sample was fixed on a tensile tester (AUTOGRAPH AG-10KNI) manufactured by Shimadzu Corporation. When it is fixed, in order to be surely along 9〇. The direction was peeled off and the jig was attached, and the load at the time of peeling 50 mm at a speed of about 5 〇 mm/min was measured and the calculation was performed every! The strength of the cm. &lt;elasticity&gt; A polyimine film of 3 mm x 50 mm was stretched with a test length of 50 mm and a test speed of 50 mm/min using a tens. 7^(7) tensile test apparatus manufactured by OLIENTEC Co., Ltd. The rate is from 0.4% to 1.0 by the tensile elongation of the polyesterimine film. /. Calculated between the stress gradients between them. (When a sample of 5 mm is broken when it is stretched to 100 mm, it is referred to as "tensile elongation at break is 100%".) <trouser tear strength> Polyacetate The amine film was cut into 50 mm x 1 50 mm samples, and the RTG-1210 tensile tester manufactured by OLIENTEC Co., Ltd. (installed with the UR-5〇ND type load cell manufactured by the same company) was used as JIS K7. The method described in 12 8 -1 was measured at a test speed of 50 mm/min. &lt;warp&gt; The laminate of copper foil/polyacetal imide was cut into a size of 10 cm x 10 cm, and it was placed in a constant temperature and humidity chamber at 23 ° C and a humidity of 50% for one day. After 134489.doc -42· 200948862, the distance between the four sides of the sample and the set surface was measured, and the average value of the measured distance was used as the value of warpage. Here, the case of curling toward the polyester quinone side is taken as the value of (+). &lt;heating peak temperature (a)〇c, temperature width ΔT=((b)_(a))&lt;Jc&gt; A tetracarboxylic acid having an ester structure represented by the formula (19) weighing about 5 mg A dianhydride (hereinafter referred to as TABP), which is placed in an attached aluminum sample container, covered with a lid, and crimped to prepare a measurement sample: [Chem. 56] ❹

(19) Similarly, the unmeasured sample container and the lid were crimped and used as a standard material. The standard substance and the measurement sample were placed in a heating furnace equipped with a differential scanning meter (Prison-60, manufactured by Shimadzu Corporation) at a temperature increase rate of HTC/min, N2, at room temperature to 35 rpm.

The internal measurement I takes the temperature of the heat of dissolution as (4). C, the temperature at which the temperature toward the melting heat wave peak rises is taken as the temperature at the intersection of the hypothetical tangent of the joint point and the straight line of the substantially straight (four) point along the refining wave peak as (4), and the temperature is wide (8)·(4) again, (4) Mark = correction with heat flow. Shell Unsubscribe/Dish (Example 1) (Synthesis Example 1) Synthesis of TABP in 1 L1 Separate-type bottle-shaped moi-based stupid tricarboxylic acid gas (made by Tokyo Chemical Industry Co., Ltd. 彳 Cold &amp; N, N_Dimethyl 134489.doc -43· 200948862 In the carbamide solution, it is cooled to the next generation in a nitrogen bath in an ice bath. Thereafter, the temperature becomes the machine below, and the time is 2 hours. Ah, the mixing speed, 5G ml of N, N-dimethylformamide, 5 () mi ^ than the bite dissolved 4,4, _ biguanide solution was added to the flask, and then at room temperature The drop is given for 6 hours. If the drop is started, the solution turns red. 'A yellow precipitate is formed as the drop is added.

继 Then, the precipitates were washed with hydrazine, dimethyl dimethyl decylamine, and washed with water, and then filtered twice, and the filtrate was dried to obtain yellow-white crystals containing TABP. Thereafter, the surface was decompressed with a vacuum drier, and the surface was heated and dried at a temperature of 1 () for 1 hour to obtain a yellow crystal which was not purified TABP. &lt;Purification of TABP&gt; In a 3 〇〇mi flask, 10 g of the obtained unpurified ΤΑΒρ was placed in 15 〇ml of 7·-butyrolactone solution, and heated to 2 〇〇&lt;5 with an oil bath. (:, it was dissolved while stirring for 3 minutes. At this time, no insoluble matter was found. Thereafter, the oil bath was stopped and stirred, and slowly cooled to room temperature. The solution was slowly separated into 2 by standing at room temperature. The layer was simultaneously precipitated with needle-like yellow-white crystals. The precipitates were separated by filtration, and decompressed by a vacuum dryer. The surface was heated at a heating rate of 1 G for 13 hours, and then dried for 2 hours, and then w1 (rc) / The temperature rise rate is heated and dried at 20 ° C for 6 hours, and after cooling to room temperature while maintaining the degree of vacuum, the pressure is adjusted to atmospheric pressure, and then the high purity TABP yellow crystal of the target is obtained. Using a differential scanning calorimeter (DSC_60, The product obtained by Shimadzu Corporation was measured for 5 mg of TABP. The results are shown in Table 2. The peak temperature (3) of the heat of fusion 134489.doc -44- 200948862 was 325. (:, temperature is 厶 = = (13 )-0)) = 3.2. (:. &lt;polymerization of polyacetate precursors Evaluation of properties of ruthenium iodide and polyester-coated imine film&gt; To a well-dried closed reaction vessel equipped with a stirrer, 12.84 mmol of a diamine having an ester structure represented by the formula (33) was added (hereinafter referred to as For BPIP)', add 61 ml of 2N methyl-2-pyrrolidone, and warm the solution to 80 C to dissolve. After dissolving, slowly add 13.38 mmol of the above-obtained TABp powder to the solution. Minute, and the viscosity of the solution is sharply increased. Further stirring for 4 hours, a transparent, uniform and viscous polyester phthalimide precursor solution having a repeating unit represented by the formula 获得) is obtained. And &amp; is a divalent aromatic group represented by the formula (1〇): [Chem. 57]

[化58]

[化59]

(10). The polyester vinegar imide was flooded with gp at room temperature and 2 Torr. Placement under 〇 134489.doc •45· 200948862 Also no precipitation or gelation occurred at all, indicating a high solution storage stability. The 12 0 „! thick copper foil (Nippon Electrolytic Co., Ltd., USLp foil) was placed on the metal coating table with the roughened side as the surface. The surface temperature of the coated crucible was set to 90 C, using a doctor blade The polyester yttrium imide precursor gluten solution was applied to the roughened surface of the copper foil. Thereafter, it was allowed to stand on the coating table for 30 minutes, and further allowed to stand at 100 Torr in a drier for 30 minutes to obtain a non-viscous f. The laminate of the raw steel crucible/polyester phthalimide precursor (the thickness of the polyester bismuth imide precursor layer is 47 μηη and 24 μηι). Then, the copper foil/polyester phthalimide precursor is taped. The laminate is adhered to a metal plate of SUS, and is heated at a temperature of 5 〇C/min in a hot air dryer at a temperature of 15 Torr in a nitrogen atmosphere for 30 minutes. H and hydrazine imidization were carried out, and hydrazine imidization was carried out for 1 hour at 400 C. Thereafter, the metal plate of SUS was removed to obtain a laminated sheet of non-crimped copper foil/polyester yttrium. Or under heating conditions of 50 C or less, using a three-iron solution (manufactured by Tsurumi Soda Untrain Co., Ltd., 40 Bomei, A copper foil with a thickness of 26 μm and 12 μηι is obtained by etching a copper foil of a ruthenium ruthenium/polyaniline yttrium laminate with a thickness of 3 7% or more. .

The polyester bismuth iodide having a film thickness of 26 μm was passed through 〇8〇. The bending test did not break and showed flexibility. The polyester quinone imine film does not exhibit solubility in an organic solvent such as N-methyl-2-pyrrolidinone or dimethylacetamide. Further, as determined by TMA, the polyesterimide film showed a low coefficient of thermal expansion equivalent to that of copper foil of 22 ppm/〇c (average value between 5 Å &lt; t to 2 〇〇 C). The coefficient of hygroscopic expansion was measured and found to be 5.0 ppm/. /. RH (average between 30% RH and 70% RH 134489.doc -46- 200948862), showing very low absorption; , ~% service factor. The flame retardancy of the polyester bismuth iodide having a film thickness of 12 μηι was evaluated, and the performance of UL94VTM-0 was not known. X, showing good solder heat resistance, boiled Tanxi financial track. The elastic modulus is 5.1 (10) lower. The crepe tear strength of the vinegar-like imine oxime is 62 mN high tear strength. (Example 2) Ο

G To a well-dried closed reaction vessel with a blender, add 6.42 mmol of BPIP, 6.42 匪〇1 of the diamine (hereinafter referred to as APAB) represented by formula (37), and then add 61... The meaning of methyl 2 · pyrrolidone, the solution was warmed to 8 〇t to dissolve. After the dissolution, 13.3 8 mmol of the TABp powder obtained in Example 1 was slowly added to the solution. The viscosity of the solution was sharply increased by stirring for 30 minutes. Further stirring for 4 hours', a transparent, uniform and viscous polyg which has a repeating unit represented by the formula (11) and the formula (12) and a molar ratio of the formula (H) and the formula (12) to the formula is obtained. Ester imine precursor solution. Here, in the formula (12), 'B2 is a divalent aromatic group represented by the formula (16): [Chem. 60] [Chem. 61] 134489.doc ου • 47- (12) 200948862, human Δ人ΗΛ2,

Ar

Lhy yh _ (6) 醯 The oxime imidization was carried out according to the method described in Example 1, and a polyester quinone imine film was produced, and physical properties were evaluated in the same manner. The physical property values are shown in Table 1. Except as shown in Table 1, the amount of distortion is i mm, which also shows good values. (Example 3) To a sufficiently dried mixer vessel equipped with a stirrer, 8.99 mm of BPkBPIP and 3.85 of 3.81 加入1 were added, and then added. N-methyl 2 is slightly ketone, and the solution is warmed to &amp; 〇 to dissolve. After the dissolution, 13·38 mmol of the TABP ° obtained in Example 1 was slowly added to the solution to increase the viscosity of the solution sharply by mixing 3 G minutes. Further, the mixture is stirred for 4 hours to obtain a repeating unit represented by the formula (1)) and a repeating unit represented by the formula (12), and the molar ratio of the formula (11) and the formula (12) is a general formula. (11) / A transparent, uniform and viscous polyacetal imide precursor solution of the formula (12) = 7g / 3 (). Here, in the formula (12), &amp; is a divalent aromatic group represented by the formula (16). Film formation and oxime imidization were carried out in accordance with the method described in Example 1, and a polyester phthalimide film was produced by 134489.doc • 48· 200948862, and physical properties were evaluated in the same manner. The physical property values are shown in Table 1. Except as shown in Table 1, the amount of warpage was 10 rnm, which also showed a good value. (Example 4) To a sufficiently dried closed reaction vessel equipped with a stirrer, 6.88 mmol of BPIP and 6,88 mmol of a diamine having an amine structure represented by the formula (38) (hereinafter referred to as DAB A) was added. 'Additionally 65 ml of N-methyl-2-0 ridicone, the solution was warmed to 80 t to dissolve. After the dissolution, 14.33 mmol of the TABP powder obtained in Example 1 was slowly added to the solution. The viscosity of the solution was sharply increased by stirring for 30 minutes. Further, the mixture is stirred for 4 hours to obtain a repeating unit represented by the formula (11) and a repeating unit represented by the formula (12), and the molar ratio of the formula (u) to the formula (12) is A transparent, uniform and viscous polyimide precursor precursor solution of the formula (Π) / formula (12) = 50/50. Here, in the formula (12), b2 is a divalent aromatic aromatic group represented by the formula (17): [Chem. 63] (38) [Chem. 64] (9). Film formation and hydrazine imidization were carried out in accordance with the method described in Example 1, and a polyester phthalimide film was produced, and physical properties were evaluated in the same manner. The physical property values are shown in Table 134489.doc -49· 200948862 1. Except as shown in Table 1, the amount of warpage was 1 mm, which also showed a good value. (Example 5) To a sufficiently dried closed reaction vessel equipped with a stirrer, 9.63 mmol of BPIP and 4.13 mmol of an amine represented by the formula (39) were added.

The structure of the diamine (hereinafter referred to as BPTP), then add 71 ml of 2 N-methyl-2-pyrrolidone, and warm the solution to 8 (rc to dissolve it. After dissolution, slowly add 14.79 mmol to the solution. The TABp powder obtained in the example was stirred for 30 minutes to increase the viscosity of the solution sharply, and further stirred for 4 hours to obtain a repeating unit represented by the formula (11) and represented by the formula (12). a repeating unit, and the molar ratio of the general formula (n) to the general formula (12) is a transparent, uniform and viscous polyester yam of the formula (11) / general formula (12) == 70/30. An amine precursor solution. Here, in the formula (丨2), &amp; is a divalent aromatic aromatic group represented by the formula (18): [Chem. 65]

[化66]

(18) The film properties and the oxime imidization were carried out in accordance with the method described in Example 1, and a polyester phthalimide film was produced. The physical property values are shown in Table 1. Except for Table 1, the amount of warpage was -3 mm, which also showed good values. 134489.doc -50- 200948862 Here, the term "-3 mm" refers to the side of the copper foil. (Example 6) 5 〇mmol of BPIP was added to a well-dried sealed reaction vessel equipped with a stirrer, and dissolved in 191 ml of N-methyl-2-° pirone, and then into the solution. The TABP powder obtained in Example i of 50 mm 〇i was slowly added. After 30 minutes, the viscosity of the solution increased sharply. Further, it was stirred at 8 ° C for 4 hours to obtain a transparent, uniform and viscous polyester quinone imide. The obtained poly(6) imine precursor was precipitated and gelled at room temperature and at _2 Torr for one month, indicating a high storage stability of the solution. In the N-methyl-2 - ° ratio, the intrinsic viscosity of the polyester quinone imine precursor measured by the Ostwald's viscometer at 3 〇 and 〇 5 mass % is 2 · 8 dL/g. The polyester quinone imine precursor was subjected to ruthenium under a pressure of 3 kg/cm 2 under a nitrogen pressure of 5 μm to obtain a target polyimine precursor. Film formation and hydrazine imidization were carried out in accordance with the method described in Example 1, whereby a pale brown polyester phthalimide film having a film thickness of 25 μm and 12 μηι was obtained, and physical properties were evaluated in the same manner. The physical property values are shown in Table 3. The polyester quinone imine film passes through 180. The bending test also did not break, indicating flexibility. Also, no solubility is exhibited at all for any organic solvent. Further, the polyester phthalimide precursor obtained above was spin-coated on a 6-inch sand wafer by a spin coater (MS-250 'Mikasa Co., Ltd.), and dried at 100 ° C in a drier. After 30 minutes, a non-tacky polystyrene precursor/Shixi wafer laminate (the thickness of the polyuranium precursor layer was 17 μπι) was obtained. Thereafter, in a nitrogen atmosphere, in a hot air dryer, 134489.doc 200948862 at a heating rate of 5 ° C / min, the laminate was subjected to iminomination at i5 ° C for 30 minutes at 200 ° C. The imidization was carried out for 1 hour, and i-imidation was carried out at 400 ° C for 1 hour. Thereafter, the polyester-imide film was peeled off from the twin crystal by hydrofluoric acid to obtain a polyester quinone film having a thickness of 10 μm. A tensile test was conducted on the obtained polyester-imide film to obtain a modulus of elasticity of 54 GPa and a fracture elongation of 53%. Here, the intrinsic viscosity (η) is obtained by measuring 0.5% by mass of a polyesterimide precursor using a Kosher viscosity meter at 301:. ❹

(Example 7) 10 g of unpurified TABP obtained in Synthesis Example 1 and 150 ml of cyclobutyl hydrazine obtained in Synthesis Example 1 were placed in a 300 ml flask, and heated to an hydrazine (9) in an oil bath, and dissolved while stirring for 3 minutes. . Thereafter, the evaluation of TABP was carried out in the same manner as in Example 。. The obtained ΤΑΒρ was measured by a differential scanning calorimeter (DSC_6〇, manufactured by Shimadzu Corporation), and as a result, the peak temperature (4) of the heat of fusion was 322.5. 〇, the temperature is wide △T=((bHa))=4.5°C. When the ratio of the acid dianhydride to the diamine is 〇.99, the molecular weight becomes the largest. Further, the inherent viscosity of the polyester quinone imine precursor obtained by the input ratio of 〇.99 was 2.4 dL/g. Then, film formation and hydrazine imidization were carried out in accordance with the methods described in Examples j and 6, and a polyesterimine film was produced, and physical properties were evaluated in the same manner. The physical property values are shown in Table 3. (Comparative Example 1) To a well-dried sealed reaction vessel equipped with a stirrer, 9 27 1 of BPIP was added, followed by 48 μ of N_decylbibilol. Ketone, warm the solution to 8 (TC to dissolve it. After dissolution, slowly add 9 ^ I34489.doc -52- 200948862 mmol of tetradecanoic acid with ester structure represented by formula (20) to the solution. A dianhydride (hereinafter referred to as TAHQ). The viscosity of the solution is sharply increased by stirring for 3 ' minutes. Further, it is allowed to fall for 4 hours to obtain a transparent, uniform and viscous polyester phthalimide precursor solution: [Chem. 67]

(20) 〇

薄膜 Film formation and hydrazine imidization were carried out in accordance with the method described in Example 1 to prepare a polyesterimine oxime, and the physical properties were evaluated in the same manner. The physical property values are shown in Table 1. The polyesterimide film exhibits a linear thermal expansion coefficient close to that of the copper foil, high thermal stability and flexibility, low modulus of elasticity, and relatively high adhesion, but a coefficient of hygroscopic expansion of 7-6 ppm/% RH. , relatively high, the tear strength in the polyester film of 26 μηι is 42 mN, which is lower. Also, the 12 μιη thick film has a low flame retardancy, and the performance of UL94VTM-0 was not obtained. (Comparative Example 2) In Example 2, TAhQ was used instead of hydrazine, and 1 〇 49 mol of APAB and 2.62 mol of 4,4,-diaminodiphenyl ester (referred to as 〇DA by ητ) were used as the diamine. In the same manner as described in Example 2, a polyester phthalimide precursor was polymerized, and then a film was formed and yttrium imidized to prepare a polyester-bromide film, and physical properties were evaluated in the same manner. The physical property values are shown in Table 1. The polyacetal imide film showed a thermal expansion coefficient close to that of the copper pig, high geothermal stability, and flexibility, and the coefficient of hygroscopic expansion was 8 3 ppm/. /. RH is relatively higher than 134489.doc •53·200948862, the elastic modulus is higher at 7·9 GPa, and then the strength is lower than 0.3 N/mm, and the 'clothing strength is 42 in the polyurethane bismuth oxime of 26 μΐΏ. mN is lower. Moreover, the flame retardancy of the film of 12 μηι thick is better than that of _ ^ ., and the performance of UL94VTM-0 is not obtained. (Comparative Example 3) ^ The diamine (in terms of Budma APB) is represented as a diamine, and the other aspects described in the comparison (1) are used.

The method of polymerizing a polyester quinone imine precursor, followed by hydrazine and hydrazine imidization to produce a polyester phthalimide film, and similarly evaluating the physical properties: [Chem. 68]

(2 3), the physical property values are not shown in Table 1. The polyesterimide film exhibits a higher glass transition temperature and a higher adhesion. The modulus of elasticity shows a lower value of 5 2 GPa 'but the coefficient of linear thermal expansion shows a higher value of 32 ppm / lt; t, moisture absorption The higher coefficient of expansion is 13 2 ppm/% RH 'the tear strength in the polyester film of 26 μπι is 45 claws\low. Further, in the solder heat resistance test, a bulge was found, and the flame retardancy of the film of 12 μη thick was low, and the performance of UL94VTM-0 was not obtained. (Comparative Example 4) In Comparative Example 1, the ruthenium obtained in Example 1 was used instead of TAHQ, and ruthenium was used as the diamine, and the polyester ruthenium imine precursor was used in accordance with the method described in Comparative Example 1. The material was combined, and then film-forming, 醯134489.doc •54· 200948862 imidization, and a polyester phthalimide film was produced, and the physical property evaluation was performed in the same manner. The physical property values are shown in Table 1. The polyester phthalimide film exhibits high thermal stability and flexibility, and evaluates the flame retardancy of a polyimide film having a low moisture absorption coefficient, a high tear strength, and a film thickness of 12 μm. Shows the performance of UL94VTM-0, but the linear thermal expansion coefficient is 13 ppm/t:, showing a lower coefficient of linear thermal expansion compared to steel foil, followed by a lower strength of 0.4 N/mm, and the modulus of elasticity shows a higher value of 7.7. GPa. ❹ 134489.doc •55- 200948862

Tear strength mN (film thickness) 62 26 μηη 85 26 μιη 80 26 μηι 68 26 μιη 1 72 26 μιη 42 26 μιη i 42 26 μηι 45 26 μηη 73 26 μιη 90 degree copper foil strength (N/mm) 00 d Rn OS d d Elasticity rate GPa inch ON OO iri ON t&gt; (N in Γ Γ *^ CHE ppm/%RH wo CN cs cn »〇m OO 13.2 00 — Flame retardant VTM-0 〇〇〇〇〇XXX 〇Boiling soldering heat 〇〇〇〇〇〇〇X 〇Welding to heat 〇〇〇〇〇〇〇X 〇CTE (Ppm/°C) &lt;N &lt;N CN CS CN Os 卜 cn cn m ^ 6 440 00 5 ry 422 413 ! in $ o cn 453 Molecular weight 133000 103000 115000 107000 74000 143000 114000 104000 84000 Composition (diamine molar ratio) TABP/BPIP TABP/BPIP/APAB (BPIP/APAB=50/50) TABP/BPIP/ APAB (BPIP/APAB=70/30) &lt;ζ 〇&lt; ® 9 JL Oh $ P Oh CQ &amp; H OQ TABP/BPIP/BPTP (BPIP/BPTP=70/30) TAHQ/BPIP TAHQ/APAB/ODA (APAB/ODA=80/20) TAHQ/BAPB ΤΑΒΡ/ΑΡΑΒ Example 1 Example 2| Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 13448 9.doc -56- 200948862

Temperature width T=((b)-(a)) rc) 1___________________ &lt;Ν melting peak temperature (a) CC) JQ m 322.5 .1 Μ PH 3 CU 3 HH 0 134489.doc Flame retardant VTM -0 〇o -=w S ^ mm in Elasticity GPa inch uS CHE ppm/% RH Boiled solder for heat 〇〇 solder heat resistance 〇〇90° copper foil strength kg/cm CTE (ppm/°C) &lt;N CN CM &lt;N ^ 6 清 清 varnish filter o (η (dL/g) 00 CN 寸 CN lt NU Μ 1« ^ _ Ί 0.99 0.99 Composition (Mo Erbi) TABP/BPIP 100/100 TABP/BPIP 100/100 Example 6 Example 7 57· 200948862 [Industrial Applicability] The polyester phthalimide of the present invention is suitably used as an electrical insulating film, a flexible printed wiring board, and various electronic devices. The substrate for a display, the substrate for an electronic paper, and the substrate for a solar cell are particularly preferably used as a substrate for a flexible printed wiring board. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a curve displayed by a differential scanning calorimeter. ❹

134489.doc 58-

Claims (1)

200948862 X. Patent application scope: 1' A polyester quinone imine precursor characterized by having a repeating unit represented by a description: [1] (1) B γ VH. ❹ (2) (3) (4) (5) 134489.doc (6) 200948862 [Chem. 6] [Chemistry 7] [化8] (7) [Chemistry 9] R! represents a luminescent group having a carbon number of 1 to 6; and Rz to R4 represents a burning group having a carbon number of 1 to 6, The hydrogen atom's are independently independent and may be the same or different; R5 represents a carbon number of 2. If there is 3. an alkyl group of 6; Re~R9 represents an alkyl group having a carbon number of 1 to 6, a gas atom) A polyester quinone imine precursor, wherein the repeating unit represented by the formula (3) or the formula (4) in the formula (1). The polyester quinone imine precursor of claim 1, wherein the repeating unit represented by the formula (4) in the formula (1). 4. The polyester quinone imine precursor of claim 1, wherein the repeating unit represented by formula (10) is: 134489.doc (10). 200948862 [化 ίο] A polyester quinone imine precursor having a repeating unit represented by the following formula (11) and formula (12), wherein the molar ratio of the formula (11) and the formula (12) is a formula ( 11) / formula (12) = 20/80 to 80/20 ratio: [Chem. 11] (11) Ar (12) (In the formulae (11) and (12), Ar is a tetravalent aromatic group represented by the formula (2); and in the formula (12), 'Β2 is selected from the formula (13) to the formula (17). To small-, 2-valent aromatic group: species [12] 134489.doc (2) (13) 200948862 [Chem. 13] (14) Ιν (15) [16] (16) (17); R1G to R18 represent an alkyl group having 1 to 6 carbon atoms and a hydrogen atom, and these may be independently and may be the same or different). 6. The polyester quinone imine precursor according to claim 5, wherein in the formula (12), B2 is a repeating unit represented by the formula (16), the formula (17) or the formula (18): 134489.doc ( 18) 200948862 [Chem. 18] 7' The polyester quinone imine precursor of claim 5 is a repeating unit represented by the formula (16). 8. For example, the polyester bismuth imide precursor of the 求 求 为 is 30,000 or more and 400,000 or less. The precursor of the polyacetal imine of claim 5 is 30,000 or more and 400,000 or less. 10. The precursor of the polyester quinone imine of claim 6 is 30,000 or more and 400,000 or less. ❹ In the formula (12), B2g 'its weight average molecular weight Mw 'its weight average molecular weight Mw 'its weight average molecular weight Mw η · such as the polyester ylide precursor of the claim 7, the weight average molecular weight Mw is More than 30,000, less than 400,000. ❹ 12. The polyester quinone imine precursor of the claim ,, wherein the tetracarboxylic carboxylic acid containing the ester group represented by the formula (19) used in obtaining the polyester quinone imine precursor is The peak temperature of the heat of fusion indicated by the differential scanning calorimeter (DSC) is (a) °C, and the temperature at which the temperature at which the peak of the melting heat wave rises and the peak of the peak slope are stabilized as the intersection of the tangent to the joint point is set as (b) )t, and when the temperature is set to AT=((b)-(a)rC, (a)g 322°C and 5°C are satisfied: [Chem. 19] 134489.doc (19). 200948862 13. The polyester quinone imine precursor according to claim 5, wherein the tetracarboxylic dianhydride containing the ester group represented by the formula (19) used in obtaining the polyester quinone imine precursor is The peak temperature of the heat of fusion indicated by the differential scanning calorimeter (DSC) is (b) °C, and the temperature at which the temperature at which the melting heat peak is raised and the peak of the peak is stabilized as the intersection of the tangent to the joint point is set as (b) )*t, and set the temperature width ΔΤ=((1)Η3))β(:, satisfy (a) $ 322 C and Δτ guest 5°C : [Chem. 19] ❹ θ (19). 14. The polyester phthalimide precursor of claim 6, wherein the polyester ylide precursor obtained by the formula (19) is an acid-containing tetra-acid dianhydride, which is to be The peak heat of fusion shown by the scanning calorimeter (DSC) is taken as (a). 〇, the temperature at which the temperature rising toward the dissolved heat peak and the temperature at which the peak slope is stable are taken as the intersection of the tangent to the joint point, and the temperature is set to (b) ° C, and when the set temperature is wide, '(a) g 322 ° C and △TSSt : [Chem. 19] (19) 15. The polyester quinone imine precursor of claim 7, wherein the polyglycolide is obtained by using the ketone-containing tetracarboxyl 134489 represented by the formula (19). Doc 9 200948862 Acid dianhydride, as the junction point, the peak temperature of the heat of fusion indicated by the differential scanning calorimeter (DSC) is (a) °C, and the temperature at which the temperature toward the peak of the melting heat wave is stabilized and the slope of the peak is stabilized. The temperature at the intersection of the tangent is set to (1)) ° 〇, and the set temperature is wide = ((1)) - (&amp;)). (:, (&amp;) 2 322 ° C and ΔΤ $ 5 ° C : ' [Chem. 19] ❹ 16. The polyacetate precursor of claim 11, wherein the ester-containing tetracarboxylic dianhydride represented by formula (19) used in obtaining the polyacetate precursor is used in The peak temperature of the heat of fusion indicated by the differential scanning calorimeter (DSC) is (b) °C, and the temperature at which the temperature at which the melting heat peak is raised and the peak of the peak is stabilized as the intersection of the tangent to the joint point is set as (b) ) ° C, and set the temperature width Δ Τ = (( ΐ 3 Η &amp;) Γ (:, (a) g 322 ° C and Δ Τ $ 5 ° C: (19) 〇 17. A polyacetamide imino group, which is characterized in that it is obtained by imidating a W t polyester oxime imide precursor. 5 Poly 18, a polyester quinone imine, which is characterized in that it is obtained by imidating the phthalocyanine precursor of the claim. 134489.doc 200948862 19. A polyacetamide imine which is obtained by imidating a phthalocyanine precursor of claim 6 . Poly(polyimide), which is obtained by imidating the ester quinone imine precursor of claim 7. *21, a polyester quinone imine, which is obtained by the imidization of a polyamidene hydrazine hydrazide as claimed in claim U. A polyester quinone imine characterized in that it is obtained by imidating a poly-S-imine of the claim 丨5. A polyester quinone imine which is obtained by imidating a polyester oxime imide precursor of claim 16. A laminate comprising a polyester quinone layer and a metal layer, and the polyester quinone layer is composed of the polyester quinone imine of claim 17. A laminated board characterized by comprising a polyester quinone layer and a metal layer, and the polyester quinone layer is composed of the polyester quinone imine of claim 18. A laminated board characterized in that it has a polyester quinone layer and a metal layer ' and the acetazide layer is composed of the polyester quinone imine of claim 19. 27. A laminate comprising: a polyester quinone layer and a metal layer&apos; and the polyester quinone layer is comprised of the polyester quinone imine of claim 2. 28. A laminate comprising: a polyester quinone layer and a metal layer ' and the polyester quinone layer is comprised of the polyester quinone imine 134489.doc 200948862 of claim 21. By. 29. A laminate comprising: a polyester quinone layer and a metal layer&apos; and the polyester quinone layer is comprised of the polyester quinone imine of claim 22. 30. A laminated board characterized by having a polyester quinone layer and a metal layer, and the polyester quinone layer is composed of the polyester quinone imine of claim 23. ❹ 31. The laminate of claim 24, which is obtained by applying the polyacetal imide precursor of claim 1 to a metal foil, drying it, heating it, or imidating the hydrazine with a dehydrating reagent. By. 32. The laminate of claim 25, which is obtained by applying a polyester phthalimide precursor as claimed in claim A to a metal box, drying, heating or denitrifying the hydrazine with a dehydrating reagent. By. 33. The laminate of claim 26, which is obtained by applying a polyacetal imide precursor as claimed in claim 6 to a metal drop, drying it, heating it, or imidating the hydrazine with a dehydrating reagent. By. 34. The laminate according to claim 27, which is obtained by applying a poly(tetra)imine precursor as claimed to a metal case, drying it, heating it, or aminating it with a dehydrating reagent. . 3 5. The laminate of claim 28, which is coated with a polyester bismuth imide precursor of claim 11 on a metal crucible by Jiang Rumo, and dried, heated or dehydrated. The one obtained by imidating the oxime. 36. The laminate of claim 29, which is heated by a coating of the (IV)-imine precursor prior to drying on the metal as described in the request, or by 134489.doc 200948862 using a dehydrating reagent to make the quinone imine The winner. 37. The laminate according to claim 3, which is obtained by coating a polyacetate precursor of claim 16 on a metal flute, drying it, and heating it with a dehydrating reagent to imidize it. By. ❹ 134489.doc