KR101743330B1 - Flame retardant thermoplastic resin composition and article comprising the same - Google Patents
Flame retardant thermoplastic resin composition and article comprising the same Download PDFInfo
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Abstract
The thermoplastic resin composition of the present invention comprises a base resin comprising a polycarbonate resin and a rubber-modified aromatic vinyl copolymer resin; Phosphorus-based flame retardants including phosphoric acid compounds and phosphazene-based compounds; And a wollastonite, wherein the content of the phosphoric acid compound is 1 to 20 parts by weight based on 100 parts by weight of the base resin, the weight ratio of the phosphoric acid compound and the phosphazene compound is 5: 1 to 20: 1, Phosphoric acid compound and wollastonite is 4: 1 to 20: 1. The thermoplastic resin composition has a flame retardancy of UL94 flame retardancy of 5VB grade and is excellent in heat resistance, impact resistance, fluidity, and physical properties.
Description
The present invention relates to a flame retardant thermoplastic resin composition and a molded article containing the same. More specifically, the present invention relates to a flame retardant thermoplastic resin composition having excellent flame retardancy of UL94 flame retardancy and 5VB grade and excellent in heat resistance, impact resistance, flowability, physical properties and the like, and a molded article comprising the flame retardant thermoplastic resin composition.
Polycarbonate resin is an engineering plastic excellent in mechanical strength, heat resistance and transparency. The polycarbonate resin is used in various fields such as office automation equipment, electric / electronic parts, and building materials. Particularly, when a rubber-modified aromatic vinyl copolymer resin such as acrylonitrile-butadiene-styrene (ABS) is mixed with the above polycarbonate resin, the polycarbonate resin can be produced without degrading the impact resistance, heat resistance, Can be improved. As such, the blend of the polycarbonate resin and the rubber-modified aromatic vinyl copolymer resin as the thermoplastic resin can provide excellent physical properties as compared with the rubber-modified aromatic vinyl copolymer resin, and the cost can be reduced compared to the polycarbonate resin So that it is utilized for various purposes.
Such a resin composition (blend) comprising a polycarbonate resin and a rubber-modified aromatic vinyl copolymer resin is representative of a PC / ABS alloy (U.S. Patent No. 3,130,177, etc.). The PC / ABS alloy is a blend of a polycarbonate resin and an ABS resin and is used for interior / exterior materials such as electric / electronic products which require high gloss, high flow and high impact. However, reinforcing materials (thermoplastic resin compositions) reinforced by an inorganic filler, a flame retardant, or the like have been developed because PC / ABS alone has poor modulus and flame retardancy.
Generally, when an inorganic filler such as glass fiber is blended with a thermoplastic resin, mechanical properties such as tensile strength, flexural strength and flexural modulus of the resin can be improved due to inherent characteristics of the inorganic filler, and excellent heat resistance is exhibited. It is suitable for parts that are to receive or withstand constant heat. In particular, it is widely used for interior / exterior materials of automobiles, electric and electronic products which require flame retardancy, impact resistance and mechanical properties by adding flame retardant.
However, in the case of a flame retardant thermoplastic resin composition using ABS or the like, an excessively large amount of a flame retardant agent is required to overcome the fluidity and flame retardancy as the rubber content increases, and a decrease in heat resistance There is a concern.
In addition, since the inorganic filler usually has poor compatibility and adhesiveness with the thermoplastic resin, there is a fear that when added to the resin composition, the impact resistance and the moldability are greatly lowered.
Furthermore, in order to form a thin film of a thermoplastic resin composition containing a polycarbonate resin and a rubber-modified aromatic vinyl copolymer resin in accordance with the trend of lighter weight and thinner products, high impact strength, high flowability and thin film flame retardant properties This is a required situation.
Accordingly, development of a flame retardant thermoplastic resin composition having excellent flame retardancy with UL94 flame retardancy (specimen thickness: 1.5 to 3.0 mm) of 5VB grade and excellent in heat resistance, impact resistance, fluidity, and physical properties balance thereof has been demanded.
An object of the present invention is to provide a flame retardant thermoplastic resin composition having excellent flame retardancy of UL94 flame retardancy and 5VB grade and excellent in heat resistance, impact resistance, flowability, physical properties and the like, and a molded article comprising the flame retardant thermoplastic resin composition.
Another object of the present invention is to provide an environmentally friendly flame retardant thermoplastic resin composition and a molded article comprising the same, without using a halogen-based flame retardant.
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 base resin comprising a polycarbonate resin and a rubber-modified aromatic vinyl-based copolymer resin; Phosphorus-based flame retardants including phosphoric acid compounds and phosphazene-based compounds; And a wollastonite, wherein the content of the phosphoric acid compound is 1 to 20 parts by weight based on 100 parts by weight of the base resin, the weight ratio of the phosphoric acid compound and the phosphazene compound is 5: 1 to 20: 1, Phosphoric acid compound and wollastonite is 4: 1 to 20: 1.
In an embodiment, the rubber-modified aromatic vinyl-based copolymer resin comprises 10 to 100% by weight of a graft copolymer resin obtained by graft copolymerizing an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer in a rubbery polymer; And 0 to 90% by weight of an aromatic vinyl-based copolymer resin in which an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer are copolymerized.
In an embodiment, the phosphate compound may be represented by the formula:
[Chemical Formula 1]
Wherein R 1 and R 4 are each independently a hydrogen atom, a C 6 -C 20 aryl group, or a C 6 -C 20 aryl group substituted with a C 1 -
In an embodiment, the phosphazene-based compound may be represented by the following formula:
(2)
In Formula 2, each of R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 independently represents a C 1 -C 6 alkyl group, a C 6 -C 20 aryl group , C1-C6 is a substituted C6-C20 aryl group, alkyl group, alkoxy group of C6-C20 aralkyl group, C1-C6, the aryloxy group of C6-C20, amino group or hydroxy group, R 16 is a C6-C30 An arylene group or a C6-C30 arylene group substituted with a C1-C6 alkyl group, a and b are an integer of 0 to 10, and an average value of n is 0.3 to 3. [
In an embodiment, the wollastonite may have an average height (diameter) of 5 to 1,000 μm and an aspect ratio (length to width) of 1: 3 to 1:15.
In an embodiment, the content of the polycarbonate resin is 50 to 99% by weight of the entire base resin, and the content of the rubber-modified aromatic vinyl copolymer resin may be 1 to 50% by weight of the entire base resin.
In a specific example, the thermoplastic resin composition may have a flame retardancy of 5 VB measured according to UL94 standard for a specimen having a thickness of 1.5 to 3.0 mm.
In the specific example, the thermoplastic resin composition has an Izod impact strength of 10 to 70 kgf · cm / cm measured in accordance with ASTM D256, a heat distortion temperature (HDT) measured according to ASTM D648, And the melt index (MI) measured at 220 DEG C and 10 kgf according to ASTM D1238 may be 5 to 60 g / 10 min.
Another aspect of the present invention relates to a molded article formed from the thermoplastic resin composition.
In an embodiment, the molded article may be a thin film type outer cover material having a thickness of 1.0 to 3.0 mm.
The present invention relates to a flame retardant thermoplastic resin composition having excellent flame retardancy with UL94 flame retardancy (specimen thickness: 1.5 to 3.0 mm) of 5VB grade and excellent heat resistance, impact resistance, fluidity and balance of physical properties thereof and an environmentally friendly flame retardant thermoplastic resin The present invention provides the composition and the molded article containing the same.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing the length (a) and the width (b) of wollastonite according to an embodiment of the present invention.
Hereinafter, the present invention will be described in detail.
The thermoplastic resin composition according to the present invention comprises (A) a base resin, (B1) a phosphoric acid compound and (B2) a phosphazene-based compound comprising a polycarbonate resin (A1) and a rubber-modified aromatic vinyl- (B) a phosphorus flame retardant; And (C) wollastonite.
(A) Base resin
(A1) Polycarbonate resin
As the polycarbonate resin to be used in the present invention, a usual thermoplastic polycarbonate resin can be used without limitation. For example, an aromatic polycarbonate resin prepared by reacting at least one diphenol (aromatic dihydroxy compound) with a carbonate precursor such as phosgene, halogen formate, or carbonic acid diester can be used.
Specific examples of the diphenols include 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) Propane, mixtures thereof, and the like, but are not limited thereto. Examples of the above diphenols include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 1,1- -Hydroxyphenyl) cyclohexane, and specifically 2,2-bis (4-hydroxyphenyl) propane, also referred to as bisphenol-A, can be used.
The polycarbonate resin may be used in the form of a branched chain. For example, 0.05 to 2 mol% of a trifunctional or more polyfunctional compound, for example, trivalent or more, And further adding a compound having a phenol group. The polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin or a blend thereof. The polycarbonate resin may be partially or wholly substituted with an aromatic polyester-carbonate resin obtained by polymerization reaction in the presence of an ester precursor such as a bifunctional carboxylic acid.
In embodiments, the weight average molecular weight (Mw) of the polycarbonate resin may be 10,000 to 50,000 g / mol, such as, but not limited to, 15,000 to 40,000 g / mol.
In an embodiment, the polycarbonate resin may comprise 50 to 99 wt%, for example 60 to 85 wt%, of 100 wt% of the total base resin. The impact resistance and mechanical properties of the thermoplastic resin composition may be excellent in the above range.
(A2) Rubber-modified aromatic vinyl-based copolymer resin
The rubber-modified aromatic vinyl-based copolymer resin used in the present invention is a rubber-modified aromatic vinyl-based copolymer resin in which 10 to 100% by weight of (a1) graft copolymer resin in which an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer are graft- And 0 to 90% by weight of an aromatic vinyl-based copolymer resin (a2) in which an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer are copolymerized. That is, in the rubber-modified aromatic vinyl copolymer resin of the present invention, the graft copolymer resin (a1) may be used alone or in the form of a mixture of the graft copolymer resin (a1) and the aromatic vinyl copolymer resin (a2) .
In an embodiment, the graft copolymer resin (a1) can be polymerized by adding an aromatic vinyl monomer, a monomer copolymerizable with the aromatic vinyl monomer, and the like to the rubbery polymer, and the aromatic vinyl copolymer resin (a2) Can be polymerized by adding an aromatic vinyl monomer, a monomer copolymerizable with the aromatic vinyl monomer, and the like. The polymerization can be carried out by a known polymerization method such as emulsion polymerization, suspension polymerization and bulk polymerization. In the case of the above-mentioned bulk polymerization, the graft copolymer resin (a1) can be produced by a single step reaction process without separately preparing the graft copolymer resin (a1) and the aromatic vinyl copolymer resin (a2) A rubber-modified aromatic vinyl-based copolymer resin in a form dispersed in the coalescing resin (a2) can be produced.
In a specific example, the content of the rubber (rubbery polymer) in the final rubber-modified aromatic vinyl-based copolymer resin component is preferably 5 to 50% by weight. In addition, the particle size of the rubber may be 0.05 to 6.0 탆 in Z-average. In the above range, physical properties such as impact resistance are excellent.
Hereinafter, the graft copolymer resin (a1) and the aromatic vinyl copolymer resin (a2) will be described in more detail as follows.
(a1) graft copolymer resin
The graft copolymer resin can be obtained by graft copolymerizing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer to a rubbery polymer, and may further include a monomer which imparts processability and heat resistance, if necessary .
Specific examples of the rubbery polymer include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene) and saturated rubbers hydrogenated with the diene rubbers, isoprene rubber, polybutylacrylic acid Acrylic rubber, ethylene-propylene-diene monomer terpolymer (EPDM), and the like. For example, a diene rubber can be used, and specifically, a butadiene rubber can be used. The content of the rubbery polymer may be 5 to 65% by weight, for example, 10 to 60% by weight, specifically 20 to 50% by weight, based on the total weight of the graft copolymer resin (a1). It is possible to obtain a good balance of impact strength and mechanical properties in the above range. 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, specifically 0.25 to 3.5 탆. The impact strength and appearance can be excellent in the above range.
The aromatic vinyl-based monomer may be graft-copolymerized with the rubbery copolymer. Examples of the aromatic vinyl monomer include styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, , Monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like, but the present invention is not limited thereto. Specifically, styrene can be used. The content of the aromatic vinyl monomer may be 15 to 94% by weight, for example, 20 to 80% by weight, specifically 30 to 60% by weight, based on the total weight of the graft copolymer resin (a1). It is possible to obtain a good balance of impact strength and mechanical properties in the above range.
Examples of the monomer copolymerizable with the aromatic vinyl monomer include vinyl cyanide compounds such as acrylonitrile and unsaturated nitrile compounds such as ethacrylonitrile and methacrylonitrile. Or more. 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, specifically 10 to 30% by weight, based on the total weight of the graft copolymer resin. It is possible to obtain a good balance of impact strength and mechanical properties in the above range.
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 the like. The content of the monomer for imparting the above processability and heat resistance may be 0 to 15% by weight, for example, 0.1 to 10% by weight, based on the total weight of the graft copolymer resin. The workability and heat resistance can be imparted without deteriorating the other properties within the above range.
(a2) an aromatic vinyl-based copolymer resin
The aromatic vinyl-based copolymer resin used in the present invention can be produced by using a monomer mixture excluding the rubber (rubbery polymer) among the components of the graft copolymer resin (a1), and the ratio of the monomers varies depending on the compatibility and the like . For example, the aromatic vinyl-based copolymer resin can be obtained by copolymerizing the aromatic vinyl-based monomer and the monomer copolymerizable with the aromatic vinyl-based monomer.
Examples of the aromatic vinyl monomers include aromatic vinyl monomers such as styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromo Styrene, vinylnaphthalene, and the like, but is not limited thereto. Specifically, styrene can be used.
Examples of the monomer copolymerizable with the aromatic vinyl monomer include vinyl cyanide compounds such as acrylonitrile and unsaturated nitrile compounds such as ethacrylonitrile and methacrylonitrile. Two or more of them may be used in combination.
The aromatic vinyl-based copolymer resin may further contain a monomer which imparts the above processability and heat resistance, if necessary. 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 the like.
In the aromatic vinyl-based copolymer resin, the content of the aromatic vinyl-based monomer is 50 to 95% by weight, for example, 60 to 90% by weight, specifically 70 to 80% by weight, based on the total weight of the aromatic vinyl- . It is possible to obtain a good balance of impact strength and mechanical properties in the above range.
The content of the copolymerizable monomer with the aromatic vinyl-based monomer may be 5 to 50% by weight, for example, 10 to 40% by weight, specifically 20 to 30% by weight, based on the total weight of the aromatic vinyl-based copolymer resin. It is possible to obtain a good balance of impact strength and mechanical properties in the above range.
The content of the monomer for imparting workability and heat resistance may be from 0 to 30% by weight, for example, from 0.1 to 20% by weight, based on the total weight of the aromatic vinyl-based copolymer resin. The workability and heat resistance can be imparted without deteriorating the other properties within the above range.
The weight average molecular weight of the aromatic vinyl-based copolymer resin may be 50,000 to 500,000 g / mol, but is not limited thereto.
Non-limiting examples of the rubber-modified aromatic vinyl copolymer resin (A2) of the present invention include copolymers of styrene monomer, which is an aromatic vinyl compound, and acrylonitrile monomer, which is an unsaturated nitrile compound, grafted to a center butadiene rubber- Butadiene-styrene copolymer resin (ABS resin), acrylonitrile-ethylene-propylene rubber-styrene copolymer resin (AES resin (a-1) (A1) such as acrylonitrile-acrylic rubber-styrene copolymer resin (AAS resin), acrylonitrile-acrylic rubber-styrene copolymer resin (AAS resin) and the like. Here, the ABS resin may be one in which the g-ABS is dispersed in the styrene-acrylonitrile copolymer resin (SAN resin) as the aromatic vinyl copolymer resin (a2) as the graft copolymer resin (a1) have.
In an embodiment, the rubber-modified aromatic vinyl-based copolymer resin may be contained in an amount of 1 to 50% by weight, for example, 15 to 40% by weight, based on 100% by weight of the total base resin. The impact resistance and mechanical properties of the thermoplastic resin composition may be excellent in the above range.
(B) Phosphorous flame retardant
The phosphorus flame retardant used in the present invention includes a phosphoric acid compound (B1) and a phosphazene compound (B2).
(B1) Phosphate
The phosphate compound of the present invention may be a phosphate compound, a phosphonate compound or the like, or may be used by mixing two or more kinds thereof. For example, the phosphate compound may be represented by the following formula (1).
[Chemical Formula 1]
In Formula 1, R 1 and R 4 are each independently a hydrogen atom, C6-C20 (C 6 -C 20) aryl group, or an aryl group of C1-C10 with C6-C20 alkyl group is substituted for a, R 2, and R 5 are each independently a hydrogen atom, a hydroxy group, C6-C20 aryl group or aryloxy group, or a C1-C10 of the C6-C20 alkyl group is substituted with the aryl group or aryloxy group and R 3 is aryl of C6-C20 (Parts excluding alcohols), m is a number average degree of polymerization, and an average value of m is from 0 to 4 to be.
In embodiments, non-limiting examples of such phosphate compounds include diaryl phosphates such as diphenyl phosphate, diphenyl phenyl phosphonate, triphenyl phosphate, tricresyl phosphate, triazylenyl phosphate, tri (2,6- (2,4,6-trimethylphenyl) phosphate, tri (2,4-ditertiary butylphenyl) phosphate, tri (2,6-dimethylphenyl) phosphate, bisphenol- ), Resorcinol bis (diphenylphosphate), resorcinol bis [bis (2,6-dimethylphenyl) phosphate], resorcinol bis [bis (2,4-ditertiarybutylphenyl) phosphate], hydroquinone Bis [bis (2,6-dimethylphenyl) phosphate], and hydroquinone bis [bis (2,4-ditertiary butylphenyl) phosphate]. The aromatic phosphoric acid compounds may be used alone or in the form of a mixture of two or more thereof.
In an embodiment, the content of the phosphoric acid compound may be 1 to 20 parts by weight, for example 5 to 15 parts by weight, based on 100 parts by weight of the base resin. Within the above range, flame retardancy can be improved without deteriorating other physical properties of the thermoplastic resin composition.
(B2) phosphazene-based compound
As the phosphazene compound used in the present invention, a phosphazene compound used in a conventional flame retardant thermoplastic resin composition can be used without limitation. For example, the phosphazene-based compound may be represented by the following formula (2).
(2)
In Formula 3, R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 each independently represent a C 1 -C 6 alkyl group, a C 6 -C 20 aryl group , C1-C6 is a substituted C6-C20 aryl group, alkyl group, alkoxy group of C6-C20 aralkyl group, C1-C6, the aryloxy group of C6-C20, amino group or hydroxy group, R 16 is a C6-C30 C6-C30 allylene groups substituted with an arylene group or a C1-C6 alkyl group such as those derived from an aromatic dialcohol such as resorcinol, hydroquinone, bisphenol-A, and bisphenol-S (a portion excluding an alcohol) A and b are integers of 0 to 10, n is a number average degree of polymerization, and an average value of n is 0.3 to 3. [
In an embodiment, the weight ratio (B1: B2) of the phosphoric acid compound (B1) and the phosphazene compound (B2) may be from 5: 1 to 20: 1, for example from 8: 1 to 15: 1. A flame retardant thermoplastic resin composition having UL94 flame retardancy (specimen thickness: 1.5 to 3.0 mm) of 5VB class can be obtained in the above range.
(C) Wollastonite
The wollastonite used in the present invention can further improve the UL94 5VB flame retardancy of the thermoplastic resin composition. The wollastonite is a calcium-based mineral, and the white acicular minerals having a hydrophobic coating on at least a part of the surface may be used. The wollastonite used in the present invention has an average length (a) length (diameter) of 5 to 1,000 mu m, for example, 30 to 100 mu m, an aspect ratio (length (a): width (b) 15, such as 1: 3 to 1: 13 (see Fig. 1). Within the above range, the flame retardancy of the thermoplastic resin composition can be further improved, and the impact resistance can be excellent.
In an embodiment, the weight ratio of the phosphoric acid compound (B1) and the wollastonite (C) may be from 4: 1 to 20: 1, for example from 8: 1 to 15: 1. Within the above range, the flame retardancy can be improved without deteriorating the other physical properties of the thermoplastic resin composition, and excellent impact resistance, mechanical properties, physical properties and the like can be obtained.
The thermoplastic resin composition according to the present invention may further contain conventional additives as required. Examples of the additives include, but are not limited to, antioxidants, antifoaming agents, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, and mixtures thereof. When the additive is used, the content thereof may be 0.01 to 10 parts by weight based on 100 parts by weight of the thermoplastic resin, but is not limited thereto.
The thermoplastic resin composition of the present invention is excellent in heat resistance, impact resistance, fluidity, and physical properties balance of UL94 flame retardancy (specimen thickness: 1.5 to 3.0 mm) and 5VB grade.
In an embodiment, the thermoplastic resin composition may have a flame retardancy of 5 VB measured according to UL94 standard for a specimen having a thickness of 1.5 to 3.0 mm.
The thermoplastic resin composition may have an Izod impact strength of 10 to 70 kgf · cm / cm, for example, 20 to 60 kgf · cm / cm, of the 1/8 "thick specimen measured according to ASTM D256.
The thermoplastic resin composition may have a heat distortion temperature (HDT) measured according to ASTM D648 of 70 to 120 ° C, for example, 75 to 100 ° C.
The thermoplastic resin composition may have a melt index (MI) of 5 to 60 g / 10 min, for example, 10 to 50 g / 10 min, measured at 220 캜 and 10 kgf according to ASTM D1238.
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. Since the molded article has a flame retardancy of UL94 flame retardancy (specimen thickness: 1.5 to 3.0 mm) of 5VB grade and is excellent in heat resistance, impact resistance, fluidity and balance of physical properties thereof, it is suitable for automobile parts, parts of electric and electronic products, useful. Specifically, it can be used for a thin film type exterior material having a thickness of 1.0 to 3.0 mm.
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) Base resin
(A1) As the polycarbonate resin, CALIBER 200-3 (flow index (MI): 3 g / 10 min.) Manufactured by LG-DOW was used.
(A2) An acrylonitrile-butadiene-styrene copolymer (ABS) resin (manufactured by LG Chem, product name: MA201) was used as the rubber-modified aromatic vinyl copolymer resin.
(B) Phosphorous flame retardant
(B1) phosphoric acid compound, aromatic polyphosphate (manufacturer: DAIHACHI, product name: CR-741) was used.
As the phosphazene compound (B2), a phenoxy cyclic phosphazene compound (manufacturer: Otsuka Chemical Company, product name: SPS-100) was used.
(C) Wollastonite
(NYCO, product name: NYGLOS 4W) having an average diameter (length) of 7 μm (aspect ratio (length (a): width (b)) of 1: 9 was used.
Examples 1 to 2 and Comparative Examples 1 to 6
The components were mixed in a tumbler mixer for 10 minutes and then added to a twin screw type extruder having an L / D of 44 and a diameter of 45 mm according to the composition and content of the following Table 1, And then melted and extruded at 250 rpm to prepare pellets. The pellets were dried at 80 DEG C for 5 hours or more, and then ejected from a 250 DEG C extruder (manufacturer: LG Cable, product name: LGH-140N) 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) Heat resistance evaluation: The heat distortion temperature (HDT, unit: 占 폚) was measured according to ASTM D648.
(2) Melt Index (MI, unit: g / 10 min): Measured at 220 캜 and 10 kgf according to the evaluation method specified in ASTM D1238.
(3) IZOD Impact Strength (Unit: kgf · cm / cm): Based on the evaluation method described in ASTM D256, a notch was formed on a 1/8 "thick Izod sample to evaluate it.
(4) Evaluation of flame retardancy: A specimen having a thickness of 1.2 mm (V) and 1.5 mm (5 V) was prepared and evaluated by a UL94 Vertical Burning Flame Test method for flame retardancy (burning time, 10 seconds and 60 seconds Number of burns, number of burning drips).
(B1: B2 weight ratio)
(B1: C weight ratio)
V
Flame retardancy
(sec)
(22.8)
(21.5)
(84.4)
(35.3)
(21.2)
(30.1)
(39.9)
(10.1)
5V
Flame retardancy
(sec)
(65.5)
(60.7)
(104.1)
(68.3)
(72.6)
(56.9)
(66.4)
(63.1)
(B1) parts by weight: parts by weight based on 100 parts by weight of (A1) + (A2)
From the above results, it can be seen that the flame-retardant thermoplastic resin composition according to the present invention has excellent flame retardancy with UL94 flame retardancy (specimen thickness: 1.5 to 3.0 mm) of 5VB grade and excellent heat resistance, impact resistance, fluidity and balance of physical properties .
On the other hand, when the phosphazene compound and wollastonite were not used (Comparative Example 1), it was found that the flame retardancy was significantly lowered and the heat resistance and fluidity were lowered compared with the examples, and the phosphoric acid compound and the wollastonite (Comparative Example 2), it is understood that the impact resistance is greatly lowered as compared with the Examples. In addition, it can be seen that when wollastonite is not used (Comparative Example 3), it has no flame retardancy with UL94 flammability (specimen thickness: 1.5 to 3.0 mm) and 5VB grade, and when wollastonite is used in excess (Comparative Example 4) It can be seen that the impact resistance is significantly lower than that of the example.
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 (10)
Phosphorus-based flame retardants including phosphoric acid compounds and phosphazene-based compounds; And
Wollastonite,
Wherein the content of the phosphate compound is 1 to 20 parts by weight based on 100 parts by weight of the base resin and the weight ratio of the phosphate compound and the phosphazene compound is 5: 1 to 20: 1, and the phosphoric acid compound and the wollastonite The weight ratio is 4: 1 to 20: 1,
The Izod impact strength of the 1/8 "thick specimen measured according to ASTM D256 is 10 to 70 kgf / cm / cm, and the flame retardancy measured according to UL94 standard is 5VB with respect to the 1.5 to 3.0 mm thick specimen. By weight of the thermoplastic resin composition.
[Chemical Formula 1]
Wherein R 1 and R 4 are each independently a hydrogen atom, a C 6 -C 20 aryl group, or a C 6 -C 20 aryl group substituted with a C 1 -C 10 alkyl group, and R 2 and R 5 are each independently an aryl group or an aryloxy group of a hydrogen atom, a hydroxy group, C6-C20, or C1-C10 of the C6-C20 alkyl group is substituted with the aryl group or aryloxy group and R 3 is an aryl group of C6-C20, m average values of Lt; / RTI >
(2)
In Formula 2, each of R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 independently represents a C 1 -C 6 alkyl group, a C 6 -C 20 aryl group , C1-C6 of the C6-C20 alkyl group is substituted in the aryl group, an aralkyl aryloxy group, C1-C6 alkoxy group, a C6-C20 of C7-C20, amino group or hydroxy group, R 16 is a C6-C30 An arylene group or a C6-C30 arylene group substituted with a C1-C6 alkyl group, a and b are an integer of 0 to 10, and an average value of n is 0.3 to 3. [
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| KR1020140131850A KR101743330B1 (en) | 2014-09-30 | 2014-09-30 | Flame retardant thermoplastic resin composition and article comprising the same |
| PCT/KR2015/001582 WO2016052821A1 (en) | 2014-09-30 | 2015-02-16 | Flame-retardant thermoplastic resin composition and molded product comprising same |
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