KR20040070877A - Epoxy Resin Composition Containing Bisphenol A Epoxy Resin and Printed Circuit Board Using the Same - Google Patents

Abstract

PURPOSE: An epoxy resin composition containing a bisphenol A-type epoxy resin and a circuit board prepared by using the composition are provided, to compensate the deterioration of mechanical properties such as adhesive strength without the deterioration of other properties if an inorganic filler is used, thereby allowing the content of an inorganic filler to be increased. CONSTITUTION: The composition comprises 100 parts by weight of a bisphenol A-type epoxy resin having an average epoxy equivalence of 400-1,000; 5-80 parts by weight of a polymer-type bisphenol A-type epoxy resin having an average epoxy equivalence of 2,000-10,000; 1-100 parts by weight of a multifunctional epoxy resin; 1-4 parts by weight of an amine-based curing agent; 0.01-1 parts by weight of an imidazole-based curing accelerator; and optionally an inorganic filler and a dispersant. Preferably the amine-based curing agent is selected from the group consisting of 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl methane, dicyandiamide and their mixtures; and the imidazole-based curing accelerator is selected from the group consisting of 2-ethyl-methylimidazole, 1-(2-cyanoethyl)-2-alkylimidazole, 2-phenylimidazole and their mixtures.

Description

Epoxy resin composition containing bisphenol A type epoxy resin and a circuit board using the same {Epoxy Resin Composition Containing Bisphenol A Epoxy Resin and Printed Circuit Board Using the Same}

The present invention relates to an epoxy resin composition containing a bisphenol A epoxy resin and a circuit board using the same. More specifically, the bisphenol A epoxy resin having an average epoxy equivalent of 400 to 1000 and the polymer bisphenol A epoxy resin having an average epoxy equivalent of 2,000 to 10,000, and include a polyfunctional epoxy resin, an amine curing agent, and an imidazole curing accelerator. Including an inorganic filler and a dispersing agent to satisfy the required physical properties of the existing circuit board material, the epoxy resin composition containing a bisphenol A-type epoxy resin having a high inorganic filler content in the circuit board material and a circuit board using the same will be.

Recently, due to the multifunctional and light and simple reduction of electronic products, it is more thermally and mechanically stable than the material used for the conventional printed circuit board, and the circuit board material itself includes the function of the surface-mount passive device, which is used as the inner layer of the circuit board. Techniques to embed are emerging.

Therefore, in order to overcome the limitations of the physical properties of the polymer materials used as conventional circuit board materials and to give a desired function, inorganic fillers are used. However, when a large amount of the inorganic filler is included in the circuit board material, brittleness of the material increases, and problems such as poor adhesion between the resin and the copper foil occur. Therefore, there exists a problem that content of the inorganic substance in a circuit board material is restrict | limited.

In order to solve the above problems, the present invention, in order to utilize the desired physical properties by the inorganic filler, satisfying the required physical properties of the existing circuit board material and containing a bisphenol A type epoxy resin having a high inorganic filler content in the circuit board material It is an object to provide an epoxy resin composition.

The above and other objects of the present invention can be achieved by the present invention described below.

The present invention to achieve the above object,

5 to 80 parts by weight of a polymer bisphenol A type epoxy resin having an average epoxy equivalent of 2,000 to 10,000 with respect to 100 parts by weight of a bisphenol A type epoxy resin having an average epoxy equivalent of 400 to 1,000; 1 to 100 parts by weight of the multifunctional epoxy resin; 1 to 4 parts by weight of an amine curing agent; Provided is an epoxy resin composition containing a bisphenol A epoxy resin comprising 0.01 to 1 part by weight of an imidazole series curing accelerator.

The epoxy resin composition containing the bisphenol A epoxy resin may further include an inorganic filler and a dispersant.

The inorganic fillers include barium tiatanum oxide, barium strontium titanate, titanium titanate, lead ziroconium titanate, lead lentaum zir Lead lanthanum zirconate titanate, rim magnesium niobate-lead titanate, silver, nickel, nickel-coated polymer spheres, gold-coated polymer spares (gold-coated polymer spheres), tin solder, graft, tantalum nitides, metal silcon nitride, carbon black, silica It may be selected from the group consisting of, clay and aluminum borate.

The dispersant may be selected from the group consisting of carboxylates, sulfonates and phosphates.

The amine-based curing agent may be selected from the group consisting of 4,4'-diamino diphenyl sulfone (DDS), 4,4'-diamino diphenyl methane, dicyan diamide (Dicy) and mixtures thereof. .

The imidazole series curing accelerator may be selected from the group consisting of 2-ethyl-methyl imidazole, 1- (2-cyanoethyl) -2-alkyl imidazole, 2-phenyl imidazole, and mixtures thereof.

In addition, the present invention provides a circuit board manufactured using the epoxy resin composition containing the bisphenol A epoxy resin.

Hereinafter, described in detail with respect to the present invention is as follows.

Bisphenol A epoxy resin (a) having an average epoxy equivalent of 400 to 1,000 used in the present invention is dissolved in a mixed solvent such as methyl ethyl ketone (MEK), dimethyl formamide (DMF), methyl cellosolve (MCS), and the like. It can be used, bromine is contained in 15 to 55% by weight, which is to impart flame retardancy to the circuit board manufactured by molding the resin.

Polymer bisphenol A epoxy resin (b) having an average epoxy equivalent of 2,000 to 10,000 can be dissolved in mixed solvents such as methyl ethyl ketone (MEK), dimethyl formamide (DMF) and methyl cellosolve (MCS). The polymer bisphenol A epoxy resin (b) is preferably in the range of 5 to 70 parts by weight, more preferably in the range of 10 to 60 parts by weight based on 100 parts by weight of the bisphenol A epoxy resin (a).

When the polymer bisphenol A epoxy (b) is used, the copper foil adhesion and toughness of the resin composition are increased, but when 70 parts by weight or more compared to the bisphenol A epoxy (a), the glass transition temperature (Tg) of the resin composition may be reduced. have.

The polyfunctional epoxy resin (c) has three or more epoxy functional groups per molecule, and generally has trifunctional, tetrafunctional and novolak resins, methyl ethyl ketone (MEK), dimethyl formamide (DMF) and methyl cell. It can be used by melt | dissolving in mixed solvents, such as Rosolve (MCS).

The polyfunctional epoxy is suitably in the range of 200 to 400 equivalent weight and the weight average molecular weight in the range of 200 to 1,500, the polyfunctional epoxy resin is in the range of 1 to 100 parts by weight based on 100 parts by weight of bisphenol A epoxy resin (a) Is preferred, and more preferably in the range of 3 to 50 parts by weight. If the polyfunctional epoxy is 100 parts by weight or more, the crosslinking density of the resin is increased to improve heat resistance, but the brittleness of the epoxy composition is increased, which may cause a quantitative limitation in the use of the inorganic filler.

Examples of the amine curing agent (d) include aliphatic amine curing agents, alicyclic amine curing agents, aromatic amine curing agents, and the like. In particular, 4,4'- diamino diphenyl sulfone (henceforth "DOS"), 4,4'- diamino diphenyl methane, dicyan diamide (DICY), etc. are preferable. These can be used individually or in combination of 2 or more types, The 1-50 weight part is preferable with respect to 100 weight part of bisphenol-A epoxy resins (a), More preferably, the range of 2-10 is preferable. When the amine curing agent is 1 part by weight or less, sufficient curing is not achieved. When the amine curing agent is 50 parts by weight or more, rapid curing occurs and adhesiveness and storage stability are lowered.

The imidazole series curing accelerator (e) can make imidazole compounds such as 2-ethyl-4methyl imidazole, 1- (2-cyanoethyl) -2-alkyl imidazole, and 2-phenyl imidazole. These can be used individually or in combination of 2 or more types, The range of 0.01-1 weight part is preferable with respect to 100 weight part of bisphenol-A epoxy resins (a), More preferably, the range of 0.05-0.3 is preferable. If the imidazole-based curing accelerator is 0.01 parts by weight or less, the curing rate is significantly lowered, uncured, and if more than 1 part by weight, rapid curing occurs and the adhesion and storage stability is lowered.

There is no particular limitation on the inorganic filler (f) that can be used in the present invention, depending on the desired physical properties barium titanium oxide (barium tiatanum oxide), barium strontium titanate, titanium oxide (titanium oxide) Lead ziroconium titanate, lead lanthanum zirconate titanate, lead magnesium niobate-lead titanate, silver, nickel, nickel Nickel-coated polymer spheres, gold-coated polymer spheres, tin solder, graft, tantalum nitides, metal silicon knits Metal silcon nitride, carbon black, silica, clay and aluminum borate may be used, and 0.1 to 10 μm as observed under an electron microscope Preference is given to using powders having an average particle size of.

There is no particular limitation on the dispersing agent (g) which can be used in the present invention, and various kinds such as carboxylate, sulfonate, and phosphate may be used depending on the inorganic filler (f). have. The dispersant (g) is preferably in the range of 0.005 to 0.05 parts by weight, more preferably in the range of 0.01 to 0.03 parts by weight based on 1 part by weight of the inorganic filler (f).

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.

[Examples 1 to 7 and Comparative Examples 1 to 4]: An epoxy resin composition and a copper clad laminate were added according to the composition of Table 1 below to prepare Examples and Comparative Examples as follows.

Example 1

100 g of bisphenol A type epoxy resin (Beklite, LER1222) having an average epoxy equivalent of 400 to 1,000, 5 g of a polyfunctional epoxy resin (Berlite, LER451), a polymer bisphenol A type epoxy resin having an average epoxy equivalent of 2,000 to 10,000 ( Kukdo Chemical, YD019) 20g, amine-based curing agent dicyandiamide (2.7g), imidazole-based curing accelerator 2PI (2-Phenylimidazole) 0.15g of methyl ethyl ketone: dimethyl formamide in a ratio of 1: 1 The varnish was prepared by melting 45% of the solids.

The varnish prepared above was impregnated with glass fibers (Nitobo, Japan, 7628), followed by hot air drying to prepare a prepreg. After the five prepregs were laminated, the copper foil having a thickness of 35 µm was placed on both sides, and the laminated sheets were laminated.

Example 2

A varnish was prepared in the same manner as in Example 1, except that the content of the polymer bisphenol A epoxy resin was increased to 40 g in Example 1, and then a circuit board of 1 mm was prepared.

Example 3

A varnish was prepared in the same manner as in Example 1, except that the content of the polymer bisphenol A epoxy resin was increased to 70 g in Example 1, and then a circuit board of 1 mm was prepared.

Comparative Example 1

100 g of bisphenol A type epoxy resin (Becklite, Inc., LER1222) having an average epoxy equivalent of 400 to 1,000, 5 g of a polyfunctional epoxy resin (Berlite, Inc., LER451), 2.7 g of an amine curing agent Dicyandiamide, imida A varnish was prepared by dissolving 0.3 g of a sol-based curing accelerator 2PI (2-Phenylimidazole) in a mixed solution having a ratio of methyl ethyl ketone: dimethyl formamide at a ratio of 1: 1 to 45% solids. At this time, the polymer bisphenol A epoxy resin of Example 1 was not added.

The varnish prepared above was impregnated with glass fibers (Nitobo, Japan, 7628), followed by hot air drying to prepare a prepreg. After the five prepregs were laminated, the copper foil having a thickness of 35 µm was placed on both sides, and the laminated sheets were laminated.

Comparative Example 2

100 g of bisphenol A type epoxy resin (Becklite, Inc., LER1222) having an average epoxy equivalent of 400 to 1,000, 5 g of a polyfunctional epoxy resin (Berlite, Inc., LER451), 2.7 g of an amine curing agent Dicyandiamide, imida 0.15 g of 2-sol (Phenylimidazole) sol accelerator, 5 g of butadiene acrylonitrile copolymer rubber (Nippon Zeon, NBR1031) having a weight average molecular weight in the range of 200,000 to 300,000, and a reactive polyvinyl acetal having a weight average molecular weight in the range of 100,000 to 300,000. A varnish was prepared by dissolving 10 g of a resin (KS-23Z, Sekisui Co., Ltd.) in a mixed solution having a ratio of methyl ethyl ketone: dimethyl formamide so that the solid content was 45%.

The varnish prepared above was impregnated with glass fibers (Nitobo, Japan, 7628), followed by hot air drying to prepare a prepreg. After the five prepregs were laminated, the copper foil having a thickness of 35 µm was placed on both sides, and the laminated sheets were laminated.

Example 4

100 g of bisphenol A type epoxy resin (Beklite, LER1222) having an average epoxy equivalent of 400 to 1,000, 5 g of a polyfunctional epoxy resin (Berlite, LER451), a polymer bisphenol A type epoxy resin having an average epoxy equivalent of 2,000 to 10,000 ( Kukdo Chemical, YD019) 40g, amine-based curing agent dicyandiamide (2.7g), imidazole-based curing accelerator 2PI (2-Phenylimidazole) 0.15g of methyl ethyl ketone: dimethyl formamide in a ratio of 1: 1 The varnish was prepared by melting 45% of the solids.

As an inorganic filler, put 300g of ferroelectric ceramic BaTiO3 powder (BK05, Sakai, Japan), 60g mixed solution with a MEK: DMF ratio of 1: 1, and 5g of a dispersant (BYK-chemie, BYK-W9010) in a ball mill container for 2 hours. After the ball mill was used to disperse the inorganic filler, it was mixed with the varnish prepared in Example 2 to prepare a slurry. The slurry prepared above was impregnated with glass fiber (Nitobo, Japan, 7628), followed by hot air drying to prepare a prepreg. After the five prepregs were laminated, copper foil having a thickness of 35 μm was laminated on both sides, and then laminated, and then heated and pressed at 180 ° C. for 90 minutes using a press to prepare a circuit board having a thickness of 1 mm.

Example 5

In Example 4, except that the inorganic filler was increased to 750 g and the dispersant was increased to 10 g, a slurry was prepared in the same manner as in Example 4, and a circuit board having a thickness of 1 mm was prepared.

Example 6

In Example 4, the slurry was added in the same manner as in Example 4, except that the imidazole-based curing accelerator 2PI (2-Phenylimidazole) was increased to 0.3 g, the inorganic filler was increased to 750 g, and the dispersant was increased to 10 g. After manufacturing, a circuit board having a thickness of 1 mm was prepared.

Example 7

Except for increasing the imidazole-based curing accelerator 2PI (2-Phenylimidazole) to 0.3g in Example 4, and to increase the inorganic filler to 750g, after the slurry was prepared in the same manner as in Example 4, a circuit having a thickness of 1mm The substrate was prepared.

Comparative Example 3

750 g of inorganic filler (BT05), 100 g of a mixed solution having a ratio of MEK: DMF 1: 1, and 10 g of a dispersant (BYK-chemie, BYK-W9010) were placed in a ball mill and ball milled for 2 hours to disperse the inorganic filler. A slurry was prepared by mixing with the varnish prepared in Comparative Example 1. The slurry prepared above was impregnated with glass fiber (Nitobo, Japan, 7628), followed by hot air drying to prepare a prepreg.

After the five prepregs were laminated, the copper foil having a thickness of 35 µm was placed on both sides, and the laminated sheets were laminated.

[Comparative Example 4]

750 g of inorganic filler (BT05), 100 g of a mixed solution having a 1: 1 ratio of dimethyl formamide, and 10 g of a dispersant (BYK-chemie, BYK-W9010) were put into a ball mill and ball milled for 2 hours. After dispersing, it was mixed with the varnish prepared in Comparative Example 2 to prepare a slurry. The slurry prepared above was impregnated with glass fiber (Nitobo, Japan, 7628), followed by hot air drying to prepare a prepreg. After the five prepregs were laminated, the copper foil having a thickness of 35 μm was placed on both sides, and the laminate was laminated. Then, a circuit board having a thickness of 1 mm was manufactured by heating and pressing at 180 ° C. for 90 minutes using a press.

Example (g) Comparative Example (g) One 2 3 4 5 6 7 One 2 3 4 Bisphenol A epoxy resin (standard equivalent 400 to 1,000) 100 100 100 100 100 100 100 100 100 100 100 Multifunctional Epoxy Resin 5 5 5 5 5 5 5 5 5 5 5 Polymer bisphenol A epoxy resin (standard equivalent 2,000 to 10,000) 20 40 70 40 40 40 40 - - - - Butadiene Acrylonitrile Copolymer Rubber - - - - - - - - 5 - 5 Responsive Polyvinyl Acetal Resin - - - - - - - - 10 - 10 Amine Curing Agents Dicyandiamide 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 Imidazole series curing accelerator 0.15 0.15 0.15 0.15 0.15 0.3 0.3 0.3 0.15 0.3 0.15 Inorganic filler - - - 300 750 750 750 - - 750 750 Dispersant - - - 5 10 10 5 - - 10 10

With the specimens prepared in Examples and Comparative Examples, the glass transition temperature (Tg), the copper foil adhesion, the thermal expansion coefficient and the dielectric constant in the range of 30 to 260 ℃ of the resin composition were measured. Glass transition temperature was measured using DSSI (DSC, Q100). Copper foil adhesion of the specimen was measured at room temperature using a tensile strength meter of ZWICK (ZWICK) at a rate of 50mm / min, was measured while peeling the copper foil 1cm in width. The thermal expansion rate of 30 to 260 ° C was used as a TMA (TMA), and the thermal expansion coefficient of the specimen was measured by increasing the temperature at a rate of 10 ° C / min in the range of 30 to 260 ° C. In addition, the dielectric constant of the specimen was measured by the Heispec Pec (HP) Impedance analyzer (impedance analyzer, 4194A) by the JIS method and the results are shown in Table 2 below.

Example (g) Comparative Example (g) One 2 3 4 5 6 7 One 2 3 4 Glass transition temperature (℃) 131 128 112 115 94 96 117 132 130 116 85 Copper foil adhesive strength (35㎛, kgf / cm) 2.2 2.5 2.4 1.8 1.5 1.4 1.5 2.0 1.3 1.0 0.6 Z-axis expansion rate (%) (30 ~ 260 ℃) 3.5 3.6 3.6 3.1 2.4 2.4 2.4 3.5 3.7 2.4 2.6 permittivity 4.7 4.7 4.8 14 20 21 20 4.6 4.2 20 16

The Examples and Comparative Examples are for manufacturing a circuit board material for a built-in storage battery using an inorganic filler, and from the results of Table 2, the target according to the amount of the inorganic filler in Examples 4 to 7 and Comparative Examples 3 and 4 It can be seen that the dielectric constant of the material becomes larger. However, when the amount of the inorganic filler is increased in order to obtain a product having a high dielectric constant, the amount of the epoxy resin serving as a binder of the inorganic filler is relatively decreased, resulting in a decrease in mechanical properties of the product, Examples 4 to 7 and Comparative Examples 3 and 4 As can be seen from the results of the use of the dispersant according to the inorganic filler phenomenon that the glass transition temperature drops.

Therefore, in order to compensate the mechanical properties according to the inorganic filler containing polymer bisphenol A epoxy resin was added in Examples 1 to 7, butadiene acrylonitrile copolymer rubber (Nippon Zeon, NBR1031) of the other polymer material in Comparative Examples 2 and 4 ) Or reactive polyvinyl acetal resin (KS-23Z from Sekisui) was added.

As can be seen from the above results, when an appropriate amount of the polymer bisphenol A epoxy resin was added, it was confirmed that the copper foil adhesion of the epoxy resin composition itself except the inorganic material was improved within the range that the glass transition temperature did not drop significantly. When the filler is added, the dielectric constant is increased, but it was confirmed that the copper foil adhesive strength drops.

As described above, the present invention can produce a circuit board material having excellent physical properties using only the epoxy resin composition itself containing no inorganic filler by using the polymer bisphenol A type epoxy, while satisfying the desired physical properties when using the inorganic filler. It is a useful invention that the effect of increasing the inorganic filler content in the epoxy resin composition can be compensated for the mechanical properties such as copper foil adhesion strength using the inorganic filler without deteriorating other physical properties.

While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and modifications fall within the scope of the appended claims. It is also natural.

Claims (7)

To 100 parts by weight of bisphenol A epoxy resin having an average epoxy equivalent of 400 to 1,000, 5 to 80 parts by weight of a polymer type bisphenol A epoxy resin having an average epoxy equivalent of 2,000 to 10,000; 1 to 100 parts by weight of the multifunctional epoxy resin; 1 to 4 parts by weight of an amine curing agent; And 0.01 to 1 part by weight of imidazole series curing accelerator; Epoxy resin composition containing a bisphenol A epoxy resin comprising a. The method of claim 1, The epoxy resin composition containing a bisphenol A epoxy resin, characterized in that it further comprises an inorganic filler and a dispersant. The method of claim 2, The inorganic fillers include barium tiatanum oxide, barium strontium titanate, titanium titanate, lead ziroconium titanate, lead lentaum zir Lead lanthanum zirconate titanate, rim magnesium niobate-lead titanate, silver, nickel, nickel-coated polymer spheres, gold-coated polymer spares (gold-coated polymer spheres), tin solder, graft, tantalum nitides, metal silcon nitride, carbon black, silica Epoxy resin composition containing bisphenol A type epoxy resin, characterized in that it is selected from the group which consists of the following), a clay, and aluminum borate. The method of claim 2, The dispersant is an epoxy resin composition containing a bisphenol A epoxy resin, characterized in that selected from the group consisting of carboxylate, sulfonate and phosphate. The method of claim 1, The amine-based curing agent is selected from the group consisting of 4,4'-diamino diphenyl sulfone (DDS), 4,4'-diamino diphenyl methane, dicyane diamide (Dicy) and mixtures thereof An epoxy resin composition containing a bisphenol A type epoxy resin. The method of claim 1, The imidazole series curing accelerator is selected from the group consisting of 2-ethyl-methyl imidazole, 1- (2-cyanoethyl) -2-alkyl imidazole, 2-phenyl imidazole and mixtures thereof. An epoxy resin composition containing a bisphenol A epoxy resin. A circuit board manufactured using the epoxy resin composition containing the bisphenol A epoxy resin of claim 1.