KR102135414B1 - Liquid crystal polymer resin composite and printed circuit board comprising isolation using the same - Google Patents

Abstract

여기서, R¹ 내지 R¹²는 각각 H, Cl, Br, F, C₁~C₃ 알킬, C₂~C₃ 알켄, C₂~C₃ 알킨으로 구성된 그룹에서 선택될 수 있다.The liquid crystal polymer resin composition according to an embodiment of the present invention includes a resin containing a liquid crystal polymer compound, and an inorganic filler, and the liquid crystal polymer compound includes a repeating unit represented by the following Chemical Formula 1.
[Formula 1]

Here, R ¹ to R ¹² may be selected from the group consisting of H, Cl, Br, F, C ₁ to C ₃ alkyl, C ₂ to C ₃ alkene, and C ₂ to C ₃ alkyne, respectively.

Description

A printed circuit board including a liquid crystal polymer resin composition and an insulating layer using the same{LIQUID CRYSTAL POLYMER RESIN COMPOSITE AND PRINTED CIRCUIT BOARD COMPRISING ISOLATION USING THE SAME}

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

The printed circuit board includes a circuit pattern formed on an insulating layer, and various electronic components can 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.

With the high integration and high capacity of electronic components, interest in heat dissipation problems of printed circuit boards is growing. In general, 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 low viscosity, and thus has a problem of lack of curability, mechanical strength, toughness, and the like.

Accordingly, an epoxy resin composition containing a crystalline epoxy compound containing a mesogen structure has been used. The epoxy resin composition has excellent storage stability and curing properties before curing, but has limitations in obtaining required levels of heat resistance and thermal conductivity.

Technical problem to be achieved by the present invention is to provide a printed circuit board comprising a liquid crystal polymer resin composition and an insulating layer using the same.

The liquid crystal polymer resin composition according to an embodiment of the present invention includes a resin containing a liquid crystal polymer compound, and an inorganic filler, and the liquid crystal polymer compound includes a repeating unit represented by the following Chemical Formula 1.

[Formula 1]

Here, R ¹ to R ¹² may be selected from the group consisting of H, Cl, Br, F, C ₁ to C ₃ alkyl, C ₂ to C ₃ alkene, and C ₂ to C ₃ alkyne, respectively.

The liquid crystal polymer compound may include the structure of Formula 2 below.

[Formula 2]

Here, R ¹ to R ¹² may be selected from the group consisting of H, Cl, Br, F, C ₁ to C ₃ alkyl, C ₂ to C ₃ alkene, and C ₂ to C ₃ alkyne, respectively.

The liquid crystal polymer compound may include the structure of Formula 3 below.

[Formula 3]

The liquid crystal polymer compound may include p-acetoxyacetanilide-p-acetoxybenzoic acid-isophthalic acid copolymer (p-acetoxyacetanilide-p-acetoxybenzoic acid-isophthalic acid copolymer).

Further comprising a curing agent,

The resin may further include an amorphous epoxy compound.

The amorphous epoxy compound includes a bisphenol A-type epoxy compound, and the curing agent may include diaminodiphenylsulfone.

The amorphous epoxy compound may be included in an amount of 30 parts by weight or less based on 10 parts by weight of the liquid crystal polymer compound.

The resin may include 3 to 35 wt%, and the inorganic filler 65 to 97 wt%.

The inorganic filler may include one of alumina, boron nitride, aluminum nitride, silicon carbide, crystalline silica, silicon nitride, and mixtures selected from them.

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 is a resin comprising a liquid crystal polymer compound And, including an inorganic filler, the liquid crystal polymer compound is made of a liquid crystal polymer resin composition comprising a repeating unit of the following formula.

Here, R ¹ to R ¹² may be selected from the group consisting of H, Cl, Br, F, C ₁ to C ₃ alkyl, C ₂ to C ₃ alkene, and C ₂ to C ₃ alkyne, respectively.

According to the embodiment of the present invention, it is possible to obtain a liquid crystal polymer resin composition excellent in thermal conductivity. Using this, an insulating material having high heat resistance, moldability, and heat conductivity can be obtained, and heat dissipation performance and reliability of the printed circuit board can be improved.

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

The present invention can be applied to various changes and can have various embodiments, and specific embodiments will be illustrated and described in the drawings. However, this is not intended to limit the present invention to specific embodiments, and 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 other components. For example, the second component may be referred to as a first component without departing from the scope of the present invention, and similarly, the first component may also be referred to as a second component. The term and/or includes a combination of a plurality of related described items or any one of a plurality of related described items.

The terms used in this 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 this application, terms such as “include” or “have” are intended to indicate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, and that one or more other features are present. It should be understood that the existence or addition possibilities of fields or numbers, steps, operations, components, parts or combinations thereof are not excluded in advance.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. Terms, such as those defined in a commonly used dictionary, should be interpreted as having meanings consistent with meanings in the context of related technologies, and should not be interpreted as ideal or excessively formal meanings unless explicitly defined in the present application. Does not.

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

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

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

According to an embodiment of the present invention, there is provided a liquid crystal polymer resin composition comprising a resin containing a liquid crystal polymer compound and an inorganic filler.

The liquid crystal polymer resin composition according to an embodiment of the present invention is 3 wt% to 35 wt%, 5 wt% to 30 wt%, more preferably 5 wt% to 20 wt%, more preferably 7 wt% to the total liquid crystal polymer resin composition 13wt% resin and 65-97wt% inorganic filler. When the resin is 3 wt% or more of the total liquid crystal polymer resin composition and is contained in 35 wt% or less, adhesion is good, and thickness control may be easy. In addition, when the inorganic filler is included at 65 wt% to 97 wt%, high thermal conductivity, low thermal expansion and high temperature heat resistance of the liquid crystal polymer 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 is added, but not improved according to the volume fraction, and are improved dramatically from the specific amount added. However, if the addition amount of the inorganic filler is more than 97wt%, the viscosity increases and the moldability is weakened.

The liquid crystal polymer compound included in the liquid crystal polymer resin composition according to an embodiment of the present invention may include a repeating unit represented by the following Chemical Formula 1.

[Formula 1]

Here, R ¹ to R ¹² may be selected from the group consisting of H, Cl, Br, F, C ₁ to C ₃ alkyl, C ₂ to C ₃ alkene, and C ₂ to C ₃ alkyne, respectively.

The liquid crystal polymer compound included in the liquid crystal polymer resin composition according to an embodiment of the present invention may include Formula 2 below.

[Formula 2]

Here, R ¹ to R ¹⁶ may be selected from the group consisting of H, Cl, Br, F, C ₁ to C ₃ alkyl, C ₂ to C ₃ alkene, and C ₂ to C ₃ alkyne, respectively.

The liquid crystal polymer compound of Formula 2 may include Formula 3 below.

[Formula 3]

Here, the weight average molecular weight of the liquid crystal polymer compound may be a number average molecular weight (Mn) of the liquid crystal polymer compound is 1000 to 30000, preferably 10000 to 20000, and the weight average molecular weight (Mw) is 1000 to 40000, preferably 10000 It may be ~35000, and may be referred to as p-acetoxyacetanilide-p-acetoxybenzoic acid-isophthalic acid copolymer (p-acetoxyacetanilide-p-acetoxybenzoic acid-isophthalic acid copolymer). Here, the unit of number average molecular weight (Mn) or weight average molecular weight (Mw) may be g/mol.

The liquid crystal polymer compound has a flowable optical anisotropy, and in a predetermined temperature region, sufficient energy is not given such that each molecule freely rotates in the same form as in a liquid. Due to this, interactions between molecules occur, and molecules may form regions parallel to each other. At this time, the formed liquid crystal polymer compound has many nematic forms parallel to the long axis direction of the molecule. In addition, the liquid crystal polymer compound has very little change in structure and change in entropy in the solid state and in the molten state.

Representative characteristics of the liquid crystal polymer compound are high heat resistance, strength, and elastic modulus. In addition, when processing, the melt viscosity is low, molding shrinkage is low, it has good dimensional stability, low linear expansion coefficient, low moisture absorption properties, and excellent chemical resistance.

The liquid crystal polymer compound may be included in 1 wt% to 35 wt% of the total liquid crystal polymer resin composition, preferably 3 wt% to 30 wt%, more preferably 5 wt% to 25 wt%, and more preferably 7 wt% to 20 wt%. If the liquid crystal polymer compound is contained lower than 1 wt% of the total liquid crystal polymer resin composition, a desired level of thermal conductivity may not be obtained. In addition, when the liquid crystal polymer compound is contained in an amount exceeding 35 wt% of the total liquid crystal polymer resin composition, the content of the inorganic filler may be lowered, resulting in lower thermal conductivity and poor room temperature storage or flowability.

In the liquid crystal polymer resin composition according to an embodiment of the present invention, the resin may further include an amorphous epoxy resin.

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

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-dihydride Hydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2, Dihydric phenols such as 8-dihydroxynaphthalene, allylates or polyallyliates of the above dihydroxynaphthalene, bisphenol allylated, bisphenol allylated, and phenol novolak allylated, 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-butylpyrrologalol, allylated pyrogallol, polyallylation pyrogallol, 1,2,4-benzenetriol, 2, 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 them It may be a glycidyl etherate derived from.

An example of the bisphenol A-type epoxy compound is as shown in Chemical Formula 4.

[Formula 4]

Here, n is an integer of 1 or more.

An example of the bisphenol F-type epoxy compound is as shown in Chemical Formula 5.

[Formula 5]

According to one embodiment of the present invention, the amorphous epoxy compound with respect to 10 parts by weight of the liquid crystal polymer compound may be included in an amount of 0.0001 parts by weight or more and 30 parts by weight or less, preferably 15 parts by weight or less, and more preferably 5 parts by weight or less have. When the amorphous epoxy compound of 0.0001 parts by weight or more and 30 parts by weight or less based on 10 parts by weight of the liquid crystal polymer compound is further included, room temperature storage property, flowability, and physical properties required for the process may be further improved.

Meanwhile, the curing agent included in the liquid crystal polymer resin composition according to one embodiment of the present invention is 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 It may include at least one of the curing agent.

The amine-based curing agent may be, for example, 4, 4'-diamino diphenyl sulfone. The following Chemical Formula 6 is an example of diaminodiphenylsulfone.

[Formula 6]

Other examples of the amine curing agent may be aliphatic amines, polyether polyamines, alicyclic amines, aromatic amines, and the like, and aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, and hexa Methylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, And N-hydroxyethyl ethylenediamine, tetra(hydroxyethyl)ethylenediamine, and the like. The polyether polyamines may be one of triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and mixtures selected from them. Examples of the alicyclic amines include isophorone diamine, metasendiamine, N-aminoethyl piperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, and 3,9-bis(3 -Aminopropyl)2,4,8,10-tetraoxaspiro(5,5)undecane, norbornenediamine, and the like. As aromatic amines, 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 selected from them.

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'-dihydride Hydroxydiphenylsulfone, 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 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-butylpyrogalol, allylated pyrogallol, polyallyl Huapirogalol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydride Hydroxynaphthalene, 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-dihydroxynaphthalene, allyl of the dihydroxynaphthalene It may be one of cargo or polyallylate, allylated bisphenol A, allylated bisphenol F, allylated phenol novolac, allylated pyrogallol, and mixtures selected therefrom.

Acid anhydride-based curing agents include, for example, dodecenyl anhydrous succinic acid, polyadipic acid anhydride, polyazelinic acid anhydride, polysevacinic acid anhydride, poly(ethyl octadecane diacid) anhydride, poly(phenylhexadecane diacid) anhydride, methyl tetrahydro Phthalic anhydride, methyl hexahydro anhydride phthalic acid, hexahydro anhydride phthalic anhydride, methyl hymic anhydride, tetrahydro anhydride phthalic acid, trialkyltetrahydro anhydride phthalic acid, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, phthalic anhydride, Trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, hetic 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 selected from them.

The curing agent may be included in 0.9 to 1.1 parts by weight based on 10 parts by weight of the amorphous epoxy resin. That is, the liquid crystal polymer compound has high moldability and does not require a separate curing agent. Therefore, in the liquid crystal polymer resin composition according to an embodiment of the present invention, the curing agent does not need to be added in an excessive amount, and the problem of reducing thermal conductivity due to the residual curing agent can be reduced.

Meanwhile, the inorganic filler included in the liquid crystal polymer resin composition according to an embodiment of the present invention may be one of alumina, boron nitride, aluminum nitride, silicon carbide, crystalline silica, silicon nitride, and a mixture selected from them.

The liquid crystal polymer resin composition according to an embodiment of the present invention may further include a curing accelerator. Curing accelerators include, for example, amine curing accelerators, imidazole curing accelerators, organic phosphine curing accelerators, Lewis acid curing accelerators, etc., specifically, 1,8-diazabicyclo(5,4,0) Ter-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol and other tertiary amines, 2-methylimidazole, 2-phenylimidazole, 2-phenyl- Imidazoles such as 4-methylimidazole and 2-heptadecylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine, Tetra substituted phosphonium, tetra substituted borate, 2-ethyl-4-methylimidazole, tetra such as tetraphenyl phosphonium, tetraphenyl borate, tetraphenyl phosphonium, ethyl triphenyl borate, tetrabutyl phosphonium, tetrabutyl borate, etc. And tetraphenyl boron salts such as phenyl borate and N-methylmorpholine/tetraphenyl borate.

The liquid crystal polymer resin composition according to an embodiment of the present invention may include a release agent. As a mold release agent, wax, for example, stearic acid, montanic acid, montanic acid ester, phosphoric acid ester, or the like can be used.

The liquid crystal polymer resin composition according to an embodiment of the present invention may include a catalyst.

The catalyst may include, for example, an imidazole-based additive.

When the liquid crystal polymer resin composition according to an embodiment of the present invention includes an imidazole-based additive, adhesion to a metal may be enhanced. As a result, the adhesion between the insulating layer and the circuit pattern made of copper is increased, and the possibility of breakage and disconnection of the circuit pattern is lowered, so that processing of the printed circuit board is facilitated and reliability of the printed circuit board is increased.

The liquid crystal polymer resin composition according to an 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 alloys 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 and nickel.

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

By curing the liquid crystal polymer 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.

Hereinafter, examples and comparative examples will be described in more detail.

<Example 1>

1 wt% of the liquid crystal polymer compound of Formula 3 (Mn: 18567, Mw: 30811), 9 wt% of bisphenol A-type epoxy compound of Formula 4, 0.9 wt% of 4, 4'-diaminodiphenylsulfone, 1 wt% of phenoxy MEK ( After dissolving in Methyl Ethly Ketone) for 20 minutes, 88.1 wt% of alumina was further added and stirred for 2 hours. After the stirring was completed, the solution was coated on a copper plate, and then pressurized at 150°C for 1 hour and 30 minutes to obtain a liquid crystal polymer resin composition of Example 1.

<Example 2>

3 wt% of liquid crystal polymer compound of formula 3 (Mn: 18567, Mw: 30811), 7 wt% of bisphenol A-type epoxy compound of formula 4, 0.7 wt% of 4, 4'-diaminodiphenylsulfone, 1 wt% of phenoxy MEK ( After dissolving in Methyl Ethly Ketone for 20 minutes, 88.3 wt% of alumina was further added and stirred for 2 hours. After the stirring was completed, the solution was coated on a copper plate and pressed at 150° C. for 1 hour and 30 minutes to obtain a liquid crystal polymer resin composition of Example 2.

<Example 3>

5 wt% of liquid crystal polymer compound of formula 3 (Mn: 18567, Mw: 30811), 5 wt% of bisphenol A type epoxy compound of formula 4, 0.5 wt% of 4, 4'-diaminodiphenylsulfone, 1 wt% of phenoxy MEK ( After dissolving in Methyl Ethly Ketone) for 20 minutes, 88.5 wt% of alumina was further added and stirred for 2 hours. After the stirring was completed, the solution was coated on a copper plate, and then pressurized at 150°C for 1 hour and 30 minutes to obtain the liquid crystal polymer resin composition of Example 3.

<Example 4>

Liquid crystal polymer compound of formula (Mn: 18567, Mw: 30811) 7wt%, bisphenol A-type epoxy compound of formula 4 3wt%, 4, 4'-diaminodiphenylsulfone 0.3wt%, phenoxy 1wt% MEK ( After dissolving in Methyl Ethly Ketone) for 20 minutes, 88.7 wt% of alumina was further added and stirred for 2 hours. After the stirring was completed, the solution was coated on a copper plate and pressed at 150° C. for 1 hour and 30 minutes to obtain the liquid crystal polymer resin composition of Example 4.

<Example 5>

After dissolving 10 wt% of the liquid crystal polymer compound of Formula 3 (Mn: 18567, Mw: 30811) and 1 wt% of phenoxy in MEK (Methyl Ethly Ketone) for 20 minutes, 89 wt% of alumina was further added and stirred for 2 hours. After the stirring was completed, the solution was coated on a copper plate, and then pressurized at 150°C for 1 hour and 30 minutes to obtain the liquid crystal polymer resin composition of Example 5.

<Example 6>

After dissolving 5 wt% of the liquid crystal polymer compound of Formula 3 (Mn: 18567, Mw: 30811) and 1 wt% of phenoxy in MEK (Methyl Ethly Ketone) for 20 minutes, 94 wt% of alumina was further added and stirred for 2 hours. After the solution of stirring was coated on a copper plate, the resin composition of Example 6 was obtained by pressing at 150° C. for 1 hour 30 minutes.

<Example 7>

After dissolving 3 wt% of the liquid crystal polymer compound of Formula 3 (Mn: 18567, Mw: 30811) and 1 wt% of phenoxy in MEK (Methyl Ethly Ketone) for 20 minutes, 96 wt% of alumina was further added and stirred for 2 hours. After the stirring was completed, the solution was coated on a copper plate and pressed at 150° C. for 1 hour and 30 minutes to obtain the resin composition of Example 7.

<Comparative Example 1>

After dissolving 10 wt% of the bisphenol A-type epoxy compound of Formula 4, 1 wt% of 4, 4'-diaminodiphenylsulfone, and 1 wt% of phenoxy in MEK (Methyl Ethly Ketone) for 20 minutes, 88 wt% of alumina was further added. Stir for 2 hours. After the stirring was completed, the solution was coated on a copper plate and pressed at 150° C. for 1 hour and 30 minutes to obtain the resin composition of Comparative Example 1. <Comparative Example 2>

After dissolving 5 wt% of the bisphenol A-type epoxy compound of Formula 4, 0.5 wt% of 4, 4'-diaminodiphenylsulfone, and 1 wt% of phenoxy in MEK (Methyl Ethly Ketone) for 20 minutes, 93.5 wt% of alumina was further added. It was added and stirred for 2 hours. After the stirring solution was coated on a copper plate, the resin composition of Comparative Example 2 was obtained by pressing at 150° C. for 1 hour 30 minutes.

<Comparative Example 3>

After dissolving 3 wt% of the bisphenol A type epoxy compound of Formula 4, 0.3 wt% of 4, 4'-diaminodiphenylsulfone, and 1 wt% of phenoxy in MEK (Methyl Ethly Ketone) for 20 minutes, 95.7 wt% of alumina was further added. It was added and stirred for 2 hours. After the stirring solution was coated on a copper plate, the resin composition of Comparative Example 3 was obtained by pressing at 150° C. for 1 hour and 30 minutes.

<Comparative Example 4>

After dissolving 40 wt% of the bisphenol A-type epoxy compound of Formula 4, 4 wt% of 4, 4'-diaminodiphenylsulfone, and 1 wt% of phenoxy in MEK (Methyl Ethly Ketone) for 20 minutes, 55 wt% of alumina was further added. Stir for 2 hours. After the stirring solution was coated on a copper plate, the resin composition of Comparative Example 2 was obtained by pressing at 150° C. for 1 hour 30 minutes.

<Comparative Example 5>

After dissolving 40 wt% of the liquid crystal polymer compound of Formula 3 (Mn: 18567, Mw: 30811) and 1 wt% of phenoxy in MEK (Methyl Ethly Ketone) for 20 minutes, 59 wt% of alumina was further added and stirred for 2 hours. After the stirring was completed, the solution was coated on a copper plate and pressed at 150° C. for 1 hour and 30 minutes to obtain the resin composition of Comparative Example 5.

<Comparative Example 6>

After dissolving 1 wt% of the bisphenol A type epoxy compound of Formula 4, 0.1 wt% of 4, 4'-diaminodiphenylsulfone, and 1 wt% of phenoxy in MEK (Methyl Ethly Ketone) for 20 minutes, 97.9 wt% of alumina was further added. It was added and stirred for 2 hours. After the stirring was completed, the solution was coated on a copper plate, and then pressed at 150°C for 1 hour and 30 minutes to obtain the resin composition of Comparative Example 6.

<Comparative Example 7>

After dissolving 1 wt% of the liquid crystal polymer compound of Formula 3 (Mn: 18567, Mw: 30811) and 1 wt% of phenoxy in MEK (Methyl Ethly Ketone) for 20 minutes, 98 wt% of alumina was further added and stirred for 2 hours. After the stirring was completed, the solution was coated on a copper plate and pressed at 150° C. for 1 hour and 30 minutes to obtain the resin composition of Comparative Example 7.

<Experimental Example>

The thermal conductivity of the resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7 was measured by an abnormal heating method using a LFA447 type thermal conductivity meter manufactured by NETZSCH. Tables 1 to 4 show the results.

Experiment number Thermal conductivity (W/m.K) Example 1 7.23 Example 2 7.89 Example 3 8.35 Example 4 9.37 Example 5 11.19 Comparative Example 1 6.75

Experiment number Thermal conductivity (W/m.K) Example 6 9.12 Comparative Example 2 7.12

Experiment number Thermal conductivity (W/m.K) Example 7 9.37 Comparative Example 3 7.41

Experiment number Thermal conductivity (W/m.K) Comparative Example 4 2 Comparative Example 5 3.32 Comparative Example 6 2.1 Comparative Example 7 2.45

As shown in Table 1, it can be seen that the thermal conductivity of Examples 1 to 5 including the liquid crystal polymer compound is higher than that of Comparative Example 1 without the liquid crystal polymer compound. In particular, compared to Example 1 containing more than 30 parts by weight of the amorphous epoxy compound with respect to 10 parts by weight of the liquid crystal polymer compound, Examples 2 to 10 containing less than 30 parts by weight of the amorphous epoxy compound with respect to 10 parts by weight of the liquid crystal polymer compound It can be seen that the thermal conductivity of 5 is further increased.

Similarly, as shown in Tables 2 and 3, the thermal conductivity of Examples 6 to 7 containing the liquid crystal polymer compound does not include the liquid crystal polymer compound, and the thermal conductivity of Comparative Examples 2 to 3 containing the amorphous epoxy compound. It can be seen that it is high.

In addition, as shown in Table 4, the thermal conductivity of Comparative Examples 4 to 7 including the inorganic filler in an amount of less than 65 wt% or more than 97 wt%, in Examples 1 to 7 including the inorganic filler in 65 to 97 wt% It can be seen that it is significantly lower than the thermal conductivity.

The liquid crystal polymer resin composition according to an embodiment of the present invention can be variously applied to not only the insulating layer of the printed circuit board, but also to electronic components requiring heat dissipation and insulation performance. For example, the liquid crystal polymer resin composition according to an embodiment of the present invention may be implemented as a heat dissipation sheet of an electronic component.

Although described above with reference to preferred embodiments of the present invention, those skilled in the art variously modify and change the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. You can understand that you can.

Claims (9)

A resin comprising a liquid crystal polymer compound and an amorphous epoxy compound, and
Contains inorganic filler,
The liquid crystal polymer compound includes the structure of the following formula,
The number average molecular weight of the liquid crystal polymer compound is 1000 to 30000 g/mol, and the weight average molecular weight is 1000 to 40000 g/mol,
The liquid crystal polymer resin composition containing 10 parts by weight or more and 30 parts by weight or less of the amorphous epoxy compound relative to 10 parts by weight of the liquid crystal polymer compound:
[Formula]

Here, R ¹ to R ¹⁶ may be selected from the group consisting of H, Cl, Br, F, C ₁ to C ₃ alkyl, C ₂ to C ₃ alkene, and C ₂ to C ₃ alkyne, respectively, n is 2 or more It is an integer. delete According to claim 1,
The liquid crystal polymer compound is a liquid crystal polymer resin composition comprising the structure of Formula 3:
[Formula 3]

Here, n is an integer of 2 or more. According to claim 1,
A liquid crystal polymer resin composition further comprising a curing agent. According to claim 4,
The amorphous epoxy compound includes a bisphenol A-type epoxy compound, and the curing agent is a liquid crystal polymer resin composition comprising diaminodiphenylsulfone. delete According to claim 1,
The resin 3 to 35wt% and the liquid crystal polymer resin composition comprising the inorganic filler 65 to 97wt%. According to claim 1,
The inorganic filler is a liquid crystal polymer resin composition comprising one of alumina, boron nitride, aluminum nitride, silicon carbide, crystalline silica, silicon nitride, and mixtures selected therefrom. Metal Plate,
An insulating layer formed on the metal plate, and
It includes a circuit pattern formed on the insulating layer,
The insulating layer is a printed circuit board made of the liquid crystal polymer resin composition according to claim 1.

Images