KR102639840B1 - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

The thermoplastic resin composition of the present invention includes 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; 30 to 60 parts by weight of 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, and balance of physical properties.

Description

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

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

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

A method of imparting flame retardancy to an aromatic vinyl resin includes an additive flame retardant method that adds a flame retardant and a flame retardant auxiliary. Typically, flame retardancy is achieved by adding a flame retardant containing an inert element such as halogen or phosphorus. However, in the case of halogen-based flame retardants, the use is gradually being restricted due to harmful gas emissions and environmental issues.

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

Therefore, there is a need to develop a thermoplastic resin composition that has excellent flame retardancy, impact resistance, and balance of physical properties even when applying a non-halogen-based flame retardant to an aromatic vinyl resin composition.

The background technology of the present invention is disclosed in Korean Patent Publication No. 10-2010-0068954, etc.

The purpose of the present invention is to provide a thermoplastic resin composition with excellent flame retardancy, impact resistance, and balance of physical properties.

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 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 first or second embodiment, the rubber-modified vinyl-based graft copolymer may be a product obtained by graft polymerizing a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to a rubbery polymer.

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

5. In embodiments 1 to 4, the phosphorus-nitrogen 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 embodiments 1 to 5 above, the aliphatic sulfonic acid metal salt may be represented by the following formula (1):

[Formula 1]

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

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

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

9. In 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 embodiments 1 to 9, the thermoplastic resin composition may have a flame resistance of V-0 or higher for a 1.5 mm thick injection molded specimen measured by the UL94 vertical test method, and a 1.5 mm thick injection molded specimen measured by the UL94 5V burning test method. The flame resistance of the specimen may be 5VB or higher.

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

12. Another aspect of the present 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 items 1 to 11 above.

The present invention has the effect of providing a thermoplastic resin composition with excellent flame retardancy, impact resistance, balance of physical properties, etc., and a molded article 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) polyester resin; (C) phosphorus-nitrogen flame retardant; (D) titanium dioxide; and (E) aliphatic sulfonic acid metal salts.

In this specification, “a to b” indicating 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, and appearance properties of a thermoplastic resin composition, and includes (A1) a rubber-modified vinyl-based graft copolymer and (A2) It may include an aromatic vinyl-based copolymer resin.

(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 polymerizing a monomer mixture containing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to a rubbery polymer. For example, the rubber-modified vinyl-based graft copolymer can be obtained by graft polymerizing a monomer mixture containing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to a rubbery polymer. If necessary, the monomer mixture may be provided with processability and Graft polymerization can be performed by further including a monomer that provides heat resistance. The polymerization may be performed by known polymerization methods such as emulsion polymerization and 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 a specific example, the rubbery polymer includes diene-based rubbers such as polybutadiene, poly(styrene-butadiene), and poly(acrylonitrile-butadiene), saturated rubber obtained by adding hydrogen to the diene-based rubber, isoprene rubber, and carbon atoms of 2 to 2. Examples include a 10 alkyl (meth)acrylate rubber, a copolymer of an alkyl (meth)acrylate with 2 to 10 carbon atoms and styrene, and ethylene-propylene-diene monomer terpolymer (EPDM). These can be applied alone or in combination of two or more types. For example, diene-based rubber, (meth)acrylate rubber, etc. can be used, and specifically, butadiene-based rubber, butylacrylate rubber, etc. can be used.

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

In a specific example, 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 total rubber-modified vinyl graft copolymer, and the monomer mixture (aromatic vinyl monomer and The content of vinyl cyanide-based monomer (including vinyl cyanide monomer) may be 30 to 80% by weight, for example, 40 to 75% by weight, based on 100% by weight of the total rubber-modified vinyl-based graft copolymer. Within the above range, the thermoplastic resin composition may have excellent impact resistance, appearance characteristics, etc.

In a specific example, the aromatic vinyl monomer can be graft-copolymerized to the rubbery polymer, and includes styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinylxylene, Examples include monochlorostyrene, dichlorostyrene, dibromostyrene, and vinylnaphthalene. These can be used individually or in combination of two or more types. The content of the aromatic vinyl 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, impact resistance, etc. of the thermoplastic resin composition may be excellent.

In a specific example, the vinyl cyanide monomer is copolymerizable with the aromatic vinyl monomer, and includes acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, etc. It can be exemplified. These can be used individually or in combination of two or more types. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide 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, mechanical properties, etc.

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 to provide the processability and heat resistance, its content 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 can be imparted to the thermoplastic resin composition without deterioration of other physical properties.

In a specific example, the rubber-modified vinyl-based graft copolymer includes a copolymer (g-ABS) in which styrene monomer, an aromatic vinyl-based compound, and acrylonitrile monomer, a vinyl cyanide-based compound, are grafted onto a butadiene-based rubber polymer (g-ABS), butyl acrylic. Examples include acrylate-styrene-acrylonitrile graft copolymer (g-ASA), which is a copolymer in which styrene monomer, an aromatic vinyl compound, and acrylonitrile monomer, a vinyl cyanide compound, are grafted onto a latex-based rubbery polymer. there is.

In a specific example, the rubber-modified vinyl-based graft copolymer (A1) may be included in 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, molding processability, etc.

(A2) Aromatic vinyl-based 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 a specific example, the aromatic vinyl-based copolymer resin can be obtained by mixing aromatic vinyl-based monomers, vinyl cyanide-based monomers, etc., and then polymerizing them, and the polymerization may be performed through known polymerization such as emulsion polymerization, suspension polymerization, and bulk polymerization. It can be performed by this method.

In specific examples, the aromatic vinyl monomers include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, and dibromostyrene. , vinylnaphthalene, etc. can be used. These can be applied alone or in combination of two or more types. 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 aromatic vinyl-based copolymer resin. Within the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity, and appearance characteristics.

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

In a specific example, the aromatic vinyl-based copolymer resin may be polymerized by further including a monomer for providing processability and heat resistance to the monomer mixture. Monomers for providing the processability and heat resistance include (meth)acrylic acid and N-substituted maleimide, but are not limited thereto. When using a monomer to provide the processability and heat resistance, its content 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 can be imparted to the thermoplastic resin composition without deterioration of other physical properties.

In a specific example, 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 mechanical strength, molding processability, etc. of the thermoplastic resin composition may be excellent.

In a specific example, 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, and appearance characteristics.

(B) Polyester resin

The polyester resin according to one embodiment of the present invention can improve self-extinguishing properties of thermoplastic resin compositions and improve flame retardancy, etc., and the 1,4-cyclohexanedimethanol content of the total diol components is 20 to 100 mol%. Phosphorus glycol-modified polyester resin can be used.

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

In a specific example, 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-chloro phenol solvent at 25°C. Within the above range, the thermoplastic resin composition may have excellent flame retardancy and mechanical properties.

In a specific example, 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-based 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, there is a risk that the flame retardancy of the thermoplastic resin composition may decrease, and if it exceeds 60 parts by weight, the thermoplastic resin There is a risk that the impact resistance, etc. of the composition may decrease.

(C) Phosphorus-nitrogen flame retardants

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

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

In a specific example, the piperazine pyrophosphate, melamine pyrophosphate, and melamine phosphate may be used without limitation, including those used in conventional flame-retardant thermoplastic resin compositions.

In an embodiment, 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; for example 30 to 40% by weight, and 3 to 15% by weight of the melamine phosphate; For example, it may contain 5 to 10% by weight. Within the above range, the flame retardancy, impact resistance, and balance of physical properties of the thermoplastic resin composition may be excellent.

In an embodiment, the phosphorus-nitrogen 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 flame retardant is less than 70 parts by weight based on 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, there is a risk that the flame retardancy of the thermoplastic resin composition may be reduced, and if it exceeds 100 parts by weight, There is a risk that the impact resistance, etc. 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 rubber-modified aromatic vinyl-based copolymer resins and polyester resins along with phosphorus-nitrogen-based flame retardants and aliphatic sulfonic acid metal salts to improve mechanical properties such as impact resistance of thermoplastic resin compositions. Deterioration of physical properties can be minimized and the flame retardancy of thermoplastic resin compositions can be greatly improved to the 5VB level.

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

In a specific example, 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. If the content of titanium dioxide is less than 1 part by weight based on 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, there is a risk that the flame retardancy of the thermoplastic resin composition may decrease, and if it exceeds 10 parts by weight, the thermoplastic resin composition may There is a risk that impact properties, etc., may decrease.

In a specific example, the weight ratio (C:D) of the phosphorus-nitrogen 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 flame retardancy, impact resistance, and balance of physical properties of the thermoplastic resin composition may be excellent.

(E) Aliphatic sulfonic acid metal salts

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

[Formula 1]

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

In a specific example, the aliphatic sulfonic acid metal salt includes 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, Examples include metal salts of perfluorohexanesulfonic acid and metal salts of perfluoroheptanesulfonic acid. These may be used in combination of one or more types. 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 and the like are particularly preferable.

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

In a specific example, 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 that the flame retardancy of the thermoplastic resin composition may decrease, and if it exceeds 0.3 parts by weight, the thermoplastic resin may There is a risk that the impact resistance, etc. of the composition may decrease.

In a specific example, the weight ratio (C:E) of the phosphorus-nitrogen 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 flame retardancy, impact resistance, and balance of physical properties of the thermoplastic resin composition may be excellent.

In a specific example, 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 flame retardancy, impact resistance, and balance of physical properties of the thermoplastic resin composition may be excellent.

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 additives include, but are not limited to, impact modifiers, antioxidants, anti-dripping agents, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, and mixtures thereof. When using the additive, its content 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 a pellet obtained by mixing the above components and melt-extruding the mixture 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 resistance of V-0 or higher for a 1.5 mm thick injection specimen measured by the UL94 vertical test method.

In a specific example, the thermoplastic resin composition may have a flame resistance of 5VB or more for a 1.5 mm thick injection specimen measured by the UL94 5V burning test method.

In an embodiment, the thermoplastic resin composition has a notched Izod impact strength of a 1/4" thick specimen measured according to ASTM D256 of 6 to 10 kgf·cm/cm, for example, 6.3 to 8 kgf·cm/cm. You can.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition can be manufactured in the form of pellets, and the manufactured pellets can be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. This forming method is well known to those skilled in the art. The molded product is environmentally friendly as it does not use halogen-based flame retardants, and has excellent flame retardancy, impact resistance, and balance of physical properties, so it is useful as interior and exterior materials for electrical and electronic products.

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

Example

Hereinafter, the specifications of each component used in the examples and comparative examples are as follows.

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

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

(A1) Rubber-modified vinyl-based graft copolymer

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

(A2) Aromatic vinyl-based copolymer resin

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

(B) Polyester resin

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

(C) Phosphorus-nitrogen flame retardants

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); A phosphorus-nitrogen flame retardant containing 8% by weight of melamine phosphate (manufacturer: BASF, product name: Melapur®MP) was used.

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

(E) Sulfonic acid metal salts

(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

Each of the above components was added in the amounts shown in Tables 1 and 2 below, and then extruded at 210°C to prepare pellets. For extrusion, a twin-screw extruder with L/D = 44 and a diameter of 45 mm was used, and the manufactured pellets were dried at 80℃ for more than 4 hours and then injection molded in a 6 oz injection machine (molding temperature: 210℃, mold temperature: 60℃). A specimen was prepared. The physical properties of the manufactured 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 resistance: The flame resistance of a 1.5 mm thick injection sample was measured using the UL94 vertical test method, and the 5VB flame resistance of a 1.5 mm thick injection sample was measured using the UL94 5V burning test method.

(2) Notched Izod impact strength (unit: kgf·cm/cm): Based on ASTM D256, the notched Izod impact strength of the 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) (part 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 retardant 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) (part 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 retardant 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, and the balance of these physical properties.

On the other hand, when the polyester resin is applied in an amount less than the content range of the present invention (Comparative Example 1), it can be seen that the flame retardancy of the thermoplastic resin composition decreases, and when the polyester resin is applied in an amount exceeding the content range of the present invention (Comparative Example 2 ), it can be seen that the impact resistance of the thermoplastic resin composition decreases. When the phosphorus-nitrogen 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 decreases, and when applied exceeding the content range of the present invention ( In Comparative Example 4), it can be seen that the impact resistance, etc. of the thermoplastic resin composition decreases. When titanium dioxide is applied in an amount less than the content range of the present invention (Comparative Example 5), it can be seen that the flame retardancy of the thermoplastic resin composition decreases, and when it is applied in an amount exceeding the content range of the present invention (Comparative Example 6), the thermoplastic resin composition decreases. It can be seen that the impact resistance of the resin composition decreases. In addition, when the aliphatic sulfonic acid metal salt is applied in an amount less than the content range of the present invention (Comparative Example 7), it can be seen that the flame retardancy of the thermoplastic resin composition decreases, and when it is applied in an amount exceeding the content range of the present invention (Comparative Example 8) ), it can be seen that the impact resistance of the thermoplastic resin composition decreases, and when potassium salt (E2) of diphenyl sulfonic acid-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 decreases.

So far, the present invention has been examined focusing on the embodiments. A person skilled in the art to which the present invention pertains will understand that the present invention may be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered from an illustrative rather than a restrictive perspective. The scope of the present invention is indicated in the claims rather than the foregoing description, and all differences within the equivalent scope should be construed as being included in the present invention.

Claims (12)

100 parts by weight of rubber-modified aromatic vinyl-based copolymer resin;
30 to 60 parts by weight of 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 includes a rubber-modified vinyl-based graft copolymer.
The thermoplastic resin composition according to claim 2, wherein the rubber-modified vinyl-based graft copolymer is graft-polymerized with a rubbery polymer and 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 a 1,4-cyclohexanedimethanol content of 20 to 100 mol% of the total diol components.
The thermoplastic material according to claim 1, wherein the phosphorus-nitrogen 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 the following formula (1):
[Formula 1]

In Formula 1, M is lithium (Li), sodium (Na), or potassium (K), and n is an integer of 1 to 10 carbon atoms.
The thermoplastic resin composition according to claim 1, wherein the weight ratio of the phosphorus-nitrogen flame retardant and the titanium dioxide is 1:0.02 to 1:0.1.
The thermoplastic resin composition according to claim 1, wherein the weight ratio of the phosphorus-nitrogen flame retardant and the aliphatic sulfonic acid metal salt is 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 retardancy of V-0 or higher for a 1.5 mm thick injection sample measured by the UL94 vertical test method, and a flame retardancy of a 1.5 mm thick injection sample measured by the UL94 5V burning test method. A thermoplastic resin composition characterized in that it is 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 for a 1/4" thick specimen measured according to ASTM D256.
A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 11.