JP2012514067A - Aromatic polyesteramide copolymer, polymer film, prepreg, prepreg laminate, metal foil laminate and printed wiring board - Google Patents

Abstract

An aromatic polyester amide copolymer, a polymer film, a prepreg, a prepreg laminate, a metal foil laminate and a printed wiring board are provided. The aromatic polyesteramide copolymer is composed of 20 to 40 mol% of repeating units (A) derived from aromatic diol, repeating units (B) derived from aromatic amine having a phenolic hydroxyl group, and aromatic diamine. It contains 20 to 40 mol% of at least one repeating unit (B ′) derived from the repeating unit (C) and 20 to 60 mol% derived from an aromatic dicarboxylic acid, and is derived from an aromatic diol. The repeat unit (A) comprises a repeat unit (RCN) derived from resorcinol.
[Selection figure] None

Description

  The present invention relates to an aromatic polyesteramide copolymer, a polymer film, a prepreg, a prepreg laminate, a metal foil laminate, and a printed wiring board. More specifically, an aromatic polyester amide copolymer having low thermal expansion coefficient, low dielectric constant and low dielectric loss and improved transparency, a polymer film employing the aromatic polyester amide copolymer, prepreg, prepreg lamination The present invention relates to a body, and a metal foil laminate and a printed wiring board employing the prepreg or prepreg laminate.

  Recently, due to miniaturization and multi-functionalization of electronic devices, printed wiring boards have been increased in density and miniaturization, and copper foil laminates are excellent in stamping workability and drill workability, and are low in price. Widely used as a printed circuit board for electronic equipment.

The prepreg used in the copper foil laminate for such a printed wiring board must satisfy the following main characteristics so as to be suitable for the performance of the semiconductor and the conditions of the semiconductor packaging manufacturing process.
(1) Low thermal expansion coefficient compatible with metal thermal expansion coefficient (2) Low dielectric constant and dielectric stability in a high frequency region of 1 GHz or higher (3) Heat resistance to a reflow process of about 270 ° C

  The prepreg is produced by impregnating a glass woven fabric with a resin derived from epoxy or bismaleimide triazine and then semi-curing the prepreg. Next, a copper foil is laminated on the prepreg, and the resin is cured to produce a copper foil laminate. Such a copper foil laminate is made into a thin film and undergoes a high-temperature process such as a reflow process at 270 ° C. However, since it undergoes such a high-temperature process, the copper foil laminate in the form of a thin film is thermally deformed, resulting in a decrease in yield. There are problems such as. In addition, epoxy or bismaleimide triazine resins are required to be improved to low absorbency due to their high hygroscopicity, and particularly deteriorate the dielectric characteristics in a high frequency region of 1 GHz or higher, and can perform high frequency and high speed processing. There is a problem that it is difficult to apply to the required printed wiring board for semiconductor packaging. Therefore, there is a need for a low dielectric prepreg that does not cause such problems.

  Recently, as an alternative to epoxy or bismaleimide triazine resin, there is an example in which aromatic liquid crystal polyester is used for forming a prepreg. Such a prepreg is produced by impregnating an aromatic polyester with an organic or inorganic woven fabric. In particular, an aromatic polyester prepreg may be produced using an aromatic polyester resin and an aromatic polyester woven fabric. Specifically, an aromatic polyester is dissolved in a solvent containing a halogen element such as chlorine to produce a solution composition, the aromatic polyester woven fabric is impregnated with the solution composition, and then dried. A polyester prepreg is produced. However, in this method, it is difficult to completely remove the solvent containing a halogen element, and the halogen element corrodes the copper foil. Therefore, improvement to use of a non-halogen solvent is required.

  One embodiment of the present invention provides an aromatic polyesteramide copolymer having a low coefficient of thermal expansion, a low dielectric constant, and a low dielectric loss.

  Another embodiment of the present invention provides an aromatic polyesteramide copolymer having high transparency.

  Still another embodiment of the present invention provides a prepreg and a prepreg laminate having a low thermal expansion coefficient, a low dielectric constant, and a low dielectric loss and improved transparency by employing the aromatic polyesteramide copolymer. To do.

  Still another embodiment of the present invention provides a metal foil laminate and a printed wiring board employing the prepreg or prepreg laminate.

One aspect of the present invention is a repeating unit A derived from an aromatic diol.
20 to 40 mol%, at least one repeating unit B derived from an aromatic amine having a phenolic hydroxyl group, and at least one repeating unit B 'derived from an aromatic diamine, and an aromatic dicarboxylic acid Repeating unit C derived from acid
The repeating unit A derived from the aromatic diol comprising 20 to 60 mol% provides an aromatic polyester amide copolymer including the repeating unit RCN derived from resorcinol.

The repeating unit A derived from the aromatic diol further includes a repeating unit HQ derived from at least one compound of biphenol and hydroquinone. In this case, the content of the repeating unit RCN and the content of the repeating unit HQ satisfy the following conditions:
0 <n (RCN) / [n (RCN) + n (HQ)] <1
Here, n (RCN) and n (HQ) are the number of moles of the repeating unit RCN and the repeating unit HQ contained in the aromatic polyesteramide copolymer, respectively.

  Another aspect of the present invention provides a polymer film including the aromatic polyesteramide copolymer.

  Still another aspect of the present invention provides a prepreg including a base material impregnated with the aromatic polyester amide copolymer.

  Still another aspect of the present invention provides a prepreg laminate including two or more of the prepregs.

  Still another aspect of the present invention provides a metal foil laminate in which a metal thin film is formed on at least one surface of the prepreg or the prepreg laminate.

  Still another aspect of the present invention provides a printed wiring board obtained by etching a metal thin film of the metal foil laminate.

  Still another aspect of the present invention provides a printed wiring board formed by printing a metal circuit pattern on at least one surface of the polymer film.

  Hereinafter, an aromatic polyesteramide copolymer according to an embodiment of the present invention and a prepreg including a base material impregnated with the copolymer will be described in detail.

The aromatic polyester amide copolymer according to this embodiment is a repeating unit A derived from an aromatic diol.
20 to 40 mol%, at least one repeating unit B derived from an aromatic amine having a phenolic hydroxyl group, and at least one repeating unit B 'derived from an aromatic diamine, and an aromatic dicarboxylic acid Repeating unit C derived from acid
And the repeating unit A derived from the aromatic diol comprises the repeating unit RCN derived from resorcinol.

  If the content of the repeating unit A is less than 20 mol%, the solubility in a solvent is lowered, which is not desirable, and if it exceeds 40 mol%, the melting temperature is excessively increased.

The repeating unit A derived from the aromatic diol further includes a repeating unit HQ derived from at least one compound of biphenol and hydroquinone. In this case, the number of moles n (RCN) of the repeating unit RCN and the number of moles n (HQ) of the repeating unit HQ included in the aromatic polyesteramide copolymer satisfy the following conditions:
0 <n (RCN) / [n (RCN) + n (HQ)] <1

  The molar ratio of the repeating unit RCN to the repeating unit HQ is appropriately selected in consideration of the transparency of the aromatic polyesteramide copolymer to be produced.

  Further, if the total content of the repeating unit B and the repeating unit B ′ is less than 20 mol%, the solubility in the solvent is undesirably lowered, and if it exceeds 40 mol%, the melting temperature is excessively increased. Absent.

  The repeating unit B includes a repeating unit derived from one or more compounds selected from the group consisting of 3-aminophenol, 4-aminophenol and 2-amino-6-naphthol, and the repeating unit B ′ includes It contains repeating units derived from one or more compounds selected from the group consisting of 1,4-phenylenediamine, 1,3-phenylenediamine and 2,6-naphthalenediamine.

  On the other hand, if the content of the repeating unit C is less than 20 mol%, the solubility in a solvent is lowered, which is not desirable, and if it exceeds 60 mol%, the melting temperature is lowered, which is not desirable.

  The repeating unit C includes a repeating unit derived from one or more compounds selected from the group consisting of isophthalic acid, naphthalene dicarboxylic acid and terephthalic acid.

  Specifically, each repeating unit included in the aromatic polyesteramide copolymer is represented by any one of the following chemical formulas:

(1) Repeating unit A derived from an aromatic diol:

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

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

(4) Repeating unit C derived from aromatic dicarboxylic acid:

In the above formula, R ₁ and R ₂ are the same or different and each is a halogen atom, carboxyl group, amino group, nitro group, cyano group, substituted or unsubstituted C ₁ to C ₂₀ alkyl group, substituted or unsubstituted A C ₁ to C ₂₀ alkoxy group, a substituted or unsubstituted C ₂ to C ₂₀ alkenyl group, a substituted or unsubstituted C ₂ to C ₂₀ alkynyl group, a substituted or unsubstituted C ₁ to C ₂₀ hetero An alkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted or unsubstituted C ₇ to C ₃₀ arylalkyl group, a substituted or unsubstituted C ₅ to C ₃₀ heteroaryl group, or a substituted or unsubstituted Represents an unsubstituted C ₃ to C ₃₀ heteroarylalkyl group. In this 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 thereof.

  Such an aromatic polyester amide copolymer includes: (1) an aromatic diol containing resorcinol and hydroquinone and / or biphenol, or a derivative for forming an ester thereof; (2) an aromatic amine having a phenolic hydroxyl group, or an amide formation thereof. And at least one selected from the group consisting of aromatic diamines or derivatives for forming amides; and (3) aromatic dicarboxylic acids or derivatives for forming esters thereof.

  The derivative for forming an ester of the aromatic diol means one in which those hydroxyl groups react with carboxylic acids to form an ester bond.

  In addition, the derivative for forming an ester of the aromatic hydroxycarboxylic acid or the aromatic dicarboxylic acid is a highly reactive derivative such as an acid chloride or an acid anhydride, or an alcohol or ethylene glycol. It may form an ester bond.

  In addition, the aromatic amine or the amide-forming derivative of the aromatic diamine may have an amine group that forms an amide bond with a carboxylic acid.

  The aromatic polyesteramide copolymer prepared as described above is dissolved in a solvent, and preferably a thermotropic liquid crystal polyesteramide copolymer capable of forming a melt exhibiting optical anisotropy at 400 ° C. or lower. Can be coalesced. Specifically, the aromatic polyester amide copolymer may have a melting temperature of 250 ° C. to 400 ° C. and a number average molecular weight of 1,000 to 20,000.

  Moreover, since the aromatic polyesteramide copolymer manufactured as mentioned above contains the repeating unit RCN derived from resorcinol, the transparency is improved, and the prepreg or prepreg laminate employing the same has high transparency.

  The aromatic polyester amide copolymer as described above is manufactured through a general aromatic liquid crystal polyester manufacturing method, for example, an aromatic diol corresponding to the repeating unit RCN and the repeating unit HQ, and the repeating unit B and Acylation product is obtained by acylating the phenolic hydroxyl group and / or amine group of aromatic amine and / or aromatic diamine corresponding to repeating unit B ′ with an excess of fatty acid anhydride, and the resulting acylated product and aromatic dicarboxylic acid A method of performing melt polymerization by performing an ester exchange reaction with an acid can be mentioned.

  In the acylation reaction, the amount of fatty acid anhydride added may be 1.0 to 1.2 times the total equivalent weight of the phenolic hydroxyl group and amine group, for example, 1.04 to 1.07 times equivalent. . If the amount of the fatty acid anhydride added is large, coloring of the aromatic polyester amide copolymer tends to be remarkable. Tend to be. The acylation reaction is preferably performed at 130 to 170 ° C. for 30 minutes to 8 hours, more preferably at 140 to 160 ° C. for 2 to 4 hours.

  Examples of the fatty acid anhydride used in the acylation reaction include acetic anhydride, propionic anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, and butyric anhydride, and are not particularly limited thereto. Also, two or more of them can be mixed and used. In terms of economy and handling, it is desirable to use acetic anhydride.

  The transesterification and amide exchange reactions are preferably performed at 130 to 400 ° C. at a temperature rising rate of 0.1 to 2 ° C./min, and at 140 to 350 ° C., 0.3 to 1 ° C./min. It is more desirable to perform in.

  In order to shift the equilibrium when the fatty acid ester and carboxylic acid obtained by acylation in this way are transesterified and transamidated, the by-produced fatty acid and unreacted anhydride are reacted by evaporation or distillation. It can be discharged out of the system.

  The acylation reaction, transesterification reaction and amide exchange reaction are carried out in the presence of a catalyst. The catalyst is conventionally known as a catalyst for polyester, and includes magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, N, N-dimethylamino. Examples include pyridine and N-methylimidazole. The catalyst is usually charged simultaneously with the monomer when the monomer is charged, and acylation and transesterification occur in the presence of the catalyst.

  The polycondensation by the ester exchange reaction and the amide exchange reaction is usually carried out by melt polymerization, but melt polymerization and solid phase polymerization can be used in combination.

  The polymerization reactor used for 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 for the acylation step and the polymerizer for the melt polymerization step, and different reactors may be used for each step.

  The solid phase polymerization is carried out by pulverizing the prepolymer discharged in the melt polymerization step to form a flake or powder and then proceeding with the polymerization. Such solid phase polymerization is carried out by heat treatment in a solid state at 200 to 350 ° C. for 1 to 30 hours in an inert atmosphere such as nitrogen, for example. The solid phase polymerization may be performed with stirring or may be performed without stirring. In addition, a reactor equipped with appropriate stirring equipment can be used in combination as a melt polymerization tank and a solid phase polymerization tank.

  The aromatic polyesteramide copolymer produced as described above has a coefficient of thermal expansion of 3 ppm / K or less.

  The obtained aromatic polyesteramide copolymer may be formed into pellets by a known method and then molded, or may be fiberized by a known method. In addition, such an aromatic polyester amide copolymer can be dissolved in a solvent as described later, applied to a metal thin film, and then dried and heat-treated to form a polymer film. used.

  The prepreg according to this embodiment includes a base material impregnated with the aromatic polyesteramide copolymer.

  The prepreg is, for example, impregnated with an organic or inorganic woven fabric and / or a nonwoven fabric substrate with a composition solution in which the aromatic polyesteramide copolymer is dissolved in a solvent, or with the composition solution as described above. After forming by applying to a woven fabric and / or non-woven fabric substrate, it is produced by removing the solvent.

  At this time, examples of a usable molding method include a solution impregnation method or a varnish impregnation method.

  The solvent for dissolving the aromatic polyester amide copolymer may be used in a content of 100 to 100,000 parts by weight with respect to 100 parts by weight of the aromatic polyester amide copolymer, and the content of the solvent is 100 parts by weight. If the amount is less than 100% by weight, the viscosity of the solution increases and there is a problem in processing. If the amount exceeds 100,000 parts by weight, the amount of the aromatic polyester amide copolymer is small, and thus the productivity tends to decrease. Not desirable.

  As the solvent for dissolving the aromatic polyester amide copolymer, a non-halogen solvent is preferably used. However, the present invention is not limited to this, and polar aprotic compounds, halogenated phenols, o-dichlorobenzene, chloroform, methylene chloride, tetrachloroethane, etc. may be used alone or in combination of two or more. . In particular, the aromatic polyester amide copolymer is well dissolved in a non-halogen solvent, and it is not necessary to use a solvent containing a halogen element. Therefore, the metal foil laminate or printed wiring board containing the aromatic polyester amide copolymer does not have to be used. When the foil uses a solvent containing a halogen element, it is possible to prevent a problem that the foil is corroded by the halogen element in advance.

  As the base material, aromatic polyester fiber, glass fiber, carbon fiber, glass paper, or a woven fabric and / or a non-woven fabric containing a mixture of two or more thereof is used.

  When the impregnation method is used in the prepreg manufacturing process, the time for impregnating the substrate with the composition solution in which the aromatic polyesteramide copolymer is dissolved in a solvent is usually preferably 0.001 minute to 1 hour. If the impregnation time is less than 0.001 minutes, the aromatic polyesteramide copolymer is not uniformly impregnated, and if it exceeds 1 hour, the productivity is lowered.

  The temperature at which the substrate is impregnated with the composition solution in which the aromatic polyester amide copolymer is dissolved in a solvent can be in the range of 20 to 190 ° C., and is preferably performed at room temperature.

The substrate has a thickness of 5 to 200 μm, and the amount of the aromatic polyester amide copolymer impregnated per unit area of the substrate is in the range of 0.1 to 1,000 g / m ² . It is desirable that When the impregnation amount is less than 0.1 g / m ² , the productivity is undesirably lowered, and when it exceeds 1,000 g / m ² , the solution has a high viscosity and is difficult to process. Absent.

  In the composition solution in which the aromatic polyesteramide copolymer is dissolved in a solvent, silica, aluminum hydroxide, calcium carbonate and the like are used in order to adjust the dielectric constant and the coefficient of thermal expansion within a range not damaging the object of the invention. Inorganic fillers; organic fillers such as cured epoxy and cross-linked acrylic are added. In particular, an inorganic filler having a high dielectric constant may be added. As such an inorganic filler, titanates such as barium titanate and strontium titanate; those obtained by substituting a part of titanium or barium of barium titanate with other metals, and the like can be used. The content of the inorganic filler and / or organic filler is desirably 0.0001 to 100 parts by weight with respect to 100 parts by weight of the aromatic polyesteramide copolymer. If the addition amount of the inorganic filler and / or organic filler is less than 0.0001 parts by weight, the dielectric constant of the prepreg tends to be sufficiently increased or the coefficient of thermal expansion tends not to be lowered, and the amount exceeds 100 parts by weight. For example, the effect of the aromatic polyester amide copolymer as a binder tends to decrease.

  The prepreg according to this embodiment uses an aromatic liquid crystal polyesteramide copolymer having low hygroscopicity and low dielectric properties, and an organic or inorganic woven fabric and / or non-woven fabric having excellent mechanical strength. Excellent heat resistance, low thermal deformation, and hard, which is advantageous for via hole drilling and lamination.

  In addition, since the prepreg according to the present embodiment includes an aromatic polyesteramide copolymer including the recurring unit RCN derived from resorcinol, the prepreg can have high transparency by appropriately adjusting the content of the recurring unit RCN. .

  In the impregnation method for producing the prepreg, the base material is impregnated with a composition solution in which the aromatic polyesteramide copolymer is dissolved in a solvent, or after the composition solution is applied to the base material, The method for removing the solvent is not particularly limited, but it is desirable to use evaporation of the solvent. For example, evaporation by a method such as heating, decompression, ventilation or the like can be mentioned. Among them, solvent heating evaporation is desirable in terms of applicability to existing prepreg manufacturing processes, production efficiency, and handling, and it is more desirable to evaporate by ventilation heating.

  In the solvent removing step, the heating temperature is preliminarily dried in the range of 20 to 190 ° C. for 1 minute to 2 hours with respect to the composition solution of the aromatic polyester amide copolymer obtained by the production method of the present invention. It is desirable to perform the heat treatment in the range of 350 ° C. to 1 minute to 10 hours.

  The prepreg according to the present embodiment thus obtained has a thickness of about 5 to 200 μm, preferably about 30 to 150 μm. The prepreg has a unidirectional coefficient of thermal expansion of 10 ppm / K or less, a dielectric constant of 3.5 or less, and a dielectric loss of 0.01 or less. Here, the dielectric loss means an energy loss that is lost by heat in the dielectric when an AC electric field is applied to the dielectric. If the coefficient of thermal expansion exceeds 10 ppm / K, a prepreg peeling phenomenon occurs, which is not desirable. Further, if the dielectric constant exceeds 3.5 or the dielectric loss exceeds 0.01, it is not desirable because it is not suitable as an insulating base material in a high frequency region.

  A prepreg laminate can be produced by laminating a predetermined number of the prepregs and heating and pressing them.

  Moreover, a metal foil laminated board can be manufactured by arrange | positioning metal thin films, such as copper foil, silver foil, and aluminum foil, on one surface or both surfaces of the said prepreg or the said prepreg laminated body, and heating and pressurizing similarly to the above.

  In the metal foil laminate, the thicknesses of the prepreg or the prepreg laminate and the metal thin film are not particularly limited, but are preferably 0.1 to 300 μm. If the thickness of the prepreg or prepreg laminate is less than 0.1 μm, cracks are likely to occur at the time of the winding method, and if it exceeds 300 μm, the number of layers of the multilayer stack having a limited thickness is reduced. Limited and undesirable. If the thickness of the metal thin film is less than 0.1 μm, cracks are likely to occur when the metal thin films are laminated, and if it exceeds 300 μm, it is disadvantageous for multilayer lamination and is not desirable.

  The heating and pressurizing steps applied during the production of the metal foil laminate are preferably performed at a temperature of 150 to 180 ° C. and a pressure of about 9 to 20 MPa. However, the prepreg characteristics and the reaction of the aromatic polyesteramide copolymer composition are preferably performed. Since it can be determined appropriately in consideration of the properties, the capacity of the press, the thickness of the target metal foil laminate, etc., there is no particular limitation.

  In addition, the metal foil laminate according to this embodiment further includes an adhesive layer interposed between the prepreg laminate and the metal thin film in order to increase the bonding strength between them. As the adhesive layer, a thermoplastic resin composition or a thermosetting resin composition is used. The adhesive layer may have a thickness of 0.1 to 100 μm. If the thickness is less than 0.1 μm, the adhesive strength is undesirably low, and if it exceeds 100 μm, the thickness becomes excessively large.

  Moreover, a printed wiring board can be manufactured by etching the metal thin film of the said metal foil laminated board, and forming a circuit. Moreover, a printed wiring board can also be manufactured by printing a metal circuit pattern on at least one surface of the polymer film. Moreover, a through hole etc. can also be formed in the said printed wiring board as needed. In the multilayer printed wiring board of this embodiment, for example, a predetermined number of the prepregs are arranged between constituent materials such as an inner layer base material and a metal thin film in accordance with the desired thickness of the insulating layer, and heated and pressurized. Can be manufactured by molding. The heating and pressurizing conditions at this time are appropriately determined similarly to the conditions at the time of manufacturing the metal foil laminate. Examples of the inner layer base material include a prepreg laminate, a metal foil laminate or a printed wiring board used as an electrical insulating material, and two or more of them may be used in combination.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to this.

Example 1
In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer and reflux condenser, hydroquinone 110.1 g (1.0 mol), resorcinol 110.1 g (1.0 mol), 4-aminophenol 327.4 g (3.0 mol), 830.7 g (5.0 mol) of isophthalic acid and 1,123 g (11 mol) of acetic anhydride were added.

  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 the mixture was refluxed for 3 hours while maintaining this temperature.

  Next, while acetic acid and unreacted acetic anhydride flowing out were distilled off, the temperature was raised to 320 ° C. for 180 minutes, and the content was discharged considering that the time when the torque increased was regarded as completion of the reaction. The obtained solid content was cooled to room temperature, pulverized with a fine pulverizer, and then solid-phase polymerization was performed while maintaining at 260 ° C. for 5 hours under a nitrogen atmosphere to obtain an aromatic polyester amide copolymer powder. It was.

  7 g of the aromatic polyesteramide copolymer powder thus obtained was added to 93 g of N-methylpyrrolidinone (NMP) and stirred at 120 ° C. for 4 hours to obtain a composition solution of the aromatic polyesteramide copolymer. Got.

A glass woven fabric (IPC) was added to this composition solution.
2116) was impregnated at a temperature of 80 ° C. and passed between double rollers to remove excess composition solution and to keep the thickness constant. Next, after the contents were put into a high-temperature hot air dryer and the solvent was removed at 120 ° C., heat treatment was performed at 300 ° C. for 60 minutes to obtain a prepreg in which an aromatic polyester amide copolymer was impregnated with a glass woven fabric. It was.

Example 2
An aromatic polyester amide copolymer was produced in the same manner as in Example 1 except that no hydroquinone was used as the aromatic diol and only 220.2 g (2.0 mol) of resorcinol was used. In addition, an aromatic polyesteramide copolymer composition solution and a prepreg were produced in the same manner as in Example 1.

Comparative Example 1
An aromatic polyester amide copolymer was produced in the same manner as in Example 1 except that resorcinol was not used as an aromatic diol and only 220.2 g (2.0 mol) of hydroquinone was used. In addition, an aromatic polyesteramide copolymer composition solution and a prepreg were produced in the same manner as in Example 1.

  The prepreg produced in Examples 1 and 2 was subjected to resin powder removal and electrical property evaluation as compared with Comparative Example 1 as follows.

  First, the prepreg produced in Examples 1 and 2 and the prepreg produced in Comparative Example 1 were each immersed in a soldering bath having a soldering temperature of 290 ° C. for 1 minute, and the surface state was observed. In the prepregs produced in Examples 1 and 2 and Comparative Example 1, neither deformation nor blister occurred.

  Further, the dielectric constant and dielectric loss of the prepreg produced in Examples 1 and 2 and the prepreg produced in Comparative Example 1 were measured using an impedance analyzer, and are shown in Table 1 below.

  Moreover, the solubility with respect to N-methylpyrrolidinone (NMP) of the aromatic polyesteramide copolymer manufactured in the said Example 1 and 2 and the aromatic polyesteramide copolymer manufactured in the comparative example 1 was measured, and the following It is shown in Table 1.

  Moreover, with respect to the aromatic polyesteramide copolymer produced in Examples 1 and 2 and the aromatic polyesteramide copolymer produced in Comparative Example 1, each was measured using a differential scanning calorimeter (DSC). The melting temperature was measured and shown in Table 1 below.

  Moreover, with respect to the prepreg manufactured in Examples 1 and 2 and the prepreg manufactured in Comparative Example 1, each thermal expansion coefficient was measured using TMA (manufactured by TMA, Q400). Indicated.

  Here, as described above, a prepreg laminate, a metal foil laminate, and a printed wiring board using a prepreg are used to manufacture the prepreg laminate, metal using the prepreg produced in the above-described embodiment. A foil laminated board and a printed wiring board can be manufactured.

  Although the present invention has been described with reference to exemplary embodiments, this is illustrative only and those skilled in the art will appreciate that various modifications and equivalent other embodiments are possible. It will be possible. Therefore, the true technical protection scope of the present invention must be determined by the technical ideas of the claims.

Claims (17)

20 to 40 mol% of repeating units (A) derived from an aromatic diol,
20 to 40 mol% of at least one repeating unit among the repeating unit (B) derived from an aromatic amine having a phenolic hydroxyl group and the repeating unit (B ′) derived from an aromatic diamine;
20 to 60 mol% of repeating units (C) derived from aromatic dicarboxylic acids,
The repeating unit (A) derived from the aromatic diol is an aromatic polyester amide copolymer containing a repeating unit (RCN) derived from resorcinol.   The aromatic polyester amide copolymer according to claim 1, wherein the repeating unit (A) derived from the aromatic diol further comprises a repeating unit (HQ) derived from at least one compound of biphenol and hydroquinone. The aromatic polyesteramide copolymer according to claim 2, wherein the content of the repeating unit (RCN) and the content of the repeating unit (HQ) satisfy the following conditions:
0 <n (RCN) / [n (RCN) + n (HQ)] <1
Here, n (RCN) and n (HQ) are the number of moles of repeating units (RCN) and repeating units (HQ) contained in the aromatic polyesteramide copolymer, respectively.   The repeating unit (B) is derived from one or more compounds selected from the group consisting of 3-aminophenol, 4-aminophenol and 2-amino-6-naphthol, and the repeating unit (B ′) is Derived from one or more compounds selected from the group consisting of 1,4-phenylenediamine, 1,3-phenylenediamine and 2,6-naphthalenediamine, the repeating unit (C) is isophthalic acid, naphthalenedicarboxylic acid The aromatic polyester amide copolymer according to claim 1, which is derived from one or more compounds selected from the group consisting of terephthalic acid and terephthalic acid.   The aromatic polyester amide copolymer according to claim 1, having a number average molecular weight of 1,000 to 20,000 and a melting temperature of 250 to 400 ° C.   A polymer film comprising the aromatic polyesteramide copolymer according to any one of claims 1 to 5.   A prepreg comprising a base material impregnated with the aromatic polyesteramide copolymer according to any one of claims 1 to 5. The substrate has a thickness of 5 to 200 μm, and the amount of the aromatic polyester amide copolymer impregnated per unit area of the substrate is in the range of 0.1 to 1,000 g / m ^2. Item 8. The prepreg according to Item 7.   The prepreg according to claim 7, wherein the base material includes at least one selected from the group consisting of aromatic polyester fiber, glass fiber, carbon fiber, and glass paper.   The organic filler and inorganic filler added to the substrate are further included at a ratio of 0.0001 to 100 parts by weight with respect to 100 parts by weight of the aromatic polyesteramide copolymer. The prepreg described in 1.   The prepreg according to claim 7, wherein the coefficient of thermal expansion in one direction is 10 ppm / K or less.   The prepreg according to claim 7, wherein the dielectric constant is 3.5 or less and the dielectric loss is 0.01 or less.   A prepreg laminate comprising two or more prepregs according to claim 7. The prepreg according to claim 7,
A metal foil laminate comprising: at least one metal thin film disposed on at least one surface of the prepreg.   The metal foil laminate according to claim 14, wherein the prepreg is at least two prepreg laminates.   A printed wiring board obtained by etching a metal thin film of the metal foil laminate according to claim 14.   A printed wiring board formed by printing a metal circuit pattern on at least one surface of the polymer film according to claim 6.