KR20230032027A - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

A thermoplastic resin composition of the present invention contains 100 parts by weight of a rubber-modified aromatic vinyl copolymer resin; 30 to 60 parts by weight of a polyester resin; 70 to 100 parts by weight of a phosphorus-nitrogen flame retardant mixture containing piperazine pyrophosphate and melamine pyrophosphate; 1 to 10 parts by weight of titanium dioxide; and 0.03 to 0.3 parts by weight of an aliphatic sulfonic acid metal salt. The thermoplastic resin composition is excellent in flame retardancy, impact resistance, balance of physical properties thereof, and the like.

Description

Thermoplastic resin composition and molded article manufactured therefrom

The present invention relates to a thermoplastic resin composition and a molded article made therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent flame retardancy, impact resistance, balance of physical properties thereof, and a molded article manufactured therefrom.

Aromatic vinyl-based resins (rubber-modified aromatic vinyl-based copolymer resins) such as acrylonitrile-butadiene-styrene copolymer (ABS) resins have excellent mechanical properties and moldability, and are widely used in various fields. However, the aromatic vinyl-based resin has a problem in that it has no flame resistance, and when a flame is ignited by an external ignition factor, the resin itself decomposes to provide raw materials to expand and sustain combustion.

As a method for imparting flame retardancy to an aromatic vinyl resin, there is an addition-type flame retardation method in which a flame retardant and a flame retardant auxiliary are added. Typically, flame retardation is achieved by adding a flame retardant containing an inactive element such as halogen or phosphorus. However, in the case of halogen-based flame retardants, their use is gradually limited due to emission of harmful gases and environmental issues.

However, when a phosphorus-based flame retardant, which is a non-halogen flame retardant, is applied to an aromatic vinyl-based resin, the flame retardance is V-2 level, and there is a problem in that flame retardancy performance is greatly reduced compared to halogen-based additives. In addition, when the phosphorus-nitrogen-based flame retardant is applied to an aromatic vinyl-based resin, impact resistance is greatly reduced, making it difficult to apply it to actual products.

Therefore, even when a non-halogen flame retardant is applied to an aromatic vinyl resin composition, it is necessary to develop a thermoplastic resin composition having excellent flame retardancy, impact resistance, and balance of physical properties thereof.

The background art of the present invention is disclosed in Korean Patent Publication No. 10-2010-0068954 and the like.

An object of the present invention is to provide a thermoplastic resin composition excellent in flame retardancy, impact 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 all be achieved by the present invention described below.

1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition includes 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; 30 to 60 parts by weight of a polyester resin; 70 to 100 parts by weight of a phosphorus-nitrogen flame retardant mixture containing piperazine pyrophosphate and melamine pyrophosphate; 1 to 10 parts by weight of titanium dioxide; and 0.03 to 0.3 parts by weight of an aliphatic sulfonic acid metal salt.

2. In the first embodiment, the rubber-modified aromatic vinyl-based copolymer resin may include a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin.

3. In the embodiment 1 or 2, the rubber-modified vinyl-based graft copolymer may be obtained by graft-polymerizing a rubbery polymer with a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.

4. In the embodiments 1 to 3, the polyester resin may be a glycol-modified polyester resin having a content of 20 to 100 mol% of 1,4-cyclohexanedimethanol in the total diol component.

5. In the above 1 to 4 embodiments, the phosphorus-nitrogen-based flame retardant may include 45 to 70% by weight of the piperazine pyrophosphate, 25 to 50% by weight of the melamine pyrophosphate, and 3 to 15% by weight of melamine phosphate there is.

6. In the embodiments 1 to 5, the aliphatic sulfonic acid metal salt may be represented by Formula 1 below:

[Formula 1]

In Formula 1, M is lithium (Li), sodium (Na) or potassium (K), and n is an integer having 1 to 10 carbon atoms.

7. In embodiments 1 to 6, the weight ratio of the phosphorus-nitrogen-based flame retardant and the titanium dioxide may be 1:0.02 to 1:0.1.

8. In the embodiments 1 to 7, the weight ratio of the phosphorus-nitrogen-based flame retardant and the aliphatic sulfonic acid metal salt may be 1:0.001 to 1:0.006.

9. In the embodiments 1 to 8, the weight ratio of the titanium dioxide and the aliphatic sulfonic acid metal salt may be 1:0.01 to 1:0.08.

10. In the embodiments 1 to 9, the thermoplastic resin composition may have a flame retardancy of V-0 or more in a 1.5 mm thick injection-molded specimen measured by the UL94 vertical test method, and a 1.5 mm thick injection molding material measured by the UL94 5V burning test method The flame retardance of the specimen may be 5VB or more.

11. In the embodiments 1 to 10, the thermoplastic resin composition may have a notched Izod impact strength of 6 to 10 kgf·cm/cm of a 1/4″ thick specimen measured according to ASTM D256.

12. Another aspect of the invention relates to molded articles. The molded article is characterized in that it is formed from the thermoplastic resin composition according to any one of the above 1 to 11.

The present invention has the effect of providing a thermoplastic resin composition excellent in flame retardancy, impact resistance, balance of physical properties thereof, and molded articles formed therefrom.

Hereinafter, the present invention will be described in detail as follows.

The thermoplastic resin composition according to the present invention includes (A) a rubber-modified aromatic vinyl-based copolymer resin; (B) a polyester resin; (C) a phosphorus-nitrogen based flame retardant; (D) titanium dioxide; and (E) an aliphatic sulfonic acid metal salt.

In this specification, "a to b" representing a numerical range is defined as "≥a and ≤b".

(A) rubber-modified aromatic vinyl-based copolymer resin

The rubber-modified aromatic vinyl-based copolymer resin according to one embodiment of the present invention can improve the mechanical properties, processability, appearance characteristics, etc. of a thermoplastic resin composition, and includes (A1) a rubber-modified vinyl-based graft copolymer and (A2) An aromatic vinyl-based copolymer resin may be included.

(A1) Rubber-modified vinyl-based graft copolymer

The rubber-modified vinyl-based graft copolymer according to one embodiment of the present invention may be obtained by graft polymerization of a rubbery polymer with a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer. For example, the rubber-modified vinyl-based graft copolymer can be obtained by graft polymerization of a monomer mixture containing an aromatic vinyl-based monomer and a cyanide-based vinyl monomer on a rubbery polymer, and, if necessary, processability and Graft polymerization may be performed by further including a monomer imparting heat resistance. The polymerization may be performed by a known polymerization method such as emulsion polymerization or suspension polymerization. In addition, the rubber-modified vinyl-based graft copolymer may form a core (rubber polymer)-shell (copolymer of monomer mixture) structure, but is not limited thereto.

In embodiments, the rubbery polymer includes diene-based rubber such as polybutadiene, poly(styrene-butadiene), and poly(acrylonitrile-butadiene), and saturated rubber obtained by adding hydrogen to the diene-based rubber, isoprene rubber, and having 2 to 2 carbon atoms. An alkyl (meth)acrylate rubber of 10, a copolymer of an alkyl (meth)acrylate of 2 to 10 carbon atoms and styrene, an ethylene-propylene-diene monomer terpolymer (EPDM), and the like can be exemplified. These may be applied alone or in combination of two or more. For example, diene-based rubber, (meth)acrylate rubber, and the like can be used, and specifically, butadiene-based rubber, butyl acrylate rubber, and the like can be used.

In embodiments, the rubbery polymer (rubber particle) may have an average particle size of 0.05 to 6 μm, for example, 0.15 to 4 μm, specifically 0.25 to 3.5 μm. Within the above range, the thermoplastic resin composition may have excellent impact resistance and appearance characteristics. Here, the average particle size (z-average) of the rubbery polymer (rubber particle) can be measured using a light scattering method in a latex state. Specifically, the rubbery polymer latex is filtered through a mesh to remove the coagulum generated during polymerization of the rubbery polymer, and a solution obtained by mixing 0.5 g of latex and 30 ml of distilled water is poured into a 1,000 ml flask and filled with distilled water to prepare a sample. , 10 ml of the sample is transferred to a quartz cell, and the average particle size of the rubbery polymer can be measured with a light scattering particle size meter (Malvern, nano-zs).

In embodiments, the content of the rubbery polymer may be 20 to 70% by weight, for example, 25 to 60% by weight, based on 100% by weight of the rubber-modified vinyl-based graft copolymer, and the monomer mixture (aromatic vinylic monomer and including the vinyl cyanide-based monomer) may be 30 to 80% by weight, for example, 40 to 75% by weight, based on 100% by weight of the entire rubber-modified vinyl-based graft copolymer. Within the above range, the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.

In embodiments, the aromatic vinyl-based monomer may be graft-copolymerized with the rubbery polymer, and may include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinylxylene, Monochloro styrene, dichloro styrene, dibromo styrene, vinyl naphthalene, etc. can be illustrated. These may be used alone or in combination of two or more. The content of the aromatic vinyl-based monomer may be 10 to 90% by weight, for example, 40 to 90% by weight based on 100% by weight of the monomer mixture. Within the above range, the processability and impact resistance of the thermoplastic resin composition may be excellent.

In specific embodiments, the vinyl cyanide-based monomer is copolymerizable with the aromatic vinyl-based monomer, such as acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. can be exemplified. These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide-based monomer may be 10 to 90% by weight, for example, 10 to 60% by weight, based on 100% by weight of the monomer mixture. Within the above range, the thermoplastic resin composition may have excellent chemical resistance and mechanical properties.

In specific examples, monomers for imparting processability and heat resistance may include (meth)acrylic acid, maleic anhydride, and N-substituted maleimide, but are not limited thereto. When using a monomer for imparting processability and heat resistance, the content thereof may be 15% by weight or less, for example, 0.1 to 10% by weight based on 100% by weight of the monomer mixture. Within the above range, processability and heat resistance may be imparted to the thermoplastic resin composition without deterioration of other physical properties.

In a specific embodiment, the rubber-modified vinyl-based graft copolymer is a copolymer (g-ABS) in which a styrene monomer, which is an aromatic vinyl compound, and an acrylonitrile monomer, which is a vinyl cyanide compound, are grafted onto a butadiene-based rubbery polymer (g-ABS), butyl acryl An acrylate-styrene-acrylonitrile graft copolymer (g-ASA), which is a copolymer in which a styrene monomer, which is an aromatic vinyl compound, and an acrylonitrile monomer, which is a vinyl cyanide compound, are grafted onto a rubbery latex polymer, can be exemplified. there is.

In embodiments, the rubber-modified vinyl-based graft copolymer (A1) may be included in an amount of 10 to 65% by weight, for example, 20 to 60% by weight, based on 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin. Within the above range, the thermoplastic resin composition may have excellent impact resistance and molding processability.

(A2) Aromatic vinyl copolymer resin

The aromatic vinyl-based copolymer resin according to one embodiment of the present invention may be an aromatic vinyl-based copolymer resin used in conventional rubber-modified aromatic vinyl-based copolymer resins. For example, the aromatic vinyl-based copolymer resin may be a polymer of a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.

In embodiments, the aromatic vinyl-based copolymer resin may be obtained by mixing an aromatic vinyl-based monomer, a vinyl cyanide-based monomer, and the like, and then polymerizing them, and the polymerization is known polymerization such as emulsion polymerization, suspension polymerization, and bulk polymerization. method can be performed.

In embodiments, the aromatic vinyl monomers include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, and dibromostyrene. , vinyl naphthalene, etc. can be used. These may be applied alone or in combination of two or more. The content of the aromatic vinyl-based monomer may be 20 to 90% by weight, for example, 30 to 80% by weight based on 100% by weight of the entire aromatic vinyl-based copolymer resin. Within the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity, appearance characteristics, and the like.

In specific examples, examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, and fumaronitrile. These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide-based monomer may be 10 to 80% by weight, for example, 20 to 70% by weight, based on 100% by weight of the entire aromatic vinyl-based copolymer resin. Within the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity, heat resistance, appearance, and the like.

In embodiments, the aromatic vinyl-based copolymer resin may be polymerized by further including a monomer for imparting processability and heat resistance to the monomer mixture. Examples of the monomer for imparting processability and heat resistance include (meth)acrylic acid and N-substituted maleimide, but are not limited thereto. When using a monomer for imparting processability and heat resistance, the content thereof may be 15% by weight or less, for example, 0.1 to 10% by weight based on 100% by weight of the monomer mixture. Within the above range, processability and heat resistance may be imparted to the thermoplastic resin composition without deterioration of other physical properties.

In embodiments, the aromatic vinyl-based copolymer resin may have a weight average molecular weight (Mw) of 10,000 to 300,000 g/mol, for example, 20,000 to 200,000 g/mol, as measured by gel permeation chromatography (GPC). Within the above range, the thermoplastic resin composition may have excellent mechanical strength and molding processability.

In embodiments, the aromatic vinyl-based copolymer resin (A2) may be included in 35 to 90% by weight, for example, 40 to 80% by weight, based on 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin (A). Within the above range, the thermoplastic resin composition may have excellent impact resistance, molding processability, appearance characteristics, and the like.

(B) polyester resin

The polyester resin according to one embodiment of the present invention is capable of improving the self-extinguishing properties of the thermoplastic resin composition, improving flame retardancy, etc., and the 1,4-cyclohexanedimethanol content of the total diol component is 20 to 100 mol% A phosphorus glycol-modified polyester resin can be used.

In embodiments, the glycol-modified polyester resin is a dicarboxylic acid component including terephthalic acid and 20 to 100 mol% of 1,4-cyclohexanedimethanol (CHDM), for example, 35 to 100 mol% and 2 to 10 carbon atoms It can be prepared by polycondensation of a diol component containing 80 mol% or less of the alkylene glycol of 6, for example, 65 mol% or less. Within the above range, the thermoplastic resin composition may have excellent flame retardancy and impact resistance.

In embodiments, the polyester resin may have an intrinsic viscosity [η] of 0.5 to 1.5 dl/g, for example, 0.6 to 1.3 dl/g, as measured using an o-chlorophenol solvent at 25°C. Within the above range, the thermoplastic resin composition may have excellent flame retardancy and mechanical properties.

In embodiments, the polyester resin may be included in an amount of 30 to 60 parts by weight, for example, 35 to 55 parts by weight, based on 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. If the content of the polyester resin is less than 30 parts by weight based on 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, flame retardancy of the thermoplastic resin composition may deteriorate, and if it exceeds 60 parts by weight, the thermoplastic resin There is a possibility that the impact resistance of the composition and the like may decrease.

(C) phosphorus-nitrogen flame retardant

The phosphorus-nitrogen-based flame retardant according to one embodiment of the present invention is applied to a rubber-modified aromatic vinyl-based copolymer resin and a polyester resin together with titanium dioxide and an aliphatic sulfonic acid metal salt to facilitate char formation of the thermoplastic resin composition. And, as capable of greatly improving the flame retardancy of the thermoplastic resin composition to the level of 5VB, it includes piperazine pyrophosphate and melamine pyrophosphate.

In embodiments, the phosphorus-nitrogen-based flame retardant may include piperazine pyrophosphate melamine, pyrophosphate and melamine phosphate.

In embodiments, the piperazine pyrophosphate, melamine pyrophosphate and melamine phosphate may be used without limitation piperazine pyrophosphate, melamine pyrophosphate and melamine phosphate used in conventional flame retardant thermoplastic resin compositions.

In embodiments, the phosphorus-nitrogen-based flame retardant is 45 to 70% by weight of the piperazine pyrophosphate; For example, 50 to 60% by weight, 25 to 50% by weight of the melamine pyrophosphate; eg 30 to 40% by weight, and 3 to 15% by weight of the melamine phosphate; For example, it may include 5 to 10% by weight. Within the above range, the thermoplastic resin composition may have excellent flame retardancy, impact resistance, balance of physical properties thereof, and the like.

In embodiments, the phosphorus-nitrogen-based flame retardant may be included in an amount of 70 to 100 parts by weight, for example, 75 to 95 parts by weight, based on 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin. If the content of the phosphorus-nitrogen-based flame retardant is less than 70 parts by weight based on 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, there is a concern that the flame retardancy of the thermoplastic resin composition may be reduced, and if it exceeds 100 parts by weight, There is a possibility that the impact resistance and the like of the thermoplastic resin composition may decrease.

(D) titanium dioxide

Titanium dioxide (TiO ₂ ) according to an embodiment of the present invention is applied to a rubber-modified aromatic vinyl-based copolymer resin and a polyester resin together with a phosphorus-nitrogen-based flame retardant and an aliphatic sulfonic acid metal salt, thereby improving mechanical properties such as impact resistance of the thermoplastic resin composition. It is possible to minimize the deterioration of physical properties and greatly improve the flame retardancy of the thermoplastic resin composition to the level of 5VB.

In embodiments, the average particle diameter (D50) of the titanium dioxide may be 0.01 to 2 μm, for example, 0.05 to 0.7 μm. Within the above range, the thermoplastic resin composition may have excellent impact resistance and flame retardancy. Here, the average particle diameter (D50) is a number average particle diameter measured by a particle size analyzer (Beckman Coulter Co., LS 13 320), and is a specific value as D50 (particle diameter at the point where the distribution rate is 50%).

In embodiments, the titanium dioxide may be included in an amount of 1 to 10 parts by weight, for example, 2 to 9 parts by weight, based on 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin. When the content of the titanium dioxide is less than 1 part by weight based on 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, there is a concern that the flame retardancy of the thermoplastic resin composition may decrease, and when it exceeds 10 parts by weight, the thermoplastic resin composition There is a risk that the impact resistance of the

In embodiments, the weight ratio (C:D) of the phosphorus-nitrogen-based flame retardant (C) and the titanium dioxide (D) may be 1:0.02 to 1:0.1, for example, 1:0.022 to 1:0.093. Within the above range, the thermoplastic resin composition may have excellent flame retardancy, impact resistance, balance of physical properties thereof, and the like.

(E) aliphatic sulfonic acid metal salt

The aliphatic sulfonic acid metal salt according to an embodiment of the present invention is applied to a rubber-modified aromatic vinyl-based copolymer resin and a polyester resin together with a phosphorus-nitrogen-based flame retardant and titanium dioxide to reduce mechanical properties such as impact resistance of a thermoplastic resin composition. It can be minimized and greatly improve the flame retardancy of the thermoplastic resin composition to the level of 5VB, and can be represented by Formula 1 below.

[Formula 1]

In Formula 1, M is lithium (Li), sodium (Na) or potassium (K), and n is an integer having 1 to 10 carbon atoms.

In embodiments, the aliphatic sulfonic acid metal salt is a metal salt of perfluoromethanesulfonic acid, a metal salt of perfluoroethanesulfonic acid, a metal salt of perfluoropropanesulfonic acid, a metal salt of perfluorobutanesulfonic acid, a metal salt of perfluoropentanesulfonic acid, A metal salt of perfluorohexanesulfonic acid, a metal salt of perfluoroheptanesulfonic acid, and the like can be exemplified. You may use these in combination of 1 type or more. In addition, suitable metals used in the metal salt of the perfluoroalkanesulfonic acid include Group I metals (alkali metals) such as sodium and potassium. Among these, the potassium salt of perfluorobutanesulfonic acid, etc. are especially preferable.

In embodiments, the aliphatic sulfonic acid metal salt may have an average particle diameter of 100 to 400 μm, for example, 150 to 350 μm. Within the above range, the thermoplastic resin composition may have excellent impact resistance and flame retardancy.

In embodiments, the aliphatic sulfonic acid metal salt may be included in an amount of 0.03 to 0.3 parts by weight, for example, 0.05 to 0.25 parts by weight, based on 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin. If the content of the aliphatic sulfonic acid metal salt is less than 0.03 parts by weight based on 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, there is a risk of deterioration in flame retardancy of the thermoplastic resin composition, and if it exceeds 0.3 parts by weight, the thermoplastic resin There is a possibility that the impact resistance of the composition and the like may decrease.

In embodiments, the weight ratio (C:E) of the phosphorus-nitrogen-based flame retardant (C) and the aliphatic sulfonic acid metal salt (E) may be 1:0.001 to 1:0.006, for example, 1:0.0015 to 1:0.0059. . Within the above range, the thermoplastic resin composition may have excellent flame retardancy, impact resistance, balance of physical properties thereof, and the like.

In embodiments, the weight ratio (D:E) of the titanium dioxide (D) and the aliphatic sulfonic acid metal salt (E) may be 1:0.01 to 1:0.08, for example, 1:0.01 to 1:0.075. Within the above range, the thermoplastic resin composition may have excellent flame retardancy, impact resistance, balance of physical properties thereof, and the like.

The thermoplastic resin composition according to one embodiment of the present invention may further include additives included in conventional thermoplastic resin compositions. Examples of the additive include impact modifiers, antioxidants, anti-drip agents, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, mixtures thereof, and the like, but are not limited thereto. When using the additive, the content thereof may be 0.001 to 40 parts by weight, for example, 0.1 to 10 parts by weight, based on 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin.

The thermoplastic resin composition according to one embodiment of the present invention may be in the form of pellets obtained by mixing the components and melt-extruding them at 180 to 230° C., for example, 200 to 260° C., using a conventional twin-screw extruder.

In a specific example, the thermoplastic resin composition may have a flame retardance of V-0 or higher in a 1.5 mm thick injection-molded specimen measured by the UL94 vertical test method.

In one embodiment, the thermoplastic resin composition may have a flame retardance of 5VB or more in a 1.5 mm thick injection-molded specimen measured by the UL94 5V burning test method.

In embodiments, the thermoplastic resin composition has a notched Izod impact strength of a 1/4 "thick specimen measured in accordance with ASTM D256 of 6 to 10 kgf cm / cm, for example 6.3 to 8 kgf cm / cm can

A molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be manufactured in the form of pellets, and the manufactured pellets may be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such a molding method is well known to those skilled in the art to which the present invention belongs. The molded article is eco-friendly because it does not use a halogen-based flame retardant, and is useful as an interior and exterior material for electrical and electronic products because it has excellent flame retardancy, impact resistance, and balance of physical properties thereof.

Hereinafter, the present invention will be described in more detail through examples, but these examples are only for the purpose of explanation 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) rubber-modified aromatic vinyl-based copolymer resin

(A1) 45% by weight of a rubber-modified vinyl-based graft copolymer and (A2) 55% by weight of an aromatic vinyl-based copolymer resin were mixed and used.

(A1) Rubber-modified vinyl-based graft copolymer

A core-shell type graft copolymer (g-ABS) prepared by graft copolymerizing styrene and acrylonitrile (weight ratio: 75/25) with 55 wt% of butadiene rubber having an average particle size of 0.3 μm was used.

(A2) Aromatic vinyl copolymer resin

A SAN resin (weight average molecular weight: 125,000 g/mol) in which 78% by weight of styrene and 22% by weight of acrylonitrile were polymerized was used.

(B) polyester resin

A 1,4-cyclohexanedimethanol-modified polyester resin (manufacturer: SK Chemicals, product name: S2008) was used.

(C) phosphorus-nitrogen flame retardant

Piperazine pyrophosphate (Manufacturer: Hainan Zhongxin Chemical, Cas No.: 66034-17-1) 56% by weight; 36% by weight of melamine pyrophosphate (manufacturer: Budenheim, product name: Budit 311MPP); And 8% by weight of melamine phosphate (manufacturer: BASF, product name: Melapur® MP); a phosphorus-nitrogen-based flame retardant containing was used.

(D) Titanium dioxide (TiO ₂ , manufacturer: Cristal, product name: Tiona RCL 288) was used.

(E) sulfonic acid metal salt

(E1) Potassium perfluorobutane sulfonate (manufacturer: Wuhan chemical industry, product name: BU-C4K) was used.

(E2) Potassium diphenyl sulfone-3-sulfonate (manufacturer: SEAL SANDS CHEMICALS, product name: KSS) was used.

Examples 1 to 9 and Comparative Examples 1 to 9

After adding each of the above constituents in an amount as shown in Tables 1 and 2 below, pellets were prepared by extrusion at 210 °C. For extrusion, a twin-screw extruder with L/D = 44 and a diameter of 45 mm was used. After drying the pellets at 80 ° C for more than 4 hours, injection molding was performed in a 6 oz injection machine (molding temperature: 210 ° C, mold temperature: 60 ° C). Thus, specimens were prepared. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Tables 1 and 2 below.

How to measure physical properties

(1) Flame retardancy: The flame retardancy of the 1.5 mm thick injected specimen measured by the UL94 vertical test method was measured, and the 5VB flame retardancy of the 1.5 mm thick injected specimen measured by the UL94 5V burning test method was measured.

(2) Notched Izod impact strength (unit: kgf cm/cm): In accordance with ASTM D256, the notched Izod impact strength of a 1/4" thick specimen was measured.

Example One 2 3 4 5 6 7 8 9 (A) (parts by weight) 100 100 100 100 100 100 100 100 100 (B) (parts by weight) 35 43 55 43 43 43 43 43 43 (C) (parts by weight) 86 86 86 75 95 86 86 86 86 (D) (parts by weight) 5 5 5 5 5 2 8 5 5 (E1) (parts by weight) 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.05 0.25 (E2) (parts by weight) - - - - - - - - - flame retardancy V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Flame Retardant (5V) 5VB 5VB 5VB 5VB 5VB 5VB 5VB 5VB 5VB Notched Izod Impact Strength 7.3 7.0 6.4 7.7 6.3 7.4 6.5 7.2 6.5

comparative example One 2 3 4 5 6 7 8 9 (A) (parts by weight) 100 100 100 100 100 100 100 100 100 (B) (parts by weight) 25 65 43 43 43 43 43 43 43 (C) (parts by weight) 86 86 65 105 86 86 86 86 86 (D) (parts by weight) 5 5 5 5 0.5 15 5 5 5 (E1) (parts by weight) 0.15 0.15 0.15 0.15 0.15 0.15 0.01 0.4 - (E2) (parts by weight) - - - - - - - - 0.15 flame retardancy V-0 V-0 FAIL V-0 V-0 V-0 V-0 V-0 V-0 Flame Retardant (5V) FAIL 5VB FAIL 5VB FAIL 5VB FAIL 5VB FAIL Notched Izod Impact Strength 7.4 5.6 8.9 5.2 7.5 5.5 7.4 5.9 7.1

From the above results, it can be seen that the thermoplastic resin composition of the present invention is excellent in flame retardancy, impact resistance, balance of physical properties thereof, and the like.

On the other hand, when the polyester resin is applied below the content range of the present invention (Comparative Example 1), it can be seen that the flame retardancy of the thermoplastic resin composition is lowered, and when applied in excess of the content range of the present invention (Comparative Example 2 ), it can be seen that the impact resistance of the thermoplastic resin composition is lowered. When the phosphorus-nitrogen-based flame retardant of the present invention is applied below the content range of the present invention (Comparative Example 3), it can be seen that the flame retardancy of the thermoplastic resin composition is lowered, and when applied in excess of the content range of the present invention ( In Comparative Example 4), it can be seen that the impact resistance of the thermoplastic resin composition is lowered. When titanium dioxide is applied below the content range of the present invention (Comparative Example 5), it can be seen that the flame retardancy of the thermoplastic resin composition is lowered, and when applied in excess of the content range of the present invention (Comparative Example 6), thermoplastic It can be seen that the impact resistance of the resin composition is lowered. In addition, when the aliphatic sulfonic acid metal salt is applied below the content range of the present invention (Comparative Example 7), it can be seen that the flame retardancy of the thermoplastic resin composition is lowered, and when applied in excess of the content range of the present invention (Comparative Example 8 ), it can be seen that the impact resistance of the thermoplastic resin composition is reduced, and when potassium salt (E2) of diphenyl sulfone-3-sulfonic acid, which is an aromatic sulfonic acid metal salt, is applied instead of the aliphatic sulfonic acid metal salt of the present invention (Comparative Example 9) , it can be seen that the flame retardancy of the thermoplastic resin composition is lowered.

So far, the present invention has been looked at mainly through embodiments. Those skilled in the art to which the present invention pertains will be able to understand that the present invention can be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments are to be considered in an illustrative rather than a limiting sense. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the equivalent scope will be construed as being included in the present invention.

Claims (12)

100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin;
30 to 60 parts by weight of a polyester resin;
70 to 100 parts by weight of a phosphorus-nitrogen flame retardant mixture containing piperazine pyrophosphate and melamine pyrophosphate;
1 to 10 parts by weight of titanium dioxide; and
A thermoplastic resin composition comprising 0.03 to 0.3 parts by weight of an aliphatic sulfonic acid metal salt.
The thermoplastic resin composition according to claim 1, wherein the rubber-modified aromatic vinyl-based copolymer resin comprises a rubber-modified vinyl-based graft copolymer.
The thermoplastic resin composition according to claim 2, wherein the rubber-modified vinyl-based graft copolymer is obtained by graft polymerization of a rubbery polymer with a monomer mixture including an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer. .
The thermoplastic resin composition according to claim 1, wherein the polyester resin is a glycol-modified polyester resin having 20 to 100 mol% of 1,4-cyclohexanedimethanol in the total diol component.
The thermoplastic according to claim 1, wherein the phosphorus-nitrogen-based flame retardant comprises 45 to 70% by weight of the piperazine pyrophosphate, 25 to 50% by weight of the melamine pyrophosphate, and 3 to 15% by weight of melamine phosphate. resin composition.
The thermoplastic resin composition according to claim 1, wherein the aliphatic sulfonic acid metal salt is represented by Formula 1 below:
[Formula 1]

In Formula 1, M is lithium (Li), sodium (Na) or potassium (K), and n is an integer having 1 to 10 carbon atoms.
The thermoplastic resin composition according to claim 1, wherein the weight ratio of the phosphorus-nitrogen-based flame retardant and the titanium dioxide ranges from 1:0.02 to 1:0.1.
The thermoplastic resin composition according to claim 1, wherein the phosphorus-nitrogen flame retardant and the aliphatic sulfonic acid metal salt have a weight ratio of 1:0.001 to 1:0.006.
The thermoplastic resin composition according to claim 1, wherein the weight ratio of the titanium dioxide and the aliphatic sulfonic acid metal salt is 1:0.01 to 1:0.08.
The method of claim 1, wherein the thermoplastic resin composition has a flame retardance of V-0 or more of a 1.5 mm thick injection-molded specimen measured by the UL94 vertical test method, and a flame retardance of a 1.5 mm thick injection-molded specimen measured by the UL94 5V burning test method A thermoplastic resin composition, characterized in that 5VB or more.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a notched Izod impact strength of 6 to 10 kgf·cm/cm of a 1/4″ thick specimen measured according to ASTM D256.
A molded article characterized in that it is formed from the thermoplastic resin composition according to any one of claims 1 to 11.