KR20100075078A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE: A thermoplastic resin composition is provided to secure the shock resistance and the transparency of the composition, and to prevent a flow mark from being generated. CONSTITUTION: A thermoplastic resin composition contains 30~99wt% of polycarbonate resin, and 1~70wt% of rubber modified vinyl graft copolymer including an acrylic monomer. The thermoplastic resin composition additionally contains 1~60 parts of vinyl copolymer by weight including the acrylic monomer, for 100 parts of thermoplastic resin composition. The polycarbonate resin is produced by reacting diphenol with a compound selected from the group consisting of phosgene, halogen formate, carbonate, or their combination.

Description

Thermoplastic composition {THERMOPLASTIC RESIN COMPOSITION}

The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition which is excellent in scratch resistance, impact resistance and transparency, and hardly generates a flow mark.

Blends of polycarbonate / vinyl-based copolymers are resin mixtures having improved processability while maintaining excellent impact resistance, heat resistance and mechanical strength, and are generally used in automobile parts, computer housings, or other office equipment.

However, the blend of the polycarbonate / vinyl copolymer has a problem of low scratch resistance, so that polymethyl methacrylate (PMMA) having excellent scratch resistance may be added. However, in this case, there is a problem in that a flow mark occurs due to a difference in refractive index when PMMA is added. On the other hand, studies to improve the generation of the flow mark while increasing the scratch resistance of the polycarbonate / vinyl-based copolymer has not progressed much.

One embodiment of the present invention is to provide a thermoplastic resin composition which is excellent in all scratch resistance, impact resistance and transparency as well as almost no flow mark.

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

However, technical problems to be achieved by the present invention are not limited to the above-mentioned problems, and other technical problems will be clearly understood by those skilled in the art from the following description.

One embodiment of the present invention is (A) polycarbonate resin 30 to 99% by weight; And (B) it provides a thermoplastic resin composition comprising 1 to 70% by weight of a rubber-modified vinyl graft copolymer comprising an acrylic monomer.

The thermoplastic resin composition further includes 1 to 60 parts by weight of a vinyl copolymer containing (C) an acrylic monomer based on 100 parts by weight of the thermoplastic resin composition.

Another embodiment of the present invention provides a molded article prepared from the thermoplastic resin composition.

Other specific details of embodiments of the present invention are included in the following detailed description.

Thermoplastic resin composition according to an embodiment of the present invention is not only excellent in scratch resistance, impact resistance and transparency, but also rarely generates a flow mark, portable mobile communication devices, precision electrical and electronic components, It can be usefully applied to molded products such as office equipment, automotive precision parts, sundries, and the like.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Thermoplastic resin composition according to an embodiment of the present invention (A) 30 to 99% by weight of a polycarbonate resin; And (B) 1 to 70% by weight of a rubber-modified vinyl graft copolymer comprising an acrylic monomer.

Hereinafter, each component of the thermoplastic resin composition according to the exemplary embodiment of the present invention will be described in detail.

(A) polycarbonate resin

The polycarbonate resin may be prepared by reacting a compound selected from the group consisting of diphenols represented by the following Chemical Formula 1 with phosgene, halogen formate, carbonate, and combinations thereof.

[Formula 1]

(In the formula 1,

A is a single bond, substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, substituted or unsubstituted alkylidene group having 2 to 5 carbon atoms, substituted or unsubstituted cycloalkylene group having 5 to 6 carbon atoms, substituted or unsubstituted A cycloalkylidene group having 5 to 10 carbon atoms, CO, S, and SO ₂ ;

Each R ₁ and R ₂ are each independently a substituent selected from the group consisting of a substituted or unsubstituted C1-30 alkyl group, and a substituted or unsubstituted C6-30 aryl group,

n ₁ and n ₂ are each independently an integer of 0 to 4,

The "substituted" is a group in which a hydrogen atom is composed of a halogen group, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a combination thereof Substituted with a substituent selected from.)

The diphenols represented by the formula (1) may combine two or more kinds to constitute a repeating unit of the polycarbonate resin. Specific examples of the diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane (also called 'bisphenol-A'), 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydrate Hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, etc. are mentioned. 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, or 1,1-bis- in the said diphenols (4-hydroxyphenyl) -cyclohexane can be preferably used. Also, 2,2-bis- (4-hydroxyphenyl) -propane can be used more preferably.

The polycarbonate resin may preferably use a weight average molecular weight of 10,000 to 200,000 g / mol, and more preferably 15,000 to 80,000 g / mol, but is not limited thereto. It is possible to obtain physical properties such as excellent impact strength in the above molecular weight range, to have a suitable fluidity can be obtained excellent workability.

The polycarbonate resin may be a mixture of copolymers prepared from two or more kinds of diphenols. In addition, the polycarbonate resin may be used a linear polycarbonate resin, branched (branched) polycarbonate resin, polyester carbonate copolymer resin and the like.

Bisphenol-A type | system | group polycarbonate resin etc. are mentioned as said linear polycarbonate resin. Examples of the branched polycarbonate resins include those produced by reacting polyfunctional aromatic compounds such as trimellitic anhydride, trimellitic acid, and the like with diphenols and carbonates. The polyfunctional aromatic compound is preferably contained in 0.05 to 2 mol% based on the total amount of the branched polycarbonate resin. As said polyester carbonate copolymer resin, what was manufactured by making bifunctional carboxylic acid react with diphenols and a carbonate is mentioned. In this case, as the carbonate, diaryl carbonate such as diphenyl carbonate, ethylene carbonate, or the like may be used. 　

The polycarbonate resin is included in 30 to 99% by weight, preferably 40 to 60% by weight based on the total amount of the thermoplastic resin composition. When the polycarbonate resin is included in the above range it can secure excellent impact resistance and moldability.

(B) Rubber modified vinyl graft copolymer

The rubber modified vinyl graft copolymer is a rubber modified vinyl graft copolymer containing an acrylic monomer.

Specifically, the rubber-modified vinyl graft copolymer according to one embodiment of the present invention may be prepared by graft polymerization of 20 to 90 wt% of a vinyl monomer to 10 to 80 wt% of a rubbery polymer.

The vinyl monomer may include an acrylic monomer, and may further include an aromatic vinyl monomer and an unsaturated nitrile monomer.

The acrylic monomer may be selected from the group consisting of (meth) acrylic acid alkyl esters, (meth) acrylic acid esters, maleic anhydride, alkyl or phenyl N-substituted maleimides, and combinations thereof. In this case, the alkyl means alkyl having 1 to 10 carbon atoms. Specific examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like, of which methyl (meth) Acrylate may be preferably used.

The aromatic vinyl monomer may be selected from the group consisting of styrene, alkyl or halogen substituted styrene having 1 to 10 carbon atoms, and combinations thereof. Specific examples of the alkyl substituted styrene include o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, alphamethyl styrene, and the like.

The unsaturated nitrile monomer may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and combinations thereof.

The rubbery polymer may include butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, terpolymer (EPDM) of ethylene-propylene-diene, polyorganosiloxane / polyalkyl ( Meth) acrylate rubber composites, and combinations thereof may be used.

The rubber modified vinyl graft copolymer may be used alone or in the form of a mixture of two or more thereof.

Preferred examples of the rubber-modified vinyl graft copolymer according to one embodiment of the present invention are butadiene rubber, acrylic rubber, or styrene / butadiene rubber in the form of a mixture of styrene, acrylonitrile, and (meth) acrylic acid methyl ester monomers. The graft copolymerized thing is mentioned.

Further preferred examples include those obtained by graft copolymerization of (meth) acrylic acid methyl ester monomer to butadiene rubber, acrylic rubber, or styrene / butadiene rubber.

When the vinyl monomer according to the embodiment of the present invention is in the form of a mixture of an acrylic monomer, an aromatic vinyl monomer, and an unsaturated nitrile monomer, 9 to 80 wt% of an acrylic monomer, 10 to 50 wt% of an aromatic vinyl monomer, and an unsaturated nitrile It is preferred to consist of 1 to 20% by weight of monomer.

In preparing the rubber-modified vinyl graft copolymer, the particle diameter of the rubber particles may be in the range of 0.05 kPa to 4 μm in order to improve impact resistance and surface properties of the molded product. If the particle size of the rubber particles in the above range can be secured excellent impact strength.

The rubber-modified vinyl-based graft copolymer is well known to those skilled in the art, and may be any of emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization. As a preferable manufacturing method, the above-mentioned vinyl-type monomer mixture is thrown in presence of a rubbery polymer, and emulsion polymerization or block polymerization using a polymerization initiator is mentioned.

The rubber-modified vinyl graft copolymer is included in the amount of 1 to 70% by weight, preferably 10 to 40% by weight based on the total amount of the thermoplastic resin composition. When the rubber-modified vinyl-based graft copolymer is included in the above range, it is excellent in impact resistance and scratch resistance and hardly generates a flow mark.

(C) vinyl copolymer

The thermoplastic resin composition according to the embodiment of the present invention may further include a vinyl copolymer.

The vinyl copolymer is a vinyl copolymer including an acrylic monomer.

Specifically, the vinyl copolymer according to the embodiment of the present invention includes an acrylic monomer, and may further include an aromatic vinyl monomer and an unsaturated nitrile monomer.

The acrylic monomer may be selected from the group consisting of (meth) acrylic acid alkyl esters, (meth) acrylic acid esters, maleic anhydride, alkyl or phenyl N-substituted maleimides, and combinations thereof. In this case, the alkyl means alkyl having 1 to 10 carbon atoms. Specific examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like, of which methyl (meth) Acrylate may be preferably used.

The aromatic vinyl monomer may be selected from the group consisting of styrene, alkyl or halogen substituted styrene having 1 to 10 carbon atoms, and combinations thereof. Specific examples of the alkyl substituted styrene include o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, alphamethyl styrene, and the like.

The unsaturated nitrile monomer may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and combinations thereof.

The vinyl copolymer may be produced as a by-product in the preparation of the rubber modified vinyl graft copolymer, and is particularly used for grafting excess vinyl monomer mixture to a small amount of rubbery polymer or as a molecular weight regulator. This can occur even more when the chain transfer agent is used in excess.

Preferred examples of the vinyl copolymer according to one embodiment of the present invention include copolymers of styrene, acrylonitrile, and methacrylic acid methyl esters; copolymers of α-methylstyrene, acrylonitrile, and methacrylic acid methyl esters; Or copolymers of styrene, α-methylstyrene, acrylonitrile, and methacrylic acid methyl ester. The vinyl copolymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and it is preferable to use a weight average molecular weight of 15,000 kPa to 300,000 g / mol.

Further preferred examples include those prepared from monomer mixtures of methacrylic acid methyl ester monomers and optionally acrylic acid methyl esters. The vinyl copolymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and it is preferable to use a weight average molecular weight of 20,000 kPa to 250,000 g / mol.

When the vinyl copolymer according to the embodiment of the present invention is composed of an acrylic monomer, an aromatic vinyl monomer, and an unsaturated nitrile monomer, 10 to 85% by weight of an acrylic monomer, 10 to 90% by weight of an aromatic vinyl monomer, and an unsaturated nitrile monomer 1 It is good to consist of 50 to 50% by weight.

The vinyl copolymer is included in an amount of from 1 to 60 parts by weight based on 100 parts by weight of the thermoplastic resin composition, preferably 5 to 40 parts by weight. When the vinyl copolymer is included in the above range, excellent impact resistance, scratch resistance, and moldability can be secured, and a flow mark hardly occurs.

(D) other additives

The thermoplastic resin composition according to the embodiment of the present invention may further include an additive.

The additives include antibacterial agents, heat stabilizers, antioxidants, mold release agents, light stabilizers, compatibilizers, dyes, inorganic additives, surfactants, coupling agents, plasticizers, impact modifiers, admixtures, colorants, stabilizers, lubricants, antistatic agents, pigments, flame retardants, Weathering agents, colorants, sunscreens, fillers, nucleating agents, adhesion aids, pressure sensitive adhesives, and mixtures thereof.

As said antioxidant, a phenol type, a phosphide type, a thioether type, or an amine type antioxidant can be used preferably.

As the mold release agent, a fluorine-containing polymer, silicone oil, a metal salt of stearyl acid, a metal salt of mon carbonate, a montanic acid ester wax, or a polyethylene wax can be preferably used.

As said weathering agent, a benzophenone type or an amine type weathering agent can be used preferably.

As said coloring agent, dye or a pigment can be used preferably.

Titanium oxide or carbon black may be preferably used as the sunscreen.

As the filler, glass fiber, carbon fiber, silica, mica, alumina, clay, calcium carbonate, calcium sulfate, or glass beads may be preferably used, and when such filler is added, mechanical properties such as mechanical strength and heat resistance may be improved. You can.

As the nucleating agent, talc or clay can be preferably used.

The additive may be included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the thermoplastic resin composition. When the additive is included in the above range it is possible to obtain the effect of the additive according to each application and to obtain excellent mechanical properties and improved appearance of the surface.

The thermoplastic resin composition according to one embodiment of the present invention may be prepared by a known method. For example, after mixing the components and additives of the present invention described above, it can be melt-extruded in an extruder and produced in pellet form.

According to another embodiment of the present invention, there is provided a molded article manufactured by molding the thermoplastic resin composition of one embodiment of the present invention. The thermoplastic resin composition may be applied to molded products in the fields where scratch resistance, impact resistance and transparency are important. For example, the thermoplastic resin composition may be used in molded articles such as portable mobile communication devices, precision electric and electronic parts, office equipment, automotive precision parts, and sundries. It can be usefully applied.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

EXAMPLE

Each component used in the preparation of the thermoplastic resin composition according to the embodiment of the present invention is as follows.

(A) polycarbonate resin

As bisphenol-A linear polycarbonate having a weight average molecular weight of 25,000 g / mol, PANLITE L-1250WP of TEIJIN, Japan was used.

(B) Rubber modified vinyl graft copolymer

(B-1) Transparent g-ABS was used in which 55% by weight of butadiene rubber was grafted to 45% by weight of a mixture composed of acrylonitrile / styrene / methylmethacrylate. Wherein the mixture consisted of 7% by weight of acrylonitrile, 20.6% by weight of styrene, and 72.4% by weight of methyl methacrylate.

(B-2) g-ABS grafted 42% by weight of a mixture of acrylonitrile / styrene to 58% by weight of butadiene rubber was used. Wherein the mixture consisted of 29% by weight of acrylonitrile and 71% by weight of styrene.

(C) vinyl copolymer

As a copolymer composed of 5% by weight of acrylonitrile, 21% by weight of styrene, and 74% by weight of methyl methacrylate, g-ABS (CHCM, Cheil Industries, Ltd.) product having a weight average molecular weight of 120,000 g / mol was used.

(D) polymethyl methacrylate

As polymethyl methacrylate, L-84 of MRC Corporation having a weight average molecular weight of 95,000 g / mol was used.

Examples 1 to 3, and Comparative Examples 1 and 2

The above mentioned components were added to the contents as shown in Table 1 below, feed rate 60 kg / hr, screw rpm 250, temperature 250 to 300 ° C., screw configuration 45φ Regular, L / D It reacted by adding to the reaction extruder which is = 36.

Thereafter, the reactant was extruded at a temperature range of 180 to 240 ° C. in a conventional twin screw extruder, and then the extrudate was prepared in pellet form.

[Test Example]

After drying the pellets prepared according to Examples 1 to 3, and Comparative Examples 1 and 2 for 4 hours or more at 80 ℃, using an injection molding machine of 10 Oz, molding temperature 220 to 280 ℃, mold temperature 60 to 100 ℃ Injecting under the condition of to prepare a physical specimen. The prepared physical specimens were measured by the following method and the results are shown in Table 1 below.

(1) Scratch resistance: 1kg load is applied using tungsten carbide stylus, the tip of which has a diameter of 0.7mm, and a surface profiler after applying scratch to the specimen at a speed of 75mm / min. The profile was observed using a surface profiler, and the scratch width was measured.

(2) Impact resistance: Notch was evaluated on 1/8 "Izod specimens by ASTM D256 evaluation method.

(3) Flow mark: A 60 x 90 injection molded product having a thickness step (1, 2, 3 mm) was evaluated.

TABLE 1

* Flow mark: 1-severe, 5-hardly occur

Through Table 1, it can be seen that Examples 1 to 3 according to the present invention not only have excellent scratch resistance and impact resistance, but also hardly generate a flow mark.

On the other hand, in Comparative Examples 1 and 2 using a rubber-modified vinyl graft copolymer not containing an acrylic monomer, it can be seen that the flow mark is severely generated or the scratch resistance is reduced.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (7)

(A) 30 to 99% by weight of polycarbonate resin; And (B) 1 to 70% by weight of rubber modified vinyl graft copolymer containing acrylic monomer Thermoplastic resin composition comprising a. The method of claim 1, The thermoplastic resin composition further comprises 1 to 60 parts by weight of the vinyl copolymer containing (C) an acrylic monomer based on 100 parts by weight of the thermoplastic resin composition. The method of claim 1, The (A) polycarbonate resin is a thermoplastic resin composition prepared by reacting diphenols with a compound selected from the group consisting of phosgene, halogen formate, carbonate, and combinations thereof. The method of claim 1, The (B) rubber-modified vinyl-based graft copolymer is a thermoplastic resin composition 20 to 90% by weight of the vinyl monomer containing an acrylic monomer is grafted to 10 to 80% by weight of the rubbery polymer. The method of claim 4, wherein The vinyl monomer may include 9 to 80% by weight of an acrylic monomer selected from the group consisting of (meth) acrylic acid alkyl esters, (meth) acrylic acid esters, maleic anhydride, alkyl or phenyl N-substituted maleimides, and combinations thereof; 10 to 50 weight percent of an aromatic vinyl monomer selected from the group consisting of styrene, alkyl or halogen substituted styrene, and combinations thereof; And 1 to 20% by weight of an unsaturated nitrile monomer selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and combinations thereof. The method of claim 2, The (C) vinyl copolymer is 10 to 85 weight of the acrylic monomer selected from the group consisting of (meth) acrylic acid alkyl ester, (meth) acrylic acid ester, maleic anhydride, alkyl or phenyl N-substituted maleimide, and combinations thereof %; 10 to 90 weight percent of an aromatic vinyl monomer selected from the group consisting of styrene, alkyl or halogen substituted styrene, and combinations thereof; And 1 to 50% by weight of an unsaturated nitrile monomer selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and combinations thereof. The molded article manufactured from the thermoplastic resin composition of any one of Claims 1-6.