KR102303031B1 - Method for preparing glass fiber-reinforced Polycarbonate resin composition with good appearance, surface property and impact resistance - Google Patents

Abstract

The present invention relates to a method for preparing a glass fiber-reinforced polycarbonate resin composition with excellent appearance, surface properties, and impact resistance and, more specifically, to a method for preparing a glass fiber-reinforced polycarbonate resin composition which exhibits both an excellent impact resistance and significantly improved appearance and surface properties, by extruding a glass fiber-reinforced polycarbonate resin composition comprising a polycarbonate base resin, a polysiloxane-polycarbonate copolymer, a branched polycarbonate, a copolymer compatibilizer, a flame retardant, an impact modifier, and a glass fiber under specific conditions.

Description

TECHNICAL FIELD [0002] Method for preparing glass fiber-reinforced polycarbonate resin composition with good appearance, surface property and impact resistance

The present invention relates to a method for producing a glass fiber-reinforced polycarbonate resin composition having excellent appearance, surface properties and impact resistance, and more particularly, polycarbonate base resin, polysiloxane-polycarbonate copolymer, branched polycarbonate, copolymer By extruding a glass fiber-reinforced polycarbonate resin composition comprising a body compatibilizer, a flame retardant, an impact modifier and glass fiber under specific conditions, a glass fiber-reinforced polycarbonate resin composition that simultaneously exhibits significantly improved appearance and surface properties and excellent impact resistance It relates to a method by which it can be manufactured.

In accordance with the recent design trend in the mobile industry, a painting process is being carried out on the surface of the device cover and housing. Materials that were used a lot for housings of mobile devices used to give a rather cheap feeling, and to overcome such an image, plating or painting processes are added to add a luxurious feel to the plastic. For this purpose, excellent appearance and surface properties are required, and furthermore, in order to be applied to mobile materials, material properties with high impact resistance and high modulus of elasticity are required.

Polycarbonate resin has excellent heat resistance and mechanical properties, so it is widely used as electrical and electronic materials, housings of home appliances, and materials for automobiles. In general, a polycarbonate resin reinforced with glass fibers has a high modulus of elasticity, but the appearance and surface properties tend to deteriorate, which acts as a cause of deterioration of the efficiency and effect of the painting process.

Therefore, there is a continuous demand for a method for manufacturing a glass fiber-reinforced material that satisfies both excellent appearance and surface properties, high impact resistance, etc. while maintaining the unique advantages of polycarbonate material.

An object of the present invention is to provide a method for producing a glass fiber-reinforced polycarbonate resin composition that simultaneously exhibits significantly improved appearance and surface properties and excellent impact resistance while maintaining the advantages of the physical properties of the polycarbonate material.

In order to solve the above technical problem, the present invention provides a method for producing a polycarbonate resin composition, comprising: (A) a polycarbonate base resin; (B) a polysiloxane-polycarbonate copolymer; (C) branched polycarbonate; (D) copolymeric compatibilizers; (E) flame retardants; (F) impact modifiers; and (G) glass fibers; extruding the composition in an extruder, wherein the number of kneading block zones in the extruder is 2 to 4, and the glass fibers are introduced into the extruder. The number of kneading block regions passed after is at least two, and the extrusion is performed at an extrusion screw rotation speed of 400 to 640 rpm, a composition feed rate of 410 to 600 kg/hr, and an extrusion temperature condition of 261 to 300° C. A method is provided.

According to the present invention, since it exhibits excellent mechanical properties such as high strength, high modulus of elasticity, high impact strength, and has excellent appearance and surface properties and has excellent compatibility in post-treatment painting and plating, a material in the field of information communication and electrical and electronic fields, In particular, it is possible to effectively prepare a glass fiber-reinforced polycarbonate resin composition that can be very suitably used as a material for covers and housings of mobile devices.

Hereinafter, the present invention will be described in detail.

A method for producing a polycarbonate resin composition of the present invention, (A) a polycarbonate base resin; (B) a polysiloxane-polycarbonate copolymer; (C) branched polycarbonate; (D) copolymeric compatibilizers; (E) flame retardants; (F) impact modifiers; and (G) glass fibers; extruding the composition comprising the extruder in an extruder.

(A) Polycarbonate (PC) base resin

As the polycarbonate base resin, a thermoplastic aromatic polycarbonate resin may be used, and the thermoplastic aromatic polycarbonate resin may be prepared from 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 both functional groups such as an alkyl group, sulfide, ether, sulfoxide, sulfone, and ketone, and a case where there is no functional group at all. 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. Here, when n and/or m is 0, it means that _{R 1} and/or R _{2 are hydrogen.}

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 a dihydric phenol, a carbonate precursor, and a molecular weight modifier, for example, a linear polycarbonate resin, a branched polycarbonate resin, a copolycarbonate resin, a polyester carbonate resin, etc. There is this.

On the other hand, in exemplary embodiments of the present invention, it is preferable to use 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 17,000 to 30,000.} It is more preferable to use 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 may occur in processing the resin due to an increase in melt viscosity. In particular, in terms of mechanical properties such as impact strength and tensile strength, the viscosity average molecular weight is preferably 20,000 or more, and in view of workability, the viscosity average molecular weight is preferably 30,000 or less.

The polycarbonate resin composition may contain 10 to 70 parts by weight of the polysiloxane-polycarbonate copolymer based on 100 parts by weight of the total composition. If the content of the polycarbonate base resin in the total 100 parts by weight of the composition is excessively less than the above level, compatibility may be reduced, and on the contrary, if it is excessively greater than the above level, the impact strength may deteriorate.

In one embodiment, in the total 100 parts by weight of the polycarbonate resin composition, the polycarbonate base resin is, for example, 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, or 35 parts by weight or more. It may be included in an amount, and may be included in an amount of 65 parts by weight or less, 60 parts by weight or less, 55 parts by weight or less, or 50 parts by weight or less, but is not particularly limited thereto.

(B) polysiloxane-polycarbonate (Si-PC) copolymer

The polysiloxane-polycarbonate copolymer is used to improve the impact resistance of the resin composition.

The polysiloxane-polycarbonate copolymer includes hydroxy terminated siloxane and a polycarbonate block as repeating units.

In one embodiment, the weight average molecular weight (Mw) of the hydroxy-terminated siloxane included in the polysiloxane-polycarbonate copolymer may be 2,500 to 15,000, more specifically 3,500 to 13,000, and more specifically 4,000 to 9,000. can be If the weight average molecular weight of the hydroxy-terminated siloxane is less than 2,500, the effect of improving the low-temperature impact resistance 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.

In one embodiment, the content of the hydroxy-terminated siloxane in the polysiloxane-polycarbonate copolymer may be 6.1 wt% or more, 6.5 wt% or more, or 7 wt% or more, based on 100 wt% of the copolymer. The upper limit of the content of hydroxy-terminated siloxane in the copolymer is not particularly limited, but may be 15 wt% or less, 10 wt% or less, or 9 wt% or less in consideration of economic feasibility.

In one embodiment, the hydroxy terminated siloxane in the polysiloxane-polycarbonate copolymer has Formula 1a or Formula 1 below:

[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 group 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 of 30 to 200, preferably an integer of 40 to 170, more preferably an integer of 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, wherein 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 substituted or unsubstituted with a halogen atom, an aliphatic group containing an oxygen, nitrogen or sulfur atom in the backbone, or an 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 hydroxy group, a carboxyl group, an alkyl group (having 1 to 20 carbon atoms), an alkoxy group, or an aryl group.

In one embodiment, the polycarbonate block in the polysiloxane-polycarbonate copolymer has the 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 straight line 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 straight, 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 (Resorcinol), hydroquinone (Hydroquine), 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-hydro Roxyphenyl)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 is not limited thereto. . A representative of these is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). Other functional dihydric phenols (dihydric phenol) may refer to US Pat. Nos. 2,999,835, US 3,028,365, US 3,153,008, and US 3,334,154, and the like, 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 significantly reduced, and if it exceeds 30,000, problems in processing the resin may occur due to an increase in melt viscosity.

The polycarbonate resin composition may contain 6 to 45 parts by weight of the polysiloxane-polycarbonate copolymer based on 100 parts by weight of the total composition. If the content of the polysiloxane-polycarbonate copolymer in the total 100 parts by weight of the composition is excessively less than the above level, the impact resistance of the composition is deteriorated. have.

In one embodiment, in a total of 100 parts by weight of the polycarbonate resin composition, the polysiloxane-polycarbonate copolymer is, for example, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, 10 parts by weight or more, 11 parts by weight or more. It may be included in an amount of more than 1 part by weight, 12 parts by weight or more, 13 parts by weight or more, 14 parts by weight or more, or 15 parts by weight or more, and also 44 parts by weight or less, 43 parts by weight or less, 42 parts by weight or less, 41 parts by weight or less, 40 parts by weight or less. It may be included in an amount of less than or equal to 39 parts by weight, less than or equal to 38 parts by weight, less than or equal to 37 parts by weight, less than or equal to 36 parts by weight or less than or equal to 35 parts by weight, but is not particularly limited thereto.

(C) branched polycarbonate

The branched polycarbonate included in the polycarbonate resin composition is distinct from the polycarbonate base resin (A), and reacts with the elastomer-modified copolymer in the resin composition to improve impact resistance, and reactivity with other additives used to improve

The branched polycarbonate uses bisphenol A and an organic compound having three or more functional groups as a branching agent [Japanese Patent Publication No. 60-11733, U.S. Patent No. 4,415,753], a phenol having a trivalent or tetravalent hydroxyl group. or an aromatic compound containing trivalent or tetravalent chloroformate [U.S. Patent No. 5,021,521, U.S. Patent No. 5,283,314] and the like. That is, as the branching agent, an organic compound having three or more functional groups, a phenol having a trivalent or tetravalent hydroxyl group, or an aromatic compound containing a trivalent or tetravalent chloroformate group may be used.

In one embodiment, the general structure of the branched polycarbonate resin may be represented by the following Chemical Formula 5:

[Formula 5]

In Formula 5, A is a moiety derived from a branching agent, and may be, for example, tetravalent phenyl.

In one embodiment, the branched polycarbonate may have a viscosity average molecular weight (Mv) of 10,000 to 20,000, more specifically 15,000 to 20,000.

In the polycarbonate resin composition, based on 100 parts by weight of the total composition, the branched polycarbonate may be included in an amount of 1 to 30 parts by weight. If the content of branched polycarbonate in the total 100 parts by weight of the composition is too less than the above level, the desired effect may not be obtained by its use. can

In one embodiment, in a total of 100 parts by weight of the polycarbonate resin composition, the branched polycarbonate is, for example, 1.5 parts by weight or more, 2 parts by weight or more, 2.5 parts by weight or more, 3 parts by weight or more, 3.5 parts by weight or more. , 4 parts by weight or more, 4.5 parts by weight or more, or 5 parts by weight or more, and also 29 parts by weight or less, 28 parts by weight or less, 27 parts by weight or less, 26 parts by weight or less, 25 parts by weight or less, 24 parts by weight or less Hereinafter, it may be included in an amount of 23 parts by weight or less, 22 parts by weight or less, 21 parts by weight or less, or 20 parts by weight or less, but is not particularly limited thereto.

(D) copolymeric compatibilizer

The copolymeric compatibilizer included in the polycarbonate resin composition is used to improve impact resistance and increase adhesion and compatibility between the resin component and the inorganic additive.

In one embodiment, as the copolymerizable compatibilizer, an elastomer-modified copolymer may be used, and more specifically, a polymer grafted with maleic anhydride (MAH), for example, grafted with maleic anhydride. Styrene-butadiene-styrene (SBS) resin (SBS-g-MAH), styrene-ethylene-butylene-styrene (SEBS) resin grafted with maleic anhydride (SEBS-g-MAH), grafted with maleic anhydride acrylonitrile-butadiene-styrene (ABS) resin (ABS-g-MAH), polypropylene (PP) resin grafted with maleic anhydride (PP-g-MAH), or a combination thereof may be used, However, the present invention is not limited thereto.

The polycarbonate resin composition may contain 0.5 to 9.5 parts by weight of the copolymerizable compatibilizer based on 100 parts by weight of the total composition. If the content of the copolymerizable compatibilizer in 100 parts by weight of the total composition is excessively less than the above level, impact resistance may be deteriorated, and conversely, if it is excessively greater than the above level, appearance and surface properties may deteriorate.

In one embodiment, in a total of 100 parts by weight of the polycarbonate resin composition, the copolymerizable compatibilizer is, for example, 1 part by weight or more, 1.5 parts by weight or more, 2 parts by weight or more, 2.5 parts by weight or more, or 3 parts by weight or more. and may be included in an amount of 9 parts by weight or less, 8.5 parts by weight or less, 8 parts by weight or less, 7.5 parts by weight or less, or 7 parts by weight or less, but is not particularly limited thereto.

(E) flame retardant

The flame retardant included in the polycarbonate resin composition not only imparts flame retardancy to the resin composition, but also lowers the melting point of the polycarbonate components in the resin composition and covers the inorganic material protruding from the surface while coming out to the surface of the composition during the solidification process, For example, it plays a role in improving the appearance and surface properties of injection products).

In one embodiment, as the flame retardant, a phosphate-based flame retardant, a phosphonate-based flame retardant, a phosphinate-based flame retardant, a polysiloxane-based flame retardant, a phosphazene-based flame retardant, a melamine-based flame retardant, or a combination thereof may be used, but particularly limited thereto it doesn't happen

More specifically, in consideration of processing stability, appearance and surface improvement, etc., a phosphazene-based flame retardant, and more specifically, a cyclotriphosphazene phosphoric acid flame retardant may be used, which lowers the viscosity of the resin composition during melt processing and reduces the polymer chain It reduces the attractive force between them and increases the flow properties, flexibility, elasticity and adhesion processability by lowering the glass transition temperature.

In the polycarbonate resin composition, based on 100 parts by weight of the total composition, the flame retardant may be included in an amount of 0.5 to 9.5 parts by weight. If the content of the flame retardant in the total 100 parts by weight of the composition is excessively less than the above level, appearance and surface properties may be deteriorated.

In one embodiment, in a total of 100 parts by weight of the polycarbonate resin composition, the flame retardant is, for example, 0.7 parts by weight or more, 1 part by weight or more, 1.2 parts by weight or more, 1.5 parts by weight or more, 1.7 parts by weight or more, or 2 parts by weight or more. It may be included in an amount of parts or more, and may be included in an amount of 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less, but is not particularly limited thereto.

(F) Impact modifier

The impact modifier is used in order to improve the impact resistance of the composition, in particular to secure the appropriate impact strength required for mobile and electrical and electronic components.

In one embodiment, the impact modifier is, for example, one selected from (meth) acrylate-based copolymer, ethylene-(meth) acrylate-based copolymer, silicone-containing copolymer and polyalkyl (meth) acrylate-based copolymer It may be the above copolymer, but is not particularly limited thereto. More specifically, as the impact modifier, ethylene-methyl acrylate copolymer (EMA) may be used.

In the polycarbonate resin composition, based on 100 parts by weight of the total composition, the impact modifier may be included in an amount of 0.5 to 9.5 parts by weight. If the content of the flame retardant in the total 100 parts by weight of the composition is too less than the above level, the impact resistance may be deteriorated.

In one embodiment, in a total of 100 parts by weight of the polycarbonate resin composition, the impact modifier is, for example, 0.7 parts by weight or more, 1 part by weight or more, 1.2 parts by weight or more, 1.5 parts by weight or more, 1.7 parts by weight or more, or 2 parts by weight or more. It may be included in an amount greater than or equal to 9 parts by weight, and may be included in an amount of 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, 5 parts by weight or less, or 4 parts by weight or less, but is not particularly limited thereto. does not

(G) fiberglass

The polycarbonate resin composition includes glass fibers to improve mechanical properties of the composition, such as impact resistance, elastic modulus, heat resistance, and dimensional stability.

In one embodiment, the glass fiber may be, for example, a chopped strand of 3 to 4 mm in length, but is not particularly limited thereto. In addition, the diameter of the glass fiber may be, for example, 7 to 14 μm, but is not particularly limited thereto.

The polycarbonate resin composition may contain the glass fiber in an amount of 1 to 35 parts by weight based on 100 parts by weight of the total composition. If the content of glass fibers in the total 100 parts by weight of the composition is too less than the above level, mechanical properties such as impact resistance of the composition may deteriorate. may be lowered.

In one embodiment, in the total 100 parts by weight of the polycarbonate resin composition, the glass fiber may be included in an amount of, for example, 2 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, or 5 parts by weight or more, and It may be included in an amount of 30 parts by weight or less, 25 parts by weight or less, 20 parts by weight or less, or 15 parts by weight or less, but is not particularly limited thereto.

The polycarbonate resin composition may further include one or more other additives commonly added to the thermoplastic resin composition for injection molding or extrusion molding in addition to the above components. Such other additives include, for example, diffusing agents, antioxidants, lubricants, ultraviolet absorbers, light stabilizers, matting agents, or mixtures of two or more thereof.

For example, the dispersing agent may be organic or inorganic particles, and more specifically, the organic particles include acrylic (eg, methyl methacrylate (MMA)) cross-linked particles, silicone-based cross-linked particles, styrene-based cross-linked particles, or two of them. It may be a mixture of two or more species, and the inorganic particles include calcium carbonate particles, barium sulfate particles, titanium oxide particles, aluminum hydroxide particles, silica particles, glass particles, mica particles, magnesium oxide particles, zinc oxide particles, or a mixture of two or more thereof. may be, but is not particularly limited thereto. The organic particles and inorganic particles may be used alone or in combination of two or more.

The antioxidant may be, for example, a phenol-based compound, a phosphite-based compound, a thioester-based compound, or a mixture of two or more thereof, but is not particularly limited thereto.

The lubricant may be, for example, a polyethylene compound, an ethylene-ester compound, an ethylene glycol-glycerin ester compound, a montan compound, an ethylene glycol-glycerin montanic acid ester compound, or a mixture of two or more thereof, but particularly However, the present invention is not limited thereto.

As the ultraviolet absorber, commercially available products may be used without particular limitation.

The light stabilizer may be, for example, a benzotriazole-based compound, a hydroxyphenyltriazine-based compound, a pyrimidine-based compound, a cyanoacrylate-based compound, or a mixture of two or more thereof, but is not particularly limited thereto.

The matting agent may be inorganic or organic, and more specifically, the inorganic matting agent may be, for example, silica, magnesium oxide, zirconia, alumina, titania, or a mixture of two or more thereof, and the organic matting agent It may be a crosslinked vinyl copolymer, and the monomer of the vinyl copolymer may be at least one selected from styrene, acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate. However, it is not particularly limited thereto.

The content of the other additives is not particularly limited, and may be used in an amount that can be used to add additional functions in a range that does not impair the desired physical properties of the polycarbonate resin composition. For example, the content of each of the other additives may be 0.1 to 5 parts by weight, more specifically, 0.5 to 2 parts by weight, based on 100 parts by weight of the resin composition, but is not particularly limited thereto.

The method for producing a polycarbonate resin composition of the present invention includes the step of extruding the polycarbonate resin composition as described above in an extruder.

In one embodiment, the extruder may be a single screw type extruder or a twin screw type extruder, and more specifically, a twin screw extruder.

In the present invention, the number of kneading block zones in the extruder is 2-4. If the number of kneading block regions in the extruder is less than two, the appearance of the prepared composition is poor, and if it exceeds four, decomposition and migration of the resin component become severe.

In one embodiment, the number of kneading block regions in the extruder may be two or three, more specifically three.

In the present invention, the number of kneading block regions through which the glass fiber passes after input into the extruder is two or more. If the number of kneading block regions through which the glass fibers pass after being introduced into the extruder is less than two, the appearance of the prepared composition deteriorates.

In one embodiment, the number of kneading block regions through which the glass fiber passes after being introduced into the extruder may be two or three, and more specifically, two.

In the present invention, the total number of kneading blocks present in the extruder may be 13 to 20 pieces. If the total number of kneading blocks present in the extruder is less than the above level, the appearance and/or impact resistance of the composition may deteriorate, and if it exceeds the above level, the workability and efficiency of the process may deteriorate.

In one embodiment, the total number of kneading blocks present in the extruder may be 13 or more, 14 or more, 15 or more, or 16 or more, and may also be 20 or less, 19 or less, or 18 or less.

In the present invention, the number of kneading blocks passing through the glass fiber after input into the extruder may be 6 to 11 pieces. If the number of kneading blocks passed after the glass fiber is introduced into the extruder is less than the above level, the appearance and/or impact resistance of the composition may deteriorate, and if it exceeds the above level, the workability and efficiency of the process may deteriorate.

In one embodiment, the number of kneading blocks through which the glass fiber passes after input into the extruder may be 6 or more or 7 or more, and may also be 11 or less, 10 or less, or 9 or less.

In the present invention, the extrusion is performed under conditions of an extrusion screw rotation speed of 400 to 640 rpm. If the extrusion screw rotation speed is less than 400 rpm, mixing of the composition components may not be sufficient, and if it exceeds 640 rpm, the impact resistance of the prepared composition is deteriorated.

In one embodiment, the extrusion screw rotation speed may be 420 rpm or more, 450 rpm or more, 470 rpm or more, or 500 rpm or more, and also 630 rpm or less, 620 rpm or less, 610 rpm or less, or 600 rpm or less.

In the present invention, the extrusion is performed under conditions of a composition feed rate of 410 to 600 kg/hr. Here, the “composition feed rate” refers to the total input amount (kg) of raw material components input per hour during the operation of the extruder. If the composition feed rate is less than 410 kg/hr, the impact resistance of the prepared composition is deteriorated, and if it exceeds 600 kg/hr, mixing of the composition components may not be sufficient.

In one embodiment, the composition feed rate may be 420 kg/hr or more, 430 kg/hr or more, 440 kg/hr or more, or 450 kg/hr or more, and also 580 kg/hr or less, 550 kg/hr or less, 530 or less. kg/hr or less or 500 kg/hr or less.

In the present invention, the extrusion is carried out under the extrusion temperature conditions of 261 to 300 ℃. Here, “extrusion temperature” refers to the operating temperature of the extruder when operating, and represents the operating temperature of the remaining parts except for the hopper part of the extruder. If the extrusion temperature is less than 261 ℃, the impact resistance and appearance of the prepared composition deteriorates, and if it exceeds 300 ℃, one or more of the composition components may be thermally decomposed.

In one embodiment, the extrusion temperature may be 262 °C or higher, 265 °C or higher, 267 °C or higher, or 270 °C or higher, and 295 °C or lower, 290 °C or lower, 285 °C or lower, or 280 °C or lower.

According to a preferred embodiment of the present invention, the extruder is a twin screw extruder, the number of kneading block areas in the extruder is three, and the number of kneading block areas through which the glass fiber passes after input into the extruder is two, and the extrusion The screw rotation speed is 400 to 600 rpm, the composition feed rate is 410 kg/hr to 550 kg/hr, and the extrusion temperature may be 270 to 300 °C.

The polycarbonate resin composition produced by the method according to the present invention exhibits excellent mechanical properties such as high strength, high modulus of elasticity, and high impact strength, and has excellent appearance and surface properties and has excellent compatibility in post-treatment painting and plating, information It can be very suitably used as a material in the communication field and in the electrical and electronic field, in particular, as a material for covers and housings of mobile devices.

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]

Examples 1-3 and Comparative Examples 1-7

[Composition Components]

(A): 47.5 parts by weight of polycarbonate base resin (viscosity average molecular weight (Mv): 17,000 to 30,000) (TRIREX, Samyang Corporation)

(B): 20 parts by weight of polysiloxane-polycarbonate copolymer (hydroxy-terminated siloxane content: 6.1% by weight or more, Mv: 26,000) (Samyang Corporation)

(C): 10 parts by weight of branched polycarbonate (branched polycarbonate derived from bisphenol-A using phenol having a tetravalent hydroxyl group as a branching agent, Mv: 18,000) (Samyang Corporation)

(D): 5 parts by weight of a copolymeric compatibilizer (styrene-ethylene-butylene-styrene resin grafted with maleic anhydride) (SCONA, BYK)

(E): 3.5 parts by weight of flame retardant (cyclotriphosphazene phosphoric acid flame retardant) (HPCTP, Hunan Chemical)

(F): 3 parts by weight of impact modifier (ethylene-methyl acrylate copolymer)

(G): 10 parts by weight of glass fiber (short glass fiber with a length of 3 to 4 mm) (chopped strand, OCV company)

(H): 1 part by weight of other additives (antioxidant)

The composition components were mixed with a tumbler mixer for 10 minutes, added to a twin screw type extruder, and melted and extruded under the conditions shown in Table 1 below to prepare resin composition pellets. The manufactured pellets were dried at 100-120° C. for 4 hours or more, and then injected in an injection machine at 260-280° C. (manufacturer: LG Electric Wire, product name: LGH-200N) to prepare a specimen. The prepared specimens were evaluated for physical properties by the following method, and the results are shown in Table 1 below.

[Measurement and evaluation of physical properties]

Impact strength (kgf cm/cm, IZOD)

Based on the evaluation method specified in ASTM D256, a notch was made and measured in 1/8" thick Izod specimen.

Tensile strength (kgf/cm ² )

It was measured under the condition of 50 mm/min according to the evaluation method specified in ASTM D638.

Flexural modulus (kgf/cm) ² )

Based on the evaluation method specified in ASTM D790, it was measured under the condition of 2.8 mm/min.

Flow index (g/10min)

According to ASTM D1238, the flow index (MI) was calculated by measuring the amount of resin flowing out for 5 minutes at 300°C using a 1.2 kg weight.

fall evaluation

A weight of 300 g was dropped from a height of 30 cm to the corners of 4 parts of the specimen in the shape of a mobile rear case, and the occurrence of cracks in the specimen was evaluated. The evaluation of falling vertebrae was repeated three times per part. The evaluation criteria are as follows.

○: Good (No cracks)

△: Normal (cracks occur in parts 1 to 3)

X: Bad (cracks everywhere)

Appearance evaluation

After injection of an 80 x 80 x 2 mm square specimen and a specimen in the shape of a mobile rear case, the appearance was observed to visually observe whether agglomeration of additives or protrusion of inorganic substances occurred. When the glass fiber protrudes, a shiny appearance can be observed due to the difference in the refractive index of the surface of the injection product. The evaluation criteria are as follows.

◎: very good

○: good

△: Normal

X: bad

[Table 1]

As can be seen from the results of Table 1, the compositions of Examples prepared according to the present invention exhibited excellent impact resistance and excellent appearance and surface properties at the same time, and were also excellent in tensile strength, elastic modulus and flow properties. On the other hand, the compositions prepared in Comparative Examples have poor impact resistance (Comparative Examples 2, 3, 4, 5, 6), poor appearance (Comparative Examples 1 and 4), poor flow properties (Comparative Example 5), or tensile strength and low flexural modulus (Comparative Examples 2, 4, 5), and at least one of the evaluated items was poor.

Claims (10)

(A) polycarbonate base resin; (B) a polysiloxane-polycarbonate copolymer; (C) branched polycarbonate; (D) copolymeric compatibilizers; (E) flame retardants; (F) impact modifiers; and (G) glass fibers; extruding the composition comprising the extruder in an extruder,
Here, the number of kneading block zones in the extruder is 2 to 4, the number of kneading block zones through which the glass fiber passes after input into the extruder is 2 or more, and the extrusion is performed at 400 to 640 rpm. Extrusion screw rotation speed, composition feed rate of 410 to 600 kg / hr and extrusion temperature of 261 to 300 ° C.
A method for producing a polycarbonate resin composition. According to claim 1,
It is a thermoplastic aromatic polycarbonate resin,
The polysiloxane-polycarbonate copolymer comprises a hydroxy terminated siloxane and a polycarbonate block as repeating units,
Styrene-butadiene-styrene resin grafted with maleic anhydride, styrene-ethylene-butylene-styrene resin grafted with maleic anhydride, acrylonitrile-butadiene-styrene resin grafted with maleic anhydride, as copolymeric compatibilizers. , a polypropylene resin grafted with maleic anhydride, or a combination thereof,
The flame retardant is a phosphazene-based flame retardant,
The glass fibers are short glass fibers 3-4 mm long,
A method for producing a polycarbonate resin composition. The method for producing a polycarbonate resin composition according to claim 1, wherein the extruder is a single screw extruder or a twin screw extruder. The method for producing a polycarbonate resin composition according to claim 1, wherein the number of kneading block regions in the extruder is two or three. The method of claim 1, wherein the total number of kneading blocks present in the extruder is 13 to 20, the polycarbonate resin composition. The method of claim 1, wherein the number of kneading blocks passed after the glass fiber is put into the extruder is 6 to 11, the polycarbonate resin composition manufacturing method. The method of claim 1, wherein the extrusion screw rotation speed is 400 to 620 rpm. The method of claim 1, wherein the composition feed rate is 410 to 580 kg/hr. The method of claim 1, wherein the extrusion temperature is 265 to 300°C. The extrusion according to any one of claims 1 to 9, wherein the extruder is a twin screw extruder, the number of kneading block regions in the extruder is three, and the number of kneading block regions through which the glass fibers pass after being introduced into the extruder is two, The screw rotation speed is 400 to 600 rpm, the composition feed rate is 410 kg / hr to 550 kg / hr, the extrusion temperature is 270 to 300 ℃, a method for producing a polycarbonate resin composition.