KR101708934B1 - Composition for preparing thermosetting resin, cured product of the composition, prepreg and prepreg laminate having the cured product, and metal clad laminate and printed circuit board having the prepreg or the prepreg laminate - Google Patents

Abstract

A composition for the production of a thermosetting resin and a cured product thereof, a prepreg and a prepreg laminate comprising the cured product, and a metal-clad laminate and printed wiring board employing the prepreg or prepreg laminate. The disclosed composition for preparing a thermosetting resin includes an aromatic polyester amide copolymer having an amino end group and pyromellitic dianhydride.

Description

TECHNICAL FIELD The present invention relates to a composition for preparing a thermosetting resin and a cured product thereof, a prepreg and a prepreg laminate including the cured product, and a metal-clad laminate and printed circuit board employing the prepreg or prepreg laminate the composition, prepreg and prepreg laminate having the cured product, and metal clad laminate and printed circuit board having the prepreg or the prepreg laminate}

A composition for the production of a thermosetting resin and a cured product thereof, a prepreg and a prepreg laminate comprising the cured product, and a metal-clad laminate and printed wiring board employing the prepreg or prepreg laminate. More specifically, the present invention relates to a composition for preparing a thermosetting resin comprising an aromatic polyester amide copolymer having an amino end group and pyromellitic dianhydride and a cured product thereof, a prepreg and a prepreg laminate including the cured product, A metal-clad laminate and a printed wiring board using a prepreg or a prepreg laminate are disclosed.

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 applied to the copper-clad laminate for a printed circuit board should 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 cloth with an epoxy resin or bismaleimide triazine resin, followed by drying and semi-curing. Next, a copper foil is laminated on the prepreg or prepreg laminate, and the resin is completely 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 resin or the bismaleimide triazine resin is required to be improved in hygroscopicity due to its high hygroscopicity. Particularly, the epoxy resin or the bismaleimide triazine resin is required to have low hygroscopicity, There is a problem that it is difficult to apply it to a printed wiring board for packaging. Therefore, a low dielectric constant prepreg which does not cause such a problem is required.

In recent years, aromatic polyesters have been used for preparing prepregs as an alternative to epoxy resins 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 resin in a solvent containing a halogen element such as chlorine, impregnating the solution composition with an aromatic polyester woven fabric, and then drying to prepare 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.

One embodiment of the present invention provides a composition for producing a thermosetting resin comprising an aromatic polyester amide copolymer having an amino end group and pyromellitic dianhydride.

Another embodiment of the present invention provides a thermosetting resin film comprising a cured product of the composition for preparing a thermosetting resin.

Another embodiment of the present invention provides a prepreg and a prepreg laminate including a cured product of the composition for preparing a thermosetting resin.

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,

10 to 30 mol% of a repeating unit (A) derived from an aromatic hydroxycarboxylic acid having an amino end group; 15 to 25 mol% of at least one repeating unit derived from an aromatic amine (B) derived from an aromatic amine having a phenolic hydroxyl group and a repeating unit (B ') derived from an aromatic diamine; 15 to 30 mol% of a repeating unit (C) derived from an aromatic diol; And 30 to 60 mol% of a repeating unit derived from an aromatic dicarboxylic acid (D); And

And 10 to 900 parts by weight of pyromellitic dianhydride.

Wherein the repeating unit (A) is derived from at least one compound selected from the group consisting of parahydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, the repeating unit (B) And 2-amino-6-naphthol. The repeating unit (B ') is derived from at least one compound selected from the group consisting of 1,4-phenylenediamine, 1,3-phenylenediamine and 2,6 -Naphthalenediamine, the repeating unit (C) is derived from at least one compound selected from the group consisting of resorcinol, biphenol and hydroquinone, and the repeating unit (C) is derived from at least one compound selected from the group consisting of The repeating unit (D) may be derived from at least one compound selected from the group consisting of isophthalic acid and naphthalene dicarboxylic acid.

The content of the repeating unit (B), the repeating unit (B '), the repeating unit (C) and the repeating unit (D) may satisfy the following conditions:

(B) + n (B) + n (C)] / n (D) < 1.5.

Here, n (B), n (B '), n (C) and n (D) represent the repeating units (B), repeating units (B' C) and the number of repeating units (D).

According to another aspect of the present invention,

And a thermosetting resin film containing a cured product of the thermosetting resin composition.

According to another aspect of the present invention,

materials; And

There is provided a prepreg comprising a cured product of the composition for the production of a thermosetting resin contained in the substrate.

The total content of the composition for preparing a thermosetting resin and the cured product thereof per unit area of the substrate may range from 0.1 to 1,000 g / m ² .

The base material may include at least one selected from the group consisting of aromatic polyester fibers, aromatic polyester amide fibers, glass fibers, carbon fibers and paper.

The prepreg may further contain 0.0001 to 100 parts by weight of at least one filler selected from the group consisting of an organic filler and an inorganic filler based on 100 parts by weight of the total amount of the thermosetting resin composition and the cured product thereof.

The thermal expansion coefficient of the prepreg in one direction measured after fully curing the cured product contained in the prepreg can be 20 ppm / K or less.

The dielectric constant of the prepreg may be 4.0 or less and the dielectric loss may be 0.01 or less, as measured after fully curing the cured product contained in the prepreg.

The flexural modulus of the prepreg measured after fully curing the cured product contained in the prepreg may be 10 to 30 GPa.

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,

The prepreg; And

And at least one metal thin film disposed on at least one surface of the prepreg.

The prepreg may be at least two prepreg laminates.

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 another aspect of the present invention,

And a printed circuit board formed by printing a metal circuit pattern on at least one surface of the thermosetting resin film.

According to one embodiment of the present invention, a composition for producing a thermosetting resin that can be dissolved in a non-halogen solvent can be provided by including an aromatic polyester amide copolymer having an amino end group and pyromellitic dianhydride.

According to another embodiment of the present invention, there is provided a thermosetting resin film, a prepreg and a prepreg laminate having a low thermal expansion coefficient, a low dielectric constant, a low dielectric loss, a low hygroscopicity and a high flexural modulus by including a cured product of the composition for preparing a thermosetting resin .

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 composition for preparing a thermosetting resin, a cured product thereof, and a prepreg including the cured product according to an embodiment of the present invention will be described in detail.

The composition for preparing a thermosetting resin according to one embodiment of the present invention comprises 100 parts by weight of an aromatic polyester amide copolymer having an amino end group and 10 to 900 parts by weight of pyromellitic dianhydride.

When the content ratio of the aromatic polyester amide copolymer and the pyromellitic dianhydride is within the above range, the cured product (that is, the crosslinked resin) of the composition for preparing a thermosetting resin has a low thermal expansion property and a low dielectric property, High hygroscopicity due to high crosslinking density, and high transparency and high flexural modulus.

Wherein the aromatic polyester amide copolymer comprises 10 to 30 mol% of a repeating unit (A) derived from an aromatic hydroxycarboxylic acid; 15 to 25 mol% of at least one repeating unit derived from an aromatic amine (B) derived from an aromatic amine having a phenolic hydroxyl group and a repeating unit (B ') derived from an aromatic diamine; 15 to 30 mol% of a repeating unit (C) derived from an aromatic diol; And 30 to 60 mol% of a repeating unit (D) derived from an aromatic dicarboxylic acid.

When the content of the repeating unit (A) is within the above range, the aromatic polyester amide copolymer has a high mechanical strength and excellent thermal characteristics, and the total content of the repeating unit (B) and the repeating unit (B ' , The aromatic polyester amide copolymer has a high solubility in a solvent and an appropriate level of melting temperature, and when the content of the recurring unit (C) is within the above range, the aromatic polyester amide copolymer has a high (D) is within the above range, the aromatic polyester amide copolymer exhibits a high solubility in solvents, a low thermal expansion property and a low dielectric property in terms of solubility, an appropriate level of melting temperature and high transparency. .

The repeating unit (A) may be derived from at least one compound selected from parahydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, and the repeating unit (B) Aminophenol, and 2-amino-6-naphthol. The repeating unit (B ') may be derived from at least one compound selected from the group consisting of 1,4-phenylenediamine, 1,3-phenyl And the repeating unit (C) may be one derived from at least one compound selected from the group consisting of lanthanine, biphenol, and hydroquinone , And the repeating unit (D) may be derived from at least one compound selected from the group consisting of isophthalic acid and naphthalene dicarboxylic acid.

The content of the repeating unit (B), the repeating unit (B '), the repeating unit (C) and the repeating unit (D) may satisfy the following conditions:

(B) + n (B) + n (C)] / n (D) < 1.5.

Here, n (B), n (B '), n (C) and n (D) represent the repeating units (B), repeating units (B' C) and the number of repeating units (D).

When the content ratio {[n (B) + n (B ') + n (C)] / n (D)} is within the above range, the aromatic polyester amide copolymer contains a plurality of amino end groups and / And a curing reaction with the epoxy resin to form a thermosetting resin having a high crosslinking density.

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

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

&Lt; Formula 1 >

(2)

(3)

&Lt; Formula 4 >

&Lt; Formula 5 >

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

(6)

&Lt; Formula 7 >

(8)

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

&Lt; Formula 9 >

&Lt; Formula 10 >

&Lt; Formula 11 >

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

&Lt; Formula 12 >

&Lt; Formula 13 >

&Lt; Formula 14 >

&Lt; Formula 15 >

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

&Lt; Formula 16 >

&Lt; Formula 17 >

&Lt; Formula 18 >

(19)

(20)

&Lt; Formula 21 >

(22)

&Lt; Formula 23 >

Wherein,

R ₁ and R ₂ 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 "substitution" means that hydrogen is substituted with a halogen group, a hydroxyl group, an alkyl group, an alkoxy group, an amino group, or two or more of them.

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

The ester-forming derivative of the aromatic hydroxycarboxylic acid or aromatic dicarboxylic acid may be a highly reactive derivative such as an acid chloride or an acid anhydride, or may form an ester bond with an alcohol, ethylene glycol or the like.

Further, the amide-forming derivative of the aromatic amine or aromatic diamine may be such that its amino group forms an amide bond with the carboxylic acid.

In addition, the ester-forming derivative of the aromatic diol may be such that its hydroxy group forms an ester bond with the carboxylic acid.

The aromatic polyester amide copolymer prepared as described above may be dissolved in a solvent and may be, for example, a thermotropic liquid crystal polyester amide copolymer capable of forming a melt exhibiting optical anisotropy at 400 ° C or lower have. For example, the aromatic polyester amide copolymer may have a melting temperature of 250 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 the following method. That is, the aromatic polyester amide copolymer may contain an aromatic amine corresponding to the aromatic hydroxycarboxylic acid corresponding to the repeating unit (A), the repeating unit (B) and / or the repeating unit (B ') and / Or an aromatic diamine and an aromatic diol corresponding to the recurring unit (C) are acylated with a fatty acid anhydride to obtain an acylate, and the resulting acylate and an aromatic dicarboxylic acid are subjected to ester exchange to effect a melt polymerization &Lt; / RTI &gt; At this time, by appropriately controlling the amount of the fatty acid anhydride to be used, an aromatic polyester amide copolymer having an amino end group and having a predetermined degree of polymerization can be produced. For example, when the amount of the fatty acid anhydride is increased, the number of amino end groups decreases and the number of carboxyl end groups and the degree of polymerization increase in the resulting aromatic polyester amide copolymer, and when the amount is reduced, the number of amino end groups increases And the number and degree of polymerization of the carboxy end groups are decreased.

The addition amount of the fatty acid anhydride in the acylation reaction may be 0.9 to 1.2 times, for example, 0.95 to 1.05 times the equivalent of the total amount of the hydroxyl group and the amino group. If the addition amount of the fatty acid anhydride is within the above range, the resultant aromatic polyester amide copolymer has an amino end group, the coloring of the resulting aromatic polyester amide copolymer is reduced, and the resulting aromatic polyester amide copolymer The sublimation of monomers and the like does not occur, and the amount of phenol gas generated is also reduced. Such an acylation reaction may be carried out at 130-170 ° C for 30 minutes to 8 hours, for example at 140-160 ° C for 2-4 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. Two or more of these may be used in combination.

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.

When fatty acid esters obtained by acylation and an aromatic dicarboxylic acid thus obtained are subjected to transesterification and amide exchange reaction, in order to increase the reaction rate by transferring the equilibrium, the by-produced fatty acids and unreacted anhydrides are removed by evaporation or distillation, It can be discharged outside.

In addition, the acylation reaction, transesterification reaction and amide exchange reaction can be carried out in the presence of a catalyst. The catalyst is conventionally known as a catalyst for producing a polyester resin. Examples of the catalyst include a metal salt such as magnesium acetate, stannous acetate, tetrabutyl titanate, acetic acid, sodium acetate, potassium acetate, antimony trioxide, N, Imidazole and the like. The catalyst is usually added at the same time as the monomers when the monomer is added, and the acylation reaction and transesterification reaction occur in the presence of the catalyst.

The polycondensation by the transesterification reaction and the amide exchange reaction can be carried out by melt polymerization, and the resultant aromatic polyester amide copolymer is crosslinked (i.e., cured) with the epoxy resin in the future, so that the polymerization degree is high and the mechanical strength is excellent. So that solid phase polymerization is unnecessary.

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 aromatic polyester amide copolymer according to an embodiment of the present invention having the above-described structure has an amino end group and can cause a highly crosslinking reaction with pyromellitic dianhydride.

The aromatic polyester amide copolymer may have a thermal expansion coefficient of 3 ppm / K or less.

The composition for preparing a thermosetting resin according to an embodiment of the present invention may be prepared by mixing the aromatic polyester amide copolymer and pyromellitic dianhydride in a predetermined ratio.

On the other hand, a thermosetting resin film can be produced from the composition for preparing a thermosetting resin by using a general solvent casting method.

Further, such a composition for producing a thermosetting resin can be dissolved in a solvent. Therefore, the prepreg can be prepared by impregnating or applying the composition for preparing a thermosetting resin, followed by drying and thermosetting (mainly semi-curing). In this case, by the above-mentioned thermosetting, the constituent components of the above-mentioned thermosetting resin composition contained in the prepreg are partially crosslinked to form a crosslinked resin. That is, the amino end group of the aromatic polyester amide copolymer, which is one component of the composition for preparing a thermosetting resin, and the pyromellitic dianhydride as the other constituent component partially undergo crosslinking reaction to form a crosslinked resin (that is, a cured product) . The cured product retains the physical properties of the aromatic polyester amide copolymer and has a low thermal expansion coefficient, a low dielectric constant and a low dielectric loss, as well as a low moisture absorption rate and a high flexural modulus.

In the present specification, the term &quot; semi-curing &quot; means that when the curing reaction of the composition for producing a resin proceeds to some extent and the heat is applied, the resulting resin is not melted by heat but becomes soft. Is not dissolved in the solvent but is swollen. The resin obtained by semi-curing the composition is generally referred to as a B-stage resin. The term &quot; completely cured &quot; means a state in which the curing reaction of the composition is completely proceeded and the resulting resin is neither softened by heat nor swelled by the solvent. The resin obtained by completely curing the composition is generally referred to as a C-stage resin.

In addition, the composition for preparing a thermosetting resin may be used for various purposes other than the prepreg.

The prepreg can be prepared by, for example, impregnating an organic or inorganic woven fabric substrate and / or an organic or inorganic non-woven fabric substrate with a solution of the composition in which the composition for the preparation of a thermosetting resin is dissolved in a solvent, Applying the composition solution to the woven and / or non-woven fabric substrate, drying and semi-curing the same. Examples of the molding method that can be used at this time include a solution impregnation method or a varnish impregnation method.

The solvent for dissolving the thermosetting resin composition may be used in an amount of 100 to 100,000 parts by weight based on 100 parts by weight of the thermosetting resin composition. When the content of the solvent is within the above range, However, productivity is good.

As the solvent for dissolving the composition for preparing a thermosetting resin, a non-halogen solvent may be used. However, the present invention is not limited thereto. As the solvent, a polar aprotic compound, halogenated phenol, o-dichlorobenzene, chloroform, methylene chloride, tetrachloroethane, etc. may be used alone or in combination of two or more.

As described above, since the composition for preparing a thermosetting resin is well dissolved in a non-halogen solvent and does not require the use of a solvent containing a halogen element, it is possible to produce a metal-clad laminate or a printed wiring board containing a cured product of the composition, It is possible to prevent the phenomenon that the metal thin film is corroded by the halogen element, which is a problem that occurs when a solvent is used.

As the base material, woven and / or nonwoven fabrics including aromatic polyester fibers, aromatic polyester amide fibers, glass fibers, carbon fibers and paper or a mixture of two or more thereof may be used.

When the impregnation method is used in the prepreg manufacturing step, the time for impregnating the composition solution into the substrate may be, for example, 0.001 minutes to 1 hour. When the impregnation time is within the above range, the composition solution is uniformly impregnated and the productivity is high.

In addition, the temperature at which the composition solution is impregnated into the substrate may be 20 to 190 ° C.

In addition, the amount of the base material to be impregnated into the thermosetting resin composition may be in the range of 0.1 to 1,000 g / m ² . When the amount of impregnation of the composition for thermosetting resin is within the above range, the productivity is high and processing is easy. Accordingly, the prepreg after the curing may include a composition for preparing a thermosetting resin of about 0.1 to 1,000 g / m ² based on the unit area of the substrate and a cured product thereof.

The composition solution may contain an inorganic filler such as silica, aluminum hydroxide or calcium carbonate to control dielectric constant and thermal expansion coefficient; 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. As such an inorganic filler, a titanate such as barium titanate or strontium titanate, or a titanium or barium titanate in which a part of titanium or barium is replaced with another metal may be used. The content of the inorganic filler and / or the organic filler in the composition solution may be 0.0001 to 100 parts by weight based on 100 parts by weight of the thermosetting resin composition. If the content of the inorganic filler and / or organic filler is within the above range, not only the dielectric constant of the prepreg becomes high and the coefficient of thermal expansion becomes low, but also the effect as a binder of the thermosetting resin- have. Accordingly, the prepreg after the curing may contain 0.0001 to 100 parts by weight of an inorganic filler and / or an organic filler based on 100 parts by weight of the total amount of the thermosetting resin composition and the cured product thereof.

The prepreg according to one embodiment of the present invention is a cured product of the composition for preparing a thermosetting resin having a low thermal expansion coefficient, a low dielectric constant, a low hygroscopicity and a high flexural modulus, an organic or inorganic woven fabric having excellent mechanical strength, and / Since it contains an inorganic nonwoven fabric, it is advantageous for via hole drilling and lamination processing because it is excellent in dimensional stability, less thermal deformation, hard and soft. Therefore, the prepreg can be applied to various fields as a flexible substrate material.

In the impregnation method for preparing the prepreg, a method for impregnating the substrate with the composition solution or applying the composition solution to the substrate and then removing the solvent is not particularly limited, can do. For example, evaporation methods such as heating, depressurization or ventilation are possible. Further, the prepreg impregnated with the composition solution may be dried at 20 to 190 ° C for 1 minute to 2 hours to remove the solvent.

Thereafter, the dried prepreg is heat-treated at 120 to 320 ° C for 1 to 8 hours to semi-cure the composition for preparing a thermosetting resin contained in the prepreg.

The prepreg according to one embodiment of the present invention thus obtained may have a thickness of about 5 to 200 탆, for example, about 30 to 150 탆.

Also, when the cured product (i.e., semi-cured resin) contained in the prepreg is completely cured, the thermal expansion coefficient of the prepreg in one direction may be 20 ppm / K or less. If the coefficient of thermal expansion of the prepreg is within the above range, peeling does not occur in the metal-clad laminate using the prepreg.

Also, when the cured product contained in the prepreg is fully cured, the dielectric constant of the prepreg may be 4.0 or less and the dielectric loss may be 0.01 or less. Herein, the term 'dielectric loss' means an energy loss which disappears as heat in the dielectric when an alternating electric field is applied to the dielectric. When the dielectric constant and the dielectric loss are within the respective ranges, the prepreg including the cured product in a high frequency region is suitable for use as an insulating substrate.

When the cured product contained in the prepreg is fully cured, the flexural modulus of the prepreg may be 10 GPa to 30 GPa. If the flexural modulus of the prepreg is within the above range, warpage does not occur.

The thermal expansion rate, dielectric property and flexural modulus of the prepreg can be generally measured by the following method. That is, a metal thin film is laminated on both surfaces of the prepreg (that is, the semi-cured state of the composition for thermosetting resin impregnated in the substrate), and then the metal foil laminate is heated and pressed to produce a thin metal film The prepreg can be analyzed to measure the thermal expansion coefficient, dielectric constant, dielectric loss and flexural modulus of the prepreg. The semi-hardened resin is completely cured when heated and pressurized.

On the other hand, a predetermined number of prepregs are laminated, and the prepreg laminate can be manufactured by heating and pressing the prepregs. At the time of heating and pressing, the semi-cured resin is completely cured and is mostly converted into a crosslinked resin.

Further, a metal foil laminate such as a copper foil, a silver foil or an aluminum foil may be disposed on one side or both sides of the prepreg or the prepreg laminate, and then heated and pressurized. When the semi-cured resin is present at the time of heating and pressurization, it is completely cured and converted into a mostly cross-linked resin.

In the metal-clad laminate, the thickness of the prepreg or prepreg laminate and the metal thin film may be 0.1 to 300 탆, respectively. When the thickness of the prepreg or the prepreg laminate is within the above range, cracks do not occur during processing in the winding method, which is advantageous for multilayer lamination with a limited thickness. If the thickness of the metal thin film is within the above range, cracks do not occur well during the lamination of the metal thin film, which is advantageous for multilayer lamination.

The heating and pressing conditions applied to the metal foil laminates may be, for example, 150 to 250 ° C and 10 to 30 MPa. However, the properties of the prepreg, the reactivity of the composition for producing a thermosetting resin, It is not particularly limited as it can be appropriately determined in consideration of the thickness of the film.

In addition, the metal foil laminates according to one embodiment of the present invention may further include an adhesive layer interposed therebetween in order to increase the bonding strength between the prepreg laminate and the metal foil. In the production of the adhesive layer, a thermoplastic resin or a thermosetting resin may be used. The thickness of the adhesive layer may be 0.1 to 100 mu m. When the thickness of the adhesive layer is within the above range, the thickness is adequate and the adhesive strength is high.

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. A printed circuit board can also be produced by printing a metal circuit pattern on at least one surface of the thermosetting resin film. In addition, if necessary, a through hole or the like may be formed in the printed wiring board.

The multilayered printed circuit board according to one embodiment of the present invention is a multilayered printed circuit board in which a predetermined number of prepregs are arranged between constituent members such as an inner layer substrate and a metal thin film in accordance with the thickness of an intended insulating layer, And then molding it. The heating and pressurizing conditions at this time may be the same as those at the time of manufacturing the metal foil laminates. As the inner layer substrate, a prepreg laminate, a metal foil laminate or a printed wiring board used as an electrical insulating material may be used, 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

(Production of copper clad laminate)

Example  One

Step 1: Preparation of aromatic polyester amide copolymer

(1.3 moles) of parahydroxybenzoic acid, 245.5 g (2.3 moles) of 4-aminophenol, and 198.2 g (1.8 moles) of hydroquinone were placed in a reactor equipped with a stirrer, a torque meter, a nitrogen gas introducing tube, a thermometer and a reflux condenser, , 44.0 g (0.4 mol) of resorcinol, 731.0 g (4.4 mol) of isophthalic acid and 1,123 g (11 mol) of acetic anhydride. 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 resulting solid was cooled to room temperature and pulverized with a pulverizer to obtain an aromatic polyester amide copolymer powder without further solid-phase polymerization.

Step 2: Preparation of composition solution for preparing thermosetting resin

500 g of the aromatic polyester amide copolymer powder prepared in the above step 1 and 50 g of pyromellitic dianhydride were added to 450 g of N-methylpyrrolidinone (NMP) and stirred at 25 DEG C for 4 hours to obtain a thermosetting resin composition solution .

Step 3: Prepreg  Produce

A glass woven fabric (IPC 1078) was impregnated into the composition solution prepared in the above step 2 at room temperature and passed through double rollers to remove the excess composition solution and to make the thickness constant. Then, the contents were placed in a hot hot air dryer and the solvent was removed at 180 ° C to obtain a prepreg.

Step 4: Copper foil Laminate  Produce

Each of the electrolytic copper foils having a thickness of 18 占 퐉 was placed on both sides of the prepreg prepared in Step 3, and then the laminated body was heated and pressed under the conditions of 200 占 폚 and 30 MPa for 3 hours by hot plate press to produce a metal foil- Respectively.

Example  2

A composition for preparing a thermosetting resin was prepared in the same manner as in Example 1 except that 55 g of the same aromatic polyester amide copolymer powder as in Example 1, and 495 g of pyromellitic dianhydride were used. Also, a prepreg and a copper clad laminate were produced in the same manner as in Example 1 above.

Comparative Example  One

Only a 550 g portion of the same aromatic polyester amide copolymer powder as that prepared in the step 1 of Example 1 was used to prepare a thermosetting resin composition solution (no pyromellitic dianhydride was used). Also, a prepreg and a copper clad laminate were produced in the same manner as in Example 1 above.

Comparative Example  2

A composition for preparing a thermosetting resin was prepared in the same manner as in Example 1 except that 524 g of the aromatic polyester amide copolymer powder as prepared in Step 1 of Example 1 and 26 g of pyromellitic dianhydride were used. Also, a prepreg and a copper clad laminate were produced in the same manner as in Example 1 above.

Comparative Example  3

A composition for producing a thermosetting resin was prepared in the same manner as in Example 1, except that 54.5 g of the same aromatic polyester amide copolymer powder as in Example 1, and 495.5 g of pyromellitic dianhydride were used. Respectively. Also, a prepreg and a copper clad laminate were produced in the same manner as in Example 1 above.

Evaluation example

After removing all of the two copper foils from the copper-clad laminate produced in each of Examples 1 and 2 and Comparative Examples 1 to 3, the prepreg portion was analyzed to determine the degree of crosslinking of the resin, the coefficient of thermal expansion of the prepreg, And flexural modulus were measured and are shown in Table 1 below.

Evaluation items Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Crosslinking degree of resin (%) 99.8 99.8 0 99.8 99.8 Thermal expansion coefficient (ppm / K) of prepreg 12 16 12 12 21 Dielectric constant of prepreg 3.8 3.9 3.6 3.7 4.5 Dielectric loss of prepreg 0.007 0.009 0.006 0.006 0.012 The flexural modulus (GPa) of the prepreg 13 19 6 8 20

In Table 1, the crosslinking degree was measured by analyzing an exothermic peak obtained by raising the temperature from room temperature to 300 ° C at a rate of 20 ° C / min using a differential scanning calorimeter (DSC) (DS Instrument, DSC 2910) TMA Q400). The dielectric constant and dielectric loss were measured at room temperature using an impedance analyzer, and flexural modulus was measured according to IPC-TM650.

Referring to Table 1, it can be seen that the copper-clad laminates produced in Examples 1 and 2 and Comparative Examples 2 and 3 contain a crosslinking resin, but the copper-clad laminate produced in Comparative Example 1 contains no crosslinking resin at all have. Thus, the copper-clad laminates produced in Examples 1 and 2 and Comparative Examples 2 and 3 have superior heat resistance, chemical resistance, and mechanical strength as compared with the copper clad laminates produced in Comparative Example 1. [ On the other hand, the copper-clad laminate produced in Examples 1 and 2 had a low thermal expansion coefficient, low dielectric constant, low dielectric loss and high flexural modulus except for the copper foil (i.e., prepreg portion) The copper-clad laminate has a disadvantage in that the flexural modulus of the portion excluding the copper foil is low. In addition, the copper-clad laminate produced in Comparative Example 3 had a poor thermal expansion coefficient and dielectric property in comparison with Examples 1 and 2 and Comparative Examples 1 and 2 except for the copper foil.

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 (16)

10 to 30 mol% of a repeating unit (A) derived from an aromatic hydroxycarboxylic acid having an amino end group; 15 to 25 mol% of at least one repeating unit derived from an aromatic amine (B) derived from an aromatic amine having a phenolic hydroxyl group and a repeating unit (B ') derived from an aromatic diamine; 15 to 30 mol% of a repeating unit (C) derived from an aromatic diol; And 30 to 60 mol% of a repeating unit derived from an aromatic dicarboxylic acid (D); And
And 10 to 900 parts by weight of pyromellitic dianhydride. The method according to claim 1,
Wherein the repeating unit (A) is derived from at least one compound selected from the group consisting of parahydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, the repeating unit (B) Amino-6-naphthol, and the repeating unit (B ') is derived from at least one compound selected from the group consisting of 1,4-phenylenediamine, 1,3-phenylenediamine and 2,6- (C) is derived from at least one compound selected from the group consisting of resorcinol, biphenol and hydroquinone, and the repeating unit (D) is derived from at least one compound selected from the group consisting of ) Is a composition derived from at least one compound selected from the group consisting of isophthalic acid and naphthalenedicarboxylic acid. The method according to claim 1,
The content of the repeating unit (B), the repeating unit (B '), the repeating unit (C) and the repeating unit (D) satisfies the following conditions:
(B) + n (B) + n (C)] / n (D) &lt; 1.5.
Here, n (B), n (B '), n (C) and n (D) represent the repeating units (B), repeating units (B' C) and the number of repeating units (D). A thermosetting resin film comprising a cured product of the composition for preparing a thermosetting resin according to any one of claims 1 to 3. materials; And
A prepreg comprising a cured product of the composition for preparing a thermosetting resin according to any one of claims 1 to 3 contained in the above-mentioned substrate. 6. The method of claim 5,
Wherein the total content of the composition for preparing a thermosetting resin and the cured product thereof per unit area of the substrate is in the range of 0.1 to 1,000 g / m ² . 6. The method of claim 5,
Wherein the substrate comprises at least one selected from the group consisting of aromatic polyester fibers, aromatic polyester amide fibers, glass fibers, carbon fibers and paper. 6. The method of claim 5,
Further comprising 0.0001 to 100 parts by weight of at least one filler selected from the group consisting of an organic filler and an inorganic filler based on 100 parts by weight of the total amount of the thermosetting resin composition and the cured product thereof. 6. The method of claim 5,
The prepreg having a thermal expansion coefficient of 20 ppm / K or less in one direction measured after fully curing the cured product contained in the prepreg. 6. The method of claim 5,
A prepreg having a dielectric constant measured after fully curing the cured product contained in the prepreg is 4.0 or less and a dielectric loss is 0.01 or less. 6. The method of claim 5,
Wherein the prepreg has a flexural modulus of 10 to 30 GPa as measured after fully curing the cured product contained in the prepreg. A prepreg laminate comprising at least one prepreg according to claim 5. A prepreg according to claim 5; And
And at least one metal thin film disposed on at least one surface of the prepreg. 14. The method of claim 13,
Wherein the prepreg is at least two prepreg laminated layers. A printed wiring board obtained by etching a metal thin film of the metal-clad laminate according to claim 13. A printed wiring board formed by printing a metal circuit pattern on at least one surface of a thermosetting resin film according to claim 4.