KR101277719B1 - Blend composition of polycarbonate resin and vinyl copolymer and molded product using the same - Google Patents

Abstract

(A) Polycarbonate resin and vinyl containing (A-1) polycarbonate resin and (A-2) base resin containing vinyl type copolymer, and (B) acrylic copolymer containing at least 1 type of acrylic monomer A blend composition of a system copolymer and a molded article using the same are provided.

Polycarbonate resin, vinyl copolymer, polyacrylic copolymer, weld strength

Description

Blend composition of polycarbonate resin and vinyl-based copolymer and molded article using the same {BLEND COMPOSITION OF POLYCARBONATE RESIN AND VINYL COPOLYMER AND MOLDED PRODUCT USING THE SAME}

The present invention relates to a blend composition of a polycarbonate resin and a vinyl copolymer and a molded article using the same.

In general, the polycarbonate resin has a relatively high molding temperature and melt viscosity, so that residual stresses are present in the molded article during injection molding. In addition, the chemical resistance is weak and can be hydrolyzed by moisture. In order to solve this problem, in order to improve mechanical properties and heat resistance, a blend of a polycarbonate resin and a vinyl copolymer is introduced and used.

The blend of the polycarbonate resin and the vinyl copolymer is a resin mixture having improved processability while maintaining excellent impact resistance, heat resistance, and mechanical strength, and is a resin that is widely used in automobile parts, computer housings, and other office equipment. However, when the blend of the polycarbonate resin and the vinyl copolymer is in a molten state under certain conditions, phase-clumping of the dispersed phase occurs. Due to the low compatibility between the polycarbonate and the vinyl copolymer, low mechanical strength is exhibited at the weld site generated during molding of an injection product having two or more gates.

On the other hand, it is known that the weld strength is increased when the viscosity of the blend is lowered by increasing the molecular weight of the polycarbonate in the polycarbonate resin and the vinyl copolymer blend. However, they are complicated due to low viscosity or when thin film molding, the work should be performed at a temperature higher than the molding temperature of the general polycarbonate resin and vinyl copolymer blend. Increasing the molding temperature has a problem that the effect of the improved weld strength improvement through the viscosity decreases there is a problem in use.

In addition, in order to improve the low compatibility between the polycarbonate resin and the vinyl copolymer, a methyl methacrylate compatibilizer having a medium compatibility with the two components may be used, but the methyl methacrylate is a polycarbonate resin. And at 250 to 280 ° C., which is a general molding temperature of the vinyl copolymer, compatibility with the polycarbonate resin decreases, and moldability decreases when an excessive amount of the copolymer is applied. Therefore, there are restrictions on use for the purpose of improving the weld strength.

One aspect of the present invention is to provide a blend composition of a polycarbonate resin and a vinyl-based copolymer having excellent weld strength and impact resistance.

Another aspect of the present invention is to provide a molded article prepared from the blend composition of the polycarbonate resin and the vinyl copolymer.

One aspect of the invention (A) (A-1) a base resin comprising 20 to 90% by weight of the polycarbonate resin (A-2) and 10 to 80% by weight of the vinyl copolymer (A-2); And (B) 0.1 to 20 parts by weight of an acrylic copolymer containing one or more acrylic monomers, based on 100 parts by weight of the basic resin (A).

The polycarbonate resin (A-1) may be prepared by reacting diphenols with phosgene, halogen formate, carbonate ester or a combination thereof.

The vinyl copolymer (A-2) may be a rubber modified vinyl graft copolymer, a chain vinyl copolymer, or a combination thereof.

The rubber-modified vinyl graft copolymer may include 50 to 95% by weight of the first vinyl monomer of an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof; And a vinyl series composed of 5 to 50% by weight of an unsaturated nitrile monomer, an acrylic monomer that is heterogeneous with the acrylic monomer, a second vinyl monomer having a heterocyclic monomer with the heterocyclic monomer, or a combination thereof. 5 to 95% by weight of the polymer is butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, terpolymer (EPDM) rubber of ethylene-propylene-diene, polyorgano Siloxane / polyalkyl (meth) acrylate rubber composites or copolymers grafted to 5 to 95% by weight of a rubbery polymer of a combination thereof, wherein the chain-based vinyl copolymer is an aromatic vinyl monomer, an acrylic monomer, a hetero ring. 50 to 95 weight percent of the first vinyl monomers of the monomer or a combination thereof; And a copolymer comprising an unsaturated nitrile monomer, an acrylic monomer heterogeneous with the acrylic monomer, a second vinyl monomer heterogeneous heterocyclic monomer with the heterocyclic monomer, or a combination thereof, from 5 to 50 wt%. Can be.

The acrylic copolymer (B) is 2 to 90% by weight of the first monomer of an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer or a combination thereof; And second monomers 10 to 10 of the aromatic vinyl monomer and the aromatic vinyl monomer hetero, the acrylic monomer and the hetero monomer, the hetero ring monomer and the hetero hetero monomer, or a combination thereof. 98 wt% is copolymerized, and an acrylic monomer may be present in at least one of the first monomer and the second monomer, and specifically, may be a copolymer of an acrylic monomer and an acrylic monomer different from the acrylic monomer. And more specifically, a copolymer of methyl methacrylate and ethyl acrylate. In addition, the acrylic copolymer (B) may be a copolymer of the first monomer is grafted to the second monomer.

The weight average molecular weight of the acrylic copolymer (B) may be 100,000 to 30,000,000 g / mol, specifically, 1,000,000 to 30,000,000 g / mol.

The blend composition of the polycarbonate resin and the vinyl copolymer is an antibacterial agent, a heat stabilizer, an antioxidant, a release agent, a light stabilizer, a compatibilizer, an inorganic additive, a surfactant, a coupling agent, a plasticizer, a admixture, a stabilizer, a lubricant, an antistatic agent, a flame retardant. It may further include additives of a weathering agent, a colorant, a sunscreen, a filler, a nucleating agent, an adhesion aid, an adhesive, or a combination thereof.

Another aspect of the present invention provides a molded article prepared from the blend composition of the polycarbonate resin and the vinyl copolymer.

Other aspects of the present invention are included in the following detailed description.

Excellent weld strength and shock resistance and excellent balance of physical properties such as fluidity, heat resistance, heat stability, workability, and the like, can be widely applied to electrical and electronic housings, computer housings or other office equipment requiring complex molding of thin films.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the present specification, "substituted" means that a hydrogen atom in the compound is a halogen group, C1 to C30 alkyl group, C1 to C30 haloalkyl group, C6 to C30 aryl group, C2 to C30 heteroaryl group or Mean substituted by alkoxy group of C1 to C20.

Also, unless stated otherwise in the present specification, “hetero ring monomer” means a monomer having at least one hetero atom of N, O, S or P present in the ring compound.

In addition, unless otherwise specified in the present specification, "heterogeneous" means different kinds, and "heterogeneous acrylic monomer" refers to different acrylic monomers as "heterologous aromatic vinyl monomers." "Different aromatic vinyl monomers, and" heterocyclic monomers "means different heterocyclic monomers.

According to one embodiment, (A) a base resin comprising a (A-1) polycarbonate resin and (A-2) vinyl copolymer, and (B) an acrylic copolymer comprising at least one acrylic monomer To provide a blend composition of a polycarbonate resin and a vinyl-based copolymer.

Hereinafter, each component included in the blend composition of the polycarbonate resin and the vinyl copolymer according to one embodiment will be described in detail.

(A) Base resin

(A-1) polycarbonate resin

The polycarbonate resin may be prepared by reacting diphenols represented by the following Chemical Formula 1 with phosgene, halogen formate, carbonate ester, or a combination thereof.

[Formula 1]

(In the formula 1,

A is a single bond, substituted or unsubstituted C1 to C30 straight or branched alkylene group, substituted or unsubstituted C2 to C5 alkenylene group, substituted or unsubstituted C2 to C5 alkylidene group, substituted Or unsubstituted C1 to C30 straight or branched haloalkylene group, substituted or unsubstituted C5 to C6 cycloalkylene group, substituted or unsubstituted C5 to C6 cycloalkenylene group, substituted or unsubstituted C5 to C10 cycloalkylidene group, substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted C1 to C20 linear or branched alkoxylene group, halogen acid ester group, carbonate ester group, CO , S or SO ₂ ,

Each of R ₁ and R ₂ is independently a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

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

The diphenols represented by the above formula (1) may be composed of two or more of them to form a repeating unit of a polycarbonate resin. Specific examples of the diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (also referred to as bisphenol- (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis Bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) Ether, and the like. Among the diphenols, preferably 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 1,1-bis (4-hydroxy Oxyphenyl) cyclohexane can be used. Among these, 2, 2-bis (4-hydroxyphenyl) propane can be used more preferably.

The polycarbonate resin may have a weight average molecular weight of 10,000 to 200,000 g / mol, specifically 15,000 to 80,000 g / mol, but is not limited thereto.

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

Examples of the linear polycarbonate resin include a bisphenol-A polycarbonate resin and the like. Examples of the branched polycarbonate resin include those prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride, trimellitic acid and the like with a diphenol and a carbonate. The polyfunctional aromatic compound may be contained in an amount of 0.05 to 2 mol% based on the total amount of the branched polycarbonate resin. Examples of the polyester carbonate copolymer resin include those prepared by reacting a bifunctional carboxylic acid with a diphenol and a carbonate. As the carbonate, diaryl carbonate such as diphenyl carbonate, ethylene carbonate and the like can be used.

The polycarbonate resin may be included in 20 to 90% by weight, specifically, 30 to 80% by weight based on the total amount of the base resin including the polycarbonate resin and the vinyl copolymer. When the polycarbonate resin is included in the above content range, the balance of physical properties of impact strength, heat resistance and processability is excellent.

(A-2) Vinyl Copolymer

The vinyl copolymer may be a rubber modified vinyl graft copolymer, a chain-based vinyl copolymer, or a combination thereof.

The rubber-modified vinyl graft copolymer may be a copolymer in which 5 to 95 wt% of the vinyl polymer is grafted to 5 to 95 wt% of the rubbery polymer.

Wherein the vinyl polymer comprises 50 to 95% by weight of a first vinyl monomer of an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof; And 5 to 50% by weight of an unsaturated nitrile monomer, an acrylic monomer that is heterogeneous with the acrylic monomer, a heterocyclic monomer that is heterogeneous with the heterocyclic monomer, or a second vinyl monomer of a combination thereof.

As the aromatic vinyl monomer, styrene, C1 to C10 alkyl-substituted styrene, halogen-substituted styrene, or a combination thereof may be used. Specific examples of the alkyl-substituted styrene include o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and -methylstyrene.

As the acrylic monomer, alkyl (meth) acrylate, (meth) acrylic acid ester, or a combination thereof may be used. Wherein said alkyl means C1 to C10 alkyl. 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. Meta) acrylates may be used.

The heterocyclic monomers may be substituted or unsubstituted C2 to C20 heterocycloalkyl compounds, substituted or unsubstituted C2 to C20 heterocycloalkenyl compounds, or substituted or unsubstituted C2 to C20 heterocycloalkynyl compounds . Specific examples of the heterocyclic monomers include maleic anhydride, alkyl or phenyl N-substituted maleimide.

As the unsaturated nitrile monomer, acrylonitrile, methacrylonitrile, ethacrylonitrile, or a combination thereof may be used.

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

The rubber particle size of the rubber-modified vinyl graft copolymer may be 0.05 to 4 μm in order to improve impact resistance and surface properties of the molded product. When the rubber particle size is 0.05 to 4 μm, the impact strength is excellent. Can be secured.

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

Specific examples of the rubber-modified vinyl graft copolymers include graft copolymerization of styrene, acrylonitrile and optionally methyl (meth) acrylate in the form of a mixture of butadiene rubber, acrylic rubber or styrene / butadiene rubber. have.

Specific examples of the rubber-modified vinyl-based graft copolymer include graft-copolymerized methyl (meth) acrylate with butadiene rubber, acrylic rubber or styrene / butadiene rubber.

More specific examples of the rubber-modified graft copolymer include acrylonitrile butadiene styrene copolymer (ABS) graft copolymer.

The method for producing the rubber-modified vinyl-based graft copolymer is well known to those skilled in the art, and any of emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization can be used, For example, the aforementioned aromatic vinyl monomer may be added in the presence of a rubbery polymer and emulsion polymerization or bulk polymerization may be carried out using a polymerization initiator.

The chain vinyl copolymer may include an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer, or a combination of first vinyl monomers; And a copolymer comprising an unsaturated nitrile monomer, an acrylic monomer that is heterogeneous with the acrylic monomer, a heterocyclic monomer that is heterogeneous with the heterocyclic monomer, or a second vinyl monomer of a combination thereof.

As the aromatic vinyl monomer, styrene, C1 to C10 alkyl-substituted styrene, halogen-substituted styrene, or a combination thereof may be used. Specific examples of the alkyl-substituted styrene include o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and -methylstyrene.

As the acrylic monomer, alkyl (meth) acrylate, (meth) acrylic acid ester, or a combination thereof may be used. Wherein said alkyl means C1 to C10 alkyl. 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. (Meth) acrylates can be used.

The heterocyclic monomers may be substituted or unsubstituted C2 to C20 heterocycloalkyl compounds, substituted or unsubstituted C2 to C20 heterocycloalkenyl compounds, or substituted or unsubstituted C2 to C20 heterocycloalkynyl compounds . Specific examples of the heterocyclic monomers include maleic anhydride, alkyl or phenyl N-substituted maleimide.

As the unsaturated nitrile monomer, acrylonitrile, methacrylonitrile, ethacrylonitrile, or a combination thereof may be used.

The chain-based vinyl copolymer may be composed of 50 to 95% by weight of the first vinyl monomer and 5 to 50% by weight of the second vinyl monomer, and when made in the ratio, thermochromic and chemical resistance may be improved. Can be.

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

Specific examples of the chain-based vinyl copolymers include monomer mixtures of styrene, acrylonitrile and optionally methyl methacrylate; monomer mixtures of α-methylstyrene, acrylonitrile and optionally methylmethacrylate; Or those prepared from monomer mixtures of styrene, α-methylstyrene, acrylonitrile and optionally methyl methacrylate.

The chain-based vinyl copolymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and may have a weight average molecular weight of 15,000 to 300,000 g / mol.

Other specific examples of chained vinyl copolymers include those prepared from mixtures of methyl methacrylate and optionally methyl acrylate. The chain-based vinyl copolymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and may have a weight average molecular weight of 20,000 to 250,000 g / mol.

Another specific example of the chain-based vinyl copolymer is a copolymer of styrene and maleic anhydride, which may be prepared using a continuous bulk polymerization method and a solution polymerization method. The composition ratio of the styrene and maleic anhydride may vary in a wide range, specifically, the content of maleic anhydride may be 5 to 50% by weight based on the total amount of the vinyl copolymer. A wide range of the weight average molecular weight of the styrene and maleic anhydride copolymer may also be used. Specifically, a weight average molecular weight of 20,000 to 200,000 g / mol may be used, and an inherent viscosity of 0.3 to 0.9 dl / g. Can be used.

The vinyl copolymer may be used by mixing the rubber-modified vinyl graft copolymer and the chain-type vinyl copolymer.

The vinyl-based copolymer may be included in 10 to 80% by weight, specifically, 20 to 70% by weight based on the total amount of the base resin including the polycarbonate resin and the vinyl-based copolymer. When the vinyl copolymer is included in the above range, it is excellent in impact resistance, flame resistance and heat resistance.

(B) acrylic copolymer

When the acrylic copolymer is added to the mixture of the polycarbonate resin and the vinyl copolymer, inter molecular diffusion may be enhanced, and miscibility between the polycarbonate resin and the vinyl copolymer may be improved. As a result, phase separation between the polycarbonate resin and the vinyl copolymer can be effectively reduced, thereby improving weld strength.

The acrylic copolymer includes one or more acrylic monomers, the first monomer comprising an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof; And a second monomer of the aromatic vinyl monomer and the aromatic vinyl monomer hetero, the acrylic monomer and the hetero monomer, the hetero ring monomer and the hetero ring monomer hetero, or a combination thereof. In this case, at least one of the first monomer and the second monomer may be an acrylic monomer. Specifically, the acrylic copolymer may be a copolymer of an acrylic monomer and an acrylic monomer which is heterogeneous with the acrylic monomer, and more specifically, may be a copolymer of methyl methacrylate and ethyl acrylate.

Specifically, the acrylic copolymer may be one in which the first monomer is grafted to the second monomer and copolymerized, and in the case of the grafted copolymer, the impact strength is excellent.

As the aromatic vinyl monomer, styrene, C1 to C10 alkyl-substituted styrene, halogen-substituted styrene, or a combination thereof may be used. Specific examples of the alkyl-substituted styrene include o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and -methylstyrene.

As the acrylic monomer, alkyl (meth) acrylate, (meth) acrylic acid ester, or a combination thereof may be used. Wherein said alkyl means C1 to C10 alkyl. 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. Meta) acrylates may be used.

The heterocyclic monomers may be substituted or unsubstituted C2 to C20 heterocycloalkyl compounds, substituted or unsubstituted C2 to C20 heterocycloalkenyl compounds, or substituted or unsubstituted C2 to C20 heterocycloalkynyl compounds . Specific examples of the heterocyclic monomers include maleic anhydride, alkyl or phenyl N-substituted maleimide.

The acrylic copolymer may be composed of 2 to 90% by weight of the first monomer and 10 to 98% by weight of the second monomer, and when made in the above ratio, improves miscibility with the polycarbonate resin.

The acrylic copolymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and may have a weight average molecular weight of 100,000 to 30,000,000 g / mol, and specifically, 1,000,000 to 30,000,000 g / mol. It can be used, and more specifically, it can be used in the range of 1,000,000 kPa to 10,000,000 g / mol, and most specifically, can be used of 1,000,000 kPa to 7,000,000 g / mol. When the acrylic copolymer has a weight average molecular weight in the above range, the morphology between the components is stabilized without impairing the fluidity in the shear rate region at the time of injection.

The acrylic copolymer may be used alone or in the form of a mixture of two or more thereof.

The acrylic copolymer may be included in an amount of 0.1 to 20 parts by weight, specifically, 0.5 to 18 parts by weight, and more specifically 1 to 100 parts by weight of the base resin including the polycarbonate resin and the vinyl copolymer. To 15 parts by weight. When the acrylic copolymer is included in the above range, it is excellent in impact resistance and heat resistance.

(C) other additives

Blend composition of the polycarbonate resin and the vinyl copolymer according to one embodiment may further comprise an additive.

The additives include antibacterial agents, heat stabilizers, antioxidants, mold release agents, light stabilizers, compatibilizers, inorganic additives, surfactants, coupling agents, plasticizers, admixtures, stabilizers, lubricants, antistatic agents, flame retardants, weathering agents, colorants, sunscreen agents, fillers. , Nucleating agents, adhesion aids, pressure-sensitive adhesives, or a combination thereof can be used.

The antioxidant may be a phenol, phosphite, thioether or amine antioxidant, the release agent is a fluorine-containing polymer, silicone oil, metal salt of stearic acid, montanic acid Metal salts, montanic acid ester waxes or polyethylene waxes may be used. Further, benzophenone type or amine type endurance agent can be used as the weathering agent, and a dye or pigment can be used as the coloring agent. Titanium dioxide (TiO ₂ ) or carbon black can be used as the ultraviolet ray blocking agent. As the filler, glass fiber, carbon fiber, silica, mica, alumina, clay, calcium carbonate, calcium sulfate, or glass beads may be used, and when such a filler is added, physical properties such as mechanical strength and heat resistance may be improved. have. As the nucleating agent, talc or clay may be used.

The additive may be included in an amount of 40 parts by weight or less based on 100 parts by weight of the base resin including the polycarbonate resin and the vinyl copolymer, and specifically, 0.1 to 20 parts by weight. 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 blend composition of the polycarbonate resin and the vinyl copolymer according to one embodiment may be prepared by a known method for preparing a resin composition, for example, by mixing the components and other additives at the same time, followed by melt extrusion in an extruder It can be prepared in the form of pellets.

According to another embodiment, a molded article manufactured by molding the blend composition of the polycarbonate resin and the vinyl copolymer is provided. The blend composition of the polycarbonate resin and the vinyl copolymer is used for molding products in the fields requiring weld strength, durability, and heat resistance, such as automobiles, machinery parts, electrical and electronic parts, office equipment such as computers, and general merchandise. Can be used. In particular, it can be usefully applied to the housing of electrical and electronic products such as televisions, computers, printers, washing machines, cassette players, audio, mobile phones, etc., and is widely used in electrical and electronic housings, computer housings or other office equipment requiring complex molding of thin films. Applicable

Hereinafter, the present embodiments of the present invention. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

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 blend composition of the polycarbonate resin and the vinyl-based copolymer according to one embodiment is as follows.

(A) Base resin

(A-1) polycarbonate resin

Bisphenol-A polycarbonate (SC-1080, Cheil Industries Co., Ltd.) having a weight average molecular weight (Mw) of 25,000 g / mol was used.

(A-2) Vinyl Copolymer

A copolymer copolymerized with 31.5 wt% styrene, 10.5 wt% acrylonitrile and 58 wt% butadiene was prepared. The copolymer was washed with water, dehydrated and dried to prepare an ABS (acrylonitrile-butadiene-styrene) copolymer in powder form.

(B) acrylic copolymer

A graft copolymer (K125P, Rohm and Haas, K125P) having a weight average molecular weight of 3,000,000 g / mol of poly (methyl methacrylate-ethyl acrylate) was used.

(B ') Polymethylmethacrylate (PMMA) Polymer

As a comparative example, a polymethyl methacrylate (PMMA) polymer having a weight average molecular weight of 80,000 g / mol was used.

Examples 1-5 and Comparative Examples 1-3

Each component component is added to the mixer in the content as shown in Table 1 below, mixed and extruded under a nozzle temperature of 260 ° C. using a twin screw extruder having L / D = 35 and Φ = 45 mm. Prepared in pellet form. The prepared pellets were dried at 80 ° C. for at least 5 hours before injection molding.

Specimens for measuring physical properties were prepared using a 10 oz injection machine at an injection temperature of 250 ° C., and specimens for measuring weld strength were prepared using a 10 oz injection machine at an injection temperature of 250 ° C.

[Table 1]

division Example Comparative example One 2 3 4 5 One 2 3 (A) Base resin (A-1) polycarbonate resin (% by weight) 65 65 65 65 65 65 65 65 (A-2) vinyl copolymer (% by weight) 35 35 35 35 35 35 35 35 (B) Acrylic copolymer (parts by weight *) One 3 5 8 15 - - - (B ') PMMA polymer (parts by weight *) - - - - - - 3 8

* Weight part: The content unit with respect to 100 weight part of base resin (A) is shown.

After the specimens prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were allowed to stand at 23 ° C. and 50% of relative humidity (RHD) for 48 hours, the physical properties were evaluated in the following manner, and the results are shown in the following table. 1 is shown.

(1) Izod impact strength: Izod impact strength (1/4 ", 1/8" notch) was measured according to ASTM D256.

(2) Weld Impact Strength: After forming a weld at the center of the specimen through both side gates, the Izod impact strength (1/8 ") was measured according to ASTM D256.

(3) Flow index: measured at 250 ℃, 10kg conditions in accordance with ASTM D1238.

(4) Spiral 1t (270 ° C): Measured under a barrel temperature of 270 ° C and a mold temperature of 70 ° C.

[Table 2]

Example Comparative example One 2 3 4 5 One 2 3 Izod
Impact strength
(kgf · cm / cm) 1/4 " 45 45 46 45 42 42 40 38 1/8 " 65 64 64 62 59 56 60 54 Weld impact strength
(1/8 ", kgfcm / cm) 18 16 20 27 18 11 13 10 Flow index
(g / 10 min) 35 30 26 20 15 35 36 40 Spiral 1t (270 ℃) 170 169 169 169 168 170 172 175

Through Tables 1 and 2, in the case of Examples 1 to 5 using the acrylic copolymer including a polycarbonate resin, a vinyl copolymer and at least one acrylic monomer according to one embodiment, do not use an acrylic copolymer Compared with Comparative Example 1 and Comparative Examples 2 and 3 using the polymethyl methacrylate (PMMA) polymer instead of the acrylic copolymer, it can be seen that it shows excellent weld strength and Izod impact strength. This can be seen that the acrylic copolymer is added to the blend composition of the polycarbonate resin and the vinyl copolymer, thereby reducing phase separation between the polycarbonate resin and the vinyl copolymer.

This can also be confirmed through FIGS. 1 to 4. 1 shows a transmission electron microscope (TEM) picture of a blend composition of a polycarbonate resin and a vinyl copolymer according to Comparative Example 1, and FIGS. 2 to 4 show polycarbonate resins and vinyl systems according to Examples 1 to 3, respectively. A transmission electron microscope (TEM) photograph of the blend composition of the copolymer is shown. Referring to FIGS. 1 to 4, in Comparative Example 1 in which the acrylic copolymer is not added, severe phase separation occurs, whereas phase separation decreases as the acrylic copolymer is added and increased according to Examples 1 to 3.

Thus, it can be seen that the reduction of phase separation at the weld portion where two kinds of resins meet can increase the impact strength at the weld.

On the other hand, Figure 5 is a graph of the viscosity measurement results according to the shear force for the blend composition of the polycarbonate resin and vinyl copolymer according to Examples 2 and 4 and Comparative Examples 1 and 2. The viscosity is the result measured by the temperature of 270 ℃, strain 5%, dynamic frequency sweep.

Referring to FIG. 5, it can be seen that the blend composition of the polycarbonate resin and the vinyl copolymer according to Examples 2 and 4 has a high viscosity in a region having a low shear force. This has the effect of preventing the coalescence of the dispersed phase. In addition, the blend composition of the polycarbonate resin and the vinyl-based copolymer according to Examples 2 and 4 has almost the same viscosity in the region having high shear force, so that when these two kinds of resins are applied to the weld portion, high impact without phase separation It is effective to maintain strength. On the other hand, when the acrylic copolymer is not used as in Comparative Examples 1 and 2, or when the PMMA polymer is applied instead of the acrylic copolymer, it is difficult to prevent the fusion effect due to the low viscosity in the region having a low shear force.

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.

1 is a transmission electron microscope (TEM) photograph of a blend composition of a polycarbonate resin and a vinyl copolymer according to Comparative Example 1. FIG.

2 is a transmission electron microscope (TEM) photograph of the blend composition of the polycarbonate resin and the vinyl copolymer according to Example 1. FIG.

3 is a transmission electron microscope (TEM) photograph of the blend composition of the polycarbonate resin and the vinyl copolymer according to Example 2. FIG.

4 is a transmission electron microscope (TEM) photograph of the blend composition of the polycarbonate resin and the vinyl copolymer according to Example 3. FIG.

Figure 5 is a graph of the viscosity measurement results according to the shear force for the blend composition of the polycarbonate resin and the vinyl-based copolymer according to Examples 2 and 4 and Comparative Examples 1 and 2.

Claims (13)

(A) a base resin comprising 20 to 90 weight% of polycarbonate resin (A-1) and 10 to 80 weight% of (A-2) vinyl copolymer; And Based on 100 parts by weight of the base resin (A), (B) 0.1 to 20 parts by weight of an acrylic copolymer containing at least one acrylic monomer, The acrylic copolymer (B) is 2 to 90% by weight of the first monomer of an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer or a combination thereof; And second monomers 10 to 10 of the aromatic vinyl monomers and heteroaromatic monomers heterogeneous, the acrylic monomers and heterogeneous acrylic monomers, the heterocyclic monomers and heterocyclic monomers or combinations thereof. 98% by weight is copolymerized, Blend composition of a polycarbonate resin and a vinyl copolymer in which at least one of the first monomer and the second monomer is an acrylic monomer. The method of claim 1, The polycarbonate resin (A-1) is a blend composition of a polycarbonate resin and a vinyl-based copolymer is prepared by reacting with diphenols, phosgene, halogen formate, carbonate ester or a combination thereof. The method of claim 1, The vinyl copolymer (A-2) is a blend composition of a polycarbonate resin and a vinyl copolymer, which is a rubber modified vinyl graft copolymer, a chain vinyl copolymer, or a combination thereof. The method of claim 3, The rubber-modified vinyl graft copolymer may include 50 to 95% by weight of the first vinyl monomer of an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof; And a vinyl polymer composed of 5 to 50% by weight of an unsaturated nitrile monomer, an acrylic monomer that is heterogeneous with the acrylic monomer, a heterocyclic monomer that is heterogeneous with the heterocyclic monomer, or a second vinyl monomer of a combination thereof. 5 to 95% by weight, Butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM) rubber, polyorganosiloxane / polyalkyl (meth) acrylic A blend composition of a polycarbonate resin and a vinyl copolymer, which is a copolymer grafted to 5 to 95% by weight of a rubbery polymer of a latex rubber composite or a combination thereof. The method of claim 3, The chain type vinyl copolymer may include 50 to 95 wt% of a first vinyl monomer of an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof; And a copolymer composed of 5 to 50% by weight of an unsaturated nitrile monomer, an acrylic monomer that is heterogeneous with the acrylic monomer, a heterocyclic monomer that is heterogeneous with the heterocyclic monomer, or a combination thereof, and a second vinyl monomer. Blend composition of a polycarbonate resin and a vinyl copolymer. delete The method of claim 1, The acrylic copolymer (B) is a blend composition of a polycarbonate resin and a vinyl copolymer in which the first monomer is grafted to the second monomer and copolymerized. The method of claim 1, The acrylic copolymer (B) is a blend composition of a polycarbonate resin and a vinyl copolymer, which is a copolymer of an acrylic monomer and an acrylic monomer having a different kind of the acrylic monomer. The method of claim 1, The acrylic copolymer (B) is a blend composition of polyvinyl carbonate resin and vinyl-based copolymer that is a copolymer of methyl methacrylate and ethyl acrylate. The method of claim 1, Blend composition of a polycarbonate resin and a vinyl copolymer of the weight average molecular weight of the acrylic copolymer (B) is 100,000 to 30,000,000 g / mol. The method of claim 1, Blend composition of a polycarbonate resin and a vinyl-based copolymer that the weight average molecular weight of the acrylic copolymer (B) is 1,000,000 to 30,000,000 g / mol. The method of claim 1, The blend composition of the polycarbonate resin and the vinyl copolymer is an antibacterial agent, a heat stabilizer, an antioxidant, a mold release agent, a light stabilizer, a compatibilizer, an inorganic additive, a surfactant, a coupling agent, a plasticizer, a admixture, a stabilizer, a lubricant, an antistatic agent, a flame retardant. A blend composition of a polycarbonate resin and a vinyl copolymer further comprising additives of a weathering agent, a colorant, a sunscreen, a filler, a nucleating agent, an adhesion aid, an adhesive, or a combination thereof. A molded article prepared from the blend composition of the polycarbonate resin and the vinyl-based copolymer of any one of claims 1 to 5 and 13.

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