KR101855786B1 - Epoxy resin compostion and printed circuit board comprising isolation layer using the same - Google Patents

Abstract

(단 화학식 1에서 x는 하기 화학식 2로 표시되고, n은 1 내지 10 의 정수를 나타낸다.)
[화학식 2]

The present invention relates to a printed circuit board comprising an epoxy resin composition and an insulating layer using the same. The epoxy resin composition according to an embodiment of the present invention comprises 5 to 40% by weight of an epoxy compound, 1 to 30% by weight of a curing agent and 40 to 92% by weight of an inorganic filler.
The epoxy compound may include a naphthalene epoxy compound represented by the following formula (1).
[Chemical Formula 1]

(Provided that in the general formula (1), x is represented by the following general formula (2), and n represents an integer of 1 to 10.)
(2)

Description

EPOXY RESIN COMPOSITION AND PRINTED CIRCUIT BOARD COMPRISING ISOLATION LAYER USING THE SAME Technical Field [1] The present invention relates to an epoxy resin composition,

An epoxy resin composition and an insulating layer using the epoxy resin composition.

Current automobiles are implemented with precise control systems by adding electric / electronic elements to existing mechanical elements and it is recognized that the role of electric / electronic elements and devices of automobiles is very important.

Recently, as eco-friendly vehicles such as electric cars and hybrid cars are gradually developed, the number of electronic device components flowing in high voltage / high current of the electric control system is increasing, and the demand for heat dissipation for electronic device components is gradually increasing.

A metal printed circuit board (PCB) is applied to dissipate the heat of the heating element of the electronic component. The metal printed circuit board is also referred to as a metal CCL (Copper Clad Laminate), and has a basic form in which a copper (Cu, copper) circuit layer, an insulating layer, and a metal substrate are laminated.

The printed circuit board includes a circuit pattern on an electrically insulating substrate, and various electrical and electronic elements can be mounted on the printed circuit board. As heat dissipated by electric and electronic elements increases with the increase in the degree of integration and high capacity of electronic components, there is a growing interest in heat dissipation problems and reliability life of printed circuit boards.

Accordingly, the printed circuit board is intended to give heat radiation and high reliability to the printed circuit board itself together with a structure for heat dissipation in order to radiate the heat from the heat generating element of the electronic component to the outside. Particularly, the thermal conductivity and the heat resistance of the insulating layer in the printed circuit board have a great influence on the heat dissipation and reliability of the printed circuit board.

The insulating layer having high reliability of the printed circuit board and excellent thermal conductivity

An epoxy resin composition is generally used. At this time, in order to enhance the heat radiation performance, the inorganic filler can be filled with high density to ensure the heat radiation performance. However, when the inorganic filler is charged at a high density, the withstand voltage performance and reliability of the insulating layer may be affected.

One embodiment of the present invention provides a printed circuit board comprising an epoxy resin composition and an insulating layer using the epoxy resin composition. The present invention provides a printed circuit board comprising an epoxy resin composition and an insulating layer using the epoxy resin composition.

The epoxy resin composition according to an embodiment of the present invention comprises 5 to 40% by weight of an epoxy compound, 1 to 30% by weight of a curing agent and 40 to 92% by weight of an inorganic filler.

The epoxy compound may include a naphthalene epoxy compound represented by the following formula (1).

[Chemical Formula 1]

(Provided that in the general formula (1), x is represented by the following general formula (2), and n represents an integer of 1 to 10.)

(2)

The epoxy compound may further comprise a triphenylmethane novolak epoxy compound represented by the following formula (3).

(3)

(Wherein, in the general formula (3), x is represented by the general formula (2), n represents an integer of 1 to 5, m represents an integer of 1 to 4, and 1 represents an integer of 0 to 5.)

The epoxy compound may further include an amorphous epoxy compound.

The amorphous epoxy compound may include a bisphenol A type epoxy compound represented by the following general formula (4).

[Chemical Formula 4]

(Wherein, in the general formula (4), x is represented by the general formula (2), n represents an integer of 1 to 5, and R ¹ and R ² each independently represent hydrogen, a halogen element, a hydroxy group or an alkyl group.

30 to 60 parts by weight of the naphthalene epoxy compound represented by the general formula (1), 30 to 60 parts by weight of the triphenylmethane novolak epoxy compound represented by the general formula (3), and the bisphenol A epoxy And 10 to 40 parts by weight of the compound.

The curing agent may be at least one selected from an amine curing agent, a phenol curing agent, an acid anhydride curing agent, a polymercaptan curing agent, a polyaminoamide curing agent, an isocyanate curing agent and a block isocyanate curing agent.

The inorganic filler may be at least one selected from alumina, boron nitride, aluminum nitride, alumina, boron nitride, aluminum nitride, crystalline silica and aluminum nitride.

The inorganic filler may have an average particle size of 0.1 to 30 占 퐉.

90 to 93.5 parts by weight of alumina and 6.5 to 10 parts by weight of boron nitride may be contained in 100 parts by weight of the inorganic filler.

0.1 to 5 parts by weight of a silane coupling additive may be further added to 100 parts by weight of the epoxy resin composition.

The glass transition temperature of the epoxy resin composition may be 120 ° C or higher.

The thermal conductivity of the epoxy resin composition may be from 2.0 W / mK to 5.0 W / mK.

A printed circuit board according to an embodiment of the present invention includes a metal substrate, an insulating layer formed on the metal substrate, and a circuit layer formed on the insulating layer.

The insulating layer may comprise 5 to 40 wt% of an epoxy compound, 1 to 30 wt% of a curing agent, and 40 to 92 wt% of an inorganic filler.

The epoxy compound may include a naphthalene epoxy compound represented by the following formula (1).

[Chemical Formula 1]

(Provided that in the general formula (1), x is represented by the following general formula (2), and n represents an integer of 1 to 10.)

(2)

The insulating layer may have a peel strength of 1.0 to 2.0 Kgf / cm and a breakdown voltage of 5.0 to 7.0 kV.

The insulating layer can be subjected to heat treatment at 200 占 폚 for 1000 hours, and then the rate of decrease in peel strength may be 10% or less and the rate of decrease in breakdown voltage may be 20% or less.

(Note that the rate of decrease in peel strength is calculated as ([Peel strength after heat treatment] - [Peel strength before heat treatment] / [Peel strength before heat treatment] * 100, Breakdown voltage]) / [breakdown voltage before heat treatment] * 100)

The epoxy resin composition and the printed circuit board according to an embodiment of the present invention have improved thermal conductivity of the insulating layer and secured the long-term reliability of the insulating layer by using the multi-functional epoxy resin and the curing agent composition.

It is possible to improve the thermal conductivity of the insulating layer while minimizing the content of the inorganic filler by using an epoxy resin including a mesogen structure for enhancing the crystallinity in order to improve the thermal conductivity of the insulating layer.

In order to have a glass transition temperature higher than the operating temperature of the heating element of the electronic component, it is possible to secure the glass transition temperature and reliability of the insulating layer by using a polyfunctional epoxy resin in the epoxy composition.

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

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and the manner of achieving them, will be apparent from and elucidated with reference to the embodiments described hereinafter in conjunction with the accompanying drawings. However, it is to be understood that the present invention is not limited to the disclosed embodiments, but may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. It is intended that the disclosure of the present invention be limited only by the terms of the appended claims. Like reference numerals refer to like elements throughout the specification.

When referring to a portion as being "on" or "on" another portion, it may be directly on or over another portion, or may involve another portion therebetween. In contrast, when referring to a part being "directly above" another part, no other part is interposed therebetween.

As used herein, unless otherwise defined, "substituted" means a C1 to C30 alkyl group; C1 to C10 alkylsilyl groups; A C3 to C30 cycloalkyl group; A C6 to C30 aryl group; A C2 to C30 heteroaryl group; A C1 to C10 alkoxy group; A C1 to C10 trifluoroalkyl group such as a fluoro group and a trifluoromethyl group; Or cyano group.

In the present specification, the term "combination thereof" means that two or more substituents are bonded to each other via a linking group or two or more substituents are condensed and bonded.

As used herein, unless otherwise defined, the term " alkyl group "means a" saturated alkyl group "which does not include any alkene or alkynyl group; Or an "unsaturated alkyl group" comprising at least one alkene group or alkyne group. Means a substituent in which at least two carbon atoms are composed of at least one carbon-carbon double bond, and "alkynyl group" means a substituent in which at least two carbon atoms are composed of at least one carbon-carbon triple bond . The alkyl group may be branched, straight-chain or cyclic.

The alkyl group may be a C1 to C20 alkyl group, more specifically a C1 to C6 lower alkyl group, a C7 to C10 intermediate alkyl group, or a C11 to C20 higher alkyl group.

For example, C1 to C4 alkyl groups mean that from 1 to 4 carbon atoms are present in the alkyl chain, which includes methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t- Indicating that they are selected from the group.

Typical examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an ethenyl group, a propenyl group, a butenyl group, a cyclopropyl group, Pentyl group, cyclohexyl group, and the like.

Thus, in some embodiments, well-known techniques are not specifically described to avoid an undesirable interpretation of the present invention. Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. Whenever a component is referred to as "including" an element throughout the specification, it is to be understood that the element may include other elements, not the exclusion of any other element, unless the context clearly dictates otherwise. Also, singular forms include plural forms unless the context clearly dictates otherwise.

The epoxy resin composition according to an embodiment of the present invention comprises 5 to 40% by weight of an epoxy compound, 1 to 30% by weight of a curing agent and 40 to 92% by weight of an inorganic filler. Hereinafter, each configuration will be described in detail.

The epoxy compound is contained in an amount of 5 to 40% by weight based on 100% by weight of the epoxy resin composition. The high reliability of the insulating layer can be ensured by being included in the range described above. More specifically, the epoxy compound may be contained in an amount of 7 to 20% by weight.

In one embodiment of the present invention, the epoxy compound may include a naphthalene epoxy compound represented by the following formula (1).

[Chemical Formula 1]

(Provided that in the general formula (1), x is represented by the following general formula (2), and n represents an integer of 1 to 10.)

(2)

Since the naphthalene epoxy compound represented by the general formula (1) includes a mesogen structure which enhances crystallinity, the thermal conductivity of the insulating layer can be improved while minimizing the content of the inorganic filler.

More specifically, in formula (1), n may be 2. When n is 2, the naphthalene epoxy compound may be represented by the following general formula (5).

[Chemical Formula 5]

The naphthalene epoxy compound may have an area percentage of gel permeation chromatography of 80% or more, an equivalent weight of 135 to 160 g / eq, and a melting point of 45 to 55 ° C.

The epoxy compound may further comprise a triphenylmethane novolak epoxy compound represented by the following formula (3). By further including a triphenylmethane novolak epoxy compound, reliability can be further increased and the withstand voltage and glass transition temperature can be improved.

(3)

(Wherein, in the general formula (3), x is represented by the general formula (2), n represents an integer of 1 to 5, m represents an integer of 1 to 4, and 1 represents an integer of 0 to 5.)

More specifically, in formula (3), n and m may be 1.

The epoxy compound may further include an amorphous epoxy compound in addition to the above-described crystalline epoxy compound. By further containing an amorphous epoxy compound, stability at room temperature can be further secured.

Examples of amorphous epoxy compounds include bisphenol A, bisphenol F, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl Sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, fluorene bisphenol, 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 Dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydro Dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2, 8-dihydroxynaphthalene, allyl or polyallylate of the dihydroxynaphthalene, allylated bisphenol A, allylated Bisphenol F, and allylated phenol novolac; and divalent phenols such as phenol novolak, bisphenol A novolak, o-cresol novolac, m-cresol novolak, p- -Hydroxystyrene, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, fluoroglycinol, pyrogallol, Allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene resin, etc. A trivalent or higher phenol, a halogenated bisphenol such as tetrabromobisphenol A, and a mixture selected from the foregoing.

Specifically, the amorphous epoxy compound may include a bisphenol A type epoxy compound represented by the following formula (4).

[Chemical Formula 4]

(Wherein, in the general formula (4), x is represented by the general formula (2), n represents an integer of 1 to 5, and R ¹ and R ² each independently represent hydrogen, a halogen element, a hydroxy group or an alkyl group.

More specifically, in the general formula (4), n is 1, and R ¹ and R ² may be an alkyl group. More specifically, R ¹ and R ² may be a methyl group.

When the epoxy compound contains both the naphthalene epoxy compound represented by the formula (1), the triphenylmethane novolac epoxy compound represented by the formula (3) and the bisphenol A type epoxy compound represented by the formula (4) 30 to 60 parts by weight of the naphthalene epoxy compound represented by the formula (1), 30 to 60 parts by weight of the triphenylmethane novolak epoxy compound represented by the formula (3) and 10 to 40 parts by weight of the bisphenol A type epoxy compound represented by the formula . When the naphthalene epoxy compound and the triphenylmethane novolac epoxy compound are contained in too small amounts, the withstand voltage and the glass transition temperature characteristics may deteriorate. If the naphthalene epoxy compound and the triphenylmethane novolac epoxy compound are contained too much, problems may arise in terms of thermal conductivity and heat resistance.

The curing agent is contained in an amount of 1 to 30% by weight based on 100% by weight of the epoxy resin composition. The high reliability of the insulating layer can be ensured by being included in the range described above. More specifically, the curing agent may be contained in an amount of 3 to 10% by weight.

The curing agent may be at least one selected from an amine curing agent, a phenol curing agent, an acid anhydride curing agent, a polymercaptan curing agent, a polyaminoamide curing agent, an isocyanate curing agent and a block isocyanate curing agent.

Other examples of the amine-based curing agent may be aliphatic amines, polyether polyamines, alicyclic amines, aromatic amines and the like. Examples of the aliphatic amines include ethylenediamine, 1,3-diaminopropane, (Hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tetraethylenepentamine, pentaerythritol tetramine, tetraethylenepentamine, pentaerythritol hexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine, and the like. Examples of the polyether polyamines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamine, and mixtures thereof. Examples of the alicyclic amines include isophoronediamine, methadecenediamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9- -Aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane, norbornenediamine, and the like. Examples of the aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4- , 4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4- (M-aminophenyl) ethylamine, [alpha] - (p-amino) benzylamine, benzyldimethylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, Phenyl) ethylamine, diaminodiethyldimethyldiphenylmethane,?,? '- bis (4-aminophenyl) -p-diisopropylbenzene and mixtures thereof. Specifically, the amine-based curing agent may be diamino diphenyl methane.

Examples of the phenolic curing agent include 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'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'- 4,4'-dihydroxydiphenyl ester, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10- (2,5-dihydroxyphenyl ) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolak, bisphenol A novolac, o- cresol novolak, m- cresol novolac, p- cresol novolac, , Poly-p-hydroxystyrene, hydroquinone, resorcin, catechol, t-butyl catechol, t-butyl hydroquinone, fluoroglycinol, pyrogallol, t- butyl pyrogallol, allyl pyrogallol, polyallyl 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-di Dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, , 3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8- Allylated bisphenol A, allylated bisphenol F, allylated phenol novolacs, allylated pyrogallol, and mixtures thereof. [0031] The present invention also provides a process for producing the above-mentioned dihydroxynaphthalene. More specifically, the phenolic curing agent may be phenol novolak.

Examples of the acid anhydride-based curing agent include dodecenylsuccinic anhydride, polyadipic acid anhydride, polyazelaic anhydride, poly sebacic anhydride, poly (ethyloctadecanedioic) anhydride, poly (phenylhexadecanedioic) anhydride, methyltetrahydro There may be mentioned phthalic anhydride, phthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhydromic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, phthalic anhydride , Anhydrous trimellitic acid, anhydrous pyromellitic acid, benzophenonetetracarboxylic anhydride, ethylene glycol bistrimellitate, anhydrous hic acid, anhydrous nadic acid, methylnadic anhydride, 5- (2,5-dioxotetrahydro- 3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid anhydride, 1 -Methyl-dicarboxy -1,2,3,4-tetrahydro-1-naphthalenesuccinic acid anhydride and mixtures thereof.

According to one embodiment of the present invention, a phenol-based curing agent having a high decomposition temperature at a high temperature may be used, or two or more kinds of curing agents may be mixed and used.

The inorganic filler is contained in an amount of 40 to 92% by weight based on 100% by weight of the epoxy resin composition. By being included in the range described above, it is possible to secure excellent thermal conductivity and withstand voltage characteristics. More specifically, the inorganic filler may be contained in an amount of 70 to 85% by weight.

The inorganic filler may include at least one selected from alumina, boron nitride, aluminum nitride, alumina, boron nitride, aluminum nitride, crystalline silica and aluminum nitride. More specifically alumina and boron nitride.

When the inorganic filler comprises alumina and boron nitride, 90 to 93.5 parts by weight of alumina and 6.5 to 10 parts by weight of boron nitride may be contained per 100 parts by weight of the inorganic filler. If the amount of boron nitride is too small, there may be a problem in terms of thermal conductivity. If too much boron nitride is contained, a problem may arise in terms of peel strength and withstand voltage due to the boron nitride volume. More specifically, 92.5 to 93.5 parts by weight of alumina and 6.5 to 7.5 parts by weight of boron nitride may be contained.

The inorganic filler having an average particle size of 0.1 to 30 占 퐉 may be used. If the average particle size is too small, the specific surface area may be wide and the dielectric constant may be increased and the thermal conductivity may be lowered. If the average particle size is too large, problems may arise in the thermal conductivity. More specifically, the inorganic filler may have an average particle size of from 2 to 20 mu m.

The epoxy resin composition according to one embodiment of the present invention may further include additives in addition to the above-described essential components. Specifically, 0.1 to 5 parts by weight of a silane coupling additive may be added to 100 parts by weight of the epoxy resin composition.

The glass transition temperature of the epoxy resin composition composed of the above-described components may be 120 ° C or higher. Further, the thermal conductivity may be 2.0 W / mK to 5.0 W / mK.

The epoxy resin composition according to one embodiment of the present invention can be applied to a printed circuit board. 1 is a cross-sectional view of a printed circuit board 100 according to an embodiment of the present invention.

1, a printed circuit board 100 according to an embodiment of the present invention includes a metal substrate 10, an insulating layer 20 formed on the metal substrate 10, and an insulating layer 20 formed on the insulating layer 20 And a circuit layer (30) formed thereon.

The metal substrate 10 may be made of copper, aluminum, nickel, gold, platinum and alloys thereof. Specifically, aluminum alloy series 5052 series or heat treated 6061 series aluminum alloy can be used.

On the metal substrate 10, an insulating layer 20 made of an epoxy resin composition according to an embodiment of the present invention is formed. The insulating layer 20 serves to insulate the metal substrate 10 from the circuit layer 30. As described above, the insulating layer 20 according to an embodiment of the present invention can provide a printed circuit board 100 with excellent heat dissipation performance, withstand voltage performance, and long-term reliability. Since the constitution of the insulating layer has been described in detail with respect to the epoxy resin composition, a duplicate description will be omitted.

The insulating layer 20 may have a peel strength of 1.0 to 2.0 Kgf / cm and a breakdown voltage of 5.0 to 7.0 kV.

Further, the insulating layer 20 may be subjected to a heat treatment at 200 占 폚 for 1000 hours, and then the rate of decrease in peel strength may be 10% or less and the rate of breakdown voltage increase may be 20% or less.

In this case, the rate of decrease in peel strength is calculated as ([Peel strength after heat treatment] - [Peel strength before heat treatment] / [Peel strength before heat treatment] * 100, Breakdown voltage] / [breakdown voltage before heat treatment] * 100.

On the insulating layer 20, a circuit layer 30 is formed. The circuit layer 30 may be made of a metal such as copper, nickel, or the like, and may have a uniform pattern.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited to the following examples.

Example  One

4.20% by weight of a naphthalene epoxy compound represented by the following formula (5), a triphenylmethane novolak epoxy compound (wherein n is 2) represented by the following formula (6), 2.10% by weight of a bisphenol A type epoxy compound represented by the following formula Was prepared as an epoxy compound.

[Chemical Formula 5]

[Chemical Formula 6]

(7)

1% by weight of a silane coupling agent was added as an additive, and 76.84% by weight of alumina (Al ₂ O _{3 ,} average diameter of about 15 μm) and 5.38% by weight of boron nitride (average diameter of about 15 μm) 5.88% by weight of phenol novolak was added and stirred for 2 hours. The solution having been stirred was coated on a 6061 series aluminum alloy plate and then pressurized at 150 DEG C for 1 hour and 30 minutes to obtain an epoxy resin composition of Example 1.

Example  2 to 6

The same procedure as in Example 1 was carried out except that the content of each component was changed as summarized in Table 1 below.

Example  7

Except that the biphenyl phenol novolac epoxy compound represented by the following formula (8) was used in place of the triphenylmethane novolak epoxy compound, and the content of each component was changed as summarized in Table 2 below.

[Chemical Formula 8]

Example  8

The same procedure as in Example 1 was carried out except that diaminodiphenylmethane was used instead of phenol novolac as a curing agent and the content of each component was changed as summarized in Table 2 below.

Example  9

The procedure of Example 1 was repeated except that 82.62% by weight of alumina was used as the inorganic filler without boron nitride, and the content of each component was changed as summarized in Table 2 below.

Example  10

The same procedure as in Example 1 was carried out except that the content of each component was changed as summarized in Table 2 below.

Example  11

The same procedure as in Example 1 was carried out except that the content of each component was changed as summarized in Table 2 below.

Comparative Example  One

Except that a biphenyl epoxy compound represented by the following formula (9) was used instead of the naphthalene epoxy compound, and a biphenyl phenol novolac epoxy compound represented by the above formula (8) was used instead of the triphenylmethane novolac epoxy compound And the content of each component was changed as summarized in Table 2 below.

[Chemical Formula 9]

Comparative Example  2

Except that naphthalene epoxy compounds were not used and the biphenylphenol novolak epoxy compounds represented by the above formula 8 were used instead of triphenylmethane novolac epoxy compounds. 2, as shown in Fig.

Composition Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Furtherance Epoxy compound Naphthalene epoxy 4.2 3.2 5.18 4.71 2.1 4.2 Biphenyl epoxy - - - - - - Triphenylmethane novolak epoxy 4.2 5.33 3.11 4.71 4.2 2.1 Biphenyl phenol novolac epoxy - - - - - - Bisphenol A epoxy 2.1 2.13 2.07 2.36 4.2 4.2 Hardener Phenol novolac 5.88 5.72 6.03 6.59 5.88 5.88 Diaminodiphenylmethane - - - - - - Inorganic filler Al ₂ O ₃ 76.84 76.84 76.84 74.99 76.84 76.84 Boron nitride 5.78 5.78 5.78 5.64 5.78 5.78 additive Silane coupling agent One One One One One One

Composition Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1 Comparative Example 2 Furtherance Epoxy compound Naphthalene epoxy 4.2 4.2 4.2 4.2 4.2 - - Biphenyl epoxy - - - - - 4.2 - Triphenylmethane novolak epoxy - 4.2 4.2 4.2 4.2 - - Biphenyl phenol novolac epoxy 4.2 - - - - 4.2 4.2 Bisphenol A epoxy 2.1 2.1 2.1 2.1 2.1 2.1 6.3 Hardener Phenol novolac 5.88 - 5.88 5.88 5.88 5.88 5.88 Diaminodiphenylmethane - 5.88 - - - - - Inorganic filler Al ₂ O ₃ 76.84 76.84 82.62 73.62 88 76.84 76.84 Boron nitride 5.78 5.78 - 9 - 5.78 5.78 additive Silane coupling agent One One One One One One One

Experimental Example

The compositions obtained from Examples 1 to 11 and Comparative Examples 1 to 2 were cured.

The following methods were used to measure the peel strength, breakdown voltage, solder resistance, thermal conductivity, glass transition temp, reduction rate of peel strength, Are shown in Tables 3 and 4 below.

Peel Strength: The peel strength of the copper foil 10 mm pattern was measured at a rate of 50 mm / min and a length of 60 mm at an angle of 90 degrees using a YM-DL100 instrument manufactured by Y.M.RTC.

Breakdown voltage: The withstand voltage was obtained by etching the periphery of the copper foil on the circuit board using KIKUSUI equipment TOS5101, leaving a circular part with a diameter of 25 mm, immersing it in insulating oil, applying an AC voltage between the copper foil and the aluminum plate at room temperature, The withstand voltage was measured based on D149.

Soldering Resistance: According to IPC-TM-650 2.4.13, the metal printed circuit board was cut into 50mm * 50mm size and placed on the soldering bath at 288 ℃, and the time for the parts or peeling of the copper foil or insulating layer was measured.

Thermal conductivity: The thermal conductivity was measured using a T3Ster DynTIM instrument from Mentor Graphics. For the measurement of thermal conductivity, the insulating layer was processed into a 12.7-mm circle with thicknesses (75, 100, and 115 탆), and the thermal conductivity was measured according to ASTM-D5470.

Glass Transition Temperature: The glass transition temperature can be measured with a dynamic viscoelasticity measuring device (DMA). The device was measured using a DMA 1 instrument from Mettler Toledo at a heating rate of 3 ° C / min and a measurement frequency of 1 Hz.

Percent reduction in peel strength: The cured composition was heat-treated at 200 占 폚 for 1000 hours, and then the peel strength was measured and calculated as ((Peel strength after heat treatment - Peel strength before heat treatment) / Respectively.

Breakdown voltage lowering rate: The cured composition was heat treated at 200 ° C for 1000 hours, and then the breakdown voltage was measured and calculated as ([Breaking voltage after heat treatment] - [Breakdown voltage before heat treatment]] / [Breakdown voltage before heat treatment] * 100 Respectively.

Property evaluation data Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Peel strength
(kgf / cm @ Cu 2 oz) 1.8 1.75 1.75 1.85 1.8 1.8 Breakdown voltage (kV) 6.7 6.5 6.5 6 6 6 Soldering Resistance
(min @ 288 < 0 > C) 50 50 50 50 50 50 Thermal conductivity
(W / mK) 2.5 2.5 2.5 2.4 2.5 2.5 Glass transition temperature (캜) 150 155 155 150 130 135 Peel strength
Decrease rate (%) 0 0 0 0 10 15 Breakdown voltage drop rate (%) 15 15 15 15 30 25

Property evaluation data Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1 Comparative Example 2 Peel strength
(kgf / cm @ Cu 2 oz) 1.7 1.9 2 One 1.8 1.7 1.6 Breakdown voltage (kV) 6.3 6.3 6.4 6.3 6.2 6.3 5 Soldering Resistance
(min @ 288 < 0 > C) 50 50 50 50 50 50 50 Thermal conductivity
(W / mK) 2.4 2.5 1.8 3.2 2.7 2.4 2 Glass transition temperature (캜) 140 175 150 150 150 145 135 Decrease rate of peel strength (%) 5 15 5 5 10 5 10 Breakdown voltage drop rate (%) 25 40 20 20 45 30 35

As shown in Table 3 and Table 4, the epoxy resin composition according to one embodiment of the present invention is excellent in various physical properties such as peel strength, breakdown voltage, soldering resistance, thermal conductivity, glass transition temperature, reduction rate of peel strength, .

In particular, it was confirmed that Examples 1 to 4, in which a specific amount of an epoxy compound, a curing agent, and an inorganic filler were used in specific amounts, can secure more excellent physical properties.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

100: printed circuit board, 10: metal substrate,
20: insulating layer, 30: circuit layer

Claims (15)

5 to 40% by weight of an epoxy compound,
1 to 30% by weight of a phenolic curing agent and
And 40 to 92% by weight of an inorganic filler containing boron nitride,
Wherein the epoxy compound comprises 30 to 60 parts by weight of a naphthalene epoxy compound represented by the following formula (1) based on 100 parts by weight of the epoxy compound, 30 to 60 parts by weight of a triphenylmethane novolak epoxy compound represented by the following formula (3) And 10 to 40 parts by weight of a compound.
[Chemical Formula 1]

(Provided that in the general formula (1), x is represented by the following general formula (2), and n represents an integer of 1 to 10.)
(2)

(3)

(Wherein, in the general formula (3), x is represented by the general formula (2), n represents an integer of 1 to 5, m represents an integer of 1 to 4, and 1 represents an integer of 0 to 5.) delete delete The method according to claim 1,
Wherein the amorphous epoxy compound comprises a bisphenol A type epoxy compound represented by the following formula (4).
[Chemical Formula 4]

(Wherein, in the general formula (4), x is represented by the general formula (2), n represents an integer of 1 to 5, and R ¹ and R ² each independently represent hydrogen, a halogen element, a hydroxy group or an alkyl group. delete delete delete The method according to claim 1,
Wherein the inorganic filler has an average particle size of 0.1 to 30 占 퐉. The method according to claim 1,
Wherein the inorganic filler comprises 90 to 93.5 parts by weight of alumina and 6.5 to 10 parts by weight of boron nitride based on 100 parts by weight of the inorganic filler. The method according to claim 1,
Wherein the epoxy resin composition further comprises 0.1 to 5 parts by weight of a silane coupling additive based on 100 parts by weight of the epoxy resin composition. The method according to claim 1,
Wherein the epoxy resin composition has a glass transition temperature of 120 ° C or higher. The method according to claim 1,
Wherein the epoxy resin composition has a thermal conductivity of 2.0 W / mK to 5.0 W / mK. Metal substrate,
An insulating layer formed on the metal substrate, and
And a circuit layer formed on the insulating layer,
Wherein the insulating layer comprises 5 to 40% by weight of an epoxy compound,
1 to 30% by weight of a phenolic curing agent and
And 40 to 92% by weight of an inorganic filler containing boron nitride,
Wherein the epoxy compound comprises 30 to 60 parts by weight of a naphthalene epoxy compound represented by the following formula (1) based on 100 parts by weight of the epoxy compound, 30 to 60 parts by weight of a triphenylmethane novolak epoxy compound represented by the following formula (3) And 10 to 40 parts by weight of a compound.
[Chemical Formula 1]

(Provided that in the general formula (1), x is represented by the following general formula (2), and n represents an integer of 1 to 10.)
(2)

(3)

(Wherein, in the general formula (3), x is represented by the general formula (2), n represents an integer of 1 to 5, m represents an integer of 1 to 4, and 1 represents an integer of 0 to 5.) 14. The method of claim 13,
Wherein the insulating layer has a peel strength of 1.0 Kgf / cm to 2.0 Kgf / cm and a breakdown voltage of 5.0 to 7.0 kV. 15. The method of claim 14,
Wherein the insulating layer is subjected to a heat treatment at 200 캜 for 1000 hours, wherein the rate of decrease in peel strength is 10% or less and the rate of decrease in breakdown voltage is 20% or less.
(Note that the rate of decrease in peel strength is calculated as ([Peel strength after heat treatment] - [Peel strength before heat treatment] / [Peel strength before heat treatment] * 100, Breakdown voltage]) / [breakdown voltage before heat treatment] * 100)

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