KR102008585B1 - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

The thermoplastic resin composition of the present invention is a polycarbonate resin; Modified (meth) acrylic copolymer resins; First polycarbonate-polysiloxane copolymer resin; And a second polycarbonate-polysiloxane copolymer resin, wherein the first polycarbonate-polysiloxane copolymer resin has an average polymerization degree of 30 to 45 of the polysiloxane block, and the second polycarbonate-polysiloxane copolymer resin of the polysiloxane block It is characterized by the average degree of polymerization of 70 to 100. The thermoplastic resin composition is excellent in transparency, impact resistance, scratch resistance and the like.

Description

Thermoplastic resin composition and molded article manufactured therefrom {THERMOPLASTIC RESIN COMPOSITION AND ARTICLE PRODUCED THEREFROM}

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 are applied to electric / electronic products, automotive parts, lenses, and glass substitute materials because of their excellent toughness, impact resistance, thermal stability, self-extinguishing, dimensional stability, and heat resistance. However, when the polycarbonate resin is applied to a product requiring transparency, scratch resistance is very low as compared with glass materials, and yellowing occurs when exposed to sunlight for a long time.

Acrylic resins, such as polymethyl methacrylate (PMMA) resin, are excellent in weather resistance, transparency, flexural strength, flexural strain rate, adhesiveness, and the like, and are used as lighting materials and building materials. However, the conventional acrylic resin has a low impact strength, its use is limited to a product thinner than a certain thickness that can sufficiently secure impact resistance.

When the polycarbonate resin and the acrylic resin are alloyed, the impact resistance and the scratch resistance are expected to be secured at the same time, but in actual application, the compatibility between the two resins is low and the difference in refractive index is large, resulting in opacity and appearance. There is a disadvantage that the quality is lowered, the impact resistance and scratch resistance is lowered.

Therefore, there is a need for development of a thermoplastic resin composition having excellent transparency, impact resistance, scratch resistance, balance of physical properties, and the like.

Background art of the present invention is disclosed in the Republic of Korea 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, balance of physical properties thereof 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. The thermoplastic resin composition is a polycarbonate resin; Modified (meth) acrylic copolymer resins; First polycarbonate-polysiloxane copolymer resin; And a second polycarbonate-polysiloxane copolymer resin, wherein the first polycarbonate-polysiloxane copolymer resin has an average polymerization degree of 30 to 45 of the polysiloxane block, and the second polycarbonate-polysiloxane copolymer resin of the polysiloxane block It is characterized by the average degree of polymerization of 70 to 100.

In embodiments, the thermoplastic resin composition is 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 the first polycarbonate-polysiloxane copolymer resin; And 5 to 25 wt% 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 1: 0.1 to 1: 0.4.

In embodiments, the modified (meth) acrylic copolymer resin may be a polymer of a monomer mixture comprising an aromatic or cycloaliphatic (meth) acrylic monomer and a monofunctional unsaturated monomer represented by Formula 1 below:

[Formula 1]

In Formula 1, 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 Is a sulfur atom, a is an integer from 0 to 10 and b is 0 or 1;

In embodiments, the monofunctional unsaturated monomers are alkyl (meth) acrylates having 1 to 8 carbon atoms; Unsaturated carboxylic acids including (meth) acrylic acid; Acid anhydrides including maleic anhydride; (Meth) acrylate containing a hydroxyl group; (Meth) acrylamide; Unsaturated nitrile compounds; Allyl glycidyl ether; Glycidyl (meth) acrylate; And one or more of aromatic vinyl compounds.

In embodiments, 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 include 1 to 10 wt% of polysiloxane blocks and 90 to 99 wt% of polycarbonate blocks.

In an embodiment, the second polycarbonate-polysiloxane copolymer resin may include 1 to 10 wt% of polysiloxane blocks and 90 to 99 wt% of polycarbonate blocks.

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

In an embodiment, the thermoplastic resin composition may have a haze of 3% or less and a light transmittance of 90% or more of 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 for a 1/8 ″ thick specimen having a weld line in the middle of the specimen.

In an embodiment, the thermoplastic resin composition may have a pencil hardness of 2.5 mm or thicker specimens measured in accordance with JIS K5401 or greater than H, and a scratch width of BSP (Ball-type Scratch Profile) test of 290 μm or less.

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

This invention has the effect of providing the thermoplastic resin composition excellent in transparency, impact resistance, scratch resistance, the balance of these physical properties, etc., and the molded article formed therefrom.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention includes (A) a polycarbonate resin; (B) modified (meth) acrylic copolymer resin; (C) 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 in a conventional thermoplastic resin composition may be used. For example, an aromatic polycarbonate resin produced by reacting diphenols (aromatic diol compounds) with precursors such as phosgene, halogen formate, and carbonic acid diester can be used.

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

In embodiments, the polycarbonate resin may be a branched chain, for example, 0.05 to 2 mol% of a trivalent or more polyfunctional compound, specifically, 3 to the total diphenols used for polymerization It is also possible to use a branched polycarbonate resin prepared by adding a compound having a phenol group or more.

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

In embodiments, 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. In the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity (processability), and the like.

In embodiments, the polycarbonate resin may be included in 5 to 25% by weight, for example 7 to 20% by weight of the total 100% by weight of the thermoplastic resin composition. In the above range, the thermoplastic resin composition may have excellent transparency, impact resistance, scratch resistance, and the like.

(B) Modified (meth) acrylic copolymer resin

The modified (meth) acrylic copolymer resin according to one embodiment of the present invention is capable of improving scratch resistance and the like without lowering the transparency of the thermoplastic resin composition, and (b1) an aromatic or cycloaliphatic (meth) acrylic monomer and ( b2) polymers of monomer mixtures comprising monofunctional unsaturated monomers.

Unless otherwise stated herein, "(meth) acryl" means that both "acryl" and "methacryl" are possible. For example, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible.

(b1) aromatic or alicyclic (meth) acrylic monomers

An aromatic or cycloaliphatic (meth) acrylic monomer according to one embodiment of the present invention may be represented by the following formula (1).

[Formula 1]

In Formula 1, 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. For example, R ₂ may be a cyclohexyl group, a phenyl group, methylphenyl group, methylethylphenyl group, methoxyphenyl group, cyclohexylphenyl group, chlorophenyl group, bromophenyl group, benzylphenyl group, or the like. 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.

In embodiments, the aromatic or cycloaliphatic (meth) acrylic monomers include cyclohexyl (meth) acrylate, phenoxy (meth) acrylate, 2-ethylphenoxy (meth) acrylate, benzyl (meth) acrylate, Phenyl (meth) acrylate, 2-ethylthiophenyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 3-phenylpropyl (meth) acrylate, 4-phenylbutyl (meth) acrylate, 2- 2-methylphenylethyl (meth) acrylate, 2-3-methylphenylethyl (meth) acrylate, 2-4-methylphenylethyl (meth) acrylate, 2- (4-propylphenyl) ethyl (meth) acrylate, 2 -(4- (1-methylethyl) phenyl) ethyl (meth) acrylate, 2- (4-methoxyphenyl) ethyl (meth) acrylate, 2- (4-cyclohexylphenyl) ethyl (meth) acrylate To 2- (2-chlorophenyl) ethyl (meth) acrylate, 2- (3-chlorophenyl) ethyl (meth) acrylate, and 2- (4-chlorophenyl) (Meth) acrylate, 2- (4-bromophenyl) ethyl (meth) acrylate, 2- (3-phenylphenyl) ethyl (meth) acrylate, and 2- (4-benzylphenyl) ethyl (meth) Acrylate, these combinations, etc. can be illustrated. For example, cyclohexyl (meth) acrylate, phenyl (meth) acrylate and the like can be used.

In embodiments, the aromatic or cycloaliphatic (meth) acrylic monomer may be included in 10 to 90% by weight, for example 20 to 80% by weight of 100% by weight of the total monomer mixture. In the above range, the thermoplastic resin composition may have excellent transparency, scratch resistance, and the like.

(b2) monofunctional unsaturated monomers

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

In embodiments, the monofunctional unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( Meta) acrylic acid, maleic anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, monoglycerol (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile , Allyl glycidyl ether, glycidyl (meth) acrylate, styrene, alpha-methylstyrene and the like can be exemplified. For example, methyl (meth) acrylate etc. can be used.

In embodiments, the monofunctional unsaturated monomer may be included in 10 to 90% by weight, for example 20 to 80% by weight of 100% by weight of the total monomer mixture. In the above range, the thermoplastic resin composition may have excellent transparency, scratch resistance, and the like.

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 polymer production field, for example, bulk polymerization, emulsion polymerization, suspension polymerization, and the like. For example, it may be prepared through a manufacturing method including the step of polymerizing by adding a polymerization initiator to the monomer mixture.

In embodiments, the polymerization initiator is a radical polymerization initiator, the polymerization may be a suspension polymerization in consideration of the refractive index and the like, the suspension polymerization may be carried out in the presence of a suspension stabilizer and a chain transfer agent. That is, a reaction mixture can be prepared by adding a radical polymerization initiator and a chain transfer agent to the monomer, and the prepared reaction mixture can be added to an aqueous solution in which a suspension stabilizer is dissolved, thereby preparing a copolymer resin (suspension polymerization). In addition, at the time of the said superposition | polymerization, superposition | polymerization temperature and superposition | polymerization time can be adjusted suitably. The polymerization temperature may be 65 to 125 ° C., for example 70 to 120 ° C., and the polymerization time may be 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 embodiments, 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. In the above range, the thermoplastic resin composition may have excellent transparency, scratch resistance, and the like.

In an embodiment, the modified (meth) acrylic copolymer resin may have a refractive index of 1.495 to 1.590, measured at 20 ° C. using a refractive index meter (manufacturer: ATAGO, device name: Abbe refractometer DR-A1). For example, it may be 1.510 to 1.590. In the above range, the refractive index of the modified (meth) acrylic copolymer resin may be the same as or similar to that of the polycarbonate resin, so that transparency, compatibility, and the like of the thermoplastic resin composition may be excellent.

In embodiments, the modified (meth) acrylic copolymer resin may be included in 15 to 30% by weight, for example 15 to 25% by weight of the total 100% by weight of the thermoplastic resin composition. In the above range, the thermoplastic resin composition may have excellent transparency, impact resistance, scratch resistance, and the like.

(C) 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 impact resistance and the like without deteriorating transparency, scratch resistance, etc. of the thermoplastic resin composition. As possible, polysiloxane blocks and polycarbonate blocks having an average degree of polymerization of 30 to 45, for example 35 to 40, are included. When the average degree of polymerization of the polysiloxane block is less than 30, the impact resistance and the like may be lowered. When the average degree of polymerization is more than 45, the transparency and the like may be lowered.

In embodiments, the polycarbonate block may include a structural unit derived from the aforementioned polycarbonate resin (A), and the polysiloxane block may include a structural unit represented by the following Chemical Formula 2.

[Formula 2]

In Formula 2, R ₃ and R ₄ are each independently a hydrogen atom, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C1 to C20 alkoxy group, C3 to C30 cycloalkyl group, C3 to C30 Cycloalkenyl group, C3 to C30 cycloalkynyl group, C6 to C30 aryl group, C6 to C30 aryloxy group, or NRR ', wherein R and R' are each independently a hydrogen atom or a C1 to C20 alkyl group , m (average degree of polymerization) is 30 to 45.

In an embodiment, the first polycarbonate-polysiloxane copolymer resin can be prepared according to conventional polycarbonate-polysiloxane copolymer production methods. For example, it can manufacture by making polysiloxane and diphenols (aromatic diol compound) containing the structural unit represented by the said Formula 2 react with precursors, such as a phosgene, a halogen formate, and a carbonic acid diester. The reaction can be carried out by a conventional polymerization method such as interfacial polymerization, melt polymerization, for example, it can be carried out by interfacial polymerization using phosgene.

In an embodiment, the first polycarbonate-polysiloxane copolymer resin comprises 1 to 10 weight percent polysiloxane blocks, for example 1 to 7 weight percent, specifically 4 to 6 weight percent and 90 to 99 weight percent polycarbonate blocks, eg For example, it may include 93 to 99% by weight, specifically 94 to 96% by weight. In the above range, the impact resistance and the like of the thermoplastic resin composition may be excellent.

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

In embodiments, the first polycarbonate-polysiloxane copolymer resin may be included in 40 to 75% by weight, for example 45 to 70% by weight of the total 100% by weight of the thermoplastic resin composition. In the above range, the thermoplastic resin composition may have excellent transparency, impact resistance, scratch resistance, and the like.

(D) 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 impact resistance and the like without deterioration of transparency, scratch resistance, etc. of the thermoplastic resin composition. As possible, polysiloxane blocks and polycarbonate blocks having an average degree of polymerization of 70 to 100, for example 75 to 95, are included. If the average degree of polymerization of the polysiloxane block is less than 70, impact resistance may be lowered. If the average degree of polymerization is more than 100, heat resistance, scratch resistance, etc. may be lowered.

In embodiments, the polycarbonate block may include a structural unit derived from the aforementioned polycarbonate resin (A), and the polysiloxane block may include a structural unit represented by the following Chemical Formula 3.

[Formula 3]

In Formula 3, R ₅ and R ₆ are each independently a hydrogen atom, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C1 to C20 alkoxy group, C3 to C30 cycloalkyl group, C3 to C30 Cycloalkenyl group, C3 to C30 cycloalkynyl group, C6 to C30 aryl group, C6 to C30 aryloxy group, or NRR ', wherein R and R' are each independently a hydrogen atom or a C1 to C20 alkyl group , n (average degree of polymerization) is 70 to 100.

In an embodiment, the second polycarbonate-polysiloxane copolymer resin can be prepared according to conventional polycarbonate-polysiloxane copolymer production methods. For example, it can manufacture by making polysiloxane and diphenols (aromatic diol compound) containing the structural unit represented by the said Formula (3) react with precursors, such as a phosgene, a halogen formate, and carbonic acid diester. The reaction can be carried out by a conventional polymerization method such as interfacial polymerization, melt polymerization, for example, it can be carried out by interfacial polymerization using phosgene.

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

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

In embodiments, the second polycarbonate-polysiloxane copolymer resin may be included in 5 to 25% by weight, for example 7 to 20% by weight of the total 100% by weight of the thermoplastic resin composition. In the above range, the thermoplastic resin composition may have excellent transparency, impact resistance, scratch resistance, and the like.

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

The thermoplastic resin composition according to an embodiment of the present invention may further include an additive such as a release agent, a lubricant, a nucleating agent, a plasticizer, a heat stabilizer, a light stabilizer, a flame retardant, a flame retardant aid, an antidropping agent, an antioxidant, a mixture thereof, and the like.

In an embodiment, as the additive, an additive used in a conventional thermoplastic resin composition may be used without limitation. For example, the additives include mold release agents such as polyethylene wax, fluorine-containing polymer, silicone oil, metal salt of stearyl acid, metal salt of montanic acid and montanic acid ester wax; Nucleating agents such as clay and talc; Antioxidants such as hindered phenol compounds; Mixtures thereof and the like may be used, but are 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 pellets which are mixed with the above components and melt-extruded at 200 to 280 ° C, for example, 250 to 260 ° C, using a conventional twin screw extruder.

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

In one embodiment, the thermoplastic resin composition has an Izod impact strength of 15 kgf · cm / cm or more, for example, measured in accordance with ASTM D256 for a 1/8 ”thick specimen with a weld-line in the middle of the specimen. 20 to 50 kgf cm / cm.

In embodiments, the thermoplastic resin composition has a pencil hardness of H or more 2.5 mm thick specimen measured according to JIS K5401, the scratch width by BSP (Ball-type Scratch Profile) test is 290 ㎛ or less, for example 250 To 280 μm.

The molded article according to the present invention is formed from the thermoplastic resin composition. For example, the thermoplastic resin composition may be manufactured through various molding methods such as injection molding, extrusion molding, vacuum molding, casting molding, and the like. Such molding methods are well known by those skilled in the art. Since the molded article is excellent in transparency, impact resistance, scratch resistance, balance of physical properties, and the like, it is useful as an interior / exterior material of an automotive part or an electric and electronic product. In particular, it can be used for interior and exterior materials of mobile phones, notebook computers, etc., without a clear coating process.

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

Example

Hereinafter, the specification of each component used in the Example and the comparative example is as follows.

(A) polycarbonate resin

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

(B) 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% by weight of methyl methacrylate and 35% by weight of phenyl methacrylate by a conventional suspension polymerization method was used. It was.

(C) first polycarbonate-polysiloxane copolymer resin

A polycarbonate-polysiloxane copolymer resin (manufacturer: Idemitsu Kosan, product name: FC1760) having an average polymerization degree of polysiloxane block of 40 was used (polysiloxane block: 6 wt%, polycarbonate block 94 wt%, weight average molecular weight: 21,000 g / mol).

(D) Second Polycarbonate-Polysiloxane Copolymer Resin

Polycarbonate-polysiloxane copolymer resin (manufacturer: Idemitsu Kosan, product name: FG1760) having an average polymerization degree of polysiloxane block of 90 was used (polysiloxane block: 6 wt%, polycarbonate block 94 wt%, weight average molecular weight: 21,000 g / mol).

(E) Polycarbonate-Polysiloxane Copolymer Resin

Polycarbonate-polysiloxane copolymer resin having an average degree of polymerization of polysiloxane blocks of 55 was used (polysiloxane block: 6 wt%, polycarbonate block 94 wt%, weight average molecular weight: 21,000 g / mol).

Examples 1 to 3 and Comparative Examples 1 to 4

Each of the components was added in an amount as described in Table 1 below, followed by extrusion at 250 ° C. to prepare pellets. Extrusion was performed using a twin screw extruder having a diameter of L / D = 36, 45 mm, the prepared pellets were dried at 100 ℃ for 4 hours or more, and then injected in a 6 oz injection machine (molding temperature 300 ℃) to prepare a specimen. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Table 1 below.

Property measurement method

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

(2) Light transmittance (unit:%): According to ASTM D1003, the light transmittance (total light transmittance: total light transmittance) of a 2.0 mm thick specimen was measured using a haze meter (manufacturer: Nippon Denshoku, product name: NDH 5000W). Measured.

(3) Weld Izod impact strength (unit: kgfcm / cm): 1/8 "thick specimen with weld-line in the middle of the specimen in an un-notched state, in accordance with ASTM D256. Izod impact strength was measured.

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

(5) Scratch width (unit: micrometer): It measured according to the BSP (Ball-type Scratch Profile) test method. Scratch lengths of 10 to 20 mm were applied to a 90 mm × 50 mm × 2.5 mm specimen surface using a 0.7 mm diameter spherical metal tip with a load of 1,000 g and a scratch speed of 75 mm / min. The profile of the applied scratch was surface scanned with a metal stylus tip 2 mm in diameter using Ambios' Contact Surface Profile Analyzer (XP-1) to determine 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 (kgfcm / cm) 25 25 27 44 10 26 12 Pencil hardness H H H F H H H Scratch width (μm) 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, balance of these properties and the like.

On the other hand, in Comparative Example 1 in which the first polycarbonate-polysiloxane copolymer resin (C) was not used, it was found that transparency (haze, light transmittance), scratch resistance, and the like were deteriorated, and the second polycarbonate-polysiloxane air In the case of the comparative example 2 which does not use copolymer resin (D), it turns out that impact resistance fell. In addition, in the case of Comparative Example 3 using a polycarbonate-polysiloxane copolymer resin (E) in which the average degree of polymerization of the polysiloxane block instead of the first polycarbonate-polysiloxane copolymer resin (C) was outside the scope of the present invention, transparency was lowered. As can be seen, in the case of Comparative Example 4 using a polycarbonate-polysiloxane copolymer resin (E) having an average degree of polymerization of the polysiloxane block instead of the second polycarbonate-polysiloxane copolymer resin (D) outside the scope of the present invention, impact resistance It can be seen that the back is deteriorated.

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

Claims (13)

7 to 20 wt% polycarbonate resin;
15 to 25% by weight of modified (meth) acrylic copolymer resin;
45 to 70 wt% of a first polycarbonate-polysiloxane copolymer resin; And
7 to 20 wt% of a second polycarbonate-polysiloxane copolymer resin,
The first polycarbonate-polysiloxane copolymer resin has an average degree of polymerization of polysiloxane blocks of 30 to 45, the second polycarbonate-polysiloxane copolymer resin has an average degree of polymerization of polysiloxane blocks of 75 to 95, and the first polycarbonate- The weight ratio of the polysiloxane copolymer resin and the second polycarbonate-polysiloxane copolymer resin is 1: 0.1 to 1: 0.4,
The thermoplastic resin composition, characterized in that the haze of the 2.0 mm thick specimen measured according to ASTM D1003 is 0.5 to 1.4% and the light transmittance is 92 to 99%.
delete delete The thermoplastic resin 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 Formula 1 below. Composition:
[Formula 1]

In Formula 1, 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 Is a sulfur atom, a is an integer from 0 to 10 and b is 0 or 1;
The method of claim 4, wherein the monofunctional unsaturated monomer is selected from the group consisting of alkyl (meth) acrylate having 1 to 8 carbon atoms; Unsaturated carboxylic acids including (meth) acrylic acid; Acid anhydrides including maleic anhydride; (Meth) acrylate containing a hydroxyl group; (Meth) acrylamide; Unsaturated nitrile compounds; Allyl glycidyl ether; Glycidyl (meth) acrylate; And at least one of aromatic vinyl compounds.
The thermoplastic resin composition of 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 wt% of polysiloxane blocks and 90 to 99 wt% of polycarbonate blocks.
The thermoplastic resin composition of claim 1, wherein the second polycarbonate-polysiloxane copolymer resin comprises 1 to 10 wt% of polysiloxane blocks and 90 to 99 wt% of polycarbonate blocks.
The thermoplastic resin composition of claim 1, wherein the first and second polycarbonate-polysiloxane copolymer resins have a weight average molecular weight of 15,000 g / mol to 50,000 g / mol.
delete 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 measured according to ASTM D256 for a 1/8 ”thick specimen having a weld line in the middle of the specimen. .
According to claim 1, wherein the thermoplastic resin composition has a pencil hardness of H or more 2.5 mm thick specimen measured according to JIS K5401, the scratch width by the BSP (Ball-type Scratch Profile) test is 290 ㎛ or less Thermoplastic resin composition.
A molded article formed from the thermoplastic resin composition according to any one of claims 1, 4, 9, 11, and 12.