KR20110090389A - Flexible printed circuit board comprising an aromatic polyester amide copolymer resin, a polymer film containing the aromatic polyester amide copolymer resin, a flexible metal foil laminate comprising the polymer film, and the flexible metal foil laminate - Google Patents

Abstract

Flexible printed circuit board (FPCB) comprising an aromatic polyester amide copolymer resin, a polymer film comprising the aromatic polyester amide copolymer resin, a flexible metal foil laminate comprising the polymer film, and the flexible metal foil laminate board) is disclosed. The disclosed aromatic polyester amide copolymer resin has a repeating unit (RCN) derived from resorcinol and a repeating unit (HQ) derived from other aromatic diol compounds with 0.3 <n (RCN) / [n (RCN) + n (HQ). )] <Molar ratio of 0.7.

Description

A flexible printed circuit board comprising an aromatic polyester amide copolymer resin, a polymer film comprising the aromatic polyester amide copolymer resin, a flexible metal foil laminate comprising the polymer film, and the flexible metal foil laminate. , polymer film having the copolymer resin, flexible metal clad laminate having the polymer film, and flexible printed circuit board having the metal clad laminate}

Disclosed is a flexible printed circuit board comprising an aromatic polyester amide copolymer resin, a polymer film comprising the aromatic polyester amide copolymer resin, a flexible metal foil laminate comprising the polymer film, and the flexible metal foil laminate. More specifically, repeating units (RCN) derived from resorcinol and repeating units (HQ) derived from other aromatic diol compounds are 0.3 <n (RCN) / [n (RCN) + n (HQ)] <0.7 A flexible printed circuit board comprising an aromatic polyester amide copolymer resin, a polymer film comprising the aromatic polyester amide copolymer resin, a flexible metal foil laminate comprising the polymer film, and the flexible metal foil laminate comprising a molar ratio of Is initiated.

Recently, as devices using flexible printed circuit boards are gradually miniaturized and multifunctional, use of flexible metal foil laminates for flexible printed circuit boards is gradually increasing. The flexible metal foil laminate consists of two layers, a metal layer such as copper foil or aluminum foil, and a polymer film layer.

The polymer film applied to the metal foil laminate for the flexible printed circuit board should satisfy the following main characteristics to be suitable for the performance of the semiconductor and the manufacturing conditions of the semiconductor packaging process.

(1) Low thermal expansion rate that can correspond to metal thermal expansion rate

(2) Low dielectric constant and dielectric stability in high frequency region of 1GHz or more

(3) Heat resistance to reflow process of about 270 ° C

(4) low hygroscopicity for improved reliability

Conventional resin coated metal thin films are produced by using polyimide resins having high heat resistance and transparency in a casting manner. In addition, the flexible metal foil laminate is produced by applying a polyamic acid solution to the metal thin film and then curing by heat treatment under appropriate conditions. The flexible metal foil laminate thus manufactured has a structure in which a polyimide resin layer is formed on a metal thin film. Therefore, the flexible metal foil laminate has excellent flexibility and heat resistance, which are the inherent characteristics of the polyimide resin, but also causes warpage due to a difference in thermal expansion coefficient between the polyimide resin layer and the metal thin film and due to the high hygroscopicity of the polyimide resin itself. Improvement to low hygroscopicity is required.

As an alternative to the polyimide resin, there is also an example of a method of using an aromatic liquid crystal polyester resin or teflon having high heat resistance in the manufacture of a flexible metal foil laminate. In this case, however, there is a problem in that the manufactured flexible metal foil laminate is opaque and thus cannot perform optical inspection after the flexible printed circuit board is manufactured. Furthermore, in order to manufacture an aromatic liquid crystal polyester resin solution (varnish), a solvent containing a halogen element such as chlorine should be used, in which case the metal thin film due to the halogen element during the manufacturing process of the flexible metal foil laminate and the flexible printed circuit board. Since problems such as corrosion occur, improvement in the use of non-halogen solvents is required.

One embodiment of the present invention provides a repeating unit (RCN) derived from resorcinol and a repeating unit (HQ) derived from other aromatic diol compounds, wherein 0.3 <n (RCN) / [n (RCN) + n (HQ)]. It provides an aromatic polyester amide copolymer resin containing in a molar ratio of <0.7.

Another embodiment of the present invention provides a polymer film comprising the aromatic polyester amide copolymer resin.

Another embodiment of the present invention provides a flexible metal foil laminate including the polymer film and a flexible printed circuit board including the flexible metal foil laminate.

One aspect of the invention,

18-22 mol% of repeating units (A) derived from aromatic hydroxy carboxylic acid;

18 to 22 mol% of at least one repeating unit selected from the group consisting of a repeating unit (B) derived from an aromatic amine having a phenolic hydroxyl group and a repeating unit (B ') derived from an aromatic diamine;

18-22 mol% of repeating units (C) derived from an aromatic diol; And

It contains 38-42 mol% of repeating units (D) derived from an aromatic dicarboxylic acid,

The repeating unit (C) derived from the aromatic diol is derived from another aromatic diol compound including a repeating unit (RCN) derived from resorcinol and at least one compound selected from the group consisting of biphenol and hydroquinone. Includes a repeating unit (HQ),

The content of the repeating unit (RCN) and the content of the repeating unit (HQ) provide an aromatic polyester amide copolymer resin satisfying the following conditions:

0.3 <n (RCN) / [n (RCN) + n (HQ)] <0.7

Here, n (RCN) and n (HQ) are the moles of repeating units (RCN) and repeating units (HQ) contained in the aromatic polyester amide copolymer resin, respectively.

The repeating unit (A) is derived from at least one compound of para hydroxy benzoic acid and 2-hydroxy-6-naphthoic acid, and the repeating unit (B) is 3-aminophenol and 4-aminophenol. And 2-amino-6-naphthol, which is derived from at least one compound selected from the group consisting of 1,4-phenylene diamine, 1,3-phenylene diamine, and 2,6. -It is derived from at least one compound selected from the group consisting of naphthalene diamine, and the repeating unit (D) may be derived from at least one compound of isophthalic acid and naphthalene dicarboxylic acid.

The aromatic polyester amide copolymer resin may have a number average molecular weight of 1,000 to 20,000, and a melting temperature of 200 to 350 ° C.

Another aspect of the invention,

It provides a polymer film comprising the aromatic polyester amide copolymer resin.

The polymer film may further include 0.0001 to 100 parts by weight of at least one filler selected from the group consisting of an organic filler and an inorganic filler based on 100 parts by weight of the aromatic polyester amide copolymer resin.

The polymer film may have a thermal expansion coefficient of 15 ppm / K or less in one direction.

The polymer film may have a dielectric constant of 3.5 or less and a dielectric loss of 0.01 or less.

The polymer film may have a moisture absorption of 0.5% by weight or less.

The polymer film may have a light transmittance of 50 to 90%.

Another aspect of the invention,

The polymer film; And

It provides a flexible metal foil laminate comprising at least one metal thin film disposed on at least one surface of the polymer film.

The metal thin film may include at least one of copper foil and aluminum foil.

Another aspect of the invention,

Provided is a flexible printed circuit board obtained by etching a metal thin film of the flexible metal foil laminate.

Another aspect of the invention,

It provides a flexible printed circuit board formed by printing a metal circuit pattern on at least one surface of the polymer film.

According to an embodiment of the present invention, the repeating unit (RCN) derived from resorcinol and the repeating unit (HQ) derived from other aromatic diol compounds are 0.3 <n (RCN) / [n (RCN) + n (HQ). )] By including a molar ratio of <0.7 can provide an aromatic polyester amide copolymer resin having a low thermal expansion coefficient, low dielectric constant, low dielectric loss, low moisture absorption rate and high light transmittance.

According to another embodiment of the present invention, the polymer film having a low thermal expansion coefficient, low dielectric constant, low dielectric loss, low moisture absorption rate and high light transmittance may be provided by including the aromatic polyester amide copolymer resin.

According to still another embodiment of the present invention, a flexible metal foil laminate including the polymer film and a flexible printed circuit board including the flexible metal foil laminate may be provided.

Hereinafter, an aromatic polyester amide copolymer resin according to an embodiment of the present invention, a polymer film including the aromatic polyester amide copolymer resin, and a flexible metal foil laminate comprising the polymer film and a flexible sheet including the flexible metal foil laminate The printed circuit board will be described in detail.

The aromatic polyester amide copolymer resin according to one embodiment of the present invention is a repeating unit (B) derived from an aromatic amine having 18 to 22 mol% of the repeating unit (A) derived from an aromatic hydroxy carboxylic acid and a phenolic hydroxyl group (B). 18-22 mol% of at least one repeating unit selected from the group which consists of a repeating unit (B ') derived from aromatic diamine), 18-22 mol% of repeating units (C) derived from aromatic diol, and aromatic dicarboxyl It contains 38-42 mol% of repeating units (D) derived from an acid, The repeating unit (C) derived from the said aromatic diol consists of a repeating unit (RCN) derived from resorcinol, and a biphenol and hydroquinone. A repeating unit (HQ) derived from another aromatic diol compound including at least one compound selected from the group, wherein the content of the repeating unit (RCN) and the content of the repeating unit (HQ) are Enough:

0.3 <n (RCN) / [n (RCN) + n (HQ)] <0.7

Here, n (RCN) and n (HQ) are the moles of repeating units (RCN) and repeating units (HQ) contained in the aromatic polyester amide copolymer resin, respectively.

When the content of the repeating unit (A) is within the above range, the aromatic polyester amide copolymer resin has an appropriate level of thermal characteristics, and the total content of the repeating unit (B) and the repeating unit (B ′) is within the above range. If within the aromatic polyester amide copolymer resin has an appropriate level of solubility in the solvent and a hygroscopicity of the appropriate level, if the content of the repeating unit (C) is within the above range the aromatic polyester amide copolymer resin is When the content of the repeating unit (D) is in the above range, the aromatic polyester amide copolymer resin has an appropriate level of solubility in a solvent.

In addition, if the content ratio {n (RCN) / [n (RCN) + n (HQ)]} is within the above range, it has a suitable melting temperature and light transmittance.

The repeating unit (A) may be derived from at least one compound of para hydroxy benzoic acid and 2-hydroxy-6-naphthoic acid, and the repeating unit (B) is 3-aminophenol, 4- It may be derived from at least one compound selected from the group consisting of aminophenol and 2-amino-6-naphthol, the repeating unit (B ') is 1,4-phenylene diamine, 1,3-phenylene diamine And it may be derived from at least one compound selected from the group consisting of 2,6-naphthalene diamine, the repeating unit (D) may be derived from at least one compound of isophthalic acid and naphthalene dicarboxylic acid have.

For example, each repeating unit included in the aromatic polyester amide copolymer resin may be represented by any one of the following formulas:

(1) Repeating unit (A) derived from aromatic hydroxy carboxylic acid:

<Formula 1>

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

 (2) Repeating unit (B) derived from aromatic amine having phenolic hydroxyl group:

<Formula 6>

<Formula 7>

<Formula 8>

(3) Repeating unit (B ') derived from aromatic diamine:

<Formula 9>

<Formula 10>

<Formula 11>

(4) Repeating unit (C) derived from aromatic diol:

<Formula 12>

<Formula 13>

<Formula 14>

&Lt; Formula 15 >

 (5) Repeating unit (D) derived from aromatic dicarboxylic acid:

<Formula 16>

<Formula 17>

&Lt; Formula 18 >

(19)

<Formula 20>

<Formula 21>

<Formula 22>

<Formula 23>

In the above formula,

R ₁ and R ₂ each independently represent a halogen atom, a carboxy group, an amino group, a nitro group, a cyano group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, Substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₁ -C ₂₀ heteroalkyl group, substituted or unsubstituted C ₆ -C ₃₀ aryl Group, a substituted or unsubstituted C ₇ -C ₃₀ arylalkyl group, a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group, or a substituted or unsubstituted C ₃ -C ₃₀ heteroarylalkyl group. In the present specification, the term 'substituted' means that hydrogen is substituted with a halogen group, a hydroxy group, an alkyl group, an alkoxy group, an amine group or two or more of them.

Such aromatic polyester amide copolymer resins include (1) aromatic hydroxy carboxylic acids or derivatives for ester formation thereof; (2) at least one member selected from the group consisting of an aromatic amine having a phenolic hydroxyl group or a derivative for forming an amide, and an aromatic diamine or a derivative for forming an amide; (3) aromatic diols or derivatives for ester formation thereof; And (4) polymerizing an aromatic dicarboxylic acid or a derivative for forming an ester thereof.

The derivative for forming an ester of the aromatic hydroxy carboxylic acid or aromatic dicarboxylic acid may be a highly reactive derivative such as an acid chloride or an acid anhydride, or may form an ester bond with alcohols or ethylene glycol.

In addition, the derivative for forming an amide of the aromatic amine or aromatic diamine may be one in which the amine group forms an amide bond with carboxylic acids.

In addition, the derivative for forming an ester of the aromatic diol may be one whose hydroxy group forms an ester bond with carboxylic acids.

The aromatic polyester amide copolymer resin prepared as described above may be dissolved in a solvent. For example, the aromatic polyester amide copolymer resin has a melting temperature of 200 to 350 ° C. and a number average molecular weight of 1,000 to 20,000 days. Can be.

In addition, since the aromatic polyester amide copolymer resin prepared as described above contains a repeating unit (RCN) derived from resorcinol, light transmittance may be improved, and a polymer film including the copolymer resin may also have a high light transmittance. Will have

The aromatic polyester amide copolymer resin as described above can be produced by the following method. That is, the aromatic polyester amide copolymer resin is an aromatic hydroxy carboxylic acid corresponding to the repeating unit (A), an aromatic amine corresponding to the repeating unit (B) and / or the repeating unit (B '), and And / or the aromatic diamine and the phenolic hydroxyl group and / or amine group of the aromatic diol corresponding to the repeating unit (C) are acylated by fatty acid anhydride to obtain an acyl compound, and the acyl compound and aromatic dicarboxylic acid thus obtained are esterified. It can manufacture by the method of melt-polymerizing by exchange reaction.

In the acylation reaction, the amount of fatty acid anhydride added may be 1.0 to 1.2 times the equivalent of, for example, 1.0 to 1.1 times the equivalent of the phenolic hydroxyl group and the amine group. When the amount of the fatty acid anhydride added is within the above range, the coloring of the resulting aromatic polyester amide copolymer resin is reduced, and the resulting aromatic polyester amide copolymer resin does not sublimate such as raw material monomers and generates less phenol gas. You lose. The acylation reaction may be performed for 30 minutes to 8 hours at 130 to 170 ° C, for example, for 1 to 3 hours at 140 to 160 ° C.

Fatty acid anhydrides used in the acylation reaction include acetic anhydride, propionic anhydride, isobutyric anhydride, gil acetic anhydride, pivalic anhydride, butyric anhydride, and the like, and are not particularly limited thereto. Moreover, 2 or more types of these can be mixed and used.

The transesterification and amide exchange reaction may be carried out at a temperature increase rate of 0.1 to 2 ℃ / min at 130 ~ 400 ℃, for example, at a temperature increase rate of 0.3 ~ 1 ℃ / min at 140 ~ 350 ℃.

In the transesterification reaction and the amide exchange reaction of the fatty acid ester and the aromatic dicarboxylic acid obtained by acylating in this way, in order to increase the reaction rate by shifting the equilibrium, the by-product fatty acid and unreacted anhydride are reacted by evaporation or distillation. Can be drained out.

In addition, the acylation reaction, transesterification reaction and amide exchange reaction can proceed in the presence of a catalyst. The catalyst is conventionally known as a catalyst for producing a polyester resin, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, N, N-dimethylaminopyridine, N-methyl Imidazole and the like. The catalyst is usually added simultaneously with the monomer when the monomer is added, and the acylation reaction and the transesterification reaction take place in the presence of the catalyst.

The polycondensation by the transesterification and the amide exchange reaction may be carried out by melt polymerization, or may be used in combination with melt polymerization and solid phase polymerization.

The polymerizer used for the melt polymerization is not particularly limited, and may be a reactor equipped with a stirring apparatus generally used for high viscosity reactions. At this time, the same reactor may be used as the reactor of the acylation process and the polymerizer of the melt polymerization process or different reactors may be used for each process.

The solid phase polymerization may be performed by pulverizing the prepolymer discharged from the melt polymerization process into a flake or powder phase and then proceeding with the polymerization. Such solid phase polymerization can be carried out by, for example, heat treatment in a solid state for 1 to 30 hours at 200 to 350 ° C. in an inert atmosphere such as nitrogen. Further, the solid phase polymerization may be carried out under stirring or may be carried out in an unstirred state. Moreover, the reactor equipped with the suitable stirring apparatus can also be used together with a melt polymerization tank and a solid state polymerization tank.

The aromatic polyester amide copolymer resin prepared as described above may have a thermal expansion rate of 15 ppm / K or less.

The obtained aromatic polyester amide copolymer resin may be pelletized by a known method and then molded, or may be fiberized by a known method. In addition, as described later, after dissolving in a solvent, it is applied to a metal thin film, and then dried and heat-treated to form a polymer film, and may be used for the manufacture of a flexible metal foil laminate.

Such aromatic polyester amide copolymer resin may be dissolved in a solvent. Therefore, a flexible metal foil laminate may be prepared by applying a composition solution in which the aromatic polyester amide copolymer resin is dissolved in a solvent, followed by drying and heat treatment. The polymer film is formed in a form attached to the metal thin film by the drying and heat treatment.

In addition, the aromatic polyester amide copolymer resin may be used in various applications in addition to the polymer film and the flexible metal foil laminate.

The solvent for dissolving the aromatic polyester amide copolymer resin may be used in an amount of 100 to 100,000 parts by weight with respect to 100 parts by weight of the aromatic polyester amide copolymer resin, the aromatic if the content ratio of the solvent is within the above range Although polyester amide copolymer resin melt | dissolves fully, productivity is good.

A non-halogen solvent may be used as the solvent for dissolving the aromatic polyester amide copolymer resin. However, the present invention is not limited thereto, and as the solvent, polar aprotic compounds, halogenated phenols, o-dichlorobenzene, chloroform, methylene chloride, tetrachloroethane and the like may be used alone or in combination of two or more thereof.

As described above, the aromatic polyester amide copolymer resin dissolves well in a non-halogen solvent and uses a flexible metal foil laminate or flexible printed circuit board containing the aromatic polyester amide copolymer resin without using a solvent containing a halogen element. It can manufacture. If a solvent containing a halogen element is used, it may cause problems in the manufacturing process, and in particular, an environmental hormone harmful to a human body may be generated when the halogen element is incinerated or decomposed.

The composition solution in which the aromatic polyester amide copolymer resin is dissolved in a solvent includes an inorganic filler such as silica, aluminum hydroxide or calcium carbonate in order to adjust the dielectric constant and the coefficient of thermal expansion; And / or organic fillers such as cured epoxy or crosslinked acrylics may be added. For example, an inorganic filler of high dielectric constant may be added. As the inorganic filler, a titanate such as barium titanate or strontium titanate, or a part of titanium or barium of barium titanate may be replaced with another metal. The content of the inorganic filler and / or the organic filler in the composition solution may be 0.0001 to 100 parts by weight based on 100 parts by weight of the aromatic polyester amide copolymer resin. When the content of the inorganic filler and / or the organic filler is within the above range, not only the dielectric constant of the polymer film is lowered and the thermal expansion coefficient is lowered, but also the effect as a binder possessed by the aromatic polyester amide copolymer resin can be sufficiently maintained. . Therefore, the polymer film may include 0.0001 to 100 parts by weight of the inorganic filler and / or the organic filler based on 100 parts by weight of the aromatic polyester amide copolymer resin.

Flexible metal foil laminate according to an embodiment of the present invention includes an aromatic polyester amide copolymer resin having a low thermal expansion coefficient, low dielectric properties, low moisture absorption and high light transmittance, and a metal thin film having excellent mechanical strength. Therefore, the flexible metal foil laminate may be applied to various fields as a transparent and flexible substrate material.

In addition, the thermal expansion coefficient of the polymer film may be 15 ppm / K or less. When the thermal expansion coefficient of the polymer film is within the above range, warpage or shrinkage may not occur in the flexible metal foil laminate including the polymer film.

In addition, the dielectric constant of the polymer film is 3.5 or less, the dielectric loss may be 0.01 or less. In the present specification, 'dielectric loss' refers to an energy loss lost by heat in the dielectric when an alternating electric field is applied to the dielectric. When the dielectric constant and the dielectric loss are each within the above range, the polymer film is suitable for use as an insulating substrate in the high frequency region.

In addition, the moisture absorption rate of the polymer film may be 0.5% or less. When the moisture absorption rate of the polymer film is within the above range, the resistance to moisture is high and the reliability of the flexible metal foil laminate becomes high.

In addition, the light transmittance of the polymer film may be 50 ~ 90%. If the light transmittance of the polymer film is within the above range, optical inspection is possible.

The thermal expansion coefficient, dielectric constant, dielectric loss, moisture absorption rate and light transmittance of the above-described polymer film can be generally measured by the following method. That is, after coating a composition solution in which the aromatic polyester amide copolymer resin is dissolved in a solvent on a metal thin film, drying and heat-treating to produce a flexible metal foil laminate, after removing all metal thin films from the flexible metal foil laminate, the remaining polymer The physical properties can be measured by analyzing the film.

The metal thin film may include at least one selected from the group consisting of copper foil and aluminum foil.

In the flexible metal foil laminate, the polymer film and the metal thin film thickness may be 0.1 to 300 μm, respectively. When the thickness of the polymer film and the metal thin film is within the above range, cracks are less likely to occur during the processing of the winding method, and are advantageous for multilayer lamination of a limited thickness. When the thickness of the metal thin film is within the above range, cracks are less likely to occur when the metal thin film is laminated, which is advantageous for multilayer lamination.

Meanwhile, the flexible printed circuit board may be manufactured by etching the metal thin film of the flexible metal foil laminate and forming a circuit. In addition, a flexible printed circuit board may be manufactured by printing a metal circuit pattern on at least one surface of the polymer film. In addition, a through hole or the like may be formed in the flexible printed circuit board as necessary.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example

(Manufacture of Copper Foil Laminate)

Example  One

Step 1: Preparation of Aromatic Polyester Amide Copolymer Resins

264.2 g (2.0 mol) of para hydroxy benzoic acid, 218.3 g (2.0 mol) of 4-aminophenol, 110.1 g (1.0 mol) of hydroquinone in a reactor equipped with a stirring device, a torque meter, a nitrogen gas introduction tube, a thermometer, and a reflux condenser. , 110.1 g (1.0 mole) of resorcinol, 664.6 g (4.0 mole) of isophthalic acid, and 510.5 g (5 mole) of acetic anhydride were added thereto. After sufficiently replacing the inside of the reactor with nitrogen gas, the temperature was raised to 150 ° C. over 30 minutes under a nitrogen gas stream, and refluxed for 2 hours while maintaining this temperature.

Thereafter, the distilled acetic acid and unreacted acetic anhydride were distilled off, and the temperature was raised to 320 ° C. for 180 minutes, and the contents were discharged considering the end of the reaction as the time when the torque was increased. The obtained solid content was cooled to room temperature, and it grind | pulverized with the fine grinding machine, and obtained aromatic polyester amide copolymer resin powder.

Step 2: Preparation of a Composition Solution of Aromatic Polyester Amide Copolymer Resins

50 g of N-methylpyrrolidinone (NMP) is added to 50 g of the aromatic polyester amide copolymer resin powder prepared in step 1, followed by stirring at room temperature (25 ° C.) for 4 hours to form a solution of the composition of the aromatic polyester amide copolymer resin. Got.

Step 3: copper foil Laminate  Produce

The composition solution of the aromatic polyester amide copolymer resin prepared in step 2 was coated on the copper foil surface having a thickness of 18 μm. Thereafter, the composition solution of the coated aromatic polyester amide copolymer resin was dried at 150 ° C. Next, in order to further improve the physical properties, the copper foil laminate was manufactured by further increasing the reaction temperature to 280 ° C. The copper foil laminate thus produced includes a polymer film of the type attached to the copper foil.

Example  2

211.36 g (1.6 mol) of para hydroxy benzoic acid, 152.81 g (1.4 mol) of 4-aminophenol, 77.07 g (0.7 mol) of hydroquinone, 77.07 g (0.7 mol) of resorcinol, 515.065 g (3.1 mol) of isophthalic acid, and An aromatic polyester amide copolymer resin was prepared in the same manner as in Example 1, except that 367.56 g (3.6 mol) of acetic anhydride was used. In addition, a composition solution of the aromatic polyester amide copolymer resin and a copper foil laminate were prepared in the same manner as in Example 1.

Comparative example  One

An aromatic polyester amide copolymer resin was prepared in the same manner as in Example 1, except that only 220.2 g (2.0 mol) of resorcinol was used without using any hydroquinone as the aromatic diol. In addition, a composition solution of the aromatic polyester amide copolymer resin and a copper foil laminate were prepared in the same manner as in Example 1.

Comparative example  2

An aromatic polyester amide copolymer resin was prepared in the same manner as in Example 1, except that only 220.0 g (2.0 mol) of hydroquinone was used without using any resorcinol as the aromatic diol. In addition, a composition solution of the aromatic polyester amide copolymer resin and a copper foil laminate were prepared in the same manner as in Example 1.

Comparative example  3

Parahydroxy benzoic acid 396.3 g (3 mol), 4-aminophenol 218.3 g (2.0 mol), hydroquinone 55.05 g (0.5 mol), resorcinol 55.05 g (0.5 mol), isophthalic acid 664.6 g (4.0 mol) and An aromatic polyester amide copolymer resin was prepared in the same manner as in Example 1, except that 459.45 g (4.5 mol) of acetic anhydride was used. In addition, a composition solution of the aromatic polyester amide copolymer resin and a copper foil laminate were prepared in the same manner as in Example 1.

Comparative example  4

Parahydroxy benzoic acid 264.2 g (2.0 mol), 4-aminophenol 327.45 g (3 mol), hydroquinone 55.05 g (0.5 mol), resorcinol 55.05 g (0.5 mol), isophthalic acid 664.6 g (4.0 mol) and An aromatic polyester amide copolymer resin was prepared in the same manner as in Example 1, except that 510.5 g (5 mol) of acetic anhydride was used. In addition, a composition solution of the aromatic polyester amide copolymer resin and a copper foil laminate were prepared in the same manner as in Example 1.

Evaluation example

Evaluation example  1: Evaluation of Physical Properties of Aromatic Polyester Amide Copolymer Resin

The number average molecular weights and melting temperatures of the aromatic polyester amide copolymer resins prepared in Examples 1 to 2 and Comparative Examples 1 to 4, respectively, were measured and shown in Table 1 below.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Number average molecular weight 4238 4207 4012 4364 4113 3981 Melting temperature (℃) 222 218 143 272 257 231

In Table 1, the number average molecular weight was measured at THF eluent, 30 ° C using GPC, and the melting temperature was measured while raising the temperature to 20 ° C / min using DSC.

Referring to Table 1, the number average molecular weight was found to have no significant difference in each Example and Comparative Example, but due to the structural difference of the final polymer chain, the melting temperature was found to have a lot of difference. In particular, the aromatic polyester amide copolymer resin of Comparative Example 1 was found to have a very low melting temperature. Therefore, the copolymer resin prepared in Comparative Example 1 has a low thermal property of itself, and thus it is difficult to pass the reflow process even after the additional heat treatment process.

Evaluation example  2: copper foil On laminate  Evaluation of Properties of Polymer Films Contained

After removing all the copper foils from the copper foil laminates prepared in Examples 1 to 2 and Comparative Examples 1 to 4 through etching, the remaining polymer film was analyzed, and the thermal expansion coefficient, dielectric property, moisture absorption rate and light of the polymer film were analyzed. The transmittance was measured and shown in Table 2 below.

Evaluation items Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Thermal expansion
(ppm / K) 14.2 13.5 19.2 11.5 12.5 16.3 Dielectric constant 3.3 3.4 3.5 3.5 3.7 4.2 Dielectric loss 0.005 0.006 0.007 0.006 0.005 0.008 Hygroscopicity (wt%) 0.4 0.5 1.1 0.4 0.7 1.1 Light transmittance (%) 72 80 93 10 42 35

In Table 2, the coefficient of thermal expansion was measured in a temperature range of 50 ~ 150 ℃ using TMA (TMA Q400), dielectric constant and dielectric loss was measured using an impedance analyzer, the moisture absorption is IPC-TM-650 standard The light transmittance was measured using a spectrophotometer.

Referring to Table 2, the coefficient of thermal expansion, the dielectric constant, and the dielectric loss were not significantly different in each of the Examples and Comparative Examples, but the moisture absorption rate and the light transmittance were found to be very different. In the case of Comparative Example 2, the optical transmittance is very low as compared with the case of Example 1 and Comparative Example 1, so that the optical inspection is impossible when applied to the flexible printed circuit board. In Comparative Example 3, the coefficients of thermal expansion are lower than those in Examples 1 and 2, which may cause warpage or shrinkage during fabrication of the flexible printed circuit board. In addition, in case of Comparative Example 4, warpage or shrinkage may not occur, but may have a high dielectric constant and a high hygroscopicity, which may cause a problem in reliability of the flexible printed circuit board, and optical inspection may not be smooth.

Although the present invention has been described with reference to the examples, these are merely exemplary, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.

Claims (13)

18-22 mol% of repeating units (A) derived from aromatic hydroxy carboxylic acid;
18 to 22 mol% of at least one repeating unit selected from the group consisting of a repeating unit (B) derived from an aromatic amine having a phenolic hydroxyl group and a repeating unit (B ') derived from an aromatic diamine;
18-22 mol% of repeating units (C) derived from an aromatic diol; And
It contains 38-42 mol% of repeating units (D) derived from an aromatic dicarboxylic acid,
The repeating unit (C) derived from the aromatic diol is derived from another aromatic diol compound including a repeating unit (RCN) derived from resorcinol and at least one compound selected from the group consisting of biphenol and hydroquinone. Includes a repeating unit (HQ),
The content of the repeating unit (RCN) and the content of the repeating unit (HQ) is an aromatic polyester amide copolymer resin satisfying the following conditions:
0.3 <n (RCN) / [n (RCN) + n (HQ)] <0.7
Here, n (RCN) and n (HQ) are the moles of repeating units (RCN) and repeating units (HQ) contained in the aromatic polyester amide copolymer resin, respectively. The method of claim 1,
The repeating unit (A) is derived from at least one compound of para hydroxy benzoic acid and 2-hydroxy-6-naphthoic acid, and the repeating unit (B) is 3-aminophenol, 4-aminophenol and It is derived from at least one compound selected from the group consisting of 2-amino-6-naphthol, and the repeating unit (B ′) is 1,4-phenylene diamine, 1,3-phenylene diamine and 2,6-naphthalene An aromatic polyester amide copolymer resin derived from at least one compound selected from the group consisting of diamines, wherein the repeating unit (D) is derived from at least one compound of isophthalic acid and naphthalene dicarboxylic acid. The method of claim 1,
Aromatic polyester amide copolymer resin whose number average molecular weight is 1,000-20,000, and melting temperature is 200-350 degreeC. A polymer film comprising the aromatic polyester amide copolymer resin according to any one of claims 1 to 3. The method of claim 4, wherein
A polymer film further comprising 0.0001 to 100 parts by weight of at least one filler selected from the group consisting of an organic filler and an inorganic filler based on 100 parts by weight of the aromatic polyester amide copolymer resin. The method of claim 4, wherein
A polymer film having a thermal expansion coefficient of 15 ppm / K or less in one direction. The method of claim 4, wherein
A polymer film having a dielectric constant of 3.5 or less and a dielectric loss of 0.01 or less. The method of claim 4, wherein
Polymer film whose moisture absorption is 0.5 weight% or less. The method of claim 4, wherein
Polymer film having light transmittance of 50 to 90%. The polymer film according to any one of claims 1 to 3; And
A flexible metal foil laminate comprising at least one metal thin film disposed on at least one surface of the polymer film. The method of claim 10,
The metal thin film is a flexible metal foil laminate comprising at least one of copper foil and aluminum foil. A flexible printed circuit board obtained by etching a metal thin film of the flexible metal film laminate according to claim 10. The flexible printed circuit board formed by printing a metal circuit pattern on at least one surface of the polymer film according to claim 4.