KR102172293B1 - Epoxy resin composite and printed circuit board comprising the same - Google Patents

Abstract

The epoxy resin composition according to an embodiment of the present invention comprises 10 to 70 wt% of an epoxy compound and a curing agent, and 30 to 90 wt% of an inorganic filler including a hollow filler and boron nitride, and 10 parts by weight of the hollow filler The boron nitride is included in an amount of 0.1 to 100 parts by weight.

Description

Epoxy resin composition and a printed circuit board comprising the same TECHNICAL FIELD [EPOXY RESIN COMPOSITE AND PRINTED CIRCUIT BOARD COMPRISING THE SAME}

The present invention relates to an epoxy resin composition, and more particularly, to an epoxy resin composition and a printed circuit board including the same.

A printed circuit board (PCB) includes a circuit pattern layer formed on an insulating layer, and various electronic components may be mounted on the printed circuit board. The electronic component mounted on the printed circuit board may be, for example, a heating element. The heat emitted by the heating element may degrade the performance of the printed circuit board.

As electronic components become highly integrated and have higher capacity, interest in the heat dissipation problem of a printed circuit board is increasing. In order to solve the heat dissipation problem of a printed circuit board, an insulating layer having high thermal conductivity and low dielectric constant is required.

When the epoxy resin composition included in the insulating layer of the printed circuit board is filled with a high-density inorganic filler, the thermal conductivity is improved, but the dielectric constant is increased.

The technical problem to be achieved by the present invention is to provide an epoxy resin composition and a printed circuit board including the same.

The epoxy resin composition according to an embodiment of the present invention comprises 10 to 70 wt% of an epoxy compound and a curing agent, and 30 to 90 wt% of an inorganic filler including a hollow filler and boron nitride, and 10 parts by weight of the hollow filler The boron nitride is included in an amount of 0.1 to 100 parts by weight.

The hollow filler may include a hollow glass bubble.

The surface of the hollow glass sphere may be coated with aluminum oxide.

The inorganic filler may further include aluminum oxide.

The boron nitride may be included in an amount of 1 to 20 parts by weight, and the aluminum oxide may be included in an amount of 1 to 35 parts by weight based on 10 parts by weight of the hollow glass sphere.

The diameter of the hollow glass sphere may be 10 to 30 μm, and the air volume of the hollow glass sphere may be 70 to 90 vol% of the hollow glass sphere.

The aluminum oxide may be coated to a thickness of 5 to 20 μm.

The epoxy compound may include a dicyclopentadiene (DCPD) type epoxy compound, and the curing agent may include dicyandiamide.

A printed circuit board according to an embodiment of the present invention includes a substrate, an insulating layer formed on the substrate, and a circuit pattern formed on the insulating layer, and the insulating layer includes an epoxy compound, a curing agent, and a hollow filler ( hollow filler) and an inorganic filler including boron nitride, and the boron nitride is 0.1 to 100 parts by weight based on 10 parts by weight of the hollow filler.

A printed circuit board according to an embodiment of the present invention includes a plurality of circuit pattern layers that are sequentially disposed, and a plurality of insulating layers formed between the plurality of circuit pattern layers, and at least some of the plurality of insulating layers The insulating layer includes an epoxy compound, a curing agent, and an inorganic filler including a hollow filler and boron nitride, and the boron nitride is 0.1 to 100 parts by weight based on 10 parts by weight of the hollow filler. Include.

According to an embodiment of the present invention, an epoxy resin composition having a low dielectric constant as well as high heat dissipation performance can be obtained. Accordingly, by dissipating heat generated during operation of a component mounted on or under a printed circuit board, the temperature of the component can be reduced, and life and reliability of the component can be improved.

1 is a cross-sectional view of a hollow glass sphere according to an embodiment of the present invention.
2 is a cross-sectional view of a hollow glass sphere coated with aluminum oxide according to an embodiment of the present invention.
3 is a cross-sectional view of a printed circuit board according to an embodiment of the present invention.
4 is a cross-sectional view of a four-layer printed circuit board according to an embodiment of the present invention.
5 is a cross-sectional view of a four-layer printed circuit board according to another embodiment of the present invention.
6 is a cross-sectional view of a 10-layer printed circuit board according to an embodiment of the present invention.
7 is a cross-sectional view of a 10-layer printed circuit board according to another embodiment of the present invention.
8 is a cross-sectional view of a 12-layer printed circuit board according to an embodiment of the present invention.
9 is a cross-sectional view of a 12-layer printed circuit board according to another embodiment of the present invention.

The present invention is intended to illustrate and describe specific embodiments in the drawings, as various changes may be made and various embodiments may be provided. However, this is not intended to limit the present invention to a specific embodiment, it is to be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

Terms including ordinal numbers, such as second and first, may be used to describe various elements, but the elements are not limited by the terms. These terms are used only for the purpose of distinguishing one component from another component. For example, without departing from the scope of the present invention, a second component may be referred to as a first component, and similarly, a first component may be referred to as a second component. The term and/or includes a combination of a plurality of related listed items or any of a plurality of related listed items.

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof, does not preclude in advance.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms as defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and should not be interpreted as an ideal or excessively formal meaning unless explicitly defined in this application. Does not.

When a part of a layer, film, region, plate, etc. is said to be "on" another part, this includes not only the case where the other part is "directly above", but also the case where there is another part in the middle. Conversely, when one part is "right above" another part, it means that there is no other part in the middle.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings, but the same reference numerals are assigned to the same or corresponding components regardless of the reference numerals, and redundant descriptions thereof will be omitted.

In the present specification, wt% may be replaced by parts by weight.

The epoxy resin composition according to an embodiment of the present invention includes an epoxy compound and a curing agent, and an inorganic filler including a hollow filler and boron nitride.

Here, the epoxy compound and the curing agent are included in 10 to 70 wt%, preferably 20 to 50 wt% of the total epoxy resin composition, and the inorganic filler is included in 30 to 90 wt%, preferably 50 to 80 wt% of the total epoxy resin composition. I can. When the epoxy compound and the curing agent are contained in an amount of 10 wt% or more and 70 wt% or less of the total epoxy resin composition, adhesion is good and thickness control may be easy. In addition, when the inorganic filler is included in an amount of 30 to 90 wt%, high thermal conductivity, low thermal expansion, and high temperature heat resistance of the epoxy resin composition may be improved. High thermal conductivity, low thermal expansion, and high temperature heat resistance are better as the amount of the inorganic filler added increases, but does not improve according to the volume fraction, and improves drastically from a specific amount. However, when the amount of the inorganic filler added is greater than 90 wt%, the viscosity increases and moldability is weakened.

The epoxy compound included in the epoxy resin composition according to an embodiment of the present invention may include at least one of a DCPD (Dicyclopentadien) type epoxy compound and a novolac type epoxy compound.

The DCPD-type epoxy compound may include, for example, Formula 1 below. However, the present invention is not limited thereto, and various DCPD-type epoxy compounds may be included in addition to Formula 1.

[Formula 1]

The novolak-type epoxy compound may contain, for example, Formula 2 below. However, the present invention is not limited thereto, and various novolak-type epoxy compounds may be included in addition to Formula 2.

[Formula 2]

And, the epoxy resin composition according to an embodiment of the present invention may further include an amorphous epoxy compound. The amorphous epoxy compound may be included in an amount of 1 to 40 parts by weight based on 10 parts by weight of a DCPD-type epoxy compound or a novolac-type epoxy compound. When the amorphous epoxy compound is included in such a ratio, room temperature stability can be improved.

The amorphous epoxy compound may be a conventional amorphous epoxy compound having two or more epoxy groups in the molecule.

An amorphous epoxy compound is, for example, bisphenol A, bisphenol F, 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl Sulfone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylketone, fluorenebisphenol, 4,4'-biphenol,3,3',5,5'-tetra Methyl-4,4'-dihydroxybiphenyl, 2,2'-biphenol, resorcin, catechol, t-butylcatechol, hydroquinone, t-butylhydroquinone, 1,2-dihydroxynaphthalene, 1 ,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydr Roxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2, Divalent phenols such as 8-dihydroxynaphthalene, allylated or polyallylated dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, allylated phenol novolac, or phenol novolac, bisphenol A novolac , o-cresol novolac, m-cresol novolac, p-cresol novolac, xylenol novolac, poly-p-hydroxystyrene, tris-(4-hydroxyphenyl)methane, 1,1,2,2 -Tetrakis(4-hydroxyphenyl)ethane, fluoroglycinol, pyrogallol, t-butyl pyrogallol, allylated pyrogallol, polyallyled pyrogallol, 1,2,4-benzenetriol, 2, One of trivalent or higher phenols such as 3,4-trihydroxybenzophenone, phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene resin, halogenated bisphenols such as tetrabromobisphenol A, and mixtures selected from these It may be a glycidyl ether product derived from.

An example of the amorphous epoxy compound is the same as in Formula 3. Formula 3 is a bisphenol A type epoxy compound.

[Formula 3]

The curing agent included in the epoxy resin composition according to an embodiment of the present invention may include at least one of an amine-based curing agent, a xylol-based curing agent, an acid anhydride-based curing agent, a phenolic curing agent, a DCPD-based curing agent, and a TCPD-based curing agent. For example, the curing agent included in the epoxy resin composition according to an embodiment of the present invention, dicyandiamide of Formula 4, diaminodiphenylsulfone of Formula 5, and DOPO-ATN of Formula 6 It may be at least one of (6-H-dibenz[c,e][1,2]oxaphosphorin-6-[2,5-bis(oxiranylmethoxy)phenyl]-6-oxide-Aminotriazine Novolac).

[Formula 4]

[Formula 5]

[Formula 6]

The epoxy resin composition according to an embodiment of the present invention may contain 0.6 to 1.1 equivalents of a curing agent per 1 equivalent of the epoxy compound. For example, 0.1 to 10 parts by weight, preferably 1 to 6 parts by weight, and more preferably 2 to 4 parts by weight, based on 10 parts by weight of the DCPD-type epoxy compound of Chemical Formula 1 may be included. When the epoxy compound and the curing agent are included in these numerical ranges, adhesion is good and thickness control may be easy.

The epoxy resin composition according to an embodiment of the present invention may further include a curing accelerator. The curing accelerator includes, for example, an amine curing accelerator, an imidazole curing accelerator, a urea curing accelerator, an acid curing accelerator, and the like. Specifically, 1,8-diazabicyclo (5,4,0 ) Tertiary amines such as undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol, 2-methylimidazole, 2-phenylimidazole, 2- And imidazoles such as phenyl-4-methylimidazole and 2-heptadecylimidazole.

Formula 7 is an example of an imidazole curing accelerator.

[Formula 7]

The epoxy resin composition according to an embodiment of the present invention includes a hollow filler and an inorganic filler including boron nitride. Here, the hollow filler may include a hollow glass bubble (HGB). A cross section of a hollow glass sphere is illustrated in FIG. 1. Referring to FIG. 1, a hollow glass bubble (HGB, 100) has an air gap (110) formed in the center portion, and the hollow glass sphere has a density of about 0.6 g/cc and a strength of about It is 200 MPa, has a diameter of 10 to 30 µm, and an air volume of the air gap is 70 to 90 vol% of the hollow glass sphere. When the hollow glass sphere is included as an inorganic filler in this way, the dielectric constant of the epoxy resin composition can be lowered. In particular, when the diameter and the amount of air of the hollow glass sphere are within these numerical ranges, high thermal conductivity and low dielectric constant can be maintained.

In this case, boron nitride may be included in an amount of 0.1 to 100 parts by weight based on 10 parts by weight of the hollow filler. When the hollow filler and boron nitride are included within such a numerical range, an epoxy resin composition having high thermal conductivity and low dielectric constant can be obtained.

Meanwhile, the surface of the hollow glass sphere may be coated with aluminum oxide. 2 shows a cross-section of a hollow glass sphere (Al-HGB) coated with aluminum oxide. Referring to FIG. 2, the thickness of the aluminum oxide 120 coated on the hollow glass sphere 100 may be 5 to 20 μm. When aluminum oxide is coated to a thickness of 5 to 20 μm, the heat conduction performance of the hollow glass sphere may be increased.

And, according to an embodiment of the present invention, the inorganic filler may further include aluminum oxide. At this time, boron nitride may be included in an amount of 1 to 20 parts by weight, and aluminum oxide may be included in an amount of 1 to 35 parts by weight based on 10 parts by weight of the hollow glass sphere. When hollow glass spheres, boron nitride, and aluminum oxide are included within such a numerical range, an epoxy resin composition having high thermal conductivity and low dielectric constant can be obtained.

In addition, the epoxy resin composition according to an embodiment of the present invention comprises at least one of a ceramic inorganic filler including at least one of aluminum nitride, silicon nitride, silicon carbide, beryllium oxide and cerium oxide, diamond, carbon nanotubes, and graphene. It may further include at least one of the included carbon-based inorganic filler and insulation-treated metal particles.

According to one embodiment of the present invention, the epoxy compound, the hardener and the inorganic filler are ball mill, impeller mixing, bead mill, basket mill, planetary mill, dino mill, It can be mixed using a 3 roll mill or the like. At this time, a solvent and a dispersant may be added for even dispersion. The solvent may be added to adjust the viscosity, and the viscosity of the solvent may be 1 to 100,000 Cps. The solvent is, for example, water, methanol, ethanol, isopropanol, butyl carbitol, MEK, toluene, xylene, diethylene glycol, formamide, α-terpineneol, γ-butyrolactone, methylcellulose, propyl It may contain at least one of methylcellulose, cyclopentanone, BCE (Butyl Cellosolve), and DBE (Dibasic ester). In addition, the dispersant may be selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, octyl alcohol and acrylic and urethane polymers.

The epoxy resin composition according to an embodiment of the present invention may further include a silane-based additive to increase bonding between particles. The silane-based additives are, for example, 1-trimethylsilylbut-1 (yne)-3-ol, aryltrimethylsilane, trimethylsilyl methanesulfonate, trimethylsilyl tricholoacetate, methyl trimethylsilylacetate, trimethylsilyl propionic acid, etc. to be.

The epoxy resin composition according to an embodiment of the present invention may further contain phosphorus (P) to increase flame retardancy. Phosphorus may be included in 0.5 to 4 wt% of the epoxy compound, the curing agent and the curing accelerator.

The epoxy resin composition according to an embodiment of the present invention may be applied to a printed circuit board.

3 is a cross-sectional view of a printed circuit board according to an embodiment of the present invention.

Referring to FIG. 3, the printed circuit board 300 includes a substrate 310, an insulating layer 320, and a circuit pattern 330.

The substrate 310 may be a metal plate made of copper, aluminum, nickel, gold, platinum, and an alloy selected from these. The substrate 310 is not limited to a metal plate and may be made of various materials having excellent thermal conductivity.

An insulating layer 320 made of an epoxy resin composition according to an embodiment of the present invention is formed on the substrate 310.

A circuit pattern 330 is formed on the insulating layer 320. The circuit pattern 330 may be made of a metal such as copper or nickel.

The insulating layer 320 insulates between the substrate 310 and the circuit pattern 330.

4 is a cross-sectional view of a four-layer printed circuit board according to an embodiment of the present invention, and FIG. 5 is a cross-sectional view of a four-layer printed circuit board according to another embodiment of the present invention.

Referring to FIG. 4, a four-layer printed circuit board 400 includes a plurality of circuit pattern layers 410 that are sequentially disposed, and a plurality of insulating layers 420 formed between the plurality of circuit pattern layers 410. do. That is, the printed circuit board 400 includes an insulating layer 420-1 having a circuit pattern layer 410-1 formed on the lower surface thereof, and an insulating layer having circuit pattern layers 410-2 and 410-3 formed on the upper and lower surfaces thereof ( 420-2) and an insulating layer 420-3 on which the circuit pattern layer 410-4 is formed on the upper surface.

Here, the insulating layer 420 insulates the circuit pattern layer 410. In addition, the circuit pattern layer 410 may be made of a metal such as copper or nickel. Although not shown, the four-layer printed circuit board 400 may be formed on the substrate. Here, the substrate may include copper, aluminum, nickel, gold, platinum, and an alloy selected from these, but is not limited thereto.

Referring to FIG. 5, the four-layer printed circuit board 400 may further include a through hole 430 connecting some of the plurality of circuit pattern layers 410. That is, it is formed to penetrate the entire printed circuit board 400 like the through hole 430-1, or penetrate a part of the printed circuit board 400 like the through hole 430-2 or the through hole 430-3. It can be formed to be.

The inside of the through hole 430 may be surface-plated with copper (Cu) and then filled with an epoxy resin or filled with copper.

4 to 5, at least one of the plurality of insulating layers includes an epoxy resin composition according to an embodiment of the present invention. For example, the insulating layer 420-1 formed between the circuit pattern layer 410-1 and the circuit pattern layer 410-2, that is, the lowermost insulating layer 420-1 and the circuit pattern layer 410- 3) At least one of the insulating layer 420-3 formed between the circuit pattern layer 410-4, that is, the uppermost insulating layer 420-3 contains an epoxy resin composition according to an embodiment of the present invention. do. In this way, when an insulating layer containing an epoxy resin composition having a high thermal conductivity and a low dielectric constant is disposed on at least one of the top and bottom portions of the printed circuit board, heat generated by the heating element is transferred not only in the horizontal direction but also in the vertical direction. Can be dispersed.

In addition, some of the remaining insulating layers 420-2 among the plurality of insulating layers may include glass fibers impregnated with an epoxy resin. Glass fibers impregnated with an epoxy resin may include, for example, FR (Flame Retardant)-4.

6 is a cross-sectional view of a 10-layer printed circuit board according to an embodiment of the present invention, and FIG. 7 is a cross-sectional view of a 10-layer printed circuit board according to another embodiment of the present invention.

6 to 7, the 10-layer printed circuit board 600 includes a plurality of circuit pattern layers 610 that are sequentially disposed, and a plurality of insulating layers 620 formed between the plurality of circuit pattern layers 610. Includes.

For example, a plurality of circuit pattern layers 610-1, ..., 610-10 are sequentially disposed, and a plurality of circuit pattern layers 610-1, ..., 610-10 Insulating layers 620-1, ..., 620-9 may be formed.

Here, at least some of the plurality of insulating layers 620-1, ..., 620-9 may include the epoxy resin composition according to an embodiment of the present invention. For example, an insulating layer 620-1 formed between the circuit pattern layer 610-1 and the circuit pattern layer 610-2, that is, the lowermost insulating layer 620-1 and the circuit pattern layer 610- 9) and the insulating layer 620-9 formed between the circuit pattern layer 610-10, that is, at least one of the uppermost insulating layer 620-9 contains an epoxy resin composition according to an embodiment of the present invention can do.

In addition, at least one of the insulating layer 620-2 formed on the lowermost insulating layer 620-1 and the insulating layer 620-8 formed below the uppermost insulating layer 620-9 is also present in the present invention. It may include an epoxy resin composition according to an embodiment of.

8 is a cross-sectional view of a 12-layer printed circuit board according to an embodiment of the present invention, and FIG. 9 is a cross-sectional view of a 12-layer printed circuit board according to another embodiment of the present invention.

8 to 9, a 12-layer printed circuit board 800 includes a plurality of circuit pattern layers 810 that are sequentially disposed, and a plurality of insulating layers 820 formed between the plurality of circuit pattern layers 810 Includes.

For example, a plurality of circuit pattern layers 810-1, ..., 810-12 are sequentially disposed, and a plurality of circuit pattern layers 810-1, ..., 810-12 Insulating layers 820-1, ..., 820-11 may be formed.

Here, the insulating layer 820-1 formed between the circuit pattern layer 810-1 and the circuit pattern layer 810-2, that is, the lowermost insulating layer 820-1 and the circuit pattern layer 810-11 And at least one of the insulating layer 820-11 formed between the circuit pattern layer 810-12, that is, the uppermost insulating layer 820-11, may include an epoxy resin composition according to an embodiment of the present invention. have.

Alternatively, at least one of the insulating layer 820-2 formed on the lowermost insulating layer 820-1 and the insulating layer 820-10 formed under the uppermost insulating layer 820-11 is also one of the present invention. It may include the epoxy resin composition according to the embodiment.

As described above, by curing the epoxy resin composition according to an embodiment of the present invention and using it as an insulating layer, a printed circuit board having excellent heat dissipation performance and low dielectric constant can be obtained.

Hereinafter, it will be described in more detail using Examples and Comparative Examples.

<Example 1>

19.3wt% of the DCPD-type epoxy compound of Formula 1, 5.5wt% of dicyandiamide of Formula 4, and 0.2wt% of the imidazole-based curing accelerator of Formula 7 were dissolved in MEK (Methyl Ethly Ketone) for 30 minutes, and then HGB 20wt% And boron nitride 55wt% were added and stirred for 2 hours. The solution after the completion of stirring was coated on a copper plate to a thickness of 60 μm, cured at 120° C. for 1 hour and 30 minutes, and pressurized at 180° C. for 1 hour and 30 minutes at 40 kgf/cm ² to obtain the epoxy resin composition of Example 1.

<Example 2>

After dissolving 19.3 wt% of the DCPD type epoxy compound of Formula 1, 5.5 wt% of dicyandiamide of Formula 4, and 0.2 wt% of the imidazole-based curing accelerator of Formula 7 for 30 minutes in MEK (Methyl Ethly Ketone), Al-HGB 20wt% and 55wt% boron nitride were added and stirred for 2 hours. The solution after the stirring was completed was coated on a copper plate to a thickness of 60 μm, cured at 120° C. for 1 hour and 30 minutes, and then pressurized at 180° C. for 1 hour and 30 minutes at 40 kgf/cm ² to obtain the epoxy resin composition of Example 2.

<Example 3>

After dissolving 19.3 wt% of the DCPD type epoxy compound of Formula 1, 5.5 wt% of dicyandiamide of Formula 4, and 0.2 wt% of the imidazole-based curing accelerator of Formula 7 for 30 minutes in MEK (Methyl Ethly Ketone), Al-HGB 20wt%, boron nitride 40wt%, and aluminum oxide 15wt% were added and stirred for 2 hours. The solution after the completion of stirring was coated on a copper plate to a thickness of 60 μm, cured at 120° C. for 1 hour and 30 minutes, and pressurized at 180° C. for 1 hour and 30 minutes at 40 kgf/cm ² to obtain the epoxy resin composition of Example 3.

<Example 4>

After dissolving 19.3 wt% of the DCPD type epoxy compound of Formula 1, 5.5 wt% of dicyandiamide of Formula 4, and 0.2 wt% of the imidazole-based curing accelerator of Formula 7 for 30 minutes in MEK (Methyl Ethly Ketone), Al-HGB 15wt%, boron nitride 25wt%, and aluminum oxide 35wt% were added and stirred for 2 hours. The solution after the completion of stirring was coated on a copper plate to a thickness of 60 μm, cured at 120° C. for 1 hour and 30 minutes, and pressurized at 180° C. for 1 hour and 30 minutes at 40 kgf/cm ² to obtain the epoxy resin composition of Example 4.

<Example 5>

After dissolving 19.3 wt% of the DCPD type epoxy compound of Formula 1, 5.5 wt% of dicyandiamide of Formula 4, and 0.2 wt% of the imidazole-based curing accelerator of Formula 7 for 30 minutes in MEK (Methyl Ethly Ketone), Al-HGB 20wt%, boron nitride 25wt%, and aluminum oxide 30wt% were added and stirred for 2 hours. The solution after the completion of stirring was coated on a copper plate to a thickness of 60 μm, cured at 120° C. for 1 hour and 30 minutes, and pressurized at 180° C. for 1 hour and 30 minutes at 40 kgf/cm ² to obtain the epoxy resin composition of Example 5.

<Comparative Example 1>

After dissolving 19.3 wt% of the DCPD type epoxy compound of Formula 1, 5.5 wt% of dicyandiamide of Formula 4, and 0.2 wt% of the imidazole-based curing accelerator of Formula 7 for 30 minutes in MEK (Methyl Ethly Ketone), HGB 75 wt% Was added and stirred for 2 hours. The solution after the completion of stirring was coated on a copper plate to a thickness of 60 μm, cured at 120° C. for 1 hour and 30 minutes, and pressurized at 180° C. for 1 hour and 30 minutes at 40 kgf/cm ² to obtain the epoxy resin composition of Comparative Example 1.

<Comparative Example 2>

After dissolving 19.3 wt% of the DCPD type epoxy compound of Formula 1, 5.5 wt% of dicyandiamide of Formula 4, and 0.2 wt% of the imidazole-based curing accelerator of Formula 7 for 30 minutes in MEK (Methyl Ethly Ketone), boron nitride 75 wt. % Was added and stirred for 2 hours. The solution after the completion of stirring was coated on a copper plate to a thickness of 60 μm, cured at 120° C. for 1 hour and 30 minutes, and pressurized at 180° C. for 1 hour and 30 minutes at 40 kgf/cm ² to obtain the epoxy resin composition of Comparative Example 2.

<Comparative Example 3>

19.3wt% of the DCPD-type epoxy compound of Formula 1, 5.5wt% of dicyandiamide of Formula 4, and 0.2wt% of the imidazole-based curing accelerator of Formula 7 were dissolved in MEK (Methyl Ethly Ketone) for 30 minutes, and then HGB 20wt% And aluminum oxide 55wt% was added and stirred for 2 hours. The solution after the completion of stirring was coated on a copper plate to a thickness of 60 μm, cured at 120° C. for 1 hour and 30 minutes, and pressurized at 40 kgf/cm ² at 180° C. for 1 hour and 30 minutes to obtain the epoxy resin composition of Comparative Example 3.

<Comparative Example 4>

After dissolving 19.3 wt% of the DCPD type epoxy compound of Formula 1, 5.5 wt% of dicyandiamide of Formula 4, and 0.2 wt% of the imidazole-based curing accelerator of Formula 7 for 30 minutes in MEK (Methyl Ethly Ketone), Al-HGB 75wt% was added and stirred for 2 hours. The solution after the completion of stirring was coated on a copper plate to a thickness of 60 μm, cured at 120° C. for 1 hour and 30 minutes, and pressurized at 180° C. for 1 hour and 30 minutes at 40 kgf/cm ² to obtain the epoxy resin composition of Comparative Example 4.

<Comparative Example 5>

After dissolving 19.3 wt% of the DCPD type epoxy compound of Formula 1, 5.5 wt% of dicyandiamide of Formula 4, and 0.2 wt% of the imidazole-based curing accelerator of Formula 7 for 30 minutes in MEK (Methyl Ethly Ketone), Al-HGB 20wt% and aluminum oxide 55wt% were added and stirred for 2 hours. The solution after the stirring was completed was coated on a copper plate to a thickness of 60 μm, cured at 120° C. for 1 hour and 30 minutes, and pressurized at 180° C. for 1 hour and 30 minutes at 40 kgf/cm ² to obtain the epoxy resin composition of Comparative Example 5.

<Comparative Example 6>

19.3 wt% of the DCPD-type epoxy compound of Formula 1, 5.5 wt% of dicyandiamide of Formula 4, and 0.2 wt% of the imidazole-based curing accelerator of Formula 7 were dissolved in MEK (Methyl Ethly Ketone) for 30 minutes, and then HGB 15 wt% , Boron nitride 25wt%, aluminum oxide 35wt% were added and stirred for 2 hours. The solution after the completion of stirring was coated on a copper plate to a thickness of 60 μm, cured at 120° C. for 1 hour and 30 minutes, and pressurized at 180° C. for 1 hour and 30 minutes at 40 kgf/cm ² to obtain the epoxy resin composition of Comparative Example 6.

<Comparative Example 7>

19.3wt% of the DCPD-type epoxy compound of Formula 1, 5.5wt% of dicyandiamide of Formula 4, and 0.2wt% of the imidazole-based curing accelerator of Formula 7 were dissolved in MEK (Methyl Ethly Ketone) for 30 minutes, and then HGB 20wt% , Boron nitride 25wt%, aluminum oxide 30wt% were added and stirred for 2 hours. The solution after the completion of stirring was coated on a copper plate to a thickness of 60 μm, cured at 120° C. for 1 hour and 30 minutes, and pressurized at 180° C. for 1 hour and 30 minutes at 40 kgf/cm ² to obtain the epoxy resin composition of Comparative Example 7.

<Comparative Example 8>

After dissolving 19.3 wt% of the DCPD type epoxy compound of Formula 1, 5.5 wt% of dicyandiamide of Formula 4, and 0.2 wt% of the imidazole-based curing accelerator of Formula 7 for 30 minutes in MEK (Methyl Ethly Ketone), Al-HGB 10 wt%, boron nitride 25 wt%, and aluminum oxide 40 wt% were added and stirred for 2 hours. The solution after the completion of stirring was coated on a copper plate to a thickness of 60 μm, cured at 120° C. for 1 hour and 30 minutes, and pressurized at 180° C. for 1 hour and 30 minutes at 40 kgf/cm ² to obtain the epoxy resin composition of Comparative Example 8.

<Experimental Example>

After curing the epoxy resin compositions obtained from Examples 1 to 5 and Comparative Examples 1 to 8, thermal conductivity was measured using an ASTM E1461 thermal conductivity meter, and dielectric constant was measured using IPC-TM-650 2.5.5.9.

The diameter of the HGB used in Examples 1 to 5 and Comparative Examples 1 to 8 is 10 to 30 μm, the air volume is 70 to 90 vol%, and the thickness of the aluminum oxide coated on the surface of the Al-HGB is 5 To 20 μm.

Table 1 is a result of comparing the thermal conductivity and dielectric constant of Examples and Comparative Examples.

Experiment number Thermal conductivity (W/mK) Permittivity (@1GHz) Example 1 2.68 3.78 Example 2 3.21 3.84 Example 3 3.51 3.90 Example 4 3.81 3.88 Example 5 3.4 3.79 Comparative Example 1 0.71 3.10 Comparative Example 2 3.67 4.23 Comparative Example 3 1.51 3.94 Comparative Example 4 1.84 3.29 Comparative Example 5 1.78 4.04 Comparative Example 6 2.59 3.83 Comparative Example 7 2.18 3.71 Comparative Example 8 4.01 4.02

Referring to Table 1, the thermal conductivity of Example 1 including a hollow filler (diameter of 10 to 30 μm, air volume of 70 to 90 vol%) and boron nitride is 2.6 W/mK or more, and dielectric constant (@1 KHz) Silver is 4 or less, and has higher thermal conductivity than Comparative Example 1 including only the hollow filler and Comparative Example 3 including only the hollow filler and aluminum oxide, and it can be seen that the dielectric constant is lower than that of Comparative Example 2 including only boron nitride.

In addition, Example 2 including a hollow filler coated with aluminum oxide (a diameter of 10 to 30 μm, an air volume of 70 to 90 vol%, an aluminum oxide coating with a thickness of 5 to 20 μm) and boron nitride was not coated. Example 1 including a hollow filler (10 to 30 μm in diameter and 70 to 90 vol% of air volume) and boron nitride, Comparative Example 4 including only a hollow filler coated with aluminum oxide, and a hollow filler coated with aluminum oxide And it can be seen that the thermal conductivity is higher than that of Comparative Example 5 containing only aluminum oxide.

In addition, it can be seen that Examples 3 to 5 further including aluminum oxide as well as aluminum oxide-coated hollow filler and boron nitride as inorganic fillers exhibit higher thermal conductivity compared to Examples 1 or 2. In particular, it can be seen that Examples 4 to 5 exhibit higher thermal conductivity compared to Comparative Examples 6 to 7 including an uncoated hollow filler, boron nitride, and aluminum oxide.

However, despite further including aluminum oxide as well as aluminum oxide-coated hollow filler and boron nitride as inorganic filler, a value deviating from 1 to 20 parts by weight of boron nitride and 1 to 35 parts by weight of aluminum oxide based on 10 parts by weight of the hollow filler In Comparative Example 8 having a range, since the dielectric constant is 4 or more, it can be seen that it is not suitable for use as an insulating layer.

As described above, by curing the epoxy resin composition according to an embodiment of the present invention and using it as an insulating layer, a printed circuit board having a thermal conductivity of 2.6 W/mK or more and a dielectric constant of 4 or less at 1 GHz can be obtained.

Although the above has been described with reference to preferred embodiments of the present invention, those skilled in the art will variously modify and change the present invention within the scope not departing from the spirit and scope of the present invention described in the following claims. You will understand that you can do it.

Claims (10)

10 to 70 wt% of an epoxy compound and a curing agent, and
It contains 30 to 90wt% of an inorganic filler including a hollow filler and boron nitride,
The boron nitride is contained in an amount of 0.1 to 100 parts by weight based on 10 parts by weight of the hollow filler,
The hollow filler includes a hollow glass bubble,
The surface of the hollow glass sphere is coated with aluminum oxide to a thickness of 5㎛ to 20㎛ epoxy resin composition. delete delete The method of claim 1,
The inorganic filler is an epoxy resin composition further comprising aluminum oxide. The method of claim 4,
An epoxy resin composition containing 1 to 20 parts by weight of the boron nitride, and 1 to 35 parts by weight of the aluminum oxide based on 10 parts by weight of the hollow glass sphere. The method of claim 1,
The diameter of the hollow glass sphere is 10 to 30㎛, the air volume of the hollow glass sphere (air volume) is 70 to 90vol% of the hollow glass sphere epoxy resin composition. delete The method of claim 1,
The epoxy compound includes a dicyclopentadiene (DCPD) type epoxy compound, and the curing agent is an epoxy resin composition comprising dicyandiamide. Board,
An insulating layer formed on the substrate, and
It includes a circuit pattern formed on the insulating layer,
The insulating layer includes an epoxy compound, a curing agent, and an inorganic filler including a hollow filler and boron nitride, and the boron nitride is 0.1 to 100 parts by weight based on 10 parts by weight of the hollow filler. Including,
The hollow filler includes a hollow glass bubble,
The surface of the hollow glass sphere is coated with aluminum oxide to a thickness of 5 μm to 20 μm. A plurality of circuit pattern layers sequentially arranged, and
And a plurality of insulating layers formed between the plurality of circuit pattern layers,
At least some of the insulating layers of the plurality of insulating layers include an epoxy compound, a curing agent, and an inorganic filler including a hollow filler and boron nitride, and the boron nitride is 0.1 to 10 parts by weight of the hollow filler. Including an epoxy resin composition contained in 100 parts by weight,
The hollow filler includes a hollow glass bubble,
The surface of the hollow glass sphere is coated with aluminum oxide to a thickness of 5 μm to 20 μm.

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