KR102310406B1 - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

The thermoplastic resin composition of the present invention includes 100 parts by weight of a polycarbonate resin; 5 to 20 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; 0.5 to 3 parts by weight of a rubbery polymer obtained by graft polymerization of maleic anhydride; 50 to 100 parts by weight of glass fiber; 10 to 30 parts by weight of barium sulfate; and 5 to 20 parts by weight of a phosphorus-based flame retardant. The thermoplastic resin composition is excellent in impact resistance, weather resistance, flame retardancy, fluidity, etc., and has a high specific gravity characteristic.

Description

Thermoplastic resin composition and molded article formed therefrom

The present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent impact resistance, weather resistance, flame retardancy, fluidity, etc., and having a high specific gravity characteristic, and a molded article formed therefrom.

A thermoplastic resin composition containing a polycarbonate resin, etc. has excellent impact resistance, flame retardancy, processability, and the like, and is useful as a housing for electrical/electronic products and interior/exterior materials for other office equipment.

When such a thermoplastic resin composition is used for a speaker, a method is used to increase the specific gravity of the speaker material by mixing an inorganic filler such as talc, wollastonite, or glass fiber in a certain amount or more with the thermoplastic resin composition in order to improve the sound quality of the speaker.

However, when the inorganic filler is included in the thermoplastic resin composition in excess, mechanical properties, weather resistance, flame retardancy, etc. of the thermoplastic resin composition are deteriorated due to decomposition of the polycarbonate resin, etc., and in severe cases, product damage may occur.

Therefore, there is a need to develop a thermoplastic resin composition having high specific gravity for good sound quality and excellent in impact resistance, weather resistance, flame retardancy, fluidity (processability), and the like.

Background art of the present invention is disclosed in US Patent No. 5,061,745 and the like.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic resin composition having excellent impact resistance, weather resistance, flame retardancy, fluidity, and the like, and having a high specific gravity characteristic.

Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.

All of the above and other objects of the present invention can be achieved by the present invention described below.

1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition includes 100 parts by weight of a polycarbonate resin; 5 to 20 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; 0.5 to 3 parts by weight of a rubbery polymer obtained by graft polymerization of maleic anhydride; 50 to 100 parts by weight of glass fiber; 10 to 30 parts by weight of barium sulfate; and 5 to 20 parts by weight of a phosphorus-based flame retardant.

2. In the first embodiment, the rubber-modified aromatic vinyl-based copolymer resin may include a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin.

3. In embodiments 1 or 2, the rubber-modified vinyl-based graft copolymer may be a polymer obtained by graft polymerization of a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to a rubbery polymer.

4. In the above 1 to 3 embodiments, the rubbery polymer obtained by graft polymerization of maleic anhydride is ethylene-octene rubber obtained by graft polymerization of maleic anhydride (EOR-g-MAH), and maleic anhydride is graft-polymerized with ethylene-octene rubber (EOR-g-MAH). Ethylene-butene rubber (EBR-g-MAH), ethylene-propylene-diene monomer terpolymer with maleic anhydride graft polymerization (EPDM-g-MAH), styrene-ethylene-butyl with maleic anhydride graft polymerization One of ren-styrene copolymer (SEBS-g-MAH), polypropylene graft-polymerized with maleic anhydride (PP-g-MAH), and polyethylene graft-polymerized with maleic anhydride (PE-g-MAH) may include more than one.

5. In embodiments 1 to 4, the phosphorus-based flame retardant may include at least one of a phosphate compound, a phosphonate compound, a phosphinate compound, a phosphine oxide compound, and a phosphazene compound.

6. In the above 1 to 5 embodiments, the weight ratio of the maleic anhydride graft-polymerized rubber polymer and the barium sulfate may be 0.03:1 to 0.1:1.

7. In the above 1 to 6 embodiments, the weight ratio of the glass fiber and the barium sulfate may be 3:1 to 5:1.

8. In embodiments 1 to 7, the thermoplastic resin composition may have a notch Izod impact strength of 10 to 20 kgf·cm/cm of a 1/8″ thick specimen measured according to ASTM D256.

9. In the above 1 to 8 embodiments, the thermoplastic resin composition may have a yellow index difference (ΔYI) of 1 to 5 according to Equation 1 below of an injection specimen having a size of 50 mm × 90 mm × 3 mm:

[Equation 1]

ΔYI = YI ₁ - YI ₀

In Equation 1, YI ₀ is the initial yellow index value of the specimen of the thermoplastic resin composition, and YI ₁ is the yellow index value measured after exposing the specimen for 500 hours at 85° C. and 85% relative humidity.

10. In the above 1 to 9 embodiments, the thermoplastic resin composition may have a flame retardancy of V-1 or more of a 3 mm thick specimen measured according to UL-94 standards.

11. In embodiments 1 to 10, the thermoplastic resin composition may have a melt-flow index (MI) of 30 to 45 g/10 minutes measured at 250° C. and 10 kgf according to ASTM D1238. have.

12. In embodiments 1 to 11, the thermoplastic resin composition may have a specific gravity of 1.55 to 1.65 measured at 23° C. according to ASTM D792 A.

13. Another aspect of the present invention relates to a molded article. The molded article is characterized in that it is formed from the thermoplastic resin composition according to any one of 1 to 12.

The present invention has the effect of providing a thermoplastic resin composition excellent in impact resistance, weather resistance, flame retardancy, fluidity, etc., and a high specific gravity characteristic, and a molded article formed therefrom.

Hereinafter, the present invention will be described in detail as follows.

The thermoplastic resin composition according to the present invention comprises (A) a polycarbonate resin; (B) a rubber-modified aromatic vinyl-based copolymer resin; (C) a rubbery polymer graft polymerized with maleic anhydride; (D) fiberglass; (E) barium sulfate; and (F) a phosphorus-based flame retardant.

In the present specification, "a to b" representing a numerical range is defined as "≥a and ≤b".

(A) polycarbonate resin

As the polycarbonate resin according to an embodiment of the present invention, a polycarbonate resin used in a conventional thermoplastic resin composition may be used. For example, an aromatic polycarbonate resin produced by reacting diphenols (aromatic diol compounds) with a precursor such as phosgene, halogen formate or diester carbonate can be used.

In an embodiment, the diphenols include 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1 ,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl) Propane and the like may be exemplified, but the present invention is not limited thereto. For example, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, or 1,1-bis(4-hydroxyphenyl)propane ) cyclohexane, and specifically, 2,2-bis(4-hydroxyphenyl)propane called bisphenol-A may be used.

In an embodiment, the polycarbonate resin may be used with a branched chain, for example, based on the total amount of diphenols used for polymerization, from 0.05 to 2 mol% of a trivalent or higher polyfunctional compound, specifically, 3 It is also possible to use a branched polycarbonate resin prepared by adding a compound having polyvalent or higher phenolic groups.

In an embodiment, the polycarbonate resin may be used in the form of a homo polycarbonate resin, a copolycarbonate resin, or a blend thereof. In addition, the polycarbonate resin may be partially or entirely replaced with an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor, for example, a bifunctional carboxylic acid.

In an embodiment, the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 10,000 to 50,000 g/mol, for example, 15,000 to 40,000 g/mol. In the above range, the fluidity (processability) of the thermoplastic resin composition may be excellent.

In an embodiment, the polycarbonate resin may have a melt-flow index (MI) of 5 to 110 g/10 minutes measured at 300° C. and 1.2 kgf load condition based on ISO 1133. In addition, the polycarbonate resin may be a mixture of two or more polycarbonate resins having different melt flow indexes.

(B) rubber-modified aromatic vinyl-based copolymer resin

The rubber-modified aromatic vinyl-based copolymer resin according to an embodiment of the present invention may include (B1) a rubber-modified vinyl-based graft copolymer and (B2) an aromatic vinyl-based copolymer resin.

(B1) rubber-modified vinyl-based graft copolymer

The rubber-modified vinyl-based graft copolymer according to an embodiment of the present invention may be graft polymerization of a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to a rubbery polymer. For example, the rubber-modified vinyl-based graft copolymer can be obtained by graft polymerization of a monomer mixture containing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to a rubbery polymer. Graft polymerization may be performed by further including a monomer that imparts heat resistance. The polymerization may be performed by a known polymerization method such as emulsion polymerization or suspension polymerization. In addition, the rubber-modified vinyl-based graft copolymer may form a core (rubber polymer)-shell (copolymer of a monomer mixture) structure, but is not limited thereto.

In an embodiment, the rubbery polymer includes a diene rubber such as polybutadiene, poly(styrene-butadiene), poly(acrylonitrile-butadiene), and a saturated rubber hydrogenated to the diene rubber, isoprene rubber, carbon number 2 to alkyl (meth)acrylate rubber of 10, a copolymer of alkyl (meth)acrylate and styrene having 2 to 10 carbon atoms, ethylene-propylene-diene monomer terpolymer (EPDM), and the like can be exemplified. These may be applied alone or in mixture of two or more. For example, a diene-based rubber, a (meth)acrylate rubber, etc. may be used, and specifically, a butadiene-based rubber, a butyl acrylate rubber, or the like may be used.

In an embodiment, the rubbery polymer (rubber particles) may have an average particle size of 0.05 to 6 μm, for example 0.15 to 4 μm, specifically 0.25 to 3.5 μm. In the above range, the thermoplastic resin composition may have excellent impact resistance and appearance characteristics. Here, the average particle size (z-average) of the rubbery polymer (rubber particles) may be measured using a light scattering method in a latex state. Specifically, the rubbery polymer latex is filtered through a mesh to remove coagulation generated during polymerization of the rubbery polymer, and a solution of 0.5 g of latex and 30 ml of distilled water is poured into a 1,000 ml flask and distilled water is filled to prepare a sample. , 10 ml of the sample is transferred to a quartz cell, and the average particle size of the rubbery polymer can be measured with a light scattering particle size analyzer (malvern, nano-zs).

In an embodiment, the content of the rubbery polymer may be 20 to 70% by weight, for example, 25 to 60% by weight, of the total 100% by weight of the rubber-modified vinyl-based graft copolymer, and the monomer mixture (aromatic vinyl-based monomer and The content of the vinyl cyanide-based monomer) may be 30 to 80% by weight, for example, 40 to 75% by weight, based on 100% by weight of the total rubber-modified vinyl-based graft copolymer. In the above range, the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.

In an embodiment, the aromatic vinyl-based monomer may be graft copolymerized to the rubber polymer, and may include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, etc. can be illustrated. These can be used individually or in mixture of 2 or more types. The content of the aromatic vinyl-based monomer may be 10 to 90% by weight, for example, 10 to 60% by weight of 100% by weight of the monomer mixture. In the above range, the processability and impact resistance of the thermoplastic resin composition may be excellent.

In a specific embodiment, the vinyl cyanide-based monomer is copolymerizable with the aromatic vinyl-based monomer, and includes acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. can be exemplified. These can be used individually or in mixture of 2 or more types. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide-based monomer may be 10 to 90% by weight, for example, 10 to 60% by weight of 100% by weight of the monomer mixture. In the above range, the thermoplastic resin composition may have excellent chemical resistance, mechanical properties, and the like.

In embodiments, the monomer for imparting the processability and heat resistance may include (meth)acrylic acid, alkyl (meth)acrylate having 1 to 10 carbon atoms, maleic anhydride, N-substituted maleimide, and the like, but is not limited thereto. does not When the monomer for imparting the processability and heat resistance is used, the content thereof may be 90% by weight or less, for example, 30 to 80% by weight based on 100% by weight of the monomer mixture. Within the above range, processability and heat resistance may be imparted to the thermoplastic resin composition without deterioration of other physical properties.

In a specific embodiment, as the rubber-modified vinyl-based graft copolymer, a butadiene-based rubber polymer is grafted with a styrene monomer as an aromatic vinyl compound and an acrylonitrile monomer as a vinyl cyanide compound (g-ABS), a butadiene-based polymer A copolymer (g-MBS) grafted with methyl methacrylate as a monomer for imparting processability and heat resistance to a styrene monomer, which is an aromatic vinyl-based compound, and a styrene monomer, an acrylonitrile monomer and methyl to a butadiene-based rubber polymer. A methacrylate-grafted copolymer (g-MABS), a butyl acrylate-based rubber polymer with an aromatic vinyl-based compound styrene monomer and a vinyl cyanide-based compound acrylonitrile monomer grafted onto an acrylate-styrene- An acrylonitrile graft copolymer (g-ASA) etc. can be illustrated.

In an embodiment, the rubber-modified vinyl-based graft copolymer may be included in an amount of 20 to 50% by weight, for example, 25 to 45% by weight of 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin. Within the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity (molding processability), appearance characteristics, and balance of physical properties thereof.

(B2) Aromatic vinyl-based copolymer resin

The aromatic vinyl-based copolymer resin according to an embodiment of the present invention may be an aromatic vinyl-based copolymer resin used in a conventional rubber-modified aromatic vinyl-based copolymer resin. For example, the aromatic vinyl-based copolymer resin may be a polymer of a monomer mixture including an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer.

In a specific embodiment, the aromatic vinyl-based copolymer resin may be obtained by mixing an aromatic vinyl-based monomer and a monomer copolymerizable with an aromatic vinyl-based monomer, and then polymerizing it, and the polymerization is emulsion polymerization, suspension polymerization, bulk polymerization, etc. It can be carried out by a known polymerization method of

In an embodiment, the aromatic vinyl-based monomer includes styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, and dibromostyrene. , vinyl naphthalene, etc. can be used. These may be applied alone or in mixture of two or more. The content of the aromatic vinyl-based monomer may be 10 to 90% by weight, for example, 20 to 80% by weight, based on 100% by weight of the total aromatic vinyl-based copolymer resin. In the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity, and the like.

In an embodiment, the monomer copolymerizable with the aromatic vinyl-based monomer may include at least one of a vinyl cyanide-based monomer and an alkyl (meth)acrylic monomer. For example, it may be a vinyl cyanide monomer or a vinyl cyanide monomer and an alkyl (meth) acrylic monomer, specifically, a vinyl cyanide monomer and an alkyl (meth) acrylic monomer.

In embodiments, the vinyl cyanide-based monomer may be exemplified by acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like, but is not limited thereto. does not These can be used individually or in mixture of 2 or more types. For example, acrylonitrile, methacrylonitrile, etc. can be used.

In a specific embodiment, the alkyl (meth) acrylic monomer may include (meth) acrylic acid and/or an alkyl (meth) acrylate having 1 to 10 carbon atoms. These can be used individually or in mixture of 2 or more types. For example, methyl methacrylate, methyl acrylate, etc. can be used.

In an embodiment, when the monomer copolymerizable with the aromatic vinyl-based monomer is a mixture of a vinyl cyanide monomer and an alkyl (meth)acrylic monomer, the content of the vinyl cyanide monomer is 100 wt% of a monomer copolymerizable with the aromatic vinyl-based monomer It may be 1 to 40% by weight, for example, 2 to 35% by weight, and the content of the alkyl (meth)acrylic monomer is 60 to 99% by weight of 100% by weight of the monomer copolymerizable with the aromatic vinylic monomer, for example For example, it may be 65 to 98% by weight. In the above range, the thermoplastic resin composition may have excellent transparency, heat resistance, processability, and the like.

In an embodiment, the content of the monomer copolymerizable with the aromatic vinyl-based monomer may be 10 to 90% by weight, for example, 20 to 80% by weight, based on 100% by weight of the total aromatic vinyl-based copolymer resin. In the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity, and the like.

In an embodiment, the aromatic vinyl-based copolymer resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 10,000 to 300,000 g/mol, for example, 15,000 to 150,000 g/mol. In the above range, the thermoplastic resin composition may have excellent mechanical strength, moldability, and the like.

In an embodiment, the aromatic vinyl-based copolymer resin may be included in an amount of 50 to 80% by weight, for example, 55 to 75% by weight, of 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin. In the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity (molding processability), and the like.

In an embodiment, the rubber-modified aromatic vinyl-based copolymer resin (B) may be included in an amount of 5 to 20 parts by weight, for example, 7 to 15 parts by weight, based on 100 parts by weight of the polycarbonate resin (A). When the content of the rubber-modified aromatic vinyl-based copolymer resin is less than 5 parts by weight, there is a risk that the impact resistance of the thermoplastic resin composition may be lowered, and if it exceeds 20 parts by weight, the flame retardancy, fluidity, weather resistance, etc. may be reduced have.

(C) a rubbery polymer graft polymerized with maleic anhydride

The rubber polymer obtained by graft polymerization of maleic anhydride according to an embodiment of the present invention is applied together with barium sulfate and the like to improve the weather resistance, fluidity, impact resistance, heat resistance, etc. of the thermoplastic resin composition. and/or a copolymer of an aromatic vinylic monomer, etc.) may be graft-polymerized with maleic anhydride (MAH).

In an embodiment, the maleic anhydride graft-polymerized rubbery polymer is maleic anhydride graft-polymerized ethylene-octene rubber (EOR-g-MAH), maleic anhydride graft-polymerized ethylene-butene rubber (EBR) -g-MAH), ethylene-propylene-diene monomer terpolymer with maleic anhydride graft polymerization (EPDM-g-MAH), styrene-ethylene-butylene-styrene copolymer with maleic anhydride graft polymerization ( SEBS-g-MAH), polypropylene graft-polymerized with maleic anhydride (PP-g-MAH), and polyethylene graft-polymerized with maleic anhydride (PE-g-MAH). .

In an embodiment, in 100% by weight of the maleic anhydride graft copolymerized rubber, the content of maleic anhydride may be 0.1 to 5% by weight, and the content of the rubber polymer may be 95 to 99.9% by weight, It is not limited thereto.

In an embodiment, the maleic anhydride graft-polymerized rubbery polymer (C) may be included in an amount of 0.5 to 3 parts by weight, for example, 0.5 to 2 parts by weight, based on 100 parts by weight of the polycarbonate resin (A). When the content of the maleic anhydride graft-polymerized rubber polymer is less than 0.5 parts by weight, there is a risk that the weather resistance, impact resistance, thermal stability, etc. of the thermoplastic resin composition may be deteriorated, and when it exceeds 3 parts by weight, appearance properties, flame retardancy There is a possibility that the etc. may be lowered.

(D) fiberglass

The glass fiber of the present invention can increase the specific gravity of the thermoplastic resin composition and improve mechanical properties such as rigidity, impact resistance, and the like, and glass fibers used in ordinary thermoplastic resin compositions can be used.

In an embodiment, the glass fiber may be in the form of a fiber, and may have a cross-section of various shapes such as a circle, an oval, and a rectangle. For example, it may be preferable in view of mechanical properties to use fibrous glass fibers of circular and/or rectangular cross-section.

In an embodiment, the glass fiber of the circular cross-section may have a cross-sectional diameter of 5 to 20 μm and a length before processing of 2 to 20 mm, and the glass fiber of the rectangular cross-section has an aspect ratio of a cross-section (major diameter of cross-section / minor diameter of cross-section) is 1.5 to 10, the minor diameter may be 2 to 10 μm, and the length before processing may be 2 to 20 mm. In the above range, the rigidity, processability, etc. of the thermoplastic resin composition may be improved.

In an embodiment, the glass fiber may be treated with a conventional surface treatment agent.

In an embodiment, the glass fiber (D) may be included in an amount of 50 to 100 parts by weight, for example, 65 to 85 parts by weight, based on 100 parts by weight of the polycarbonate resin (A). When the content of the maleic anhydride graft-polymerized rubber polymer is less than 50 parts by weight, there is a fear that the rigidity, impact resistance, specific gravity, dimensional stability, etc. of the thermoplastic resin composition may decrease, and when it exceeds 100 parts by weight, appearance characteristics , flame retardancy, weather resistance, etc. may be deteriorated.

(E) barium sulfate

_{Barium sulfate (BaSO 4} ) according to an embodiment of the present invention is applied together with a rubber polymer obtained by graft polymerization of maleic anhydride, glass fiber, etc. to improve the weather resistance, fluidity, impact resistance, heat resistance, etc. of the thermoplastic resin composition It can be improved and increased in importance. As the barium sulfate, barium sulfate contained in a conventional thermoplastic resin composition may be used. For example, the barium sulfate may be in the form of a white powder having an average particle diameter of 1 to 2 μm.

In an embodiment, the barium sulfate (E) may be included in an amount of 10 to 30 parts by weight, for example, 15 to 25 parts by weight, based on 100 parts by weight of the polycarbonate resin (A). When the content of the inorganic filler is less than 10 parts by weight, there is a fear that the mechanical properties, weather resistance, flame retardancy, etc. of the thermoplastic resin composition may decrease, and if it exceeds 30 parts by weight, impact resistance, fluidity, etc. may be reduced.

In an embodiment, the weight ratio (C:E) of the maleic anhydride graft-polymerized rubbery polymer (C) and the barium sulfate (E) may be 0.03:1 to 0.1:1. Within the above range, the weather resistance of the thermoplastic resin composition may be more excellent.

In an embodiment, the weight ratio (D:E) of the glass fiber (D) and the barium sulfate (E) may be 3:1 to 5:1. Within the above range, specific gravity can be increased without deterioration of mechanical properties, weather resistance, etc. of the thermoplastic resin composition.

(F) Phosphorus-based flame retardant

The phosphorus-based flame retardant according to an embodiment of the present invention may be a phosphorus-based flame retardant used in a conventional flame-retardant thermoplastic resin composition. For example, phosphorus-based flame retardants such as phosphate compounds, phosphonate compounds, phosphinate compounds, phosphine oxide compounds, phosphazene compounds, and metal salts thereof can be used These can be used individually or in mixture of 2 or more types.

In an embodiment, the phosphorus-based flame retardant may include a phosphazene compound represented by Formula 1 below.

[Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted An alkenyl group having 2 to 7 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aryloxy group, a heteroaryl group having 5 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbonylalkyl group having 2 to 10 carbon atoms, an amino group or a hydroxy group.

Here, the "substitution" refers to an alkyl group having 1 to 10 carbon atoms, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. It means being substituted with a substituent such as a heterocycloalkyl group, a heteroaryl group having 4 to 10 carbon atoms, and combinations thereof.

In addition, the above "alkyl", "alkoxy" and other substituents comprising an "alkyl" moiety include both straight-chain or branched forms, and "alkenyl" has 2 to 8 carbon atoms and contains at least one double bond. includes both straight-chain or pulverized forms, and the term "cycloalkyl" includes both saturated monocyclic or saturated bicyclic ring structures having 3 to 20 carbon atoms. The "aryl" is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen atom, and a single or fused ring system comprising suitably 4 to 7, preferably 5 or 6 ring atoms in each ring. include Specifically, phenyl, naphthyl, biphenyl, tolyl, and the like can be exemplified.

The "heterocycloalkyl" refers to a cycloalkyl group containing 1 to 3 heteroatoms selected from N, O, S as saturated cyclic hydrocarbon backbone atoms, and the remaining saturated monocyclic or bicyclic ring backbone atoms are carbon. pyrrolidinyl, azetidinyl, pyrazolidinyl, oxazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, hydantoinyl, valerolactamyl, Oxiranyl, oxetanyl, dioxolanyl, dioxanyl, oxathiolanyl, oxathianyl, dithianyl, dihydrofuranyl, tetrahydrofuranyl, dihydropyranyl, tetrahydropyranyl, tetrahydropyri dinyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, tetrahydrothiopyranyl, diazepanyl, azepanyl and the like can be exemplified.

The "heteroaryl" refers to 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 carbon, wherein the heteroaryl group is a heteroaryl group and divalent aryl groups in which atoms are oxidized or quaternized to form, for example, N-oxides or quaternary salts. Specifically, furyl, thiophenyl, pyrrolyl, pyranyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazinyl and zolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and the like.

In an embodiment, the phosphorus-based flame retardant (D) may be included in an amount of 5 to 20 parts by weight, for example, 8 to 15 parts by weight, based on 100 parts by weight of the polycarbonate resin (A). When the content of the phosphorus-based flame retardant is less than 5 parts by weight, there is a fear that the flame retardancy, fluidity (formability), etc. of the thermoplastic resin composition may decrease, and if it exceeds 20 parts by weight, impact resistance, heat resistance, etc. may be reduced.

The thermoplastic resin composition according to an embodiment of the present invention may further include an additive included in a conventional thermoplastic resin composition. Examples of the additive include, but are not limited to, anti-drip agents such as fluorinated olefin resins, antioxidants, lubricants, release agents, nucleating agents, stabilizers, pigments, dyes, and mixtures thereof. When the additive is used, its content may be 0.001 to 40 parts by weight, for example, 0.1 to 10 parts by weight, based on 100 parts by weight of the thermoplastic resin.

The thermoplastic resin composition according to an embodiment of the present invention may be in the form of pellets that are melt-extruded at 200 to 280°C, for example, 220 to 250°C, by mixing the above components and using a conventional twin-screw extruder.

In an embodiment, the thermoplastic resin composition has a notch Izod impact strength of 10 to 20 kgf·cm/cm, for example, 10 to 15 kgf·cm/cm, of a 1/8″ thick specimen measured according to ASTM D256. can

In an embodiment, the thermoplastic resin composition may have a yellow index difference (ΔYI) of 1 to 5, for example, 1.5 to 3.5, according to Equation 1 below of an injection specimen having a size of 50 mm × 90 mm × 3 mm.

[Equation 1]

ΔYI = YI ₁ - YI ₀

In Equation 1, YI ₀ is the initial yellow index value of the specimen of the thermoplastic resin composition, and YI ₁ is the yellow index value measured after exposing the specimen for 500 hours at 85° C. and 85% relative humidity.

In an embodiment, the thermoplastic resin composition may have a flame retardancy of V-1 or more of a 3 mm thick specimen measured according to UL-94 standards.

In an embodiment, the thermoplastic resin composition has a melt-flow index (MI) of 30 to 45 g/10 min, for example 33 to 43, measured at 250° C. and 10 kgf according to ASTM D1238. g/10 min.

In an embodiment, the thermoplastic resin composition may have a specific gravity of 1.55 to 1.65, for example 1.60 to 1.65, measured at 23° C. according to ASTM D792 A.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be prepared in the form of pellets, and the manufactured pellets may be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such a molding method is well known by those of ordinary skill in the art to which the present invention pertains. The molded article is excellent in impact resistance, weather resistance, flame retardancy, fluidity, etc., and has a high specific gravity, and is useful as an interior/exterior material for electric/electronic products, an interior/exterior material for automobiles, an exterior material for construction, etc., in particular, useful as a speaker material do.

Hereinafter, the present invention will be described in more detail through examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example

Hereinafter, the specifications of each component used in Examples and Comparative Examples are as follows.

(A) polycarbonate resin

The following (A1) bisphenol-A-based polycarbonate resin 23% by weight and (A2) bisphenol-A-based polycarbonate resin 77% by weight were mixed and used.

(A1) A bisphenol-A-based polycarbonate resin (flow index (MI, according to ISO 1133, measured at 300°C, 1.2 kgf conditions): 90±2 g/10 min) was used.

(A2) A bisphenol-A-based polycarbonate resin (flow index (MI, according to ISO 1133, measured at 300°C, 1.2 kgf conditions): 62±5 g/10 min) was used.

(B) rubber-modified aromatic vinyl-based copolymer resin

(B1) 30% by weight of the rubber-modified aromatic vinyl-based graft copolymer and (B2) 70% by weight of the aromatic vinyl-based copolymer resin were mixed and used.

(B1) rubber-modified aromatic vinyl-based graft copolymer

Styrene, acrylonitrile and methyl methacrylate (styrene/acrylonitrile/methyl methacrylate: 20 wt%/10 wt%/70 wt%) 40 wt% to 60 wt% of butadiene rubber having an average particle size of 0.28 μm A core-shell type graft copolymer (g-MABS) prepared by graft copolymerization was used.

(B2) Aromatic vinyl-based copolymer resin

A resin prepared by polymerizing 70 wt% of methyl methacrylate, 20 wt% of styrene, and 10 wt% of acrylonitrile (weight average molecular weight: 160,000 g/mol) was used.

(C) a rubbery polymer graft polymerized with maleic anhydride

Ethylene-octene rubber obtained by graft polymerization of maleic anhydride (manufacturer: Woosung Chemical, product name: SP2000S) was used.

(D) fiberglass

Glass fiber (manufacturer: KCC, product name: CS321-EC10-3) was used.

(E) barium sulfate

Barium sulfate (manufacturer: Durichem, product name: ZJ-051) was used.

(F) Phosphorus-based flame retardant

A phosphazene compound (manufacturer: Weihai jinwei Chemindustry, product name: HPCTP) was used.

(G) inorganic fillers

Talc (manufacturer: KOCH, product name: KCP-04) was used.

Example 1 to 3 and comparative example 1 to 5

After adding each of the components in an amount as shown in Table 1 below, it was extruded at 230° C. to prepare pellets. For extrusion, a twin-screw extruder with L/D=36 and a diameter of 45 mm was used, and the prepared pellets were dried at 80° C. for 2 hours or more, and then injected in a 6 Oz injection machine (molding temperature 230° C., mold temperature: 60° C.). was prepared. The prepared specimens were evaluated for physical properties by the following method, and the results are shown in Table 1 below.

How to measure physical properties

(1) Notched Izod impact strength (unit: kgf·cm/cm): According to ASTM D256, the notched Izod impact strength of a 1/8″ thick specimen was measured.

(2) Yellow index difference (ΔYI): According to Equation 1 below, the yellow index difference (ΔYI) of a 50 mm × 90 mm × 3 mm injection specimen was calculated to evaluate weather resistance.

[Equation 1]

ΔYI = YI ₁ - YI ₀

In Equation 1, YI ₀ is the initial yellow index value of the specimen of the thermoplastic resin composition, and YI ₁ is the yellow index value measured after exposing the specimen for 500 hours at 85° C. and 85% relative humidity.

(3) Flame retardancy: In accordance with the UL-94 flammability testing standard, it was measured using a 3 mm thick specimen.

(4) Melt-flow index (MI, unit: g/10min): It was measured at 250° C. and 10 kgf according to ASTM D1238.

(5) Specific gravity: according to ASTM D792 A method, it was measured at 23 ℃ condition.

(6) Tanδ (loss tangent): It was measured using a 3 mm thick specimen at 50 to 200° C. using a TA Instrument Q800 equipment as a dynamic mechanical analysis (DMA). Here, the higher the loss factor, the higher the tanδ, and when tanδ is 1.6 or more, it is determined that the speaker has excellent sound quality.

Example comparative example One 2 3 One 2 3 4 5 (A) (parts by weight) 100 100 100 100 100 100 100 100 (B) (parts by weight) 9.6 9.6 9.6 9.6 9.6 9.6 9.6 9.6 (C) (parts by weight) 0.6 1.0 1.9 0.2 3.8 1.0 1.0 1.0 (D) (parts by weight) 73 73 73 73 73 45 105 73 (E) (parts by weight) 19.2 19.2 19.2 19.2 19.2 40 5 - (F) (parts by weight) 9.6 9.6 9.6 9.6 9.6 9.6 9.6 9.6 (G) (parts by weight) - - - - - - - 19.2 Notched Izod Impact Strength 10.5 13.1 13.9 9.2 8.5 8.5 15.5 14.2 Yellow Index Difference (ΔYI) 3.0 2.7 2.6 5.5 6.3 8.4 3.1 2.7 Flame retardancy V-1 V-1 V-1 V-1 V-1 V-2 V-1 V-1 melt flow index 41.5 36.1 35.2 45.7 35.9 62 11.9 30.5 importance 1.62 1.62 1.61 1.62 1.61 1.75 1.60 1.49 Tanδ 1.7 1.7 1.7 1.7 1.7 1.9 1.7 1.4

From the above results, it can be seen that the thermoplastic resin composition of the present invention has high specific gravity (excellent speaker sound quality), and excellent impact resistance, weather resistance, flame retardancy, fluidity, and the like.

On the other hand, in Comparative Example 1 in which a small amount of the rubbery polymer graft-polymerized with maleic anhydride was added, impact resistance and weather resistance were lowered, and Comparative Example in which an excessive amount of the rubbery polymer graft-polymerized with maleic anhydride was added. In the case of 2, it can be seen that impact resistance, weather resistance, etc. are reduced. In the case of Comparative Example 3 using a small amount of glass fiber and an excessive amount of barium sulfate, it can be seen that the impact strength, weather resistance, flame retardancy, etc. are lowered, and in Comparative Example 4 using an excessive amount of glass fiber and using a small amount of barium sulfate, It can be seen that the flow is lowered, and in the case of Comparative Example 5 using talc instead of barium sulfate, it can be seen that the specific gravity, tanδ, and the like are lowered.

Simple modifications or changes of the present invention can be easily carried out by those of ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (13)

100 parts by weight of polycarbonate resin;
5 to 20 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin;
0.5 to 3 parts by weight of a rubbery polymer obtained by graft polymerization of maleic anhydride;
50 to 100 parts by weight of glass fiber;
10 to 30 parts by weight of barium sulfate; and
A thermoplastic resin composition comprising 5 to 20 parts by weight of a phosphorus-based flame retardant.
The thermoplastic resin composition according to claim 1, wherein the rubber-modified aromatic vinyl-based copolymer resin comprises a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin.
The thermoplastic resin composition according to claim 2, wherein the rubber-modified vinyl-based graft copolymer is graft-polymerized with a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer on a rubbery polymer.
The ethylene-butene rubber of claim 1, wherein the maleic anhydride graft-polymerized rubbery polymer is maleic anhydride graft-polymerized ethylene-octene rubber (EOR-g-MAH), and maleic anhydride graft-polymerized ethylene-butene rubber. (EBR-g-MAH), ethylene-propylene-diene monomer terpolymer with maleic anhydride graft polymerization (EPDM-g-MAH), styrene-ethylene-butylene-styrene copolymer with maleic anhydride graft polymerization Copolymer (SEBS-g-MAH), maleic anhydride graft-polymerized polypropylene (PP-g-MAH) and maleic anhydride graft-polymerized polyethylene (PE-g-MAH) Thermoplastic resin composition, characterized in that.
The thermoplastic resin composition of claim 1, wherein the phosphorus-based flame retardant comprises at least one of a phosphate compound, a phosphonate compound, a phosphinate compound, a phosphine oxide compound, and a phosphazene compound.
The thermoplastic resin composition of claim 1, wherein the weight ratio of the maleic anhydride graft-polymerized rubber polymer and the barium sulfate is 0.03:1 to 0.1:1.
The thermoplastic resin composition according to claim 1, wherein the weight ratio of the glass fiber and the barium sulfate is 3:1 to 5:1.
The thermoplastic resin composition of claim 1, wherein the notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256 of the thermoplastic resin composition is 10 to 20 kgf·cm/cm.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a yellow index difference (ΔYI) of 1 to 5 according to Equation 1 below of an injection specimen having a size of 50 mm × 90 mm × 3 mm:
[Equation 1]
ΔYI = YI ₁ - YI ₀
In Equation 1, YI ₀ is the initial yellow index value of the specimen of the thermoplastic resin composition, and YI ₁ is the yellow index value measured after exposing the specimen for 500 hours at 85° C. and 85% relative humidity.
According to claim 1, wherein the thermoplastic resin composition is a thermoplastic resin composition, characterized in that the flame retardancy of a 3 mm thick specimen measured according to UL-94 is V-1 or more.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a melt-flow index (MI) of 30 to 45 g/10 minutes measured at 250° C. and 10 kgf according to ASTM D1238. resin composition.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a specific gravity of 1.55 to 1.65 measured at 23°C according to ASTM D792 A.
A molded article, characterized in that it is formed from the thermoplastic resin composition according to any one of claims 1 to 12.