KR100801597B1 - Polycarbonate resin composition and plastic article - Google Patents

Abstract

A polycarbonate-based resin composition, and a plastic molded product prepared by using the composition are provided to improve impact resistance, abrasion resistance, gloss and appearance. A polycarbonate-based resin composition comprises 100 parts by weight of a core-shell graft copolymer which a polycarbonate resin and a rubber core of a copolymer of an acrylate-based rubber and a silicone-based rubber and is grafted with a vinyl-based monomer; 0.5-10 parts by weight of a modified polyethylene terephthalate represented by the formula; and 0.5-10 parts by weight of polyethylene glycol, wherein m and n are a natural number; and the content of the polycarbonate resin and the core-shell graft copolymer is 90-99 wt% and 1-10 wt%, respectively, based on the sum of the content of the polycarbonate resin and the core-shell graft copolymer.

Description

Polycarbonate-based resin composition and plastic molded article {POLYCARBONATE RESIN COMPOSITION AND PLASTIC ARTICLE}

The present invention relates to a polycarbonate resin composition and a plastic molded article. More specifically, the present invention relates to a polycarbonate-based resin composition and a plastic molded article that enable the provision of a polycarbonate-based thermoplastic resin exhibiting excellent glossiness with excellent impact resistance and wear resistance.

In general, polycarbonate resins have been applied to various engineering plastics as they exhibit excellent mechanical strength, heat resistance, impact resistance, or thermal stability. In addition, due to the excellent properties of such polycarbonate resins, recently, polycarbonate-based thermoplastic resins using the same have been spotlighted as exterior materials of IT devices such as mobile phones or portable personal digital assistants (PDAs).

However, in the early days of applying various resins to the exterior material of the IT device, its wear resistance was hardly considered, but recently, as the resin is widely applied to the exterior material including the operation part of the IT device, the importance of the exterior material and the wear resistance of the resin applied thereto is increased. It is greatly highlighted.

Accordingly, various attempts and studies have been made to further improve wear resistance of polycarbonate-based thermoplastic resins applied to exterior materials of IT devices. For example, attempts have been made to provide a polycarbonate-based thermoplastic resin having improved wear resistance by using a polycarbonate-based resin composition including a wear-resistant Teflon compound together with a polycarbonate.

However, the polycarbonate-based thermoplastic resin provided by using such a polycarbonate-based resin composition may have poor glossiness, resulting in poor appearance and impact resistance. Therefore, it is inappropriate to be applied to an exterior material that should be beautiful in appearance while adequately protecting an internal device from external shocks.

Accordingly, the present invention is to provide a polycarbonate-based resin composition capable of providing a polycarbonate-based thermoplastic resin exhibiting excellent glossiness with excellent impact resistance and wear resistance.

Another object of the present invention to provide a plastic molded article prepared using the composition.

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

The present invention is based on 100 parts by weight of a polycarbonate resin, a rubber core copolymerized with an acrylate rubber monomer and a silicone rubber monomer, and a core-shell graft copolymer in which a vinyl monomer is grafted. 0.5 to 10 parts by weight of the modified polyethylene terephthalate; And 0.5 to 10 parts by weight of polyethylene glycol, wherein the polycarbonate resin and the core-shell graft copolymer are based on the sum of the contents of the polycarbonate resin and the core-shell graft copolymer. It provides a polycarbonate-based resin composition, which is contained in a ratio of 90 to 99% by weight and 1 to 10% by weight, respectively:

[Formula 2]

In Formula 2, m and n are each natural numbers.

The present invention also provides a plastic molded article prepared from the polycarbonate resin composition.

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

Hereinafter, specific embodiments of the present invention will be described in detail to enable those skilled in the art to clearly appreciate. However, this is presented as an example of the present invention, whereby the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

According to an embodiment of the present invention, 100 parts by weight of the polycarbonate resin, the rubber core in which the acrylate rubber monomer and the silicone rubber monomer are copolymerized, and the core-shell graft copolymer in which the vinyl monomer is grafted are added together. 0.5 to 10 parts by weight of the modified polyethylene terephthalate of Formula 2; And 0.5 to 10 parts by weight of polyethylene glycol, wherein the polycarbonate resin and the core-shell graft copolymer are based on the sum of the contents of the polycarbonate resin and the core-shell graft copolymer. Provided are polycarbonate-based resin compositions, each containing 90 to 99% by weight and 1 to 10% by weight:

[Formula 2]

In Formula 2, m and n are each natural numbers.

The polycarbonate-based resin composition includes a predetermined core-shell graft copolymer and a modified polyethylene terephthalate together with the polycarbonate resin. As a result, the impact strength of the polycarbonate-based thermoplastic resin may be reinforced by the core-shell graft copolymer, and thus may have excellent impact resistance. In addition, the wear resistance of the polycarbonate-based thermoplastic resin can be further improved by the modified polyethylene terephthalate. In addition, the polycarbonate-based resin composition may include polyethylene glycol, thereby improving the glossiness of the polycarbonate-based thermoplastic resin and making the appearance beautiful. In particular, the polycarbonate-based resin composition includes each of the components in a preferred content range, thereby enabling the provision of a polycarbonate-based thermoplastic resin exhibiting excellent glossiness with excellent impact resistance and wear resistance.

The structure of such a polycarbonate-based resin composition is specifically described below for each component.

The polycarbonate-based resin composition includes a polycarbonate resin.

Such polycarbonate resin may include, for example, an aromatic polycarbonate resin prepared by reacting a diphenol compound represented by the following Chemical Formula 1 or the like with phosgene, halogen formate or diester carbonate.

[Formula 1]

Wherein A is a single bond, C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -S- or -SO _2- .

In this case, as the diphenol compound, 4,4'-dihydroxydiphenyl, 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 or 2,2-bis- ( 3,5-dichloro-4-hydroxyphenyl) -propane and the like can be used, and among these, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5- Dichloro-4-hydroxyphenyl) -propane or 1,1-bis- (4-hydroxyphenyl) -cyclohexane can be preferably used. Further preferred is 2,2-bis- (4-hydroxyphenyl) -propane, also referred to as Bisphenol-A (BPA). However, the diphenol compound is not limited to the above-listed materials, and conventional diphenol compounds usable for preparing other polycarbonate resins may be used without limitation.

In addition, the polycarbonate resin may have a weight average molecular weight of 15,000 ~ 50,000 g / mol.

As the polycarbonate resin, not only a linear polycarbonate resin, but also a branched polycarbonate resin or a polyester carbonate copolymer resin may be used without limitation. In this case, the branched polycarbonate resin may be prepared by adding 0.05 to 2 mol% of a trivalent or more polyfunctional compound, for example, a compound having a trivalent or more phenol group, based on the total amount of the diphenol compound. Can be. In addition, the polyester carbonate copolymer resin may be prepared by a polymerization reaction in the presence of an ester precursor, for example, bifunctional carboxylic acid, using these polyester carbonate copolymer resin alone or other polycarbonate It can also be mixed with resin and used.

As the polycarbonate resin, a homo polycarbonate resin or a copolycarbonate resin can be used without limitation, and a mixture thereof can also be used.

In addition, the polycarbonate resin described above is included in the range of 90 to 99% by weight based on the sum of the contents of the polycarbonate resin and the core-shell graft copolymer described later.

The polycarbonate-based resin composition also includes a predetermined core-shell graft copolymer. The core-shell graft copolymer is a core-shell structure by forming a hard shell by grafting a vinyl monomer on a mixed copolymer (rubber core) of a core structure in which an acrylate rubber monomer and a silicone rubber monomer are copolymerized together. It is coming true.

As the polycarbonate-based resin composition includes such a core-shell graft copolymer, the impact strength of the polycarbonate-based thermoplastic resin formed from the polycarbonate-based resin composition may be reinforced to have excellent impact resistance.

Such core-shell graft copolymers preferably comprise, for example, 20-90% by weight of the rubber core and 10-80% by weight of the shell grafted to the rubber core. As a result, the mechanical properties of the polycarbonate-based thermoplastic resin, for example, impact resistance, can be more effectively compensated.

In addition, as the acrylate rubber monomer for obtaining the core-shell graft copolymer, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl Acrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, and the like can be used, and a mixture of two or more selected from these can also be used. And as a hardening | curing agent for superposing | polymerizing such an acrylate rubber monomer, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1, 3- butylene glycol dimethacrylate, or 1, 4- butylene glycol di Methacrylate, allyl methacrylate, triallyl cyanurate and the like can be used.

Moreover, as said silicone type rubber monomer, a cyclosiloxane type compound, for example, hexamethylcyclo trisiloxane, octamethylcyclo tetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, trimethyl triphenyl cyclotrisiloxane, Tetramethyltetraphenylcyclotetrosiloxane or octaphenylcyclotetrasiloxane and the like can be used, and a mixture of two or more selected from these can also be used. Moreover, as a hardening | curing agent for superposing | polymerizing the said silicone type rubber monomer, a trimethoxymethylsilane, triethoxy phenylsilane, tetramethoxysilane, tetraethoxysilane, etc. can be used.

In addition, in order to obtain the core-shell graft copolymer, methyl methacrylate, styrene, acrylonitrile, or the like may be used as the vinyl monomer grafted to the rubber core, or a mixture of two or more thereof may be used. .

In addition, among the various core-shell graft copolymers obtained using the above-mentioned various monomers, butyl acrylate is used as the acrylate rubber monomer, hexamethylcyclotrisiloxane is used as the silicone rubber monomer, and the vinyl Most preferably, a core-shell graft copolymer obtained using styrene-acrylonitrile as the total monomer can be used. By using such a core-shell graft copolymer, the impact resistance of the polycarbonate-based thermoplastic resin can be effectively improved.

Meanwhile, although various monomers usable for obtaining the core-shell graft copolymer are listed above, the core-shell graph may be used without limitation, without being limited to any acrylate rubber monomer, silicone rubber monomer or vinyl monomer. It is a matter of course that a copolymer may be obtained.

The core-shell graft copolymer described above is included in the polycarbonate-based resin composition in the range of 1 to 10% by weight based on the sum of the contents of the polycarbonate resin and the core-shell graft copolymer. If the content of the core-shell graft copolymer is less than 1% by weight, the impact strength reinforcement of the polycarbonate-based thermoplastic resin may not be sufficient, and when the content of the core-shell graft copolymer exceeds 10% by weight, the glossiness of the polycarbonate-based thermoplastic resin may be reduced. Can be degraded.

The polycarbonate-based resin composition includes a modified polyethylene terephthalate of the following general formula (2) together with the above-described polycarbonate resin and a predetermined core-shell graft copolymer:

[Formula 2]

In Formula 2, m and n are natural numbers, respectively, and may be variously adjusted depending on the molecular weight. Moreover, it is preferable that the ratio of m: n is the range of 95: 5-30: 70.

The modified polyethylene terephthalate of Chemical Formula 2 is a kind of amorphous copolyester, and has a chemical structure in which a certain amount of ethylene glycol is substituted with 1,4-cyclohexane dimethanol in polyethylene terephthalate. As the modified polyethylene terephthalate is included in the polycarbonate resin composition, wear resistance of the polycarbonate thermoplastic resin may be further improved.

Such modified polyethylene terephthalate may have a weight average molecular weight of 8000 to 30000 g / mol. If the modified polyethylene terephthalate having a weight average molecular weight of less than 8000 g / mol is included in the polycarbonate-based resin composition, the improvement of abrasion resistance of the polycarbonate-based thermoplastic resin may not be sufficient, and the weight average molecular weight is 30000 g / mol. When the modified modified polyethylene terephthalate is included, the impact resistance of the polycarbonate-based thermoplastic resin may be lowered.

In addition, the modified polyethylene terephthalate is included in the polycarbonate-based resin composition in a content range of 0.5 to 10 parts by weight based on 100 parts by weight of the polycarbonate resin and the predetermined core-shell graft copolymer. When the content of the modified polyethylene terephthalate is less than 0.5 parts by weight, the wear resistance improvement of the polycarbonate-based thermoplastic resin may not be sufficient, and when it exceeds 10 parts by weight, the impact resistance of the polycarbonate-based thermoplastic resin may be lowered.

On the other hand, the polycarbonate-based resin composition also contains polyethylene glycol.

Such polyethylene glycol is a substance having a hydroxyl group at both ends of the chain and used as a raw material for polymerization such as polyurethane. As such polyethylene glycol is included in the polycarbonate-based resin composition, glossiness of the polycarbonate-based thermoplastic resin may be further improved.

Such polyethylene glycols may have a weight average molecular weight of 400-8000 g / mol. If the polyethylene glycol having a weight average molecular weight of less than 400 g / mol is included in the polycarbonate resin composition, the glossiness improvement of the polycarbonate thermoplastic resin may not be sufficient, and the polyethylene having a molecular weight of more than 8000 g / mol When the glycol is included, the impact resistance of the polycarbonate-based thermoplastic resin may be lowered.

In addition, the polyethylene glycol is included in the polycarbonate-based resin composition in a content range of 0.5 to 10 parts by weight based on 100 parts by weight of the polycarbonate resin and the predetermined core-shell graft copolymer. When the content of the polyethylene glycol is less than 0.5 parts by weight, it may not be enough to improve the glossiness of the polycarbonate-based thermoplastic resin, and when it exceeds 10 parts by weight, the impact resistance of the polycarbonate-based thermoplastic resin may be lowered.

On the other hand, the polycarbonate-based thermoplastic resin resin or a mixture thereof is prepared by a conventional method such as mixing each of the above-described components to prepare a polycarbonate-based resin composition, melt extrusion of such a polycarbonate-based resin composition in an extruder Plastic molded articles can be produced.

According to another embodiment of the invention, there is provided a plastic molded article prepared from the polycarbonate-based resin composition described above. Such a plastic molded article is based on 100 parts by weight of a resin substrate obtained by adding a polycarbonate resin and a core-shell graft copolymer in which a vinyl monomer is grafted to a rubber core in which an acrylate rubber monomer and a silicone rubber monomer are copolymerized. 0.5 to 10 parts by weight of the modified polyethylene terephthalate of Chemical Formula 2 dispersed in the resin substrate; And 0.5 to 10 parts by weight of polyethylene glycol dispersed in the resin substrate, wherein the polycarbonate resin and the core-shell graft copolymer are the sum of the contents of the polycarbonate resin and the core-shell graft copolymer. It may be contained in a ratio of 90 to 99% by weight and 1 to 10% by weight, respectively.

That is, such a plastic molded article includes a predetermined core-shell graft copolymer and a modified polyethylene terephthalate uniformly dispersed in a resin substrate made of the polycarbonate resin. Therefore, the impact strength is reinforced by the core-shell graft copolymer and the wear resistance is improved by the modified polyethylene terephthalate, thereby exhibiting excellent impact resistance and wear resistance. In addition, by including polyethylene glycol uniformly dispersed in the resin substrate, it has excellent glossiness and a beautiful appearance.

 Therefore, the plastic molded article exhibits excellent glossiness with excellent impact resistance and abrasion resistance, and thus can be preferably applied to exterior materials of various IT devices.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

The specific component specifications of (A) polycarbonate resin, (B) core-shell graft copolymer, (C) modified polyethylene terephthalate, and (D) polyethylene glycol which are used by the Example and comparative example which are mentioned later are as follows. .

(A) polycarbonate resin

As the polycarbonate resin, a bisphenol-A polycarbonate ('PANLITE L-1250WP' manufactured by Teijin, Japan) having a weight average molecular weight (Mw) of 25,000 g / mol was used.

(B) core-shell graft copolymer

Core-shell graft copolymer, a core-shell graft copolymer in which styrene-acrylonitrile is grafted to a mixed copolymer of butyl acrylate and hexamethylcyclotrisiloxane having an average particle diameter of 0.1 µm (Japan MRC 'RK-200') was used.

(C) modified polyethylene terephthalate

As modified polyethylene terephthalate, K2012 (weight average molecular weight 26,000 g / mol) of SK Chemicals, Korea was used.

(D) polyethylene glycol

As the polyethylene glycol, 'SANYO PEG' manufactured by Sanyo Chemical Co., Ltd., Japan was used.

Examples 1-2 and Comparative Examples 1-4

The composition of each component used in Examples and Comparative Examples is as shown in Table 1 below. Each polycarbonate resin composition was prepared by mixing each component according to the composition shown in Table 1, using a twin screw extruder having L / D = 36, Φ = 45 mm, fixed temperature of 260 ° C., screw rotation speed of 250 rpm, about − The polycarbonate resin composition was extruded under pellets under conditions of a first vent pressure of 600 mmHg and a self feeding rate of 60 kg / h to prepare pellets. The pellets were dried at 100 ° C. for 4 hours, and injected at a injection temperature of 280 ° C. in a 10 oz injection machine to prepare specimens for measuring various physical properties.

First, the notched Izod impact strength (1/4 ", kg · cm / cm) of the specimen was measured according to ASTM D256, a US standard measurement method for measuring the Izod impact strength of plastics using a weight of constant weight ( Impact resistance evaluation).

Next, one 10 cm × 10 cm specimen and two circular specimens having a diameter of 5 cm were prepared, and friction loss was measured before and after friction by rubbing for 10,000 cycles at 90 rpm using a Taber friction tester (abrasion resistance evaluation).

Finally, the glossiness of ten 10 cm x 10 cm specimens was measured in a 60 Hz direction using a gloss meter, and the average value was described (gloss evaluation).

The physical properties of each specimen measured through this method are shown in Table 1 below.

TABLE 1

Referring to Table 1 above, the specimens of Examples 1 and 2 include modified polyethylene terephthalate and polyethylene glycol, it is confirmed that compared to the specimen of 1 does not include all compared to the specimen of 1 wear resistance.

In addition, it is confirmed that the specimens of Examples 1 and 2 exhibited excellent glossiness and impact resistance compared to the specimens of Comparative Example 2 not containing polyethylene glycol.

In addition, as the specimens of Examples 1 and 2 include the core-shell graft copolymer, it is confirmed that the specimens exhibit superior impact resistance compared to the specimens of Comparative Example 4 that do not include the same.

In addition, it is confirmed that the specimens of Examples 1 and 2 exhibited excellent glossiness compared to the specimens of Comparative Example 3 outside the content range, as polyethylene glycol and the like contained in a preferable content range.

According to the present invention, there can be provided a polycarbonate-based resin composition that enables the provision of a polycarbonate-based thermoplastic resin exhibiting excellent glossiness and beautiful appearance with excellent impact resistance and abrasion resistance.

Therefore, the polycarbonate-based thermoplastic resin can be preferably applied to exterior materials of various IT devices.

Claims (9)

Based on 100 parts by weight of a polycarbonate resin, a rubber core copolymerized with an acrylate rubber monomer and a silicone rubber monomer, and a core-shell graft copolymer in which a vinyl monomer is grafted, 0.5 to 10 parts by weight of the modified polyethylene terephthalate of Formula 2; And A polycarbonate resin composition comprising 0.5 to 10 parts by weight of polyethylene glycol, The polycarbonate resin and core-shell graft copolymer is contained in a ratio of 90 to 99% by weight and 1 to 10% by weight based on the sum of the contents of the polycarbonate resin and the core-shell graft copolymer, respectively. Polycarbonate Resin Composition: [Formula 2]

In Formula 2, m and n are each natural numbers. The polycarbonate-based resin composition of claim 1, wherein the polycarbonate resin comprises an aromatic polycarbonate resin prepared by reacting a diphenol compound represented by Chemical Formula 1 with phosgene, halogen formate, or diester carbonate. [Formula 1]

Wherein A is a single bond, C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -S- or -SO _2- . The polycarbonate-based resin composition of claim 1, wherein the polycarbonate resin has a weight average molecular weight of 15,000 to 50,000 g / mol. The method of claim 1, wherein the acrylate rubber monomer is methyl acrylate, ethyl acrylate, n-propyl acrylate, n- butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate and 2-ethylhexyl methacryl One monomer selected from the group consisting of a rate or a mixture of two or more, The silicone rubber monomers include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane and octaphenylcyclotetrasiloxane Polycarbonate-based resin composition comprising one monomer or a mixture of two or more selected from the group consisting of. The polycarbonate-based resin composition of claim 1, wherein the vinyl monomer comprises one monomer selected from the group consisting of methyl methacrylate, styrene, and acrylonitrile, or a mixture of two or more thereof. The polycarbonate-based resin composition of claim 1, wherein the modified polyethylene terephthalate has a weight average molecular weight of 8000 to 30000 g / mol. The polycarbonate-based resin composition of claim 1, wherein the polyethylene glycol has a weight average molecular weight of 400 to 8000 g / mol. The plastic molded article manufactured from the polycarbonate-type resin composition in any one of Claims 1-7. Core-shell graft in which a vinyl monomer is grafted to a rubber core copolymerized with a polycarbonate resin, an acrylate rubber monomer and a silicone rubber monomer On the basis of 100 parts by weight of the resin substrate combined the copolymer, 0.5 to 10 parts by weight of the modified polyethylene terephthalate of Formula 2 dispersed in the resin substrate; And As a plastic molded article containing 0.5 to 10 parts by weight of polyethylene glycol dispersed in the resin substrate, The polycarbonate resin and core-shell graft copolymer is contained in a ratio of 90 to 99% by weight and 1 to 10% by weight based on the sum of the contents of the polycarbonate resin and the core-shell graft copolymer, respectively. Plastic moldings: [Formula 2]

In Formula 2, m and n are each natural numbers.