KR20120003667A - 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

PURPOSE: A composition for manufacturing thermosetting resin is provided to obtain a prepreg and a prepreg laminate, which have low thermal expansion ratio, low permittivity, dielectric loss and low moisture absorbency. CONSTITUTION: A composition for manufacturing thermosetting resin comprises 100.0 parts by weight aromatic polyester amide copolymer and 10-900 parts by weight pyromellitic dianhydride. The aromatic polyester amide copolymer comprises: 10-30 mol% repeating unit, which has at least one terminal group among amino terminal group or hydroxy terminal group, originated from aromatic hydroxy carboxylic acid; 15-25 mol% repeating unit, which has phenolic hydroxy group, originated from aromatic amine or aromatic diamine; 15-25 mol% repeating unit originated from aromatic diol; and 30-60 mol% repeating unit originated from dicarboxylic acid.

Description

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 foil laminate and a printed wiring board employing the prepreg or a 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}

The composition for thermosetting resin manufacture, its hardened | cured material, the prepreg and the prepreg laminated body containing the said hardened | cured material, and the metal foil laminated board and printed wiring board which employ | adopted the said prepreg or the prepreg laminated body are disclosed. In more detail, the composition for thermosetting resin manufacture containing the aromatic polyester amide copolymer which has an amino terminal group, and a pyromellitic dianhydride, its hardened | cured material, the prepreg and prepreg laminated body containing the said hardened | cured material, and the said Disclosed are a metal foil laminate and a printed wiring board employing a prepreg or a prepreg laminate.

BACKGROUND ART With the recent miniaturization and multifunctionalization of electronic devices, the densification and miniaturization of printed wiring boards are progressing. Copper foil laminates are widely used as substrates for printed wiring boards of electronic devices due to their excellent stamping processability and drillability, and low cost.

The prepreg applied to the copper foil laminate for such a printed wiring board must satisfy the following main characteristics to suit the performance of the semiconductor and the manufacturing conditions of the semiconductor packaging process.

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

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

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

The prepreg is prepared by impregnating a glass cloth with an epoxy resin or bismaleimide triazine resin, followed by drying and semi-curing. Next, copper foil is laminated on the prepreg or the prepreg laminate, and the resin is completely cured to produce a copper foil laminate. Such a copper foil laminate is thinned and subjected to a high temperature process such as a reflow process at 270 ° C. There is a problem that the yield is reduced due to thermal deformation of the copper foil laminate in the form of a thin film. In addition, epoxy resin or bismaleimide triazine resin is required to be improved to low hygroscopicity due to its high hygroscopicity. In particular, a semiconductor requiring high frequency and high speed treatment due to poor dielectric properties in the high frequency region of 1 GHz or more. There is a problem that is difficult to apply to a printed wiring board for packaging. Therefore, a low dielectric prepreg that does not cause such a problem is desired.

In addition, recently, there has been an example in which aromatic polyester is used for prepreg production as an alternative to epoxy resin or bismaleimide resin. Such prepregs are prepared by impregnating aromatic polyesters with organic or inorganic woven fabrics. In particular, an aromatic polyester prepreg may be produced using an aromatic polyester resin and an aromatic polyester woven fabric. Specifically, an aromatic polyester resin is dissolved in a solvent containing a halogen element such as chlorine to prepare a solution composition. The solution composition is impregnated with an aromatic polyester woven fabric and then dried to produce an aromatic polyester prepreg. However, this method is difficult to completely remove the solvent containing a halogen element, and since the halogen element can corrode copper foil, the improvement by the use of a non-halogen solvent is calculated | required.

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

Another embodiment of the present invention provides a thermosetting resin film including 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 foil laminate and a printed wiring board employing the prepreg or the prepreg laminate.

One aspect of the invention,

10-30 mol% of repeating units (A) which have an amino terminal group and originate in aromatic hydroxy carboxylic acid; 15-25 mol% of repeating units of at least one of the repeating unit (B) derived from the aromatic amine which has a phenolic hydroxyl group, and the repeating unit (B ') derived from aromatic diamine; 15-30 mol% of repeating units (C) derived from an aromatic diol; And 100 parts by weight of the aromatic polyester amide copolymer comprising 30 to 60 mol% of repeating units (D) derived from aromatic dicarboxylic acid; And

It provides a composition for producing a thermosetting resin comprising 10 to 900 parts by weight of pyromellitic dianhydride.

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

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

1.0 ≦ [n (B) + n (B ′) + n (C)] / n (D) <1.5.

Wherein n (B), n (B '), n (C) and n (D) are the repeating units (B), repeating units (B') and repeating units (B) included in the aromatic polyester amide copolymer, C) and the number of moles of the repeating unit (D).

Another aspect of the invention,

It provides the thermosetting resin film containing the hardened | cured material of the said composition for thermosetting resin manufacture.

Another aspect of the invention,

materials; And

It provides a prepreg comprising a cured product of the composition for producing a thermosetting resin contained in the substrate.

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

The substrate 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 comprise 0.0001 to 100 parts by weight of at least one filler of the organic filler and the inorganic filler based on 100 parts by weight of the total content of the composition for preparing the thermosetting resin and the cured product thereof.

The coefficient of thermal expansion in one direction of the prepreg, measured after the cured product contained in the prepreg is completely cured, may be 20 ppm / K or less.

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

The flexural modulus of the prepreg, measured after completely curing the cured product included in the prepreg, may be 10 to 30 GPa.

Another aspect of the invention,

A prepreg laminate including at least one of the prepregs is provided.

Another aspect of the invention,

The prepreg; And

Provided is a metal foil laminate comprising at least one metal thin film disposed on at least one surface of the prepreg.

The prepreg may be at least two prepreg laminates.

Another aspect of the invention,

The printed wiring board obtained by etching the metal thin film of the said metal foil laminated board is provided.

Another aspect of the invention,

Provided is a printed wiring 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, by including an aromatic polyester amide copolymer having an amino end group and pyromellitic dianhydride, a composition for preparing a thermosetting resin which can be dissolved in a non-halogen solvent can be provided.

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

According to another embodiment of the present invention, a metal foil laminate and a printed wiring board employing the prepreg or the 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 an embodiment of the present invention includes 100 parts by weight of aromatic polyester amide copolymer having amino end groups 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 low thermal expansion characteristics and low dielectric properties, and the degree of crosslinking is It has high hygroscopicity and low hygroscopicity, and also has high transparency and high flexural modulus.

The aromatic polyester amide copolymer is 10 to 30 mol% of repeating units (A) derived from aromatic hydroxy carboxylic acid; 15-25 mol% of repeating units of at least one of the repeating unit (B) derived from the aromatic amine which has a phenolic hydroxyl group, and the repeating unit (B ') derived from aromatic diamine; 15-30 mol% of repeating units (C) derived from an aromatic diol; And 30 to 60 mol% of repeating units (D) derived from an aromatic dicarboxylic acid.

When the content of the repeating unit (A) is within the above range, the mechanical strength of the aromatic polyester amide copolymer is high and the thermal property is excellent, and the total content of the repeating unit (B) and the repeating unit (B ′) is within the above range. If within the aromatic polyester amide copolymer has a high solubility in solvents and a melting temperature of the appropriate level, if the content of the repeating unit (C) is within the above range, the aromatic polyester amide copolymer is high in the solvent It has solubility, proper melting temperature and high transparency, and if the content of the repeating unit (D) is within the above range, the aromatic polyester amide copolymer has high solubility in solvents, low thermal expansion and low dielectric properties. Will have

In addition, the repeating unit (A) may be derived from at least one compound of para hydroxy benzoic acid and 2-hydroxy-6-naphthoic acid, and the repeating unit (B) may be 3-aminophenol, It may be derived from at least one compound selected from the group consisting of 4-aminophenol and 2-amino-6-naphthol, wherein the repeating unit (B ′) is 1,4-phenylene diamine, 1,3-phenyl It may be derived from at least one compound selected from the group consisting of lene diamine and 2,6-naphthalene diamine, the repeating unit (C) is at least one selected from the group consisting of resorcinol, biphenol and hydroquinone It may be derived from a compound of, The repeating unit (D) may be derived from at least one compound of isophthalic acid and naphthalene dicarboxylic acid.

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

1.0 ≦ [n (B) + n (B ′) + n (C)] / n (D) <1.5.

Wherein n (B), n (B '), n (C) and n (D) are the repeating units (B), repeating units (B') and repeating units (B) included in the aromatic polyester amide copolymer, C) and the number of moles of the repeating unit (D).

When the content ratio {[n (B) + n (B ') + n (C)] / n (D)} is within the above range, the aromatic polyester amide copolymer has a plurality of amino end groups and / or hydroxides. It includes a hydroxy end group, and subsequently cures with an epoxy resin to form a thermosetting resin having a high crosslinking density.

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

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

<Formula 1>

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

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

<Formula 6>

<Formula 7>

<Formula 8>

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

<Formula 9>

<Formula 10>

<Formula 11>

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

<Formula 12>

<Formula 13>

<Formula 14>

&Lt; Formula 15 >

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

<Formula 16>

<Formula 17>

&Lt; Formula 18 >

(19)

<Formula 20>

<Formula 21>

<Formula 22>

<Formula 23>

In the above formula,

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

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

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

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

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

The aromatic polyester amide copolymer prepared as described above may be a thermotropic liquid crystalline polyester amide copolymer which may be dissolved in a solvent, for example, to form 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 prepared by the following method. That is, the aromatic polyester amide copolymer is an aromatic hydroxy carboxylic acid corresponding to the repeating unit (A), an aromatic amine corresponding to the repeating unit (B) and / or the repeating unit (B '), and / or Or an acylated compound by acylating the hydroxyl group or amino group of the aromatic diamine and the aromatic diol corresponding to the repeating unit (C) with fatty acid anhydride, followed by melt polymerization by transesterifying the acyl compound and aromatic dicarboxylic acid thus obtained. It can be produced by the method. At this time, by appropriately adjusting the amount of the fatty acid anhydride used, an aromatic polyester amide copolymer having an amino terminal group and having a predetermined degree of polymerization can be produced. For example, increasing the amount of the fatty acid anhydride increases the number of amino end groups in the aromatic polyester amide copolymer produced, increases the number of carboxy end groups and the degree of polymerization, and decreases the amount of amino end groups. And the number and degree of polymerization of the carboxy end groups are reduced.

In the acylation reaction, the amount of fatty acid anhydride added may be 0.9 to 1.2 times the equivalent of, for example, 0.95 to 1.05 times the equivalent of the total equivalent of the hydroxy group and the amino group. When the amount of the fatty acid anhydride added is within the above range, the resulting aromatic polyester amide copolymer has an amino end group, the coloring of the resulting aromatic polyester amide copolymer is reduced, and the raw material in the resulting aromatic polyester amide copolymer Sublimation of the monomer and the like does not occur, and the amount of phenol gas generated is also reduced. The acylation reaction may be performed for 30 minutes to 8 hours at 130 to 170 ° C, for example, for 2 to 4 hours at 140 to 160 ° C.

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

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

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

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

The polycondensation by the transesterification reaction and the amide exchange reaction may be carried out by melt polymerization, and the resulting aromatic polyester amide copolymer is subsequently crosslinked with the epoxy resin (ie, cured) to have a high degree of polymerization and excellent mechanical strength. Solid phase polymerization is unnecessary because it forms a cargo.

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

Aromatic polyester amide copolymer according to an embodiment of the present invention having the above configuration has an amino end group can cause a high crosslinking reaction with pyromellitic dianhydride.

In addition, the aromatic polyester amide copolymer may have a thermal expansion rate 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.

In addition, a thermosetting resin film can be manufactured from the said composition for thermosetting resin manufacture using a general solvent casting method.

In addition, such a composition for preparing a thermosetting resin may be dissolved in a solvent. Therefore, the prepreg can be manufactured by impregnating or apply | coating the said composition for thermosetting resin manufacture to a base material, and drying and thermosetting (mainly semi-hardening). In this case, by the thermosetting, the components of the above-mentioned composition for preparing a thermosetting resin contained in the prepreg are partially crosslinked to form a crosslinked resin. That is, the amino terminal group of the aromatic polyester amide copolymer as one component of the composition for preparing a thermosetting resin and the pyromellitic dianhydride as another component are partially crosslinked to form a crosslinked resin (ie, cured product). . The cured product has the physical properties of the aromatic polyester amide copolymer as it is, has a low thermal expansion coefficient, a low dielectric constant and a low dielectric loss, as well as a low moisture absorption rate and high flexural modulus.

In the present specification, the term 'semi-curing' means that when the curing reaction of the composition for preparing a resin proceeds to some extent and heat is applied, the resultant resin is not melted by heat but becomes soft, and when the resin is in contact with a specific solvent, It does not dissolve in solvent but means swelling state. The resin obtained by semi-curing a composition is generally called B-stage resin. "Full hardening" means a state in which the curing reaction of the composition proceeds completely, and the resulting resin does not become soft by heat or swell by a solvent. The resin obtained by completely hardening a composition is generally called C-stage resin.

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

The prepreg may be, for example, impregnating a composition solution obtained by dissolving the composition for preparing a thermosetting resin in a solvent, in an organic or inorganic fabric, and / or in an organic or inorganic non-fabrics substrate, or It can be prepared by applying the composition solution to the woven and / or nonwoven substrate and then drying and semi-curing it. The molding method that can be used at this time is a solution impregnation method or varnish impregnation method.

The solvent for dissolving the composition for preparing the thermosetting resin may be used in an amount of 100 to 100,000 parts by weight based on 100 parts by weight of the composition for preparing the thermosetting resin, and the composition for preparing the thermosetting resin is sufficiently dissolved when the content ratio of the solvent is within the above range. At the same time, productivity is good.

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

As described above, the composition for producing a thermosetting resin is well dissolved in a non-halogen solvent and does not have to use a solvent containing a halogen element. Thus, in the manufacture of a metal foil laminate or printed wiring board containing a cured product of the composition, the composition contains a halogen element. 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 using a solvent.

As the substrate, woven and / or nonwoven fabrics comprising aromatic polyester fibers, aromatic polyester amide fibers, glass fibers, carbon fibers and paper or mixtures of two or more thereof may be used.

When the impregnation method is used in the prepreg manufacturing process, the time for impregnating the composition solution to 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 for impregnating the composition solution to the substrate may be 20 ~ 190 ℃.

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

The composition solution may include an inorganic filler such as silica, aluminum hydroxide or calcium carbonate in order to adjust the dielectric constant and the coefficient of thermal expansion; And / or organic fillers such as cured epoxy or crosslinked acrylics may be added. For example, an inorganic filler of high dielectric constant may be added. As the inorganic filler, a titanate such as barium titanate or strontium titanate, or a part of titanium or barium of barium titanate may be replaced with another metal. The content of the inorganic filler and / or the organic filler in the composition solution may be 0.0001 to 100 parts by weight based on 100 parts by weight of the composition for preparing the thermosetting resin. When the content of the inorganic filler and / or the organic filler is within the above range, not only the dielectric constant of the prepreg increases and the thermal expansion rate decreases, but also the effect as a binder possessed by the composition for preparing a thermosetting resin and cured product thereof after semi-curing can be sufficiently maintained. have. Therefore, the prepreg after semi-curing may include 0.0001 to 100 parts by weight of the inorganic filler and / or the organic filler based on 100 parts by weight of the total content of the composition for preparing the thermosetting resin and the cured product thereof.

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

In the impregnation method for producing the prepreg, the method of impregnating the composition solution to the substrate or removing the solvent after applying the composition solution to the substrate is not particularly limited, but may be achieved by solvent evaporation. can do. For example, evaporation methods such as heating, reduced pressure or ventilation are possible. In addition, the prepreg impregnated with the composition solution may be dried at 20 ~ 190 ℃ for 1 minute to 2 hours to remove the solvent.

Thereafter, the dried prepreg may be 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.

Prepreg according to an embodiment of the present invention obtained as described above may have a thickness of about 5 ~ 200㎛, for example, about 30 ~ 150㎛.

In addition, when the cured product (ie, the semi-cured resin) contained in the prepreg is completely cured, the thermal expansion coefficient in one direction of the prepreg may be 20 ppm / K or less. When the coefficient of thermal expansion of the prepreg is within the above range, no peeling phenomenon occurs in the metal foil laminated plate employing the prepreg.

In addition, when the cured product included in the prepreg is completely cured, the prepreg may have a dielectric constant of 4.0 or less and a dielectric loss of 0.01 or less. In the present specification, 'dielectric loss' refers to an energy loss lost by heat in the dielectric when an alternating electric field is applied to the dielectric. When the dielectric constant and the dielectric loss are each within the above ranges, the prepreg including the cured product in the high frequency region is suitable for use as an insulating substrate.

In addition, when the cured product contained in the prepreg is completely cured and measured, the flexural modulus of the prepreg may be 10 ~ 30GPa. If the flexural modulus of the prepreg is within the above range, warpage does not occur.

The coefficient of thermal expansion, dielectric properties, and flexural modulus of the prepreg described above can usually be measured by the following method. That is, after laminating metal thin films on both sides of the prepreg (that is, the semi-cured composition for preparing a thermosetting resin impregnated into the base material), heating and pressurizing to prepare a metal foil laminate, then a metal thin film from the metal foil laminate After removing all, the prepreg portion can be analyzed to determine the thermal expansion rate, dielectric constant, dielectric loss and flexural modulus of the prepreg. Upon heating and pressing, the semi-cured resin is completely cured.

On the other hand, a prepreg laminated body can be manufactured by laminating a predetermined number of said prepregs, and heating and pressurizing it. Upon heating and pressurizing, the semi-cured resin is completely cured and mostly converted to the crosslinked resin.

In addition, a metal foil laminate may be manufactured by disposing a metal thin film such as copper foil, silver foil or aluminum foil on one or both surfaces of the prepreg or prepreg laminate, and heating and pressing. Upon heating and pressurization, the semi-cured resin, if present, is completely cured and converted into a crosslinked resin mostly.

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

The heating and pressurization conditions applied during the production of the metal foil laminate may be, for example, 150 to 250 ° C. and 10 to 30 MPa, but the properties of the prepreg, the reactivity of the composition for preparing the thermosetting resin, the ability of the press, and the metal foil laminate for the purpose. It may be appropriately determined in consideration of the thickness and the like, and is not particularly limited.

In addition, the metal foil laminate according to an 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 thin film. In the preparation of the adhesive layer, a thermoplastic resin or a thermosetting resin may be used. In addition, the thickness of the adhesive layer may be 0.1 ~ 100㎛. When the thickness of the adhesive layer is within the above range, the thickness is moderate and the adhesive strength is high.

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 said thermosetting resin film. Moreover, a through hole etc. can also be formed in the said printed wiring board as needed.

In the multilayer printed wiring board according to the embodiment of the present invention, for example, a predetermined number of sheets of the prepreg are disposed between constituent materials, such as an inner substrate or a metal thin film, in accordance with a desired thickness of an insulating layer, and heated and pressed. It can be produced by molding. Heating and pressurization conditions at this time may be the same as the conditions at the time of manufacturing the metal foil laminate. In addition, as the inner substrate, a prepreg laminate, a metal foil laminate, a printed wiring board, or the like used as an electrical insulation material may be used, and two or more kinds thereof 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

(Manufacture of Copper Foil Laminate)

Example  One

Step 1: Preparation of Aromatic Polyester Amide Copolymer

179.6 g (1.3 mol) of parahydroxy benzoic acid, 245.5 g (2.3 mol) of 4-aminophenol, and 198.2 g (1.8 mol) of hydroquinone in a reactor equipped with a stirring device, a torque meter, a nitrogen gas introduction tube, a thermometer, and a reflux condenser. , 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 were added thereto. After sufficiently replacing the inside of the reactor with nitrogen gas, the temperature was raised to 150 ° C. over 30 minutes under a nitrogen gas stream and refluxed for 3 hours while maintaining the temperature.

Thereafter, the distilled acetic acid and unreacted acetic anhydride were distilled off, and the temperature was raised to 320 ° C. for 180 minutes, and the contents were discharged considering the end of the reaction as the time when the torque was increased. The obtained solid content was cooled to room temperature, and pulverized with a fine grinding machine to obtain an aromatic polyester amide copolymer powder without a separate solid phase polymerization reaction.

Step 2: preparing a composition solution for preparing a thermosetting resin

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

STEP 3: Prepreg  Produce

The composition solution prepared in step 2 was impregnated with a glass cloth (IPC 1078) at room temperature, and passed through a double roller to remove excess composition solution and to have a constant thickness. Thereafter, the contents were placed in a high temperature hot air dryer to remove the solvent at 180 ° C. to obtain a prepreg.

Step 4: Copper Foil Laminate  Produce

After placing each of the electrolytic copper foil having a thickness of 18 ㎛ on each side of the prepreg prepared in step 3, the laminate was heated and pressed for 3 hours under conditions of 200 ℃ and 30MPa using a hot plate press to produce a metal foil laminate It was.

Example  2

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

Comparative example  One

Using only 550 g of the aromatic polyester amide copolymer powder as prepared in step 1 of Example 1, a composition solution for preparing a thermosetting resin was prepared (without pyromellitic dianhydride). In addition, a prepreg and a copper foil laminate were manufactured in the same manner as in Example 1.

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 aromatic polyester amide copolymer powder and 26 g of pyromellitic dianhydride were used as prepared in Step 1 of Example 1. In addition, a prepreg and a copper foil laminate were manufactured in the same manner as in Example 1.

Comparative example  3

A composition for preparing a thermosetting resin was prepared in the same manner as in Example 1, except that 54.5 g of aromatic polyester amide copolymer powder and 495.5 g of pyromellitic dianhydride were used as prepared in Step 1 of Example 1. It was. In addition, a prepreg and a copper foil laminate were manufactured in the same manner as in Example 1.

Evaluation example

After removing all two pieces of copper foil from the copper foil laminates prepared in Examples 1 to 2 and Comparative Examples 1 to 3, the prepreg portion was analyzed to determine the degree of crosslinking of the resin contained therein, the thermal expansion coefficient of the prepreg, and the dielectric properties. And the flexural modulus was measured and shown in Table 1 below.

Evaluation items Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 % Crosslinking of resin 99.8 99.8 0 99.8 99.8 Thermal expansion coefficient of prepreg (ppm / K) 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 Flexural modulus of prepreg (GPa) 13 19 6 8 20

In Table 1, the degree of crosslinking was measured by analyzing the exothermic peak obtained by heating at 20 ° C./min from room temperature to 300 ° C. using a differential scanning thermal analyzer (DSC) (TA Instrument, DSC 2910), and the coefficient of thermal expansion was TMA ( TMA Q400) was used in the temperature range of 50 ~ 200 ℃, dielectric constant and dielectric loss were measured at room temperature using an impedance analyzer, flexural modulus was measured according to IPC-TM650.

Referring to Table 1, it can be seen that the copper foil laminates prepared in Examples 1 to 2 and Comparative Examples 2 to 3 contain crosslinked resins, but the copper foil laminates prepared in Comparative Example 1 do not contain any crosslinked resins. have. Therefore, the copper foil laminated sheets manufactured in Examples 1-2 and Comparative Examples 2-3 have the outstanding heat resistance, chemical resistance, and mechanical strength compared with the copper foil laminated sheets manufactured by Comparative Example 1. On the other hand, in the copper foil laminates prepared in Examples 1 to 2, the portion except for the copper foil (that is, the prepreg portion) has a low thermal expansion coefficient, a low dielectric constant, a low dielectric loss, and a high flexural modulus, whereas the copper foil laminates prepared in Comparative Examples 1 and 2 The copper foil laminate has a disadvantage in that the flexural modulus is low except for the copper foil. In addition, the copper foil laminate produced in Comparative Example 3 has a poor thermal expansion coefficient and dielectric properties in portions excluding copper foil compared to Examples 1 and 2 and Comparative Examples 1 and 2.

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

Claims (16)

10-30 mol% of repeating units (A) which have an amino terminal group and originate in aromatic hydroxy carboxylic acid; 15-25 mol% of repeating units of at least one of the repeating unit (B) derived from the aromatic amine which has a phenolic hydroxyl group, and the repeating unit (B ') derived from aromatic diamine; 15-30 mol% of repeating units (C) derived from an aromatic diol; And 100 parts by weight of the aromatic polyester amide copolymer comprising 30 to 60 mol% of repeating units (D) derived from aromatic dicarboxylic acid; And
A composition for producing a thermosetting resin containing 10 to 900 parts by weight of pyromellitic dianhydride. The method of claim 1,
The repeating unit (A) is derived from at least one compound of para hydroxy benzoic acid and 2-hydroxy-6-naphthoic acid, and the repeating unit (B) is 3-aminophenol, 4-aminophenol and It is derived from at least one compound selected from the group consisting of 2-amino-6-naphthol, and the repeating unit (B ′) is 1,4-phenylene diamine, 1,3-phenylene diamine and 2,6-naphthalene Derived from at least one compound selected from the group consisting of diamines, and 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 (D ) Is a composition for producing a thermosetting resin derived from at least one compound of isophthalic acid and naphthalene dicarboxylic acid. The method of claim 1,
The content of the repeating unit (B), repeating unit (B '), repeating unit (C) and repeating unit (D) is a composition for producing a thermosetting resin that satisfies the following conditions:
1.0 ≦ [n (B) + n (B ′) + n (C)] / n (D) <1.5.
Wherein n (B), n (B '), n (C) and n (D) are the repeating units (B), repeating units (B') and repeating units (B) contained in the aromatic polyester amide copolymer, respectively. C) and the number of moles of the repeating unit (D). The thermosetting resin film containing the hardened | cured material of the composition for thermosetting resin manufacture of any one of Claims 1-3. materials; And
A prepreg containing the hardened | cured material of the composition for manufacturing the thermosetting resin of any one of Claims 1-3 contained in the said base material. The method of claim 5,
The total content of the composition for producing a thermosetting resin and the cured product thereof contained per unit area of the substrate is in the range of 0.1 to 1,000 g / m ² . The method of claim 5,
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. The method of claim 5,
A prepreg further comprising 0.0001 to 100 parts by weight of at least one filler of the organic filler and the inorganic filler with respect to the total content of the thermosetting resin production composition and 100 parts by weight of the cured product thereof. The method of claim 5,
A prepreg having a thermal expansion coefficient in one direction of 20 ppm / K or less measured after completely curing the cured product contained in the prepreg. The method of claim 5,
A prepreg having a dielectric constant of 4.0 or less and a dielectric loss of 0.01 or less after fully curing the cured product included in the prepreg. The method of claim 5,
A prepreg having a flexural modulus of 10 to 30 GPa measured after completely curing the cured product included in the prepreg. A prepreg laminate comprising at least one prepreg according to claim 5. A prepreg according to claim 5; And
A metal foil laminate comprising at least one metal thin film disposed on at least one surface of the prepreg. The method of claim 13,
The said prepreg is a metal foil laminated board which is a prepreg laminated body of at least 2 sheets. The printed wiring board obtained by etching the metal thin film of the metal foil laminated board of Claim 13. The printed wiring board formed by printing a metal circuit pattern on at least one surface of the thermosetting resin film of Claim 4.