TWI535785B - 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

Description

a composition for preparing a thermosetting resin, a cured product of the composition, a prepreg, a prepreg layer having a cured product, and a metal clad laminate Printed circuit board with prepreg or prepreg [Reciprocal reference to related patent applications]

The present application claims the benefit of the Korean Patent Application No. 10-2010-0064396 filed on Jul. 5, 2010, the entire disclosure of which is hereby incorporated by reference.

The present invention relates to a composition for preparing a thermosetting resin, a cured product of a composition, a prepreg and a prepreg layer having a cured product, and a metal clad laminate and a printed circuit board having a prepreg or a prepreg layer And particularly relates to a composition and composition for preparing a thermosetting resin comprising an aromatic polyester guanamine copolymer having at least one of a terminal amino group and a terminal hydroxyl group, an epoxy resin and a selective bismaleimide A cured product, a prepreg, and a prepreg layer having a cured product, and a metal clad laminate and a printed circuit board having a prepreg or a prepreg layer.

As electronic components become smaller and more compact, and printed circuit boards become more refined and smaller, copper clad laminates have been widely used due to their excellent stamp formability and drillability and low cost. As a substrate for a printed circuit board of an electronic component.

The prepreg applied to the copper clad laminate for preparing a printed circuit board must have the following main characteristics suitable for the performance of the semiconductor and the manufacturing process of the semiconductor package.

(1) Low thermal expansion coefficient equivalent to the coefficient of thermal expansion of metal

(2) Low dielectric constant and dielectric at high frequency fields of 1 GHz or higher

Heat resistance of a reflow treatment at a temperature stability of about 270 ° C. A prepreg is obtained by impregnating glass fibers with epoxy resin or bismaleimide triazine resin with dry and semi-cured resins. preparation. Then, the copper foil is laminated on the prepreg or prepreg, and the resin is completely cured to prepare a copper clad laminate. The copper clad laminate is thinned and heat treated (for example, hot reflux at 270 ° C). The thin layer of the copper clad laminate may be thermally deformed during the heat treatment to reduce the yield. Further, the high moisture absorption property of the epoxy resin or the bis-methyleneimine triazine resin needs to be lowered. In particular, since epoxy resin or bis-methyleneimine-imine triazine resin has poor dielectric properties (high) at a high frequency field of 1 GHz or higher, it is difficult to epoxy or bis-butenylene The imine triazine resin is applied to a printed circuit board of a semiconductor package (which must be processed at a high frequency field and at a high speed). Therefore, a prepreg having excellent (low) dielectric properties is required.

Recently, aromatic polyesters have been substituted for epoxy resins or bis-methyleneimine triazine resins for the preparation of prepregs, which are prepared by incorporating an organic or inorganic fabric into an aromatic polyester. In particular, aromatic polyester prepregs can be prepared using aromatic polyester resins and aromatic polyester fabrics. Specifically, the dissolved aromatic polyester resin is dissolved in a solvent containing a halogen element (for example, a composition solution is prepared using chlorine) to prepare an aromatic polyester prepreg, and the aromatic polyester fabric is impregnated in the combined solution, and then Dry impregnated aromatic polyester fabric. However, it is difficult to completely remove the solvent of the halogen-containing element, and the halogen element corrodes the copper foil. Therefore, it is necessary to use a solvent of a non-halogen element.

The present invention provides a composition for preparing a thermosetting resin comprising an aromatic polyester guanamine copolymer having at least one of a terminal amino group and a terminal hydroxyl group, an epoxy resin, and a selective bismaleimide.

The present invention provides a thermosetting resin film comprising a cured product of a composition for preparing a thermosetting resin.

The present invention also provides a prepreg and a prepreg layer comprising a cured product of a composition for preparing a thermosetting resin.

The invention also provides a metal clad laminate and a printed circuit board comprising a prepreg or a prepreg layer.

According to one aspect of the present invention, there is provided a composition for preparing a thermosetting resin comprising: 100 parts by weight of an aromatic polyester guanamine copolymer having a terminal amino group selected from a terminal group At least one of the groups consisting of hydroxyl groups and comprising: 10 to 30 mole percent (mol%) of repeating unit A derived from aromatic hydroxy carboxylic acid; 15 to 25 mole percent selected from At least one of a group consisting of a repeating unit B derived from an aromatic amine having a phenolic hydroxyl group and a repeating unit B' derived from an aromatic diamine; 15 to 25 mole percentage of repeating unit C derived from aromatic diol; 30 to 60 mole percent of repeating unit D derived from aromatic dicarboxylic acid; 10 to 900 parts by weight Epoxy resin.

Repeat unit A is derived from a selected group of p-hydroxybenzoic acid At least one compound of a group consisting of (p-hydroxybenzoic acid) and 2-hydroxy-6-naphthoic acid. The repeating unit B is derived from a group consisting of 3-amino phenol, 4-amino phenol, and 2-amino-6-naphthol. At least one compound. The repeating unit B' is derived from a group selected from 1,4-phenylene diamine, 1,3-phenylene diamine and 2,6-naphthalenediamine (2,6). -naphthalene diamine) at least one compound of the group consisting of repeating unit C derived from at least one compound selected from the group consisting of resorcinol, biphenol, and hydroquinone, repeated Unit D is derived from at least one compound selected from the group consisting of isophthalic acid and naphthalene dicarboxylic acid.

The amount of repeating unit B, repeating unit B', repeating unit C, and repeating unit D meets the following conditions: 1.0 [n(B)+n(B ' )+n(C)]/n(D)<1.5

Here, n(B), n(B'), n(C), and n(D) are repeating unit B, repeating unit B', repeating unit C, and repeating unit in the aromatic polyester guanamine copolymer, respectively. The number of moles of D.

The composition for preparing the thermosetting resin may further contain 5 to 30 parts by weight of bismaleamide based on 100 parts by weight of the aromatic polyester guanamine copolymer.

According to another aspect of the present invention, there is provided a cured product of a thermosetting resin film comprising a cured product of a composition for preparing a thermosetting resin.

According to another aspect of the present invention, a prepreg comprising a base is provided And a cured product of a composition for preparing a thermosetting resin contained in a substrate.

The total amount of the composition for preparing the thermosetting resin and the cured product of the composition contained in the unit area of the substrate ranges from 0.1 to 1,000 g/m ² .

The substrate may comprise 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 a 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 cured composition of the thermosetting resin and the cured product of the composition. At least one filler of the ethnic group.

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 prepreg measured at a frequency of 1 GHz after the cured product contained in the prepreg is completely cured may have a dielectric constant of 4.0 or less and a dielectric loss of 0.01 or less.

The glass transition temperature of the cured product ranges from 170 to 270 °C.

According to another aspect of the invention, a prepreg layer comprising at least one prepreg is provided.

According to another aspect of the present invention, there is provided a metal clad laminate comprising: a prepreg or a prepreg; and at least one metal foil disposed on at least one surface of the prepreg.

According to another aspect of the present invention, a printed circuit board prepared by etching a metal clad laminate metal foil is provided.

According to another aspect of the present invention, a printed circuit board prepared by printing a metal circuit pattern on at least one surface of a thermosetting resin film is provided.

The following is a detailed description of the invention.

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

The composition for preparing a curable resin according to an embodiment of the present invention comprises 100 parts by weight of an aromatic polyester decylamine copolymer having at least one of a terminal amino group and a terminal hydroxyl group, and 10 to 900 parts by weight of an epoxy resin.

If the amount of the aromatic polyester guanamine copolymer and the epoxy resin is within the above range, the cured product of the composition for preparing a thermosetting resin (for example, a crosslinked resin) has low thermal expansion characteristics, low dielectric properties, Low moisture absorption properties (high crosslink density due to high degree of crosslinking).

The aromatic polyester guanamine copolymer may comprise: 10 to 30 mole percent of repeating unit A derived from aromatic hydroxy carboxylic acid; 15 to 25 mole percent selected from phenol-derived At least one of a repeating unit B of an aromatic amine of a phenolic hydroxyl group and a repeating unit B ' derived from an aromatic diamine; 15 to 25 mol% Repeating unit C derived from an aromatic diol; and 30 to 60 mole percent of repeating unit D derived from an aromatic dicarboxylic acid.

If the amount of the repeating unit A is between the above ranges, the aromatic polyester guanamine copolymer has high mechanical strength and excellent thermal properties. If the total amount of the repeating unit B and the repeating unit B ' is between the above ranges, the aromatic polyester decylamine copolymer has high solubility in a solvent and has a suitable melting temperature. If the amount of the repeating unit C is between the above ranges, the aromatic polyester decylamine copolymer has high solubility in a solvent and has a suitable melting temperature. If the amount of the repeating unit D is between the above ranges, the aromatic polyester guanamine copolymer has high solubility in a solvent, has low thermal expansion characteristics, and has low dielectric properties.

Further, the repeating unit A may be derived from at least one compound selected from the group consisting of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid. The repeating unit B may be derived from at least one compound selected from the group consisting of 3-aminophenol, 4-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-phenylenediamine, and 2,6-naphthalenediamine. The repeating unit C may be derived from at least one compound selected from the group consisting of resorcin, bisphenol, and hydroquinone. 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 amount of 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

Here, n(B), n(B'), n(C), and n(D) are repeating unit B, repeating unit B', repeating unit C, and repeating unit in the aromatic polyester guanamine copolymer, respectively. The number of moles of D.

If {[n(B)+n(B ' )+n(C)]/n(D)} is in the above range, the aromatic polyester guanamine copolymer contains a plurality of terminal amino groups and/or terminal hydroxyl groups, and The curing reaction is carried out with an epoxy resin and/or a bismaleimide resin to form a thermosetting resin having a high crosslinking density.

For example, each of the repeating units A, B, B', C, and D contained in the aromatic polyester guanamine copolymer may be represented by any one of the following chemical formulas.

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

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

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

(4) Repeating unit C derived from aromatic diol:

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

Here, R ₁ and R ₂ may each independently be 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, substituted or not. Substituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl (alkynyl) Group), substituted or unsubstituted C ₁ -C ₂₀ heteroalkyl group, substituted or unsubstituted C ₆ -C ₃₀ aryl group, substituted or unsubstituted C _7- C ₃₀ arylalkyl group, substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group, or substituted or unsubstituted C ₃ -C ₃₀ heteroaryl alkane Heteroarylalkyl group. "Substituted" here means that at least one hydrogen atom of the compound is substituted by a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an amino group or a combination of at least two thereof.

The aromatic polyester guanamine copolymer can be obtained by polymerizing (1) an aromatic hydroxycarboxylic acid or a derivative thereof for forming an ester; (2) an aromatic amine having a phenolic hydroxyl group for forming a guanamine or a derivative thereof And at least one of an aromatic diamine or a derivative thereof for forming a guanamine; (3) an aromatic diol or a derivative thereof for forming an ester; (4) an aromatic diol for forming an ester Prepared from a carboxylic acid or a derivative thereof.

The derivative of the aromatic hydroxycarboxylic acid or aromatic dicarboxylic acid used to form the ester may be a highly reactive derivative such as an acid chloride, an acid anhydride, or an alcohol. Ethylene glycol or other analogs form ester bond derivatives.

Further, a derivative of an aromatic amine or an aromatic diamine for forming a guanamine may have an amine group which forms a guanamine bond with a carboxylic acid.

The derivative of the aromatic diol used to form the ester may have a hydroxyl group which forms an ester bond with the carboxylic acid.

The aromatic polyester guanamine copolymer prepared as described above can be dissolved in a solvent, and can be a thermotropic liquid crystalline polyamide copolymer (which can form optical anisotropy at a temperature of 400 ° C or lower ( Optical anisotropy) For example, the aromatic polyester guanamine 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 guanamine copolymer can be prepared by the following method. That is, it is prepared by melt polymerization, which comprises acylating a hydroxyl group or an amino group of an aromatic hydroxycarboxylic acid corresponding to the repeating unit A, and an aromatic group corresponding to the repeating unit B and/or the repeating unit B', respectively. An amine and/or an aromatic diamine and an aromatic diol corresponding to the repeating unit C, and a transesterification between the deuterated product and the aromatic dicarboxylic acid. Thus, the aromatic polyester guanamine copolymer may have a terminal amino group and/or a terminal hydroxyl group without a terminal carboxyl group, and may have a predetermined degree of polymerization by controlling the amount of the fatty acid anhydride. For example, in the case of producing an aromatic polyester guanamine copolymer, if the amount of the fatty acid anhydride is increased, the number of terminal amino groups and/or terminal hydroxyl groups is decreased, and the number of terminal carboxyl groups and degree of polymerization are increased. Conversely, if the amount of fatty acid anhydride is decreased, the number of terminal amino groups and/or terminal hydroxyl groups is increased, and the number of terminal carboxyl groups and degree of polymerization are decreased.

In the deuteration reaction, the amount of the fatty acid anhydride may be in the range of 0.9 to 1.2 times the total amount of the hydroxyl group and the amino group in the stoichiometric calculation (example) Such as 0.95 to 1.05 times). If the amount of the fatty acid anhydride is within the above range, the resulting aromatic polyester guanamine copolymer has terminal amino groups and/or terminal hydroxyl groups without terminal carboxyl groups, and the resulting coloring of the aromatic polyester guanamine copolymer It is reduced that the monomer used in the resulting aromatic polyester guanamine copolymer does not sublime, and the amount of phenol gas generated is reduced. The deuteration reaction can be carried out at a temperature of 130 to 170 ° C for 30 minutes to 8 hours, for example, at a temperature of 140 to 160 ° C for 2 to 4 hours.

The fatty acid anhydride used in the deuteration reaction includes acetic anhydride, propionic anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, butyric anhydride ( Butyric anhydride) and the like, but is not limited thereto. The fatty acid anhydride can be used in combination of at least two of the above.

The transesterification and the transamination can be carried out at a heating rate of 0.1 to 2 ° C / min and at a temperature of 130 to 400 ° C, for example, at a heating rate of 0.3 to 1 ° C / min and a temperature of 140 to 350 ° C.

When the transesterification and transamination of the fatty acid ester and the aromatic dicarboxylic acid are carried out, the fatty acid which is produced as a by-product and the unreacted fatty acid anhydride can be evaporated or distilled to be excluded from the reaction system. The chemical equilibrium state is moved to increase the reaction rate.

Further, the deuteration reaction, the transesterification reaction, and the transamination reaction can be carried out in the presence of a catalyst. The catalyst may be any catalyst known for the preparation of polyester resins, such as magnesium acetate, tin(II) acetate, tetrabutyl titanate, Lead acetate, sodium acetate, potassium acetate, antimony trioxide, N,N-dimethylaminopyridine and N-methylimidazole (N-methyl imidazole). Usually, the catalyst can be simultaneously added to the reaction system along with the monomer, and the deuteration reaction, the transesterification reaction and the transamination reaction are carried out in the presence of a catalyst.

The polycondensation reaction by the transesterification reaction and the transamination reaction can be carried out by melt polymerization. Since the resulting aromatic polyester guanamine copolymer is crosslinked (i.e., cured) with the epoxy resin thereafter, a cured product having high degree of polymerization and high mechanical strength can be formed, and thus solid state polymerization is not necessary. of.

The polymerization apparatus used for the melt polymerization may be any reactor equipped with a stirrer which is usually used for the reaction of a high viscosity material. In this regard, the reactor for the melt polymerization may be the same as or different from the reactor for the deuteration reaction.

The aromatic polyester guanamine copolymer according to the present embodiment has a terminal amino group and/or a terminal hydroxyl group, but does not have a terminal carboxyl group. Therefore, the aromatic polyester guanamine copolymer can be highly crosslinked with an epoxy resin and a selective bismaleamide, which will be described later.

Further, the aromatic polyester guanamine copolymer may have a coefficient of thermal expansion of 3 ppm/K or less.

The epoxy resin may comprise at least one of a group consisting of a bi-functional epoxy resin and a tri- or higher-functional epoxy resin. The bifunctional epoxy resin can be, for example, a bisphenol A type epoxy tree. Hydrogenated, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bixylenol Type epoxy resin or biphenol type epoxy resin. Further, the tri- or higher functional epoxy resin may be, for example, a novolac type epoxy resin, a phenol novolac type epoxy resin, a bisphenol type epoxy resin, or a cresol novolac. Type epoxy resin, N-glycidyl type epoxy resin, phenolic epoxy resin of bisphenol A, biphenol novolac type epoxy resin, chelate type epoxy resin , glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadienephenolic epoxy resin, four Tetrakisphenolethane type epoxy resin, diglycidylphthalate resin, heterocyclic epoxy resin, tetraglycidylxylenoylethane resin, hydrazine Silicon-modified epoxy resin or ε-caprolactone-modified epoxy resin.

The composition for preparing a thermosetting resin according to the present embodiment can be prepared by mixing a predetermined ratio of an aromatic polyester guanamine copolymer, an epoxy resin, and a selective bismaleimide.

Meanwhile, a thermosetting resin film can be prepared by using a composition for preparing a thermosetting resin by using a solvent casting method.

In addition, the composition for preparing the thermosetting resin can be dissolved in the solvent because Thus, the prepreg can be prepared by impregnating or coating the substrate with the composition from which the thermosetting resin is prepared and drying and thermally curing (generally semi-cured) the impregnated or coated substrate. In this regard, the components of the composition for preparing the thermosetting resin contained in the prepreg are partially crosslinked with each other via heat curing to form a crosslinked resin. That is, one component of the composition for preparing the thermosetting resin (ie, the aromatic polyester guanamine copolymer) is a terminal amino group and/or a terminal hydroxyl group and other components of the composition (ie, an epoxy resin and a selective double horse. The benzidine is partially crosslinked to form a crosslinked resin (ie, a cured product). This cured product has the same characteristics as the aromatic polyester guanamine copolymer, and thus has a low coefficient of thermal expansion, a low dielectric constant, and a low dielectric loss.

The term "semi-cured" as used herein refers to a state in which a curing treatment of a composition for preparing a resin is partially performed. The resin produced by the semi-cured composition is not melted by heat but softened, and is not dissolved but swelled in the solvent. Generally, a resin obtained via a semi-cured composition is referred to as a B-stage resin. The term "completely cured" as used herein refers to a state in which the curing treatment of the composition for preparing a resin is completely performed. The resin produced by completely curing the composition is not softened by heat and does not swell in the solvent. Generally, a resin obtained via a fully cured composition is referred to as a C-stage resin.

The composition for preparing the thermosetting resin can be used in various ways in addition to the preparation of the prepreg.

For example, by impregnating an organic or inorganic textile substrate and/or an organic or inorganic non-woven substrate with a composition solution prepared by dissolving a composition for preparing a thermosetting resin in a solvent, or by fabricating a fabric and/or Non-woven substrate coated with a solution solution and dried and semi-cured by impregnated or coated product Prepare prepreg. Thus, the prepreg can be prepared using solution impregnation or varnish impregnation.

The amount of the solvent used to dissolve the composition for preparing the thermosetting resin ranges from 100 to 100,000 parts by weight based on 100 parts by weight of the composition for preparing the thermosetting resin. If the amount of the solvent is within the above range, the composition for preparing the thermosetting resin is sufficiently dissolved in the solvent, and the yield of the composition solution is increased.

The solvent which dissolves the composition for preparing the thermosetting resin may be a non-halogen solvent. However, the invention is not limited thereto. The solvent may also be a polar aprotic compound, a halogenated phenol, an o-dichlorobenzene, a chloroform, a methylene chloride, a tetrachloroethane or the like. It may be used alone or in combination of at least two of the above compounds.

Thus, since the composition for preparing the thermosetting resin is dissolved in the non-halogen solvent, it is not necessary to use a solvent containing the halogen element. Therefore, corrosion of the metal foil caused when a solvent containing a halogen element is used in a printed circuit board for preparing a metal clad laminate or a cured product containing the composition can be prevented in advance.

The substrate may comprise an aromatic polyester fiber, an aromatic polyester guanamine fiber, a glass fiber, carbon fiber, paper or a fabric and/or a non-woven fabric comprising at least both of the above.

If the impregnation treatment is used during the preparation of the prepreg, the substrate may be immersed in the composition solution for 0.001 minute to 1 hour. If the impregnation time is within the above range, the substrate is uniformly impregnated in the composition solution, and the prepreg The yield is increased.

Further, the substrate may be impregnated in the composition solution at a temperature of 20 to 190 °C.

Further, the amount of the composition for preparing the thermosetting resin impregnated in the unit area of the substrate is in the range of 0.1 to 1,000 g/m ² . If the amount of the impregnated composition for preparing the thermosetting resin is within the above range, the prepreg yield and workability are increased. Therefore, in the prepreg after the semi-curing process, the amount of the composition of the thermosetting resin and the cured product of the composition may be from about 0.1 to about 1,000 g/m ² based on the unit area of the substrate.

In order to control the dielectric constant and the coefficient of thermal expansion, an inorganic filler such as silica, aluminum hydroxide or calcium carbonate; and/or an organic filler such as a cured epoxy resin or a crosslinked acrylic resin may be added. To the composition solution. The inorganic filler may be a titanate such as barium titanate or strontium titanate, or titanium or tantalum by substituting another metal portion for barium titanate. (barium) a compound prepared. The amount of the inorganic filler and/or the organic filler contained in the composition solution is in the range of 0.0001 to 100 parts by weight based on 100 parts by weight of the composition for preparing the thermosetting resin. If the amount of the inorganic filler and/or the organic filler is within the above range, the coefficient of thermal expansion of the prepreg is reduced, and the composition of the thermosetting resin prepared after the semi-curing treatment and the cured product of the composition have a function sufficient as an adhesive. . Therefore, the amount of the inorganic filler and/or the organic filler contained in the prepreg after the semi-curing is in the range of 0.0001 to 100 parts by weight based on 100 parts by weight of the total amount of the cured composition of the thermosetting resin and the cured product of the composition. Inside.

Since the prepreg according to the present embodiment contains a cured product of a composition for preparing a thermosetting resin (having a low coefficient of thermal expansion, a low hygroscopic property, and a low dielectric property, and the organic or inorganic fabric and/or the organic or inorganic non-woven fabric has High mechanical strength) makes the prepreg have high dimensional stability, is not susceptible to thermal deformation, and is hard. Therefore, this prepreg is suitable for via-hole drill processing and laminating processing.

In the impregnation process for preparing the prepreg, after the substrate is impregnated or coated with the composition solution, the solvent can be removed by evaporation, but the method of removing the solvent is not limited. For example, evaporation can be carried out by heating, vacuum evaporation, or ventilation. The solvent can also be removed by drying the prepreg, which is impregnated in the composition solution, at a temperature of 20 to 190 ° C for 1 minute to 2 hours.

Then, the dried prepreg is heated at a temperature of 120 to 320 ° C for 1 to 8 hours to semi-cure the composition of the thermosetting resin contained in the prepreg.

The thickness of the prepreg according to the present embodiment may range from about 5 to about 200 μm, for example, from about 30 to about 150 μm.

The coefficient of thermal expansion in one direction of the prepreg measured after the cured product contained in the prepreg (i.e., the cured resin (B-stage resin)) was completely cured was 20 ppm/K or less. If the thermal expansion coefficient of the prepreg is within the above range, the metal clad laminate containing the prepreg is not peeled off.

Further, after the cured product contained in the prepreg is completely cured, the dielectric constant of the prepreg measured at a frequency of 1 GHz may be 4.0 or more. Low and dielectric loss is 0.01 or lower. "Dielectric loss" as used herein refers to the energy lost from the dielectric material due to heat when an alternating electric field is applied to the dielectric material. If the dielectric constant and the dielectric loss are each within the above range, the prepreg containing the cured product in the high frequency field is suitable as the insulating substrate.

Further, the glass transition temperature of the cured product may be in the range of 170 to 270 °C. If the glass transition temperature of the cured product is within the above range, the cured product has high heat resistance and does not wrap.

The thermal expansion coefficient and dielectric properties of the prepreg and the glass transition temperature of the cured product are usually measured by the following methods. That is, the metal foil is laminated on both surfaces of the prepreg prepared by semi-curing the composition for preparing the thermosetting resin impregnated in the substrate, and heating and compressing the laminate to prepare a metal package The laminate is laminated and the metal foil is then removed from the metal clad laminate. Then, the coefficient of thermal expansion and dielectric properties of the prepreg and the glass transition temperature of the cured product contained in the prepreg can be measured by analyzing the prepreg. The semi-cured resin will cure completely while heating and compressing.

At the same time, the prepreg layer can be prepared by laminating a predetermined number of prepregs and heating and compressing the laminate. The semi-cured resin is fully cured to convert the cross-linked resin while heating and compressing.

The metal clad laminate may also be prepared by disposing a metal foil (e.g., copper foil, silver foil, aluminum foil) on one or both surfaces of the prepreg or prepreg and heating and compressing the laminate. In the case of a semi-cured resin, the semi-cured resin is completely cured to convert the cross-linked resin while heating and compressing.

The thickness of the prepreg or prepreg and the metal foil in the clad laminate is in the range of 0.1 to 300 μm, respectively. If prepreg or pre When the thickness of the impregnated layer body is within the above range, cracking does not occur during the winding process, and a multilayered laminate having a finite thickness can be obtained. If the thickness of the metal foil is within the above range, cracking may not occur when the metal foil is laminated, and a multilayered laminate may be obtained.

The conditions for the heating and compression treatment applied to the preparation of the metal clad laminate may be, for example, a temperature of 150 to 250 ° C and a pressure of 10 to 30 MPa. However, the conditions vary depending on the characteristics of the prepreg, the reactivity of the composition for preparing the thermosetting resin, the properties of the compression device, and the thickness required for the metal clad laminate without limitation.

The metal clad laminate according to the present embodiment may further comprise an adhesive layer between the prepreg layer and the metal foil to increase the bonding strength between each other. A thermoplastic resin or a thermosetting resin can be used for the preparation of the adhesive layer. Further, the thickness of the adhesive layer may be in the range of 0.1 to 100 μm. If the thickness of the adhesive layer is within the above range, the adhesive strength is increased and the adhesive layer has an appropriate thickness.

A printed circuit board can be prepared by etching a metal foil of a metal clad laminate and forming a circuit thereon. The printed circuit board may also be prepared by printing a metal circuit pattern on at least one surface of the thermosetting resin film. The printed circuit board can also have a through hole if desired.

The multilayer printed circuit board according to the embodiment can be prepared, for example, by arranging a predetermined number of prepregs and heating and compressing the laminate between members such as an inner substrate or a metal foil, etc., depending on the thickness of the insulating layer required. In this regard, the conditions of the heating and compression treatment may be the same as those of the metal clad laminate. In addition, prepreg, metal clad laminate or printed circuit board (as The electrically insulating material can be used as an inner substrate, or a combination of at least two of them can be used.

Hereinafter, one or more embodiments of the present invention will be described in more detail with reference to the following examples. However, these examples are not intended to limit the scope of one or more embodiments of the invention.

Instance

Preparation of copper clad laminate

Example 1

Operation 1: Preparation of aromatic polyester guanamine copolymer

207.2 grams (1.5 moles) of p-hydroxybenzoic acid, 245.5 grams (2.3 moles) of 4-aminophenol, 185.8 grams (1.7 moles) of terephthalic acid Hydroquinone, 61.9 grams (0.6 mole) of resorcinol, 747.6 grams (4.5 moles) of isophthalic acid and 1,123 grams (11 moles) of acetic anhydride (acetic) The anhydride is fed to a reactor equipped with a stirrer, a torque meter, a nitrogen inlet, a thermometer, and a reflux condenser. The inside of the reactor was thoroughly flushed with nitrogen, and then the reactor was heated to 150 ° C for 30 minutes under a nitrogen atmosphere, and refluxed at the same temperature for 3 hours.

Then, the reactor was heated to 320 ° C for 180 minutes while removing effluent acetic acid and unreacted acetic anhydride by distillation. The point in time when the moment begins to increase is considered to be the end of the reaction, and the contents of the reactor are discharged. The obtained solid was cooled to room temperature, and powdered using a powder machine, and as a result, an aromatic polyester decylamine copolymer powder was obtained (no solid state polymerization was carried out).

Operation 2: Preparation of a composition solution of a thermosetting resin

300 g of the aromatic polyester amide copolymer powder prepared as in operation 1 and 30 g of epoxy resin (manufactured by Huntsman, model MY-721) were added to 400 g of N-methylpyrolidone (N-methylpyrolidone). , NMP), and the mixture was stirred at 25 ° C for 4 hours to obtain a composition solution for preparing a thermosetting resin.

Operation 3: Preparation of prepreg

The glass fabric (IPC 1078) was impregnated in the composition solution prepared as in Operation 2 at room temperature, and the excess composition solution was removed by a double roller and the thickness was controlled. Then, the solvent was removed at 180 ° C in a hot-air dryer to obtain a prepreg.

Operation 4: Preparation of copper clad laminate

An electrolytic copper foil having a thickness of 18 μm was placed on two opposite surfaces of the prepreg prepared as in Operation 3 to obtain a laminate, and the laminate was heated at a temperature of 200 ° C and a hot plate press at a pressure of 30 MPa ( Hot plate press) was compressed for 3 hours to produce a copper clad laminate.

Example 2

A composition solution for preparing a thermosetting resin was prepared in the same manner as in Example 1 except that 300 g of the aromatic polyester phthalamide copolymer powder prepared in the operation 1 of Example 1 was used, and a 2700 gram ring was used. Oxygen resin (manufactured by Huntsman, model MY-721). The preparation of the prepreg and the copper clad laminate was also the same as in the method of Example 1.

Example 3

Aromatic polyester prepared in accordance with operation 1 of Example 1 except 300 g A composition solution for preparing a thermosetting resin was prepared in the same manner as in Example 1 except that the guanamine copolymer powder was used, and 200 g of an epoxy resin (manufactured by Huntsman Co., model MY-721) and a double of 30 g were used. Malayan amide. The preparation of the prepreg and the copper clad laminate was also the same as in the method of Example 1.

Comparative example 1

A composition solution for preparing a thermosetting resin was prepared using only 100 g of the aromatic polyester phthalamide copolymer powder prepared in the operation 1 of Example 1 (without using an epoxy resin). The preparation of the prepreg and the copper clad laminate was also the same as in the method of Example 1.

Comparative example 2

A composition solution for preparing a thermosetting resin was prepared in the same manner as in Example 1 except that 300 g of the aromatic polyester phthalamide copolymer powder prepared in the operation 1 of Example 1 was used, and 15 g of epoxy was used. Resin (manufactured by Huntsman, model MY-721). The preparation of the prepreg and the copper clad laminate was also the same as in the method of Example 1.

Comparative example 3

A composition solution for preparing a thermosetting resin was prepared in the same manner as in Example 1 except that 300 g of the aromatic polyester phthalamide copolymer powder prepared in the operation 1 of Example 1 was used, and a 3000 gram ring was used. Oxygen resin (manufactured by Huntsman, model MY-721). The preparation of the prepreg and the copper clad laminate was also the same as in the method of Example 1.

Evaluation example

Copper clad laminate prepared in Examples 1 to 3 and Comparative Examples 1 to 3 After the two layers of copper foil were removed from the layer, the prepreg portion was analyzed. The degree of crosslinking of the resin contained in the prepreg, the glass transition temperature, and the measurement of the thermal expansion coefficient and dielectric properties of the prepreg were measured, and the results are shown in Table 1.

In Table 1, the degree of crosslinking was measured by analyzing the exothermic peak by using differential scanning calorimetry (DSC, manufactured by TA Instrument, model DSC 2910). (exothermic peak) to measure, this exothermic peak is obtained by increasing the temperature from room temperature to 300 ° C at a rate of 20 ° C / min; the glass transition temperature is increased from room temperature to 20 ° C / min 300 ° C and measured using DSC (manufactured by TA Instrument, model DSC 2910); thermal expansion coefficient is measured at a temperature of 50 ° C to 200 ° C using a thermomechanical analyzer (manufactured by TMA Corporation, model Q400); dielectric compensation And the dielectric loss is measured at room temperature using an impedance meter.

Referring to Table 1, the copper clad laminates prepared according to Examples 1 to 3 and Comparative Examples 2 to 3 contained a crosslinked resin, and the copper clad laminate prepared according to Comparative Example 1 did not contain a crosslinked resin. Therefore, the copper clad laminates prepared according to Examples 1 to 3 and Comparative Examples 2 to 3 have better heat resistance, chemical resistance, and mechanical strength than the copper clad laminates prepared in Comparative Example 1. Meanwhile, the portion of the copper clad laminate prepared in Examples 1 to 3 which does not contain the copper foil (for example, the prepreg portion) has a low coefficient of thermal expansion, a low dielectric constant, and a low dielectric loss, and is included in the prepreg. The resin in the body has a high glass transition temperature. On the other hand, the portion of the copper clad laminate prepared in Comparative Examples 1 to 2 which did not contain the copper foil had a low glass transition temperature. Although the portion of the copper clad laminate prepared in Comparative Example 3 which did not contain the copper foil had a high glass transition temperature, the portion had a high thermal expansion coefficient, a high dielectric constant, and a high dielectric loss.

According to an embodiment, there is provided a composition for preparing a thermosetting resin comprising an aromatic polyester guanamine copolymer having at least one of a terminal amino group and a terminal hydroxyl group, an epoxy resin, and a selective bismaleide, And therefore dissolved in a non-halogen solution.

According to another embodiment, there is provided a curable resin film, a prepreg, and a prepreg layer having a low thermal expansion coefficient, a low dielectric constant, and a low dielectric property by containing a cured product of a composition for preparing a thermosetting resin. Loss and low moisture absorption characteristics. In addition, this cured product has a high glass transition temperature.

According to another embodiment, a metal clad laminate and a printed circuit board comprising a prepreg or a prepreg layer are provided.

While the present invention has been shown and described with reference to the embodiments of the present invention, it will be understood by those of ordinary skill in the art that the present invention may be modified in form and detail without departing from the spirit and scope of the invention. The scope of protection depends on the scope of the patent application below.

Claims (16)

A composition for preparing a thermosetting resin, comprising: 100 parts by weight of an aromatic polyester guanamine copolymer having at least one selected from the group consisting of a terminal amino group and a terminal hydroxyl group, and comprising: 10 to 30 moles Percentage of repeating unit A derived from aromatic hydroxycarboxylic acid; 15 to 25 mole percent of repeating unit B derived from aromatic amine having phenolic hydroxyl group and repeating unit B' derived from aromatic diamine At least one of the population; 15 to 25 mole percent of repeating unit C derived from an aromatic diol; and 30 to 60 mole percent of repeating unit D derived from an aromatic dicarboxylic acid; and 5 to 30 weight Parts of bismaleimide; and 10 to 900 parts by weight of epoxy resin. The composition for preparing a thermosetting resin according to claim 1, wherein the repeating unit A is derived from at least one compound selected from the group consisting of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid. The repeating unit B is derived from at least one compound selected from the group consisting of 3-aminophenol, 4-aminophenol, and 2-amino-6-naphthol, and the repeating unit B' is derived from a group selected from 1,4-phenylenediamine. At least one compound of a group consisting of 1,3-phenylenediamine and 2,6-naphthalenediamine, the repeating unit C being derived from at least one group selected from the group consisting of resorcinol, bisphenol and hydroquinone A compound, the repeating unit D being derived from at least one compound selected from the group consisting of isophthalic acid and naphthalene dicarboxylic acid. The composition for preparing a thermosetting resin according to claim 1, wherein the amount of the repeating unit B, the repeating unit B', the repeating unit C, and the repeating unit D meets 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 respectively in the aroma The number of moles of the repeating unit B, the repeating unit B', the repeating unit C, and the repeating unit D in the family polyester guanamine copolymer. A thermosetting resin film comprising a cured product of a composition for preparing a thermosetting resin according to any one of claims 1 to 3. A prepreg comprising: a substrate; and the method of any one of claims 1 to 3 included in the substrate A cured product of a composition of a thermosetting resin. The prepreg according to claim 5, wherein a range of the total amount of the composition for preparing a thermosetting resin and the cured product of the composition contained in a unit area of the substrate is 0.1 to 1,000 g/m ² . The prepreg according to 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. By. The prepreg according to claim 5, which further comprises 0.0001 to 100 parts by weight based on 100 parts by weight of the composition of the thermosetting resin and the cured product of the composition. At least one filler from a group consisting of an organic filler or an inorganic filler. The prepreg according to claim 5, wherein after the cured product contained in the prepreg is completely cured, the measured coefficient of thermal expansion of the prepreg in one direction may be 20ppm/K or lower. The prepreg according to claim 5, wherein after the cured product in the prepreg is completely cured, the dielectric constant of the prepreg measured at a frequency of 1 GHz is 4.0 or lower, and the dielectric loss is 0.01 or lower. The prepreg according to claim 5, wherein the cured product has a glass transition temperature of 170 to 270 °C. A prepreg layer comprising at least two prepregs as described in claim 5 of the patent application. A metal clad laminate comprising: the prepreg according to claim 5; and at least one metal foil disposed on at least one surface of the prepreg. The metal clad laminate according to claim 13, wherein the prepreg is a prepreg layer containing at least two prepregs. A printed circuit board prepared by etching the metal foil of the metal clad laminate according to claim 13 of the patent application. A printed circuit board prepared by printing a metal circuit pattern on at least one surface of a thermosetting resin film as described in claim 4 of the patent application.