KR102024426B1 - Polycarbonate resin composition having improved appearance and flowability - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition, and more particularly, to a polycarbonate resin composition which includes a polycarbonate resin, an inorganic filler, and a Tg regulator, significantly improves appearance and fluidity, and is suitable for exterior materials such as mobile phones.

Description

Polycarbonate resin composition with improved appearance and fluidity {POLYCARBONATE RESIN COMPOSITION HAVING IMPROVED APPEARANCE AND FLOWABILITY}

The present invention relates to a polycarbonate resin composition, and more particularly, to a polycarbonate resin composition which improves appearance and fluidity and is suitable for exterior materials of electronic devices such as mobile phones.

Inorganic filler-reinforced thermoplastics have high flexural strength and can exhibit excellent stiffness, and thus have been applied to some parts such as automobiles and electronic devices. However, when the inorganic filler is added to the thermoplastic resin, the impact resistance is greatly reduced, making it difficult to use for a component that may be destroyed by an external impact, and the fluidity is significantly lowered to increase the injection temperature for molding. Has

Among these inorganic filler reinforced thermoplastic resins, glass fiber reinforced polycarbonate resin has the advantage of improving tensile and flexural strength while maintaining excellent moldability of the polycarbonate resin. In particular, such a resin has been used mainly as an exterior material of an electronic device such as a mobile phone because it exhibits excellent flexural modulus and heat resistance, and is suitable for a part that is subjected to continuous load or endures continuous heat.

However, in the case of glass fiber reinforced polycarbonate resin, the impact resistance is superior to other glass fiber reinforced thermoplastic resins, but the glass fiber protrudes on the surface after injection, and the appearance is degraded, and additives are added to prevent appearance degradation and improve fluidity. When used, there is a problem that the impact resistance is reduced.

Korean Patent Laid-Open Publication No. 10-2009-0018569 discloses glass fiber-reinforced polycarbonate having excellent flowability and impact resistance by adding modified polyolefin. However, the improvement of flowability is insignificant and the appearance of the injection molded product is reduced, resulting in blasting. There is a problem that requires an additional process.

In order to solve the above problems, an object of the present invention is to provide a polycarbonate resin composition with improved appearance and fluidity. More specifically, by reducing the Tg by including a glass transition temperature regulator (hereinafter, Tg regulator) containing phosphorus in the polycarbonate resin reinforced with an inorganic filler, to provide a polycarbonate resin composition with improved appearance and fluidity without reducing mechanical properties It aims to do it.

Moreover, an object of this invention is to provide the molded article manufactured from the polycarbonate resin composition.

The present invention for achieving the above object is (A) polycarbonate resin; (B) an inorganic filler; And (C) phosphorus-containing Tg regulator; relates to a polycarbonate resin composition with improved appearance and fluidity.

According to one embodiment of the invention, (A) 50 to 85% by weight of the polycarbonate resin, (B) inorganic filler 10 to 40% by weight and (C) phosphorus may contain 1 to 10% by weight of the Tg regulator. have.

According to an embodiment of the present invention, the (A) polycarbonate resin may have a weight average molecular weight (Mw) of 10,000 to 200,000 g / mol.

According to an embodiment of the present invention, the inorganic filler may be selected from at least one of glass fiber, carbon fiber, ceramic fiber, calcium carbonate, silica, alumina, aluminum hydroxide, talc, clay, mica, barium sulfate and whiskers.

According to an embodiment of the present invention, the (C) phosphorus containing Tg regulator may be a compound having the structure of formula (I):

[Formula 1]

In Formula 1, R ₁ to R ₆ are each independently hydrogen, halogen, (C1-C20) alkyl, (C2-C7) alkenyl, (C3-C20) cycloalkyl, (C2-C20) heterocycloalkyl , (C1-C20) alkoxy, (C6-C20) aryl, (C5-C20) heteroaryl, (C1-C10) alkoxycarbonyl (C1-C10) alkyl, carbonyl (C1-C10) alkyl, amino and hydroxide Can be selected from Roxy,

The alkyl, alkenyl, cycloalkyl, heterocycloalkyl, alkoxycarbonylalkyl, carbonylalkyl is (C1-C10) alkyl, halogen, nitro, cyano, hydroxy, amino, (C6-C10) aryl, (C3 One or more selected from -C10) cycloalkyl, (C3-C10) heterocycloalkyl or (C4-C10) heteroaryl may be further substituted.

According to an embodiment of the present invention, the (C) phosphorus-containing Tg modulator may be selected from at least one compound having the structure of Formula 2 to Formula 4:

[Formula 2]

[Formula 3]

[Formula 4]

In Formula 4, R ₁₁ to R ₆₁ may be each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl or benzyl.

According to one embodiment of the invention, the polycarbonate resin composition is antibacterial, heat stabilizer, antioxidant, release agent, light stabilizer, surfactant, coupling agent, plasticizer, compatibilizer, lubricant, antistatic agent, colorant, pigment, dye, It may further include an additive selected from the group consisting of flame retardants, flame retardant aids, anti drip agents, weathering agents, ultraviolet absorbers, sunscreens and mixtures thereof.

In addition, the present invention for achieving the above object relates to a molded article produced from the polycarbonate resin composition described above.

According to one embodiment of the present invention, the molded article may satisfy the following equations 1 to 3:

50 ≤ Gloss ≤ 90 [Equation 1]

80 ≤ Yp ≤ 100 [Equation 2]

150 ≤ Spiral length ≤ 200 [Equation 3]

In Equation 1, Gloss is a 60 ° gloss average value measured using a Glossmeter for a rectangular shaped injection specimen of 9 cm × 5 cm, Equation 2 Yp is injected into a size of 10 cm × 10 cm × 1 cm After coating 100 specimens, it is judged visually that the product with irregularities is judged as defective, and it is the coating yield (%) measured by the number of non-defective products, and the spiral length in Equation 3 is 1mm thick and 1cm wide. The flow length (mm) measured when injection molding at 310 ° C. using a spiral mold of.

According to an embodiment of the present invention, the molded article may be a mobile phone exterior material.

Since the polycarbonate resin composition according to the present invention can significantly improve the appearance and fluidity without deteriorating mechanical properties such as impact resistance and flexural modulus, the inorganic filler protrusion problem of the appearance of the molded article can be solved and the paint yield can be drastically improved. There is an advantage. Therefore, when the molded product is manufactured, it has an excellent appearance and has an advantage of providing excellent surface and physical properties to an electronic device exterior material such as a mobile phone without an additional processing process.

1 is a micrograph photographing whether or not irregularities are produced on a painted surface by preparing a molded article using a polycarbonate resin composition according to an exemplary embodiment of the present invention.

Hereinafter, the polycarbonate resin composition of the present invention will be described in detail. The following embodiments are provided as examples to ensure that the spirit of the present invention can be fully conveyed to those skilled in the art. In addition, unless there is another definition in the technical terms and scientific terms used, it has a meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and unnecessarily obscure the subject matter of the present invention in the following description. Description of known functions and configurations that may be omitted.

The inventors of the present invention have studied to develop a polycarbonate resin composition having excellent fluidity and excellent molding processability and appearance properties without deteriorating mechanical properties such as impact resistance, and thus, containing polycarbonate resin, inorganic filler and phosphorus. The present invention was completed by providing a polycarbonate resin composition including a Tg modifier, surprisingly improving fluidity without remarkably decreasing the mechanical properties of impact resistance and flexural modulus, thereby dramatically improving appearance characteristics and coating yield. .

Hereinafter, each component is demonstrated in detail.

The polyester resin composition of this invention contains the Tg regulator containing (A) polycarbonate resin, (B) inorganic filler, and (C) phosphorus.

Hereinafter, each component is demonstrated in detail.

(A) polycarbonate resin

Polycarbonate resin according to an embodiment of the present invention can exhibit mechanical properties such as stiffness and impact strength, appearance characteristics and excellent molding processability. It will not restrict | limit if it is a polycarbonate resin manufactured by a conventional method. As an example, aliphatic polycarbonate resins, aromatic polycarbonate resins, copolycarbonate resins thereof, copolyester carbonate resins, polycarbonate-polysiloxane copolymer resins or mixtures thereof may be used. More specifically, aromatic polycarbonate resin can be used.

In addition, the polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin or a mixture of linear and branched polycarbonate resin in the structure, but is not limited thereto.

 Polycarbonate resin according to an embodiment of the present invention can be prepared by reacting the (A1) aromatic dihydroxy compound with the (A2) carbonate precursor.

(A1) aromatic dihydroxy compound

The aromatic dihydroxy compound (A1) may be a compound represented by the following formula (5) or a mixture thereof.

[Formula 5]

In Formula 5, X ₁ and X ₂ are each independently hydrogen, halogen, or an alkyl group of C ₁ -C ₈ ; a and b are each independently an integer between 0 and 4, Z is a single bond, an alkylene group of C ₁ -C _8, an alkylidene group of C ₂ -C ₈ , a cycloalkylene group of C ₅ -C ₁₅ , C ₅ -C ₁₅ cycloalkyl alkylidene _{group, -S-, -SO-, SO 2 -} , represents a -O-, or -CO-.

Examples of the aromatic dihydroxy compound (a1) represented by Formula 5 include bis (hydroxy aryl) alkane, bis (hydroxy aryl) cycloalkane, bis (hydroxy aryl) ether, bis (hydroxy aryl) sulfide, and bis ( Hydroxy aryl) sulfoxides, biphenyl compounds can be used, and these compounds can be used alone or in mixture of two or more.

Specifically, examples of bis (hydroxy aryl) alkanes include bis (4-hydroxy phenyl) methane, bis (3-methyl-4-hydroxy phenyl) methane, bis (3-chloro-4-hydroxy phenyl) methane , Bis (3,5-dibromo-4-hydroxy phenyl) methane, 1,1-bis (4-hydroxy phenyl) ethane, 1,1-bis (2-tert-butyl-4-hydroxy -3-methylphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis ( 2-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxy phenyl) propane, 1,1-bis (2-tertiary-butyl-4-hydroxy- 5-methyl phenyl) propane, 2,2-bis (3-chloro-4-hydroxy phenyl) propane, 2,2-bis (3-fluoro-4-hydroxy phenyl) propane, 2,2-bis ( 3-bromo-4-hydroxy phenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxy phenyl) propane, 2,2-bis (3,5-dichloro-4- hydride Hydroxy phenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxy pefe Propane, 2,2-bis (4-hydroxy phenyl) butane, 2,2-bis (4-hydroxy phenyl) octane, 2,2-bis (4-hydroxy phenyl) phenyl methane, 2,2- Bis (4-hydroxy-1-methyl phenyl) propane, 1,1-bis (4-hydroxy-tertiary-butyl phenyl) propane, 2,2-bis (4-hydroxy-3-bromo phenyl) Propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethyl phenyl) propane, 2,2-bis (4- Hydroxy-3-chloro phenyl) propane, 2,2-bis (4-hydroxy-3,5-dichloro phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromo phenyl) Propane, 2,2-bis (4-hydroxy-3,5-dibromo phenyl) propane, 2,2-bis (3-bromo-4-hydroxy-5-chloro phenyl) propane, 2,2 -Bis (3-phenyl-4-hydroxy phenyl) propane, 2,2-bis (4-hydroxy phenyl) butane, 2,2-bis (3-methyl-4-hydroxy phenyl) butane, 1,1 -Bis (2-butyl-4-hydroxy-5-methyl phenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methyl phenyl) Tan, 1,1-bis (2-tert-butyl-4-hydroxy-5-methyl phenyl) isobutane, 1,1-bis (2-tert-amyl-4-hydroxy-5-methyl phenyl ) Butane, 2,2-bis (3,5-dichloro-4-hydroxy phenyl) butane, 2,2-bis (3,5-dibromo-4-hydrophenyl) butane, 4,4-bis ( 4-hydroxy phenyl) heptane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methyl phenyl) heptane, 2,2-bis (4-hydroxy phenyl) octane, or 1, 1- (4-hydroxy phenyl) ethane, but is not limited to such.

Specifically, examples of bis (hydroxy aryl) cycloalkane include 1,1-bis (4-hydroxy phenyl) cyclopentane, 1,1-bis (4-hydroxy phenyl) cyclohexane, 1,1-bis (3) -Methyl-4-hydroxy phenyl) cyclohexane, 1,1-bis (3-cyclohexyl-4-hydroxy phenyl) cyclohexane, 1,1-bis (3-phenyl-4-hydroxy phenyl) cyclohexane Or 1,1-bis (4-hydroxy phenyl) -3,5,5-trimethylcyclohexane, but is not limited thereto.

Specifically, examples of bis (hydroxy aryl) ether include, but are not limited to, bis (4-hydroxy phenyl) ether or bis (4-hydroxy-3-methyl phenyl) ether.

Specifically, examples of bis (hydroxy aryl) sulfide include but are not limited to bis (4-hydroxy phenyl) sulfide or bis (3-methyl-4-hydroxy phenyl) sulfide.

Specifically, examples of bis (hydroxy aryl) sulfoxide include bis (hydroxy phenyl) sulfoxide, bis (3-methyl-4-hydroxy phenyl) sulfoxide or bis (3-phenyl-4-hydroxy phenyl) sulfoxide. There is a side, but is not limited thereto.

Specifically, examples of biphenyl compounds include bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, or bis (3-phenyl-4-hydroxyphenyl) sulfone Hydroxy aryl) sulfone, 4,4'-dihydroxy biphenyl, 4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4'-dihydroxy-3,3'-dimethyl Biphenyl, 4,4'-dihydroxy-3,3'-dicyclobiphenyl, 3,3-difluoro-4,4'-dihydroxy biphenyl, but are not limited thereto.

Aromatic dihydroxy compounds (A1) that can be used in addition to the compound represented by Formula 5 include dihydroxy benzene, halogen or alkyl-substituted dihydroxy benzene.

Specifically resorcinol, 3-methyl resorcinol, 3-ethyl resorcinol, 3-propy resorcinol, 3-butyl resorcinol, 3-tertiary-butyl resorcinol, 3-phenyl resorcinol , 2,3,4,6-tetrafluororesorcinol, 2,3,4,6-tetrabromoresorcinol, catechol, hydroquinone, 3-methylhydroquinone, 3-ethylhydroquinone, 3 -Propylhydroquinone, 3-butylhydroquinone, 3-tertiary-butylhydroquinone, 3-phenylhydroquinone, 3-gyumilhydroquinone, 2,5-dichlorohydroquinone, 2,3,5,6-tetramethyl Hydroquinone, 2,3,5,6-tetra-tertiary-butylhydroquinone, 2,3,5,6-tetraprohydrohydroquinone, or 2,3,5,6-tetrabromo hydroquinone may be used. May be, but is not limited thereto.

As the aromatic dihydroxy compound (A1), preferably 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) may be used.

(A2) carbonate precursor

The carbonate precursor is dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl ) Carbonate, carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide, bishaloformate and the like. These compounds may be used alone or in a mixture of two or more.

The carbonate precursor (A2) may be used in a molar ratio of 0.9 to 1.5 with respect to 1 mole of the aromatic dihydroxy compound (A1).

Polycarbonate resin according to an embodiment of the present invention may have a weight average molecular weight (Mw) may range from 10,000 to 200,000 g / mol, more preferably 15,000 to 80,000 g / mol. In this case, workability can be improved.

The content of the polycarbonate resin (A) according to an embodiment of the present invention may be 50 to 85% by weight in the total composition. More preferably, it may be 60 to 75% by weight. When the content is in the above range, the impact resistance, thermal stability and molding processability can be further improved.

 (B) inorganic filler

Inorganic filler according to an embodiment of the present invention can be added to the polycarbonate resin to improve the strength of the resin. The form and type of the inorganic filler can be used without limitation so long as it is well known in the art.

For example, at least one of a fibrous inorganic filler including glass fibers, carbon fibers, ceramic fibers, metal fibers, or the like, or calcium carbonate, silica, alumina, aluminum hydroxide, talc, clay, mica, barium sulfate, and whiskers may be selected. have.

The inorganic filler may have a cross section of various shapes such as a circle, an oval, a rectangle, and the like.

More specifically, the inorganic filler of the present invention is preferably glass fiber, it is possible to use all kinds and types of glass fiber.

Glass fiber according to an embodiment of the present invention may be a cylindrical cross-sectional glass fiber or a plate-shaped glass fiber. The cylindrical cross section glass fiber may have a cross-sectional diameter of 5 to 20 um and a length of 2 to 5 mm before processing. The plate-shaped glass fiber may have an aspect ratio of 1.5 to 10 and a length of 2 to 5 mm before processing. In this case, workability is improved, and mechanical properties such as tensile strength, impact resistance and flexural modulus of the molded article may be improved as well as appearance characteristics of the injection molded article.

The inorganic filler may be a coating of the surface treatment agent on the surface in order to increase the bonding strength with the polycarbonate resin. The surface treating agent may be, for example, a silane compound, a urethane compound, or an epoxy compound, but is not limited thereto.

The content of the inorganic filler (B) according to an embodiment of the present invention may be 10 to 40% by weight in the total composition. More preferably, it may be 20 to 35% by weight. When the content of the inorganic filler is less than 10% by weight, there is a fear that impact resistance and heat resistance may decrease. If the content is more than 40% by weight, the fluidity is lowered, so that the molding processability is reduced, and when the injection into the molded article, the inorganic filler may be protruded and the appearance may be degraded.

 (C) phosphorus containing Tg regulator

Phosphorus-containing Tg regulator according to an embodiment of the present invention can improve the fluidity by lowering the glass transition temperature (Tg) of the polycarbonate resin.

Phosphorus-containing Tg modulators may be used such as phosphate, phosphonate, phosphinate, phosphine oxide or phosphazene.

More preferably linear or cyclic phosphazenes can be used.

(C) Phosphorus-containing Tg regulator according to an embodiment of the present invention may be selected a compound having a structure of formula (1).

[Formula 1]

(In Formula 1, R _{One To} R _{6 Are} each independently hydrogen, halogen, (C1-C20) alkyl, (C2-C7) alkenyl, (C3-C20) cycloalkyl, (C2-C20) heterocyclo Alkyl, (C1-C20) alkoxy, (C6-C20) aryl, (C5-C20) heteroaryl, (C1-C10) alkoxycarbonyl (C1-C10) alkyl, carbonyl (C1-C10) alkyl, amino and Can be selected from hydroxy,

The alkyl, alkenyl, cycloalkyl, heterocycloalkyl, alkoxycarbonylalkyl, carbonylalkyl is (C1-C10) alkyl, halogen, nitro, cyano, hydroxy, amino, (C6-C10) aryl, (C3 Or one or more selected from -C10) cycloalkyl, (C3-C10) heterocycloalkyl or (C4-C10) heteroaryl may be further substituted.)

Substituents comprising the "alkyl", "alkoxy" and other "alkyl" moieties described herein include both straight and crushed forms, and "alkenyl" has 2 to 8 carbon atoms and has at least one double bond. Includes both straight chain or ground forms containing.

"Cycloalkyl" described in the present invention includes both saturated monocyclic or saturated bicyclic ring structures having 3 to 20 carbon atoms.

"Aryl" described in the present invention is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and is a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, suitably for each ring. It includes the system. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, tolyl, and the like.

"Heterocycloalkyl" described in the present invention is a cyclocyclic saturated carbonyl skeleton atom containing 1 to 3 heteroatoms selected from N, O, S, and the remaining saturated monocyclic or bicyclic ring skeleton atoms are carbon. Alkyl group means pyrrolidinyl, azetidinyl, pyrazolidinyl, oxazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, hydantoinyl, valero Lactamyl, oxiranyl, oxetanyl, dioxolanyl, dioxanyl, oxathiolanyl, oxathanyl, ditianyl, dihydrofuranyl, tetrahydrofuranyl, dihydropyranyl, tetrahydropyranyl, Tetrahydropyridinyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, tetrahydrothiopyranyl, diazepanyl and azepanyl.

"Heteroaryl" described in the present invention means an aryl group containing 1 to 3 heteroatoms selected from N, O, and S as an aromatic ring skeleton atom, and the remaining aromatic ring skeleton atoms are carbons. Heteroatoms in the ring include bivalent aryl groups that are oxidized or quaternized to form, for example, N-oxides or quaternary salts. Specific examples include furyl, thiophenyl, pyrrolyl, pyranyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxdiazolyl, triazinyl, tetrazinyl, tria Zolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl and the like.

More specifically, the Tg modifier containing the phosphorus (C) of the present invention may be selected from at least one compound having the structure of the formula (2) to (4).

[Formula 2]

[Formula 3]

[Formula 4]

(In Formula 4, R ₁₁ to R ₆₁ may be selected from each independently hydrogen, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl or benzyl.)

When using a Tg regulator containing a phosphorus selected from the formula (2) to (4), it is possible to reduce the Tg of the polycarbonate resin to improve the fluidity while maintaining excellent mechanical properties.

The content of phosphorus-containing Tg regulator (C) according to an embodiment of the present invention may be 1 to 10% by weight in the total composition. More preferably, it may be 1 to 5% by weight. When the content of the Tg regulator is less than 1% by weight, the Tg reduction effect of the polycarbonate resin is insignificant, which may not affect the fluidity improvement. In addition, when more than 10% by weight Tg is excessively reduced, mechanical properties such as impact resistance is significantly reduced, there is a fear that the problem that the inorganic filler protrudes to the appearance during injection.

The polycarbonate resin composition of the present invention may further include various additives depending on the use within the scope of not impairing the object of the present invention.

Examples include antibacterial agents, heat stabilizers, antioxidants, mold release agents, light stabilizers, surfactants, coupling agents, plasticizers, compatibilizers, lubricants, antistatic agents, colorants, pigments, dyes, flame retardants, flame retardant aids, anti drip agents, weathering agents, At least one may be selected from the group consisting of ultraviolet absorbers, sunscreens and mixtures thereof. The content of the additive can be easily determined by those skilled in the art.

The polycarbonate resin composition of the present invention can be prepared through a known method. For example, each component and additive may be mixed with a Henschel mixer, a V blender, a tumbler blender, a ribbon blender, and the like and melt-extruded at a temperature of 150 to 300 ° C. using a single screw extruder or a twin screw extruder to prepare pellets. Can be. In this case, components other than the inorganic filler may be added to the main feeder, and the inorganic filler may be added to the side feeder. More specifically, using a twin screw extruder of L / D = 29, Φ = 45mm pelletized by extrusion under the conditions of screw rotation speed of 300 ~ 600rpm, self-feeding speed of 60 ~ 600Kg / hr at 250 ~ 280 ℃ temperature Can be prepared. The prepared pellets were dried at 100 ° C. for 3 hours or more and injected into the specimens.

According to another embodiment of the present invention, there is provided a molded article improved in appearance and fluidity produced by molding the above-described polycarbonate resin composition. That is, using the polycarbonate resin composition, the molded article can be produced by various processes such as injection molding, double injection molding, blow molding, extrusion molding, thermoforming.

Moreover, it is preferable that the said molded article satisfy | fills following formula 1-formula 3.

50 ≤ Gloss ≤ 90 [Equation 1]

80 ≤ Yp ≤ 100 [Equation 2]

150 ≤ Spiral length ≤ 200 [Equation 3]

In Equation 1, Gloss is a 60 ° gloss average value measured using a Glossmeter for a rectangular shaped injection specimen of 9 cm × 5 cm, and in Equation 2, Yp is injected into a size of 10 cm × 10 cm × 1 cm. After coating 100 specimens, it is judged visually that the product with irregularities is judged as defective, and it is the coating yield (%) measured by the number of non-defective products, and the spiral length in Equation 3 is 1mm thick and 1cm wide. The flow length (mm) measured when injection molding at 310 ° C. using a spiral mold of

The molded article made of the polycarbonate resin composition of the present invention contains a polycarbonate resin, an inorganic filler and a phosphorus-containing Tg regulator, thereby improving fluidity and post-injection appearance while maintaining excellent mechanical properties and molding processability, and painting. It was found that the yield was significantly improved.

Figure 1 shows a micrograph photographing the appearance characteristics by manufacturing a molded article with a polycarbonate resin composition according to an embodiment of the present invention, referring to this, by containing a Tg regulator containing phosphorus, inorganic to the appearance of the injection molded article It can be seen that the protrusion of the filler is significantly reduced and the appearance characteristics are improved.

Therefore, it can be usefully used for exterior applications of electronic devices such as mobile phones that require such characteristics.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention.

Specifications of each component used in the following Examples and Comparative Examples are as follows.

(A1) polycarbonate resin

Cheil Industries' polycarbonate resin, INFINO SC-1190 (Melt Index (300 ° C., 1.2 kg) = 20 g / 10 min, weight average molecular weight: 24,000 g / mol) was used.

(A2) polycarbonate resin

Cheil Industries' polycarbonate resin, INFINO SC-1620 (Melt Index (300 ° C., 1.2 kg) = 65 g / 10 min, weight average molecular weight 18,000 g / mol) was used.

(B) inorganic filler

A glass fiber having an average length of 3 mm (Owen Corning 183F) was used.

(C1) phosphorus containing Tg regulator

Cyclophosphazine (Rabitle FP-110, Fushimi) was used.

(C2) phosphorus containing Tg regulator

Hexachlorocyclophosphazine (Samreal 87, Ningbo Samreal Chemical) was used.

(D) lubricant

HDPE wax type lubricant (HI-WAX 400P, MITSUI PETROCHEMICAL) was used.

(E) antioxidant

Bis (2,4-dicumylphenyl) pentaerythritol diphosphite Doverphos S-9228 PC (DOVER CHEMICAL Co., Ltd.) was used as an antioxidant.

Property measurement method

(1) Gloss measurement

Glossy 9 * 5cm rectangular specimens were measured at an angle of 60 ° using a VG7000 gloss meter from nippon denshoku.

(2) coating yield measurement

After 100 coatings of 10cm × 10cm × 1cm are applied in three levels of under-to-mid-top coating, it is judged by the naked eye to produce a good product without any irregularities. The coating yield (%) was measured by the number of good products excluding defects.

(3) impact drop test

After injecting flat specimens 1 mm thick, 5 cm wide, and 5 cm long, Aging at room temperature for 6 hours or more and impacting 20 or more specimens using a dropping test (dupont drop test, 500 g weight), 50% of the specimens The average height broken is numerically expressed in cm.

(4) flexural modulus

ASTM D790 was measured at a speed of 2.8 mm / min.

(5) spiral length

Using a spiral mold having a thickness of 1 mm and a width of 1 cm, injection molding was performed at 310 ° C. while maintaining a constant pressure, speed, and cushion amount, and the flow length of the resin was measured in mm units.

Example 1-2

To prepare a polycarbonate resin composition by dry blending by mixing (A1) polycarbonate resin, (C) phosphorus containing Tg regulator, (D) lubricant and (E) antioxidant in the amounts shown in Table 1 Then, using a twin-screw extruder of Φ = 45 mm was processed into a nozzle temperature, 250 ~ 280 ℃ to prepare a pellet. At this time, the inorganic filler (B) was put into the side feeder. The prepared pellets were injection processed into specimens after drying at 100 ° C. for 3 hours, and their physical properties are shown in Table 2 below.

Example 3

As shown in Table 1, except that the (C1) Tg regulator and (C2) Tg regulator was used in a mixed manner, was prepared in the same manner as in Example 1 and injection-molded into a specimen, the physical properties are shown in Table 2 below .

Comparative Example 1

As shown in Table 1, except that the (C) phosphorus-containing Tg regulator was not used, was prepared in the same manner as in Example 1 and injection-molded into a specimen, measured in physical properties are shown in Table 2 below.

Comparative Example 2

As shown in Table 1, except that the (D) lubricant was used in excess, was prepared in the same manner as in Example 1 and injection-molded into a specimen, measured in physical properties are shown in Table 2 below.

Comparative Example 3

As shown in Table 1, except that the (A2) polycarbonate resin having a different molecular weight was prepared in the same manner as in Example 1 and injection-molded into a specimen, measured in physical properties are shown in Table 2 below.

Comparative Example 4-5

As shown in Table 1, (C) was prepared in the same manner as in Example 1, except that the content of the Tg regulator containing phosphorus was used out of the scope of the present invention, and the injection molding into a specimen, by measuring the physical properties Table 2 shows.

TABLE 1

TABLE 2

As shown in Table 2, by applying the Tg regulator containing phosphorus from Examples 1 to 3 of the present invention, it was found that the appearance (gloss) is significantly superior to Comparative Examples 1 to 3 without applying this. In addition, the impact resistance is also good, it can be seen that it possesses the mechanical properties required for the exterior material of the portable electronic device.

In the case of Comparative Example 2 using a lubricant instead of the Tg regulator of the present invention, the fluidity is good, but the coating yield was significantly reduced, and in Comparative Example 3 to which a low molecular weight polycarbonate resin was applied, the impact resistance was remarkably reduced. .

In addition, in the case of Comparative Example 4, the amount of Tg regulator is included too little to improve the fluidity, the appearance and coating yield was reduced, and in Comparative Example 5, too much Tg regulator is included, the fluidity is excellent, but Impact resistance was reduced, the coating yield was noticeably reduced by the protrusion of the glass fiber during injection.

Therefore, by applying the Tg regulator containing phosphorus in an optimum content, the flow is improved to prevent the protrusion of the inorganic filler during injection can have a beautiful appearance characteristics, thereby significantly improving the coating yield to significantly increase productivity It can increase.

Although the preferred embodiment of the present invention has been described above, the present invention may use various changes, modifications, and equivalents. It is clear that the present invention can be applied in the same manner by appropriately modifying the above embodiments. Accordingly, the above description does not limit the scope of the invention as defined by the limitations of the following claims.

Claims (8)

A polycarbonate resin composition comprising (A) 50 to 85% by weight of polycarbonate resin, (B) 10 to 40% by weight of inorganic filler and (C) 1 to 10% by weight of Tg regulator containing phosphorus,
The polycarbonate resin (A) is an aromatic polycarbonate resin which is a polymer of an aromatic dihydroxy compound and a carbonate precursor, and has a weight average molecular weight (Mw) of 10,000 to 200,000 g / mol,
The phosphorus-containing Tg regulator (C) is selected from at least one of a compound having a structure of Formula 2 and a compound having the structure of Formula 3,
Specimens (molded article) formed from the polycarbonate resin composition is a polycarbonate resin composition, characterized in that the following formula 1 and 2:
[Formula 2]

[Formula 3]

50 ≤ Gloss ≤ 90 [Equation 1]
80 ≤ Yp ≤ 100 [Equation 2]
In Equation 1, Gloss is a 60 ° gloss average value measured using a Glossmeter for a rectangular shaped injection specimen of 9 cm × 5 cm size, in the formula 2, Yp is 10 cm × 10 cm × 1 cm After coating the 100 injected specimens, it is judged visually to determine that the product having irregularities is defective, and is the coating yield (%) measured by the number of non-defective products.
delete The polycarbonate resin composition of claim 1, wherein the inorganic filler is selected from at least one of glass fiber, carbon fiber, ceramic fiber, calcium carbonate, silica, alumina, aluminum hydroxide, talc, clay, mica, barium sulfate, and whisker.
delete delete The method of claim 1, wherein the polycarbonate resin composition is antibacterial, heat stabilizer, antioxidant, release agent, light stabilizer, surfactant, coupling agent, plasticizer, compatibilizer, lubricant, antistatic agent, colorant, pigment, dye, flame retardant, flame retardant A polycarbonate resin composition further comprising an additive selected from the group consisting of adjuvants, antidripping agents, weathering agents, ultraviolet absorbers, sunscreen agents and mixtures thereof.
A molded article prepared from the polycarbonate resin composition according to any one of claims 1, 3, and 6.
The molded article according to claim 7, wherein the molded article is a cellular phone exterior material.

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