WO2021201444A1 - Thermoplastic resin composition and molded article formed therefrom - Google Patents

Abstract

The thermoplastic resin composition of the present invention comprises: about 100 parts by weight of a thermoplastic resin; about 4 to about 10 parts by weight of melamine polyphosphate; about 2 to about 7 parts by weight of melamine phosphate; and about 10 to about 20 parts by weight of piperazine pyrophosphate, wherein a mixture of the melamine polyphosphate, melamine phosphate and piperazine pyrophosphate is characterized by having, as measured by a particle size analysis method, an average particle diameter D50 of about 6 μm or less and a particle diameter D90 of 90% of cumulative content is about 11 μm or less. The thermoplastic resin composition has excellent flame retardancy, impact resistance, external appearance characteristics, processability, and the like.

Description

Thermoplastic resin composition and molded article formed therefrom

The present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent flame retardancy, impact resistance, appearance characteristics, processability, and the like, and a molded article formed therefrom.

Thermoplastic resins such as polyolefin resins and aromatic vinyl resins have excellent mechanical, thermal, and electrical properties, and excellent chemical resistance and moldability, and are widely used in various fields. However, the polyolefin resin belongs to one of the highly flammable resins, and it is a difficult task to make the polyolefin resin have excellent flame retardancy, etc., and the aromatic vinyl resin has no resistance to flame, When the flame is ignited, there is a problem in that the resin itself decomposes and provides raw materials to expand and sustain combustion.

As an eco-friendly flame retardant system applicable to polyolefin resins, metal hydroxides, phosphorus-based flame retardants, etc. can be considered. In the case of metal hydroxides, a large amount of flame retardant is required to be input, so there is a problem in that moldability, water resistance, mechanical properties, etc. are deteriorated. In the case of phosphorus-based flame retardants, even if a relatively small amount is added compared to metal hydroxide, it is advantageous to implement flame retardancy without including halogens and heavy metals. It has limitations in terms of flame retardancy and appearance characteristics.

As a method of imparting flame retardancy to the aromatic vinyl-based resin, there is an additive-type flame retardant method in which a flame retardant and a flame retardant auxiliary are added, and in general, 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, their use is gradually restricted due to the emission of harmful gases and environmental issues. There is a problem that the flame retardant performance is lowered compared to the additive-based additive.

Therefore, there is a need for the development of a thermoplastic resin composition excellent in flame retardancy, impact resistance, appearance characteristics, processability, and the like, without these problems.

Background art of the present invention is disclosed in Korean Patent Application Laid-Open No. 10-2013-0048426, Korean Patent Publication No. 10-2010-0068954, and the like.

It is an object of the present invention to provide a thermoplastic resin composition having excellent flame retardancy, impact resistance, appearance characteristics, processability, and the like.

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

All of the above and other objects of the present invention can 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 comprises about 100 parts by weight of a thermoplastic resin; about 4 to about 10 parts by weight of melamine polyphosphate; about 2 to about 7 parts by weight of melamine phosphate; and about 10 to about 20 parts by weight of piperazine pyrophosphate; wherein, the mixture of melamine polyphosphate, melamine phosphate and piperazine pyrophosphate has an average particle diameter D50 of about 6 μm or less by particle size analysis, and a cumulative content of 90 It is characterized in that the particle diameter D90 of % is about 11 μm or less.

2. In the first embodiment, the thermoplastic resin may include at least one of a polyolefin resin and an aromatic vinyl-based resin.

3. In the second embodiment, the polyolefin resin may include at least one of polypropylene, polyethylene, and a propylene-ethylene copolymer.

4. In the second embodiment, the aromatic vinyl-based resin may include at least one of an aromatic vinyl-based polymer resin, an aromatic vinyl-based copolymer resin, a rubber-modified polystyrene resin, and a rubber-modified aromatic vinyl-based copolymer resin.

5. In the above 1 to 4 embodiments, the weight ratio of the melamine polyphosphate and the melamine phosphate may be about 1:1 to about 4:1.

6. In the above 1 to 5 embodiments, the weight ratio of the melamine polyphosphate and the piperazine pyrophosphate may be about 0.2:1 to about 0.8:1.

7. In the above 1 to 6 embodiments, the thermoplastic resin composition may have a flame retardancy of V-0 or more of a 1.5 mm thick specimen measured according to UL-94 standards.

8. In the above embodiments 1 to 7, the thermoplastic resin composition may have a notch Izod impact strength of about 3 to about 10 kgf·cm/cm of a 1/8″ thick specimen measured according to ASTM D256.

9. In the above embodiments 1 to 8, the thermoplastic resin composition may have a surface roughness (Ra) of about 2 to about 15 μm of the specimen measured using a surface roughness meter.

10. Another aspect of the present invention relates to a molded article. The molded article is characterized in that it is formed from the thermoplastic resin composition according to any one of 1 to 9.

The present invention has the effect of providing a thermoplastic resin composition excellent in flame retardancy, impact resistance, appearance characteristics, workability, and the like, 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 comprises (A) a thermoplastic resin; (B) melamine polyphosphate; (C) melamine phosphate; and (D) piperazine pyrophosphate.

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

(A) Thermoplastic resin

The thermoplastic resin according to an embodiment of the present invention may include at least one of (A1) a polyolefin resin and (A2) an aromatic vinyl-based resin.

(A1) polyolefin resin

The polyolefin resin according to an embodiment of the present invention can improve mechanical properties, processability, and appearance characteristics of the thermoplastic resin composition, and a conventional polyolefin resin can be used. For example, polyethylene such as low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylate copolymer , polyethylene-based resins such as mixtures thereof; polypropylene resins such as polypropylene, propylene-ethylene copolymer, propylene-1-butene copolymer, and mixtures thereof; polymers obtained by crosslinking them; blends comprising polyisobutene; A combination of these and the like can be used. Specifically, polypropylene, polyethylene, propylene-ethylene copolymer, combinations thereof, and the like can be used.

In an embodiment, the polyolefin resin has a melt-flow index of about 1 to about 50 g/10 min, for example, about 5 to about 30 g/10 min. In the above range, the thermoplastic resin composition may have excellent mechanical strength, molding processability, and the like.

(A2) Aromatic vinyl resin

The aromatic vinyl-based resin according to an embodiment of the present invention can improve mechanical properties, processability, and appearance characteristics of the thermoplastic resin composition, and a conventional aromatic vinyl-based resin can be used. For example, at least one of an aromatic vinyl-based polymer resin, an aromatic vinyl-based copolymer resin, a rubber-modified polystyrene resin, and a rubber-modified aromatic vinyl-based copolymer resin may be used. Specifically, a rubber-modified polystyrene resin, a rubber-modified aromatic vinyl-based copolymer resin, a combination thereof, and the like can be used.

Rubber-modified polystyrene resin

The rubber-modified polystyrene resin of the present invention is prepared by polymerizing a rubbery polymer and an aromatic vinyl monomer, and a general impact-resistant polystyrene (HIPS) resin may be used.

In an embodiment, the rubbery polymer includes a diene-based rubber such as polybutadiene and poly(acrylonitrile-butadiene), and a saturated rubber hydrogenated to the diene-based rubber, isoprene rubber, and alkyl (meth)acryl having 2 to 10 carbon atoms. Late rubber, a copolymer of an alkyl (meth)acrylate having 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 mixture of two or more. For example, a diene-based rubber, a (meth)acrylate rubber, etc. may be used, and specifically, a butadiene-based rubber, a butyl acrylate rubber, or the like may be used.

In an embodiment, the rubbery polymer (rubber particles) may have an average particle size of about 0.05 to about 6 μm, for example, about 0.15 to about 4 μm, specifically about 0.25 to about 3.5 μm. In 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 particles) may be measured using a light scattering method in a latex state. Specifically, the rubbery polymer latex is filtered through a mesh to remove coagulation generated during polymerization of the rubbery polymer, and a solution of 0.5 g of latex and 30 ml of distilled water is poured into a 1,000 ml flask and distilled water is filled 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 analyzer (malvern, nano-zs).

In an embodiment, the content of the rubbery polymer may be from about 3 to about 30% by weight, for example from about 5 to about 15% by weight, based on 100% by weight of the total rubber-modified polystyrene resin. In the above range, the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.

In an embodiment, the aromatic vinyl-based monomer includes styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, and dibromostyrene. , vinyl naphthalene, and the like can be exemplified. These can be used individually or in mixture of 2 or more types. The content of the aromatic vinyl-based monomer may be about 70 to about 97% by weight, for example, about 85 to about 95% by weight of the total 100% by weight of the rubber-modified polystyrene resin. In the above range, molding processability, impact resistance, and appearance characteristics of the thermoplastic resin composition may be excellent.

In an embodiment, the rubber-modified polystyrene resin is acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, N- during polymerization of the rubber-modified polystyrene resin in order to impart properties such as chemical resistance, processability, and heat resistance to the thermoplastic resin composition. It can polymerize by adding monomers, such as a substituted maleimide. In this case, the amount of the monomer added may be about 40% by weight or less based on 100% by weight of the total rubber-modified polystyrene resin. Chemical resistance, processability, heat resistance, etc. can be imparted to the thermoplastic resin composition without lowering other physical properties within the above range.

In an embodiment, the rubber-modified polystyrene resin may be polymerized by thermal polymerization without the presence of an initiator, or may be polymerized in the presence of an initiator. As the initiator, at least one of a peroxide-based initiator such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and cumene hydroperoxide, and an azo-based initiator such as azobis isobutyronitrile may be exemplified. The rubber-modified polystyrene resin may be prepared by known polymerization methods such as bulk polymerization, suspension polymerization, and emulsion polymerization.

Rubber-modified aromatic vinyl-based copolymer resin

The rubber-modified aromatic vinyl-based copolymer resin of the present invention may include (a1) a rubber-modified vinyl-based graft copolymer and (a2) an aromatic vinyl-based copolymer resin.

(a1) rubber-modified vinyl-based graft copolymer

The rubber-modified vinyl-based graft copolymer according to an embodiment of the present invention may be graft polymerization of a monomer mixture including 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 polymerization of a monomer mixture containing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to a rubbery polymer. Graft polymerization may be performed by further including a monomer that imparts 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 a monomer mixture) structure, but is not limited thereto.

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

In an embodiment, the rubbery polymer (rubber particles) may have an average particle size of about 0.05 to about 6 μm, for example, about 0.15 to about 4 μm, specifically about 0.25 to about 3.5 μm. In 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 particles) may be measured using a light scattering method in a latex state. Specifically, the rubbery polymer latex is filtered through a mesh to remove coagulation generated during polymerization of the rubbery polymer, and a solution of 0.5 g of latex and 30 ml of distilled water is poured into a 1,000 ml flask and distilled water is filled 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 analyzer (malvern, nano-zs).

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

In an embodiment, the aromatic vinyl-based monomer may be graft copolymerized to the rubber polymer, and may include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, etc. can be illustrated. These can be used individually or in mixture of 2 or more types. The content of the aromatic vinyl-based monomer may be about 10 to about 90% by weight, for example, about 40 to about 90% by weight of 100% by weight of the monomer mixture. In the above range, the processability and impact resistance of the thermoplastic resin composition may be excellent.

In a specific embodiment, the vinyl cyanide-based monomer is copolymerizable with the aromatic vinyl-based monomer, and includes acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. can be exemplified. These can be used individually or in mixture of 2 or more types. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide monomer may be about 10 to about 90 wt%, for example, about 10 to about 60 wt%, based on 100 wt% of the monomer mixture. In the above range, the thermoplastic resin composition may have excellent chemical resistance, mechanical properties, and the like.

In an embodiment, the monomer for imparting the processability and heat resistance may include (meth)acrylic acid, maleic anhydride, N-substituted maleimide, and the like, but is not limited thereto. When the monomer for imparting the processability and heat resistance is used, the content thereof may be 15% by weight or less, for example, about 0.1 to about 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, as the rubber-modified vinyl-based graft copolymer, a copolymer (g-ABS) in which a styrene monomer as an aromatic vinyl compound and an acrylonitrile monomer as a vinyl cyanide compound are grafted onto a butadiene-based rubber 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-based compound, and an acrylonitrile monomer, which is a vinyl cyanide-based compound, is grafted onto a rate-based rubbery polymer can be exemplified. have.

In an embodiment, the rubber-modified vinyl-based graft copolymer (a1) is included in an amount of about 10 to about 50% by weight, for example, about 15 to about 45% by weight of 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin. can In the above range, the thermoplastic resin composition may have excellent impact resistance, molding processability, and the like.

(a2) Aromatic vinyl-based copolymer resin

The aromatic vinyl-based copolymer resin according to an embodiment of the present invention may be an aromatic vinyl-based copolymer resin used in a conventional rubber-modified aromatic vinyl-based copolymer resin. 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 embodiment, the aromatic vinyl-based copolymer resin may be obtained by mixing an aromatic vinyl-based monomer, a vinyl cyanide-based monomer, etc., and then polymerizing it, and the polymerization is a known polymerization such as emulsion polymerization, suspension polymerization, and bulk polymerization. method can be carried out.

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

In an embodiment, the vinyl cyanide-based monomer may include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. These can be used individually or in mixture of 2 or more types. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide-based monomer may be about 10 to about 80 wt%, for example, about 20 to about 70 wt%, based on 100 wt% of the total aromatic vinyl-based copolymer resin. In the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity, heat resistance, and appearance.

In an embodiment, the aromatic vinyl-based copolymer resin may be polymerized by further including a monomer for imparting processability and heat resistance to the monomer mixture. As the monomer for imparting the processability and heat resistance, (meth)acrylic acid, N-substituted maleimide, and the like may be exemplified, but the present invention is not limited thereto. When the monomer for imparting the processability and heat resistance is used, the content thereof may be about 15% by weight or less, for example, about 0.1 to about 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 an embodiment, the aromatic vinyl-based copolymer resin has a weight average molecular weight (Mw) of about 10,000 to about 300,000 g/mol, for example, about 15,000 to about 150,000 g/mol, measured by gel permeation chromatography (GPC). can In the above range, the thermoplastic resin composition may have excellent mechanical strength, molding processability, and the like.

In an embodiment, the aromatic vinyl-based copolymer resin (a2) is from about 50 to about 90% by weight, for example, from about 55 to about 85% by weight of 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin (A) may be included. Within the above range, the thermoplastic resin composition may have excellent impact resistance, molding processability, and appearance characteristics.

(B) Melamine polyphosphate

The melamine polyphosphate of the present invention is applied in the form of a mixture having a specific particle size and particle size distribution together with melamine phosphate and piperazine pyrophosphate, so that even with a small content, flame retardancy, impact resistance, and appearance characteristics of the thermoplastic resin composition are improved. As one that can be improved, melamine polyphosphate used in conventional flame-retardant thermoplastic resin compositions may be used.

In an embodiment, the melamine polyphosphate may have a polymerization degree of about 100 to about 600, for example, about 200 to about 500, and a weight average molecular weight of about 20,000 to about 110,000 g/mol.

In an embodiment, the melamine polyphosphate may have a weight loss measured by TGA (Thermal Gravimetric Analysis, heating rate 20° C./min in air) of about 2% or less at 260° C., and at 300° C. , may be about 3% or less.

In an embodiment, the melamine polyphosphate may be included in an amount of about 4 to about 10 parts by weight, for example, about 5 to about 9 parts by weight, based on 100 parts by weight of the thermoplastic resin. When the content of the melamine polyphosphate is less than about 4 parts by weight based on about 100 parts by weight of the thermoplastic resin, there is a risk that the flame retardancy of the thermoplastic resin composition may be lowered, and when it exceeds about 10 parts by weight, the resistance of the thermoplastic resin composition There exists a possibility that impact property etc. may fall.

(C) melamine phosphate

The melamine phosphate of the present invention is applied in the form of a mixture having a specific particle size and particle size distribution together with melamine polyphosphate and piperazine pyrophosphate, so that even with a small content, flame retardancy, impact resistance, and appearance characteristics of the thermoplastic resin composition are improved. As one that can be improved, melamine phosphate (monomer) used in conventional flame-retardant thermoplastic resin compositions can be used.

In an embodiment, the melamine phosphate may be included in an amount of about 2 to about 7 parts by weight, for example, about 3 to about 6 parts by weight based on about 100 parts by weight of the thermoplastic resin. When the content of the melamine phosphate is less than about 2 parts by weight based on about 100 parts by weight of the thermoplastic resin, there is a fear that the flame retardancy of the thermoplastic resin composition may be lowered, and when it exceeds about 7 parts by weight, the (extrusion) of the thermoplastic resin composition ), there is a possibility that the workability may be deteriorated.

In an embodiment, the weight ratio (B:C) of the melamine polyphosphate (B) and the melamine phosphate (C) is from about 1:1 to about 4:1, for example from about 1:1 to about 3:1. have. In the above range, the thermoplastic resin composition may have excellent flame retardancy, impact resistance, appearance characteristics, (extrusion) processability, and the like.

(D) piperazine pyrophosphate

Piperazine pyrophosphate of the present invention is applied in the form of a mixture having a specific particle size and particle size distribution together with melamine polyphosphate and melamine phosphate, so that char is easy to form even with a small amount, and the composition of the thermoplastic resin composition As one capable of improving flame retardancy, impact resistance, and appearance characteristics, piperazine pyrophosphate used in conventional flame-retardant thermoplastic resin compositions may be used.

In an embodiment, the piperazine pyrophosphate may be included in an amount of about 10 to about 20 parts by weight, for example, about 12 to about 18 parts by weight, based on about 100 parts by weight of the thermoplastic resin. When the content of the piperazine pyrophosphate is less than about 10 parts by weight based on about 100 parts by weight of the thermoplastic resin, there is a risk that the flame retardancy of the thermoplastic resin composition may be deteriorated, and when it exceeds about 20 parts by weight, the amount of the thermoplastic resin composition There exists a possibility that impact resistance etc. may fall.

In an embodiment, the weight ratio (B:D) of the melamine polyphosphate (B) and the piperazine pyrophosphate (D) is from about 0.2:1 to about 0.8:1, for example from about 0.3:1 to about 0.7:1. can be In the above range, the thermoplastic resin composition may have excellent flame retardancy, impact resistance, and appearance characteristics.

The thermoplastic resin composition of the present invention may be applied after mixing the melamine polyphosphate (B), melamine phosphate (C) and piperazine pyrophosphate (D), pulverizing and separating to have a specific particle size and particle size distribution. The mixture containing the melamine polyphosphate (B), melamine phosphate (C) and piperazine pyrophosphate (D) is a particle size analysis method (of the particle size analysis method by laser diffraction and scattering, the dry method Mastersizer 2000E series (Malvern) equipment The average particle diameter D50 by the measurement using) is about 6 μm or less, for example, about 2 to about 5 μm, and the particle diameter D90 of 90% of the cumulative frequency is about 11 μm or less, for example, about 5 to about 10 μm. have. When the average particle diameter D50 of the mixture exceeds about 5 μm, there is a fear that the appearance properties of the thermoplastic resin composition may be deteriorated, and when the D90 of the mixture exceeds about 11 μm, the appearance properties of the thermoplastic resin composition, etc. There is a risk of deterioration.

The thermoplastic resin composition according to an embodiment of the present invention may further include an additive included in a conventional thermoplastic resin composition. The additives may include, but are not limited to, impact modifiers, antioxidants, anti-drip agents, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, and mixtures thereof. When the additive is used, its content may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 10 parts by weight, based on 100 parts by weight of the thermoplastic resin.

The thermoplastic resin composition according to an embodiment of the present invention is in the form of pellets that are melt-extruded at about 180 to about 250° C., for example, about 200 to about 230° C., by mixing the above components and using a conventional twin-screw extruder. can

In an embodiment, the thermoplastic resin composition may have a flame retardancy (V-test) of 1.5 mm thick specimen measured according to UL-94 standards of V-0 or more.

In an embodiment, the thermoplastic resin composition has a surface roughness (Ra) of about 2 to about 15 μm, for example, using a surface profiler (manufacturer: Kosaka laboratory, device name: Surfcorder SE3500) For example, it may be about 2 to about 10 μm.

In an embodiment, the thermoplastic resin composition has a notch Izod impact strength of about 3 to about 10 kgf·cm/cm, for example about 4 to about 9 kgf·· of a 1/8″ thick specimen measured according to ASTM D256. cm/cm.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be prepared 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 by those of ordinary skill in the art to which the present invention pertains. The molded article is eco-friendly because it does not apply a halogen-based flame retardant, and has excellent flame retardancy, impact resistance, appearance characteristics, (extrusion) processability, and balance of these 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 Examples and Comparative Examples are as follows.

(A) Thermoplastic resin

(A1) polyolefin resin

Based on ASTM D1238, a polypropylene resin (manufacturer: Lotte Chemical) having a flow index (MI) of 12 g/10 min measured at 230°C and a load of 2.16 kg was used.

(A2) Rubber-modified aromatic vinyl-based copolymer resin

25% by weight of the following (a1) rubber-modified aromatic vinyl-based graft copolymer and (a2) 75% by weight of the aromatic vinyl-based copolymer resin were mixed and used.

(a1) rubber-modified aromatic vinyl-based graft copolymer

g-ABS in which 55 wt% of styrene and acrylonitrile (weight ratio: 75/25) was graft-copolymerized on 45 wt% of butadiene rubber having a Z-average of 310 nm was used.

(a2) Aromatic vinyl-based copolymer resin

A SAN resin (weight average molecular weight: 130,000 g/mol) in which 75% by weight of styrene and 25% by weight of acrylonitrile were polymerized was used.

(A3) Rubber-modified polystyrene resin

Impact-resistant polystyrene (HIPS, manufacturer: IDEMITSU, product name: PSI060) was used.

(B) polyphosphate

(B1) Melamine polyphosphate (manufacturer: BASF, product name: Melarpur 200) was used.

(B2) oligomeric bisphenol-A diphosphate (manufacturer: Yoke Chemical, product name: YOKE BDP) was used.

(C) melamine phosphate

Melamine phosphate (manufacturer: BASF, product name: Melarpur MP) was used.

(D) piperazine pyrophosphate

Piperazine pyrophosphate (manufacturer: Henan Chemical) was used.

Examples 1 to 11 and Comparative Examples 1 to 9

The polyphosphate (B), melamine phosphate (C) and piperazine pyrophosphate were mixed in the amounts as shown in Tables 1, 2 and 3 below, and then pulverized and separated to have the following mixtures D50 and D90 (unit: μm) Pellets were prepared by treatment, addition to the thermoplastic resin (A), and extrusion at 200°C to 230°C. 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°C for 4 hours or more, and then injection molded in a 6 oz injection machine (molding temperature: 230°C, mold temperature: 70°C). Thus, a specimen was prepared. The prepared specimens were evaluated for physical properties by the following method, and the results are shown in Tables 1, 2 and 3 below.

How to measure physical properties

(1) Flame retardancy (V-test): In accordance with UL-94 standards, the flame retardancy of a 1.5 mm thick specimen was measured. (B/O (Burn Out): During the flame retardancy test, it means that the fire is lit and does not go out when it is lit again after the first combustion)

(2) Notched Izod impact strength (unit: kgf·cm/cm): According to ASTM D256, the notched Izod impact strength of a 1/8″ thick specimen was measured.

(3) Surface roughness (Ra, unit: μm): The surface roughness (Ra) of the specimen was measured using a surface profiler (manufacturer: Kosaka laboratory, device name: Surfcorder SE3500).

(4) Extrusion processability: The presence or absence of pores (diameter 0.5 mm or more) in the cross section (cut surface) of the pellets melt-extruded at 200 to 230 ° C. by mixing the components and using a conventional twin screw extruder was measured. When the number of pores is less than 1, it is evaluated as non-foaming (○), and when there are more than 2 pores, it was evaluated as foaming (x).

	Example
	One	2	3	4	5
(A1) (parts by weight)	100	100	100	100	100
(A2) (parts by weight)	-	-	-	-	-
(A3) (parts by weight)	-	-	-	-	-
(B1) (parts by weight)	5	7	9	7	7
(B2) (parts by weight)	-	-	-	-	-
(C) (parts by weight)	5	5	5	3	6
(D) (parts by weight)	15	15	15	15	15
Mixture D50 (μm)	3.5	3.5	3.5	3.5	3.5
Mixture D90 (μm)	7	7	7	7	7
Flame retardancy	V-0	V-0	V-0	V-0	V-0
Notched Izod Impact Strength	6.4	6.1	5.2	6.3	5.8
surface roughness	4	6	7	3	5
Extrusion Processability	○	○	○	○	○

	Example
	6	7	8	9	10	11
(A1) (parts by weight)	100	100	-	-	100	100
(A2) (parts by weight)	-	-	100	-	-	-
(A3) (parts by weight)	-	-	-	100	-	-
(B1) (parts by weight)	7	7	7	7	7	7
(B2) (parts by weight)	-	-	-	-	-	-
(C) (parts by weight)	5	5	5	5	5	5
(D) (parts by weight)	12	18	15	15	15	15
Mixture D50 (μm)	3.5	3.5	3.5	3.5	5	3.5
Mixture D90 (μm)	7	7	7	7	7	10
Flame retardancy	V-0	V-0	V-0	V-0	V-0	V-0
Notched Izod Impact Strength	6.5	4.5	8.3	5.5	6.3	5.9
surface roughness	5	7	6	6	10	9
Extrusion Processability	○	○	○	○	○	○

	comparative example
	One	2	3	4	5	6	7	8	9
(A1) (parts by weight)	100	100	100	100	100	100	100	100	100
(A2) (parts by weight)	-	-	-	-	-	-	-	-	-
(A3) (parts by weight)	-	-	-	-	-	-	-	-	-
(B1) (parts by weight)	One	15	-	7	7	7	7	7	7
(B2) (parts by weight)	-	-	7	-	-	-	-	-	-
(C) (parts by weight)	5	5	5	0.5	10	5	5	5	5
(D) (parts by weight)	15	15	15	15	15	5	25	15	15
Mixture D50 (μm)	4	4	4	4	4	4	4	20	4
Mixture D90 (μm)	7	7	7	7	7	7	7	7	40
Flame retardancy	B/O	V-0	V-1	B/O	-	B/O	V-0	V-0	V-0
Notched Izod Impact Strength	6.9	2.4	6.2	6.8	-	7.2	2.1	5.9	6.0
surface roughness	5	6	7	6	-	5	9	18	24
Extrusion Processability	○	○	○	○	×	○	○	○	○

From the above results, it can be seen that the thermoplastic resin compositions (Examples 1 to 11) of the present invention are excellent in flame retardancy, impact resistance, appearance characteristics, (extrusion) processability, and the like.

On the other hand, when the melamine polyphosphate 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 the melamine polyphosphate is 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, and when applying the oligomeric bisphenol-A diphosphate (B2) instead of the melamine polyphosphate (Comparative Example 3), the thermoplastic resin composition It can be seen that the flame retardancy is reduced. When the melamine phosphate is applied below the content range of the present invention (Comparative Example 4), it can be seen that the flame retardancy of the thermoplastic resin composition is lowered, and when the melamine phosphate is applied in excess of the content range of the present invention (Comparative Example 5) ), the extrusion processability of the thermoplastic resin composition is reduced, and it can be seen that the measurement of other physical properties is impossible. When piperazine pyrophosphate is applied below the content range of the present invention (Comparative Example 6), it can be seen that the flame retardancy of the thermoplastic resin composition is lowered, and when piperazine pyrophosphate is applied in excess of the content range of the present invention (Comparative example 7), it turns out that the impact resistance of a thermoplastic resin composition, etc. fall. In addition, when the average particle diameter D50 of the mixture exceeds the range of the present invention (Comparative Example 8), it can be seen that the appearance characteristics of the thermoplastic resin composition are deteriorated, and the particle diameter D90 of the cumulative degree of 90% of the mixture is within the range of the present invention. When it exceeds (Comparative Example 9), it can be seen that the appearance characteristics of the thermoplastic resin composition are deteriorated.

Up to now, the present invention has been looked at mainly with respect to the embodiments. Those of ordinary skill 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 are to be considered in an illustrative rather than a restrictive sense. The scope of the present invention is indicated in the claims rather than the foregoing description, and all differences within the scope equivalent thereto should be construed as being included in the present invention.

Claims (10)

1. about 100 parts by weight of a thermoplastic resin;

   about 4 to about 10 parts by weight of melamine polyphosphate;

   about 2 to about 7 parts by weight of melamine phosphate; and

   about 10 to about 20 parts by weight of piperazine pyrophosphate;

   The mixture of melamine polyphosphate, melamine phosphate and piperazine pyrophosphate has an average particle diameter D50 of about 6 μm or less by particle size analysis, and a particle diameter D90 of 90% of the cumulative frequency of about 11 μm or less.
2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin comprises at least one of a polyolefin resin and an aromatic vinyl-based resin.
3. The thermoplastic resin composition according to claim 2, wherein the polyolefin resin comprises at least one of polypropylene, polyethylene, and a propylene-ethylene copolymer.
4. The thermoplastic resin according to claim 2, wherein the aromatic vinyl-based resin comprises at least one of an aromatic vinyl-based polymer resin, an aromatic vinyl-based copolymer resin, a rubber-modified polystyrene resin, and a rubber-modified aromatic vinyl-based copolymer resin. composition.
5. 5. The thermoplastic resin composition of any one of claims 1 to 4, wherein the weight ratio of the melamine polyphosphate and the melamine phosphate is from about 1:1 to about 4:1.
6. 6. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the weight ratio of the melamine polyphosphate and the piperazine pyrophosphate is from about 0.2:1 to about 0.8:1.
7. The thermoplastic resin composition according to any one of claims 1 to 6, wherein the thermoplastic resin composition has a flame retardancy of 1.5 mm thick specimen measured according to UL-94 standards of V-0 or more.
8. The method according to any one of claims 1 to 7, wherein the thermoplastic resin composition has a notch Izod impact strength of about 3 to about 10 kgf·cm/cm of a 1/8″ thick specimen measured according to ASTM D256. Thermoplastic resin composition characterized in that.
9. The thermoplastic resin composition according to any one of claims 1 to 8, wherein the thermoplastic resin composition has a surface roughness (Ra) of about 2 to about 15 µm of a specimen measured using a surface roughness meter.
10. A molded article, characterized in that it is formed from the thermoplastic resin composition according to any one of claims 1 to 9.