KR20170036842A - Flame retardant thermoplastic resin composition and molded article produced therefrom - Google Patents
Flame retardant thermoplastic resin composition and molded article produced therefrom Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C08K3/0033—
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The thermoplastic resin composition of the present invention is a rubber-modified aromatic vinyl-based graft copolymer; Aromatic vinyl resins; Inorganic filler; And a phosphorus-based flame retardant comprising a first phosphorylated flame retardant having a melting point of 45 ° C or higher and a second phosphorylated flame retardant having a melting point lower than 40 ° C, wherein the aromatic vinyl-based resin comprises 70 to 80% by weight of an aromatic vinyl- Wherein the weight ratio of the first phosphorus-based flame retardant and the second phosphorus flame retardant is 1: 1 to 1: 3, and the weight ratio of the first phosphorus- do. The thermoplastic resin composition is excellent in flame retardancy, heat resistance, fluidity and the like and is suitable for a drip type flame retarding system requiring V-2 flame retardancy.
Description
The present invention relates to a flame-retardant thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition excellent in flame retardancy, heat resistance, fluidity and the like, and a molded article formed from the composition.
A rubber-modified aromatic vinyl copolymer resin such as acrylonitrile-butadiene-styrene copolymer resin (ABS resin) has excellent mechanical properties, processability and appearance characteristics, and is suitable for use in a housing for an electric / electronic product, It is widely used as exterior materials.
However, the rubber-modified aromatic styrenic 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 assisting combustion and there is a fear that the fire is continuously diffused .
As a result, researches for imparting flame retardancy to a rubber-modified styrenic copolymer resin have been continuously carried out. Halogen-based flame retardants, antimony compounds, phosphorus-based flame retardants and inorganic flame retardants have heretofore been used as flame retardants for imparting flame retardancy. However, when a halogen-based flame retardant is used, the gas generated at the time of combustion may have a fatal effect on the human body, and therefore, there is a growing interest in a flame retardancy method that does not employ a halogen-based compound. As such an erosion resistance method, a method of imparting flame retardancy to a resin composition by adding phosphorus or a compound containing nitrogen has been studied. Particularly, many methods of flame retarding using a phosphorus flame retardant have been studied.
Further, as the thickness of the electric / electronic products has become thinner and larger, there has been an increasing demand for a highly rigid flame-retardant rubber-modified aromatic styrenic copolymer resin composition in which the rigidity is enhanced by applying an inorganic filler.
However, unlike the halogen-based flame retardant, the flame retardant effect in the solid phase is important, and therefore it is difficult to impart flame retardancy to the styrene-based, acrylic-based, or olefin-based resin itself which does not form a char during combustion . Therefore, the flame retarding system using the styrene-based resin and the phosphorus flame retardant is not applicable to the V-0 and V-1 flame retardancy, and is applicable to the V-2 flame retarding system which causes the drip to cause the combustion.
However, when a phosphorus flame retardant and an inorganic filler are applied to a drip type flame retarding system requiring V-2 flame retardancy, the heat resistance and fluidity of the resin composition may be deteriorated. When the resin composition is burned, And a phenomenon of preventing dripping of the resin composition occurs, which makes it difficult to realize V-2 flame retardant.
Accordingly, it is an object of the present invention to provide a thermoplastic resin (rubber-modified aromatic styrenic copolymer resin) composition capable of realizing V-2 flame retardancy without deterioration of heat resistance and fluidity even when a phosphorus flame retardant and an inorganic filler are applied and a molded article to be.
The background art of the present invention is disclosed in Korean Patent No. 0536090 and the like.
An object of the present invention is to provide a thermoplastic resin composition excellent in flame retardancy, heat resistance and fluidity, and a molded article formed from the composition.
Another object of the present invention is to provide a flame retardant thermoplastic resin composition suitable for a drip type flame retarding system requiring V-2 flame retardance and a molded article formed from the flame retardant 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 is a rubber-modified aromatic vinyl-based graft copolymer; Aromatic vinyl resins; Inorganic filler; And a phosphorus-based flame retardant including a first phosphorus flame retardant (solid phosphorus flame retardant) having a melting point of 45 ° C or higher and a second phosphorus flame retardant having a melting point lower than 40 ° C, wherein the aromatic vinyl- Wherein the weight ratio of the first phosphorus-based flame retardant and the second phosphorus flame retardant is 1: 1 to 20: 1, and the weight ratio of the first phosphorus-based flame retardant to the second phosphorus flame retardant is 1: 1 to 1: 3.
In an embodiment, the thermoplastic resin composition comprises 100 parts by weight of a base resin comprising 5 to 20% by weight of the rubber-modified aromatic vinyl-based graft copolymer and 80 to 95% by weight of the aromatic vinyl resin, And 1 to 30 parts by weight of the phosphorus flame retardant.
In an embodiment, the rubber-modified aromatic vinyl-based graft copolymer may be one obtained by graft-copolymerizing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer in a rubber-like polymer.
In an embodiment, the inorganic filler may comprise at least one of glass fiber, wollastonite, whisker, basalt fiber, mica, talc and metal flake.
In an embodiment, the first phosphorus flame retardant is selected from the group consisting of resorcinol bis [di (2,6-dimethylphenyl) phosphate], bisphenol-A bis [di (2,6-dimethylphenyl) Dimethylphenyl) phosphate, and triphenylphosphate, and the second phosphorus flame retardant may be bisphenol-A diphosphate, bisphenol-A bis (diphenylphosphate) and resorcinol bis (diphenylphosphate) Or more.
In an embodiment, the thermoplastic resin composition may have a flame retardancy of V-2 of 2 mm thick specimen measured by UL-94 vertical test method.
In an embodiment, the thermoplastic resin composition may have a melt flow index of 50 to 140 g / 10 min measured at 220 캜 and 10 kgf according to ASTM D1238.
In a specific example, the thermoplastic resin composition may have a heat distortion temperature of 78 to 100 DEG C measured according to ASTM D648.
In a specific example, the thermoplastic resin composition may have a notched Izod impact strength of 5 kgf · cm / cm or more in a 1/8 "thick specimen measured according to ASTM D256.
Another aspect of the present invention relates to a molded article formed from the thermoplastic resin composition.
In embodiments, the molded article may be suitable for a drip type flame retardant system requiring V-2 flame retardancy.
The present invention has the effect of providing a thermoplastic resin composition which is excellent in flame retardancy, heat resistance, fluidity, and the like and is suitable for a drip type flame retardant system requiring V-2 flame retardancy and a molded article formed therefrom.
Hereinafter, the present invention will be described in detail.
The flame retardant thermoplastic resin composition according to the present invention comprises (A) a rubber-modified aromatic vinyl-based graft copolymer; (B) an aromatic vinyl resin; (C) an inorganic filler; And (D) a phosphorus-based flame retardant comprising a first phosphorus flame retardant having a melting point of 45 ° C or higher and a second phosphorus flame retardant having a melting point lower than 40 ° C, wherein the aromatic vinyl resin comprises 70 to 80% by weight of an aromatic vinyl monomer, Wherein the weight ratio of the first phosphorus flame retardant to the second phosphorus flame retardant is from 1: 1 to 1: 3, and the weight ratio of the first phosphorus flame retardant to the second phosphorus flame retardant is from 1: 1 to 1: 3 .
(A) a rubber-modified aromatic vinyl-based graft copolymer
The rubber-modified aromatic vinyl-based graft copolymer is obtained by graft-copolymerizing an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer in a rubbery polymer. For example, the rubber-modified aromatic vinyl-based graft copolymer can be obtained by adding an aromatic vinyl-based monomer, a monomer copolymerizable with the aromatic vinyl-based monomer, and the like to a rubbery polymer and then polymerizing the resultant. It is possible to further include a monomer that imparts heat resistance. The polymerization can be carried out by a known polymerization method such as emulsion polymerization, suspension polymerization and bulk polymerization.
In the specific examples, the rubbery polymer includes a diene rubber such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene), and saturated rubber in which hydrogen is added to the diene rubber, isoprene rubber, polybutylacrylic acid And an ethylene-propylene-diene monomer terpolymer (EPDM), and the like, but the present invention is not limited thereto. These may be used alone or in combination of two or more. For example, a diene rubber can be used, and specifically, a butadiene rubber can be used. The content of the rubbery polymer may be from 5 to 65% by weight, for example, from 10 to 60% by weight, based on 100% by weight of the rubber-modified aromatic vinyl-based graft copolymer. In the above range, the thermoplastic resin composition comprising the rubber-modified aromatic vinyl-based graft copolymer may have excellent mechanical properties such as impact resistance, heat resistance, and fluidity.
In an embodiment, the average particle size (Z-average) of the rubbery polymer (rubber particles) may be 0.05 to 6 탆, for example 0.15 to 4 탆. In the above range, the thermoplastic resin composition comprising the rubber-modified aromatic vinyl-based graft copolymer may have excellent mechanical properties such as impact resistance, heat resistance, and fluidity.
In an embodiment, the aromatic vinyl-based monomer may be graft-copolymerized with a rubbery copolymer, and examples thereof include styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt- , Vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like, but the present invention is not limited thereto. These may be used alone or in combination of two or more. The content of the aromatic vinyl monomer may be from 15 to 94% by weight, for example, from 20 to 80% by weight, based on 100% by weight of the rubber-modified aromatic vinyl-based graft copolymer. In the above range, the thermoplastic resin composition comprising the rubber-modified aromatic vinyl-based graft copolymer may have excellent mechanical properties such as impact resistance, heat resistance, and fluidity.
In an embodiment, the monomer copolymerizable with the aromatic vinyl-based monomer is at least one monomer selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, But the present invention is not limited thereto. These may be used alone or in combination of two or more. Specifically, acrylonitrile, methacrylonitrile and the like can be used. The content of the monomer copolymerizable with the aromatic vinyl monomer may be 1 to 50% by weight, for example, 5 to 45% by weight, based on 100% by weight of the rubber-modified aromatic vinyl-based graft copolymer. In the above range, the thermoplastic resin composition comprising the rubber-modified aromatic vinyl-based graft copolymer may have excellent mechanical properties such as impact resistance, heat resistance, and fluidity.
In the specific examples, examples of the monomer for imparting the above processability and heat resistance include, but are not limited to, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, and mixtures thereof. The content of the monomer for imparting processability and heat resistance may be 15% by weight or less, for example, 10% by weight or less, based on 100% by weight of the entire rubber-modified aromatic vinyl-based graft copolymer. The processability and heat resistance of the rubber-modified aromatic vinyl-based graft copolymer can be improved without lowering the physical properties in the above range.
In the specific examples, examples of the rubber-modified aromatic vinyl-based copolymer include a copolymer obtained by grafting an aromatic vinyl-based monomer, such as styrene, and a vinyl cyanide-based compound, acrylonitrile, to a central butadiene-based rubber- But is not limited thereto.
In a specific example, the rubber-modified aromatic vinyl-based graft copolymer is used in an amount of 5 to 20% by weight, for example, 7 to 18% by weight, based on 100% by weight of the base resin including the rubber-modified aromatic vinyl- % ≪ / RTI > by weight. The flame retardancy, heat resistance, fluidity and the like of the thermoplastic resin composition can be excellent in the above range.
(B) an aromatic vinyl resin
The aromatic vinyl-based resin reduces the aggregation phenomenon with the inorganic filler so that the thermoplastic resin composition can achieve V-2 flame retardancy. The aromatic vinyl-based resin is composed of 70 to 80% by weight, for example, 71 to 75% by weight of the aromatic vinyl- A polymer of a monomer mixture comprising 20 to 30% by weight, for example 25 to 29% by weight, of a vinyl cyanide monomer and having a weight average molecular weight measured by gel permeation chromatography (GPC) of 50,000 to 130,000 g / mol, 80,000 to 110,000 g / mol. If the content of the vinyl cyanide monomer is less than 20% by weight in the 100% by weight of the monomer mixture, the impact resistance and the like of the thermoplastic resin composition may deteriorate. If the content exceeds 30% by weight, The flame retardancy of the 2 mm thick thermoplastic resin composition measured by the UL-94 vertical test method may fail to realize V-2. If the weight average molecular weight of the aromatic vinyl resin is less than 50,000 g / mol, the impact resistance of the thermoplastic resin composition may be significantly reduced. If the weight average molecular weight is more than 130,000 g / mol, the viscosity of the thermoplastic resin composition may increase, The flame retardancy of the 2 mm thick thermoplastic resin composition measured by the UL-94 vertical test method may fail to realize V-2.
In an embodiment, the aromatic vinyl-based resin can be obtained by reacting the aromatic vinyl-based monomer and the monomer copolymerizable with the aromatic vinyl-based monomer according to a known polymerization method.
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, but the present invention is not limited thereto. These may be used alone or in combination of two or more.
In an embodiment, the monomer copolymerizable with the aromatic vinyl-based monomer is at least one monomer selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, But the present invention is not limited thereto. These may be used alone or in combination of two or more. Specifically, acrylonitrile, methacrylonitrile and the like can be used.
In an embodiment, the aromatic vinyl resin may be contained in an amount of 80 to 95% by weight, for example, 82 to 93% by weight, based on 100% by weight of the base resin comprising the rubber-modified aromatic vinyl-based graft copolymer and the aromatic vinyl resin have. The flame retardancy, heat resistance, fluidity and the like of the thermoplastic resin composition can be excellent in the above range.
(C) Inorganic filler
The inorganic filler can improve the rigidity and the like of the thermoplastic resin composition. The inorganic filler can be an inorganic filler used in a conventional thermoplastic resin composition. Examples thereof include glass fiber, wollastonite, whisker, basalt fiber, mica, talc, Metal flakes, mixtures thereof, and the like. Specifically, glass fiber can be used.
In an embodiment, the inorganic filler may have various shapes such as a fiber shape, a particle shape, a rod shape, an acicular shape, a flake shape, and an amorphous shape, and may have various shapes such as a circle, an ellipse, and a rectangle. For example, it may be preferable from the viewpoint of mechanical properties to use a glass fiber which is a fibrous inorganic filler having a circular and / or rectangular cross section.
In a specific example, the glass fiber of the circular cross section may have a cross-sectional diameter of 5 to 20 탆 and a length before shaping of 2 to 20 mm, the glass fiber of the rectangular cross-section has an aspect ratio of 1.5 to 10, May be between 2 and 20 mm. In the above range, the mechanical properties (rigidity), workability, etc. of the bending strength and impact strength of the thermoplastic resin composition can be improved.
In an embodiment, the inorganic filler may be included in an amount of 5 to 50 parts by weight, for example, 10 to 40 parts by weight, based on 100 parts by weight of the base resin. It is possible to reduce the aggregation phenomenon with the resin in the above range and to improve the rigidity and the like without deteriorating the flame retardancy and fluidity of the thermoplastic resin composition.
(D) Phosphorous flame retardant
(Phosphorus flame retardant) having a melting point of 45 占 폚 or higher and a second phosphorus flame retardant having a melting point lower than 40 占 폚 (liquid phosphorus flame retardant), wherein the phosphorus flame retardant is capable of imparting flame retardancy to the thermoplastic resin composition, The phosphorus-based flame retardant and the second phosphorus-based flame retardant are in a weight ratio of 1: 1 to 1: 3, for example, 1: 1.2 to 1: 2. If the weight ratio of the first phosphorus-based flame retardant and the second phosphorus-based flame retardant is less than 1: 1 in the phosphorus-based flame retardant, the flame retardancy and the like of the thermoplastic resin composition may deteriorate. And the like may be deteriorated.
Examples of the first phosphorus flame retardant include resorcinol bis [di (2,6-dimethylphenyl) phosphate], bisphenol-A bis [di (2,6-dimethylphenyl) phosphate] -Dimethylphenyl) phosphate, triphenylphosphate, and the like. These may be used alone or in combination of two or more.
In a specific example, examples of the second phosphorus flame retardant include bisphenol-A diphosphate, bisphenol-A bis (diphenylphosphate), and resorcinol bis (diphenylphosphate). These may be used alone or in combination of two or more.
In an embodiment, the phosphorus flame retardant may be included in an amount of 1 to 30 parts by weight, for example, 5 to 20 parts by weight, based on 100 parts by weight of the base resin. In the above range, a thermoplastic resin composition having V-2 flame retardancy suitable for a drip type flame retarding system can be obtained.
The thermoplastic resin composition according to one embodiment of the present invention may contain, in addition to the above components, a thermoplastic resin other than the base resin, for example, a polycarbonate resin, a polyester A thermoplastic resin including a resin, a polyamide resin, a combination (blend) thereof, and the like, and an additive. The additives include, but are not limited to, antioxidants, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, colorants, and mixtures thereof. When the additive is used, the content thereof may be 10 parts by weight or less based on 100 parts by weight of the base resin.
The thermoplastic resin composition according to one embodiment of the present invention is suitable for a drip type flame retardant system, and the flame retardancy of a 2 mm thick specimen measured by the UL-94 vertical test method may be V-2.
In a specific example, the thermoplastic resin composition has a melt flow index (MI) measured at 220 DEG C and 10 kgf according to ASTM D1238 of 50 to 140 g / 10 min, for example, 60 to 130 g / 10 minutes. The flowability of the thermoplastic resin composition in the above range is excellent, and thus the dripping property is increased, thereby realizing the V2 flame retardant property.
In a specific example, the thermoplastic resin composition may have a heat distortion temperature (HDT) measured in accordance with ASTM D648 of 78 to 100 占 폚, for example, 80 to 95 占 폚. Within the above range, the thermoplastic resin composition is excellent in heat resistance and can be highly resistant to thermal deformation.
In an embodiment, the thermoplastic resin composition may have a notched Izod impact strength of not less than 5 kgf · cm / cm, for example, from 5.1 to 10 kgf · cm / cm, as measured according to ASTM D256 . In the above range, the thermoplastic resin composition may have excellent physical properties such as impact resistance and flame retardancy.
The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition of the present invention can be produced by a known method for producing a thermoplastic resin composition. For example, after mixing the above components and other additives as necessary, they may be melt-extruded in an extruder to produce pellets. The produced pellets can be manufactured into various molded articles (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 can be used in automotive parts suitable for a drip-type flame-retardant system requiring V-2 flame-retardant, interior / exterior materials such as electric / electronic products, and the like. In particular, it is useful as a rear cover for a thin television which requires properties such as high fluidity, high rigidity, and flame retardancy. It is environmentally friendly and advantageous in cost reduction by the application of a non-halogen flame retardant.
Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.
Example
The specifications of each component used in the following examples and comparative examples are as follows.
(A) a rubber-modified aromatic vinyl-based graft copolymer
(Graft copolymer of g-ABS, rubber average particle size (Z-average)) prepared by graft copolymerizing 40 wt% of styrene and acrylonitrile (weight ratio 75:25) to 60 wt% of butadiene rubber, : 258 nm) was used.
(B) an aromatic vinyl resin
(B1) Resin (SAN-1) having a weight average molecular weight of 97,000 g / mol, prepared by polymerizing 71.5% by weight of styrene and 28.5% by weight of acrylonitrile, was used.
(B2) Resin (SAN-2) having a weight average molecular weight of 97,000 g / mol, prepared by polymerizing 66% by weight of styrene and 34% by weight of acrylonitrile, was used.
(B3) Resin (SAN-3) having a weight average molecular weight of 97,000 g / mol, prepared by polymerizing 82% by weight of styrene and 18% by weight of acrylonitrile, was used.
(B4) Resin (SAN-4) having a weight average molecular weight of 153,000 g / mol, prepared by polymerizing 80% by weight of styrene and 20% by weight of acrylonitrile, was used.
(B5) Resin (SAN-5) having a weight average molecular weight of 40,000 g / mol, prepared by polymerizing 80% by weight of styrene and 20% by weight of acrylonitrile was used.
(C) Inorganic filler
Glass fiber having a circular cross section (cross-sectional diameter: 26 탆, length: 3 mm) was used.
(D) Phosphorous flame retardant
(D1) first respirable flame retardant, resorcinol bis [di (2,6-dimethylphenyl) phosphate] was used.
(D2) Bisphenol-A bis (diphenylphosphate) which is a second phosphorus flame retardant was used.
Example 1 to 3 and Comparative Example 1 to 6
According to the composition and content of the following Table 1, the above components were mixed and then added to a twin screw type extruder having L / D = 35 and a diameter of 45 mm and melted and extruded at 230 DEG C to prepare pellets . The prepared pellets were dried at 80 ° C. for 2 hours or more, and then injected at an injection temperature of 230 ° C. and a mold temperature of 60 ° C. to prepare specimens. 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) Notch Izod impact strength (unit: kgf cm / cm): A notch was formed on a 1/8 "thick specimen based on the evaluation method described in ASTM D256.
(2) Melt flow index (MI, unit: g / 10 min): Measured at 220 캜 and 10 kgf according to the evaluation method defined in ASTM D1238.
(3) Heat distortion temperature (HDT, unit: 占 폚): Measured under the conditions of a load of 18.5 kgf / cm 2 and a heating rate of 120 占 폚 / hr in accordance with ASTM D648.
(4) Evaluation of flame retardancy: A specimen having a thickness of 2 mm (2T) was prepared and the flame retardancy was measured by UL-94 vertical test method.
From the above results, it can be seen that the thermoplastic resin compositions (Examples 1 to 3) according to the present invention are excellent in impact resistance, fluidity, heat resistance, and the like, in which V-2 flame retardancy is realized.
On the other hand, in the case of Comparative Example 1 in which an aromatic vinyl-based resin is excessively contained in the aromatic vinyl-based resin, the fluidity is lowered and V-2 flame retardancy can not be realized. In the aromatic vinyl-based resin, It can be seen that the impact resistance is lowered in the case of Comparative Example 2, and in the case of Comparative Example 3 in which an aromatic vinyl-based resin having an average weight-average molecular weight of more than 130,000 g / mol is used, It can be understood that flame retardancy can not be realized and that in Comparative Example 4 using an aromatic vinyl resin having a weight average molecular weight of less than 50,000 g / mol of the aromatic vinyl resin, it can be seen that the impact resistance is greatly lowered, And Comparative Example 6 in which the ratio of the second phosphorus flame retardant was outside the scope of the present invention, the V-2 flame retardant property could not be realized due to the lowered fluidity. In Comparative Example 6, That was found.
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 (11)
Aromatic vinyl resins;
Inorganic filler; And
A phosphorus flame retardant comprising a first phosphorus flame retardant having a melting point of 45 캜 or higher and a second phosphorus flame retardant having a melting point lower than 40 캜,
Wherein the aromatic vinyl resin is a polymer of a monomer mixture comprising 70 to 80% by weight of an aromatic vinyl monomer and 20 to 30% by weight of a vinyl cyanide monomer and has a weight average molecular weight of 50,000 to 130,000 g / mol,
Wherein the weight ratio of the first phosphorus-based flame retardant and the second phosphorus flame retardant is 1: 1 to 1: 3.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019124857A3 (en) * | 2017-12-22 | 2019-08-15 | 롯데첨단소재(주) | Thermoplastic resin composition and molded product manufactured therefrom |
| WO2021020741A1 (en) * | 2019-07-30 | 2021-02-04 | 롯데케미칼 주식회사 | Thermoplastic resin composition and molded article formed therefrom |
| US11661510B2 (en) | 2017-12-22 | 2023-05-30 | Lotte Chemical Corporation | Thermoplastic resin composition and molded product manufactured therefrom |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019124857A3 (en) * | 2017-12-22 | 2019-08-15 | 롯데첨단소재(주) | Thermoplastic resin composition and molded product manufactured therefrom |
| US11661510B2 (en) | 2017-12-22 | 2023-05-30 | Lotte Chemical Corporation | Thermoplastic resin composition and molded product manufactured therefrom |
| WO2021020741A1 (en) * | 2019-07-30 | 2021-02-04 | 롯데케미칼 주식회사 | Thermoplastic resin composition and molded article formed therefrom |
| KR20210014323A (en) * | 2019-07-30 | 2021-02-09 | 롯데케미칼 주식회사 | Thermoplastic resin composition and article produced therefrom |
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| Publication number | Publication date |
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| KR101790410B1 (en) | 2017-10-26 |
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