TWI395770B - Polyesterimide precursors and polyester imides - Google Patents

Description

Polyester phthalimide precursor and polyester quinone

The present invention relates to a polyester phthalimide precursor and a polyester quinone imide used in a laminate such as a flexible printed wiring board.

Polyimine is widely used in FPC (Flexible Printed Circuit) because it has excellent heat resistance and chemical resistance, radiation resistance, electrical insulation, and excellent mechanical properties. 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 increasing importance in recent years due to its simplicity in production and extremely high film purity.

As electronic devices tend to be lighter and shorter, the requirements for the properties of polyimine are also stricter year after year. Therefore, the industry is seeking a not only solder heat resistance, but also meeting the polyimide film for thermal cycling or suction. A multifunctional polyimine material having various properties such as wet 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 copper foil laminate and the FCCL (Flexible Copper Clad Laminate), which are the original plates of the FPC, 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 used, and 2) a copper foil is applied. After coating the polyimine solution, drying or drying, yttrium imidization after coating the polyimide precursor solution, or forming a copper layer on the polyimide layer by evaporation or sputtering A two-layer type, 3) a pseudo-two-layer type using a thermoplastic polyimide. If the polyimine layer is required to have a high dimensional stability, it is advantageous to use a two-layer FCCL without an adhesive.

Polyimine, which is an FPC substrate, undergoes dimensional changes due to 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 polyimide under the glass transition temperature is as low as possible, and the polyimine Matches the coefficient of thermal expansion of the metal foil. As described below, the control of the linear thermal expansion coefficient of the polyimide layer is also important from the viewpoint of lowering the residual stress generated in the 2-layer FCCL production 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, the polyimine is usually an aromatic tetracarboxylic dianhydride such as pyromellitic dianhydride (PMDA) and an aromatic diamine such as 4,4'-diaminodiphenyl ether (ODA). Reacting in an aprotic polar organic solvent such as dimethylacetamide (DMAc), first polymerizing a solution of a high degree of polymerization of a polyimide precursor, and then applying the solution of the polyimide precursor to a metal foil, for example On the copper foil, heating is carried out at 250 ° C to 400 ° C to carry out dehydration ring closure (醯imination), and film formation is carried out.

The residual stress is generated during the imidization reaction at a high temperature, and the metal/polyimine laminate is cooled to room temperature, which often causes serious problems such as warpage and peeling of the FCCL, and film breakage. Further, in the case of using a polyimine solution, the problem of residual stress is also generated in the drying-cooling step as well as in the case of using the polyimide precursor solution.

As a measure for reducing the residual stress, an effective method is to lower the linear thermal expansion coefficient of the polyimide which is an insulating film itself. The linear thermal expansion coefficient of most polyimides is in the range of 40ppm/°C~100ppm/°C, which is much larger than the linear thermal expansion coefficient of metal foil such as copper foil of 17ppm/°C. Therefore, the industry is studying the development coefficient of thermal expansion coefficient. The value of the copper foil shows a polyimine of a linear thermal expansion coefficient of about 20 ppm/° C. or less.

At present, as a practical polyimine material, a polyimine formed from 3,3',4,4'-biphenyltetracarboxylic dianhydride and p-phenylenediamine is well known. The polyimide film 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. The previous polyimine also absorbs 2% by mass to 3% by mass of water. A circuit position shift occurring simultaneously with a dimensional change due to moisture absorption of the insulating layer is a serious problem for high-density wiring or multilayer wiring. Due to the decrease in electrical characteristics, it causes a more serious problem such as corrosion (Corrosion), ion migration, and dielectric breakdown at the polyimide/conductor interface. Therefore, the hygroscopic expansion coefficient of the polyimide layer as the insulating film is required to be as low as possible.

In order to achieve a low coefficient of hygroscopic expansion, for example, it is reported that a polyester phthalimide having an acid dianhydride having an ester structure in a skeleton represented by the formula (20) is effective (refer to Patent Document 1):

However, it is generally considered that a polyester quinone imine film 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 to be a diamine. The polyester yttrium imide film having a high bending coefficient and having a high linear thermal expansion coefficient is a flammable film:

Here, if a diamine having a rigid structure of the formula (24) is used as the diamine, it has a low coefficient of thermal expansion, but has a high modulus of elasticity due to its rigidity, and thus is not suitable for applications requiring low repellency. It is assumed that the adhesion (peel strength with metal foil) will decrease:

Therefore, a polyester quinone imine using an acid dianhydride represented by the formula (19) (hereinafter referred to as TABP) has been reported (see Patent Document 2):

The polyester phthalimide obtained by using the diamine and the acid dianhydride disclosed in Patent Document 2 simultaneously exhibits a low thermal expansion coefficient and a low water absorption (1.2% to 1.9%). However, it is generally considered that a polyesterimine film having a water absorption of 1.2% is difficult to satisfy the requirement of a low hygroscopic expansion coefficient (8 ppm/% RH or less, 30% 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 rupture 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 high tear strength cannot be achieved by the composition of the polyester quinone imine described. Further, it is generally considered that the glass transition temperature is also low because a bending molecule such as the formula (21) or the formula (25) is used:

On the other hand, polyester quinone imine using a compound having an ester structure in a diamine has also been reported (see Patent Document 3). However, it is still considered that this situation is also incapable of obtaining high tear strength as described above.

Also, there may be an abnormality 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 trimellitic anhydride chloride with a diol in benzene or toluene (Patent Document 4), or a low-grade phenol. Transesterification of an alkanoate with trimellitic anhydride (Patent Document 5); crude crystals of TABP can be obtained by these methods. However, if the obtained crude crystal is used to copolymerize with an aromatic diamine, a part of the obtained polyimide intermediate precursor solution gels, and if the polyimine precursor solution is used to produce a poly The ruthenium imine film may cause an abnormality in the mechanical properties of the polyimide film.

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 a copper foil in a state in which the polymerization reactivity or the film forming processability are maintained. 30% RH-70% RH), flexibility, solder heat resistance, high glass transition temperature, high adhesion, low modulus of elasticity, and high tear strength of polyimine, which has not been known to meet this requirement Useful materials for the characteristics.

[Patent Document 1] Japanese Patent Laid-Open No. Hei 10-70157

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-336011

[Patent Document 3] Japanese Patent No. 3712164

[Patent Document 4] Japanese Patent Publication No. 43-5911

[Patent Document 5] Japanese Patent Laid-Open No. Hei 07-41472

[Non-Patent Document 1] Macromolecules, 29, 7897 (1996)

The present invention has been made in view of the above problems, and an object of the present invention is to provide a low linear thermal expansion coefficient, a high glass transition temperature, a high adhesion property, and a low flame retardancy, a low moisture absorption coefficient, and a copper foil. Polyester phthalimide with high modulus of elasticity and high tear strength.

The polyester quinone imine precursor of the present invention is characterized by having a repeating unit represented by the following formula (1):

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

R ₁ represents an alkyl group having 1 to 6 carbon atoms; R ₂ to R ₄ 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; R ₅ represents a carbon number of 1~ 6 alkyl; R ₆ to R ₉ represent an alkyl group having 1 to 6 carbon atoms, and a hydrogen atom).

In the polyester quinone imine precursor of the present invention, in the above polyester quinone imine precursor, B ₁ in the formula (1) is preferably a repeating unit represented by the formula (3) or the formula (4). Further, it is preferably a repeating unit represented by the formula (4), and particularly preferably a formula (10) in which a hydrogen atom is selected from R ₂ to R _{4 in} the formula (4):

The polyester quinone imine precursor of the present invention has a repeating unit represented by the following formula (11) and formula (12), and the molar ratio of the formula (11) and the formula (12) is a formula (11). ) / (12) = 20/80 ~ 80 / 20 ratio:

(In the formulae (11) and (12), Ar is a tetravalent aromatic group represented by the formula (2); and in the formula (12), B ₂ is selected from the group consisting of the formula (13) to the formula (17). At least one divalent aromatic group:

R ₁₀ to R ₁₈ 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).

In the polyester quinone imine precursor of the present invention, in the above polyester quinone imine precursor, B ₂ in the formula (12) is preferably a formula (16), a formula (17) or a formula (18). The repeating unit represented, and more preferably the repeating unit represented by the formula (16):

In the polyester quinone imine precursor of the present invention, the weight average molecular weight Mw is preferably 30,000 or more and 400,000 or less.

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 peak temperature 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 (b) °C, and set the temperature width ΔT=((b)-(a)) °C, satisfy (a) ≧ 322 ° C and ΔT ≦ 5 ° C:

The polyester quinone imine of the present invention is obtained by imidating the above polyester quinone imine precursor quinone.

The method for producing a polyester quinone imine according to the present invention is characterized in that the polyester quinone imine precursor is heated or the hydrazine is imidized using a dehydrating reagent to obtain a polyester quinone.

The laminate of the present invention is characterized in that it has a polyester quinone layer and a metal layer, and the polyester quinone layer is composed of the above polyester quinone.

The laminated board of the present invention is obtained by applying a polyester quinone imide precursor to a metal foil, drying it, heating it, or imidating the hydrazine using a dehydrating agent.

A flexible printed wiring board according to the present invention is characterized in that the metal layer of the laminated board is patterned by wiring.

The polyester quinone imine obtained from the polyester quinone imine precursor 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, and high subsequent The effect of sex, low modulus of elasticity, and high tear strength.

As a molecular design for thermally expanding the 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 a plurality of conformations by internal rotation). On the other hand, however, there is a fear that the entanglement of the polymer chain is reduced 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 the toughness of the film or an increase in the adhesion strength to the metal foil, but it is presumed to hinder the low-line thermal expansion property. which performed.

The ester structure of interest in the present invention has a higher internal rotation barrier 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 backbone has a degree of softness to provide a flexible film.

Further, since the ester structure is lower in polarizability than the guanamine structure or the quinone imine structure, introduction of the ester structure into the polyimide reaction is also advantageous in reducing the hygroscopic expansion coefficient.

In the present invention, a specific aromatic skeleton and an ester structure can be introduced into the polyimine by selecting a monomer having a specific aromatic skeleton and an ester structure as an acid dianhydride and a diamine, and A polyester quinone imine precursor of a repeating unit represented by the formula (1). Thereby, the polyester phthalimide 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:

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

R ₁ represents an alkyl group having 1 to 6 carbon atoms; R ₂ to R ₄ 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; R ₅ represents a carbon number of 1~ 6 alkyl; R ₆ to R ₉ represent an alkyl group having 1 to 6 carbon atoms and a hydrogen atom.

The polyester quinone imine 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, so that the obtained polyester quinone imine precursor is of a 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 an ester group is used as an essential component. At least one diamine selected from the group consisting of the formulae (26) to (33) is used. R ₁ represents an alkyl group having 1 to 6 carbon atoms. R ₂ to R ₄ 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. R ₅ represents an alkyl group having 1 to 6 carbon atoms. R ₆ to R ₉ represent an alkyl group having 1 to 6 carbon atoms and a hydrogen atom. Here, from the viewpoint of low modulus of elasticity and adhesion, the formula (26), the formula (27), and more preferably the formula (27), and particularly preferably the formula (33):

Further, from the viewpoint of warpage of the laminated sheet after curing and tear strength of the obtained polyester yimimide film, when the polyester quinone imine precursor of the present invention is polymerized, it is preferred to use TABP and (33) a diamine having an ester structure (hereinafter referred to as BPIP) as an essential component, and further using at least one diamine selected from the group consisting of formula (34) to formula (39); further preferably (37), formula (38), formula (39); in terms of the tear strength of the obtained polyester phthalimide film, particularly preferred is formula (37):

Here, R ₁₀ to R ₁₈ 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, in general, a polyester yimimide film having a linear thermal expansion coefficient equivalent to that of a copper foil has a small amount of warpage after curing, but it has been found that it is not possible to judge the cured warp only by the linear thermal expansion coefficient. As a result of the curve, it has a line thermal expansion coefficient equivalent to that of copper foil and a smaller amount of warpage is 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) = 20 / 80 to 80 / 20, the TABP and the total diamine are mixed at a ratio of about 1:1, When the total diamine is used as 100 mol%, BPIP having a diamine molar number of 20 mol% to 80 mol%, and further using a diamine molar number of 20 mol% to 80 mol% is selected from the formula (34) to 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 the formula (11) / formula (12) = 20 / The ratio of 80 to 80/20 is more preferably the ratio of the formula (11) / the formula (12) = 30/70 to 70/30.

Further, it is necessary to prepare a polyimine precursor solution of a high molecular weight body having no gel component, and a bonding strength of the metal/polyimine laminate and a tear strength of the polyimide film. The TABP used for the component is preferably a high purity one. Specifically, it is preferable that the peak temperature of the heat of fusion is set to (a) ° C in the graph of FIG. 1 displayed by the differential scanning calorimeter, and the temperature at which the peak toward the melting heat wave rises is used as a connection point. It is assumed that the temperature at the intersection of the tangent line and the straight line along the substantially straight line portion of the melting heat peak is (b) ° C, and the set temperature width ΔT = ((b) - (a)) ° C satisfies (a) ≧ 322 ° C and TABP of ΔT ≦ 5 ° C, and further preferably TABP satisfying (a) ≧ 325 ° C and ΔT ≦ 4 ° C.

The present inventors focused on the process of purifying TABP in order to make TABP high-purity, and found the following. That is, the present inventors have found that the 4,4'-bisphenol derivative represented by the formula (40) is effectively removed by recrystallization by a specific solvent, concentration, and temperature conditions, or is presumed to be An oligomer obtained by ring-opening reaction of 4,4'-bisphenol represented by the formula (41) with trimellitic anhydride ruthenium chloride, and the like, and then dried by heating and drying to remove the adhered water adhered to the crystal. And crystal water, thereby causing a part of the ring-opening tetracarboxylic acid to undergo acidification upon recrystallization, thereby obtaining high purity TABP:

(here, n is 1~5).

TABP is accompanied by an increase in purity, and the melting heat peak temperature indicated by a differential scanning calorimeter (DSC) moves toward the high temperature side, and the melting heat peak temperature is taken as (a) ° C, and the temperature at which the melting heat peak starts to rise is used as a connection. The temperature difference between (a) and (b) is obtained when the temperature at the intersection of the line and the line along the line of the substantially straight line of the melting heat peak is assumed to be (b) °C.

TABP can be obtained by a reaction obtained by reacting trimellitic anhydride ruthenium chloride with a diol in an organic solvent or transesterifying a lower alkanoate of a phenol with trimellitic acid or an anhydride thereof. The product is recrystallized under specific solvent, concentration, and temperature conditions, and then subjected to anhydrous heating and drying treatment.

As the solvent used for recrystallization to obtain high-purity TABP, a lactone solvent having a cyclic ester structure, a solvent having a cyclic ketone structure, a cyclic carbonate structure or a cyclic fluorene structure is preferred. For example, α-methylene-γ-valerolactone, α-methylene-γ-butyrolactone, γ-methylene-γ-butyrolactone, γ-valerolactone, γ-butane Ester, cyclopentanone, propylene carbonate, ethylene carbonate, cyclobutyl hydrazine. These may be used alone or in combination of two or more. Among these, γ-butyrolactone, γ-valerolactone, and cyclobutyl hydrazine are preferably used from the viewpoints of solubility, recrystallization yield, or economy.

The amount of use of the solvent, in consideration of removal of impurities and recrystallization yield, is from 1 part by weight to 150 parts by weight, particularly preferably from 4 parts by weight to 100 parts, per 1 part by weight of the product obtained by the reaction. Parts by weight. When the concentration of the ester group-containing tetracarboxylic dianhydride in the solution containing the ester group and the tetracarboxylic acid dianhydride and the solvent is used as the solid content concentration, the solid content concentration is preferably 50% or less, from the viewpoint of productivity. Better still is less than 20%.

When recrystallization is carried out, the tetracarboxylic acid dianhydride containing an ester group is mixed with a specific amount of the solvent so as to reach the above concentration, and the mixed solution is heated to 150 ° C to 300 ° C to be completely dissolved. Thereafter, a precipitate was obtained by allowing the solution to stand at room temperature, and the precipitate was filtered. By this step, the 4,4'-bisphenol derivative represented by the formula (40) produced by the reaction or the 4,4'-bisphenol represented by the formula (41) and the specimative partial benzene are obtained. The oligomer obtained by the ring-opening reaction of the trimethyl anhydride ruthenium chloride remains in the filtrate, whereby it can be efficiently removed:

(here, n is 1~5).

In an inert gas atmosphere such as nitrogen, helium or argon, at atmospheric pressure or reduced pressure, at a temperature rise rate of 1 ° C / min to 20 ° C / min, at a temperature of 200 ° C ~ 300 ° C, by filtration The obtained precipitate was subjected to an anhydrous heat treatment for 3 hours or more to remove the adhered water and the crystal water adhering to the crystal, and a part of the tetracarboxylic acid which was opened at the time of recrystallization was acidified. 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 200 ° C to 300 ° C for 3 hours or more. 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 20 ° C / min or less.

The melting heat peak temperature (a) °C indicated by the differential scanning calorimeter (DSC) is the melting point (mp) of the substance, preferably shifted from 325 ° C to the high temperature side from 325 ° C, and will begin to be toward the heat of fusion. When the temperature at which the peak rises is 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 ° 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 moisture absorption coefficient, a high-priced monomer such as a fluorinated monomer (a monomer containing a fluorine atom) is not used, and thus 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, and the present invention is not limited to the contents.

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, low hygroscopic expansion coefficient, and low equivalent to copper foil when it is made into a laminate of copper foil/polyester phthalimide and a polyester yttrium imide film. Linear thermal expansion coefficient, high glass transition temperature, flexibility, high adhesion, low modulus of elasticity, and high tear strength.

<Method for producing polyester quinone imine precursor>

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, and stirred at 0 ° C to 100 ° C, preferably 20 ° C to 90 ° C for 0.5 hour to 100 hours using a mechanical stirrer. It is preferably 1 hour to 24 hours. In this case, from the viewpoint of the degree of polymerization and the solubility of the monomer or the produced polymer, the monomer concentration is preferably from 5% by mass to 50% by mass, and more preferably from 10% by mass to 40% by mass. %, particularly preferably 10% by mass to 25% by mass. A uniform and high degree of polymerization of the polyester quinone imine precursor solution can be obtained by carrying out the polymerization within the monomer concentration range. Here, the obtained polyester quinone imide precursor solution is the same as the polyester quinone imine precursor system described in the patent application.

The weight average molecular weight (Mw) of the polyesterimide film is preferably from 30,000 to 400,000, and more preferably from 30,000 to 300,000. Also, especially good is 50,000 to 200,000. 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 molecular weight (Mw) is preferably 400,000 or less, more preferably 300,000 or less, and particularly preferably 200,000 or less.

As for the aromatic tetracarboxylic dianhydride which can be used together with TABP, in the range which does not impair the required properties of the polyester quinone imide film and the polymerization reactivity of the polyester quinone imine precursor, 3, 3' can be cited. , 4,4'-biphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic acid Dihydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, p-phenylene bis(trimellitic acid monoester anhydride), p-methylphenylene bis(trimellitic acid monoester) Anhydride), 3,3',4,4'-biphenylfluorene tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropionic acid dianhydride, 2,2'-double (3,4-Dicarboxyphenyl)propionic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and the like. Further, two or more of these may be used in combination.

The aliphatic tetracarboxylic dianhydride 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] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 5-(dioxotetrahydrofuranyl-3-methyl-3-cyclohexene-1,2-dicarboxyl Anhydride, 4-(2,5-dioxatetrahydrofuran-3yl)-tetrahydronaphthalene-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, bicyclo-3,3 ',4,4'-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, etc. Two or more of these.

It can be expressed as represented by the general formulae (26) to (39) within a range that does not significantly impair the polymerization reactivity of the polyester quinone imine precursor of the present invention and the desired properties of the polyester quinone imine. The aromatic diamine used in combination with the diamine of the ester structure is not particularly limited, and examples thereof include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, and 2, 4-diaminoxylene, 2,4-diaminotetramethyl, 4,4'-diaminodiphenylmethane, 4,4'-methylenebis(2-methylaniline), 4, 4'-methylenebis(2-ethylaniline), 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-methylenebis(2,6-di Ethyl aniline), 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diamino group Phenyl ether, 4,4'-diaminodiphenyl hydrazine, 3,3'-diaminodiphenyl hydrazine, 4,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl Ketone, 4,4'-diaminobenzimidamide, benzidine, 3,3'-dihydroxybenzidine, 3,3'-dimethoxybenzidine, o-toluidine, m-toluidine , 2,2'-bis(trifluoromethyl)benzidine, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxyl) Benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(3-aminophenoxy) Phenyl) guanidine, bis(4-(4-aminophenoxy)phenyl)anthracene, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 2,2-double (4-(4-Aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, p-terphenylphenyldiamine, and the like. Further, two or more of these may be used in combination.

It can be expressed as represented by the general formulae (26) to (39) within a range that does not significantly impair the polymerization reactivity of the polyester quinone imine precursor of the present invention and the desired properties of the polyester quinone imine. The aliphatic diamine used in combination with the diamine of the ester structure is not particularly limited, and examples thereof include 4,4'-methylenebis(cyclohexylamine), isophoronediamine, and trans-1,4-. Diaminocyclohexane, cis-1,4-diaminocyclohexane, 1,4-cyclohexanebis(methylamine), 2,5-bis(aminomethyl)bicyclo[2.2. 1] heptane, 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, 3,8-bis(aminomethyl)tricyclo[5.2.1.0]decane, 1,3- Diamine adamantane, 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(4-aminocyclohexyl)hexafluoropropane, 1,3-propanediamine, 1,4- Tetramethyldiamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine 1,9-nonamethylenediamine. Further, two or more of these may be used in combination.

The solvent to be used in the polymerization reaction is not particularly limited as long as it can dissolve the raw material monomer and the produced polyester quinone imide precursor, and the structure thereof is not particularly limited. Specific examples thereof include an amine solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone; γ-butyrolactone and γ-valerolactone; a cyclic ester solvent such as δ-valerolactone, γ-caprolactone, ε-caprolactone or α-methyl-γ-butyrolactone; a carbonate such as ethylene carbonate or propylene carbonate; a solvent; an alcohol solvent such as triethylene glycol; a phenol solvent such as m-cresol, p-cresol, 3-chlorophenol or 4-chlorophenol; acetophenone, 1,3-dimethyl-2- Imidazolidinone, cyclobutyl hydrazine, dimethyl hydrazine and the like. From the viewpoint of solubility, preferred are N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl alum An aprotic polar solvent such as 1,3-dimethyl-2-imidazolidinone.

Further, other common organic solvents may be added, namely phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 2-ethoxyethanol, 2-butyl Oxyethanol, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, Diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, turpentine , mineral spirits, petroleum essence solvents, etc.

The polyester quinone imine precursor of the present invention may be added dropwise to a large amount of a poor solvent such as water or methanol, filtered, dried, and separated as a powder.

<Method for producing polyester quinone imine>

The polyester quinone imine of the present invention can be produced by subjecting a polyester quinone imine precursor obtained by the above method to a dehydration ring-closure reaction (oxime imidization reaction). In this case, the polyester iodide can be used in the form of a laminate of a film, a metal foil/polyester quinone, a powder, a molded body, and a solution.

The polyester bismuth imide precursor solution is cast onto a metal foil such as copper foil or aluminum foil, and dried in an oven at 40 ° C to 180 ° C, preferably 50 ° C to 150 ° C. The laminated plate of the obtained metal/polyester phthalimide precursor is adhered and fixed to a metal plate made of SUS by using a tape, and is preferably in a vacuum, an inert gas such as nitrogen, or air, at 200 ° C to 430 ° C. The heating is carried out at 250 ° C to 400 ° C, whereby a metal/polyimine laminate is obtained. The metal layer of the laminate is etched away, whereby the polyester phthalimide film of the present invention can be produced. Further, there is also a method of obtaining a polyester phthalimide film by using a metal ruthenium substrate. At this time, the polyester phthalimide precursor solution is cast onto a ruthenium substrate on which a metal layer is vapor-deposited, and dried and heated by the above method to obtain a laminate of a ruthenium/polyester phthalimide layer on which a metal layer is vapor-deposited. board. Thereafter, the metal layer of the laminate is etched, and a polyester phthalimide layer (polyester phthalimide film) is peeled off from the ruthenium substrate, whereby a target product can be obtained.

Further, there is a method in which a polyester bismuth imide film is obtained by using a glass substrate. The polyester bismuth imide precursor solution is cast onto a glass substrate, and dried in an oven at 40 ° C to 180 ° C, preferably 50 ° C to 150 ° C to obtain a glass substrate / polyester phthalimide precursor layer. Laminated board. Thereafter, the polyester phthalimide precursor layer (polyester phthalimide precursor film) is peeled off from the laminated board, and the polyester phthalimide precursor film is fixed on the metal frame using a tape, and is carried out by the above method. Heating, whereby a polyester quinone film can be obtained.

From the viewpoint of the ring closure reaction of ruthenium imidation, the reaction temperature is preferably 200 ° C or more, and the reaction temperature is preferably 430 ° C from the viewpoint of thermal stability of the produced polyester fluorene imide film. the following. The ruthenium imidization is preferably carried out in a vacuum or in an inert gas, but if the ruthenium imidization temperature is not excessively high, it can also be carried out in the air.

Further, instead of the heat treatment, the oxime imidization reaction may 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. The product is imidized by heating at 200 ° C to 300 ° C or immersed in a solution containing 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 phthalimide precursor solution will be described, but the method is not limited thereto, and the mixture may be heated and dried by heating or using a dehydrating agent. The oxime imine precursor film or the separated polyester quinone imine 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 imide powder as a precipitate can be obtained. The polyester quinone imine powder is heated and compressed at 200 ° C to 450 ° C, preferably 250 ° C to 430 ° C, whereby a molded body of polyester quinone is produced.

Further, a dehydrating reagent such as N,N'-dicyclohexylcarbodiimide or trifluoroacetic anhydride is added to the polyester quinone imine precursor solution and stirred at 0 ° C to 100 ° C. The reaction is carried out at 0 ° C to 60 ° C to thereby form a polyisoimide which is an isomer of polyester quinone imine. The polyisocyanine solution is formed into a film by the same procedure as described above, and then heat-treated at 250 ° C to 450 ° C, preferably 270 ° C to 400 ° C, whereby it can be easily converted into a polyester oxime. amine. The isoindole imidization reaction may be carried out by immersing the polyester quinone imine precursor film in the above-described solution containing a dehydrating reagent.

When the polyester quinone imine is dissolved in a solvent, the polyester phthalimide precursor solution is directly diluted with the same solvent and heated to 150 ° C to 200 ° C, whereby the polyester phthalate can be easily produced. Amine solution. At this time, toluene or xylene may be added for azeotropic distillation to remove water or the like which is a by-product of ruthenium. Further, a base such as γ-methylpyridine may be added as a catalyst.

The obtained polyester phthalimide solution may be added dropwise to a large amount of a poor solvent such as water or methanol, and then filtered to separate a polyester quinone imine as a powder. Further, the polyester quinone imine powder can be redissolved in the above solvent to form a polyester quinone imine solution.

The polyester quinone imide of the present invention is obtained by imidating the polyester quinone imine 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 from 0.90 to 1.10.

The terminal structure of the obtained polyester quinone is an amine or anhydride structure depending on the molar ratio of total tetracarboxylic dianhydride to total diamine at the time of production. In the case where the terminal structure is an amine, a carboxylic acid anhydride can be used for the terminal sealing. As such examples, phthalic anhydride, 4-phenyl phthalic anhydride, 4-phenoxyphthalic anhydride, 4-phenylcarbonyl phthalic anhydride, 4-benzene can be mentioned. The sulfonyl phthalic anhydride or the like is not limited thereto. These carboxylic anhydrides may be used singly or in combination of two or more.

Further, in the case where the terminal structure is an acid anhydride, a terminal seal can be performed using a monoamine. Specific examples thereof include aniline, toluidine, aminophenol, 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, first, an aromatic diamine is dissolved in a solvent at 0 ° C to 80 ° C under an inert atmosphere such as nitrogen, helium or argon, and rapidly added at 40 ° C to 100 ° C. The tetracarboxylic dianhydride is subjected to addition polymerization for 4 hours to 8 hours. Thereby a polyester quinone imine precursor is obtained.

The polyester quinone imine solution is applied onto a substrate and dried at 40 ° C to 400 ° C, preferably at 100 ° C to 300 ° C, whereby a polyester quinone imine film can be formed.

The polyester bismuth imide precursor solution is applied onto a metal foil such as a copper foil, dried, and then iridized by the above conditions, whereby the original layer of the FPC substrate, that is, the metal layer and the polyester quinone layer can be obtained. Laminates (FCCL). Here, a copper foil is used as a metal foil, and a polyester phthalimide precursor solution is directly applied onto the copper foil, whereby a non-adhesive two-layer type composed of a copper foil and a polyester quinone layer can be obtained. Laminated board. On the other hand, a three-layer or pseudo-two-layer type in which a polyester phthalimide layer and a copper foil are attached by using an epoxy-based adhesive or a thermoplastic polyimide, as an adhesive agent, is also used as a constituent of the FCCL. However, in this case, since the adhesive must have thermoplasticity, the constituent unit of the adhesive must contain a bending component, resulting in a high coefficient of hygroscopic expansion, a decrease in glass transition temperature and heat resistance. Therefore, in the three-layer, pseudo-two-layer type laminated board, since the thermoplastic adhesive layer is interposed, a high hygroscopic expansion coefficient, a low glass transition temperature, and low heat resistance are inevitably caused. On the other hand, since the polyester quinone imine of the present invention has high adhesion, a two-layer type laminated board can be obtained without the interlayer, and the polyester quinone itself has non-thermoplasticity. Therefore, it is also possible to have both a high glass transition temperature, a high heat resistance, and a low moisture absorption coefficient.

As the metal foil of the FPC board, various metal foils can be used, but aluminum foil, copper foil, and stainless steel foil are preferable, and copper foil is especially preferable. The metal foil may be subjected to surface treatment such as roughening treatment, plating treatment, chroma treatment, aluminum alcoholate treatment, aluminum chelate treatment, or decane coupling agent treatment.

The thickness of the metal foil is not particularly limited, but is preferably 35 μm or less, more preferably 18 μm or less.

The FCCL can be manufactured, for example, in the following manner.

First, a polyester phthalimide precursor solution is applied onto a metal foil using a knife coater, a belt coater, a gravure coater or the like. Thereafter, it is dried to form a polyester phthalimide precursor layer (hereinafter also referred to as "polyester phthalimide precursor film"). The coating thickness is affected by the solid content concentration of the polyester quinone imine precursor solution. The polyester bismuth imide precursor layer is heated at 200 ° C to 400 ° C in an inert atmosphere such as nitrogen, helium or argon. The oxime is imidized, whereby a polyester quinone layer can be formed. The thickness of the polyester quinone layer is 100 μm or less, preferably 50 μm or less, more preferably 30 μm or less.

Further, the peel strength of the polyesterimide layer and the metal foil is preferably 0.8 N/mm or more, and more preferably 1.0 N/mm or more. The amount of warpage is preferably 10 mm or less, and more preferably 3 mm or less.

At room temperature or below 50 ° C, using ferric chloride aqueous solution (manufactured by Tsurumi Soda Co., Ltd., 40 Baume (specific gravity unit), ferric chloride content of 37% or more) as an etching solution pair The FCCL is etched to etch the metal layer of the laminated board 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 60 mN or more, and particularly preferably 80 mN or more in the 26 μm polyimine film. The elastic modulus is preferably 4.0 GPa to 6.5 GPa. The coefficient of hygroscopic expansion is preferably 7 ppm/% RH or less, the coefficient of linear thermal expansion is preferably 16 ppm/° C. to 25 ppm/° C., and the glass transition temperature is preferably 350° C. or higher.

In the polyester quinone imine and the precursor solution thereof of the present invention, an additive such as an oxidative stabilizer, a filler, an adhesion promoter, a decane 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.

<Polyester ylide precursor solution>

First, a diamine containing an ester structure is dissolved in N-methyl-2-pyrrolidone, and a tetracarboxylic dianhydride powder containing an ester structure is slowly added thereto, and stirred by a mechanical stirrer under heating at 80 ° C. 3~5 hours. At this time, polymerization is carried out in a monomer concentration range in which the monomer concentration is 10% by mass to 20% by mass, whereby a uniform and high degree of polymerization of the polyester quinone imine precursor solution is obtained.

<Copper foil/polyester phthalimide laminate>

A 12 μm-thick copper foil (Nippon Electrolysis Co., Ltd.: USLP foil) was placed on the metal coating table so that the roughened surface side became the surface. The surface temperature of the coating table was set to 90 ° C, and the polyester quinone imine precursor solution obtained above was applied onto the roughened surface of the copper foil by a doctor blade. Thereafter, it was allowed to stand on the coating table for 30 minutes, and further allowed to stand at 100 ° C for 30 minutes in a desiccator to obtain a non-tacky copper foil/polyester ylide precursor laminate (polyester yam) The thickness of the amine precursor layer was 47 μm and 24 μm). Then, the laminate of the copper foil/polyester ylide precursor was adhered and fixed to a metal plate made of SUS by a tape, and the temperature was raised at 150 ° C in a hot air dryer at a heating rate of 5 ° C / min in a nitrogen atmosphere. The imidization was carried out for 30 minutes, and the imidization was carried out at 200 ° C for 1 hour, and the imidization was carried out at 400 ° C for 1 hour. Thereafter, a metal plate made of SUS was removed to obtain a laminate of copper foil/polyester liminimide.

<Polyester ylide film>

The copper foil/polyester obtained above is obtained by using a ferric chloride solution (manufactured by Tsurumi Soda Co., Ltd., 40 Baume, and a ferric chloride content of 37% or more) under heating at room temperature or below 50 ° C. The copper foil of the laminate of yttrium imide was etched, thereby obtaining a polyester yimimide film having a film thickness of 26 μm and 12 μm.

<weight average molecular weight: Mw>

0.01 g of the polyester quinone imide precursor solution was measured using a precision balance, and dissolved in 10 g of the developing solvent. The developing solvent was dissolved in 1 L of dimethylformamide by using 2.61 g of lithium bromide (manufactured by Aldrich Co., Ltd.) and 5.88 g of an aqueous phosphoric acid solution (manufactured by Wako Pure Chemical Industries, Ltd., purity: 85%) (Wako Pure Chemical Industries, Ltd.) Manufactured, liquid chromatography). The solution was filtered through a 10 μm filter. Then, TSK guard column Super HH (trade name, manufactured by Tosoh Soda Co., Ltd.), which is a protective column, and TSK-GEL SUPER HM-H (trade name, manufactured by Tosoh Corporation), which is a separation column, are used. GPC (colloidal permeation chromatography, manufactured by JASCO Corporation) connected in series was used, and the molecular weight was measured at a flow rate of 0.5 ml/min using the above-mentioned developing solvent. The molecular weight is converted using polystyrene.

<glass transition temperature: Tg>

Using a thermomechanical analyzer (TMA-50) manufactured by Shimadzu Corporation, the thermodynamic analysis was carried out at a load of 5 g, a temperature increase rate of 10 ° C / min, a nitrogen atmosphere (flow rate of 20 ml / min), and a temperature of 50 ° C to 450 ° C. Within the range, the elongation of the polyesterimine film having a width of 3 mm, a length of 18 mm (the length between the chucks of 15 mm), and a thickness of 26 μm was measured, and the polyester yimimide film was obtained from the inflection point of the obtained curve. (26 μm thick) glass transition temperature.

<Line thermal expansion coefficient: CTE>

Using a thermomechanical analyzer (TMA-50) manufactured by Shimadzu Corporation, the thermodynamic analysis was carried out at a load of 5 g, a temperature increase rate of 10 ° C / min, a nitrogen atmosphere (flow rate of 20 ml / min), and a temperature of 50 ° C to 450 In the range of °C, the elongation of the polyesterimine film with a width of 3 mm, a length of 18 mm (the length between the chucks of 15 mm) and a thickness of 26 μm was measured, and the average value of the film elongation in the range of 50 ° C to 200 ° C was measured. The linear thermal expansion coefficient of the polyester yttrium imide film (26 μm thick) was obtained.

<Moisture expansion coefficient: CHE>

The thermal mechanical analysis device (TM-9400) manufactured by ULVAC Technology Co., Ltd. and the humidity environment adjustment device (HC-1) were used to measure a width of 3 mm and a length of 30 mm at 23 ° C under a load of 5 g. The elongation of the polyester yimimide film with a length of 15 mm and a thickness of 26 μm when the humidity changes from 30% RH to 70% RH is obtained by the average value of the elongation of the film in 30% RH to 70% RH. The coefficient of hygroscopic expansion of the polyesterimine film.

<Flame retardancy>

A polyester yimimide film having a thickness of 12 μm was made into 40 test pieces each having a size of 20 cm long by 5 cm. Twenty of the 40 test pieces were placed in an environment of 23 ° C and a relative humidity of 50% for 48 hours or more (accepted state), and the remaining 20 pieces were aged at a temperature of 70 ° C for 168 hours, and then the temperature was 23 ° C. Cooling in a drier with a relative humidity of 20% or less for 4 hours. Five sheets of each of the polyester phthalimide films were used, and VTM-0 evaluation was performed by a flammability test in an environment of 23 ° C and a relative humidity of 55% based on the evaluation method of the UL94 VTM test. (Furthermore, the flame used in the evaluation at this time was a blue flame of 20 mm in size, and the temperature rise time of the copper slag from 100 ° C to 700 ° C was 42.9 seconds.)

<Solder heat resistance evaluation>

The laminate of copper foil/polyester yttrium was cut into a size of 3 cm × 3 cm in width, and the center portion was shielded by 2.5 cm × 2.5 cm using a masking tape, and under the same conditions as above, three were used. A ferric chloride solution (manufactured by Tsurumi Soda Co., Ltd., 40 Bomei, and a ferric chloride content of 37% or more) was etched to obtain a test piece. The obtained test piece was allowed to stand in a desiccator at 105 ° C for 1 hour or more and dried, and then the test piece was allowed to stand on the surface of the solder bath in contact with the copper foil side in a solder bath set at 300 ° C. In the minute, the appearance change such as the occurrence of swelling or wrinkles in the copper foil and the polyester yttrium imide film was visually evaluated, and the change in appearance was not observed as a good result (○).

<Boiler solder heat resistance evaluation>

A test piece was prepared in the same manner as in the evaluation of solder heat resistance, and purified water was placed in a container equipped with a reflux cooler to impregnate the obtained test piece, and allowed to stand at 100 ° C 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. Thereafter, in each of the solder baths set to 280 ° C, each test piece was placed on the surface of the solder bath for 2 minutes in contact with the copper foil side, and visually evaluated whether there was any copper foil and polyester yttrium imide film. Appearance changes such as swelling and wrinkles occurred, and no change in appearance was observed as a good result (○).

<Continuity of copper foil and polyester bismuth layer>

The measurement method of the test piece was carried out based on the JIS C6471 specification. The laminate of copper foil/polyester yttrium was cut into a size of 15 cm × 1 cm in width, and the center portion of 1 cm was shielded by a width of 3 mm by a masking tape, and the copper foil was treated with a ferric chloride solution under the same conditions as above. Etching is performed. The obtained test piece was allowed to stand in a desiccator at 105 ° C for 1 hour or more, and then dried, and then fixed on a FR-4 substrate having a thickness of 3 mm using a double-sided tape. A conductor having a width of 3 mm was peeled off from the interface with the polyesterimide 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. At the time of fixing, a jig was attached in order to surely peel in the 90° direction, and the load at the time of peeling 50 mm at a speed of about 50 mm/min was measured, and the adhesion strength per 1 cm was calculated.

<elasticity>

Using a RTG-1210 tensile tester manufactured by OLIENTEC Co., Ltd., a polyimine film of 3 mm × 50 mm was stretched at a test length of 50 mm and a test speed of 50 mm/min. The elastic modulus was pulled by a polyester yimimide film. The elongation at break is calculated from the stress gradient between 0.4% and 1.0%. (When a 50 mm sample breaks when it is stretched to 100 mm, it is referred to as "tensile elongation at break is 100%".)

<trouser tear strength>

The polyester bismuth imide film was cut into a sample of 50 mm × 150 mm, and a tensile test device of RTG-1210 type manufactured by OLIENTEC Co., Ltd. (installation of a UR-50N-D type load cell manufactured by the same company) was used. The measurement was carried out at a test speed of 50 mm/min in accordance with the method described in JIS K7128-1.

<warp>

The laminate of copper foil/polyester ylide was cut into a size of 10 cm × 10 cm, and it was placed in a constant temperature and humidity chamber at 23 ° C and a humidity of 50% for one day. Thereafter, 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 (+).

<melting heat peak temperature (a) ° C, temperature width ΔT = ((b) - (a)) ° C >

A tetracarboxylic dianhydride (hereinafter referred to as TABP) having an ester structure represented by the formula (19) is weighed and weighed in about 5 mg, placed in an attached aluminum sample container, covered with a lid, and crimped to prepare a measurement. sample:

Similarly, the un-weighed aluminum 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 calorimeter (DSC-60, manufactured by Shimadzu Corporation) at a temperature rising rate of 10 ° C / min, N ₂ atmosphere, and room temperature ~ 350 The measurement was carried out within the range of °C. The peak temperature of the heat of fusion is taken as (a) ° C, and the temperature at which the temperature toward the peak of the heat of fusion is started is calculated as the temperature at the intersection of the assumed tangent line of the joint point and the straight line along the substantially straight portion of the heat flux peak as (b) ° C. The temperature is wide ΔT = ((b) - (a)) °C. Furthermore, the temperature and heat flux are corrected by indium standard materials.

(Example 1) (Synthesis Example 1) Synthesis of TABP

In a 1 L separable flask, 200 mmol of trimellitic anhydride ruthenium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 100 ml of N,N-dimethylformamide solution and placed in an ice bath under a nitrogen atmosphere. It was cooled to 0 °C. Thereafter, a solution of 4,4'-bisphenol was dissolved in 50 ml of N,N-dimethylformamide and 50 mL of pyridine in a manner of a temperature of 10 ° C or less for 2 hours at a stirring speed of 100 rpm. It was added dropwise to the flask, followed by stirring at room temperature for 6 hours. If the addition is started, the solution turns red, and a yellow precipitate forms as the addition is completed.

Then, the precipitate was filtered, washed with N,N-dimethylformamide, and further washed with water, and then filtered twice, and the filtrate was dried to obtain a yellow-white crystal containing TABP. Thereafter, the pressure was reduced by a vacuum dryer, and the mixture was dried by heating at 130 ° C for 2 hours at a temperature elevation rate of 10 ° C /min to obtain yellow crystals as unpurified TABP.

<purification of TABP>

In a 300 ml flask, 10 g of the obtained unpurified TABP was placed in 150 ml of a γ-butyrolactone solution, heated to 200 ° C in an oil bath, and dissolved while stirring for 30 minutes. No insoluble matter was found at this time. Thereafter, the oil bath was stopped to be heated and stirred, and slowly cooled to room temperature.

By standing at room temperature, the solution was slowly separated into two layers while acicular yellow-white crystals were precipitated. The precipitate was separated by filtration, and the mixture was heated and dried at 130 ° C for 2 hours at a temperature rising rate of 10 ° C /min in a vacuum dryer, and further dried at 200 ° C at a heating rate of 10 ° C /min. After 6 hours, while maintaining the degree of vacuum and cooling to room temperature, it was adjusted to atmospheric pressure, and then high-purity TABP yellow crystals of the target were obtained.

5 mg of the obtained TABP was measured by a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation), and the results are shown in Table 2. The peak temperature of melting heat (a) was 325 ° C, and the temperature was wide ΔT = ((b) - (a)) = 3.2 °C.

<Polymerization of oxime imine precursor, ruthenium imidization and evaluation of polyester ruthenium film characteristics>

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) (hereinafter referred to as BPIP) was added, and then 61 ml of N-methyl-2-pyrrole was added. The ketone was heated to 80 ° C to dissolve. After dissolution, 13.38 mmol of the TABP powder obtained above was slowly added to the solution. The viscosity of the solution was sharply increased by stirring for 30 minutes. Further, the mixture was stirred for 4 hours to obtain a transparent, uniform and viscous polyester quinone imine precursor solution having a repeating unit represented by the formula (1). Here, in the formula (1), B ₁ is a divalent aromatic group represented by the formula (10):

The polyester quinone imide precursor solution did not precipitate or gel at all even at room temperature and at 20 ° C for one month, thereby exhibiting high solution storage stability.

A 12 μm-thick copper foil (Nippon Electrolysis Co., Ltd., USLP foil) was placed on the metal coating table so that the roughened surface side became a surface. The surface temperature of the coating table was set to 90 ° C, and the polyester phthalimide precursor solution was applied onto the roughened surface of the copper foil by a doctor blade. Thereafter, it was allowed to stand on the coating table for 30 minutes, and further allowed to stand at 100 ° C for 30 minutes in a desiccator to obtain a laminate of a non-tacky copper foil/polyester phthalimide precursor (polyester phthalate). The thickness of the amine precursor layer was 47 μm and 24 μm). Then, the laminate of the copper foil/polyester ylide precursor was adhered to a metal plate made of SUS by a tape, and the temperature was raised at 150 ° C in a hot air dryer at a heating rate of 5 ° C / min in a nitrogen atmosphere. The imidization was carried out for 30 minutes, and the imidization was carried out at 200 ° C for 1 hour, and the imidization was carried out at 400 ° C for 1 hour. Thereafter, a metal plate made of SUS was removed to obtain a laminate of a non-crimped copper foil/polyester quinone. The copper foil/polyester phthalimide is treated with a ferric chloride solution (manufactured by Tsurumi Soda Co., Ltd., 40 Baume, and a ferric chloride content of 37% or more) under heating at room temperature or below 50 ° C. The copper foil of the laminate was etched to obtain a pale brown polyester yimimide film having a film thickness of 26 μm and 12 μm.

The polyesterimine film having a film thickness of 26 μm was not broken by a 180° bending test, thereby exhibiting flexibility. The polyester quinone imine film does not exhibit solubility in an organic solvent such as N-methyl-2-pyrrolidone or dimethylacetamide. Further, the polyesterimide film showed a low linear thermal expansion coefficient equivalent to that of the copper foil of 22 ppm/° C. (average value between 50° C. and 200° C.) as measured by TMA. The coefficient of hygroscopic expansion was measured and found to be 5.0 ppm/% RH (average value between 30% RH and 70% RH), showing an extremely low coefficient of hygroscopic expansion. The flame retardancy of the polyesterimine film having a film thickness of 12 μm was evaluated, and the results showed the performance of UL94VTM-0. Moreover, it shows good solder heat resistance and boiling solder heat resistance. The modulus of elasticity was lower at 5.1 GPa, and the blister tear strength in the 26 μm polyester quinone imide film was 62 mN high tear strength.

(Example 2)

To a well-dried closed reaction vessel equipped with a stirrer, 6.42 mmol of BPIP, 6.42 mmol of a diamine having an ester structure represented by the formula (37) (hereinafter referred to as APAB), and 61 ml of N-A were added. Base-2-pyrrolidone, the solution was warmed to 80 ° C to dissolve. After dissolution, 13.38 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 the formula (12), and the molar ratio of the formula (11) and the formula (12) is the formula (11) / formula (12) = 50. A transparent, uniform and viscous polyester bismuth imide precursor solution at a ratio of /50. Here, in the formula (12), B ₂ is a divalent aromatic group represented by the formula (16):

Film formation and hydrazine imidization were carried out in accordance with the method described in Example 1 to prepare a polyester phthalimide film, 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 1 mm, which also showed a good value.

(Example 3)

To a well-dried closed reaction vessel equipped with a stirrer, 8.99 mmol of BPIP, 3.85 mmol of APAB, and 63 ml of N-methyl-2-pyrrolidone were added, and the solution was warmed to 80 ° C to dissolve. After dissolution, 13.38 mmol of the TABP 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 (11) and the formula (12) is a general formula. (11) / A transparent, uniform and viscous polyester phthalimide precursor solution of the formula (12) = 70/30. Here, in the formula (12), B ₂ is a divalent aromatic group represented by the formula (16).

Film formation and hydrazine imidization were carried out in accordance with the method described in Example 1 to prepare a polyester phthalimide film, 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 mm, which also showed a good value.

(Example 4)

To a well-dried closed reaction vessel equipped with a stirrer, 6.88 mmol of BPIP, 6.88 mmol of a diamine having an amine structure represented by the formula (38) (hereinafter referred to as DABA), and 65 ml of N-A were added. Base-2-pyrrolidone, the solution was warmed to 80 ° C to dissolve. After 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 was 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 (11) and the formula (12) was passed. A transparent, uniform, and viscous polyester phthalimide precursor solution of the formula (11) / formula (12) = 50/50. Here, in the formula (12), B ₂ is a divalent aromatic aromatic group represented by the formula (17):

Film formation and hydrazine imidization were carried out in accordance with the method described in Example 1 to prepare a polyester phthalimide film, 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 1 mm, which also showed a good value.

(Example 5)

To a well-dried closed reaction vessel equipped with a stirrer, 9.63 mmol of BPIP, 4.13 mmol of a diamine having an amine structure represented by the formula (39) (hereinafter referred to as BPTP), and 71 ml of N-A were added. Base-2-pyrrolidone, the solution was warmed to 80 ° C to dissolve. After dissolution, 14.79 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 was 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 (11) and the formula (12) was passed. A transparent, uniform and viscous polyester phthalimide precursor solution of the formula (11) / formula (12) = 70/30. Here, in the formula (12), B ₂ is a divalent aromatic aromatic group represented by the formula (18):

Film formation and hydrazine imidization were carried out in accordance with the method described in Example 1 to prepare a polyester phthalimide film, 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 -3 mm, which also showed a good value. Here, the term "-3 mm" means that the copper foil side warps.

(Example 6)

50 mmol of BPIP was added to a well-dried closed reaction vessel with a stirrer, dissolved in 191 ml of N-methyl-2-pyrrolidone, and then 50 mmol of the obtained in Example 1 was slowly added to the solution. TABP powder. After 30 minutes, the viscosity of the solution increased sharply. Further, the mixture was stirred at 80 ° C for 4 hours to obtain a transparent, uniform and viscous polyester quinone imine precursor. The obtained polyester phthalimide precursor did not precipitate or gel at all even after being allowed to stand at room temperature and -20 ° C for one month, thereby exhibiting high solution storage stability. In N-methyl-2-pyrrolidone, the inherent viscosity of the polyester quinone imine precursor measured by Ostwald's viscometer at 30 ° C and 0.5% by mass is 2.8 dL/g. . The polyester quinone imine precursor was filtered through a 5 μm membrane filter under a pressurized condition of nitrogen gas of 3 kg/cm ² to obtain a target polyester quinone imine precursor.

Film formation and hydrazine imidization were carried out in accordance with the method described in Example 1, whereby a pale brown polyester quinone imine film having a film thickness of 25 μm and 12 μm was obtained, and physical properties were evaluated in the same manner. The physical property values are shown in Table 3. The polyesterimine film did not break even after the 180° bending test, thereby exhibiting flexibility. Also, the solubility was not exhibited at all for any organic solvent.

Further, the polyester phthalimide precursor obtained above was spin-coated on a 6 吋 wafer by a spin coater (MS-250, manufactured by Mikasa Co., Ltd.), and allowed to stand at 100 ° C in a drier. After 30 minutes, a non-tacky polyesterimide precursor/germanium wafer laminate (the thickness of the polyester quinone imine precursor layer was 17 μm) was obtained. Thereafter, the laminate was subjected to a hydrazine imidization at 150 ° C for 30 minutes in a hot air dryer at a heating rate of 5 ° C / minute, and at room temperature of 200 ° C for 1 hour. The oxime imidization was carried out at 400 ° C for 1 hour. Thereafter, the polyesterimide film was peeled off from the tantalum wafer by hydrofluoric acid to obtain a polyesterimine film having a thickness of 10 μm. The obtained polyester phthalimide film was subjected to a tensile test to obtain a result of an elastic modulus of 5.4 GPa and a fracture elongation of 53%.

Here, the intrinsic viscosity (η) is obtained by measuring 0.5% by mass of a polyester quinone imine precursor by an Oswald viscometer at 30 °C.

(Example 7)

To a 300 ml flask, 10 g of the unpurified TABP obtained in Synthesis Example 1 and 150 ml of cyclobutyl hydrazine were placed, and the mixture was heated to 180 ° C in an oil bath, and dissolved while stirring for 30 minutes. Thereafter, evaluation of TABP was carried out in the same manner as in Example 1. The obtained TABP was measured by a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation), and the results are shown in Table 2. The peak temperature of melting heat (a) was 322.5 ° C, and the temperature was wide ΔT = (( b)-(a)) = 4.5 °C. When the ratio of the acid dianhydride to the diamine is 0.99, the molecular weight becomes maximum. Further, the inherent viscosity of the polyester quinone imide precursor obtained at an input ratio of 0.99 was 2.4 dL/g. Then, film formation and hydrazine imidization were carried out in accordance with the methods described in Examples 1 and 6, and a polyesterimide 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 closed reaction vessel equipped with a stirrer, 9.27 mmol of BPIP was added, and then 48 ml of N-methyl-2-pyrrolidone was added, and the solution was warmed to 80 ° C to dissolve. After the dissolution, 9.66 mmol of a tetracarboxylic dianhydride having an ester structure represented by the formula (20) (hereinafter referred to as TAHQ) was slowly added to the solution. The viscosity of the solution was sharply increased by stirring for 30 minutes. Further stirring for 4 hours gave a clear, homogeneous and viscous polyester phthalimide precursor solution:

Film formation and hydrazine imidization were carried out in accordance with the method described in Example 1 to prepare a polyester phthalimide film, and 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 26 μm polyesterimine film is 42 mN, which is low. In addition, the 12 μm thick film has low flame retardancy and does not have the performance of UL94VTM-0.

(Comparative Example 2)

In Example 2, TAHQ was used instead of TABP, and 10.49 mol of APAB and 2.62 mol of 4,4'-diaminodiphenyl ester (hereinafter referred to as ODA) were used as the diamine, except in Example 2 In the method described, the polyester quinone imine precursor was polymerized, and then film formation and hydrazine imidization were carried out to prepare a polyester quinone imine film, and physical properties were evaluated in the same manner. The physical property values are shown in Table 1. The polyester yttrium imide film exhibits a thermal expansion coefficient close to that of the copper foil, high geothermal stability, and flexibility. The coefficient of hygroscopic expansion is relatively high at 8.3 ppm/% RH, and the modulus of elasticity is higher at 7.9 GPa. The strength was lower at 0.3 N/mm, and the tear strength in the 26 μm polyester quinone imide film was lower at 42 mN. In addition, the 12 μm thick film has low flame retardancy and does not have the performance of UL94VTM-0.

(Comparative Example 3)

In Comparative Example 1, a polyester quinone imine precursor was polymerized according to the method described in Comparative Example 1, except that the diamine represented by the formula (23) (hereinafter referred to as BAPB) was used as the diamine. Further, film formation and hydrazine imidization were carried out to prepare a polyester quinone imine film, and physical properties were evaluated in the same manner:

The physical property values are shown in Table 1.

The polyester bismuth imide film shows a higher glass transition temperature and higher adhesion, and the elastic modulus shows a lower value of 5.2 GPa, but the linear thermal expansion coefficient shows a higher value of 32 ppm/° C., and the hygroscopic expansion coefficient is higher. At 13.2 ppm/% RH, the tear strength in the 26 μm polyesterimine film was 45 mN lower. Further, in the solder heat resistance test, bulging was observed, and the film having a thickness of 12 μm was low in flame retardancy, and the performance of UL94VTM-0 was not obtained.

(Comparative Example 4)

In Comparative Example 1, the TABP obtained in Example 1 was used instead of TAHQ, and APAB was used as the diamine. In addition, the polyester quinone imine precursor was blended according to the method described in Comparative Example 1, and then Film formation and hydrazine imidization were carried out to prepare a polyester quinone film, and physical properties were evaluated in the same manner. The physical property values are shown in Table 1. The polyester yttrium imide film exhibits high thermal stability and flexibility, and the flame retardancy of the polyimide film having a low moisture absorption coefficient, high tear strength, and film thickness of 12 μm is evaluated. The performance of UL94VTM-0, but the linear thermal expansion coefficient is 13ppm/°C, showing a lower coefficient of linear thermal expansion compared to copper foil, followed by a lower strength of 0.4 N/mm and a higher modulus of elasticity of 7.7 GPa.

[Industrial availability]

The polyester phthalimide of the present invention is suitably used as an electrical insulating film, a flexible printed wiring board, a substrate for a display, a substrate for an electronic paper, and a substrate for a solar cell in various electronic devices, and is particularly suitably used as a flexible printed wiring. Substrate for board.

Figure 1 is a graph showing a curve displayed by a differential scanning calorimeter.

Claims (35)

A polyester quinone imine precursor having a repeating unit represented by the following formula (1): (in the formula (1), Ar is a tetravalent aromatic group represented by the formula (2), B ₁ is a divalent aromatic group selected from at least one of the formulae (3) to (9) R ₁ represents an alkyl group having 1 to 6 carbon atoms; R ₂ to R ₄ 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; R ₅ represents a carbon number of 1~ 6 alkyl; R ₆ to R ₉ represent an alkyl group having 1 to 6 carbon atoms; a hydrogen atom; wherein, in the formula (1), B1 has a repeating unit represented by the formula (4). The polyester quinone imine precursor of claim 1, wherein in the formula (1), B ₁ has a repeating unit represented by the formula (10): 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)/ The ratio of formula (12)=20/80~80/20: (In the formulae (11) and (12), Ar is a tetravalent aromatic group represented by the formula (2); and in the formula (12), B ₂ is selected from the group consisting of the formula (13) to the formula (17). At least one divalent aromatic group: R ₁₀ to R ₁₈ 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). The polyester quinone imine precursor of claim 3, wherein in the formula (12), B ₂ is a repeating unit represented by the formula (16), the formula (17) or the formula (18): The polyester quinone imine precursor of claim 3, wherein in the formula (12), B ₂ is a repeating unit represented by the formula (16). The polyester quinone imine precursor of claim 1 has a weight average molecular weight Mw of 30,000 or more and 400,000 or less. The polyester quinone imine precursor of claim 3 has a weight average molecular weight Mw of 30,000 or more and 400,000 or less. The polyester quinone imine precursor of claim 4 has a weight average molecular weight Mw of 30,000 or more and 400,000 or less. The polyester quinone imine precursor of claim 5 has a weight average molecular weight Mw of 30,000 or more and 400,000 or less. The polyester quinone imine precursor of claim 1, wherein the polyester phthalic acid precursor is used to obtain the ester group-containing tetracarboxylic dianhydride represented by formula (19), which is to be scanned by differential scanning The peak temperature of the heat of fusion shown by (DSC) is (b) °C as the temperature at the intersection of the temperature at which the temperature toward the peak of the melting heat wave and the peak of the peak is stabilized as the tangent to the junction point at (a) ° C, and When the temperature is set to ΔT=((b)-(a)) °C, (a) ≧ 322 ° C and ΔT ≦ 5 ° C are satisfied: A polyester quinone imine precursor according to claim 3, wherein the ester-containing tetracarboxylic dianhydride represented by formula (19) used in obtaining the polyester quinone imide precursor is subjected to differential scanning calorimetry The peak temperature of the heat of fusion shown by (DSC) is (b) °C as the temperature at the intersection of the temperature at which the temperature toward the peak of the melting heat wave and the peak of the peak is stabilized as the tangent to the junction point at (a) ° C, and When the temperature is set to ΔT=((b)-(a)) °C, (a) ≧ 322 ° C and ΔT ≦ 5 ° C are satisfied: The polyester quinone imine precursor of claim 4, wherein the ester carboxylic acid-containing tetracarboxylic dianhydride represented by formula (19) used in obtaining the polyester quinone imine precursor is subjected to differential scanning calorimetry The peak temperature of the heat of fusion shown by (DSC) is (b) °C as the temperature at the intersection of the temperature at which the temperature toward the peak of the melting heat wave and the peak of the peak is stabilized as the tangent to the junction point at (a) ° C, and When the temperature is set to ΔT=((b)-(a)) °C, (a) ≧ 322 ° C and ΔT ≦ 5 ° C are satisfied: The polyester quinone imine precursor of claim 5, wherein the ester carboxylic acid-containing tetracarboxylic dianhydride represented by formula (19) used in obtaining the polyester quinone imine precursor is subjected to differential scanning calorimetry The peak temperature of the heat of fusion shown by (DSC) is (b) °C as the temperature at the intersection of the temperature at which the temperature toward the peak of the melting heat wave and the peak of the peak is stabilized as the tangent to the junction point at (a) ° C, and When the temperature is set to ΔT=((b)-(a)) °C, (a) 322 322 ° C and ΔT ≦ 5 ° C are satisfied: The polyester quinone imine precursor of claim 9, wherein the ester-containing tetracarboxylic dianhydride represented by formula (19) used in obtaining the polyester quinone imine precursor is subjected to differential scanning calorimetry The peak temperature of the heat of fusion shown by (DSC) is (b) °C as the temperature at the intersection of the temperature at which the temperature toward the peak of the melting heat wave and the peak of the peak is stabilized as the tangent to the junction point at (a) ° C, and When the temperature is set to ΔT=((b)-(a)) °C, (a) ≧ 322 ° C and ΔT ≦ 5 ° C are satisfied: A polyester quinone imine which is obtained by imidating a polyester quinone imine precursor of claim 1 . A polyester quinone imine which is obtained by imidating a polyester quinone imine precursor of claim 3. A polyester quinone imine which is obtained by imidating a polyester quinone imine precursor of claim 4. A polyester quinone imine which is obtained by imidating a polyester quinone imine precursor of claim 5. A polyester quinone imine which is obtained by imidating a polyester quinone imine precursor of claim 9. A polyester quinone imine which is obtained by imidating a polyester quinone imine precursor of claim 13. A polyester quinone imine which is obtained by imidating a polyester quinone imine precursor of claim 14. 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 15. 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 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 having 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 by having a polyester quinone layer and a metal layer, and the polyester quinone layer is composed of the polyester quinone imine of claim 19. 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 20. 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 21. The laminate of claim 22, which is obtained by applying the polyester phthalimide precursor of claim 1 to a metal foil, drying it, heating it, or imidating the hydrazine with a dehydrating reagent. The laminate according to claim 23, which is obtained by applying the polyester quinone imide precursor of claim 3 to a metal foil, drying it, heating it, or imidating the hydrazine with a dehydrating reagent. The laminate according to claim 24, which is obtained by applying the polyester quinone imide precursor of claim 4 to a metal foil, drying it, heating it, or imidating the hydrazine with a dehydrating reagent. The laminate according to claim 25, which is obtained by applying the polyester quinone imide precursor of claim 5 to a metal foil, drying it, heating it, or imidating the hydrazine with a dehydrating reagent. The laminate according to claim 26, which is obtained by applying the polyester quinone imide precursor of claim 9 to a metal foil, drying it, heating it, or imidating the hydrazine with a dehydrating reagent. The laminate according to claim 27, which is obtained by applying the polyester quinone imide precursor of claim 13 to a metal foil, drying it, heating it, or imidating the hydrazine with a dehydrating reagent. The laminate according to claim 28, which is obtained by applying the polyester phthalimide precursor of claim 14 to a metal foil, drying it, heating it, or imidating the hydrazine with a dehydrating reagent.