KR101767682B1 - Wholly aromatic polyester amide copolymer resin, and polymer film, flexible metal clad laminate and printed circuit board comprising the same - Google Patents

Abstract

Disclosed is a wholly aromatic polyester amide copolymer resin, a polymer film comprising the wholly aromatic polyester amide copolymer resin, a flexible metal foil laminate including the polymer film, and a flexible printed circuit board comprising the flexible metal foil laminate. The disclosed wholly aromatic polyester amide copolymer resin comprises 20 to 50 parts by mole of the repeating unit (A) derived from an aromatic hydroxycarboxylic acid; At least one repeating unit selected from the group consisting of a repeating unit derived from an aromatic amine having a phenolic hydroxyl group (B) and a repeating unit derived from an aromatic diamine (B '); 20 to 40 molar parts of the repeating unit derived from an aromatic dicarboxylic acid (C); And 1 to 10 parts by mole of a repeating unit (D) derived from an aromatic phosphorus compound containing a hydroxyl group.

Description

TECHNICAL FIELD The present invention relates to a wholly aromatic polyester amide copolymer resin, a polymer film containing the same, a flexible metal foil laminate, and a printed circuit board,

Disclosed is a wholly aromatic polyester amide copolymer resin, a polymer film comprising the wholly aromatic polyester amide copolymer resin, a flexible metal foil laminate including the polymer film, and a flexible printed circuit board comprising the flexible metal foil laminate. More particularly, the present invention relates to a wholly aromatic polyester amide copolymer resin having improved thermal expansion coefficient, a polymer film containing the wholly aromatic polyester amide copolymer resin, a flexible metal foil laminate including the polymer film, A flexible printed circuit board is disclosed.

2. Description of the Related Art Recently, as a device using a flexible printed circuit board gradually becomes smaller and more versatile, the use of a flexible metal film laminate for a flexible printed circuit board is increasing. The flexible metal foil-clad laminate is composed of two layers of a metal layer such as a copper foil or an aluminum foil, and a polymer film layer.

The polymer film applied to the metal foil laminate for a flexible printed circuit board should satisfy the following main characteristics in order to meet the semiconductor performance and semiconductor packaging manufacturing process conditions.

(1) a low thermal expansion coefficient capable of coping with the thermal expansion coefficient of metal

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

(3) Heat resistance for reflow process of about 260 캜

(4) Low hygroscopicity to improve reliability

The conventional resin-coated metal thin film is manufactured by using a polyimide resin having high heat resistance in a casting method. The flexible metal foil laminate is prepared by applying a polyamic acid solution to the metal thin film and then curing by heat treatment under appropriate conditions. The thus fabricated flexible metal foil laminate has a structure in which a polyimide resin layer is formed on a metal foil. Therefore, although the flexible metal foil laminate has excellent flexibility and heat resistance, which are inherent characteristics of the polyimide resin, the flexible metal foil laminate has dimensional stability due to warpage due to the difference in thermal expansion coefficient between the polyimide resin layer and the metal foil and high hygroscopicity of the polyimide resin itself This is a low problem.

Recently, as an alternative to the polyimide resin, there has been examined a method of using a wholly aromatic polyester resin having high heat resistance or Teflon in the production of a flexible metal clad laminate. However, in order to produce a wholly aromatic liquid-crystalline polyester resin varnish, a solvent containing a halogen element such as chlorine should be used. In this case, in the manufacturing process of the flexible metal laminate and the flexible printed circuit board, Problems such as corrosion of the thin film occur, and therefore, improvement in the use of a non-halogen solvent is required.

One embodiment of the present invention relates to a method for producing an aromatic diamine, which comprises reacting a repeating unit (A) derived from an aromatic hydroxycarboxylic acid, a repeating unit (B) derived from an aromatic amine having a phenolic hydroxyl group, and a repeating unit (D) derived from an aromatic phosphorus compound containing a repeating unit (C) derived from an aromatic dicarboxylic acid and a hydroxyl group at a predetermined ratio, To provide a copolymer resin.

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

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

According to an aspect of the present invention,

20 to 50 parts by mole of the repeating unit (A) derived from an aromatic hydroxycarboxylic acid;

At least one repeating unit selected from the group consisting of a repeating unit derived from an aromatic amine having a phenolic hydroxyl group (B) and a repeating unit derived from an aromatic diamine (B ');

20 to 40 molar parts of the repeating unit derived from an aromatic dicarboxylic acid (C); And

And 1 to 10 parts by mole of a repeating unit (D) derived from an aromatic phosphorus compound containing a hydroxyl group.

The repeating unit (A) may be selected from the group consisting of parahydroxybenzoic acid, metahydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 3-hydroxy- Hydroxy-1-naphthoic acid; and at least one compound selected from the group consisting of hydroxy-1-naphthoic acid; The repeating unit (B) is at least one compound selected from the group consisting of 3-aminophenol, 4-aminophenol, 5-amino-1-naphthol, 8-amino- ≪ / RTI > The repeating unit (B ') may be at least one selected from the group consisting of 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 2,3-diaminonaphthalene and 1,8-diaminonaphthalene Lt; RTI ID = 0.0 > of: < / RTI > The repeating unit (C) is derived from at least one compound selected from the group consisting of isophthalic acid, naphthalene dicarboxylic acid and terephthalic acid; The repeating unit (D) may be derived from a compound represented by the following formula (1): < EMI ID =

[Chemical Formula 1]

The wholly aromatic polyester amide copolymer resin may have a weight average molecular weight of 1,000 to 20,000 and a glass transition temperature of 200 to 300 ° C.

According to another aspect of the present invention,

And a polymer film comprising the wholly aromatic polyester amide copolymer resin.

The polymer film may further comprise 5 to 30 parts by weight of at least one filler selected from the group consisting of organic fillers and inorganic fillers per 100 parts by weight of the wholly aromatic polyester amide copolymer resin.

The polymer film may have a coefficient of thermal expansion in one direction of 14 ppm / K or less.

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 rate of 0.5% by weight or less.

The polymer film may have a glass transition temperature of 250 to 350 ° C.

According to another aspect of the present invention,

The polymer film; And

And at least one metal thin film disposed on at least one surface of the polymer film, wherein the metal thin film includes at least one of a copper foil and an aluminum foil.

According to another aspect of the present invention,

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

According to another aspect of the present invention,

There is provided a flexible printed circuit board formed by printing a metal circuit pattern on at least one side of the polymer film.

According to one embodiment of the present invention, a wholly aromatic polyester amide copolymer resin having low thermal expansion coefficient, low moisture absorption rate, low dielectric constant and low dielectric loss can be provided.

According to another embodiment of the present invention, by including the wholly aromatic polyester amide copolymer resin, a polymer film having a low thermal expansion coefficient, a low moisture absorption rate, a high dimensional stability, a low dielectric constant and a low dielectric loss, a flexible metal foil- A circuit board may be provided.

Hereinafter, the wholly aromatic polyester amide copolymer resin according to one embodiment of the present invention, the polymer film including the wholly aromatic polyester amide copolymer resin, the flexible metal foil laminate including the polymer film, and the flexible metal foil laminate A flexible printed circuit board (FPCB) will be described in detail.

The wholly aromatic polyester amide copolymer resin according to an embodiment of the present invention comprises 20 to 50 parts by mole of the repeating unit (A) derived from an aromatic hydroxycarboxylic acid, a repeating unit derived from an aromatic amine having a phenolic hydroxyl group (B And 20 to 40 parts by mole of a repeating unit derived from an aromatic dicarboxylic acid (C) and at least one repeating unit derived from an aromatic diamine (B '), (D) derived from an aromatic phosphorus compound.

When the content of the recurring unit (A) is within the above range, the wholly aromatic polyester amide copolymer resin has an appropriate level of thermal properties; If the total content of the repeating unit (B) and the repeating unit (B ') is within the above range, the wholly aromatic polyester amide copolymer resin has an appropriate level of solubility to the solvent and an appropriate moisture absorption rate; When the content of the recurring unit (C) is within the above range, the wholly aromatic polyester amide copolymer resin has an appropriate level of solubility to the solvent. When the content of the recurring unit (D) The wholly aromatic polyester amide copolymer resin has a low thermal expansion coefficient.

The repeating unit (A) may be selected from the group consisting of parahydroxybenzoic acid, metahydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 3-hydroxy- Hydroxy-1-naphthoic acid; and at least one compound selected from the group consisting of hydroxy-1-naphthoic acid; The repeating unit (B) is at least one compound selected from the group consisting of 3-aminophenol, 4-aminophenol, 5-amino-1-naphthol, 8-amino- ≪ / RTI > The repeating unit (B ') may be at least one selected from the group consisting of 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 2,3-diaminonaphthalene and 1,8-diaminonaphthalene Lt; RTI ID = 0.0 > of: < / RTI > The repeating unit (C) is derived from at least one compound selected from the group consisting of isophthalic acid, naphthalene dicarboxylic acid and terephthalic acid; The repeating unit (D) may be derived from a compound represented by the following formula (1).

[Chemical Formula 1]

Each of the repeating units contained in the wholly aromatic polyester amide copolymer resin may be represented by, for example, any one of the following formulas:

(1) a repeating unit derived from an aromatic hydroxycarboxylic acid (A):

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

(2) a repeating unit derived from an aromatic amine having a phenolic hydroxyl group (B):

[Chemical Formula 6]

(7)

[Chemical Formula 8]

(3) repeating unit (B ') derived from an aromatic diamine:

[Chemical Formula 9]

[Chemical formula 10]

(11)

(4) repeating units derived from an aromatic dicarboxylic acid (C):

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

(5) repeating units derived from an aromatic phosphorus compound containing a hydroxyl group (D):

[Chemical Formula 20]

Wherein,

R ₁ to R ₃ each independently represent a halogen atom, a carboxyl 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, A substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, a substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, a substituted or unsubstituted C ₁ -C ₂₀ heteroalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl 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. As used herein, the term "substituted" means that the hydrogen in each of the above formulas 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 a wholly aromatic polyester amide copolymer resin includes (1) an aromatic hydroxycarboxylic acid or an ester-forming derivative thereof; (2) at least one member selected from the group consisting of an aromatic amine having a phenolic hydroxy group or an amide-forming derivative thereof, and an aromatic diamine or an amide-forming derivative thereof; (3) an aromatic dicarboxylic acid or an ester-forming derivative thereof; And (4) an aromatic phosphorus compound containing a hydroxy group or an ester-forming derivative thereof.

The ester-forming derivative of an aromatic phosphorus compound containing an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and / or a hydroxyl group may be a highly reactive derivative such as an acid chloride or an acid anhydride thereof, or an ester with an alcohol, ethylene glycol, To form bonds.

In addition, the amide-forming derivative of the aromatic amine and / or aromatic diamine may be such that its amine group forms an amide bond with carboxylic acids.

The wholly aromatic polyester amide copolymer resin prepared as described above can be dissolved in a solvent.

The wholly aromatic polyester amide copolymer resin may have a weight average molecular weight of 1,000 to 20,000 and a glass transition temperature of 200 to 300 ° C.

In addition, since the wholly aromatic polyester amide copolymer resin prepared as described above contains the repeating unit (D) derived from an aromatic phosphorus compound containing a hydroxyl group, the wholly aromatic polyester amide copolymer resin has a lower The thermal expansion coefficient is obtained.

The wholly aromatic polyester amide copolymer resin as described above can be produced by the following method. That is, the wholly aromatic polyester amide copolymer resin comprises an aromatic hydroxycarboxylic acid corresponding to the recurring unit (A), an aromatic amine having a phenolic hydroxyl group corresponding to the recurring unit (B) B ') and / or a hydroxy group and / or an amine group of an aromatic phosphorus compound containing a hydroxy group corresponding to the repeating unit (D) is acylated with an acid anhydride to obtain an acylate , And a method of performing melt polymerization by reacting the thus obtained acylate with an aromatic dicarboxylic acid and / or an aromatic hydroxycarboxylic acid (i.e., an ester exchange reaction and / or an amide exchange reaction).

The addition amount of the acid anhydride in the acylation reaction may be 1.0-1.2 times the equivalent of the hydroxyl group and the amine group, for example, 1.0-1.1 times the equivalent. If the addition amount of the acid anhydride is within the above range, coloration of the resulting wholly aromatic polyester amide copolymer resin is reduced, sublimation of raw material monomers and the like does not occur in the produced wholly aromatic polyester amide copolymer resin, . The acylation reaction may be carried out at 130-170 ° C for 30 minutes to 8 hours, for example, at 140-160 ° C for 1 hour to 3 hours.

The acid anhydrides used in the acylation reaction may include acetic anhydride, propionic anhydride, isobutyric anhydride, anhydrous acetic anhydride, anhydrous pivalic acid, anhydrous butyric acid, or a combination thereof.

The transesterification and amide exchange reaction may be carried out at a temperature raising rate of from 0.1 to 2 ° C / minute at 130 to 400 ° C, for example, at a temperature raising rate of from 0.3 to 1 ° C / minute at 140 to 350 ° C.

In addition, during the ester exchange reaction and / or the amide exchange reaction, the by-produced acid and unreacted anhydride may be discharged out of the reaction system by evaporation or distillation in order to shift the chemical equilibrium and increase the reaction rate.

In addition, the acylation reaction, transesterification reaction and amide exchange reaction can be carried out in the presence of a catalyst. The catalyst may include magnesium acetate, stannous acetate, tetrabutyl titanate, acetic acid, sodium acetate, potassium acetate, antimony trioxide, N, N-dimethylaminopyridine, N-methylimidazole or combinations thereof . The catalyst may be added at the same time as the monomer when the monomer is added, and an acylation reaction and an ester exchange reaction may occur in the presence of the catalyst.

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

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

The solid-state polymerization may be carried out by pulverizing the prepolymer discharged from the melt polymerization step to form a flake or powder phase, and then conducting polymerization. Such solid phase polymerization can be carried out, for example, by heat treatment in a solid state at 250 to 450 ° C for 1 to 30 hours in an inert atmosphere such as nitrogen. In addition, the solid state polymerization may be carried out under agitation or in a non-crosslinked state. Further, a reactor equipped with an appropriate stirring equipment may be used in combination with a melt polymerization reactor and a solid phase polymerization reactor.

The wholly aromatic polyester amide copolymer resin thus prepared may have a thermal expansion coefficient of 14 ppm / K or less.

The obtained wholly aromatic polyester amide copolymer resin may be pelletized by a known method and then molded or may be formed into a fiber by a known method.

Such a wholly aromatic polyester amide copolymer resin can be dissolved in a solvent.

Accordingly, the wholly aromatic polyester amide copolymer resin may be applied to a metal thin film in the form of a varnish dissolved in a solvent for the production of a flexible metal foil laminate, and then dried and heat treated to form a polymer film. That is, the polymer film is formed by attaching to the metal thin film by the above drying and heat treatment.

In addition, the wholly aromatic polyester amide copolymer resin can be used in various applications other than the flexible metal foil laminate.

The solvent for dissolving the wholly aromatic polyester amide copolymer resin may be used in an amount of 100 to 100,000 parts by weight based on 100 parts by weight of the wholly aromatic polyester amide copolymer resin. When the content ratio of the solvent is within the above range The wholly aromatic polyester amide copolymer resin is sufficiently dissolved, and productivity is good.

As the solvent for dissolving the wholly aromatic polyester amide copolymer resin, a non-halogen solvent such as N, N-dimethylacetamide (DMAc) or N-methyl-2-pyrrolidone (NMP) may be used. However, the present invention is not limited thereto. The polar aprotic compound, halogenated phenol, o-dichlorobenzene, chloroform, methylene chloride, tetrachloroethane or a combination thereof may be used as the solvent.

As described above, the wholly aromatic polyester amide copolymer resin is well soluble in a non-halogen solvent and can be used for producing a flexible metal foil laminate or a flexible printed circuit board without using a solvent containing a halogen element. The use of a solvent containing a halogen element may cause problems in the manufacturing process. In particular, when the halogen element is incinerated or decomposed, an environmental hormone harmful to the human body may be generated.

An inorganic filler such as talc, mica, clay, glass fiber, silica, aluminum hydroxide or calcium carbonate may be added to the composition solution in which the wholly aromatic polyester amide copolymer resin is dissolved in a solvent. And / or an organic filler such as a cured epoxy or crosslinked acrylic can be added. For example, an inorganic filler of high dielectric constant can be added. Such inorganic fillers include titanate such as barium titanate or strontium titanate; Or titanium or barium titanate partially replaced by another metal, or the like may be used. The content of the inorganic filler and / or organic filler in the composition solution may be 5 to 30 parts by weight based on 100 parts by weight of the wholly aromatic polyester amide copolymer resin. If the content of the inorganic filler and / or the organic filler is within the above range, not only the warpage property of the polymer film is improved, the coefficient of thermal expansion is lowered but also the effect as a binder of the wholly aromatic polyester amide copolymer resin can be sufficiently maintained have. Accordingly, the polymer film may contain 5 to 30 parts by weight of inorganic filler and / or organic filler per 100 parts by weight of the wholly aromatic polyester amide copolymer resin.

The flexible metal foil laminate according to one embodiment of the present invention includes a film of a wholly aromatic polyester amide copolymer resin having a low thermal expansion coefficient, a low dielectric constant and a low moisture absorption rate, and a metal thin film having excellent mechanical strength. Therefore, the flexible metal foil laminate is excellent in dimensional stability and can be applied to various fields as a flexible substrate material.

In addition, the thermal expansion coefficient of the polymer film may be 14 ppm / K or less. If the coefficient of thermal expansion of the polymer film is within the above range, the flexible metal foil laminate including the polymer film may not warp or shrink.

The dielectric constant of the polymer film may be 3.5 or less, and the dielectric loss may be 0.01 or less. Herein, the term 'dielectric loss' refers to a loss of energy in the dielectric when an alternating electric field is applied to the dielectric (ie, polymer film). If the dielectric constant and the dielectric loss are within the respective ranges, the polymer film can be used as an insulating substrate in a high frequency region.

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, so that the reliability of the flexible metal film laminate is enhanced.

The glass transition temperature of the polymer film may be 250 to 350 ° C. When the glass transition temperature of the polymer film is within the above range, it can have high heat resistance in a reflow process in the production of a flexible printed circuit board.

The dimensional stability, thermal expansion coefficient, dielectric constant, dielectric loss, moisture absorption rate and glass transition temperature of the above polymer film can be measured after the following process. That is, after coating a composition solution (that is, a solution prepared by dissolving the wholly aromatic polyester amide copolymer resin in a solvent) in a metal thin film, drying and heat-treating the metal thin film to produce a flexible metal foil laminate, After removing all of them, the remaining polymer film can be analyzed to measure the physical properties.

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-clad laminate, the thickness of the polymer film may be 1 to 100 탆. When the thickness of the polymer film is within the above range, cracks do not occur during processing in the winding system, which is advantageous for multilayer lamination with a limited thickness.

The thickness of the metal thin film may be 1 to 70 mu m. When the thickness of the metal thin film is within the above range, it is suitable for light weight shortening and easy to form a pattern.

On the other hand, a flexible printed circuit board can be manufactured by etching a metal thin film of the flexible metal foil laminate and forming a circuit. Further, a flexible printed circuit board may be manufactured by printing a metal circuit pattern on at least one side of the polymer film. Further, if necessary, a through hole or the like may be formed in the flexible printed circuit board.

The thickness of the flexible printed circuit board may be 2 to 170 탆. When the thickness of the flexible printed circuit board is within the above range, the flexible printed circuit board is suitable for light weight shortening and the flexible printed circuit board can have flexibility.

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

Example

≪ Examples 1 to 2 and Comparative Examples 1 to 8 >

(1) Step 1: Wholly aromatic  Production of polyester amide copolymer resin

(HNA), 4-aminophenol (AP), isophthalic acid (IPA) and the compound represented by the above formula (1) in a reactor equipped with a stirrer, a nitrogen gas introducing tube, a thermometer and a reflux condenser, An aromatic phosphorus compound (DOPO-HQ) containing a hydroxyl group was introduced and nitrogen gas was injected to make the internal space of the reactor inactive. Acetic anhydride (Ac ₂ O) was further added to the reactor. The contents (moles) of the monomers charged to the reactor are shown in Table 1 below. Thereafter, the reactor temperature was raised to 140 ° C over 1 hour and the hydroxyl groups of the monomers were acetylated while refluxing at that temperature for 2 hours . Next, the acetic acid generated in the acetylation reaction was removed, and the temperature of the reactor was elevated to 300 ° C over 4 hours to prepare a wholly aromatic polyester amide copolymer prepolymer by condensation polymerization of monomers. In addition, acetic acid was further produced as a by-product in the preparation of the prepolymer. The acetic acid was also continuously removed during the preparation of the prepolymer together with the acetic acid generated in the acetylation reaction. Next, the prepolymer was recovered from the reactor and cooled and solidified.

Then, the above wholly aromatic polyester amide copolymer prepolymer was pulverized to an average particle size of 1 mm, 20 kg of the pulverized wholly aromatic liquid crystal polyester prepolymer was put into a 100-liter capacity rotary kiln reactor, nitrogen was supplied at a flow rate of 1 Nm 3 / The temperature was raised to 200 deg. C, which is the weight loss starting temperature, over 1 hour, and then the temperature was raised to 320 deg. C over 10 hours and maintained for 3 hours to produce a wholly aromatic liquid crystal polyester resin. Then, the reactor was cooled to room temperature over 1 hour, and the wholly aromatic liquid-crystalline polyester resin was recovered from the reactor.

(2) Step 2: Wholly aromatic  Preparation of Composition Solution of Polyester Amide Copolymer Resin

60 g of talc was added to 700 g of N-methyl-2-pyrrolidone (NMP) and stirred. 300 g of the wholly aromatic polyester amide copolymer resin powder prepared in the above step 1 was added and heated at a high temperature Followed by stirring to obtain a composition solution of a wholly aromatic polyester amide copolymer resin.

 (3) Step 3: Copper foil Laminate  Produce

The solution of the composition of the wholly aromatic polyester amide copolymer resin prepared in the above step 2 was coated on the surface of the copper foil having a thickness of 18 탆. Thereafter, the composition solution of the coated wholly aromatic polyester amide copolymer resin was dried at 160 캜. Next, in order to further increase the physical properties, the temperature was raised to 300 DEG C and the reaction was further continued to produce a copper clad laminate. The thus produced copper clad laminate includes a polymer film in the form attached to a copper foil.

HBA
(Moles) HNA
(Moles) AP
(Moles) IPA
(Moles) DOPO-HQ
(Moles) Ac ₂ O
(Moles) Example 1 15 20 30 30 5 110 Example 2 20 20 30 25 5 110 Comparative Example 1 9 9 40 35 7 110 Comparative Example 2 27 27 20 20 6 110 Comparative Example 3 25 25 5 40 5 110 Comparative Example 4 10 10 50 25 5 110 Comparative Example 5 25 25 40 5 5 110 Comparative Example 6 10 10 25 50 5 110 Comparative Example 7 15 20 35 30 0 110 Comparative Example 8 10 10 30 30 20 110

≪ Comparative Example 9 &

A copper-clad laminate (Pyralux AC) containing a polyimide resin film was obtained from SD Flex.

Evaluation example

≪ Evaluation Example 1: Evaluation of physical properties of resin &

The weight average molecular weight and glass transition temperature of each of the wholly aromatic polyester amide copolymer resins prepared in Examples 1 to 2 and Comparative Examples 1 to 8 were measured and are shown in Table 2 below. However, the physical property data of the resin contained in the copper-clad laminate of Comparative Example 9 was not obtained.

Weight average molecular weight Glass transition temperature (캜) Example 1 12,000 240 Example 2 13,000 250 Comparative Example 1 7,000 190 Comparative Example 2 10,000 230 Comparative Example 3 9,500 225 Comparative Example 4 8,000 200 Comparative Example 5 11,000 235 Comparative Example 6 9,000 200 Comparative Example 7 12,000 235 Comparative Example 8 10,000 225 Comparative Example 9 - -

In Table 2, the weight average molecular weight was measured at 30 ° C in a THF eluent using GPC and the glass transition temperature was measured at 20 ° C / min using DSC.

Referring to Table 2 above, the weight average molecular weight was very low in Comparative Example 1. In addition, the glass transition temperature was also found to be extremely low in the case of Comparative Example 1. Therefore, the copolymer resin produced in Comparative Example 1 has a low thermal property, so that it is difficult to pass through the reflow process even after the additional heat treatment process.

≪ Evaluation Example 2: Evaluation of Physical Properties of Polymer Film Contained in Copper Clad Laminate >

The copper foil laminates of Examples 1 to 2 and Comparative Examples 1 to 9 were all removed by etching to remove the copper foil and the remaining polymer films were analyzed to determine the thermal expansion coefficient, dielectric property, bending property, moisture absorption rate, The glass transition temperature was measured and shown in Table 3 below. In the case of dimensional stability, the smaller the number, the higher the dimensional stability.

Thermal expansion rate
(ppm / K) Dielectric constant
(@ 1 GHz) Dielectric loss
(@ 1 GHz) Bending characteristic
(mm) Moisture absorption rate
(weight%) Glass transition temperature
(° C) Example 1 14 3.2 0.006 5 0.4 285 Example 2 13 3.2 0.006 4 0.4 290 Comparative Example 1 17 3.5 0.007 11 0.5 235 Comparative Example 2 15 3.3 0.006 7 0.7 270 Comparative Example 3 16 3.6 0.007 8 0.9 265 Comparative Example 4 17 3.5 0.008 10 0.4 235 Comparative Example 5 16 3.6 0.008 7 0.5 270 Comparative Example 6 20 3.7 0.008 13 0.6 230 Comparative Example 7 16 3.3 0.006 7 0.5 250 Comparative Example 8 13 3.8 0.008 4 0.5 265 Comparative Example 9 18 3.6 0.012 5 1.5 280

In Table 3, the coefficient of thermal expansion was measured using TMA (TMA Q400) at a temperature range of 50 to 150 ° C. Dielectric constant and dielectric loss were measured using an impedance analyzer (Agilent, E4991A) -TM-650 was measured using 2.6.2.1 standard, and the dimensional stability was measured using IPC-TM-650 2.2.4 standard. Glass transition temperature was measured using IPC-TM-650 2.4.24.2 standard .

Referring to Table 3, the polymer film prepared in Example 1-2 is superior in terms of thermal expansion coefficient, dielectric constant, dielectric loss and glass transition temperature as compared with the polymer film prepared in Comparative Examples 1 to 9, And the moisture absorption rate. The polymer film of Comparative Example 6 may have warpage or shrinkage in the manufacture of flexible printed circuit boards due to its high coefficient of thermal expansion and low flexural properties, and reliability may also be a problem.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

Claims (12)

20 to 50 parts by mole of the repeating unit (A) derived from an aromatic hydroxycarboxylic acid;
At least one repeating unit selected from the group consisting of a repeating unit derived from an aromatic amine having a phenolic hydroxyl group (B) and a repeating unit derived from an aromatic diamine (B ');
20 to 40 molar parts of the repeating unit derived from an aromatic dicarboxylic acid (C); And
(D) derived from an aromatic phosphorus compound containing a hydroxyl group. The method according to claim 1,
The repeating unit (A) may be selected from the group consisting of parahydroxybenzoic acid, metahydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 3-hydroxy- Hydroxy-1-naphthoic acid; and at least one compound selected from the group consisting of hydroxy-1-naphthoic acid; The repeating unit (B) is at least one compound selected from the group consisting of 3-aminophenol, 4-aminophenol, 5-amino-1-naphthol, 8-amino- ≪ / RTI > The repeating unit (B ') may be at least one selected from the group consisting of 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 2,3-diaminonaphthalene and 1,8-diaminonaphthalene Lt; RTI ID = 0.0 > of: < / RTI > The repeating unit (C) is derived from at least one compound selected from the group consisting of isophthalic acid, naphthalene dicarboxylic acid and terephthalic acid; Wherein the repeating unit (D) is derived from a compound represented by the following general formula (1): < EMI ID =
[Chemical Formula 1]

The method according to claim 1,
A weight average molecular weight of 1,000 to 20,000 and a glass transition temperature of 200 to 300 占 폚. A polymer film comprising a wholly aromatic polyester amide copolymer resin according to any one of claims 1 to 3. 5. The method of claim 4,
Further comprising 5 to 30 parts by weight of at least one filler selected from the group consisting of organic fillers and inorganic fillers per 100 parts by weight of the wholly aromatic polyester amide copolymer resin. 5. The method of claim 4,
A polymer film having one directional thermal expansion coefficient of 14 ppm / K or less. 5. The method of claim 4,
A polymer film having a dielectric constant of 3.5 or less and a dielectric loss of 0.01 or less. 5. The method of claim 4,
A polymer film having a moisture absorption rate of 0.5% by weight or less. 5. The method of claim 4,
A polymer film having a glass transition temperature of 250 to 350 占 폚. A polymer film according to claim 4; And
And at least one metal thin film disposed on at least one surface of the polymer film. A flexible printed circuit board obtained by etching a metal thin film of the flexible metal foil laminate according to claim 10. A flexible printed circuit board formed by printing a metal circuit pattern on at least one surface of a polymer film according to claim 4.