KR102022430B1 - Epoxy resin composite and printed circuit board comprising isolation using the same - Google Patents

Abstract

Epoxy resin composition according to an embodiment of the present invention comprises an epoxy compound of the following formula including a mesogen structure, a curing agent, an inorganic filler, and an additive for improving the adhesion to the metal, the curing agent is diaminodiphenyl sulfone R ¹ to R ¹⁴ may each be selected from the group consisting of H, Cl, Br, F, C ₁ -C ₃ alkyl, C ₂ -C ₃ alkenes, C ₂ -C ₃ alkyne, m, n Are 1, 2 or 3 respectively.

Description

A printed circuit board comprising an epoxy resin composition and an insulating layer using the same {EPOXY RESIN COMPOSITE AND PRINTED CIRCUIT BOARD COMPRISING ISOLATION USING THE SAME}

The present invention relates to an epoxy resin composition, and more particularly, to an epoxy resin composition used as an insulating layer of a printed circuit board.

The printed circuit board includes a circuit pattern formed on the 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 heat generating element. Heat emitted by the heating element may degrade the performance of the printed circuit board.

Background Art With the high integration and high capacity of electronic components, interest in heat dissipation problems of printed circuit boards is increasing. Generally, an epoxy resin composition containing a bisphenol A type epoxy compound or a bisphenol F type epoxy compound is used for an insulating layer of a printed circuit board. However, the bisphenol A-type epoxy compound or the bisphenol F-type epoxy compound has a problem of low viscosity and insufficient curability, mechanical strength, toughness, and the like.

Thereby, the epoxy resin composition containing the crystalline epoxy compound containing a mesogenic structure is used. Such an epoxy resin composition is excellent in storage stability before curing and curability, etc., but has a limit in obtaining required levels of heat resistance and thermal conductivity.

On the other hand, if the adhesive strength between the insulating layer and the metal is low, problems may occur during processing of the printed circuit board. In order to increase the adhesive force between them, the method of bonding a metal and an insulating layer, and then heating for a predetermined time is used. However, even with this method, there is a limit in obtaining the required level of adhesion, and there is a problem that additional time and process are required.

It is an object of the present invention to provide a printed circuit board including an epoxy resin composition and an insulating layer using the same.

Epoxy resin composition according to an embodiment of the present invention comprises an epoxy compound containing a mesogen structure, a curing agent, an inorganic filler, and additives for enhancing the adhesion to the metal, the epoxy compound has a structure of the formula Includes diaminodiphenylsulfone.

Wherein R ¹ to R ¹⁴ may each be selected from the group consisting of H, Cl, Br, F, C ₁ -C ₃ alkyl, C ₂ -C ₃ alkenes, C ₂ -C ₃ alkyne, m, n are 1, 2 or 3 respectively.

The epoxy compound may include an epoxy compound of the following formula.

The additive may include at least one of an imidazole-based additive and a fluorine-based additive.

The fluorine-based additive is R-NH ₂ BF ₃ , R may be a C ₁ ~ C ₃ alkyl group.

The epoxy compound is included in an amount of 3 to 40 parts by weight, the curing agent is included in an amount of 0.5 to 30 parts by weight, the inorganic filler is included in an amount of 30 to 97 parts by weight, and the additive is 0.1 to 5 parts by weight based on the entire epoxy resin composition. May be included.

A printed circuit board according to an embodiment of the present invention includes a metal plate, an insulating layer formed on the metal plate, and a circuit pattern formed on the insulating layer, the insulating layer comprising an epoxy including a mesogen structure A compound, a curing agent, an inorganic filler, and an additive for enhancing adhesion with a metal, wherein the epoxy compound has a structure of the above formula, and the curing agent includes diaminodiphenylsulfone.

The thermal conductivity of the insulating layer may be 9 W / Km or more.

Peel strength of the insulating layer may be 1.2 Kgf / cm or more.

The glass transition temperature of the insulating layer may be 100 ° C. or more.

According to the embodiment of the present invention, an epoxy resin composition having excellent glass transition temperature, thermal conductivity, and adhesion to a metal can be obtained. By using this, an insulating layer having high heat resistance and high thermal conductivity can be obtained, and heat dissipation performance of a printed circuit board can be improved. Moreover, the process of a printed circuit board can be made easy. In particular, it is possible to increase the adhesion between the insulating layer and the metal without additional processing.

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

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in the drawings. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all modifications, 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 components, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the second component may be referred to as the first component, and similarly, the first component may also be referred to as the second component. The term and / or includes a combination of a plurality of related items or any item of a plurality of related items.

The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art and shall not be construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.

When a portion of a layer, film, region, plate, etc. is said to be "on top" of another part, this includes not only when the other part is "right over" but also when there is another part in the middle. On the contrary, when a part is "just above" another part, there is no other part in the middle.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings, and the same or corresponding components will be given the same reference numerals regardless of the reference numerals, and redundant description thereof will be omitted.

In this specification, wt% may be used in combination with parts by weight.

According to one embodiment of the present invention, an epoxy resin composition including an epoxy compound including a mesogen structure, a curing agent, an inorganic filler, and an additive for enhancing adhesion with a metal is provided. Here, mesogen is a basic unit of liquid crystal and includes a rigid structure. Mesogens may comprise rigid structures such as, for example, biphenyl.

The epoxy resin composition according to an embodiment of the present invention may include 3 wt% to 40 wt%, preferably 5 wt% to 35 wt%, and more preferably 10 wt% to 30 wt% of the epoxy compound based on the total epoxy resin composition. . When the epoxy compound is 3 wt% or more and 40 wt% or less of the total epoxy resin composition, the adhesiveness is good and the thickness can be easily adjusted. In this case, the epoxy resin composition may include 3 wt% or more, preferably 3 wt% to 20 wt% of the crystalline epoxy compound with respect to the total epoxy resin composition. When 3 wt% or more of the crystalline epoxy compound is included in the total epoxy resin composition, crystallization is easy and the heat conduction effect is high.

Here, the crystalline epoxy compound may be an epoxy compound including a mesogen structure as shown in the following formula (1).

[Formula 1]

Here, R ¹ to R ^{1 4} may be selected from the group consisting of H, Cl, Br, F, C ₁ ~ C ₃ alkyl, C ₂ ~ C ₃ alkenes, C ₂ ~ C ₃ alkyne, respectively. Here, m, n may be 1, 2 or 3, respectively.

Compounds of Formula 1 include compounds of Formula 2.

[Formula 2]

Formula 2 may be referred to as 4,4'-biphenolether diglycidyl ether. The physical properties of the epoxy compound according to Formula 2 is 158 ℃ melting point (melting point), ¹ H NMR (CDCL ₃ -d6, ppm) results are δ = 8.58 (s, 2H), δ = 8.17-8.19 (d, 4H), δ = 7.99-8.01 (d, 4H), δ = 7.33 (s, 4H), δ = 4.69-4.72 (d, 1H), δ = 4.18-4.22 (m, 1H), δ = 3.36-3.40 (m, 1H), delta = 2.92-2.94 (m, 1H) and delta = 2.74-2.77 (m, 1H). Melting | fusing point was measured at the temperature increase rate of 10 degree-C / min using the differential scanning calorimetry apparatus (DSC Q100 by TA company). NMR was measured in H-NMR after dissolving in CDCL ₃ -d6.

The epoxy resin composition may further include a conventional amorphous epoxy compound having two or more epoxy groups in the molecule, in addition to the crystalline epoxy compound according to Formula 1 or Formula 2. If the amorphous epoxy compound is further included in addition to the crystalline epoxy compound, the room temperature stability can be improved.

The 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-dihydrate Loxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2, 8-dihydroxynaphthalene, allylide or polyallylate of the dihydroxynaphthalene, allylated bisphenol A, allylated Bivalent phenols, such as bisphenol F and allylated phenol novolak, or phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cresol novolak, xylenol novolak, poly-p -Hydroxystyrene, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, fluoroglycinol, pyrogallol, t-butylpyrogallol, Allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene resin, etc. And trivalent or higher phenols, halogenated bisphenols such as tetrabromobisphenol A, and glycidyl ether derivatives derived from one of them.

The epoxy resin composition according to one embodiment of the present invention may include a curing agent. 0.5 wt% to 30 wt%, preferably 1 wt% to 20 wt%, and more preferably 3 wt% to 10 wt%, based on the total epoxy resin composition, may be included. When the curing agent is contained in 0.5wt% to 30wt% of the total epoxy resin composition, the adhesion is good, it may be easy to control the thickness. The epoxy resin composition may include at least one of an amine curing agent, a phenol curing agent, an acid anhydride curing agent, a polycapcaptan curing agent, a polyaminoamide curing agent, an isocyanate curing agent, and a block isocyanate curing agent.

The amine curing agent may be, for example, 4, 4'-diamino diphenyl sulfone. Formula 3 is an example of diaminodiphenylsulfone. The epoxy resin composition according to one embodiment of the present invention may include 3 wt% to 10 wt%, preferably 6 wt% to 10 wt% of diaminodiphenyl sulfone with respect to the total epoxy resin composition.

[Formula 3]

Other examples of the amine curing agent may be aliphatic amines, polyether polyamines, alicyclic amines, aromatic amines, and the like, and as aliphatic amines, ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexa Methylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethyl ethylene diamine, tetra (hydroxyethyl) ethylene diamine, etc. are mentioned. The polyether polyamines may be one of triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamine, and a mixture thereof. Examples of the alicyclic amines include isophoronediamine, metacenediamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3 -Aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane, norbornenediamine, etc. are mentioned. Examples of the aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2 , 4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodi Phenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (m-aminophenyl) ethylamine, α- (p-amino Phenyl) ethylamine, diaminodiethyldimethyldiphenylmethane, α, α'-bis (4-aminophenyl) -p-diisopropylbenzene and mixtures thereof.

The phenolic curing agent is, for example, bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis (4-hydroxyphenoxy ) Benzene, 1,3-bis (4-hydroxyphenoxy) benzene, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylketone, 4,4'-dihydrate Oxydiphenylsulfone, 4,4'-dihydroxydiphenylester, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10- (2,5-dihydroxyphenyl ) -10H-9-oxa-10-phosphafaphenanthrene-10-oxide, phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cresol novolak, xylenol novolak , Poly-p-hydroxystyrene, hydroquinone, resorcin, catechol, t-butylcatechol, t-butylhydroquinone, fluoroglycinol, pyrogallol, t-butylpyrogallol, allylated pyrogallol, polyallyl Pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-di Doxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2 , 3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydrate Hydroxynaphthalene, allyl or polyallylate of the dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, allylated pyrogallol and mixtures thereof.

The acid anhydride-based curing agent is, for example, dodecenyl anhydrous succinic acid, polyadipic anhydride, polyazelate anhydride, polycebacic anhydride, poly (ethyloctadecane diacid) anhydride, poly (phenylhexadecane diacid) anhydride, methyltetrahydro Phthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl himic acid, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, phthalic anhydride, Trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, ethylene glycol bistrimellitate, hept anhydride, nadic anhydride, methylnadic anhydride, 5- (2,5-dioxotetrahydro-3 -Furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 1- Methyl-dicarboxy-1 , 2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride and mixtures thereof.

You may mix and use two or more types of hardening | curing agents.

The epoxy resin composition according to one embodiment of the present invention may further include a curing accelerator. Examples of the curing accelerator include amine curing accelerators, imidazole curing accelerators, organic phosphine curing accelerators, Lewis acid curing accelerators, and the like. Specifically, 1,8-diazabicyclo (5,4,0) is found. Tertiary amines such as sen-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-phenyl- Imidazoles such as 4-methylimidazole and 2-heptadecyl imidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, Tetra substituted phosphonium tetra substituted borate, such as tetraphenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium ethyl triphenyl borate, tetrabutyl phosphonium tetrabutyl borate, and 2-ethyl-4-methylimidazole tetra Phenylborate, N-methylmorpholine te La and the like tetraphenyl boron salts such as borate.

The epoxy resin composition according to one embodiment of the present invention may include 30 wt% to 97 wt% of an inorganic filler with respect to the total epoxy resin composition. When the inorganic filler is included in 30wt% to 97wt%, the 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 it does not improve depending on the volume fraction thereof, but improves dramatically from the specific amount added. However, when the amount of the inorganic filler added is greater than 97 wt%, the viscosity becomes high and the moldability is weakened.

The inorganic filler can be, for example, one of alumina, aluminum nitride, silicon nitride, boron nitride, crystalline silica, silicon carbide and a mixture selected from them. The average particle diameter of an inorganic filler may be 30 micrometers or less, for example. It is because the fluidity | liquidity of an epoxy resin composition may be impaired and intensity | strength may fall when an average particle diameter of an inorganic filler is larger than 30 micrometers.

The epoxy resin composition according to one embodiment of the present invention may include a release agent. As the release agent, waxes such as stearic acid, montanic acid, montanic acid esters, phosphate esters and the like can be used.

The epoxy resin composition according to one embodiment of the present invention may include an additive (hereinafter, may be mixed with an adhesion promoting additive) for increasing adhesion with a metal. The adhesion promoting additive may be included in an amount of 0.1 wt% to 5 wt%, preferably 0.2 wt% to 3 wt%, and more preferably 0.3 wt% to 2 wt%, based on the total epoxy resin composition. When the adhesion promoting additive is contained in an amount of 0.1wt% to 5wt%, the adhesion with the epoxy resin composition and the metal is increased.

As a result, the adhesion between the circuit pattern made of an epoxy resin composition and copper according to an embodiment of the present invention is increased, and the possibility of the circuit pattern being separated and disconnected is lowered, thereby facilitating the processing of the printed circuit board, and thus the printed circuit board. Increases the reliability.

The adhesion promoting additive may include, for example, at least one of an imidazole-based additive and a fluorine-based additive. The imidazole-based additive may be represented by the following formula (4).

[Formula 4]

R ¹⁵ to R ¹⁷ may be selected from the group consisting of H, Cl, Br, F, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkene and C ₂ -C ₂₀ alkyne, respectively.

The imidazole additive of Formula 4 may include the following Formula 5.

[Formula 5]

The fluorine-based additive may be represented by, for example, the following formula (6).

[Formula 6]

R ¹⁸ -NH ₂ BF ₃

Wherein R ¹⁸ may be selected from the group consisting of H, Cl, Br, F, C ₁ -C ₃ alkyl, C ₂ -C ₃ alkenes, C ₂ -C ₃ alkyne. Preferably, R ¹⁸ may be a methyl group.

The epoxy resin composition according to one embodiment of the present invention may be applied to a printed circuit board. 1 is a cross-sectional view of a printed circuit board according to an embodiment of the present invention.

Referring to FIG. 1, the printed circuit board 100 includes a metal plate 110, an insulating layer 120, and a circuit pattern 130.

The metal plate 110 may be made of copper, aluminum, nickel, gold, platinum, and an alloy selected from them.

On the metal plate 110, an insulating layer 120 made of an epoxy resin composition according to an embodiment of the present invention is formed.

The circuit pattern 130 is formed on the insulating layer 120. The circuit pattern 130 may be made of metal such as copper or nickel.

The insulating layer 120 insulates between the metal plate 110 and the circuit pattern 130.

By curing the epoxy resin composition according to one embodiment of the present invention and using it as an insulating layer, a printed circuit board having excellent heat dissipation performance can be obtained.

In particular, according to one embodiment of the present invention, an insulating layer comprising an epoxy resin composition having a thermal conductivity of 9 W / Km or more, a peel strength of 1.2 Kgf / cm, and a glass transition temperature of 100 ° C. or more is obtained. Can be. Preferably, an insulating layer containing an epoxy resin composition having a thermal conductivity of 10 W / Km or more, a peel strength of 1.4 Kgf / cm, and a glass transition temperature of 140 ° C. or more can be obtained.

Hereinafter, it demonstrates more concretely using an Example and a comparative example.

<Example 1>

10 wt% of the crystalline epoxy compound of Formula 2, 10 wt% of the bisphenol F type epoxy compound, 6 wt% of 4,4'-diaminodiphenylsulfone, 0.6 wt% of the imidazole compound of Formula 5, and a fluorine additive of Formula 6 (R ¹⁸ Silver methyl group) 0.4wt%, 65.7 wt% alumina and 7.3wt% of boron nitride were dried, heat-treated at 80 ° C for 30 minutes, and cured at 210 ° C for 2 hours to prepare the epoxy resin composition of Example 1 Got it.

<Example 2>

10wt% of the crystalline epoxy compound of Formula 2, 10wt% of the bisphenol F-type epoxy compound, 3wt% of hexamethylenediamine, 3wt% of 4,4'-diaminodiphenylsulfone, 0.3wt% of the imidazole compound additive of Formula 5, Formula 6 Fluorine-based additive (R ¹⁸ is methyl group) of 0.2wt%, alumina 66wt% and boron nitride 7.5wt% solution was dried, heat-treated at 80 ℃ for 30 minutes, and cured at 210 ℃ for 2 hours An epoxy resin composition was obtained.

<Example 3>

2 wt% of crystalline epoxy compound of Formula 2, 14 wt% of bisphenol A type epoxy compound, 4 wt% of bisphenol F type epoxy compound, 6 wt% of hexamethylenediamine, 0.6 wt% of imidazole-based additive of Formula 5, fluorine additive of Formula 6 (R ¹⁸ is a methyl group) 0.4wt%, 65.7 wt% of alumina and 7.3wt% of boron nitride was dried, heat-treated at 80 ℃ for 30 minutes, and cured at 210 ℃ for 2 hours to the epoxy resin composition of Example 3 Got.

<Example 4>

10 wt% of the crystalline epoxy compound of Formula 2, 10 wt% of the bisphenol A epoxy compound, 6 wt% of hexamethylenediamine, 0.48 wt% of the imidazole compound of Formula 5, 0.32 wt% of the fluorine additive of Formula 6 (R ¹⁸ is a methyl group), The solution containing 66 wt% alumina and 7.2 wt% boron nitride was dried, then heat treated at 80 ° C. for 30 minutes, and cured at 210 ° C. for 2 hours to obtain an epoxy resin composition of Example 4.

Example 5

10 wt% of crystalline epoxy compound of Formula 2, 10 wt% of bisphenol F type epoxy compound, 6 wt% of p-xylenediamine, 0.6 wt% of imidazole compound of Formula 5, 0.4 wt% of fluorine additive of Formula 6 (R ¹⁸ is methyl group) , 65.7 wt% of alumina and 7.3 wt% of boron nitride were dried, and then heat-treated at 80 ° C. for 30 minutes and cured at 210 ° C. for 2 hours to obtain an epoxy resin composition of Example 5.

Comparative Example 1

18 wt% bisphenol A type epoxy compound, 2 wt% bisphenol F type epoxy compound, 8 wt% p-xylenediamine, 64.8 wt% alumina, and 7.2 wt% boron nitride were dried and then heat-treated at 80 ° C. for 30 minutes. Curing for 2 hours at 210 ℃ to obtain the epoxy resin composition of Comparative Example 1.

Comparative Example 2

14 wt% bisphenol A epoxy compound, 6 wt% bisphenol F epoxy compound, 9 wt% p-xylenediamine, 64 wt% alumina, and 7 wt% boron nitride were dried, followed by heat treatment at 80 ° C. for 30 minutes, followed by 210 ° C. Cured for 2 hours to obtain an epoxy resin composition of Comparative Example 2.

Comparative Example 3

13 wt% bisphenol A epoxy compound, 7 wt% bisphenol F epoxy compound, 6 wt% p-xylenediamine, 66.6 wt% alumina, and 7.4 wt% boron nitride were dried and then heat-treated at 80 ° C. for 30 minutes. Curing for 2 hours at 210 ℃ to obtain the epoxy resin composition of Comparative Example 3.

Experimental Example

The thermal conductivity of the epoxy resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 was measured by an abnormal heating method using a LFA447 type thermal conductivity meter manufactured by NETZSCH. And the glass transition temperature of the epoxy resin composition of Example 1-Example 5 and Comparative Examples 1-3 was measured at the temperature increase rate of 10 degree-C / min using the DSC Q100 thermometer measuring apparatus by TA company. After curing the epoxy resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3, the copper foil having a width of 1 cm was adhered to each other, and then the peel strength was measured by a peel strength meter. Table 1 shows the results.

Experiment number Thermal Conductivity (W / m.K) Glass transition temperature (℃) Peel Strength (Kgf / cm) Example 1 10.2 148 1.4 Example 2 9.1 102 1.2 Example 3 6.10 77 1.4 Example 4 7.85 125 1.3 Example 5 10.01 80 1.4 Comparative Example 1 2.61 120 1.0 Comparative Example 2 3.72 108 1.0 Comparative Example 3 5.01 91 1.0

Referring to Table 1, as in Examples 1 and 2, the epoxy resin composition including the crystalline epoxy compound of Formula 2, 4, 4'-diaminodiphenylsulfone, adhesion promoting additive and inorganic filler has a thermal conductivity of 9W / It can be seen that mK or more, the glass transition temperature is 100 ° C or more, and the peel strength is 1.2 Kgf / cm or more.

In particular, as shown in Example 1, the crystalline epoxy compound of Formula 2 is contained 3wt% or more of the total epoxy resin composition, 4, 4'-diaminodiphenylsulfone is contained 6wt% or more of the total epoxy resin composition, to improve adhesion When the additive is included, it can be seen that an epoxy resin composition having a thermal conductivity of 10 W / mK or more, a glass transition temperature of 140 ° C. or more, and a peel strength of 1.4 Kgf / cm or more can be obtained.

On the other hand, it can be seen that the epoxy resin compositions of Examples 1 to 5 have a higher peel strength than the epoxy resin compositions of Comparative Examples 1 to 3. That is, it can be seen that the epoxy resin composition containing the adhesion enhancing additive has excellent adhesion with the metal.

Although described above with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and changed within the scope of the invention without departing from the spirit and scope of the invention described in the claims below I can understand that you can.

Claims (10)

Epoxy compound containing a crystalline epoxy compound of formula (1),
Curing agents comprising diaminodiphenylsulfone,
Inorganic fillers, and
It contains additives to increase the adhesion with the metal,
The additives include imidazole-based additives and fluorine-based additives,
The fluorine-based additive is R-NH ₂ BF ₃ , R is a methyl group
Epoxy resin composition:
[Formula 1]

Wherein R ¹ to R ¹⁴ may each be selected from the group consisting of H, Cl, Br, F, C ₁ -C ₃ alkyl, C ₂ -C ₃ alkenes, C ₂ -C ₃ alkyne, m, n are 1, 2 or 3 respectively. The method of claim 1,
The crystalline epoxy compound is an epoxy resin composition comprising an epoxy compound of formula (2):
[Formula 2]

delete delete The method of claim 1,
The epoxy compound is contained in 10 to 40wt% with respect to the total epoxy resin composition, the curing agent is included in 6 to 30wt%, the inorganic filler is included in 30 to 83.9wt%, the additive is 0.1 to 5wt% Included,
An epoxy resin composition containing 10 wt% or more of the crystalline epoxy compound of Formula 1 and 6 wt% or more of the diaminodiphenylsulfone based on the total epoxy resin composition. Metal plate,
An insulating layer formed on the metal plate, and
A circuit pattern formed on the insulating layer,
The insulating layer,
Epoxy compound containing a crystalline epoxy compound of formula (1),
Curing agents comprising diaminodiphenylsulfone,
Inorganic fillers, and
It contains additives to increase the adhesion with the metal,
The additives include imidazole-based additives and fluorine-based additives,
The fluorine-based additive is R-NH ₂ BF ₃ , R is a printed circuit board made of an epoxy resin composition is a methyl group:
[Formula 1]

Wherein R ¹ to R ¹⁴ may each be selected from the group consisting of H, Cl, Br, F, C ₁ -C ₃ alkyl, C ₂ -C ₃ alkenes, C ₂ -C ₃ alkyne, m, n are 1, 2 or 3 respectively. The method of claim 6,
The epoxy compound is contained in 10 to 40wt% with respect to the total epoxy resin composition, the curing agent is included in 6 to 30wt%, the inorganic filler is included in 30 to 83.9wt%, the additive is 0.1 to 5wt% Included,
10 wt% or more of the crystalline epoxy compound of Formula 1, and 6 wt% or more of the diaminodiphenyl sulfone based on the total epoxy resin composition. The method of claim 6,
The thermal conductivity of the insulating layer is 9W / Km or more printed circuit board. The method of claim 8,
Peel strength of the insulating layer is a printed circuit board of 1.2Kgf / cm or more. The method of claim 9,
The glass transition temperature of the said insulating layer is 100 degreeC or more.

Images