KR101595121B1 - Aromatic liquid-crystalline polyester amide copolymer prepreg or prepreg laminates having the copolymer and metal clad laminates and print wiring board having the prepreg or the prepreg laminates - Google Patents

Aromatic liquid-crystalline polyester amide copolymer prepreg or prepreg laminates having the copolymer and metal clad laminates and print wiring board having the prepreg or the prepreg laminates Download PDF

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KR101595121B1
KR101595121B1 KR1020080138702A KR20080138702A KR101595121B1 KR 101595121 B1 KR101595121 B1 KR 101595121B1 KR 1020080138702 A KR1020080138702 A KR 1020080138702A KR 20080138702 A KR20080138702 A KR 20080138702A KR 101595121 B1 KR101595121 B1 KR 101595121B1
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prepreg
repeating unit
derived
aromatic
polyester amide
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KR1020080138702A
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KR20100080081A (en
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구본혁
옥태준
박정원
오영택
드미트리 크라브주그
김만종
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심천 워트 어드밴스드 머티리얼즈 주식회사
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Priority to KR1020080138702A priority Critical patent/KR101595121B1/en
Priority to CN2009801532722A priority patent/CN102272200B/en
Priority to PCT/KR2009/007763 priority patent/WO2010077014A2/en
Priority to JP2011543429A priority patent/JP2012514066A/en
Priority to TW98145785A priority patent/TW201035168A/en
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0145—Polyester, e.g. polyethylene terephthalate [PET], polyethylene naphthalate [PEN]

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Polyamides (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

An aromatic polyester amide copolymer, a prepreg, a prepreg laminate, a metal foil laminate and a printed wiring board. The disclosed aromatic polyester amide copolymer contains 20 to 25 mol% of the repeating unit (A) derived from an aromatic diol with respect to all repeating units, and the repeating unit (A) derived from the aromatic diol is a repeating unit derived from resorcinol A repeating unit (RCN), and a repeating unit (HQ) derived from at least one compound of biphenol and hydroquinone.

Description

TECHNICAL FIELD The present invention relates to an aromatic polyester amide copolymer, an aromatic polyester amide copolymer, a prepreg and a prepreg laminate employing the aromatic polyester amide copolymer, and a metal-clad laminate using the prepreg or prepreg laminate and a printed wiring board , prepreg or prepreg laminates having the copolymer, and metal clad laminates and print wiring board having the prepreg or the prepreg laminates}

An aromatic polyester amide copolymer, a prepreg and a prepreg laminate employing the aromatic polyester amide copolymer, and a metal-clad laminate and printed wiring board employing the prepreg or prepreg laminate.

2. Description of the Related Art Recently, with the miniaturization and multifunctionalization of electronic devices, printed circuit boards have been increasingly densified and miniaturized, and copper-clad laminates are widely used as substrates for printed circuit boards of electronic devices because of their excellent stamping processability, drilling processability and low cost.

The prepreg used in such a copper-clad laminate for a printed-circuit board must satisfy the following main characteristics in order to meet the performance of the semiconductor and the conditions for manufacturing the semiconductor packaging.

(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 at about 270 캜

The prepreg is prepared by impregnating a glass woven fabric with a resin derived from epoxy or bismale- thyrazine, followed by drying and semi-curing. Next, a copper foil is laminated on the prepreg and the resin is cured to produce a copper clad laminate. Such a copper-clad laminate is thinned and subjected to a high-temperature process such as a reflow process at 270 ° C. In such a high-temperature process, the thin copper foil-clad laminate has problems such as reduced yield due to thermal deformation. The epoxy or bismaleimidetriazine resin is required to be improved in its low water absorbability due to its high hygroscopicity. Particularly, since the dielectric property in a high frequency region of 1 GHz or more is poor and a high frequency and high- Which is difficult to apply to a printed wiring board. Therefore, a low dielectric constant prepreg which does not cause such a problem is required.

In recent years, aromatic polyesters have been used for forming prepregs as an alternative to epoxy or bismaleimide resins. Such a prepreg is prepared 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, a solution composition is prepared by dissolving an aromatic polyester in a solvent containing a halogen element such as chlorine, impregnating the solution composition with an aromatic polyester woven fabric, and then drying to produce an aromatic polyester prepreg. However, this method is difficult to completely remove the halogen element-containing solvent, and the halogen element can corrode the copper foil, so that improvement by use of a non-halogen solvent is required.

An embodiment of the present invention provides an aromatic polyester amide copolymer having low thermal expansion coefficient, low dielectric constant and low dielectric loss.

Another embodiment of the present invention provides a prepreg and a prepreg laminate employing the aromatic polyester amide copolymer.

Another embodiment of the present invention provides a metal-clad laminate and a printed wiring board employing the prepreg or prepreg laminate.

According to an aspect of the present invention,

(A) comprising 20 to 25 mol% of a repeating unit (A) derived from an aromatic diol with respect to all repeating units, wherein the repeating unit (A) derived from the aromatic diol is a repeating unit (RCN) derived from resorcinol, (HQ) derived from at least one compound of phenol and hydroquinone.

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)] <

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 polyester amide copolymer, respectively.

The aromatic polyester amide copolymer may further contain 2 to 25 mol% of a repeating unit (B) derived from a aromatic hydroxycarboxylic acid with respect to all repeating units.

Wherein the aromatic polyester amide copolymer contains at least one repeating unit (C ') derived from an aromatic amine (C) derived from an aromatic amine having a phenolic hydroxyl group and a repeating unit (C') derived from an aromatic diamine, Mol%. &Lt; / RTI &gt;

The aromatic polyester amide copolymer may further contain 35 to 48 mol% of a repeating unit (D) derived from an aromatic dicarboxylic acid with respect to all the repeating units.

According to another aspect of the present invention,

And a substrate impregnated with the aromatic polyester amide copolymer.

According to another aspect of the present invention,

And a prepreg laminate including at least one prepreg.

According to another aspect of the present invention,

And a metal thin film is formed on at least one surface of the prepreg laminate.

According to another aspect of the present invention,

A printed wiring board obtained by etching a metal thin film of the metal foil laminate.

According to one embodiment of the present invention, an aromatic polyester amide copolymer having low thermal expansion coefficient, low dielectric constant and low dielectric loss can be provided.

According to another embodiment of the present invention, by employing the aromatic polyester amide copolymer, a prepreg and a prepreg laminate having low thermal expansion coefficient, low dielectric constant and low dielectric loss can be provided.

According to still another embodiment of the present invention, a metal-clad laminate and a printed wiring board employing the prepreg or prepreg laminate may be provided.

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

The aromatic polyester amide copolymer according to this embodiment contains 20 to 25 mol% of the repeating unit (A) derived from an aromatic diol relative to the total repeating units, and the repeating unit (A) derived from the aromatic diol is a repeating unit (RCN) derived from Nol, and a repeating unit (HQ) derived from at least one compound of biphenol and hydroquinone. When the content of the recurring unit (A) is less than 20 mol%, the solubility in a solvent is lowered, which is undesirable. When the content is more than 25 mol%, the melting temperature is excessively increased.

The molar number n (HQ) of the repeating unit (HQ) and the molar number (n (RCN)) of the repeating unit RCN contained in the aromatic polyester amide copolymer satisfy the following condition:

0 < n (RCN) / [n (RCN) + n (HQ)] <

The aromatic polyester amide copolymer may further contain 2 to 25 mol% of the repeating unit (B) derived from the aromatic hydroxycarboxylic acid with respect to the total repeating units.

If the content of the repeating unit (B) is less than 2 mol%, the mechanical strength of the aromatic polyester amide copolymer is lowered, and if it is more than 25 mol%, the thermal property of the aromatic polyester amide copolymer is deteriorated I do not.

The repeating unit (B) may contain a repeating unit derived from a compound selected from the group consisting of parahydroxybenzoic acid and 2-hydroxy-6-naphthoic acid.

The aromatic polyester amide copolymer may further contain at least one repeating unit (C ') derived from an aromatic amine (C) derived from an aromatic amine having a phenolic hydroxyl group and an aromatic diamine derived from an aromatic diamine To 25 mol%.

If the total content of the repeating unit (C) and the repeating unit (C ') is less than 20 mol%, the solubility in a solvent is lowered, and if it exceeds 25 mol%, the melting temperature is excessively increased not.

Wherein the repeating unit (C) comprises a repeating unit derived from at least one compound selected from the group consisting of 3-aminophenol, 4-aminophenol, and 2-amino- ) May contain a repeating unit derived from at least one compound selected from the group consisting of 1,4-phenylenediamine, 1,3-phenylenediamine, and 2,6-naphthalenediamine.

The aromatic polyester amide copolymer may further contain 35 to 48 mol% of a repeating unit (D) derived from an aromatic dicarboxylic acid with respect to all the repeating units.

If the content of the repeating unit (D) is less than 35 mol%, the solubility is deteriorated. If the content is more than 48 mol%, the heat resistance, low heat shrinkage and low dielectric properties are deteriorated.

The repeating unit (D) may contain a repeating unit derived from at least one compound selected from the group consisting of isophthalic acid, naphthalene dicarboxylic acid, and terephthalic acid.

Specifically, each of the repeating units contained in the aromatic polyester amide copolymer may be represented by any one of the following formulas:

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

 &Lt; Formula 1 >

Figure 112008091128115-pat00001

(2)

Figure 112008091128115-pat00002

(3)

Figure 112008091128115-pat00003

&Lt; Formula 4 >

Figure 112008091128115-pat00004

(2) a repeating unit derived from an aromatic hydroxycarboxylic acid (B):

&Lt; Formula 5 >

Figure 112008091128115-pat00005

(6)

Figure 112008091128115-pat00006

&Lt; Formula 7 >

Figure 112008091128115-pat00007

(8)

Figure 112008091128115-pat00008

&Lt; Formula 9 >

Figure 112008091128115-pat00009

 (3) a repeating unit derived from an aromatic amine having a phenolic hydroxyl group (C):

&Lt; Formula 10 >

Figure 112008091128115-pat00010

&Lt; Formula 11 >

Figure 112008091128115-pat00011

&Lt; Formula 12 >

Figure 112008091128115-pat00012

(4) a repeating unit (C ') derived from an aromatic diamine:

&Lt; Formula 13 >

Figure 112008091128115-pat00013

&Lt; Formula 14 >

Figure 112008091128115-pat00014

&Lt; Formula 15 >

Figure 112008091128115-pat00015

(5) a repeating unit derived from an aromatic dicarboxylic acid (D):

&Lt; Formula 16 >

Figure 112008091128115-pat00016

&Lt; Formula 17 >

Figure 112008091128115-pat00017

&Lt; Formula 18 >

Figure 112008091128115-pat00018

(19)

Figure 112008091128115-pat00019

(20)

Figure 112008091128115-pat00020

(21)

Figure 112008091128115-pat00021

(22)

Figure 112008091128115-pat00022

&Lt; Formula 23 >

Figure 112008091128115-pat00023

In the formula,

R 1 and R 2 are the same or different from each other and each represents 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 An 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.

These aromatic polyester amide copolymers include (1) an aromatic diol comprising resorcinol and hydroquinone and / or biphenol, or an ester forming derivative thereof; (2) an aromatic hydroxycarboxylic acid or an ester-forming derivative thereof; (3) at least one member selected from the group consisting of an aromatic amine having a phenolic hydroxyl group, an amide forming derivative thereof, and an aromatic diamine or an amide forming derivative thereof; And (4) an aromatic dicarboxylic acid or an ester-forming derivative thereof.

The ester-forming derivatives of the aromatic diols mean that their hydroxyl groups react with carboxylic acids to form an ester group.

The ester-forming derivative of the aromatic hydroxycarboxylic acid or the aromatic dicarboxylic acid may be a derivative having high reactivity such as an acid chloride or an acid anhydride or forming an ester with an alcohol or ethylene glycol it means.

In addition, amide-forming derivatives of the above aromatic amines or aromatic diamines mean that their amine groups form amides with carboxylic acids.

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

The aromatic polyester amide copolymer as described above can be produced by a general aromatic polyester producing method, for example, an aromatic diol corresponding to the repeating unit (RCN) and the repeating unit (HQ) The aromatic hydroxycarboxylic acid corresponding to the unit (B), the phenolic hydroxyl group or the amide group of the aromatic amine and / or the aromatic diamine corresponding to the repeating unit (C) and / or the repeating unit (C ' To obtain an acylate, and melt-polymerizing the resulting acylate with an aromatic dicarboxylic acid by transesterification.

The amount of the fatty acid anhydride to be added in the acylation reaction is preferably 1.0 to 1.2 times the equivalent amount of the phenolic hydroxyl group or amide group, and more preferably 1.04 to 1.07 times the equivalent amount. When the amount of the fatty acid anhydride added is large, the aromatic polyester amide copolymer tends to become remarkable in color, while when it is small, the raw material monomer or the like tends to sublimate and the amount of phenol gas to be generated tends to increase. The acylation reaction is preferably carried out at 130 to 170 ° C for 30 minutes to 8 hours, more preferably at 140 to 160 ° C for 2 to 4 hours.

The fatty acid anhydrides used in the acylation reaction include, but are not limited to, acetic anhydride, propionic anhydride, isobutyric anhydride, acetic anhydride, anhydrous pivalic acid, and butyric anhydride. These two or more kinds may be mixed and used. It is desirable to use acetic anhydride in terms of economy and handling.

The transesterification and amide exchange reaction is preferably carried out at a temperature raising rate of from 0.1 to 2 캜 / min at 130 to 400 캜, and more preferably at a temperature raising rate of from 0.3 to 1 캜 / min at 140 to 350 캜 .

When fatty acid esters obtained by acylation and carboxylic acid are subjected to transesterification and amide exchange reaction, it is preferable to evaporate the fatty acids and unreacted anhydrides which are by-produced in order to shift the equilibrium, or distill off from the reaction system.

The acylation reaction, ester exchange reaction and amide exchange reaction can be carried out using a catalyst. This catalyst has been conventionally known as a catalyst for polyester, and it is a catalyst which can be used as a catalyst for a polyester such as magnesium acetate, stannous acetate, tetrabutyl titanate, acaric acid, sodium acetate, potassium acetate, antimony trioxide, N, N-dimethylaminopyridine, &Lt; / RTI &gt; This catalyst usually performs acylation and transesterification without introducing the catalyst at the same time as the monomer and removing the catalyst when the monomer is added.

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

The polymerization reactor in the melt polymerization is not particularly limited. Generally, it is possible to use a reactor using stirring equipment used for high viscosity reaction. At this time, the reactor of the acylation process and the reactor of the melt polymerization process may be the same reactor or different ones.

It is preferable that the solid-state polymerization is carried out by a solid-phase polymerization method after pulverizing the prepolymer discharged from the melt polymerization step and converting it into a flake or powder. A specific solid state polymerization method can be carried out by heat-treating in a solid state at 200 to 350 ° C for 1 to 30 hours in an inert atmosphere such as nitrogen. Solid phase polymerization may be carried out while stirring or in a stationary state. It is also possible to provide a molten polymerizer and a solid-phase polymerizer in the same reaction tank by providing an appropriate stirring mechanism.

The polyester amide copolymer prepared as described above has a thermal expansion coefficient of 3 ppm / K or less.

The obtained aromatic polyester amide copolymer can be pelletized by a known method and provided for molding. Further, the obtained aromatic polyester amide copolymer can be made into a fiber by a known method, and can be used for producing a woven fabric or a nonwoven fabric employing the same.

The prepreg according to this embodiment includes a substrate impregnated with the aromatic polyester amide copolymer.

The prepreg may be prepared by impregnating organic or inorganic woven fabrics and / or non-woven fabrics with a composition solution obtained by dissolving the aromatic polyester amide polymer in a solvent, or by impregnating the wool and / Nonwoven fabric substrate, and then removing the solvent. Examples of the molding method usable herein include a solution impregnation method or a varnish impregnation method.

The solvent for dissolving the aromatic polyester amide copolymer may be used in an amount of 100 to 100,000 parts by weight based on 100 parts by weight of the aromatic polyester amide polymer. If the content of the solvent is less than 100 parts by weight, , And when it exceeds 100,000 parts by weight, the amount of the aromatic polyester amide copolymer tends to be small and the productivity tends to be lowered, which is not preferable.

As the solvent for dissolving the aromatic polyester amide copolymer, a non-halogen solvent is preferably used. However, the present invention is not limited thereto, and 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. Particularly, since the aromatic polyester amide copolymer is well dissolved in a non-halogen solvent and does not require the use of a solvent containing a halogen element, the metal foil of the metal foil laminate or the printed wiring board containing the aromatic polyester amide copolymer can be used in a case where a solvent containing a halogen element is used As a result, corrosion due to halogen elements can be prevented in advance.

As the substrate, woven and / or nonwoven fabrics such as aromatic polyester, glass, carbon, glass paper, or a mixture thereof may be used.

When the impregnation method is used in the prepreg manufacturing step, the time for impregnating the substrate with a solution of the composition in which the aromatic polyester amide copolymer is dissolved in a solvent is preferably 0.001 min to 1 hr. If the impregnation time is less than 0.001 minutes, the aromatic polyester amide copolymer can not be uniformly impregnated, and if it exceeds 1 hour, the productivity may be deteriorated.

The temperature for impregnating the substrate with the solution of the composition in which the aromatic polyester amide copolymer is dissolved in a solvent may be in the range of 20 to 190 캜, preferably at room temperature.

The amount of the aromatic polyester amide copolymer to be impregnated per unit area of the base material is preferably in the range of 0.1 to 1,000 g / m 2 . When the impregnation amount is less than 0.1 g / m 2 , the productivity is lowered, and when it is more than 1,000 g / m 2 , the printed wiring board is not suitable for downsizing.

The composition solution in which the aromatic polyester amide copolymer is dissolved in a solvent may contain an inorganic filler such as silica, aluminum hydroxide, calcium carbonate, a cured epoxy, a crosslinked acryl, or the like in order to control the dielectric constant and the coefficient of thermal expansion An organic filler may be added. In particular, an inorganic filler having a high dielectric constant may be added. Examples of such an inorganic filler include titanate salts such as barium titanate and strontium titanate, and titanium or barium titanate substituted with another metal. The content of the inorganic filler or organic filler is preferably 0.0001 to 100 parts by weight based on 100 parts by weight of the aromatic polyester amide copolymer. If the addition amount of the inorganic filler or the organic filler is less than 0.0001 part by weight, the dielectric constant of the prepreg may not be sufficiently increased or the thermal expansion coefficient may be difficult to be lowered. If the amount is more than 100 parts by weight, the effect of the aromatic polyester amide copolymer as a binder .

Since the prepreg according to this embodiment uses an aromatic polyester amide copolymer having low hygroscopicity and low dielectric properties and an organic or inorganic woven fabric and / or nonwoven fabric having excellent mechanical strength, it is excellent in dimensional stability, less thermal deformation, It is advantageous for processing and lamination processing.

In the impregnation method for producing the prepreg, the composition solution obtained by dissolving the aromatic polyester amide copolymer in a solvent is impregnated into the substrate, or after the composition solution is applied to the substrate, the solvent is removed The method is not particularly limited, but preferably by solvent evaporation. For example, evaporation by a method such as heating, decompression or ventilation. Among them, solvent heat-evaporation is preferable from the aspect of applicability to conventional prepreg manufacturing process, production efficiency, and handling, and it is more preferable 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 to the composition solution of the aromatic polyester amide copolymer obtained by the production method of the present invention, It is preferable to perform the heat treatment for 1 minute to 10 hours.

The prepreg according to this embodiment thus obtained preferably has a thickness of about 5 to 200 mu m, preferably about 30 to 150 mu m. In addition, the prepreg has a thermal expansion coefficient of 10 ppm / K or less in one direction, 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 which disappears as heat in the dielectric when an alternating electric field is applied to the dielectric. If the coefficient of thermal expansion exceeds 10 ppm / K, peeling of the prepreg may occur, which is not preferable. In addition, if the dielectric constant exceeds 3.5 or the dielectric loss exceeds 0.01, it is unsuitable as an insulating substrate in a high frequency range.

A predetermined number of the prepregs are laminated, and the prepreg laminate is heated and pressed.

Further, a metal foil such as copper foil, silver foil or aluminum foil may be disposed on one side or both sides of the prepreg or the prepreg laminate, and the same can be heated and pressed to produce a metal foil laminate.

In the metal-clad laminate, the thickness of each of the prepreg or prepreg laminate and the metal thin film is not particularly limited, but is preferably 0.1 to 300 μm. If the thickness of the prepreg or the prepreg laminate is less than 0.1 mu m, cracks can easily occur during the winding process. If the thickness exceeds 300 mu m, the number of layers of the multilayer laminate having a limited thickness is not preferable. If the thickness of the metal thin film is less than 0.1 mu m, it is not preferable because cracks are likely to occur when the metal thin film is laminated, and if it exceeds 300 mu m, it is disadvantageous for multilayer lamination.

The heating and pressurizing process applied in the production of the metal-clad laminate is preferably carried out at a temperature of 150 to 180 ° C and a pressure of about 9 to 20 MPa, but the prepreg characteristic, reactivity of the aromatic polyester amide copolymer composition, The thickness of the metal foil-clad laminate, and the like, so that it is not particularly limited.

In addition, the metal foil laminates according to this embodiment may further include an adhesive layer interposed therebetween in order to increase the bonding strength between the prepreg laminate and the metal foil. As the adhesive layer, a thermoplastic resin composition or a thermosetting resin composition may be used. The thickness of the adhesive layer is preferably 0.1 to 100 mu m. If the thickness is less than 0.1 mu m, the bonding strength is low, which is undesirable. When the thickness exceeds 100 mu m, the thickness becomes excessively thick, which is not preferable.

In addition, a printed wiring board can be manufactured by etching a metal thin film of the metal foil-clad laminate and forming a circuit. If necessary, a through hole or the like may be formed in the printed wiring board. The multilayered printed circuit board of this embodiment can be produced, for example, by arranging a predetermined number of prepregs between constituent materials such as an inner layer substrate and a thin metal film in accordance with the intended thickness of the insulating layer, . The heating and pressurizing conditions at this time can be appropriately determined in the same manner as in the case of producing the metal-clad laminate. Examples of the inner layer substrate include a prepreg laminate, a metal foil laminate or a printed wiring board used as an electrical insulating material, and two or more of these may be used in combination.

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

Example 1

(1.0 mol) of parahydroxybenzoic acid, 245.54 g (2.3 mol) of 4-aminophenol and 185.8 g (1.7 mol) of hydroquinone were charged in a reactor equipped with a stirrer, a torque meter, a nitrogen gas introducing tube, a thermometer and a reflux condenser, , 61.9 g (0.6 mol) of resorcinol, 747.6 g (4.5 mol) of isophthalic acid and 1,123 g (11 mol) of anhydrous acetic acid.

After sufficiently replacing the interior 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 the temperature.

Thereafter, the acetic acid and the unreacted acetic anhydride which had flowed out were removed by distillation, the temperature was raised to 320 DEG C for 180 minutes, the time point at which the torque was increased was regarded as the reaction termination, and the contents were discharged. The solid content thus obtained was cooled to room temperature, pulverized by a pulverizer, and subjected to solid phase polymerization while maintaining the temperature at 260 DEG C for 5 hours under a nitrogen atmosphere to obtain an aromatic polyester amide copolymer powder.

400 g of the obtained aromatic polyester amide copolymer powder was added to 600 g of N-methylpyrrolidinone (NMP), and the mixture was stirred at room temperature for 4 hours to obtain a composition solution of an aromatic polyester amide copolymer.

A glass woven fabric (IPC 1078) was impregnated into this composition solution at room temperature, passed through double rollers to remove the excess composition solution, and the thickness thereof was made constant. Thereafter, the contents were put in a hot hot air dryer, and the solvent was removed at 120 ° C, followed by heat treatment at 300 ° C for 60 minutes to obtain a prepreg in which the aromatic polyester amide copolymer was impregnated with glass wool.

Comparative Example 1

An aromatic polyester amide copolymer was prepared in the same manner as in Example 1 except that 253.23 g (2.3 moles) of resorcinol was used without using any hydroquinone as an aromatic diol. Further, a solution and a prepreg of an aromatic polyester amide copolymer composition were prepared in the same manner as in Example 1 above.

Comparative Example 2

An aromatic polyester amide copolymer was prepared in the same manner as in Example 1 except that 253.23 g (2.3 moles) of hydroquinone was used without using any resorcinol as the aromatic diol. Further, a solution and a prepreg of an aromatic polyester amide copolymer composition were prepared in the same manner as in Example 1 above.

Comparative Example 3

(1.0 mole) of parahydroxybenzoic acid, 109.1 g (1.0 mole) of 4-aminophenol, 289.6 g (2.63 mole) of hydroquinone, 95.8 g (0.87 mole) of resorcinol, 747.6 g An aromatic polyester amide copolymer was prepared in the same manner as in Example 1 except that 1,123 g (11 mol) of acetic anhydride was used. Further, a solution and a prepreg of an aromatic polyester amide copolymer composition were prepared in the same manner as in Example 1 above.

The resin powder was removed from the prepreg prepared in Example 1 and the electrical characteristics were evaluated in the following manner in comparison with Comparative Examples 1 to 3.

First, the prepreg obtained in Example 1 and the prepregs prepared in Comparative Examples 1 to 3 were immersed in a soldering bath at a soldering temperature of 290 ° C for three times for 10 seconds each, and the surface state was observed. It was confirmed that the prepreg produced in Example 1 did not suffer from deformation or blistering but the prepregs prepared in Comparative Examples 1 to 3 were partially removed and deformation of the prepreg itself occurred.

The dielectric constant and dielectric loss of each of the prepreg obtained in Example 1 and Comparative Examples 1 to 3 were measured using an impedance analyzer. As a result, the dielectric constant and dielectric loss of the prepreg obtained in Example 1 were 3.0 (1 GHz) and the dielectric loss was 0.005, which was low in the high frequency range. However, the dielectric constant of the prepreg obtained in Comparative Example 1 was 3.4 (1 GHz), the dielectric loss was 0.007, the dielectric constant of the prepreg obtained in Comparative Example 2 was 3.6 (1 GHz), the dielectric loss was 0.008, The dielectric constant was 3.4 (1 GHz) and the dielectric loss was 0.007, which was higher than that of Example 1.

The respective coefficients of thermal expansion of the prepreg obtained in Example 1 and the prepregs obtained in Comparative Examples 1 to 3 were measured using TMA (TMA, Q400). As a result, Was 9.2ppm / K in the temperature range of 50 ~ 120 ℃. However, the thermal expansion coefficient of the prepreg obtained in Comparative Example 1 was 14.5 ppm / K, the thermal expansion coefficient of the prepreg obtained in Comparative Example 2 was 11.5 ppm / K, and the thermal expansion coefficient of the prepreg obtained in Comparative Example 3 was 12.4 ppm / K Which was higher than that of Example 1 (> 10 ppm / K).

On the other hand, as described above, according to the conventional manufacturing method for producing the prepreg laminate, the metal foil-clad laminate, and the printed wiring board by using the prepreg, the prepreg produced in the above- And a printed wiring board can be produced.

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 (18)

(I) 20 to 25 mol% of a repeating unit (A) derived from an aromatic diol relative to all repeating units, wherein the repeating unit (A) derived from the aromatic diol is a repeating unit derived from resorcinol (RCN) , And a repeating unit (HQ) derived from at least one compound of biphenol and hydroquinone,       (Ii) 20 to 25 mol% of at least one repeating unit (C ') derived from an aromatic amine (C) derived from an aromatic amine having a phenolic hydroxyl group and a repeating unit derived from an aromatic diamine Wherein the molar ratio of the repeating unit (i) to the repeating unit (ii) is 1: 1. The method according to claim 1, 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)] < 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 polyester amide copolymer, respectively. The method according to claim 1, Further comprising 2 to 25 mol% of a repeating unit (B) derived from an aromatic hydroxycarboxylic acid with respect to all repeating units. The method of claim 3, Wherein the repeating unit (B) is derived from one compound selected from the group consisting of parahydroxybenzoic acid and 2-hydroxy-6-naphthoic acid. delete The method according to claim 1, The repeating unit (C) is derived from at least one compound selected from the group consisting of 3-aminophenol, 4-aminophenol, and 2-amino-6-naphthol, Wherein the aromatic polyester amide copolymer is derived from at least one compound selected from the group consisting of phenylenediamine, 1,3-phenylenediamine, and 2,6-naphthalenediamine. The method according to claim 1, Further comprising 35 to 48 mol% of a repeating unit (D) derived from an aromatic dicarboxylic acid with respect to all repeating units. 8. The method of claim 7, Wherein the repeating unit (D) is derived from at least one compound selected from the group consisting of isophthalic acid, naphthalene dicarboxylic acid, and terephthalic acid. The method according to claim 1, A number-average molecular weight of 1,000 to 20,000, and a melting temperature of 250 to 400 占 폚. A prepreg comprising a substrate impregnated with an aromatic polyester amide copolymer according to any one of claims 1 to 4 and 6 to 9. 11. The method of claim 10, Wherein the aromatic polyester amide copolymer has an impregnated amount per unit area in the range of 0.1 to 1,000 g / m &lt; 2 &gt; in a base material having a thickness of 5 to 200 mu m. 11. The method of claim 10, Characterized in that the substrate comprises at least one selected from the group consisting of aromatic polyester, glass, carbon, and glass paper. 11. The method of claim 10, The base material is impregnated with a composition solution in which the aromatic polyester amide copolymer is dissolved in a solvent, Wherein the composition solution further comprises an organic or inorganic filler in an amount of 0.0001 to 100 parts by weight based on 100 parts by weight of the aromatic polyester amide copolymer. 11. The method of claim 10, Wherein a thermal expansion coefficient in one direction is 10 ppm / K or less. 11. The method of claim 10, Wherein the dielectric constant is 3.5 or less and the dielectric loss is 0.01 or less. A prepreg laminate comprising at least one prepreg according to claim 10. A metal-clad laminate having a metal thin film formed on at least one surface of a prepreg laminate according to claim 16. A printed wiring board obtained by etching a metal thin film of a metal foil laminate according to claim 17.
KR1020080138702A 2008-12-31 2008-12-31 Aromatic liquid-crystalline polyester amide copolymer prepreg or prepreg laminates having the copolymer and metal clad laminates and print wiring board having the prepreg or the prepreg laminates KR101595121B1 (en)

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KR1020080138702A KR101595121B1 (en) 2008-12-31 2008-12-31 Aromatic liquid-crystalline polyester amide copolymer prepreg or prepreg laminates having the copolymer and metal clad laminates and print wiring board having the prepreg or the prepreg laminates
CN2009801532722A CN102272200B (en) 2008-12-31 2009-12-24 Aromatic polyester amide copolymer, high molecular film, prepreg, prepreg laminate, metal foil laminate, and printed circuit board
PCT/KR2009/007763 WO2010077014A2 (en) 2008-12-31 2009-12-24 Aromatic polyester amide copolymer, high molecular film, prepreg, prepreg laminate, metal foil laminate, and printed circuit board
JP2011543429A JP2012514066A (en) 2008-12-31 2009-12-24 Aromatic polyesteramide copolymer, polymer film, prepreg, prepreg laminate, metal foil laminate and printed wiring board
TW98145785A TW201035168A (en) 2008-12-31 2009-12-30 Aromatic polyester amide copolymer, polymer film, prepreg, prepreg laminate, metal clad laminate and printed circuit board

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