KR20190072882A - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

A thermoplastic resin composition of the present invention comprises: a polycarbonate resin; a modified (meth)acrylic copolymer resin; a first polycarbonate-polysiloxane copolymer resin; and a second polycarbonate-polysiloxane copolymer resin, wherein an average degree of polymerization of a polysiloxane block in the first polycarbonate-polysiloxane copolymer resin is 30 to 45, and that in the second polycarbonate-polysiloxane copolymer resin is 70 to 100. The thermoplastic resin composition is excellent in transparency, impact resistance, scratch resistance and the like.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a thermoplastic resin composition and a molded article obtained from the thermoplastic resin composition.

The present invention relates to a thermoplastic resin composition and a molded article produced therefrom. More specifically, the present invention relates to a thermoplastic resin composition excellent in transparency, impact resistance, scratch resistance and the like, and a molded article produced therefrom.

Polycarbonate resins have been applied to electric / electronic products, automobile parts, lenses and glass substitute materials because of their excellent toughness, impact resistance, thermal stability, self-extinguishing property, dimensional stability and heat resistance. However, when the polycarbonate resin is applied to a product requiring transparency, scratch resistance of the polycarbonate resin is much lower than that of a glass material, and yellowing occurs when exposed to sunlight for a long time.

BACKGROUND ART [0002] Acrylic resins such as polymethylmethacrylate (PMMA) resins are excellent in weatherability, transparency, flexural strength, flexural strain, and adhesiveness and are used as lighting materials and building materials. However, the usual acrylic resin is limited in use for a product which is thinner than a certain thickness, which has a low impact strength and can secure sufficient impact resistance.

When such a polycarbonate resin and an acrylic resin are used as alloys, it is expected that both impact resistance and scratch resistance will be ensured at the same time. However, in practical application, compatibility between the two resins is low and the difference in refractive index is large, There is a disadvantage in that the quality is deteriorated and the impact resistance and scratch resistance are deteriorated.

Therefore, it is necessary to develop a thermoplastic resin composition which is excellent in transparency, impact resistance, scratch resistance, physical properties and the like.

The background art of the present invention is disclosed in Korean Patent Publication No. 10-2010-0076643.

An object of the present invention is to provide a thermoplastic resin composition excellent in transparency, impact resistance, scratch resistance, physical properties and the like.

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

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

One aspect of the present invention relates to a thermoplastic resin composition. Wherein the thermoplastic resin composition is a polycarbonate resin; Modified (meth) acrylic copolymer resin; A first polycarbonate-polysiloxane copolymer resin; And a second polycarbonate-polysiloxane copolymer resin, wherein the first polycarbonate-polysiloxane copolymer resin has an average degree of polymerization of the polysiloxane block of 30 to 45 and the second polycarbonate-polysiloxane copolymer resin comprises a polysiloxane block And an average degree of polymerization of 70 to 100.

In an embodiment, the thermoplastic resin composition comprises 5 to 25% by weight of the polycarbonate resin; 15 to 30% by weight of the modified (meth) acrylic copolymer resin; 40 to 75% by weight of said first polycarbonate-polysiloxane copolymer resin; And 5 to 25% by weight of the second polycarbonate-polysiloxane copolymer resin.

In embodiments, the weight ratio of the first polycarbonate-polysiloxane copolymer resin and the second polycarbonate-polysiloxane copolymer resin may be from 1: 0.1 to 1: 0.4.

In an embodiment, the modified (meth) acrylic copolymer resin may be a polymer of a monomer mixture comprising an aromatic or alicyclic (meth) acrylic monomer represented by the following formula (1) and a monofunctional unsaturated monomer:

[Chemical Formula 1]

Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ is a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, X is an oxygen atom or A is an integer of 0 to 10, and b is 0 or 1.

In an embodiment, the monofunctionally unsaturated monomer is an alkyl (meth) acrylate having 1 to 8 carbon atoms; Unsaturated carboxylic acids containing (meth) acrylic acid; Acid anhydrides including maleic anhydride; (Meth) acrylate containing a hydroxy group; (Meth) acrylamide; Unsaturated nitrile compounds; Allyl glycidyl ether; Glycidyl (meth) acrylate; And an aromatic vinyl compound.

In an embodiment, the modified (meth) acrylic copolymer resin may have a refractive index of 1.495 to 1.590.

In embodiments, the first polycarbonate-polysiloxane copolymer resin may comprise from 1 to 10% by weight of the polysiloxane block and from 90 to 99% by weight of the polycarbonate block.

In embodiments, the second polycarbonate-polysiloxane copolymer resin may comprise from 1 to 10% by weight of the polysiloxane block and from 90 to 99% by weight of the polycarbonate block.

In embodiments, the weight average molecular weight of the first and second polycarbonate-polysiloxane copolymer resins may be from 15,000 g / mol to 50,000 g / mol.

In a specific example, the thermoplastic resin composition may have a haze of not more than 3% and a light transmittance of not less than 90% in a 2.0 mm thick specimen measured according to ASTM D1003.

In an embodiment, the thermoplastic resin composition may have an Izod impact strength of 15 kgf · cm / cm or more, measured according to ASTM D256, with a 1/8 "thick specimen having a weld line in the middle of the specimen.

In a specific example, the thermoplastic resin composition may have a pencil hardness of H or more and a scratch width of 290 占 퐉 or less by BSP (Ball-type Scratch Profile) test, as measured according to JIS K5401.

Another aspect of the present invention relates to a molded article. And the molded article is formed from the thermoplastic resin composition.

INDUSTRIAL APPLICABILITY The present invention has the effect of providing a thermoplastic resin composition excellent in transparency, impact resistance, scratch resistance, physical properties and the like, and a molded article formed therefrom.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention comprises (A) a polycarbonate resin; (B) a modified (meth) acrylic copolymer resin; (C) a first polycarbonate-polysiloxane copolymer resin; And (D) a second polycarbonate-polysiloxane copolymer resin.

(A) Polycarbonate resin

As the polycarbonate resin according to one embodiment of the present invention, a polycarbonate resin used for a conventional thermoplastic resin composition may be used. For example, an aromatic polycarbonate resin prepared by reacting a diphenol (aromatic diol compound) with a precursor such as phosgene, halogen formate, or carbonic acid diester can be used.

Specific examples of the diphenols include 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) Propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane. . For example, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro- Hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) cyclohexane. More specifically, bisphenol- 2,2-bis (4-hydroxyphenyl) propane referred to as A can be used.

In an embodiment, the polycarbonate resin may be used with a branched chain. For example, 0.05 to 2 mol% of a trifunctional or higher polyfunctional compound may be added to all of the diphenols used for polymerization, specifically, 3 Branched or cyclic polycarbonate resin prepared by adding a compound having a phenolic group or more.

In embodiments, the polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof. The polycarbonate resin may be partially or wholly substituted with an aromatic polyester-carbonate resin obtained by polymerization reaction in the presence of an ester precursor such as 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 20,000 to 50,000 g / mol, for example, 25,000 to 40,000 g / mol. The impact resistance, fluidity (workability) and the like of the thermoplastic resin composition can be excellent in the above range.

In an embodiment, the polycarbonate resin may be included in an amount of 5 to 25% by weight, for example, 7 to 20% by weight, based on 100% by weight of the total thermoplastic resin composition. Within the above range, transparency, impact resistance and scratch resistance of the thermoplastic resin composition can be excellent.

(B) a modified (meth) acrylic copolymer resin

The modified (meth) acrylic copolymer resin according to one embodiment of the present invention can improve the scratch resistance and the like without deteriorating the transparency of the thermoplastic resin composition. The modified (meth) acrylic copolymer resin includes (b1) an aromatic or alicyclic b2) a polymer of a monomer mixture comprising a monofunctional unsaturated monomer.

"(Meth) acrylic" means "acrylic" and "methacrylic" are both possible unless otherwise specified herein. For example, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible.

(b1) an aromatic or alicyclic (meth) acrylic monomer

The aromatic or alicyclic (meth) acrylic monomers according to one embodiment of the present invention may be represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1, R ₁ is a hydrogen atom or a methyl group, and R ₂ is a substituted or unsubstituted C6-C20 cycloalkyl group or a substituted or unsubstituted C6-C20 aryl group. For example, R ₂ may be a cyclohexyl group, a phenyl group, a methylphenyl group, a methylethylphenyl group, a methoxyphenyl group, a cyclohexylphenyl group, a chlorophenyl group, a bromophenyl group, or a benzylphenyl group. X is an oxygen atom (O) or a sulfur atom (S), a is an integer of 0 to 10, and b is 0 or 1.

Examples of the aromatic or alicyclic (meth) acrylic monomers include cyclohexyl (meth) acrylate, phenoxy (meth) acrylate, 2-ethylphenoxy (meth) acrylate, benzyl (Meth) acrylate, 2-ethylthiophenyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 3- 2-methylphenyl ethyl (meth) acrylate, 2-methylphenyl ethyl (meth) acrylate, 2- Acrylate, 2- (4-methoxyphenyl) ethyl (meth) acrylate, 2- (4-cyclohexylphenyl) ethyl (Meth) acrylate, 2- (3-chlorophenyl) ethyl (meth) acrylate, 2- (Meth) acrylate, 2- (4-bromophenyl) ethyl (meth) acrylate, 2- Acrylate, combinations thereof, and the like. For example, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, and the like can be used.

In an embodiment, the aromatic or alicyclic (meth) acrylic monomer may be contained in an amount of 10 to 90% by weight, for example 20 to 80% by weight, based on 100% by weight of the total monomer mixture. Within the above range, the transparency and scratch resistance of the thermoplastic resin composition can be excellent.

(b2) monofunctional unsaturated monomer

The monofunctional unsaturated monomer according to one embodiment of the present invention is a monomer containing an unsaturated group, for example, an alkyl (meth) acrylate having 1 to 8 carbon atoms; Unsaturated carboxylic acids containing (meth) acrylic acid; Acid anhydrides including maleic anhydride; (Meth) acrylate containing a hydroxy group; (Meth) acrylamide; Unsaturated nitrile compounds; Allyl glycidyl ether; Glycidyl (meth) acrylate; Aromatic vinyl compounds, mixtures thereof, and the like.

Examples of the monofunctional unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylic acid, maleic anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, monoglycerol , Allyl glycidyl ether, glycidyl (meth) acrylate, styrene, alpha-methylstyrene, and the like. For example, methyl (meth) acrylate and the like can be used.

In an embodiment, the monofunctionally unsaturated monomer may comprise from 10 to 90 wt%, for example 20 to 80 wt%, of 100 wt% of the total monomer mixture. Within the above range, the transparency and scratch resistance of the thermoplastic resin composition can be excellent.

The modified (meth) acrylic copolymer resin (B) according to one embodiment of the present invention may be prepared by conventional polymerization methods known in the art of polymer production, for example, bulk polymerization, emulsion polymerization, suspension polymerization, For example, a polymerization initiator may be added to the monomer mixture to polymerize the monomer mixture.

In an embodiment, the polymerization initiator is a radical polymerization initiator, and the polymerization may be a suspension polymerization in consideration of refractive index and the like, and the suspension polymerization may be carried out in the presence of a suspension stabilizer and a chain transfer agent. That is, a radical polymerization initiator and a chain transfer agent are added to the monomer to prepare a reaction mixture, and the resulting reaction mixture is added to an aqueous solution in which the suspension stabilizer is dissolved to prepare a copolymer resin (suspension polymerization). In the polymerization, the polymerization temperature and the polymerization time can be appropriately controlled. The polymerization temperature may be from 65 to 125 캜, for example from 70 to 120 캜, and the polymerization time may be from 2 to 8 hours. After the polymerization is completed, the modified (meth) acrylic copolymer resin in the form of particles may be obtained through cooling, washing, dehydration and drying processes.

In an embodiment, the modified (meth) acrylic copolymer resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 5,000 to 500,000 g / mol, for example, 10,000 to 250,000 g / mol. Within the above range, the transparency and scratch resistance of the thermoplastic resin composition can be excellent.

In a specific example, the modified (meth) acrylic copolymer resin has a refractive index of 1.495 to 1.590, a refractive index of a 2.5 mm thick specimen measured under a temperature condition of 20 ° C using a refractive index meter (manufacturer: ATAGO, Abbe refractometer DR- For example, from 1.510 to 1.590. Within this range, the refractive index of the modified (meth) acrylic copolymer resin may be the same as or similar to the refractive index of the polycarbonate resin, so that the transparency and compatibility of the thermoplastic resin composition may be excellent.

In an embodiment, the modified (meth) acrylic copolymer resin may include 15 to 30% by weight, for example, 15 to 25% by weight of 100% by weight of the total thermoplastic resin composition. Within the above range, transparency, impact resistance and scratch resistance of the thermoplastic resin composition can be excellent.

(C) a first polycarbonate-polysiloxane copolymer resin

The first polycarbonate-polysiloxane copolymer resin according to one embodiment of the present invention is applied together with the second polycarbonate-polysiloxane copolymer resin to improve the impact resistance and the like without deteriorating transparency and scratch resistance of the thermoplastic resin composition Polysiloxane blocks and polycarbonate blocks having an average degree of polymerization of from 30 to 45, for example from 35 to 40. When the average degree of polymerization of the polysiloxane block is less than 30, there is a possibility that the impact resistance and the like are lowered. When the average degree of polymerization is more than 45, transparency and the like may be lowered.

In an embodiment, the polycarbonate block may comprise a structural unit derived from the aforementioned polycarbonate resin (A), and the polysiloxane block may include a structural unit represented by the following formula (2).

(2)

Wherein R ₃ and R ₄ each independently represent a hydrogen atom, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C1 to C20 alkoxy group, a C3 to C30 cycloalkyl group, A C6 to C30 aryl group, a C6 to C30 aryloxy group, or NRR '(wherein R and R' are each independently a hydrogen atom or a C1 to C20 alkyl group), , and m (average degree of polymerization) is 30 to 45.

In embodiments, the first polycarbonate-polysiloxane copolymer resin may be prepared according to the conventional polycarbonate-polysiloxane copolymer manufacturing method. For example, it can be prepared by reacting a polysiloxane and a diphenol (aromatic diol compound) containing the structural unit represented by the formula (2) with a precursor such as phosgene, halogen formate, or carbonic acid diester. The reaction can be carried out by a conventional polymerization method such as interfacial polymerization or melt polymerization, and can be carried out, for example, by interfacial polymerization using phosgene.

In an embodiment, the first polycarbonate-polysiloxane copolymer resin comprises 1 to 10 wt%, for example 1 to 7 wt%, specifically 4 to 6 wt%, and polycarbonate block 90 to 99 wt% of a polysiloxane block, For example from 93 to 99% by weight, in particular from 94 to 96% by weight. The impact resistance and the like of the thermoplastic resin composition may be excellent in the above range.

In embodiments, the first polycarbonate-polysiloxane copolymer resin may have a weight average molecular weight (Mw) as measured by gel permeation chromatography (GPC) of from 15,000 to 50,000 g / mol, such as from 15,000 to 40,000 g / mol . The impact resistance and the like of the thermoplastic resin composition may be excellent in the above range.

In an embodiment, the first polycarbonate-polysiloxane copolymer resin may comprise from 40 to 75 wt%, for example 45 to 70 wt%, of 100 wt% of the total thermoplastic resin composition. Within the above range, transparency, impact resistance and scratch resistance of the thermoplastic resin composition can be excellent.

(D) a second polycarbonate-polysiloxane copolymer resin

The second polycarbonate-polysiloxane copolymer resin according to one embodiment of the present invention is applied together with the first polycarbonate-polysiloxane copolymer resin to improve the impact resistance and the like without deteriorating transparency and scratch resistance of the thermoplastic resin composition Polysiloxane blocks and polycarbonate blocks having an average degree of polymerization of 70 to 100, such as 75 to 95. [ If the average degree of polymerization of the polysiloxane block is less than 70, there is a possibility that the impact resistance and the like may be lowered. If the average degree of polymerization is more than 100, the heat resistance and scratch resistance may be deteriorated.

In an embodiment, the polycarbonate block may include a structural unit derived from the polycarbonate resin (A) mentioned above, and the polysiloxane block may include a structural unit represented by the following formula (3).

(3)

Wherein R ₅ and R ₆ are each independently a hydrogen atom, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C1 to C20 alkoxy group, a C3 to C30 cycloalkyl group, A C6 to C30 aryl group, a C6 to C30 aryloxy group, or NRR '(wherein R and R' are each independently a hydrogen atom or a C1 to C20 alkyl group), , and n (average degree of polymerization) is 70 to 100.

In embodiments, the second polycarbonate-polysiloxane copolymer resin may be prepared according to the usual polycarbonate-polysiloxane copolymer making process. For example, it can be prepared by reacting a polysiloxane and a diphenol (aromatic diol compound) containing the structural unit represented by the above formula (3) with a precursor such as phosgene, halogen formate, or carbonic acid diester. The reaction can be carried out by a conventional polymerization method such as interfacial polymerization or melt polymerization, and can be carried out, for example, by interfacial polymerization using phosgene.

In an embodiment, the second polycarbonate-polysiloxane copolymer resin comprises 1 to 10 wt%, for example 1 to 7 wt%, specifically 4 to 6 wt%, and polycarbonate block 90 to 99 wt% of the polysiloxane block, For example from 93 to 99% by weight, in particular from 94 to 96% by weight. The impact resistance and the like of the thermoplastic resin composition may be excellent in the above range.

In embodiments, the second polycarbonate-polysiloxane copolymer resin may have a weight average molecular weight (Mw) as measured by gel permeation chromatography (GPC) of from 15,000 to 50,000 g / mol, such as from 15,000 to 40,000 g / mol . The impact resistance and the like of the thermoplastic resin composition may be excellent in the above range.

In an embodiment, the second polycarbonate-polysiloxane copolymer resin may comprise from 5 to 25 wt%, such as 7 to 20 wt%, of 100 wt% of the total thermoplastic resin composition. Within the above range, transparency, impact resistance and scratch resistance of the thermoplastic resin composition can be excellent.

In embodiments, the weight ratio of the first polycarbonate-polysiloxane copolymer resin and the second polycarbonate-polysiloxane copolymer resin may be from 1: 0.1 to 1: 0.4. Within the above range, transparency, impact resistance, scratch resistance, etc. of the thermoplastic resin composition can be more excellent.

The thermoplastic resin composition according to an embodiment of the present invention may further contain additives such as a releasing agent, a lubricant, a nucleating agent, a plasticizer, a heat stabilizer, a light stabilizer, a flame retardant, a flame retardant aid, an antistatic agent, an antioxidant,

In the specific examples, the additive used in the conventional thermoplastic resin composition may be used without limitation. Examples of the additive include polyethylene wax, a fluorine-containing polymer, a silicone oil, a metal salt of stearic acid, a metal salt of montanic acid, a mold release agent such as montanic ester wax; Nucleating agents such as clay and talc; Antioxidants such as hindered phenol-based compounds; Mixtures thereof, and the like may be used, but the present invention is not limited thereto. The additive may be included in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the polycarbonate resin composition, but is not limited thereto.

The thermoplastic resin composition according to one embodiment of the present invention may be in the form of a pellet obtained by melt-extruding the above components and mixing them at a temperature of 200 to 280 DEG C, for example, 250 to 260 DEG C using a conventional twin-screw extruder.

In a specific example, the thermoplastic resin composition may have a haze of a 2.0 mm thick specimen measured according to ASTM D1003 of 3% or less, for example, 0.5 to 2.5%, and a light transmittance of 90% For example from 91 to 99%.

In an embodiment, the thermoplastic resin composition may have an Izod impact strength of 15 kgf · cm / cm or more, measured according to ASTM D256, with a 1/8 "thick specimen having a weld line in the middle of the specimen, 20 to 50 kgf cm / cm.

In the specific example, the thermoplastic resin composition has a pencil hardness of not less than H and a scratch width of not more than 290 占 퐉 such as BSP (Ball-type Scratch Profile) test of 2.5 mm in thickness measured according to JIS K5401 To 280 [mu] m.

The molded article according to the present invention is formed from the thermoplastic resin composition. For example, the thermoplastic resin composition can be produced from the thermoplastic resin composition through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those of ordinary skill in the art to which the present invention pertains. The molded article is excellent in transparency, impact resistance, scratch resistance, physical properties and the like, and therefore is useful as an automobile part or an interior / exterior material of an electric / electronic product. In particular, it can be used for interior / exterior materials of mobile phones and notebooks without a clear coating process.

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

Example

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

(A) Polycarbonate resin

Bisphenol-A polycarbonate resin (weight average molecular weight: 25,000 g / mol) was used.

(B) a modified (meth) acrylic copolymer resin

A modified (meth) acrylic copolymer resin (weight average molecular weight: 25,000 g / mol, refractive index: 1.550) prepared by polymerizing 65 wt% of methyl methacrylate and 35 wt% of phenyl methacrylate by a conventional suspension polymerization method was used Respectively.

(C) a first polycarbonate-polysiloxane copolymer resin

Polysiloxane block: 6 weight%, polycarbonate block: 94 weight%, weight average molecular weight: 21,000 g / cm < 2 >) was used as the polycarbonate-polysiloxane copolymer resin (Idemitsu Kosan, product name: FC1760) mol).

(D) a second polycarbonate-polysiloxane copolymer resin

Polysiloxane block: 6% by weight, polycarbonate block: 94% by weight, weight average molecular weight: 21,000 g / m < 2 >) was used as the polycarbonate- polysiloxane copolymer resin (Idemitsu Kosan, mol).

(E) Polycarbonate-polysiloxane copolymer resin

(Polysiloxane block: 6% by weight, polycarbonate block: 94% by weight, weight average molecular weight: 21,000 g / mol) having an average degree of polymerization of 55 of polysiloxane block.

Examples 1 to 3 and Comparative Examples 1 to 4

The above components were added in the amounts as shown in Table 1, and then extruded at 250 캜 to prepare pellets. The extrudate was a twin screw extruder with L / D = 36 and 45 mm diameter. The pellets were dried at 100 ℃ for more than 4 hours and injected at 6 oz injection molding machine (molding temperature 300 ℃). The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Table 1 below.

How to measure property

(1) Haze (unit:%): The haze of a 2.0 mm thick specimen was measured using a haze meter (manufacturer: Nippon Denshoku, product name: NDH 5000W) according to ASTM D1003.

(2) Light transmittance (unit:%): The light transmittance (total light transmittance) of a 2.0 mm thick specimen was measured using a haze meter (manufactured by Nippon Denshoku, product name: NDH 5000W) according to ASTM D1003 Respectively.

(3) Welded Izod impact strength (unit: kgf · cm / cm): A 1/8 "thick specimen with a weld line in the middle of the specimen was tested in an un-notched state according to ASTM D256 And the Izod impact strength was measured.

(4) Pencil hardness: The pencil hardness of a 2.5 mm thick specimen was measured under a load of 500 g according to JIS K5401.

(5) Scratch width (unit: 占 퐉): Measured according to BSP (Ball-type Scratch Profile) test method. 90 mm x 50 mm x 2.5 mm The surface of the specimen was subjected to scratching with a load of 1,000 g and a scratch speed of 75 mm / min with a length of 10 to 20 mm using a spherical metal tip of 0.7 mm in diameter. The profile of the applied scratch was surface scanned with a metal stylus tip of 2 탆 diameter using an Ambios contact surface profile analyzer (XP-1) to measure the scratch width which is a measure of scratch resistance.

Example Comparative Example One 2 3 One 2 3 4 (A) (% by weight) 17 10 8 10 10 17 17 (B) (% by weight) 23 20 22 20 20 23 23 (C) (% by weight) 45 58 60 - 70 - 45 (D) (% by weight) 15 12 10 70 - 15 - (E) (% by weight) - - - - - 45 15 Haze (%) 1.4 1.3 1.1 25.0 1.0 4.3 1.4 Light transmittance (%) 92 93 93 76 94 86 92 Weld Izod impact strength (kgf · cm / cm) 25 25 27 44 10 26 12 Pencil hardness H H H F H H H Scratch width (탆) 268 266 259 296 268 274 264

From the results of Table 1, it can be seen that the thermoplastic resin composition of the present invention is excellent in transparency, impact resistance, scratch resistance, and physical properties thereof.

On the other hand, in Comparative Example 1 in which the first polycarbonate-polysiloxane copolymer resin (C) was not used, transparency (haze, light transmittance), scratch resistance and the like were found to be lowered, and the second polycarbonate- In the case of Comparative Example 2 in which the coalescing resin (D) was not used, it can be seen that the impact resistance was lowered. In the case of Comparative Example 3 using the polycarbonate-polysiloxane copolymer resin (E) in which the average degree of polymerization of the polysiloxane block was out of the range of the present invention instead of the first polycarbonate-polysiloxane copolymer resin (C), transparency was lowered In the case of Comparative Example 4 in which the polycarbonate-polysiloxane copolymer resin (E) was used in place of the second polycarbonate-polysiloxane copolymer resin (D) in which the average degree of polymerization of the polysiloxane block was out of the range of the present invention, And so on.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (13)

Polycarbonate resin;
Modified (meth) acrylic copolymer resin;
A first polycarbonate-polysiloxane copolymer resin; And
And a second polycarbonate-polysiloxane copolymer resin,
Wherein the first polycarbonate-polysiloxane copolymer resin has an average degree of polymerization of the polysiloxane block of 30 to 45, and the second polycarbonate-polysiloxane copolymer resin has an average degree of polymerization of the polysiloxane block of 70 to 100. .
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises 5 to 25% by weight of the polycarbonate resin; 15 to 30% by weight of the modified (meth) acrylic copolymer resin; 40 to 75% by weight of said first polycarbonate-polysiloxane copolymer resin; And 5 to 25% by weight of the second polycarbonate-polysiloxane copolymer resin.
The thermoplastic resin composition of claim 1, wherein the weight ratio of the first polycarbonate-polysiloxane copolymer resin to the second polycarbonate-polysiloxane copolymer resin is from 1: 0.1 to 1: 0.4.
The thermoplastic resin composition according to claim 1, wherein the modified (meth) acrylic copolymer resin is a polymer of a monomer mixture comprising an aromatic or alicyclic (meth) acrylic monomer and a monofunctional unsaturated monomer represented by the following formula Composition:
[Chemical Formula 1]

Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ is a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, X is an oxygen atom or A is an integer of 0 to 10, and b is 0 or 1.
5. The composition according to claim 4, wherein the monofunctional unsaturated monomer is selected from the group consisting of alkyl (meth) acrylates having 1 to 8 carbon atoms; Unsaturated carboxylic acids containing (meth) acrylic acid; Acid anhydrides including maleic anhydride; (Meth) acrylate containing a hydroxy group; (Meth) acrylamide; Unsaturated nitrile compounds; Allyl glycidyl ether; Glycidyl (meth) acrylate; And an aromatic vinyl compound. The thermoplastic resin composition according to claim 1,
The thermoplastic resin composition according to claim 1, wherein the modified (meth) acrylic copolymer resin has a refractive index of 1.495 to 1.590.
The thermoplastic resin composition of claim 1, wherein the first polycarbonate-polysiloxane copolymer resin comprises 1 to 10% by weight of a polysiloxane block and 90 to 99% by weight of a polycarbonate block.
The thermoplastic resin composition of claim 1, wherein the second polycarbonate-polysiloxane copolymer resin comprises 1 to 10% by weight of a polysiloxane block and 90 to 99% by weight of a polycarbonate block.
The thermoplastic resin composition according to claim 1, wherein the weight average molecular weight of the first and second polycarbonate-polysiloxane copolymer resins is 15,000 g / mol to 50,000 g / mol.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a haze of not more than 3% and a light transmittance of not less than 90% in a 2.0 mm thick specimen measured according to ASTM D1003.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an Izod impact strength of 15 kgf · cm / cm or more as measured according to ASTM D256 in a 1/8 "thick specimen having a weld line in the middle of the specimen .
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a pencil hardness of not less than H and a scratch width of not more than 290 占 퐉 according to a BSP (Ball-type Scratch Profile) test as measured according to JIS K5401 And a thermoplastic resin composition.
A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 12.