KR101986913B1 - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

The thermoplastic resin composition of the present invention comprises 10 to 40% by weight of a rubber-modified aromatic vinyl copolymer resin and 60 to 90% by weight of a ternary copolymer resin of an aromatic vinyl monomer, maleic anhydride and maleimide monomer Suzy; And a phosphorus-based flame retardant. The thermoplastic resin composition has self-extinguishing properties and is excellent in flame retardancy, heat resistance and the like.

Description

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

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 self-extinguishing properties and excellent flame retardancy, heat resistance and the like, and a molded article formed therefrom.

As the thermoplastic resin, rubber-modified aromatic vinyl copolymer resins such as acrylonitrile-butadiene-styrene copolymer resin (ABS resin) and the like have excellent mechanical properties, processability, appearance and the like, Automobile interior / exterior materials, building exterior materials, and the like.

However, the rubber-modified aromatic vinyl-based copolymer resin itself has no resistance to combustion, and when the flame is ignited by an external ignition factor, the resin itself acts as energy that assists the combustion, and there is a fear that the fire is continuously diffused . Accordingly, researches for imparting flame retardancy to rubber-modified aromatic vinyl copolymer resins have been continuously conducted, and flame retardants such as halogen flame retardants, phosphorus flame retardants, and antimony compounds have been applied to the resin compositions. However, in the case of a rubber-modified aromatic vinyl copolymer resin, a halogen-based flame retardant is mainly applied to a resin composition aiming at self-extinguishing properties since it does not have sufficient self-extinguishing property when applied only to a phosphorus flame retardant (V-2 flame retardancy) .

However, since the halogen-based flame retardant has a problem of human health and the like, the use thereof is limited. Therefore, there is a need to develop a flame-retardant thermoplastic resin (rubber-modified aromatic vinyl copolymer resin) composition having self-extinguishing properties without using a halogen-based flame retardant .

The background art of the present invention is disclosed in Korean Patent Publication No. 10-2014-0085246.

An object of the present invention is to provide a thermoplastic resin composition having self-extinguishing properties and excellent flame retardancy and heat resistance.

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

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

One aspect of the present invention relates to a thermoplastic resin composition. Wherein the thermoplastic resin composition comprises 10 to 40% by weight of a rubber-modified aromatic vinyl-based copolymer resin, and 60 to 90% by weight of a ternary copolymer resin of an aromatic vinyl monomer, maleic anhydride and maleimide monomer; And a phosphorus flame retardant.

In a specific example, the thermoplastic resin composition may contain 1 to 50 parts by weight of the phosphorus-based flame retardant in 100 parts by weight of the base resin.

In an 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.

In an embodiment, the rubber-modified vinyl-based graft copolymer may be one obtained by graft-polymerizing a monomer mixture containing an aromatic vinyl monomer and a vinyl cyan monomer in a rubbery polymer.

In an embodiment, the aromatic vinyl-based copolymer resin may be a polymer of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.

In an embodiment, the maleimide-based monomer may be represented by the following formula:

[Chemical Formula 1]

In Formula 1, R ₁ is an aromatic hydrocarbon group having 6 to 12 carbon atoms.

In an embodiment, the ternary copolymer resin may be a polymeric mixture of a monomer mixture consisting of 30 to 60 wt% of the aromatic vinyl monomer, 0.1 to 10 wt% of maleic anhydride, and 35 to 65 wt% of the maleimide monomer have.

In an embodiment, the phosphorus flame retardant is selected from the group consisting of resorcinol bis [di (2,6-dimethylphenyl) phosphate], bisphenol-A bis [di (2,6-dimethylphenyl) ) Phosphorus flame retardant containing at least one of phosphate and triphenyl phosphate, and a phosphorus-containing flame retardant containing at least one of bisphenol-A diphosphate, bisphenol-A bis (diphenylphosphate) and resorcinol bis (diphenylphosphate) And a second phosphorus flame retardant.

In an embodiment, the weight ratio of the first phosphorus flame retardant and the second phosphorus flame retardant may be from 1: 1 to 1: 3.

In a specific example, the thermoplastic resin composition may have a flame retardancy of V-0 or more of a 3 mm thick specimen measured by UL-94 vertical test method.

In the specific examples, the thermoplastic resin composition may have a Vicat softening temperature of 140 to 160 ° C measured under a load of 5 kg and a temperature of 120 ± 12 ° C / hr according to ASTM D1525.

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

INDUSTRIAL APPLICABILITY The present invention has the effect of providing a thermoplastic resin composition having excellent self-extinguishing properties, flame retardancy, heat resistance and the like, and a molded article formed therefrom.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention comprises (A) a rubber-modified aromatic vinyl copolymer resin, (B) a ternary copolymer resin of an aromatic vinyl monomer, maleic anhydride and maleimide monomer, and (C) .

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

The rubber-modified aromatic vinyl-based copolymer resin of the present invention may comprise (A1) a rubber-modified vinyl-based graft copolymer and (A2) an aromatic vinyl-based copolymer resin.

(A1) rubber-modified aromatic vinyl-based graft copolymer

The rubber-modified vinyl-based graft copolymer according to one embodiment of the present invention may be one obtained by graft-polymerizing a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyan monomer in a rubber-like polymer. For example, the rubber-modified vinyl-based graft copolymer can be obtained by graft-polymerizing a monomer mixture containing an aromatic vinyl monomer and a vinyl cyan monomer to a rubbery polymer, and if necessary, The graft polymerization may be further carried out by further including a monomer which imparts heat resistance. The polymerization may be carried out by a known polymerization method such as emulsion polymerization or suspension polymerization. Further, the rubber-modified vinyl-based graft copolymer may form a core (rubbery polymer)-shell (copolymer of a monomer mixture) structure, but is not limited thereto.

Examples of the rubbery polymer include a diene rubber such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), a saturated rubber which is hydrogenated with the diene rubber, an isoprene rubber, A copolymer of an alkyl (meth) acrylate rubber having 2 to 10 carbon atoms, an alkyl (meth) acrylate having 2 to 10 carbon atoms and styrene, and an ethylene-propylene-diene monomer terpolymer (EPDM). These may be used alone or in combination of two or more. For example, diene rubber, (meth) acrylate rubber and the like can be used. Specifically, butadiene rubber, butyl acrylate rubber and the like can be used.

In an embodiment, the rubbery polymer (rubber particles) may have an average particle size (D50) as measured by a particle size analyzer of 0.05 to 6 mu m, for example 0.15 to 4 mu m, specifically 0.25 to 3.5 mu m. Here, the average particle size can be measured by a transmission electron microscope (TEM). Within the above range, the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.

In an embodiment, 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 as a whole, and the monomer mixture (the aromatic vinyl- Containing vinyl 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 an embodiment, the aromatic vinyl-based monomer may be graft-copolymerized with the rubbery polymer, and may be selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like. These may be used alone or in combination of two or more. 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 and impact resistance of the thermoplastic resin composition can be excellent.

In the specific examples, the vinyl cyanide monomer is copolymerizable with the aromatic vinyl system, and examples thereof include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, For example. These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile and the like 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 and mechanical properties.

In the specific examples, examples of the monomer for imparting the above processability and heat resistance include, but are not limited to, (meth) acrylic acid, maleic anhydride, N-substituted maleimide and the like. When the monomer for imparting processability and heat resistance is used, 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, the thermoplastic resin composition can be imparted with processability and heat resistance without deteriorating other physical properties.

In the specific examples, as the rubber-modified vinyl-based graft copolymer, a copolymer (g-ABS) in which an aromatic vinyl compound and an acrylonitrile monomer, which are aromatic vinyl compounds and a vinyl cyanide compound, are grafted to a butadiene rubber- Styrene-acrylonitrile graft copolymer (g-ASA), which is a copolymer obtained by grafting an aromatic vinyl compound, a styrene monomer, and an acrylonitrile monomer, which is a vinyl cyanide compound, have.

In the specific examples, the rubber-modified vinyl-based graft copolymer (A1) may be contained in an amount of 40 to 85% by weight, for example, 40 to 75% by weight, based on 100% by weight of the whole rubber-modified aromatic vinyl- have. Within the above range, the thermoplastic resin composition may have excellent impact resistance and moldability.

(A2) an aromatic vinyl-based copolymer resin

The aromatic vinyl-based copolymer resin according to one embodiment of the present invention may be a polymer of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.

In an embodiment, the aromatic vinyl-based copolymer resin may be obtained by mixing an aromatic vinyl monomer and an aromatic vinyl monomer with a vinyl cyanide monomer, and then polymerizing the aromatic vinyl monomer and the aromatic vinyl monomer. The polymerization may be carried out by emulsion polymerization, And the like.

In an embodiment, the aromatic vinyl monomer is at least one monomer selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dibromostyrene , Vinyl naphthalene and the like can be used. These may be used 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 total aromatic vinyl-based copolymer resin. The impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.

In the specific examples, examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and fumaronitrile. These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile and the like 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 total aromatic vinyl copolymer resin. The impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.

In an embodiment, the aromatic vinyl-based copolymer resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 10,000 to 300,000 g / mol, for example, 15,000 to 150,000 g / mol. Within the above range, the thermoplastic resin composition may have excellent mechanical strength and moldability.

In an embodiment, the aromatic vinyl-based copolymer resin (A2) may include 15 to 60% by weight, for example, 25 to 60% by weight of 100% by weight of the whole rubber-modified aromatic vinyl-based copolymer resin (A). Within the above range, the thermoplastic resin composition may have excellent impact resistance and moldability.

In the specific example, the rubber-modified aromatic vinyl copolymer resin (A) is a rubber-modified aromatic vinyl copolymer resin (A) containing the rubber-modified aromatic vinyl copolymer resin (A) and the terpolymer resin (B) B) of 10 to 40 wt%, for example 15 to 35 wt%, of 100 wt% of the total. Within the above range, the thermoplastic resin composition can have self-extinguishing properties, and can be excellent in flame retardancy, heat resistance, mechanical properties, and the like.

(B) a ternary copolymer resin

The ternary copolymer resin of the present invention is capable of imparting self-extinguishing properties to a thermoplastic resin composition and improving flame retardancy, heat resistance and the like without halogen-based flame retardant, and it is an aromatic vinyl-based monomer, maleic anhydride, Copolymer resin.

In an embodiment, the aromatic vinyl monomer is at least one monomer selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dibromostyrene , Vinyl naphthalene and the like can be used. These may be used alone or in combination of two or more.

In an embodiment, the maleimide-based monomer may be represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, R ₁ is an aromatic hydrocarbon group having 6 to 12 carbon atoms. Specific examples of the maleimide-based monomer include, but are not limited to, N-phenyl maleimide (PMI).

In an embodiment, the ternary copolymer resin comprises 30 to 60 wt%, for example 35 to 55 wt%, of the aromatic vinyl monomer, 0.1 to 10 wt%, such as 0.5 to 5 wt%, of the maleic anhydride and A monomer mixture composed of 35 to 65% by weight of the maleimide monomer, for example, 40 to 60% by weight, and the like. The polymerization may be carried out by emulsion polymerization, suspension polymerization, bulk polymerization And the like.

In an embodiment, the terpolymer resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 10,000 to 300,000 g / mol, for example, 15,000 to 150,000 g / mol. The flame retardancy and heat resistance of the thermoplastic resin composition may be excellent in the above range.

(A) + (B)) containing the rubber-modified aromatic vinyl copolymer resin (A) and the ternary copolymer resin (B) 60 to 90% by weight, for example 65 to 85% by weight, of the total 100% by weight. Within the above range, the thermoplastic resin composition can have self-extinguishing properties, and can be excellent in flame retardancy, heat resistance, mechanical properties, and the like.

(C) Phosphorous flame retardant

The phosphorus-based flame retardant according to one embodiment of the present invention can improve the flame retardance and the like of the thermoplastic resin composition, and a phosphorus-based flame retardant used in a conventional thermoplastic resin composition can be used.

In an embodiment, the phosphorus flame retardant is selected from the group consisting of resorcinol bis [di (2,6-dimethylphenyl) phosphate], bisphenol-A bis [di (2,6-dimethylphenyl) ) A first phosphorus flame retardant (at least a solid phosphorus flame retardant having a melting point of 45 ° C or higher) comprising at least one of phosphate and triphenyl phosphate; A second phosphorus flame retardant (liquid flame retardant having a melting point lower than 40 ° C) comprising at least one of bisphenol-A diphosphate, bisphenol-A bis (diphenylphosphate) and resorcinol bis (diphenylphosphate); Combinations of these, and the like.

In an embodiment, the phosphorus flame retardant may be a mixture of the first phosphorus flame retardant and the second phosphorus flame retardant, and the weight ratio of the first phosphorus flame retardant and the second phosphorus flame retardant is from 1: 1 to 1: 3, 1: 1.5 to 1: 2.5. The flame retardancy and the like of the thermoplastic resin composition may be excellent in the above range.

In an embodiment, the phosphorus flame retardant may be included in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, based on 100 parts by weight of the base resin. The flame retardancy and heat resistance of the thermoplastic resin composition may be excellent in the above range.

The thermoplastic resin composition according to one embodiment of the present invention may further include an additive contained in a conventional thermoplastic resin composition. Examples of the additives include fillers, antioxidants, lubricants, release agents, nucleating agents, stabilizers, pigments, dyes, and mixtures thereof. When the additive is used, 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 thermoplastic resin.

The thermoplastic resin composition according to one embodiment of the present invention may be in the form of a pellet obtained by melt-extruding the above components at a temperature of 200 to 280 DEG C, for example 220 to 250 DEG C, using a conventional twin-screw extruder.

In a specific example, the thermoplastic resin composition may have a flame retardancy of V-0 or more of a 3 mm thick specimen measured by UL-94 vertical test method.

In a specific example, the thermoplastic resin composition may have a Vicat softening temperature of 140 to 160 ° C, for example, 145 to 155 ° C, measured under a load of 5 kg and a temperature of 120 ± 12 ° C / hr according to ASTM D1525.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be produced in the form of pellets, and the produced pellets may be manufactured into various molded products through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those of ordinary skill in the art to which the present invention pertains. The molded article has self-extinguishing properties, is excellent in flame retardancy, heat resistance, and the like, and thus is useful as an interior material for electric / electronic products.

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

Example

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

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

The following rubber-modified aromatic vinyl-based graft copolymer (A1) and the following (A2) aromatic vinyl-based copolymer resin were mixed and used.

(A1) rubber-modified aromatic vinyl-based graft copolymer

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

(A2) an aromatic vinyl-based copolymer resin

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.

(B) a ternary copolymer resin

(B1) A ternary polymer resin (weight average molecular weight: 150,000 g / mol) of a monomer mixture consisting of 43% by weight of styrene, 2% by weight of maleic anhydride and 55% by weight of N-phenylmaleimide was used.

(B2) A ternary polymer resin (weight average molecular weight: 107,000 g / mol) of a monomer mixture consisting of 53% by weight of styrene, 2% by weight of maleic anhydride and 45% by weight of N-phenylmaleimide was used.

(B3) A ternary polymer resin (weight average molecular weight: 145,000 g / mol) consisting of 57% by weight of styrene, 57% by weight of N-phenylmaleimide and 12% by weight of acrylonitrile was used.

(C) Phosphorous flame retardant

(C1) resorcinol bis [di (2,6-dimethylphenyl) phosphate] was used.

(C2) bisphenol-A diphosphate was used.

Examples 1 to 4 and Comparative Examples 1 to 5

The above components were added in the amounts shown in Table 1, and then extruded at 230 캜 to prepare pellets. The pellets were extruded at a temperature of 230 ° C. and a mold temperature of 60 ° C. in a 6 Oz extruder at 80 ° C. for 2 hours or more, . The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Table 1 below.

How to measure property

(1) Evaluation of flame retardancy: The flame retardancy of a 3 mm thick specimen was measured by UL-94 vertical test method.

(2) Heat resistance evaluation: Vicat softening temperature (VST) (unit: ° C) was measured under a load of 5 kg and a temperature of 120 ± 12 ° C / hr according to ASTM D1525.

Example Comparative Example One 2 3 4 One 2 3 4 5 (A)
(weight%) (A1) 15 15 15 15 15 15 15 25 3 (A2) 15 5 15 5 15 5 85 20 2 (B)
(weight%) (B1) 70 80 - - - - - 55 95 (B1) - - 70 80 - - - - - (B3) - - - - 70 80 - - - (C1) (parts by weight) 10 10 10 10 10 10 10 10 10 (C2) (parts by weight) 20 20 20 20 20 20 20 20 20 Flame retardancy V-0 V-0 V-0 V-0 fail fail fail V-1 - Heat resistance (VST, ℃) 150 153 148 151 121 124 98 147 -

Parts by weight based on 100 parts by weight of the base resin (A) + (B)

From the above results, it can be seen that the thermoplastic resin composition of the present invention has self-extinguishing properties with a flame retardancy of V-0 or more, and is excellent in both flame retardancy and heat resistance.

On the other hand, when the terpolymer resin (B3) was used in place of the terpolymer resins (B1) and (B2) (Comparative Examples 1 and 2), or when the terpolymer resin was not used (Comparative Example 3) , The flame retardancy and the heat resistance are lowered, and the self-extinguishing property is not obtained.

In addition, when the ternary copolymer resin is used in an amount of less than 60% by weight based on 100% by weight of the base resin (Comparative Example 4), flame retardancy and the like may be lowered. Was brittle, making it impossible to prepare specimens and to measure physical properties.

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

Claims (12)

10 to 40% by weight of a rubber-modified aromatic vinyl copolymer resin, and 60 to 90% by weight of a ternary copolymer resin of an aromatic vinyl monomer, maleic anhydride and maleimide monomer; And
A phosphorus-based flame retardant composed of a first phosphorus flame retardant and a second phosphorus flame retardant,
Wherein the first phosphorus flame retardant is resorcinol bis [di (2,6-dimethylphenyl) phosphate, the second phosphorus flame retardant is bisphenol-A diphosphate, the weight ratio of the first phosphorus flame retardant and the second phosphorus flame retardant is 1: 1.5 to 1: 2.5,
Wherein the flame retardancy of the 3 mm thick specimen measured by the UL-94 vertical test method is not less than V-0.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises 1 to 50 parts by weight of the phosphorus-based flame retardant based on 100 parts by weight of the base resin.
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 and an aromatic vinyl-based copolymer resin.
The thermoplastic resin composition according to claim 3, wherein the rubber-modified vinyl-based graft copolymer is obtained by graft-polymerizing a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyan monomer in a rubbery polymer.
The thermoplastic resin composition according to claim 3, wherein the aromatic vinyl-based copolymer resin is a polymer of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.
The thermoplastic resin composition according to claim 1, wherein the maleimide-based monomer is a compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1, R ₁ is an aromatic hydrocarbon group having 6 to 12 carbon atoms.
delete delete delete The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a Vicat softening temperature of 140 to 160 ° C measured under a load of 5 kg and a temperature of 120 ± 12 ° C / hr according to ASTM D1525.
A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 6 and 10.
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