KR20220005850A - Thermoplastic resin composition having low dielectric constant and low dielectric loss and molded article prepared from the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition having a low dielectric constant and low dielectric loss and a molded article manufactured therefrom, and more specifically, to a composition which has low dielectric properties, excellent physical property balance such as fluidity, impact resistance, and the like and maintains physical properties equivalent to those of an existing polycarbonate material by including polycarbonate and a polysiloxane-polycarbonate copolymer or a mixture thereof, high-density polyethylene, a compatibilizer and a thermally stable compound in a specific amount.

Description

Thermoplastic resin composition having low dielectric constant and low dielectric loss and molded article prepared therefrom

The present invention relates to a thermoplastic resin composition having a low dielectric constant and a low dielectric loss and a molded article prepared therefrom, and more particularly, to polycarbonate and By including a polysiloxane-polycarbonate copolymer or a mixture thereof, high density polyethylene, a compatibilizer and a thermal stability compound in a specific amount, it has a low dielectric property and excellent balance of physical properties such as fluidity and impact resistance, and the existing polycarbonate It relates to a composition and molded article that maintains the same level of physical properties as the material.

Polycarbonate resin is a general-purpose thermoplastic engineering plastic manufactured by polycondensation of bisphenol A and phosgene and having a glass transition temperature of around 150°C. It is a high-heat-resistance engineering plastic that replaces glass due to its excellent quality, and its field of use is expanding day by day, such as being used as a housing for electrical/electronic products or as a plate for construction and advertising. The physical properties of the polycarbonate resin are derived from the phenyl group and the carboxyl group, and molecular structural properties such as rigidity of the molecular chain and rotational restraint affect the physical properties.

With the beginning of the 5th generation communication era, the need for materials with low dielectric constant and low dielectric loss rate characteristics for the existing polycarbonate and polycarbonate glass fiber reinforced materials used for home appliances and mobile applications is growing, and research continues accordingly. is becoming For example, Japanese Patent Laid-Open No. 2006-063297 discloses a dielectric constant insulating resin composition containing polycarbonate as a low-dielectric component, and Korean Patent Laid-Open No. 10-2017-0112997 discloses polycarbonate diol and isocyanate. A low-k resin composition comprising a urethane resin obtained by reacting is disclosed, but all of them exhibit a dielectric constant of 2.95 or more and a dielectric loss factor of 0.005 or more, indicating a result in which low dielectric properties cannot be secured.

Accordingly, a new low-k material having a low dielectric constant of less than 2.95 and a dielectric loss factor of less than 0.005, and a balance of physical properties similar to the mechanical properties (impact resistance, heat resistance, etc.) of existing polycarbonate materials. development is needed.

The present invention is intended to solve the problems of the prior art, and by including polycarbonate, high-density polyethylene, compatibilizer and thermal stability compound in a specific amount, it has low dielectric properties and balance of physical properties such as fluidity and impact resistance It is a technical task to provide a composition and molded article that is excellent and maintains the same level of physical properties as that of the existing polycarbonate material.

In order to achieve the above technical problem, the present invention, based on 100 parts by weight of the total composition, (A) a thermoplastic aromatic polycarbonate resin, polysiloxane-polycarbonate copolymer or a mixture thereof 42 to 82.5 parts by weight; (B) 6 to 29 parts by weight of high density polyethylene; (C) 0.1 to 15 parts by weight of the acrylic compatibilizer and (D) provides a low dielectric thermoplastic resin composition comprising 0.1 to 15 parts by weight of the heat-stable compound.

According to another aspect of the present invention, there is provided a molded article manufactured by processing the thermoplastic resin composition.

Since the low-k thermoplastic resin composition of the present invention contains polycarbonate, polysiloxane-polycarbonate copolymer or a mixture thereof, high-density polyethylene, compatibilizer, and thermal stability compound in a specific content, a dielectric constant of less than 2.95 when measured at 2.5 GHz and It has a low dielectric characteristic with a dielectric loss factor of less than 0.005, and at the same time has an excellent balance of properties such as fluidity and impact resistance, and can secure the same level of physical properties as existing polycarbonate materials. The molded article manufactured by processing the thermoplastic resin composition of the present invention may be applied to interior and exterior materials requiring scratch resistance and impact strength, for example, it may be applied to a mobile phone housing and a housing of an electric or electronic product.

Hereinafter, the present invention will be described in detail.

The present invention provides, based on 100 parts by weight of the total composition, (A) 42 to 82.5 parts by weight of a thermoplastic aromatic polycarbonate resin, a polysiloxane-polycarbonate copolymer, or a mixture thereof; (B) 6 to 29 parts by weight of high density polyethylene; (C) 0.1 to 15 parts by weight of the acrylic compatibilizer and (D) provides a low dielectric thermoplastic resin composition comprising 0.1 to 15 parts by weight of the heat-stable compound.

(A) a thermoplastic aromatic polycarbonate resin, a polysiloxane-polycarbonate copolymer, or a mixture thereof

Thermoplastic Aromatic Polycarbonate Resin

The thermoplastic aromatic polycarbonate resin used in the composition of the present invention may be prepared from a dihydric phenol, a carbonate precursor, and a molecular weight modifier. The dihydric phenols are, for example, monomers of polycarbonate resins having the following structures.

In the above, X includes functional groups such as an alkyl group, sulfide, ether, sulfoxide, sulfone, or ketone, or a case in which no functional group is present. Preferably X represents a straight, branched or cyclic alkylene group, more preferably X represents a straight, branched or cyclic alkylene group containing 1 to 10 carbons. R ₁ and R ₂ represent hydrogen, a halogen atom, a linear, branched or cyclic alkyl group. Meanwhile, n and m may be independently integers of 0 to 4.

Non-limiting examples of the dihydric phenols include bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, and bis(4-hydroxyphenyl)methane. Phenyl)-(4-isobutylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 1-phenyl-1, 1-bis(4-hydroxyphenyl)ethane, 1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,10-bis (4-hydroxyphenyl)decane, 2-methyl-1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), and the like; One of them is bisphenol A.

The carbonate precursor is another monomer of the polycarbonate resin, and it is preferable to use phosgene (carbonyl chloride). Non-limiting examples of carbonate precursors include carbonyl bromide, bis halo formate, diphenyl carbonate or dimethyl carbonate, and the like.

As the molecular weight control agent, a known material, that is, a monofunctional compound similar to a monomer used for manufacturing a thermoplastic aromatic polycarbonate resin may be used. By way of non-limiting example, phenol-based derivatives thereof (eg, para-isopropylphenol, para-tert-butylphenol, para-cumylphenol, para-isooctylphenol, para-isononylphenol, etc.) can be used, and various kinds of substances such as aliphatic alcohols can be used. Among them, para-tert-butylphenol (PTBP) is most preferable.

As the aromatic polycarbonate resin prepared as such dihydric phenol, carbonate precursor, and molecular weight modifier, for example, linear polycarbonate resin, branched polycarbonate resin, copolycarbonate resin, polyester carbonate resin, etc. There is this.

On the other hand, in exemplary embodiments of the present invention, it is preferable to apply a _{thermoplastic aromatic polycarbonate resin having a viscosity average molecular weight (M v ) of 15,000 to 40,000, measured in a methylene chloride solution at 25° C., and 16,000 to 32,000} It is more preferable to apply the If the viscosity average molecular weight is less than 15,000, mechanical properties such as impact strength and tensile strength may be greatly reduced, and if it exceeds 40,000, problems in processing the resin may occur due to an increase in melt viscosity. In particular, in terms of excellent mechanical properties such as impact strength and tensile strength, the viscosity average molecular weight is more preferably 16,000 or more, and more preferably 32,000 or less in terms of workability.

polysiloxane-polycarbonate copolymer

In the low dielectric thermoplastic resin composition of the present invention, a polysiloxane-polycarbonate copolymer or a polycarbonate and polysiloxane-polycarbonate copolymer may be used instead of polycarbonate, and the polysiloxane-polycarbonate copolymer is a hydroxy-terminated siloxane and polycarbonate block may be included as a repeating unit.

In the present invention, the polysiloxane-polycarbonate copolymer has a weight average molecular weight (Mw) of the hydroxy-terminated siloxane contained in the copolymer is 2,500 to 15,000, preferably 3,500 to 13,000, more preferably 4,000 to 9,000. If the weight average molecular weight of the hydroxy-terminated siloxane is less than 2,500, the effect of improving the impact strength may be insignificant, and if it exceeds 15,000, the reactivity is lowered and there may be a problem in synthesizing the polysiloxane-polycarbonate copolymer to a desired molecular weight.

The polysiloxane-polycarbonate copolymer of the present invention preferably contains 1 to 10 parts by weight, for example, 2 to 5 parts by weight, based on 100 parts by weight of the copolymer. If the content of hydroxy-terminated siloxane is less than 1 part by weight, the effect of improving the impact strength may be insignificant, and if the content exceeds 10 parts by weight, physical properties such as fluidity, heat resistance, impact strength, etc. may be deteriorated, and the manufacturing cost increases, making it economical It is not preferable in terms of phosphorus.

According to a preferred embodiment of the present invention, the hydroxy terminated siloxane in the polysiloxane-polycarbonate copolymer has the following formula (1a) or formula (1):

[Formula 1a]

In Formula 1a,

R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or an aryl group. For example, the halogen atom may be Cl or Br, the alkyl group may be an alkyl group having 1 to 13 carbon atoms, such as methyl, ethyl or propyl, and the alkoxy group may be an alkoxy group having 1 to 13 carbon atoms, such as methoxy, It may be ethoxy or propoxy, and the aryl group may be 6 to 10 aryl groups, such as phenyl, chlorophenyl or tolyl.

R ₂ independently represents a hydrocarbon group or hydroxyl group having 1 to 13 carbon atoms. For example, R ₂ is an alkyl or alkoxy group having 1 to 13 carbon atoms, an alkenyl or alkenyloxy group having 2 to 13 carbon atoms, a cycloalkyl or cycloalkoxy group having 3 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, It may be an aralkyl group or aralkoxy group having 7 to 13 carbon atoms, or an alkaryl group or alkaryloxy group having 7 to 13 carbon atoms.

R ₃ independently represents an alkylene group having 2 to 8 carbon atoms.

m is independently an integer from 0 to 4.

n is an integer from 30 to 200, preferably an integer from 40 to 170, more preferably an integer from 50 to 120.

)를 사용할 수 있으나, 반드시 이에 한정되는 것은 아니다.In one embodiment, the hydroxy-terminated siloxane of Formula 1a is a siloxane monomer from Dow Corning (

) can be used, but is not necessarily limited thereto.

[Formula 1]

In Formula 1,

R ₁ , R ₂ , R ₃ and m are as defined in Formula 1a above, and n is independently an integer from 15 to 100, preferably an integer from 20 to 80, more preferably an integer from 25 to 60. and A represents the structure of the following formula (2) or (3).

[Formula 2]

In Formula 2, X is Y or NH-Y-NH, where Y is a linear or branched aliphatic group having 1 to 20 carbon atoms, a cycloalkylene group (eg, a cycloalkylene group having 3 to 6 carbon atoms), or halogen represents a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms, unsubstituted or substituted with an atom, an alkyl group, an alkoxy group, an aryl group, or a carboxyl group. For example, Y is an aliphatic group unsubstituted or substituted with a halogen atom, an aliphatic group containing oxygen, nitrogen or sulfur atoms in the backbone, or aryl which may be derived from bisphenol A, resorcinol, hydroquinone or diphenylphenol. It may be a ren group, for example, it may be represented by the following Chemical Formulas 2a to 2h.

[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

[Formula 2e]

[Formula 2f]

[Formula 2g]

[Formula 2h]

[Formula 3]

In Formula 3, R ₄ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, an aromatic/aliphatic mixed hydrocarbon group, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Here, R ₄ may have a structure including halogen, oxygen, nitrogen, or sulfur in addition to a carbon atom. For example, R ₄ may be phenyl, chlorophenyl or tolyl (preferably phenyl).

In one embodiment, the hydroxy-terminated siloxane of Formula 1 may be a reaction product of the aforementioned hydroxy-terminated siloxane of Formula 1a (provided that n is an integer of 15 to 100) and an acyl compound. Here, the acyl compound may have, for example, an aromatic, aliphatic, or mixed structure including both aromatic and aliphatic. When the acyl compound is aromatic or mixed, it may have 6 to 30 carbon atoms, and when aliphatic, it may have 1 to 20 carbon atoms. The acyl compound may further include a halogen, oxygen, nitrogen or sulfur atom.

In another embodiment, the hydroxy-terminated siloxane of Formula 1 may be a reaction product of the hydroxy-terminated siloxane of Formula 1a (provided that n is an integer of 15 to 100) and a diisocyanate compound. Here, the diisocyanate compound may be, for example, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, or 4,4'-methylenediphenyl diisocyanate.

In another embodiment, the hydroxy-terminated siloxane of Formula 1 is a reaction product of a hydroxy-terminated siloxane of Formula 1a (provided that n is an integer of 15 to 100) and a phosphorus-containing compound (aromatic or aliphatic phosphate compound) can Here, the phosphorus-containing compound may be represented by the following Chemical Formula 1b.

[Formula 1b]

In Formula 1b, R ₄ is as defined in Formula 3 above, and Z independently represents phosphorus, a halogen atom, a hydroxyl group, a carboxyl group, an (C 1 to 20) alkyl group, an alkoxy group, or an aryl group.

Further, according to a preferred embodiment of the present invention, the polycarbonate block in the polysiloxane-polycarbonate copolymer has the following formula (4):

[Formula 4]

In Formula 4, R ₅ is a (C1 to C20) divalent alkyl group (eg, a C1 to C13 divalent alkyl group), a cycloalkyl group (eg, a C3 to C6 divalent cycloalkyl group) , an alkenyl group (eg, a divalent alkenyl group having 2 to 13 carbon atoms), an alkoxy group (eg, a divalent alkoxy group having 1 to 13 carbon atoms), or a halogen atom or nitro-substituted or unsubstituted C6-C30 A divalent aromatic hydrocarbon group is represented.

Here, the aromatic hydrocarbon group may be derived from a compound having a structure of the following Chemical Formula 4a.

[Formula 4a]

In Formula 4a, X is an alkylene group, a straight, branched, or cyclic alkylene group having no functional group, or a straight, branched group containing a functional group such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, or isobutylphenyl. represents a topographical or cyclic alkylene group, preferably, X may be a straight, branched or cyclic alkylene group having 1 to 10 carbon atoms or a cyclic alkylene group having 3 to 6 carbon atoms; R ₆ independently represents a hydrogen atom, a halogen atom, or an alkyl group, such as a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms or a cyclic alkyl group having 3 to 20 carbon atoms (preferably 3 to 6 carbon atoms); n and m are independently integers from 0 to 4.

The compound of Formula 4a is, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4-hydroxyphenyl) )-(4-isobutylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 1-phenyl-1,1 -bis(4-hydroxyphenyl)ethane, 1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,10-bis( 4-hydroxyphenyl)decane, 2-methyl-1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy Phenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) nonane, 2,2- Bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-fluoro-4-hydroxyphenyl)propane, 4-methyl-2,2-bis(4-hydroxyphenyl)pentane , 4,4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) methane, resorcinol, hydroquinone, 4,4'-dihydroxyphenyl ether [bis(4-hydroxyphenyl)ether], 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether , bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dichloro-4-hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1, 4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p,p'-dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxyphenyl, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dichloro-4- Hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis (4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)decane, 1,4-bis(4-hydroxyphenyl)propane, 1,4-bis(4-hydroxyphenyl)butane , 1,4- Bis(4-hydroxyphenyl)isobutane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, bis(3,5-dimethyl -4-hydroxyphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)- 2-Methyl-butane, 4,4'-thiodiphenol [bis (4-hydroxyphenyl) sulfone], bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3-chloro-4- Hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(3-methyl-4-hydroxyphenyl)sulfide, bis(3,5-dimethyl-4 -Hydroxyphenyl)sulfide, bis(3,5-dibromo-4-hydroxyphenyl)sulfoxide, 4,4'-dihydroxybenzophenone, 3,3',5,5'-tetramethyl- 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene, but not limited thereto. does not A representative of these is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). Other functional dihydric phenols (dihydric phenol) may refer to US Patent Nos. 2,999,835, US 3,028,365, US 3,153,008 and US 3,334,154, etc., and the dihydric phenols are singly or in combination of two or more can be used

In the case of the carbonate precursor, as another monomer of the polycarbonate resin, for example, carbonyl chloride (phosgene), carbonyl bromide, bis halo formate, diphenyl carbonate, or dimethyl carbonate may be used.

The polysiloxane-polycarbonate copolymer used in the present invention preferably has a viscosity average molecular weight (Mv) of 15,000 to 30,000, more preferably 17,000 to 22,000. If the viscosity average molecular weight of the polysiloxane-polycarbonate copolymer is less than 15,000, mechanical properties may be remarkably deteriorated, and if it exceeds 30,000, problems in processing the resin may occur due to an increase in melt viscosity.

The content of the thermoplastic aromatic polycarbonate resin, polysiloxane-polycarbonate copolymer, or mixture thereof included in the thermoplastic resin composition of the present invention is 42 parts by weight or more, 42.8 parts by weight or more, 45 parts by weight or more, based on 100 parts by weight of the total composition. , 50 parts by weight or more, 55 parts by weight or more, 60 parts by weight or more, 65 parts by weight or more, or 70 parts by weight or more, and 82.5 parts by weight or less, 82 parts by weight or less, 80 parts by weight or less, 79 parts by weight or less, 78 parts by weight or less It may be less than or equal to 77.8 parts by weight, for example, 42 to 82.5 parts by weight, 45 to 82 parts by weight, or 50 to 78 parts by weight. When the content of the thermoplastic aromatic polycarbonate resin, polysiloxane-polycarbonate copolymer, or a mixture thereof is less than 42 parts by weight, mechanical properties such as impact strength may be significantly deteriorated, and a problem may occur in thermal properties. When it exceeds 82.5 parts by weight, the dielectric loss factor measured at 2.5 GHz may increase to 0.005 or more.

According to one embodiment of the present invention, when the composition of the present invention includes a mixture of polycarbonate and polysiloxane-polycarbonate copolymer, the mixing ratio of polycarbonate: polysiloxane-polycarbonate copolymer is 99.9:0.1 to 0.1:99.9 days may be, for example, 90:10 to 10:90, 80:20 to 20:80, 70:30 to 30:70, 60:40 to 40:60, 65:45 to 45:60, 85:15 to 50:50, 85:15 to 55:45, 85:15 to 60:40, 75:25 to 50:50, 75:25 to 55:45, 75:25 to 60:40, 70:30 to 50: 50, 70:30 to 60:40, or 89:11 to 95:5.

(B) high density polyethylene

The high-density polyethylene resin (HDPE) used in the present invention may be a low-viscosity high-density polyethylene resin advantageous for application to blow molding applications requiring shape stability and melt elasticity. The high-density polyethylene resin may be a high-density polyethylene resin having a melt index of 0.2 g/10 min to 2.0 g/10 min. For example, it may be high-density polyethylene having a melt index of 0.35 g/10 min and an Izod impact strength (Notched, 23° C.) of 60 kgfcm/cm.

The content of the high-density polyethylene resin may be 6 parts by weight or more, 8 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 18 parts by weight or more, or 20 parts by weight or more, and 29 parts by weight or less, based on 100 parts by weight of the total composition. , 28 parts by weight or less, 26 parts by weight or less, 25 parts by weight or less, 23 parts by weight or less, or 22 parts by weight or less, for example, 6 to 29 parts by weight, 8 to 26 parts by weight, or 10 to 22 parts by weight. . When the content of the high-density polyethylene resin is less than 6 parts by weight, the dielectric constant measured at 2.5 GHz may be 2.95 or more or the dielectric loss factor may be 0.005 or more, and if the content exceeds 29 parts by weight, the Izod impact strength may be very low.

(C) acrylic compatibilizer

The compatibilizer used in the composition of the present invention may be an acrylic compatibilizer. As an example, ethylene-methyl acrylate may be used. The compatibilizer can make dispersion easier by increasing the compatibility between G/F and high-density propylene, and plays a decisive role in allowing the resin composition of the present invention to have a dielectric loss ratio of less than 0.005.

The content of the acrylic compatibilizer may be 0.1 parts by weight or more, 0.5 parts by weight or more, 0.8 parts by weight or more, 1 parts by weight or more, 1.5 parts by weight or more, or 2 parts by weight or more, and 15 parts by weight or more, based on 100 parts by weight of the total composition. or less, 13 parts by weight or less, 12 parts by weight or less, 10 parts by weight or less, 8 parts by weight or less, or 7 parts by weight or less, for example, 0.1 to 15 parts by weight, 0.5 to 12 parts by weight, or 1 to 7 parts by weight. have. When the content of the acrylic compatibilizer is less than 0.1 parts by weight, the dielectric loss factor measured at 2.5 GHz may be 0.005 or more. can

(D) thermostable compounds

Examples of the thermally stable compound used in the composition of the present invention include SONGNOX 1076, a hindered phenolic, as a primary antioxidant, and ALKANOX 240, a phosphite, manufactured by Miwon Corporation as a secondary antioxidant, but is not limited thereto.

The content of the heat-stable compound may be 0.1 parts by weight or more, 0.5 parts by weight or more, 0.8 parts by weight or more, 1 parts by weight or more, 1.2 parts by weight or more, or 1.5 parts by weight or more, and 15 parts by weight or less, based on 100 parts by weight of the total composition. , 13 parts by weight or less, 10 parts by weight or less, 8 parts by weight or less, 5 parts by weight or less, or 2 parts by weight or less, for example, 0.1 to 15 parts by weight, 0.5 to 10 parts by weight, or 1.5 to 2 parts by weight. . If the content of the thermally stable compound is less than 0.1 parts by weight, thermal decomposition may occur during the process, and if it exceeds 15 parts by weight, excessive gas may be generated as a result of excessive input of low molecular weight substances.

(E) glass fiber

As the glass fiber included in the low dielectric thermoplastic resin composition of the present invention, a fiber length of 3 to 4.5 mm and a filament diameter of 5 to 20 μm may be used. The content of the glass fiber may be 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less based on 100 parts by weight of the total composition. When the content of the glass fiber exceeds 40 parts by weight, the impact strength is lowered, the workability is poor, the dielectric constant is increased and the dielectric loss factor is increased at the same time.

(F) other optional additives

In addition to the components described above, the resin composition of the present invention contains inorganic fillers such as silica, silicate, alumina, glass fiber, glass beads, glass flakes, clay, talc, mica, and calcium carbonate in order to increase rigidity, heat resistance and dimensional stability. It may be additionally contained, which may be incorporated in an amount of 0.1 to 50 parts by weight based on the total resin composition.

In addition, the resin composition of the present invention may additionally contain organic fillers such as carbon fibers and carbon black in order to increase black color expression and conductivity, which may be incorporated in an amount of 0.1 to 30 parts by weight based on the total resin composition.

In addition, the resin composition of the present invention may further include antioxidants, release agents, lubricants, UV stabilizers, etc. as other processing aids, and these may be used in an amount of 0.01 to 0.5 parts by weight based on the total resin composition.

According to another aspect of the present invention, there is provided a molded article manufactured by processing the resin composition of the present invention described above. The molded article includes interior and exterior materials requiring scratch resistance and impact strength, and specifically includes, but is not limited to, cell phone housings and housings of electrical and electronic products.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited thereto.

[Example]

compound used

(A-1) Polycarbonate

Linear polycarbonate derived from bisphenol-A, viscosity average molecular weight (Mv): having a molecular weight between 16,000 and 30,200.

(A-2) Polysiloxane-polycarbonate copolymer: Siloxane 7% ST4-3022PJ (SYC)

(B) high density polyethylene

High-density polyethylene B230A (manufactured by Hanwha Total) having a melt index of 0.35 g/10 min and an Izod impact strength (Notched, 23° C.) of 60 kgfcm/cm was used.

(C) compatibilizer

(C-1) Acrylic compatibilizer: EMA (Ethylene-Metyl Acrylate copolymer), Dupont, trade name Elvaloy 1330AC

(C-2) MD-715: Maleic Anhydride modified Polyolefin elastomer

(C-3) TDSK 9103: Styrene ethylene butylene styrene block copolymer functionalized with maleic anhydride

(D) thermostable compound: SONG1076

(E) Glass fiber: Glass fiber 183F with a fiber length of 3 or 4.5 mm and a filament diameter of 13 μm (manufacturer OWENS)

Examples 1 to 10 and Comparative Examples 1 to 10

The components of the composition with the components and contents shown in Table 1 below are mixed with a Hensel mixer and uniformly dispersed, and then extruded in a twin-screw melt mixing extruder with L/D=40 and Φ=25mm at a temperature of 240 to 270° C. to form pellets. After drying for 4 hours or more in a hot air dryer at 100 to 120 ° C., the specimen was injection molded at a temperature of 260 to 280 ° C.

physical property measurement

(1) Fluidity (MI): Measured at _{300 ℃, 1.2kg f according to ASTM D1238.} In order to indicate the change in fluidity, it was expressed as MI based on the fluidity of Comparative Example 1.

(2) Appearance observation (discoloration): After injection of an 80 X 80 X 2mm square specimen, the appearance was observed and visual observation was carried out to see if a color difference occurred. If compatibility is poor, a shiny appearance can be observed due to the difference in refractive index.

(3) Measurement of elongation: Tensile elongation was measured based on 5 mm/min of reinforced material and 50 mm/min of non-reinforced material according to ASTM D638. In the case of reinforcement containing glass fiber, the specimen cannot be stretched more than 5%. In the case of a specimen having a tensile elongation of less than 5%, when the fractured surface was visually inspected, the delamination of the cross-section was reduced, and the physical properties were judged to be good.

In the case of non-reinforced materials that do not contain glass fibers, when the tensile elongation exceeds 100%, compatibility was judged to be excellent.

(3) Izod impact strength: The thickness of the specimen is 1/8", and it was measured according to ASTM D256.

(4) Thermal deformation temperature: It was measured under a load of 18.56 kgf according to ASTM D648.

(5) Permittivity measurement: It was measured using the reflection coefficient method, and the measurement range was scanned at (200MHz) in the 1.9~3.1GHz region to minimize the influence of signal interference and to reduce the deviation of the dielectric loss factor from the resonant frequency method. .

[Table 1]

[Table 2]

As can be seen from Tables 1 and 2, in Examples 1 to 10 showing the low dielectric thermoplastic resin composition of the present invention, when measured at 2.5 GHz, the dielectric constant of less than 2.95 and the dielectric loss factor of less than 0.005. It was confirmed that, at the same time, it has excellent balance of physical properties such as fluidity and impact resistance, and can secure the same level of physical properties as existing polycarbonate materials.

On the other hand, in Comparative Examples 1 to 9, which is out of the scope of the present invention, when measured at 2.5 GHz, a dielectric constant of 2.95 or more or a dielectric loss factor of 0.005 or more, or a different color of the specimen appearance occurs, and the balance of physical properties such as impact resistance is relatively poor could confirm that

In addition, when comparing the cases in which different compatibilizers were used for the non-reinforced material as in Examples 1 and 4 and Comparative Examples 2 and 3, the elongation of Examples 1 and 4 using the acrylic compatibilizer was the highest, exceeding 100 (>100). appeared excellent. On the other hand, in Comparative Examples 2 and 3 using MD-715 (polyolefin-based compatibilizer) or TDSK 9103 (Maleated Styrol-Ethylene/Butylene Styrol Block Copolymer), the elongation was as low as 51 and 75, and the compatibility was low, so peeling phenomenon This occurred.

Claims (7)

Based on 100 parts by weight of the total composition,
(A) 42 to 82.5 parts by weight of a thermoplastic aromatic polycarbonate resin, a polysiloxane-polycarbonate copolymer, or a mixture thereof;
(B) 6 to 29 parts by weight of high density polyethylene;
(C) 0.1 to 15 parts by weight of an acrylic compatibilizer; and
(D) A low dielectric thermoplastic resin composition comprising 0.1 to 15 parts by weight of a heat-stable compound. The low dielectric thermoplastic resin composition according to claim 1, further comprising glass fibers. The low dielectric thermoplastic resin composition according to claim 2, wherein the glass fiber is included in an amount of 5 to 40 parts by weight based on 100 parts by weight of the total composition. According to claim 1, wherein the dielectric constant value measured at 2.5 GHz of the composition is less than 3, the low dielectric thermoplastic resin composition. According to claim 1, wherein the dielectric loss of the composition measured at 2.5 GHz is less than 0.005, the low dielectric thermoplastic resin composition. A molded article manufactured by processing the thermoplastic resin composition of any one of claims 1 to 5. The molded article according to claim 6, which is a housing for electrical or electronic products.